CN114672065A - Preparation method of porous crystal glue by using eutectic solvent as crystallization pore-foaming agent - Google Patents
Preparation method of porous crystal glue by using eutectic solvent as crystallization pore-foaming agent Download PDFInfo
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- CN114672065A CN114672065A CN202210409180.3A CN202210409180A CN114672065A CN 114672065 A CN114672065 A CN 114672065A CN 202210409180 A CN202210409180 A CN 202210409180A CN 114672065 A CN114672065 A CN 114672065A
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- 239000002904 solvent Substances 0.000 title claims abstract description 95
- 230000005496 eutectics Effects 0.000 title claims abstract description 84
- 239000013078 crystal Substances 0.000 title claims abstract description 72
- 239000003292 glue Substances 0.000 title claims abstract description 64
- 238000002425 crystallisation Methods 0.000 title claims abstract description 26
- 230000008025 crystallization Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000004088 foaming agent Substances 0.000 title claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 230000008014 freezing Effects 0.000 claims abstract description 18
- 238000007710 freezing Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 238000002791 soaking Methods 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims description 36
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 27
- 239000011148 porous material Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 13
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 9
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 claims description 8
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 8
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 7
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 7
- 239000000463 material Substances 0.000 abstract description 12
- 230000002209 hydrophobic effect Effects 0.000 abstract description 10
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 15
- 239000004926 polymethyl methacrylate Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- 239000004342 Benzoyl peroxide Substances 0.000 description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 5
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- CRPUJAZIXJMDBK-UHFFFAOYSA-N camphene Chemical compound C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 description 4
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 238000002083 X-ray spectrum Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 231100000053 low toxicity Toxicity 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 239000003361 porogen Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Primaeres Camphenhydrat Natural products C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 2
- 229930006739 camphene Natural products 0.000 description 2
- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Natural products C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 description 2
- 239000000495 cryogel Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000036983 biotransformation Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 108010082117 matrigel Proteins 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
- C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
-
- 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
- C08J2333/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
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- 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
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to a preparation method of porous crystal glue by taking a eutectic solvent as a crystallization pore-forming agent. The preparation method of the porous crystal glue by taking the eutectic solvent as the crystallization pore-foaming agent comprises the following steps: (1) dissolving a reaction monomer in a eutectic solvent to obtain a mixed solution 1; (2) sequentially dissolving a cross-linking agent, an oxidant and a reducing agent in the mixed solution 1 to obtain a mixed solution 2; (3) after bubbles are discharged from the mixed solution 2, freezing the mixed solution at the temperature of-10 to-30 ℃ for 24 to 48 hours, and unfreezing the mixed solution in deionized water for 5 to 30min to obtain wet crystal glue; (4) and repeatedly soaking the wet crystal glue by using deionized water or ethanol, removing unreacted substances and eutectic solvents, and then carrying out vacuum drying treatment to obtain the porous crystal glue. The preparation method of the porous crystal glue with the eutectic solvent as the crystallization pore-forming agent adopts the eutectic solvent as the crystallization pore-forming solvent, and prepares the hydrophobic crystal glue material by a crystallization/freezing pore-forming method.
Description
Technical Field
The invention belongs to the technical field of porous materials, and particularly relates to a preparation method of porous crystal glue by taking a eutectic solvent as a crystallization pore-forming agent.
Background
Water as a cheap and nontoxic crystalline porogen has been widely used in the preparation process of different matrix crystalloid materials. The prepared crystal glue material has an ultra-large pore structure which is mutually communicated, and simultaneously has high specific surface area and good mechanical property. Therefore, the crystal gel material has been widely used in the fields of adsorption separation, catalyst carrier, tissue engineering and the like. However, water as a crystallization pore-forming agent cannot meet the requirements of preparation of hydrophobic crystal glue materials, and meanwhile, the crystal form of water limits the diversification of crystal glue pore structures.
In view of this, the invention provides a novel preparation method of porous crystal glue, which can prepare hydrophobic crystal glue and has rich porous structure.
Disclosure of Invention
The invention aims to provide a preparation method of porous crystal glue by taking a eutectic solvent as a crystallization pore-forming agent, wherein the eutectic solvent with low toxicity, no toxicity, simple preparation and designability is used as the crystallization pore-forming solvent to replace water and organic solvents such as benzene, cyclohexane, dioxane, formamide, camphene and the like to prepare a hydrophobic crystal glue material.
In order to realize the purpose, the adopted technical scheme is as follows:
the preparation method of the porous crystal glue by taking the eutectic solvent as the crystallization pore-foaming agent comprises the following steps:
(1) dissolving a reaction monomer in a eutectic solvent to obtain a mixed solution 1;
(2) sequentially dissolving a cross-linking agent, an oxidant and a reducing agent in the mixed solution 1 to obtain a mixed solution 2;
(3) discharging bubbles from the mixed solution 2, freezing for 24-48 h at-10 to-30 ℃, and unfreezing for 5-30 min in deionized water or ethanol to obtain wet crystal glue;
(4) and repeatedly soaking the wet crystal glue by using deionized water or ethanol, removing unreacted substances and eutectic solvents, and then carrying out vacuum drying treatment to obtain the porous crystal glue.
Further, in the step (1), the mass ratio of the reaction monomer to the eutectic solvent in the mixed solution 1 is 2-10: 100;
the eutectic solvent contains a hydrogen bond donor and a hydrogen bond acceptor, and the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is 1.5-1: 1-2.125.
Still further, the hydrogen bond donor is at least one of 1, 6-hexanediol, 1, 8-octanediol, 1, 9-nonanediol and 1, 10-decanediol;
the hydrogen bond acceptor is at least one of tetrabutylammonium chloride and tetrabutylammonium bromide;
the reaction monomer is at least one of methyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate and 4-vinylpyridine.
Further, the preparation process of the eutectic solvent comprises the following steps: and mixing the hydrogen bond donor and the hydrogen bond acceptor at 30-100 ℃ until clear liquid is formed, thus obtaining the eutectic solvent.
Further, in the step (2), the molar ratio of the cross-linking agent, the oxidant, the reducing agent and the reaction monomer is (5-100): (1-10): (1-10): 100.
further, in the step (2), the crosslinking agent is at least one of polyethylene glycol diacrylate and ethylene glycol dimethacrylate.
Further, in the step (3), bubbles are removed by means of ultrasonic treatment.
Further, in the step (4), the wet crystal glue is soaked in deionized water or ethanol, the deionized water or the ethanol is replaced after 1-2 hours, and the step is repeated for 5-10 times to remove unreacted substances and eutectic solvents.
Further, in the step (4), the temperature of vacuum drying is 40-60 ℃, and the time is 6-24 hours.
Furthermore, the pore diameter of the porous crystal glue pores is 0.1-100 mu m, and the porosity is 80-95%.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the technical scheme, the low-toxicity and non-toxic eutectic solvent is used as a crystallization pore-forming solvent, so that the method not only can be used for preparing hydrophilic crystal glue, but also can replace a toxic and harmful traditional solvent to prepare hydrophobic crystal glue. Therefore, the porous silicon dioxide can be used as a general crystalline pore-forming agent and used for preparing various matrigel materials.
2. The technical scheme of the invention can be used for preparing the hydrophobic porous crystal glue material by a one-step method without an additional hydrophobic modification process. The prepared hydrophobic porous crystal glue material has rich porous structure, good hydrophobicity and good mechanical property.
3. According to the technical scheme, the eutectic solvent is used as a crystallization pore-forming solvent, and the property of the eutectic solvent can be adjusted according to composition substances and composition proportion, so that the composition of the eutectic solvent can be adjusted according to the hydrophilicity and hydrophobicity of a reaction system to dissolve different reaction substances; and the composition molar ratio can be changed to adjust the freezing point of the eutectic solvent to adapt to the freezing condition, thereby meeting the requirements of different crystal glue materials.
4. According to the technical scheme, different eutectic solvents have different crystal morphologies, and can be used for preparing the crystal glue material with a specific pore structure.
Drawings
FIG. 1 is an optical photograph of different molar ratios of eutectic solvents (TBAC: 1, 6-hexanediol, TBAC: 1, 8-octanediol, 1, 9-nonanediol) prepared in example 6 at room temperature (25 ℃);
FIG. 2 is an infrared spectrum of a eutectic solvent (TBAC: 1, 6-hexanediol, TBAC: 1, 8-octanediol, 1, 9-nonanediol) prepared in examples 1 to 3; wherein a is example 1, B is example 2, and C is example 3;
FIG. 3 is an X-ray diffraction pattern of eutectic solvents (TBAC: 1, 6-hexanediol, TBAC: 1, 8-octanediol, 1, 9-nonanediol) prepared in examples 1 to 3; wherein, a is example 1, B is example 2, and C is example 3;
FIG. 4 is a differential scanning calorimetry curve of the eutectic solvents (TBAC: 1, 6-hexanediol, TBAC: 1, 8-octanediol, 1, 9-nonanediol) prepared in examples 1 to 3; wherein, a is example 1, B is example 2, and C is example 3;
FIG. 5 is a scanning electron micrograph of a poly (methyl methacrylate) crystal gel prepared according to examples 1 to 3; wherein, a is example 1, B is example 2, and C is example 3;
FIG. 6 is a photograph showing contact angles of poly (methyl methacrylate) crystal gels prepared in examples 1 to 3; wherein, a is example 1, B is example 2, and C is example 3.
Detailed Description
In order to further illustrate the preparation method of the porous cryogel using the eutectic solvent as the crystallization porogen and achieve the intended purpose of the invention, the following detailed description will be made with reference to the preferred embodiments of the preparation method of the porous cryogel using the eutectic solvent as the crystallization porogen. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The preparation method of the porous crystalloid glue using the eutectic solvent as the crystallization pore-forming agent according to the present invention will be further described in detail with reference to the following specific examples:
the eutectic solvent (DES) is a mixture of Hydrogen Bond Donor (HBD) and Hydrogen Bond Acceptor (HBA). Since the formation of hydrogen bonds by its component substances lowers the crystal lattice of the mixed system, which leads to a significant lowering of the freezing point, liquid solvents can be formed at room temperature by adjusting the ratio of hydrogen bond donor and hydrogen bond acceptor. The solvent has the advantages of good thermal stability, strong dissolving capacity, high conductivity, environmental protection and the like, and simultaneously, the preparation cost is low, and the preparation process is extremely simple. By researching the properties of the solvent such as solubility, viscosity, electrical conductivity, thermal conductivity and the like, the solvent is widely applied to the fields of metal electrodeposition, metal electropolishing, biotransformation, organic synthesis, gas adsorption, biodiesel purification and the like. The freezing point depression of the eutectic solvent provides a possibility for preparing the porous crystal glue by a freezing crystallization method.
The invention adopts low-toxicity, non-toxic, simple-preparation and designable eutectic solvent as crystallization pore-forming solvent to replace water and organic solvents such as benzene, cyclohexane, dioxane, formamide, camphene and the like, and prepares the hydrophobic crystal glue material by a crystallization/freezing pore-forming method. The technical scheme of the invention is as follows:
the preparation method of the porous crystal glue by taking the eutectic solvent as the crystallization pore-foaming agent comprises the following steps:
(1) dissolving a reaction monomer in a eutectic solvent to obtain a mixed solution 1;
(2) sequentially dissolving a cross-linking agent, an oxidant and a reducing agent in the mixed solution 1 to obtain a mixed solution 2;
(3) discharging bubbles from the mixed solution 2, placing the mixed solution in a mold, freezing the mixed solution for 24 to 48 hours at the temperature of between 10 ℃ below zero and 30 ℃ below zero, and unfreezing the mixed solution in deionized water for 5 to 30 minutes to obtain wet crystal glue;
(4) and repeatedly soaking the wet crystal glue by using deionized water, removing unreacted substances and eutectic solvents, and then carrying out vacuum drying treatment to obtain the porous crystal glue.
Preferably, in the step (1), the mass ratio of the reaction monomer to the eutectic solvent in the mixed solution 1 is 2-10: 100;
the eutectic solvent contains a hydrogen bond donor and a hydrogen bond acceptor, and the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is 1.5-1: 1-2.125.
More preferably, the hydrogen bond donor is at least one of 1, 6-hexanediol, 1, 8-octanediol, 1, 9-nonanediol and 1, 10-decanediol;
the hydrogen bond acceptor is at least one of tetrabutylammonium chloride and tetrabutylammonium bromide;
the reaction monomer is at least one of methyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate and 4-vinylpyridine.
Further preferably, the preparation process of the eutectic solvent is as follows: and mixing the hydrogen bond donor and the hydrogen bond acceptor at 30-100 ℃ until clear liquid is formed, thus obtaining the eutectic solvent.
Preferably, in the step (2), the molar ratio of the crosslinking agent, the oxidizing agent, the reducing agent and the reaction monomer is (5-100): (1-10): (1-10): 100.
preferably, in the step (2), the crosslinking agent is at least one of polyethylene glycol diacrylate and ethylene glycol dimethacrylate.
Preferably, in the step (3), bubbles are removed by means of ultrasonic treatment;
the mold is a cylindrical quartz tube with the diameter of 0.5-3 cm and the height of 5-20 cm.
Preferably, in the step (4), the wet crystal glue is soaked in deionized water or ethanol, the deionized water or the ethanol is replaced after 1-2 hours, and the step is repeated for 5-10 times to remove unreacted substances and the eutectic solvent.
Preferably, in the step (4), the temperature of vacuum drying is 40-60 ℃ and the time is 6-24 h.
Preferably, the pore diameter of the porous crystal glue pore is 0.1-100 μm, and the porosity is 80-95%.
Example 1.
The specific operation steps are as follows:
(1) 35.09g of tetrabutylammonium chloride and 14.91g of 1, 6-hexanediol were heated and stirred at 50 ℃ for 2 hours until a clear liquid was obtained, and then cooled to room temperature, whereby a liquid eutectic solvent (TBAC: 1, 6-hexanediol molar ratio: 1) was obtained.
(2) Subsequently, 2.5g of methyl methacrylate was dissolved in 50g of the eutectic solvent to prepare a mixed solution 1, 0.495g of a crosslinking agent (ethylene glycol dimethacrylate) and 0.083g of an oxidizing agent (benzoyl peroxide) were dissolved in the mixed solution 1 in this order, and then 0.083g of a reducing agent (N' N-dimethylaniline) was added dropwise to the mixed solution and stirred for 5 minutes to form a uniform mixed solution 2.
(3) And (3) placing the mixed solution 2 in an ultrasonic oscillator for 5-10 min to remove bubbles, subpackaging the mixture into a cylindrical quartz tube mold with the diameter of 10mm and the height of 100mm, and then placing the mold in an ethanol bath at the temperature of-20 ℃ for freezing for 24 h.
(4) And after the mold is frozen, unfreezing the frozen mold in a room-temperature water bath for 5-30 min to obtain the polymethyl methacrylate crystal glue.
(5) And taking out the polymethyl methacrylate crystal glue from the mold, soaking the polymethyl methacrylate crystal glue in deionized water or ethanol to remove the solvent and unreacted substances, replacing the deionized water or the ethanol every 1-2 hours, and repeating the steps for 5-10 times. And finally, drying for 12 hours in vacuum at 50 ℃ to obtain the dry polymethyl methacrylate crystal glue.
The eutectic solvent (TBAC: 1, 6-hexanediol in a molar ratio of 1:1) can be soaked in ethanol or deionized water, indicating that the eutectic solvent is both hydrophilic and hydrophobic.
FIGS. 2A, 3A and 4A are an infrared spectrum, an X-ray spectrum and a differential scanning calorimetry curve of the eutectic solvent prepared in example 1 of the present invention. As shown in FIGS. 2A, 3A and 4A, hydrogen bonds are formed between the two components of the synthesized eutectic solvent, eutectic is formed in the crystallization process of the eutectic solvent, and the melting point is-14.77 ℃.
Fig. 5A and 6A show scanning electron microscope pictures and contact angle pictures of the polymethylmethacrylate crystal gel prepared in example 1 of the present invention, and it can be seen from fig. 5A and 6A that the product has rich pore structures, the pore size is 20 to 75 μm, the porosity is 85.2 to 91.3% by weight method, the contact angle can reach 126.7 °, and the hydrophobicity is good.
Example 2.
The specific operation steps are as follows:
(1) 23.61g of tetrabutylammonium chloride and 26.39g of 1, 8-octanediol were heated and stirred at 60 ℃ for 2 hours until they were melted into a liquid, and cooled to room temperature to obtain a liquid eutectic solvent (TBAC: 1, 8-octanediol ═ 1: 2.125).
(2) Subsequently, 2.5g of methyl methacrylate was dissolved in 50g of the eutectic solvent to prepare a mixed solution 1, 0.495g of a crosslinking agent (ethylene glycol dimethacrylate) and 0.083g of an oxidizing agent (benzoyl peroxide) were dissolved in the mixed solution, 0.083g of a reducing agent (N' N-dimethylaniline) was added dropwise to the mixed solution, and the mixture was stirred for 5 minutes to form a uniform mixed solution 2.
(3) And (3) placing the mixed solution 2 in an ultrasonic oscillator for 5-10 min to remove bubbles, subpackaging the mixture into a cylindrical quartz tube mold with the diameter of 10mm and the height of 100mm, and then placing the mold in an ethanol bath at the temperature of-10 ℃ for freezing for 24 h.
(4) And after the mold is frozen, unfreezing the frozen mold in a room-temperature water bath for 5-30 min to obtain the polymethyl methacrylate crystal glue.
(5) And taking out the polymethyl methacrylate crystal glue from the mold, soaking the crystal glue by using ethanol to remove the solvent and unreacted substances, replacing the ethanol every 1-2 hours, and repeating the steps for 5-10 times. And finally, drying for 12 hours in vacuum at 50 ℃ to obtain the dry polymethyl methacrylate crystal glue.
FIGS. 2B, 3B and 4B are an infrared spectrum, an X-ray spectrum and a differential scanning calorimetry curve of the eutectic solvent prepared in example 2 of the present invention. As can be seen from fig. 2B, 3B, and 4B, hydrogen bonds are formed between the two components of the synthesized eutectic solvent, the eutectic solvent forms a eutectic during crystallization, and the melting point is 22.65 ℃.
Fig. 5B and 6B show a scanning electron microscope picture and a contact angle picture of the polymethylmethacrylate crystal gel prepared in example 2 of the present invention, and it can be seen from fig. 5B and 6B that the product has rich pore structures, the pore size is 15 to 60 μm, the porosity is 83.2 to 90.5% by a weighing method, the contact angle can reach 121.9 °, and the hydrophobicity is good.
Example 3.
The specific operation steps are as follows:
(1) 36.11g of tetrabutylammonium chloride and 13.88g of 1, 9-nonanediol were heated and stirred at 50 ℃ for 2 hours until a clear liquid was obtained, and then cooled to room temperature to obtain a liquid eutectic solvent (TBAC: 1, 6-hexanediol ═ 1.5: 1).
(2) Subsequently, 2.5g of methyl methacrylate was dissolved in 50g of the eutectic solvent to prepare a mixed solution 1, 0.495g of a crosslinking agent (ethylene glycol dimethacrylate) and 0.083g of an oxidizing agent (benzoyl peroxide) were dissolved in the mixed solution 1 in this order, and then 0.083g of a reducing agent (N' N-dimethylaniline) was added dropwise to the mixed solution and stirred for 5 minutes to form a uniform mixed solution 2.
(3) And (3) placing the mixed solution 2 in an ultrasonic oscillator for 5-10 min to remove bubbles, subpackaging the mixture into a cylindrical quartz tube mold with the diameter of 10mm and the height of 100mm, and then placing the mold in an ethanol bath at the temperature of-10 ℃ for freezing for 24 h.
(4) And after the mold is frozen, unfreezing the frozen mold in a room-temperature water bath for 5-30 min to obtain the polymethyl methacrylate crystal glue.
(5) And taking out the polymethyl methacrylate crystal glue from the mold, soaking the crystal glue by using ethanol to remove the solvent and unreacted substances, replacing the ethanol every 1-2 hours, and repeating the steps for 5-10 times. And finally, drying the mixture for 12 hours in vacuum at 50 ℃ to obtain the dry polymethyl methacrylate crystal glue.
FIGS. 2C, 3C and 4C are an infrared spectrum, an X-ray spectrum and a differential scanning calorimetry curve of the eutectic solvent prepared in example 1 of the present invention. As shown in FIGS. 2C, 3C and 4C, hydrogen bonds are formed between the two components of the synthesized eutectic solvent, eutectic is formed in the crystallization process of the eutectic solvent, and the melting point is-8.34 ℃.
Fig. 5C and 6C show that the polymethyl methacrylate crystal gel prepared in example 1 of the present invention has a scanning electron microscope picture and a contact angle picture, and it can be seen from fig. 5C and 6C that the product has a rich pore structure, the pore size is 5 to 30 μm, the porosity is 87.2 to 95.5% by the weight method, the contact angle can reach 124.5 °, and the hydrophobicity is good.
The infrared spectrograms of the eutectic solvents and the components constituting the eutectic solvents in examples 1 to 3 of the present invention demonstrate the successful preparation of the eutectic solvents; an X-ray diffraction spectrum proves that eutectic is formed in the crystallization process of the eutectic solvent; the melting point of the eutectic solvent was determined by differential scanning calorimetry.
Example 4.
The specific operation steps are as follows:
(1) 25.92g of tetrabutylammonium bromide and 24.07g of 1, 10-decanediol were heated and stirred at 50 ℃ until they melted to a clear liquid, and then cooled to room temperature to obtain a liquid eutectic solvent (tetrabutylammonium bromide: 1, 10-decanediol ═ 1: 1.25).
(2) Then, 1.0g of butyl methacrylate is dissolved in 50g of eutectic solvent to prepare a mixed solution 1, 0.943g of cross-linking agent (polyethylene glycol diacrylate) and 0.170g of oxidizing agent (benzoyl peroxide) are sequentially dissolved in the mixed solution 1, then 0.085g of reducing agent (N' N-dimethylaniline) is dropwise added into the mixed solution, and stirring is carried out for 5min to form a uniform mixed solution 2.
(3) And (3) placing the mixed solution 2 in an ultrasonic oscillator for 5-10 min to remove bubbles, subpackaging the mixture into a cylindrical quartz tube mold with the diameter of 5mm and the height of 200mm, and then placing the mold in an ethanol bath at the temperature of-20 ℃ for freezing for 48 h.
(4) And after the cold freezing is finished, unfreezing the frozen mould in a room-temperature water bath for 5-30 min to obtain the wet crystal glue.
(5) And taking out the wet crystal glue from the mold, soaking the wet crystal glue by using ethanol to remove the solvent and unreacted substances, replacing deionized water or ethanol every 1-2 hours, and repeating for 5-10 times. Finally, vacuum drying is carried out for 24 hours at the temperature of 40 ℃ to obtain the dry crystal glue.
Example 5.
The specific operation steps are as follows:
(1) 35.09g of tetrabutylammonium chloride and 14.91g of 1, 6-hexanediol were heated and stirred at 50 ℃ to melt into a clear liquid, and then cooled to room temperature, to obtain a liquid eutectic solvent (TBAC: 1, 6-hexanediol molar ratio ═ 1: 1).
(2) Then 5g of 4-vinylpyridine was dissolved in 50g of the eutectic solvent to prepare a mixed solution 1, 0.471g of a crosslinking agent (ethylene glycol dimethacrylate) and 0.115g of an oxidizing agent (benzoyl peroxide) were dissolved in the mixed solution 1 in this order, and then 0.058g of a reducing agent (N' N-dimethylaniline) was added dropwise to the mixed solution and stirred to form a uniform mixed solution 2.
(3) And (3) placing the mixed solution 2 in an ultrasonic oscillator for 5-10 min to remove bubbles, subpackaging the mixture into a cylindrical quartz tube mold with the diameter of 30mm and the height of 50mm, and then placing the mold in an ethanol bath at the temperature of-30 ℃ for freezing for 24 h.
(4) And after the cold freezing is finished, unfreezing the frozen mold in a room-temperature water bath for 5-30 min to obtain the wet crystal glue.
(5) And taking out the wet crystal glue from the mold, soaking the wet crystal glue in deionized water to remove the solvent and unreacted substances, replacing the deionized water every 1-2 hours, repeating the steps for 5-10 times, and performing vacuum drying at 60 ℃ for 6 hours to obtain the dry crystal glue.
Example 6.
Eutectic solvents with hydrogen bond donor and hydrogen bond acceptor molar ratios of 10:1, 1:1, and 1:10 were prepared from the eutectic solvent raw materials of examples 1-3, respectively, and then continuously heated and stirred at 50 ℃ and cooled to room temperature. The results are shown in FIG. 1.
As can be seen from fig. 1, when the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is 10:1 and 1:10, the eutectic solvent cannot form a clear solution, and thus cannot be used to prepare the porous crystalloid.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the porous crystal glue by taking the eutectic solvent as the crystallization pore-foaming agent is characterized by comprising the following steps:
(1) dissolving a reaction monomer in a eutectic solvent to obtain a mixed solution 1;
(2) sequentially dissolving a cross-linking agent, an oxidant and a reducing agent in the mixed solution 1 to obtain a mixed solution 2;
(3) after bubbles are discharged from the mixed solution 2, freezing the mixed solution at the temperature of-10 to-30 ℃ for 24 to 48 hours, and unfreezing the mixed solution in deionized water for 5 to 30min to obtain wet crystal glue;
(4) and repeatedly soaking the wet crystal glue by using deionized water or ethanol, removing unreacted substances and eutectic solvents, and then carrying out vacuum drying treatment to obtain the porous crystal glue.
2. The production method according to claim 1,
in the step (1), the mass ratio of the reaction monomer to the eutectic solvent in the mixed solution 1 is 2-10: 100;
the eutectic solvent contains a hydrogen bond donor and a hydrogen bond acceptor, and the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is 1.5-1: 1-2.125.
3. The production method according to claim 2,
the hydrogen bond donor is at least one of 1, 6-hexanediol, 1, 8-octanediol, 1, 9-nonanediol and 1, 10-decanediol;
the hydrogen bond acceptor is at least one of tetrabutylammonium chloride and tetrabutylammonium bromide;
the reaction monomer is at least one of methyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate and 4-vinylpyridine.
4. The production method according to claim 2,
the preparation process of the eutectic solvent comprises the following steps: and mixing the hydrogen bond donor and the hydrogen bond acceptor at 30-100 ℃ until clear liquid is formed, thus obtaining the eutectic solvent.
5. The production method according to claim 1,
in the step (2), the molar ratio of the cross-linking agent, the oxidant, the reducing agent and the reaction monomer is (5-100): (1-10): (1-10): 100.
6. the production method according to claim 1,
in the step (2), the cross-linking agent is at least one of polyethylene glycol diacrylate and ethylene glycol dimethacrylate.
7. The production method according to claim 1,
in the step (3), bubbles are removed by adopting an ultrasonic treatment mode.
8. The method according to claim 1,
and (4) soaking the wet crystal glue in deionized water or ethanol, replacing the deionized water or ethanol after 1-2 hours, repeating the step for 5-10 times, and removing unreacted substances and the eutectic solvent.
9. The production method according to claim 1,
in the step (4), the temperature of vacuum drying is 40-60 ℃, and the time is 6-24 hours.
10. The method according to claim 1,
the pore diameter of the porous crystal glue pores is 0.1-100 mu m, and the porosity is 80-95%.
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| WO2015128550A1 (en) * | 2014-02-28 | 2015-09-03 | Teknologian Tutkimuskeskus Vtt Oy | Deep eutectic solvents and their use |
| CN110982093A (en) * | 2019-12-25 | 2020-04-10 | 湖北理工学院 | Method for preparing quick-response temperature-sensitive hydrogel by adopting room-temperature eutectic solvent liquid front-end polymerization |
| CN111040074A (en) * | 2019-12-25 | 2020-04-21 | 湖北理工学院 | Method for preparing macroporous quick-response polyacrylamide hydrogel by adopting front-end polymerization of acrylamide eutectic solvent |
| CN112898480A (en) * | 2021-02-03 | 2021-06-04 | 合肥工业大学 | Hydroxyethyl acrylate eutectic solvent, hydroxyethyl acrylate hydrogel, preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2015128550A1 (en) * | 2014-02-28 | 2015-09-03 | Teknologian Tutkimuskeskus Vtt Oy | Deep eutectic solvents and their use |
| CN110982093A (en) * | 2019-12-25 | 2020-04-10 | 湖北理工学院 | Method for preparing quick-response temperature-sensitive hydrogel by adopting room-temperature eutectic solvent liquid front-end polymerization |
| CN111040074A (en) * | 2019-12-25 | 2020-04-21 | 湖北理工学院 | Method for preparing macroporous quick-response polyacrylamide hydrogel by adopting front-end polymerization of acrylamide eutectic solvent |
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