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`DESCRIPTION CN103467382
`
`The invention discloses a preparation method of a thiocyanate ionic liquid and the application thereof in the
`
`polyacrylonitrile spinning process. The thiocyanate ionic liquid of the present invention has the general formula
`
`[cation] [SCN], wherein [cation] comprises an imidazolium cation, a pyrrolidine cation, a pyridinium cation,
`
`and a piperidinium cation; The preparation of the acid ionic liquid is as follows: the halogenated ionic liquid and
`
`the potassium thiocyanate are added to the reaction bottle in a molar ratio, then acetone is added, the
`
`temperature is raised to 20 ° C to 100 ° C, and the reaction is kept for 12 to 48 hours; after the heat
`
`preservation reaction is completed, The mixture was cooled to 0 to 5 ° C and stirred for 2 to 4 hours, and then
`
`filtered with a cake, and the filtrate was decompressed to dryness under vacuum at 0.07 MPa to 0.09 MPa. The
`
`thiocyanate—containing ionic liquid of the invention has good solubility to polyacrylonitrile, and can be used as a
`
`solvent in polyacrylonitrile spinning, dissolution molding processing and derivatization reaction.
`
`Preparation method of thiocyanate ionic liquid and application thereof in polyacrylonitrile spinning process
`
`Technical field
`
`The invention relates to a thiocyanate ionic liquid which has excellent solubility properties for polyacrylonitrile,
`
`in particular to a preparation method of a thiocyanate ionic liquid and its application in the spinning process of
`
`polyacrylonitrile.
`
`Background technique
`
`Polyacrylonitrile is an opaque powder with a white or yellowish appearance. It is generally used in the form of
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`polyacrylonitrile fibers for daily life and industrial production. Currently, there are many different methods for
`
`producing polyacrylonitrile fibers and acrylonitrile, including wet. The methods used in the dry and dry
`
`processes, the wet processing and the spinning process are dimethylformamide, dimethylacetamide, dimethyl
`
`sulfoxide, ethylene carbonate, sodium thiocyanate, nitric acid and zinc chloride. Different solvents determine the
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`preparation conditions of the spinning solution, spinning conditions, solvent recovery methods and wastewater
`
`treatment methods, and also affect many aspects such as fire prevention, anti—virus and equipment selection.
`
`However, the use of solvents in the industry is more or less disadvantageous, such as toxicity, corrosiveness,
`
`pollution, limited solubility, solvent recovery and complicated disposal of three wastes. Therefore, it is
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`particularly important to find a solvent that is more environmentally friendly and has excellent solubility
`
`properties.
`
`An ionic liquid refers to a class of organic ionic compounds composed of an anion and a cation, and which are
`
`liquid compounds at room temperature or near room temperature. Ionic liquids have the advantages of low
`
`vapor pressure, non—flammability, and good heat stability at room temperature. In general, imidazole ionic
`
`liquids are more thermally stable, and their initial decomposition temperature is above 300—400 ° C. The ionic
`
`liquid has the advantages of easy recovery and low cost, and is also a non—polluting, non—toxic solvent to ions.
`
`The polyacrylonitrile processing method in which the liquid is a solvent system is attracting more and more
`
`attention due to its green environmental protection and simple process, and the obtained product has superior
`
`performance.
`
`Summary of the invention
`
`The object of the present invention is to provide a method for preparing a thiocyanate—containing ionic liquid
`
`and its application in polyacrylonitrile spinning processing in view of the deficiencies of the prior art. The
`
`thiocyanate—containing ionic liquid has excellent solubility for polyacrylonitrile and can be used in
`
`polyacrylonitrile dissolution, spin forming processing and derivatization.
`
`The technical solution adopted by the present invention to solve the technical problems thereof is as follows:
`
`The structure of the thiocyanate—containing ionic liquid is as follows:
`
`Containing an ionic liquid of the formula [cation] [SCN], ie an ionic liquid containing thiocyanate; wherein
`
`[cation] is a quaternary ammonium cation [NR < 1 > R < 2 > R < 3 > R] < + > , Specifically include the
`
`following:
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`[Cation] is an imidazolium cation with the following structure:
`
`[image]
`
`Wherein R is a saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms, R < 1 > is a saturated
`
`or unsaturated hydrocarbon group having 0 to 4 carbon atoms, and R < 2 > is 1 to 12 A saturated or unsaturated
`
`hydrocarbon group of a carbon atom.
`
`[cation] is a pyrrolidine cation having the following structure:
`
`[image]
`
`Wherein R is a saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms, and R < 1 > is a
`
`saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.
`
`[cation] is a pyridinium cation having the following structure:
`
`[image]
`
`Wherein R is a saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms, and R < 1 > is a
`
`saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.
`
`[Cation] is a piperidinium cation with the following structure:
`
`[image]
`
`Wherein R is a saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms, and R < 1 > is a
`
`saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.
`
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`The preparation method of the thiocyanate ionic liquid is as follows:
`
`Adding the halogenated ionic liquid and potassium thiocyanate to the reaction flask at a molar ratio of 120.9 to
`
`121.5, adding acetone, raising the temperature to 20 ° C to 100 ° C, and maintaining the reaction for 12 to 48
`
`hours; The mixture was cooled to 0 to 5 ° C and stirred for 2 to 4 hours, and then filtered with a filter cake. The
`
`filtrate was decompressed to dryness under vacuum at 0.07 MPa to 0.09 MPa, which was a thiocyanate ionic
`
`liquid.
`
`The mass of the added acetone is 3 to 10 times the mass of potassium thiocyanate.
`
`The dissolution method of polyacrylonitrile containing thiocyanate ionic liquid is as follows:
`
`100 g of the thiocyanate ionic liquid was weighed into a 250 ml round bottom flask, heated to 100 ° C with an
`
`oil bath, magnetic stirring was started, and 0.5 g to 25 g of polyacrylonitrile was added in portions. After stirring
`
`for 8 to 12 hours, the solution was clarified, indicating that the polyacrylonitrile was completely dissolved. A
`
`corresponding polyacrylonitrile solution is obtained.
`
`The preparation method of the polyacrylonitrile spinning dope is as follows:
`
`Add 19% to 21% of acrylonitrile monomer, 1% to 2% of itaconic acid monomer, and 77% to 80% of thiocyanate
`
`ionic liquid to the reaction flask at room temperature, and stir under nitrogen atmosphere to make it sufficient.
`
`Mixed to dissolve. Further, 0.1% to 0.15 of azobisisobutyronitrile is added, and the temperature is raised to 50 to
`
`80 ° C, and the reaction is kept for 6 to 8 hours. After the completion of the reaction, the temperature was
`
`lowered to room temperature, and the reaction liquid was poured into 4 to 8 times of water to coagulate the
`
`polymer. After filtration, it was washed 4 times with 2 to 4 times of 70 ° C water. 70Dry under vacuum at ° C
`
`for 24 to 36 hours. 10 g to 100 g of the polyacrylonitrile obtained above was added to 400 g of a thiocyanate ionic
`
`liquid, and the temperature was raised to 100 ° C to start stirring. After stirring for 8 to 12 hours, the solution
`
`was clarified to obtain a polyacrylonitrile spinning dope.
`
`The beneficial effects of the present invention are as follows:
`
`The solubility test of polyacrylonitrile was carried out on the four thiocyanate—containing ionic liquids as
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`described above. The test results show that these thiocyanate—containing ionic liquids have good solubility to
`
`polyacrylonitrile. In particular, the imidazolium—based cationic thiocyanate ionic liquid has excellent solubility in
`
`polyacrylonitrile. Meanwhile, the four thiocyanate ionic liquids as described above can be used as a solvent in the
`
`polymerization of acrylonitrile, and the polyacrylonitrile obtained by the polymerization can be dissolved, and
`
`the polyacrylonitrile can be further spun.
`
`Because ionic liquid is liquid at room temperature, it is stable to water, stable at high temperature, almost no
`
`vapor pressure, soluble in water, convenient for recycling, and can be recycled. It can be used as a solvent instead
`
`of other conventional solvents for polyacrylonitrile spinning, dissolution molding processing and derivatization.
`
`Providing the above ionic liquid to polyacrylonitrile solubility, the ionic liquid provided at 100 ° C can dissolve
`
`up to 20% of polyacrylonitrile, and the ionic liquid can be used for polyacrylonitrile spinning because of its
`
`superior product performance and environmental protection. Molding and other applications.
`
`Detailed ways
`
`The following examples are intended to illustrate, but are not limited to, the methods and preparations of the
`
`thiocyanate—containing ionic liquids referred to in the present invention.
`
`Example 1:
`
`100 g of 1—ethyl—3—methylimidazolium thiocyanate ionic liquid was weighed into a 250 ml round bottom flask,
`
`heated to 100 ° C with an oil bath, magnetic stirring was started, and 25 g of polyacrylonitrile was added in
`
`portions. After stirring for 8 hours, the solution was clarified, indicating that the polyacrylonitrile was completely
`
`dissolved. A 20 wt% polyacrylonitrile solution was obtained.
`
`Example 2:
`
`(Example 1, replace 1—ethyl—3—methylimidazolium thiocyanate ionic liquid into other thiocyanate—containing
`
`ionic liquid)
`
`Take 100g of various ionic liquids, add polyacrylonitrile in batches at 100 ° C until insoluble, and convert to
`
`solubility (g/g). The data obtained are as follows:
`
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`Example 3:
`
`200 g of an acrylonitrile monomer, 10 g of itaconic acid monomer, and 790 g of 1—ethyl—3—methylimidazolium
`
`thiocyanate were placed in a 2000 ml four—necked flask at room temperature, and stirred under nitrogen
`
`atmosphere to be sufficiently mixed and dissolved. Further, I g of azobisisobutyronitrile was added, and the
`
`temperature was raised to 58 ° C, and the reaction was kept for 7 hours. After the reaction was completed, the
`
`temperature was lowered to room temperature, and the reaction liquid was poured into 5000 ml of water to
`
`coagulate the polymer. After filtration, it was washed 4 times with 3000 ml of water at 70 ° C. 70Dry under
`vacuum at ° C for 24 hours.
`
`100 g of the polyacrylonitrile obtained above was added to 400 g of 1—ethyl—3—methylimidazolium thiocyanate,
`
`and the temperature was raised to 100 ° C, and stirring was started. After stirring for 8 hours, the solution was
`
`clarified to obtain a polyacrylonitrile spinning dope.
`
`Example 4:
`
`200 g of an acrylonitrile monomer, 10 g of itaconic acid monomer, and 790 g of 1—allyl—3—methylimidazolium
`
`thiocyanate were placed in a 2000 ml four—necked flask at room temperature, and stirred under nitrogen
`
`atmosphere to be sufficiently mixed and dissolved. Further, I g of azobisisobutyronitrile was added, and the
`
`temperature was raised to 58 ° C, and the reaction was kept for 7 hours. After the reaction was completed, the
`
`temperature was lowered to room temperature, and the reaction liquid was poured into 5000 ml of water to
`
`coagulate the polymer. After filtration, it was washed 4 times with 3000 ml of water at 70 ° C. 70Dry under
`vacuum at ° C for 24 hours.
`
`100 g of the polyacrylonitrile obtained above was added to 400 g of 1—allyl—3—methylimidazolium thiocyanate,
`
`and the temperature was raised to 100 ° C, and stirring was started. After stirring for 8 hours, the solution was
`
`clarified to obtain a polyacrylonitrile spinning dope.
`
`Example 5:
`
`1 S
`
`ynthesis of ethyl—3—methylimidazolium thiocyanate
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`Into a 1000 ml three—necked flask equipped with a stirrer, a thermometer, and a condenser, 146.6 g of 1—ethyl—3—
`
`methylimidazolium chloride salt, 97 g of potassium thiocyanate, and 600 ml of acetone were placed, and the
`mixture was stirred and heated to reflux.
`
`The reaction was kept for 24 hours. After the end of the heat preservation, the temperature was lowered to 0 to 5
`
`C, and the salt was separated for 2 hours, filtered, and the filter cake was rinsed with a small amount of
`
`acetone. The filtrate was decompressed to dryness at 0.07 MPa. A yellow liquid was obtained in an amount of 160
`
`g.
`
`Example 6
`
`ISynthesis of —propyl—3—methylimidazolium thiocyanate
`
`Into a 500 ml three—necked flask equipped with a stirrer, a thermometer, and a condenser, 62.2 g of 1—propyl—3—
`
`methylimidazolium chloride, 40.7 g of potassium thiocyanate, and 400 ml of acetone were placed, and the
`
`mixture was stirred and heated to reflux. The reaction was kept for 24 hours. After the end of the heat
`
`preservation, the temperature was lowered to 0 to 5 ° C, and the salt was separated for 2 hours, filtered, and the
`
`filter cake was rinsed with a small amount of acetone. The filtrate was decompressed to dryness at 0.07 MPa. A
`
`yellow liquid of 67 g was obtained.
`
`Example 7
`
`ISynthesis of hexyl—3—methylimidazolium thiocyanate
`
`Into a 250 ml three—necked flask equipped with a stirrer, a thermometer, and a condenser, 40.5 g of 1—hexyl—3—
`
`methylimidazolium chloride and 20.4 g of potassium thiocyanate and 200 ml of acetone were placed, and the
`
`mixture was stirred and heated to reflux. The reaction was kept for 36 hours. After the end of the heat
`
`preservation, the temperature was lowered to 0—5 ° C, and the salt was separated for 2 hours, filtered, and the
`
`filter cake was rinsed with a small amount of acetone. The filtrate was decompressed to dryness at 0.07 MPa. A
`
`brown liquid of 45.8 g was obtained.
`
`Example 8
`
`22-07-2019
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`

`ISynthesis of allyl—3—methylimidazolium thiocyanate
`
`Into a 1000 ml three—necked flask equipped with a stirrer, a thermometer, and a condenser, 146.6 g of 1—allyl—3—
`
`methylimidazolium chloride, 97 g of potassium thiocyanate, and 600 ml of acetone were placed, and the mixture
`
`was stirred and heated to reflux. The reaction was kept for 24 hours. After the end of the heat preservation, the
`
`temperature was lowered to 0 to 5 ° C, and the salt was separated for 2 hours, filtered, and the filter cake was
`
`rinsed with a small amount of acetone. The filtrate was decompressed to dryness at 0.07 MPa. A brown liquid of
`
`170 g was obtained.
`
`Example 9
`
`ISynthesis of —propyl—2,3—dimethylimidazolium thiocyanate
`
`Into a 250 ml three—necked flask equipped with a stirrer, a thermometer, and a condenser, 35.1 g of 1—propyl—2,3—
`
`dimethylimidazolium chloride, 20.8 g of potassium thiocyanate, and 200 ml of acetone were placed, and the
`
`mixture was stirred and heated to reflux. The reaction was kept for 36 hours. After the end of the heat
`
`preservation, the temperature was lowered to 0—5 ° C, and the salt was separated for 2 hours, filtered, and the
`
`filter cake was rinsed with a small amount of acetone. The filtrate was decompressed to dryness at 0.07 MPa. A
`
`yellow liquid was obtained 39 g.
`
`Example 10:
`
`ISynthesis of butyl—2,3—dimethylimidazolium thiocyanate
`
`Into a 250 ml three—necked flask equipped with a stirrer, a thermometer, and a condenser, 37.7 g of 1—butyl—2,3—
`
`dimethylimidazolium chloride, 20.8 g of potassium thiocyanate, and 200 ml of acetone were placed, and the
`
`mixture was stirred and heated to reflux. The reaction was kept for 36 hours. After the end of the heat
`
`preservation, the temperature was lowered to 0—5 ° C, and the salt was separated for 2 hours, filtered, and the
`
`filter cake was rinsed with a small amount of acetone. The filtrate was decompressed to dryness at 0.07 MPa. A
`
`yellow liquid was obtained 42 g.
`
`22-07-2019
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`8
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`

`Example 11
`
`Synthesis of N—butylpyridine thiocyanate
`
`Into a 250 ml three—necked flask equipped with a stirrer, a thermometer, and a condenser, 32.3 g of N—
`
`butylpyridine chloride salt, 21 g of potassium thiocyanate, and 200 ml of acetone were placed, and the mixture
`
`was stirred and heated to reflux. The reaction was kept for 24 hours. After the end of the heat preservation, the
`
`temperature was lowered to 0 to 5 ° C, and the salt was separated for 2 hours, filtered, and the filter cake was
`
`rinsed with a small amount of acetone. The filtrate was decompressed to dryness at 0.07 MPa. A yellow liquid was
`
`obtained in an amount of 36.5 g.
`
`Example 12
`
`Synthesis of N—butyl—N—methylpyrrolidine thiocyanate
`
`Into a 250 ml three—necked flask equipped with a stirrer, a thermometer, and a condenser, 35.5 g of N—butyl—N—
`
`methylpyrrolidine chloride salt, 21 g of potassium thiocyanate, and 200 ml of acetone were placed, and the
`
`mixture was stirred and heated to reflux. The reaction was kept for 24 hours. After the end of the heat
`
`preservation, the temperature was lowered to 0 to 5 ° C, and the salt was separated for 2 hours, filtered, and the
`
`filter cake was rinsed with a small amount of acetone. The filtrate was decompressed to dryness at 0.07 MPa. A
`
`yellow liquid was obtained in 37 g.
`
`Example 13
`
`Synthesis of N—butyl—N—methylpiperidine thiocyanate
`
`Into a 250 ml three—necked flask equipped with a stirrer, a thermometer, and a condenser, 38.3 g of N—butyl—N—
`
`methylpiperidine chloride salt, 21 g of potassium thiocyanate, and 200 ml of acetone were placed, and the
`
`mixture was stirred and heated to reflux. The reaction was kept for 24 hours. After the end of the heat
`
`preservation, the temperature was lowered to 0 to 5 ° C, and the salt was separated for 2 hours, filtered, and the
`
`filter cake was rinsed with a small amount of acetone. The filtrate was decompressed to dryness at 0.07 MPa. A
`
`yellow liquid was obtained 42.5 g.
`
`22-07-2019
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`22-07-2019
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