CN115260320B - Use of ionic polysaccharide derivatives as anti-icing coating materials - Google Patents

Use of ionic polysaccharide derivatives as anti-icing coating materials Download PDF

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CN115260320B
CN115260320B CN202110483393.6A CN202110483393A CN115260320B CN 115260320 B CN115260320 B CN 115260320B CN 202110483393 A CN202110483393 A CN 202110483393A CN 115260320 B CN115260320 B CN 115260320B
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polysaccharide derivative
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methylimidazole
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CN115260320A (en
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张金明
程耀辉
贺志远
张军
王健君
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    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
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    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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    • C09D103/00—Coating compositions based on starch, amylose or amylopectin or on their derivatives or degradation products
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    • C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
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    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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Abstract

The invention discloses an application of an ionic polysaccharide derivative as an anti-icing coating material, wherein the ionic polysaccharide derivative has a repeated structural unit shown in a formula I. Also disclosed are anti-icing coating compositions and anti-icing coatings comprising the polysaccharide derivatives. The ionic polysaccharide derivative can be used as a coating to obviously reduce the freezing point of water, prolong the freezing time of water at low temperature and reduce the adhesion of ice on the coating, thereby effectively preventing the formation and accumulation of ice crystals on the surface of the coating in a cold environment.
Figure DDA0003049299560000011

Description

Use of ionic polysaccharide derivatives as anti-icing coating materials
Technical Field
The invention belongs to the technical field of natural high polymer materials and fine chemicals, and particularly relates to application of an ionic polysaccharide derivative as an anti-icing coating material, and an anti-icing coating composition and an anti-icing coating containing the ionic polysaccharide derivative.
Background
Ice crystal formation in cold environments can cause damage to some infrastructure (e.g., transmission lines, wind power plants, photovoltaic plants) and vehicles (e.g., aircraft, high-speed rail, automobiles), and even cause serious damage. The anti-icing coating material can be coated on the surfaces of infrastructures such as electric transmission lines and vehicles to prevent ice crystals from forming under cold conditions, so that the damage of ice to the infrastructures and the vehicles is reduced. However, the existing anti-icing coating materials have the problems of high price, poor water resistance, complex composition, non-biodegradability and the like.
Polysaccharide derivatives are important fine chemicals, are one of the earliest high molecular materials for commercialization, and have wide application in the fields of paint, plastics, textiles, papermaking, energy sources, foods, medicines, environment and the like. Such as: cellulose Acetate Butyrate (CAB), cellulose Acetate (CA) and the like are used as paint, ink and the like in general, with tetrahydrofuran, acetone, ethyl acetate and the like as solvents. However, the existing polysaccharide derivatives have poor anti-icing effect.
Disclosure of Invention
In order to solve the technical problems, the invention provides an application of an ionic polysaccharide derivative as an anti-icing coating material, wherein the ionic polysaccharide derivative has a repeating structural unit shown in the following formula I:
Figure BDA0003049299540000021
wherein:
A 1 、A 2 、A 3 identical or different, independently of one another, from R or R'; y is selected from O or NH;
r is selected from one, two or more of the following groups:
Figure BDA0003049299540000022
r' is selected from one, two or more of the following groups:
Figure BDA0003049299540000023
* -the site represents a ligation site;
n is an integer from 1 to 20, preferably an integer from 1 to 10, exemplary being 1,2, 3, 5, 8, 10, 15;
m is an integer of 0 to 12, preferably an integer of 1 to 10, and is exemplified by 1,2, 3, 5, 6, 8, 10;
z is an integer from 0 to 20, preferably an integer from 1 to 10, exemplary being 1,2, 3, 5, 8, 10, 15;
Figure BDA0003049299540000031
is one, two or more of imidazolium salt cation, pyridinium salt cation, pyrrole salt cation, quaternary ammonium salt cation, quaternary phosphonium salt cation and piperidinium salt cation;
Figure BDA0003049299540000032
one, two or more of the following:
Figure BDA0003049299540000033
the substitution degree of R' in the ionic polysaccharide derivative is 0.5-3.0, preferably 0.8-2.0, and exemplified by 0.5, 0.8, 1.0, 1.5, 1.7, 1.8, 1.9, 2.0, 2.1, 2.3, 2.5, 3.0.
According to an embodiment of the invention, the ionic polysaccharide derivative has a degree of polymerization of 100-3000, preferably 100-2000, exemplary 100, 220, 500, 600, 650, 810, 1000, 1500, 2000, 3000.
According to an embodiment of the present invention, the ionic polysaccharide derivative is selected from at least one of a cellulose derivative, a starch derivative, a chitosan derivative, a dextran derivative and a chitin derivative.
According to an embodiment of the present invention, the ionic polysaccharide derivative may be used as an anti-icing coating material for glass, metal, silicon wafer, ceramic wafer, wood material, etc.
According to an embodiment of the invention, the ionsThe polysaccharide derivative is prepared by the following method: comprises mixing a polymer, an acylating agent and a surfactant
Figure BDA0003049299540000034
And (3) reacting the group reagent to obtain the ionic polysaccharide derivative.
According to an embodiment of the invention, the macromolecule, the acylating reagent and the aqueous composition
Figure BDA0003049299540000035
The mass ratio of the reagents of the groups is 1 (0.5-7): (3-9), and is exemplified by 1:0.5:4, 1:0.67:8, 1:2.3:8.3, 1:1.67:5, 1:3:6.
Preferably, the polymer is at least one selected from cellulose, cellulose derivatives, starch derivatives, chitosan, dextran and chitin.
Preferably, the acylating reagent is selected from at least one of 2-chloropropionyl chloride, 2-bromopropionyl bromide and chloroacetyl chloride;
preferably, the said contains
Figure BDA0003049299540000041
The reagent of the group may be, for example, one, two or more reagents selected from the group consisting of an imidazole group, a pyridine group, a pyrrole group, a quaternary ammonium salt group, a quaternary phosphonium salt group, a piperidinium salt group;
for example, the reagent containing an imidazole group is selected from at least one of 1-butylimidazole, 1-methylimidazole, 1-ethylimidazole, imidazole, and 1-allylimidazole.
For example, the quaternary phosphonium salt group-containing reagent is selected from at least one of tributylphosphine, triethylphosphine, trimethylphosphine, and triphenylphosphine.
According to an exemplary embodiment of the present invention, the preparation method of the ionic polysaccharide derivative comprises the following steps:
(1) Dissolving a polymer in the solvent 1 to obtain a polymer solution; adding an acylating reagent into the obtained polymer solution to react to obtain polymer ester;
(2) Dissolving high molecular esterObtaining a high molecular ester solution in the solvent 2; adding a solvent containing a polymer to the polymer ester solution
Figure BDA0003049299540000042
The reagent of the group reacts to obtain polysaccharide derivative;
(3) And (3) dissolving the product obtained in the step (2) in water, adding salt, performing anion exchange, filtering and separating to obtain precipitate, and washing and drying to obtain the ionic polysaccharide derivative.
The solvent 1 is selected from one, two or more of ionic liquid, sulfone solvent and amide solvent;
for example, the ionic liquid includes, but is not limited to, one of the following: 1-ethyl-3-methylimidazole chloride ionic liquid, 1-ethyl-3-methylimidazole bromide ionic liquid, 1-allyl-3-methylimidazole chloride ionic liquid (amicl), 1-allyl-3-methylimidazole bromide ionic liquid, 1-butyl-3-methylimidazole chloride ionic liquid (BmimCl), 1-butyl-3-methylimidazole bromide ionic liquid, 1-ethyl-3-methylimidazole acetate ionic liquid (EmimAc), 1-allyl-3-methylimidazole acetate ionic liquid, 1-butyl-3-methylimidazole acetate ionic liquid, N-ethylpyridine chloride ionic liquid, N-ethylpyridine bromide ionic liquid, 1, 3-dimethylimidazole dimethyl phosphate ionic liquid, 1-ethyl-3-methylimidazole diethyl phosphate ionic liquid, 3-methylimidazole formate ionic liquid, N-methylpyridine formate ionic liquid, 1-ethyl-3-methylimidazole formate ionic liquid, 1-butyl-3-methylimidazole formate ionic liquid; preferably 1-allyl-3-methylimidazole chloride ionic liquid (amicl), 1-butyl-3-methylimidazole chloride ionic liquid (BmimCl) or 1-ethyl-3-methylimidazole acetate ionic liquid (EmimAc);
for example, the sulfone-based solvent and the amide-based solvent are at least one selected from the group consisting of dimethyl sulfoxide, N-Dimethylformamide (DMF) and N, N-dimethylacetamide;
preferably, when the solvent 1 is selected from a mixed solvent of an ionic liquid and a sulfone solvent or an amide solvent, the mass ratio of the ionic liquid to the sulfone solvent or the amide solvent may be (0-9): (0-4), and examples are 0:4, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 9:1, 4:0, 4:0.5, 4:1 and 4:2.
For example, the solvent 2 is at least one selected from sulfone-based solvents and amide-based solvents, such as at least one selected from dimethyl sulfoxide, N-Dimethylformamide (DMF) and N, N-dimethylacetamide; preferably N, N-Dimethylformamide (DMF).
Preferably, in the step (1), the mass fraction of the polymer solution is 5-10%, and exemplary is 5%, 6%, 10%.
Preferably, in step (1), the temperature of the reaction is 30-60 ℃, illustratively 30 ℃,40 ℃, 50 ℃, 60 ℃. Further, the reaction time may be 1 to 4 hours, and is exemplified by 1 hour, 2 hours, 3 hours, and 4 hours.
Preferably, in step (2), the temperature of the reaction is 60-100 ℃, illustratively 60 ℃,80 ℃,100 ℃. Further, the reaction time may be 24 to 48 hours, and is exemplified by 24 hours, 30 hours, 36 hours, 42 hours, 48 hours.
Preferably, the steps (1) and (2) further comprise the steps of precipitating, solid-liquid separating (e.g. filtering), washing and drying the reaction liquid after the reaction is finished, so as to prepare a reaction product.
Preferably, in the step (3), the mass ratio of the product prepared in the step (2) to the salt is 1 (1-3), and the mass ratio is 1:1.6, 1:1.7, 1:2.0 and 1:2.5.
For example, the salt may be at least one of sodium bistrifluoromethanesulfonimide, sodium perfluorooctanoate, and sodium perfluoroheptanesulfonate.
The invention also provides an anti-icing coating composition comprising the ionic polysaccharide derivative.
According to embodiments of the present invention, the anti-icing coating composition may further include conventional components such as defoamers.
The invention also provides application of the anti-icing coating composition as an anti-icing coating of glass, metal, silicon wafer, ceramic wafer, wood material and the like. Preferably, the glass may be at least one of a camera lens, glasses, mirror, goggles, a display device, a vehicle windshield, a rear view mirror, and the like.
The invention also provides an anti-icing coating comprising the ionic polysaccharide derivative or the anti-icing coating composition.
According to an embodiment of the invention, the anti-icing temperature of the anti-icing coating is between-35 and 0 ℃, exemplary is-32 ℃, -25 ℃, -20 ℃, -15 ℃, -10 ℃, -5 ℃, 0 ℃.
According to an embodiment of the present invention, the ice adhesion force of the anti-icing coating is 10 to 100kPa, and exemplary is 16kPa, 20kPa, 25kPa, 30kPa, 33kPa, 35kPa.
The invention also provides a preparation method of the anti-icing coating, which comprises the step of coating the solution containing the ionic polysaccharide derivative on a substrate to prepare the anti-icing coating.
According to an embodiment of the invention, the mass fraction of the solution containing the ionic polysaccharide derivative is 1-50%, exemplary 1%, 5%, 8%, 10%, 20%, 30%, 40%, 50%.
According to an embodiment of the present invention, the solvent used for the solution containing the ionic polysaccharide derivative is selected from one, two or more of water, dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), chloroform, dichloromethane, 1, 2-dichloroethane, acetone, tetrahydrofuran (THF), N-methylpyrrolidone, pyridine, ethanol, methanol, isopropanol, ethyl acetate, butyl acetate, toluene, methyl ethyl ketone. Preferably one or two of water, N-Dimethylformamide (DMF), acetone and ethyl acetate.
Preferably, when the solvent is selected from two of the above solvents, the mass ratio of the two may be 4 (1-4), and exemplary are 4:1, 2:1, 1:1.
According to an embodiment of the present invention, the substrate may be selected from at least one of glass, metal, silicon wafer, ceramic wafer, wood, and the like.
The invention also provides application of the anti-icing coating in infrastructures (such as power transmission lines, wind power equipment and photoelectric equipment) and vehicles (such as aircrafts, high-speed rails and automobiles).
The invention has the beneficial effects that:
the invention introduces cationic groups on the side chains of the polysaccharide, and the obtained polysaccharide derivative can obviously reduce the freezing point of water, delay the icing time and reduce the adhesion of ice on a coating, and simultaneously improve the solubility, so that the polysaccharide derivative can be used as an anti-icing coating material to effectively prevent the formation of ice crystals on the surface of the coating in a cold environment, and has important practical value.
Drawings
FIG. 1 is a hydrogen nuclear magnetic resonance spectrum of cellulose 2-chloropropionate, cellulose butylimidazole chloride, and cellulose butylimidazole perfluorooctanoate in example 1. (test instrument: bruker AV400 Nuclear magnetic resonance spectrometer, solvent: deuterated dimethyl sulfoxide (DMSO-d) 6 )。)
FIG. 2 is an infrared spectrum of cellulose 2-chloropropionate, cellulose butylimidazole chloride, and cellulose butylimidazole perfluorooctanoate in example 1. ( Test instrument: thermo Nicolet6700 fourier transform infrared spectrometer )
FIG. 3 shows the icing of water at-30℃in the coated (example 1) and uncoated areas. ( Test instrument: optical microscope Leica Microsystems and high-speed camera Phantomv7.3 )
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
The preparation of the cellulose butyl imidazole perfluoro octoate comprises the following steps:
(1) 0.3g of cellulose was added to 7.2g of ionic liquid 1-allyl-3-methylimidazole chloride (AmimCl) and dissolved with vigorous stirring at 80℃for 1 hour to give a cellulose/AmimCl solution having a mass fraction of 4%. Cooling to 0 ℃, adding 0.7g of 2-chloropropionyl chloride, reacting for 3 hours at 40 ℃, adding ethanol for precipitation after the reaction is finished, filtering, washing and drying to obtain cellulose 2-chloropropionate;
(2) Dissolving 1g of cellulose 2-chloropropionate prepared in the step (1) in DMF, adding 2.5g of 1-butylimidazole, reacting at 80 ℃ for 24 hours, precipitating with acetone, filtering, washing and drying to obtain cellulose butylimidazole chloride;
(3) 1g of cellulose butyl imidazole chloride salt prepared in the step (2) is dissolved in water, 1.7g of sodium perfluoro octoate is added, and the mixture is stirred for 0.5h, filtered, washed and dried to obtain the cellulose butyl imidazole perfluoro octoate.
The hydrogen nuclear magnetic spectrum and the infrared spectrum of the cellulose 2-chloropropionate, the cellulose butyl imidazole chloride and the cellulose butyl imidazole perfluoro octoate prepared in the embodiment are respectively shown in figures 1 and 2, and the substitution degrees of the 2-chloropropionate, the butyl imidazole chloride and the butyl imidazole perfluoro octoate are respectively 2.0, 1.9 and 1.9 according to the ratio of the integral area of the 2-chloropropionyl group to the integral area of the hydrogen of the cellulose skeleton in the figures.
An anti-icing coating solution was prepared by dissolving 0.5g of cellulose butylimidazole perfluoro-octanoate in 9.5g of DMF. And coating the coating solution on glass, and drying to obtain the anti-icing coating. The freezing temperature of the water on the coating was-32 ℃.
As can be seen from fig. 3: the surface of the coating prepared in this example was not frozen by water at-30 ℃. And the ice adhesion of ice on the coating was 20kPa, which is far lower than the ice adhesion of 700kPa without the coating (test instrument: XY motion stage controller LAC-26, force sensor NC10E, and cold stage Linkam THMS 600).
Example 2
The preparation of the tributylphosphine perfluorooctanoate of the cellulose acetate comprises the following steps:
(1) 0.3g of cellulose acetate (substitution degree: 2.0) was added to 2.7g of DMF solution to prepare 10% by weight of a mass fraction solution, and after cooling to 0℃0.2g of chloroacetyl chloride was added. Reacting at 40 ℃ for 3 hours, adding ethanol for precipitation after the reaction is finished, filtering and washing for three times by using a sand core funnel, and drying to obtain cellulose acetate chloroacetate;
(2) Dissolving 1g of cellulose acetate chloroacetate prepared in the step (1) in DMF, adding 2.4g of tributylphosphine, reacting at 80 ℃ for 24 hours, precipitating, filtering, washing and drying to obtain cellulose acetate tributylphosphine chloride;
(3) Dissolving 1g of the cellulose acetate tributyl phosphine chloride prepared in the step (2) in water, adding 1.6g of sodium perfluoro octoate for ion exchange, stirring for 0.5h, filtering, washing and drying to obtain the cellulose acetate tributyl phosphine perfluoro octoate.
The degree of substitution of acetyl in the cellulose acetate chloroacetate, cellulose acetate tributylphosphine chloride and cellulose acetate tributylphosphine perfluorooctanoate prepared in this example was 2.0, and the degree of substitution of chloroacetate or tributylphosphine was 0.8.
An anti-icing coating solution was prepared by dissolving 1.0g of tributylphosphine perfluorooctanoate of cellulose acetate in 9.0g of DMF/acetone (mass ratio: 7:3). And (3) coating the coating solution on an iron sheet, and drying to obtain the anti-icing coating.
The icing temperature of water on the coating prepared in this example was-26℃and the ice adhesion of ice on the coating was 33kPa.
Example 3
The preparation of the starch ethylimidazole perfluoroheptanesulfonate comprises the following steps:
(1) 0.6g of starch is added into 9.4g of ionic liquid 1-butyl-3-methylimidazole chloride (BmimCl)/DMF (mass ratio: 8:2), and stirred at 80 ℃ for 1h to obtain a starch/BmimCl/DMF solution with mass fraction of 6%. Cooling to 40 ℃, adding 1.0g of 2-bromopropionyl bromide, reacting for 3 hours at 40 ℃, adding ethanol for precipitation after the reaction is finished, filtering, washing and drying to obtain starch 2-bromopropionate;
(2) Dissolving 1g of starch 2-bromopropionate prepared in the step (1) in DMF, adding 3g of 1-ethylimidazole, reacting at 80 ℃ for 48 hours, precipitating with acetone, filtering, washing and drying to obtain starch ethylimidazole chloride;
(3) 1g of the starch ethylimidazole chloride salt prepared in the step (2) is dissolved in water, 2.5g of sodium perfluor heptylate is added, and the mixture is stirred for 0.5h, filtered, washed and dried to obtain the starch ethylimidazole perfluor heptylate.
The substitution degrees of the starch 2-bromopropionate, the starch ethylimidazole chloride and the starch ethylimidazole perfluoroheptanesulfonate prepared in the example are all 1.5.
An anti-icing coating solution was prepared by dissolving 0.8g of starch ethylimidazole perfluoroheptanesulfonate in 9.2g of DMF/ethyl acetate (mass ratio: 8:2). And coating the anti-icing coating solution on a silicon wafer, and drying to obtain the anti-icing coating.
The icing temperature of water on the coating prepared in this example was-28℃and the ice adhesion of ice on the coating was 35kPa.
Example 4
The preparation of chitosan allyl imidazole bistrifluoro methanesulfonimide salt comprises the following steps:
(1) 0.5g of chitosan is added into 9.5g of ionic liquid 1-butyl-3-methylimidazole chloride (BmimCl)/DMSO (mass ratio: 9:1), and stirred at 100 ℃ for 2 hours to obtain a chitosan/BmimCl/DMSO solution with a mass fraction of 5%. Cooling to 0 ℃, adding 1.5g of 2-chloropropionyl chloride, reacting for 3 hours at 40 ℃, adding ethanol for precipitation after the reaction is finished, filtering, washing and drying to obtain chitosan 2-chloropropionate;
(2) Dissolving 1g of chitosan 2-chloropropionate prepared in the step (1) in DMF, adding 3g of 1-allylimidazole, reacting at 80 ℃ for 48 hours, precipitating with acetone, filtering, washing and drying to obtain chitosan allylimidazole chloride;
(3) 1g of chitosan allyl imidazole chloride salt prepared in the step (2) is dissolved in water, 2.5g of bistrifluoro methanesulfonimide sodium is added, and the mixture is stirred for 0.5h, filtered, washed and dried to obtain chitosan allyl imidazole bistrifluoro methanesulfonimide salt.
The substitution degrees of the chitosan 2-chloropropionate, the chitosan allyl imidazole chloride salt and the chitosan allyl imidazole bistrifluoro methanesulfonimide salt prepared in the embodiment are all 1.7.
An anti-icing coating solution was prepared by dissolving 1.5g of chitosan allyl imidazole bistrifluoromethanesulfonimide salt in 8.5g of DMF/ethyl acetate (mass ratio: 8:2). And coating the anti-icing coating solution on the ceramic sheet, and drying to obtain the anti-icing coating.
The icing temperature of water on the coating prepared in this example was-29℃and the ice adhesion of ice on the coating was 16kPa.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (34)

1. Use of an ionic polysaccharide derivative as an anti-icing coating material, characterized in that the ionic polysaccharide derivative has a repeating structural unit represented by the following formula I:
Figure FDA0004122634700000011
wherein:
A 1 、A 2 、A 3 identical or different, independently of one another, from R or R'; a is that 1 、A 2 、A 3 At least one of which is selected from R';
y is selected from O or NH;
r is selected from one, two or more of the following groups:
*-H
Figure FDA0004122634700000012
*-NO 2 *-CH 3
Figure FDA0004122634700000013
*-CH 2 COOH *-CH 2 COONa
Figure FDA0004122634700000014
r' is selected from one, two or more of the following groups:
Figure FDA0004122634700000015
* -the site represents a ligation site;
n is an integer of 1 to 20;
m is an integer of 0 to 12;
z is an integer from 0 to 20;
Figure FDA0004122634700000021
is one, two or more of imidazolium salt cation, pyridinium salt cation, pyrrole salt cation, quaternary ammonium salt cation, quaternary phosphonium salt cation and piperidinium salt cation;
Figure FDA0004122634700000022
one, two or more of the following:
Figure FDA0004122634700000023
the substitution degree of R' in the ionic polysaccharide derivative is 0.5-3.0.
2. The use according to claim 1, wherein the ionic polysaccharide derivative has a degree of polymerization of 100 to 3000.
3. The use according to claim 1, wherein the ionic polysaccharide derivative is selected from at least one of cellulose derivatives, starch derivatives, chitosan derivatives, dextran derivatives and chitin derivatives.
4. Use according to any one of claims 1 to 3, wherein the ionic polysaccharide derivative is used as an anti-icing coating material for glass, metal, silicon, ceramic, wood materials.
5. The use according to claim 1, wherein n is an integer from 1 to 10; m is an integer of 1 to 10; z is an integer from 1 to 10.
6. The use according to claim 1, wherein the degree of substitution of R' is 0.8-2.0.
7. The use according to claim 1, wherein the ionic polysaccharide derivative has a degree of polymerization of 100 to 2000.
8. Use according to any one of claims 1 to 3, wherein the ionic polysaccharide derivative is prepared by the following method: comprises mixing a polymer, an acylating agent and a surfactant
Figure FDA0004122634700000031
And (3) reacting the group reagent to obtain the ionic polysaccharide derivative.
9. The use according to claim 8, wherein the macromolecule, the acylating agent and the agent comprise
Figure FDA0004122634700000032
The mass ratio of the reagent of the group is 1 (0.5-7) to 3-9.
10. The use according to claim 8, wherein the polymer is selected from at least one of cellulose, cellulose derivatives, starch derivatives, chitosan, dextran and chitin.
11. The use according to claim 8, wherein the acylating agent is selected from at least one of 2-chloropropionyl chloride, 2-bromopropionyl bromide and chloroacetyl chloride.
12. The use according to claim 8, wherein,the said contains
Figure FDA0004122634700000033
The reagent of the group is selected from one, two or more reagents of imidazole group, pyridine group, pyrrole group, quaternary ammonium salt group, quaternary phosphonium salt group and piperidine salt group.
13. The use according to claim 12, wherein the reagent containing imidazole groups is selected from at least one of 1-butylimidazole, 1-methylimidazole, 1-ethylimidazole, imidazole and 1-allylimidazole.
14. The use according to claim 12, wherein the quaternary phosphonium salt group-containing reagent is selected from at least one of tributylphosphine, trimethylphosphine, triethylphosphine, and triphenylphosphine.
15. The use according to claim 8, wherein the process for the preparation of the ionic polysaccharide derivative comprises the steps of:
(1) Dissolving a polymer in the solvent 1 to obtain a polymer solution; adding an acylating reagent into the obtained polymer solution to react to obtain polymer ester;
(2) Dissolving high molecular ester in a solvent 2 to obtain a high molecular ester solution; adding a solvent containing a polymer to the polymer ester solution
Figure FDA0004122634700000041
The reagent of the group reacts to obtain polysaccharide derivative; and
(3) And (3) dissolving the product obtained in the step (2) in water, adding salt, performing anion exchange, filtering, separating precipitate, washing and drying to obtain the ionic polysaccharide derivative.
16. The use according to claim 15, wherein the solvent 1 is selected from one, two or more of ionic liquids, sulfone-based solvents and amide-based solvents.
17. The use according to claim 16, wherein the ionic liquid comprises, but is not limited to, one of the following: 1-ethyl-3-methylimidazole chloride ionic liquid, 1-ethyl-3-methylimidazole bromide ionic liquid, 1-allyl-3-methylimidazole chloride ionic liquid (AmimCl), 1-allyl-3-methylimidazole bromide ionic liquid, 1-butyl-3-methylimidazole chloride ionic liquid (BmimCl), 1-butyl-3-methylimidazole bromide ionic liquid, 1-ethyl-3-methylimidazole acetate ionic liquid (Emimac), 1-allyl-3-methylimidazole acetate ionic liquid, 1-butyl-3-methylimidazole acetate ionic liquid, N-ethylpyridine chloride ionic liquid, N-ethylpyridine bromide ionic liquid, 1, 3-dimethylimidazole dimethyl phosphate ionic liquid, 1-ethyl-3-methylimidazole diethyl phosphate ionic liquid, 3-methylimidazole formate ionic liquid, N-methylpyridine formate ionic liquid, 1-ethyl-3-methylimidazole formate ionic liquid, 1-butyl-3-methylimidazole formate ionic liquid.
18. The use according to claim 16, wherein the sulfone-based solvent, amide-based solvent is selected from at least one of dimethyl sulfoxide, N-Dimethylformamide (DMF) and N, N-dimethylacetamide.
19. The use according to claim 15, wherein the solvent 1 is selected from the group consisting of ionic liquids and mixed solvents of sulfone solvents and amide solvents in a mass ratio of (0-9): 0-4.
20. The use according to claim 15, wherein the solvent 2 is selected from at least one of sulfone-based solvents, amide-based solvents.
21. The use according to claim 20, wherein the solvent 2 is selected from at least one of dimethyl sulfoxide, N-Dimethylformamide (DMF) and N, N-dimethylacetamide.
22. The use according to claim 15, wherein in step (1) the mass fraction of the polymer solution is between 5 and 10%.
23. The use according to claim 15, wherein in step (1) the temperature of the reaction is 30-60 ℃ and the time of the reaction is 1-4 hours.
24. The use according to claim 15, wherein in step (2) the reaction is carried out at a temperature of 60-100 ℃ for a time of 24-48 hours.
25. The use according to claim 15, wherein in step (3), the mass ratio of the product prepared in step (2) to the salt is 1 (1-3).
26. The use of claim 15, wherein the salt is at least one of sodium bistrifluoromethanesulfonimide, sodium perfluorooctanoate, and sodium perfluoroheptanesulfonate.
27. An anti-icing coating composition comprising the ionic polysaccharide derivative of any of claims 1-3.
28. Use of the anti-icing coating composition according to claim 27 as an anti-icing coating for glass, metal, silicon, ceramic, wood materials.
29. The use of claim 28, wherein the glass is at least one of a camera lens, glasses, mirror, goggles, a display device, a vehicle windshield, and a rear view mirror.
30. An anti-icing coating comprising the ionic polysaccharide derivative of any one of claims 1-3 or the anti-icing coating composition of claim 27.
31. A method of preparing an anti-icing coating as claimed in claim 30, comprising the steps of: coating a substrate with a solution comprising the ionic polysaccharide derivative of any one of claims 1-3 to produce the anti-icing coating.
32. The method according to claim 31, wherein the mass fraction of the solution containing the ionic polysaccharide derivative is 1-50%.
33. The method according to claim 31, wherein the solvent used for the solution containing the ionic polysaccharide derivative is selected from one or more of water, dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), chloroform, dichloromethane, 1, 2-dichloroethane, acetone, tetrahydrofuran (THF), N-methylpyrrolidone, pyridine, ethanol, methanol, isopropanol, ethyl acetate, butyl acetate, toluene, methyl ethyl ketone.
34. The process according to claim 33, wherein when the solvent is selected from two of the above solvents, the mass ratio of the two solvents is 4 (1-4).
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