CN111560102A - Preparation method of polyion liquid based on biomass residue macromolecular photoinitiator - Google Patents
Preparation method of polyion liquid based on biomass residue macromolecular photoinitiator Download PDFInfo
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- CN111560102A CN111560102A CN202010402972.9A CN202010402972A CN111560102A CN 111560102 A CN111560102 A CN 111560102A CN 202010402972 A CN202010402972 A CN 202010402972A CN 111560102 A CN111560102 A CN 111560102A
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- 239000002028 Biomass Substances 0.000 title claims abstract description 56
- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 50
- 239000007788 liquid Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000001179 sorption measurement Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002608 ionic liquid Substances 0.000 claims description 36
- 239000000047 product Substances 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- -1 1-allyl-3-methylimidazole chlorine salt Chemical class 0.000 claims description 17
- 239000007791 liquid phase Substances 0.000 claims description 17
- 239000004530 micro-emulsion Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 230000001376 precipitating effect Effects 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 240000008042 Zea mays Species 0.000 claims description 10
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 10
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 10
- 235000005822 corn Nutrition 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical group C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 7
- 241000609240 Ambelania acida Species 0.000 claims description 6
- 241000207199 Citrus Species 0.000 claims description 6
- 239000010905 bagasse Substances 0.000 claims description 6
- 235000020971 citrus fruits Nutrition 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 5
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 5
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 5
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- WWVMHGUBIOZASN-UHFFFAOYSA-N 1-methyl-3-prop-2-enylimidazol-1-ium Chemical compound CN1C=C[N+](CC=C)=C1 WWVMHGUBIOZASN-UHFFFAOYSA-N 0.000 claims description 2
- CHKXIPXVBKADAA-UHFFFAOYSA-N [Br].C(=C)N1CN(C=C1)C Chemical compound [Br].C(=C)N1CN(C=C1)C CHKXIPXVBKADAA-UHFFFAOYSA-N 0.000 claims description 2
- UQHLSCXJMYBEGM-UHFFFAOYSA-N [Cl].C(=C)N1CN(C=C1)C Chemical compound [Cl].C(=C)N1CN(C=C1)C UQHLSCXJMYBEGM-UHFFFAOYSA-N 0.000 claims description 2
- DHMWATGUEVQTIY-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-methyl-3-prop-2-enylimidazol-1-ium Chemical class C[N+]=1C=CN(CC=C)C=1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F DHMWATGUEVQTIY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012263 liquid product Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000010902 straw Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 3
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2339/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
Abstract
The invention provides a preparation method of polyion liquid based on a biomass residue macromolecular photoinitiator, which comprises the following steps: s1, preparing a biomass residue macromolecular photoinitiator; s2, preparing the polyion liquid adsorption functional film. The preparation method of the polyion liquid has the following technical advantages: (1) the invention provides a method for successfully introducing biomass residues into a polyion liquid structural unit, and provides a new effective way for high-value utilization of the biomass residues; (2) according to the invention, the biomass residue is modified into the macromolecular photoinitiator, so that the macromolecular photoinitiator is grafted to the framework of the polyion liquid adsorption material, the specific surface area of the product is effectively improved, the utilization rate of functional groups is high, and the adsorption effect of the material on heavy metal ions is obviously improved; (3) the method has the advantages of cheap and easily-obtained raw materials, simple operation method, mild and easily-controlled conditions, environmental protection, low production cost and easy industrial production.
Description
Technical Field
The invention relates to a preparation method of an adsorption functional material, in particular to a preparation method of polyion liquid based on a biomass residue macromolecular photoinitiator, and belongs to the technical field of biomass resource utilization and adsorption materials.
Background
The ultraviolet polymerization technology, as a "green synthesis technology", refers to a technology in which a polymerization system generates free radicals after absorbing ultraviolet light with a certain wavelength by a photoinitiator under the irradiation of the ultraviolet light, thereby initiating a polymerization reaction of monomers. The technology has the advantages of high efficiency, energy conservation and simple and convenient operation, thereby being welcomed in the fields of polymer preparation and application.
With the continuous development of the industry and the increasing demand of resources, the recycling of biomass residues can not only reduce the dependence of petrochemical fuel resources, but also develop various high value-added products, such as adsorption functional materials, based on the functionality of the biomass residues. The polyion liquid adsorption functional film is an adsorption functional material with application potential, has the advantages of designable structure, adjustable property, excellent thermal stability, good adsorption effect on heavy metal ions in water and the like, and has been reported to attract people to pay attention. The traditional technology for synthesizing the polyionic liquid is mainly free radical polymerization, but the main problems faced at present are that the utilization rate of functional groups of the existing polyionic liquid is low, the adsorption effect on heavy metal ions is still poor, and the traditional technology cannot successfully introduce biomass residues into the framework of the polyionic liquid, so that the industrial production is difficult to realize.
Therefore, it is necessary to provide a further solution to the above problems.
Disclosure of Invention
The invention aims to provide a preparation method of polyion liquid based on a biomass residue macromolecular photoinitiator, which aims to overcome the problems in the prior art.
In order to achieve the above object, the present invention provides a method for preparing polyion liquid based on biomass residue macromolecular photoinitiator, which comprises the following steps:
s1, preparation of a biomass residue macromolecular photoinitiator:
the step S1 includes:
s10, dissolving 10g of biomass residue after ethanol/toluene (volume ratio is 1: 2) cleaning and drying treatment in 100g of ionic liquid A, and leaving a liquid-phase product;
s11, under the action of a catalyst, adding diisocyanate into the liquid-phase product obtained in the step S10, reacting for a certain time at a certain temperature, then adding a hydroxyl-containing photoinitiator, and controlling the reaction temperature until the reaction is finished;
s12, repeatedly washing and precipitating with acetone to obtain a reaction system S11, and drying in vacuum to obtain a biomass residue macromolecular photoinitiator;
s2, preparing a polyion liquid adsorption functional film:
the step S2 includes:
s20, stirring the biomass residue macromolecular photoinitiator prepared in the step S1 with a monomer, a cross-linking agent and an ionic liquid B at room temperature to prepare a clear and transparent ionic liquid microemulsion system;
s21, coating the ionic liquid microemulsion system obtained in the step S20 on a glass slide, placing under an ultraviolet lamp for irradiating for a certain time, and curing to obtain a primary product;
s22, cleaning the primary product obtained in the step S21, and drying in vacuum to obtain the porous polyion liquid adsorption functional film.
As an improvement of the preparation method of polyion liquid based on biomass residue macromolecular photoinitiator, in step S10, the biomass residue is apple pomace, citrus pomace, bagasse and corn stalks; the ionic liquid A is one or a compound of more than two of 1-vinyl-3-methylimidazole bromine salt ([ EMIm ] Br), 1-vinyl-3-methylimidazole chlorine salt ([ EMIm ] Cl), 1-allyl-3-methylimidazole chlorine salt ([ AMIm ] Cl) and 1-allyl-3-methylimidazole bromine salt ([ AMIm ] Br).
As an improvement of the preparation method of the polyion liquid based on the biomass residue macromolecular photoinitiator, in the step S11, the catalyst is dibutyltin dilaurate, and the diisocyanate is one of isophorone diisocyanate, diphenylmethane diisocyanate, and toluene diisocyanate; the photoinitiator is one of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 4- (2-hydroxy-3-tert-butyl) benzophenone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] acetone; the dosage of the liquid phase product is 40.0-49.0 parts, the dosage of the diisocyanate is 40.0-49.0 parts, and the dosage of the photoinitiator is 2.0-20.0 parts.
As an improvement of the preparation method of the polyion liquid based on the biomass residue macromolecule photoinitiator, in the step S11, when the liquid phase product containing the biomass residue reacts with diisocyanate, the reaction time is 40-60 DEGoC, stirring and reacting for 3-5 hours; adding photoinitiator, and then adding 50-70 parts of photoinitiatoroCThe reaction is stirred for 4 to 6 hours at the temperature of (2).
As an improvement of the preparation method of polyion liquid based on biomass residue macromolecular photoinitiator, in the step S20, the monomer is 1-vinyl imidazole; the cross-linking agent is one or a compound of two or more of polyethylene glycol diacrylate, ethylene glycol dimethacrylate and 3,3' -dithiodipropionic acid di (N-hydroxysuccinimide) ester; the ionic liquid B is 1-vinyl-3-methylimidazolium hexafluorophosphate ([ AEIm)]PF6) 1-vinyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt ([ AEIm)]NTf2) 1-allyl-3-methylimidazolium hexafluorophosphate ([ AMIm]PF6) 1-allyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt ([ AMIM]NTf2) One or a mixture of two or more of the above.
As an improvement of the preparation method of the polyion liquid based on the biomass residue macromolecular photoinitiator, in the step S20, the dosage of the biomass residue macromolecular photoinitiator is 2.0-12.0 parts, the dosage of the monomer is 50.0-60.0 parts, the dosage of the cross-linking agent is 20.0-25.0 parts, and the dosage of the ionic liquid B is 18.0-23.0 parts.
As an improvement of the preparation method of the polyion liquid based on the biomass residue macromolecular photoinitiator, in the step S21, the prepared ionic liquid microemulsion is irradiated under the ultraviolet light with the wavelength of 365nm, and the irradiation time is 10-120 minutes.
As an improvement of the method for preparing polyion liquid based on biomass residue macromolecular photoinitiator, the step S22 specifically includes: and (3) washing and precipitating the initial product obtained in the step S21 by using water and ethanol alternately and repeatedly, and drying in vacuum to obtain the polyion liquid adsorption functional film based on the biomass residue macromolecular photoinitiator.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a method for successfully introducing biomass residues into a polyion liquid structural unit, and provides a new effective way for high-value utilization of the biomass residues;
(2) according to the invention, the biomass residue is modified into the macromolecular photoinitiator, so that the macromolecular photoinitiator is grafted to the framework of the polyion liquid adsorption material, the specific surface area of the product is effectively improved, the utilization rate of functional groups is high, and the adsorption effect of the material on heavy metal ions is obviously improved;
(3) the method has the advantages of cheap and easily-obtained raw materials, simple operation method, mild and easily-controlled conditions, environmental protection, low production cost and easy industrial production.
Detailed Description
The principles and features of this invention are described below in conjunction with examples, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1:
s1, preparation of a biomass residue macromolecular photoinitiator:
dissolving 10g of apple pomace subjected to cleaning and drying treatment by using ethanol/toluene (volume ratio is 1: 2) in 100g of ionic liquid A1-vinyl-3-methylimidazolium bromide, and reserving a liquid-phase product; isophorone diisocyanate (49 parts by weight) was added to the above liquid phase product (49 parts by weight) under the action of dibutyltin dilaurate as a catalyst at 40oReacting for 5 hours at C, adding 2-hydroxy-2-methyl-1-phenyl-1-acetone (2 parts by weight) as a photoinitiator, and controlling the reaction temperature to be 40oC reaction 6Hours; repeatedly washing and precipitating the reaction system by using acetone, and drying in vacuum to obtain the apple pomace macromolecular photoinitiator;
s2, preparing a polyion liquid adsorption functional film:
stirring the pomace macromolecular photoinitiator (2 parts by weight) prepared in the step S1 with a monomer (60 parts by weight) of 1-vinylimidazole, a cross-linking agent (20 parts by weight) of polyethylene glycol diacrylate and an ionic liquid B1-vinyl-3-methylimidazolium hexafluorophosphate (18 parts by weight) at room temperature to prepare a clear and transparent ionic liquid microemulsion system; coating the ionic liquid microemulsion system on a glass slide, placing under an ultraviolet lamp with the wavelength of 365nm for irradiating for 10 minutes, and curing to obtain a primary product; and washing and precipitating the primary product by using water and ethanol alternately and repeatedly, and drying in vacuum to obtain the polyion liquid adsorption functional film based on the apple pomace macromolecular photoinitiator.
Example 2:
s1, preparation of a biomass residue macromolecular photoinitiator:
dissolving 10g of citrus pulp which is cleaned and dried by ethanol/toluene (volume ratio is 1: 2) in 100g of ionic liquid A1-vinyl-3-methylimidazolium chloride, and reserving a liquid phase product; to the above liquid phase product (40 parts by weight) was added diphenylmethane diisocyanate (40 parts by weight) in the presence of dibutyltin dilaurate as a catalyst at 60 deg.CoC, reacting for 3 hours, adding a photoinitiator 4- (2-hydroxy-3-tert-butyl) benzophenone (20 parts by weight), and controlling 70oC, reacting for 4 hours; repeatedly washing and precipitating the reaction system by using acetone, and drying in vacuum to obtain the citrus pulp macromolecular photoinitiator;
s2, preparing a polyion liquid adsorption functional film:
stirring the citrus pulp macro-molecular photoinitiator (12 parts by weight) prepared in the step S1 with a monomer (50 parts by weight) of 1-vinyl imidazole, a cross-linking agent ethylene glycol dimethacrylate (15 parts by weight) and an ionic liquid B1-vinyl-3-methyl imidazole bis (trifluoromethanesulfonyl) imide salt (23 parts by weight) at room temperature to prepare a clear and transparent ionic liquid microemulsion system; coating the ionic liquid microemulsion system on a glass slide, placing the glass slide under an ultraviolet lamp with the wavelength of 365nm for irradiating for 120 minutes, and curing to obtain a primary product; and washing and precipitating the primary product by using water and ethanol alternately and repeatedly, and drying in vacuum to obtain the polyion liquid adsorption functional film based on the citrus pulp macromolecular photoinitiator.
Example 3:
s1, preparation of a biomass residue macromolecular photoinitiator:
dissolving 10g of bagasse obtained after ethanol/toluene (volume ratio is 1: 2) cleaning and drying treatment in 100g of ionic liquid A1-allyl-3-methylimidazole chloride salt, and leaving a liquid phase product; toluene diisocyanate (45 parts by weight) was added to the above liquid phase product (45 parts by weight) in the presence of dibutyltin dilaurate as a catalyst at 50 deg.CoReacting for 4 hours at the temperature of C, and then adding a photoinitiator 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl]Acetone (10 parts by weight), control 60oC, reacting for 5 hours; repeatedly washing and precipitating the reaction system by using acetone, and drying in vacuum to obtain a bagasse macromolecular photoinitiator;
s2, preparing a polyion liquid adsorption functional film:
stirring 7 parts by weight of bagasse macromolecular photoinitiator prepared in step S1, 50 parts by weight of monomer 1-vinylimidazole, 23 parts by weight of cross-linking agent 3,3' -dithiodipropionic acid bis (N-hydroxysuccinimide) ester and 20 parts by weight of ionic liquid B1-allyl-3-methylimidazolium hexafluorophosphate at room temperature to prepare a clear and transparent ionic liquid microemulsion system; coating the ionic liquid microemulsion system on a glass slide, placing under an ultraviolet lamp with the wavelength of 365nm for irradiating for 60 minutes, and curing to obtain a primary product; and washing and precipitating the primary product by using water and ethanol alternately and repeatedly, and drying in vacuum to obtain the polyion liquid adsorption functional film based on the bagasse macromolecular photoinitiator.
Example 4:
s1, preparation of a biomass residue macromolecular photoinitiator:
mixing ethanol/toluene(volume ratio is 1: 2), dissolving 10g of washed and dried corn straw in 100g of ionic liquid A1-allyl-3-methylimidazolium bromide, and reserving a liquid phase product; isophorone diisocyanate (49 parts by weight) was added to the above liquid phase product (49 parts by weight) under the action of dibutyltin dilaurate as a catalyst at 40oReacting for 3 hours at C, adding 2-hydroxy-2-methyl-1-phenyl-1-acetone (2 parts by weight) as a photoinitiator, and controlling the reaction temperature to be 40oC, reacting for 4 hours; repeatedly washing and precipitating the reaction system by using acetone, and drying in vacuum to obtain the corn straw macromolecular photoinitiator;
s2, preparing a polyion liquid adsorption functional film:
stirring the corn straw macromolecular photoinitiator (2 parts by weight) prepared in the step S1 with a monomer (60 parts by weight) of 1-vinyl imidazole, a cross-linking agent (10 parts by weight) of polyethylene glycol diacrylate, ethylene glycol dimethacrylate and an ionic liquid B1-allyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (18 parts by weight) at room temperature to prepare a clear and transparent ionic liquid microemulsion system; coating the ionic liquid microemulsion system on a glass slide, placing under an ultraviolet lamp with the wavelength of 365nm for irradiating for 60 minutes, and curing to obtain a primary product; and washing and precipitating the primary product by using water and ethanol alternately and repeatedly, and drying in vacuum to obtain the polyion liquid adsorption functional film based on the corn straw macromolecular photoinitiator.
Example 5:
dissolving 10g of corn straw which is cleaned and dried by ethanol/toluene (volume ratio is 1: 2) in 100g of ionic liquid A1-vinyl-3-methylimidazole chloride salt (50 g) and 1-allyl-3-methylimidazole chloride salt (50 g), and leaving a liquid phase product; to the above liquid phase product (40 parts by weight) was added diphenylmethane diisocyanate (40 parts by weight) in the presence of dibutyltin dilaurate as a catalyst at 60 deg.CoC, reacting for 3 hours, adding a photoinitiator 4- (2-hydroxy-3-tert-butyl) benzophenone (20 parts by weight), and controlling 70oC, reacting for 4 hours; repeatedly washing with acetone, precipitating the reaction system, and vacuum dryingThen, obtaining the corn straw macromolecular photoinitiator;
s2, preparing a polyion liquid adsorption functional film:
stirring the corn straw macromolecular photoinitiator (12 parts by weight) prepared in the step S1, a monomer (50 parts by weight) of 1-vinyl imidazole, a crosslinking agent ethylene glycol dimethacrylate (7 parts by weight), 3' -dithiodipropionic acid bis (N-hydroxysuccinimide) ester (8 parts by weight), an ionic liquid B1-vinyl-3-methyl imidazole bis (trifluoromethanesulfonyl) imide salt (13 parts by weight) and 1-allyl-3-methyl imidazole bis (trifluoromethanesulfonyl) imide salt (12 parts by weight) at room temperature to prepare a clear and transparent ionic liquid microemulsion system; coating the ionic liquid microemulsion system on a glass slide, placing the glass slide under an ultraviolet lamp with the wavelength of 365nm for irradiating for 120 minutes, and curing to obtain a primary product; and washing and precipitating the primary product by using water and ethanol alternately and repeatedly, and drying in vacuum to obtain the polyion liquid adsorption functional film based on the corn straw macromolecular photoinitiator.
In summary, the preparation method of the polyion liquid adsorption functional film based on the biomass residue macromolecular photoinitiator has the following technical advantages:
(1) the invention provides a method for successfully introducing biomass residues into a polyion liquid structural unit, and provides a new effective way for high-value utilization of the biomass residues; (2) according to the invention, the biomass residue is modified into the macromolecular photoinitiator, so that the macromolecular photoinitiator is grafted to the framework of the polyion liquid adsorption material, the specific surface area of the product is effectively improved, the utilization rate of functional groups is high, and the adsorption effect of the material on heavy metal ions is obviously improved; (3) the method has the advantages of cheap and easily-obtained raw materials, simple operation method, mild and easily-controlled conditions, environmental protection, low production cost and easy industrial production.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A preparation method of polyion liquid based on a biomass residue macromolecular photoinitiator is characterized by comprising the following steps:
s1, preparation of a biomass residue macromolecular photoinitiator:
the step S1 includes:
s10, dissolving 10g of biomass residue after ethanol/toluene (volume ratio is 1: 2) cleaning and drying treatment in 100g of ionic liquid A, and leaving a liquid-phase product;
s11, under the action of a catalyst, adding diisocyanate into the liquid-phase product obtained in the step S10, reacting for a certain time at a certain temperature, then adding a hydroxyl-containing photoinitiator, and controlling the reaction temperature until the reaction is finished;
s12, repeatedly washing and precipitating with acetone to obtain a reaction system S11, and drying in vacuum to obtain a biomass residue macromolecular photoinitiator;
s2, preparing a polyion liquid adsorption functional film:
the step S2 includes:
s20, stirring the biomass residue macromolecular photoinitiator prepared in the step S1 with a monomer, a cross-linking agent and an ionic liquid B at room temperature to prepare a clear and transparent ionic liquid microemulsion system;
s21, coating the ionic liquid microemulsion system obtained in the step S20 on a glass slide, placing under an ultraviolet lamp for irradiating for a certain time, and curing to obtain a primary product;
s22, cleaning the primary product obtained in the step S21, and drying in vacuum to obtain the porous polyion liquid adsorption functional film.
2. The method for preparing polyion liquid based on biomass residue macromolecular photoinitiator according to claim 1, wherein in the step S10, the biomass residue is apple pomace, citrus pomace, bagasse and corn stalks; the ionic liquid A is one or a compound of more than two of 1-vinyl-3-methylimidazole bromine salt ([ EMIm ] Br), 1-vinyl-3-methylimidazole chlorine salt ([ EMIm ] Cl), 1-allyl-3-methylimidazole chlorine salt ([ AMIm ] Cl) and 1-allyl-3-methylimidazole bromine salt ([ AMIm ] Br).
3. The method for preparing polyionic liquid based on biomass residue macromolecular photoinitiator according to claim 1, wherein in step S11, the catalyst is dibutyltin dilaurate, and the diisocyanate is one of isophorone diisocyanate, diphenylmethane diisocyanate and toluene diisocyanate; the photoinitiator is one of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 4- (2-hydroxy-3-tert-butyl) benzophenone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] acetone; the dosage of the liquid phase product is 40.0-49.0 parts, the dosage of the diisocyanate is 40.0-49.0 parts, and the dosage of the photoinitiator is 2.0-20.0 parts.
4. The method for preparing polyion liquid based on biomass residue macromolecular photoinitiator according to claim 1, wherein in step S11, when reacting the liquid product containing biomass residue with diisocyanate, the reaction time is 40-60%oC, stirring and reacting for 3-5 hours; adding photoinitiator, and then adding 50-70 parts of photoinitiatoroAnd C, stirring and reacting for 4-6 hours.
5. The method for preparing polyion liquid based on biomass residue macromolecular photoinitiator according to claim 1, wherein in the step S20, the monomer is 1-vinyl imidazole; the cross-linking agent is one or a compound of two or more of polyethylene glycol diacrylate, ethylene glycol dimethacrylate and 3,3' -dithiodipropionic acid di (N-hydroxysuccinimide) ester; the ionic liquid B is 1-vinyl-3-methylimidazolium hexafluorophosphate ([ AEIm)]PF6) 1-vinyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt ([ AEIm)]NTf2) 1-allyl-3-methylimidazolium hexafluorophosphate ([ AMIm]PF6) 1-allyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt ([ AMIM]NTf2) One ofOr a mixture of two or more.
6. The method for preparing polyionic liquid based on biomass residue macromolecular photoinitiator according to claim 1, wherein in step S20, the biomass residue macromolecular photoinitiator is used in an amount of 2.0-12.0 parts, the monomer is used in an amount of 50.0-60.0 parts, the cross-linking agent is used in an amount of 20.0-25.0 parts, and the ionic liquid B is used in an amount of 18.0-23.0 parts.
7. The method for preparing polyion liquid based on biomass residue macromolecular photoinitiator according to claim 1, wherein in step S21, the prepared ionic liquid microemulsion is irradiated under 365nm ultraviolet light for 10-120 min.
8. The method for preparing polyion liquid based on biomass residue macromolecular photoinitiator according to claim 1, wherein the step S22 specifically comprises: and (3) washing and precipitating the initial product obtained in the step S21 by using water and ethanol alternately and repeatedly, and drying in vacuum to obtain the polyion liquid adsorption functional film based on the biomass residue macromolecular photoinitiator.
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