CN103087290A - Ultraviolet irradiation device and method for synthesis of isocyanate-cyclodextrin copolymer - Google Patents
Ultraviolet irradiation device and method for synthesis of isocyanate-cyclodextrin copolymer Download PDFInfo
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- CN103087290A CN103087290A CN2013100350335A CN201310035033A CN103087290A CN 103087290 A CN103087290 A CN 103087290A CN 2013100350335 A CN2013100350335 A CN 2013100350335A CN 201310035033 A CN201310035033 A CN 201310035033A CN 103087290 A CN103087290 A CN 103087290A
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- cyclodextrin
- necked flask
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- chlorobenzene
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Abstract
The invention relates to an ultraviolet irradiation device and a method for synthesis of isocyanate-cyclodextrin copolymer. According to the method, final product is prepared through the ultraviolet irradiation device at the bathtub temperature of 30-40 DEG C, and simultaneously, chlorobenzene solution is prepared, the final product is stirred by a magnetic stirrer for 6 hours, so that chlorobenzene is removed through adsorption, and the concentration of the chlorobenzene is measured through gas chromatography. The device has the beneficial effects of being simple in structure and convenient in operation, and the method is not limited by the environment, has high reaction speed, good chlorobenzene removal effect, strong practicability and wide application prospect.
Description
Technical field
The present invention relates to multipolymer preparation and Application Areas, relate in particular to UV curing apparatus and the method for synthesizing isocyanate-cyclodextrin copolymers.
Background technology
Cyclodextrin (Cyclodextrin is called for short CD) is to act on by CD glucosyl transferase (CGTASE) one group of cyclic oligosaccharide that starch produces.That the most frequently used is β-CD, the tapered cylinder structure that it is formed by connecting with α-Isosorbide-5-Nitrae glycosidic link by 7 glucose units.The special molecular structure of " interior hydrophobic; outer hydrophilic " just, make CD to form inclusion complex by the various effects such as ether-oxygen bond, Van der Waals force, hydrophobic interaction, charge transfer with multiple guest molecule, its molecule cavity outer wall and the numerous wetting ability hydroxyls of big opening end distribution, metal ion is had sequestering action, so he can effectively remove organic pollutant and metal ion in waste water.Simultaneously control the fields such as release, food-processing and environment protection and be used widely at chemical separation and analysis, medicine.
Beta-cyclodextrin solubleness in water is not high, and vary with temperature larger, after it and other material produce inclusion compound, water-soluble lower, easy crystallization from solution, or relying on merely the effect of hydrogen bond or Van der Waals force, inclusion compound is easily separated, and its application at sewage treatment area is extremely restricted.For repairing this textural defect of cyclodextrin, enlarge its range of application, need to carry out modification to it.Chemical modification method is in the situation that retaining ring dextrin skeleton is substantially constant, utilizes hydroxyl in its molecule and other group to carry out etherificate, esterification, oxidation and the chemical reaction such as crosslinked, obtains cross-linked polymer.This polymkeric substance had both kept the envelope recognition capability of CD preferably, have again standby polymkeric substance physical strength, stability and chemical adjustability etc. preferably concurrently, micropore with spongiform internal structure and nano level yardstick, thus can absorb efficiently with trap water in some be difficult to the organic pollution materials that maybe can't degrade with conventional water-purifying process and material.The comprehensive action of CD cavity and polymer network has improved the performance of material.
The cross-linked polymer that contains CD can be by CD molecule and any can preparation with difunctionality reagent (as di-epoxide and the two isocyanic ester etc.) reaction of hydroxyl reaction.Zheng Ying is also take epoxy chloropropane as linking agent, in alkaline medium, that β-CD is immobilized, synthesized water-fast β-CD cross-linked polymer, and investigated sound CD cross-linked polymer to the loose pollutent in simulated water sample (inorganic heavy metal ion and organic phenols, amine) absorption property, experimental result shows: β-CD cross-linked polymer is to inorganic heavy metal ion (Pb2+, Cu2+, Cd2+, Zn2+) and phenol, the removal effect of aniline is good, the former clearance reaches more than 83.60%, wherein the clearance of Pb2+ is up to 95.62%, phenol, the clearance of aniline reaches more than 95%.Shen Hanxi has further studied huge legendary turtle metal ion after this polymkeric substance and α-pyridylazo-2-Naphthol inclusion, finds that this polymkeric substance of every gram is respectively 20.3,11.2,9.45,8.92 μ mol to the saturated extent of adsorption of the metal ions such as Cu2+, Cd2+, Ni2+, Mn2+.The synthetic method of CD cross-linked polymer and the research aspect water treatment are a lot.The synthetic amine-modified β of HeBing Lin research-CD cross-linked resin (a kind of polymeric sorbent of β-CDP), and characterize absorption property with adjacent, p-NP (o-NP, p-NP), wherein diethylamine modified resins DEA one CDP improves a lot in the adsorptive power of pH=7, and they think that amine-modified β-CDP mainly presents strong adsorption with envelope, soda acid dual function p-nitrophenol.Peng Guanghuai has synthesized β-CDP with the crosslinked β-CD of vulcabond, be adsorbed in the solute concentration situation at different adsorption temps and difference, study absorption property and the desorption performance of β-CDP to p-NP, found that the Adsorption and desorption characteristics of β-CDP is all very strong, can be used as the circulation absorption material.But these synthetic methods belong to chemical agent elicitation technique mostly, and needed synthetics is many, and response procedures is complicated, and inconvenience is used in management.
Summary of the invention
The UV curing apparatus and the method that the purpose of this invention is to provide a kind of synthesizing isocyanate-cyclodextrin copolymers are to overcome at present existing method above shortcomings.
The objective of the invention is to be achieved through the following technical solutions:
A kind of UV curing apparatus of synthesizing isocyanate-cyclodextrin copolymers, comprise there-necked flask, be provided with glass stopper in left mouthful of described there-necked flask, be plugged with isobaric dropping funnel in the right mouth of there-necked flask, be plugged with ultraviolet rotary irradiation whipping device in the middle mouth of there-necked flask; Described ultraviolet rotary irradiation whipping device comprises rotary drive motor; rotary drive motor is connected with two foldable poles; foldable poles is plugged in the middle mouth of there-necked flask, and the foldable poles low side is provided with ultraviolet tube, and ultraviolet tube is provided with protecting glass outward.
A kind of method of synthesizing isocyanate-cyclodextrin copolymers said method comprising the steps of:
Step 1: at room temperature take the 3-6g cyclodextrin, be placed in the DMF solvent of 85-170ml, be stirred to cyclodextrin and all dissolve, obtain solution, described cyclodextrin is beta-cyclodextrin;
Step 2: UV curing apparatus is placed in cleansing bath tub, regulates the cleansing bath tub temperature and remain on 30-40 ℃, solution is placed in the UV curing apparatus of 200ml, open simultaneously the UV-light of 2-6kw, the adjustment rotating speed is 120r/min;
Step 3: the speed with 30/min adds 20.428 * 10 in UV curing apparatus
-3~ 40.856 * 10
-3Mol high polymer monomer isocyanate solution keeps UV-irradiation and continues stirring simultaneously, makes abundant contact reacts, and described isocyanic ester is hexamethylene diisocyanate;
Step 4: after reaction, use the resulting solid product of DMF solvent wash, and use distilled water again to wash, use at last vacuum-drying, obtain final product;
Step 5: configuration concentration is the chlorobenzene solution of 20mg/l, adds wherein the above-mentioned product of 5g, as for stirring 6 hours under magnetic stirring apparatus, gets supernatant liquor and measures chlorobenzene concentration with Gas chromatography.
Beneficial effect of the present invention is: this apparatus structure is simple, easy to operate, and the method is not subjected to environmental restraint, and speed of response is fast, and good, practical to the removal effect of chlorobenzene, prospect is extensive.
Description of drawings
The below is described in further detail the present invention with reference to the accompanying drawings.
Fig. 1 is the structural representation of the described UV curing apparatus of the embodiment of the present invention.
In figure:
1, there-necked flask; 2, glass stopper; 3, isobaric dropping funnel; 4, ultraviolet rotary irradiation whipping device; 5, rotary drive motor; 6, foldable poles; 7, ultraviolet tube; 8, protecting glass; 9, cleansing bath tub.
Embodiment
As described in Figure 1, the UV curing apparatus of the described a kind of synthesizing isocyanate-cyclodextrin copolymers of the embodiment of the present invention, comprise there-necked flask 1, be provided with glass stopper 2 in left mouthful of described there-necked flask 1, be plugged with isobaric dropping funnel 3 in right mouthful of there-necked flask 1, be plugged with ultraviolet rotary irradiation whipping device 4 in the middle mouth of there-necked flask 1; Described ultraviolet rotary irradiation whipping device 4 comprises rotary drive motor 5; rotary drive motor 5 is connected with two foldable poles 6; foldable poles 6 is plugged in the middle mouth of there-necked flask 1, and foldable poles 6 low sides are provided with ultraviolet tube 7, the outer protecting glass 8 that is provided with of ultraviolet tube 7.
The method of the described a kind of synthesizing isocyanate-cyclodextrin copolymers of the embodiment of the present invention said method comprising the steps of:
Step 1: at room temperature take the 3-6g cyclodextrin, be placed in the DMF solvent of 85-170ml, be stirred to cyclodextrin and all dissolve, obtain solution, described cyclodextrin is beta-cyclodextrin;
Step 2: UV curing apparatus is placed in cleansing bath tub 9, regulates cleansing bath tub 9 temperature and remain on 30-40 ℃, solution is placed in the UV curing apparatus of 200ml, open simultaneously the UV-light of 2-6kw, the adjustment rotating speed is 120r/min;
Step 3: the speed with 30/min adds 20.428 * 10 in UV curing apparatus
-3~ 40.856 * 10
-3Mol high polymer monomer isocyanate solution keeps UV-irradiation and continues stirring simultaneously, makes abundant contact reacts, and described isocyanic ester is hexamethylene diisocyanate;
Step 4: after reaction, use the resulting solid product of DMF solvent wash, and use distilled water again to wash, use at last vacuum-drying, obtain final product;
Step 5: configuration concentration is the chlorobenzene solution of 20mg/l, adds wherein the above-mentioned product of 5g, as for stirring 6 hours under magnetic stirring apparatus, gets supernatant liquor and measures chlorobenzene concentration with Gas chromatography.
Specific embodiment one
β-the CD that gets after the 3.0g purifying puts into 200ml there-necked flask 1 (pass into nitrogen to container, to get rid of inner air, prevent the oxygen disturbance reponse), adds 85mlDMF that β-CD is fully dissolved.The control ultraviolet light intensity is 2kW, and ultraviolet lamp tube rotating speed 120r/min adds 3.30ml(20.428 * 10 wherein with the speed of 30/min
-3Mol) hexamethylene diisocyanate solution (maintenance nitrogen environment).Use cleansing bath tub 9 heating in water bath there-necked flasks 1, make reactant react 10min under 30 ℃.Reaction is filtered to get white powder after finishing, and rinses, distills washing with DMF, and vacuum-drying obtains target product.
Specific embodiment two
β-the CD that gets after the 3.0g purifying puts into 200ml there-necked flask 1 (pass into nitrogen to container, to get rid of inner air, prevent the oxygen disturbance reponse), adds 85mlDMF that β-CD is fully dissolved.The control ultraviolet light intensity is 4kW, and ultraviolet lamp tube rotating speed 120r/min adds 3.30ml(20.428 * 10 wherein with the speed of 30/min
-3Mol) hexamethylene diisocyanate solution (maintenance nitrogen environment).The heating in water bath there-necked flask makes reactant react 10min under 30 ℃.Reaction is filtered to get white powder after finishing, and rinses, distills washing with DMF, and vacuum-drying obtains target product.
Specific embodiment three
β-the CD that gets after the 3.0g purifying puts into 200ml there-necked flask (pass into nitrogen to container, to get rid of inner air, prevent the oxygen disturbance reponse), adds 85mlDMF that β-CD is fully dissolved.UV curing apparatus is inserted flask and fixing (seeing accompanying drawing 1), and the control ultraviolet light intensity is 6kW, and ultraviolet lamp tube rotating speed 120r/min adds 3.30ml(20.428 * 10 wherein with the speed of 30/min
-3Mol) hexamethylene diisocyanate solution (maintenance nitrogen environment).The heating in water bath there-necked flask makes reactant react 10min under 30 ℃.Reaction is filtered to get white powder after finishing, and rinses, distills washing with DMF, and vacuum-drying obtains target product.
Specific embodiment four
β-the CD that gets after the 3.0g purifying puts into 200ml there-necked flask (pass into nitrogen to container, to get rid of inner air, prevent the oxygen disturbance reponse), adds 85mlDMF that β-CD is fully dissolved.The control ultraviolet light intensity is 4kW, and ultraviolet lamp tube rotating speed 120r/min adds 6.60ml(40.856 * 10 wherein with the speed of 30/min
-3Mol) hexamethylene diisocyanate solution (maintenance nitrogen environment).The heating in water bath there-necked flask makes reactant react 10min under 30 ℃.Reaction is filtered to get white powder after finishing, and rinses, distills washing with DMF, and vacuum-drying obtains target product.
Specific embodiment five
β-the CD that gets after the 6.0g purifying puts into 200ml there-necked flask (pass into nitrogen to container, to get rid of inner air, prevent the oxygen disturbance reponse), adds 170mlDMF that β-CD is fully dissolved.The control ultraviolet light intensity is 4kW, and ultraviolet lamp tube rotating speed 120r/min adds 3.30ml(20.428 * 10 wherein with the speed of 30/min
-3Mol) hexamethylene diisocyanate solution (maintenance nitrogen environment).The heating in water bath there-necked flask makes reactant react 10min under 30 ℃.Reaction is filtered to get white powder after finishing, and rinses, distills washing with DMF, and vacuum-drying obtains target product.
Specific embodiment six
β-the CD that gets after the 3.0g purifying puts into 200ml there-necked flask (pass into nitrogen to container, to get rid of inner air, prevent the oxygen disturbance reponse), adds 85mlDMF that β-CD is fully dissolved.The control ultraviolet light intensity is 4kW, and ultraviolet lamp tube rotating speed 120r/min adds 3.30ml(20.428 * 10 wherein with the speed of 30/min
-3Mol) hexamethylene diisocyanate solution (maintenance nitrogen environment).The heating in water bath there-necked flask makes reactant react 10min under 30 ℃.Reaction is filtered to get white powder after finishing, and rinses, distills washing with DMF, and vacuum-drying obtains target product.
Compound concentration is the chlorobenzene solution of 20mg/l, adds wherein multipolymer 5g, is placed in magnetic stirrer 6h, gets supernatant liquor and measures chlorobenzene concentration with Gas chromatography, and the chlorobenzene clearance reaches 95%.
The present invention is not limited to above-mentioned preferred forms; anyone can draw other various forms of products under enlightenment of the present invention; no matter but do any variation on its shape or structure; every have identical with a application or akin technical scheme, within all dropping on protection scope of the present invention.
Claims (5)
1. the UV curing apparatus of a synthesizing isocyanate-cyclodextrin copolymers, comprise there-necked flask (1), it is characterized in that: be provided with glass stopper (2) in left mouthful of described there-necked flask (1), be plugged with isobaric dropping funnel (3) in right mouthful of there-necked flask (1), be plugged with ultraviolet rotary irradiation whipping device (4) in the middle mouth of there-necked flask (1).
2. the UV curing apparatus of synthesizing isocyanate-cyclodextrin copolymers according to claim 1; it is characterized in that: described ultraviolet rotary irradiation whipping device (4) comprises rotary drive motor (5); rotary drive motor (5) is connected with two foldable poles (6); foldable poles (6) is plugged in the middle mouth of there-necked flask (1); foldable poles (6) low side is provided with ultraviolet tube (7), the outer protecting glass (8) that is provided with of ultraviolet tube (7).
3. the method for a synthesizing isocyanate-cyclodextrin copolymers, is characterized in that, said method comprising the steps of:
Step 1: at room temperature take the 3-6g cyclodextrin, be placed in the DMF solvent of 85-170ml, be stirred to cyclodextrin and all dissolve, obtain solution;
Step 2: UV curing apparatus is placed in cleansing bath tub (9), regulates cleansing bath tub (9) temperature and remain on 30-40 ℃, solution is placed in the UV curing apparatus of 200ml, open simultaneously the UV-light of 2-6kw, adjusting rotating speed is 120 rev/mins;
Step 3: add 20.428 * 10 with the speed of 30 droplets/minute in UV curing apparatus
-3~ 40.856 * 10
-3Mol high polymer monomer isocyanate solution keeps UV-irradiation and continues stirring simultaneously, makes abundant contact reacts;
Step 4: after reaction, use the resulting solid product of DMF solvent wash, and use distilled water again to wash, use at last vacuum-drying, obtain final product;
Step 5: configuration concentration is the chlorobenzene solution of 20mg/l, adds wherein the above-mentioned product of 5g, as for stirring 6 hours under magnetic stirring apparatus, gets supernatant liquor and measures chlorobenzene concentration with Gas chromatography.
4. method according to claim 3, it is characterized in that: in step 1, described cyclodextrin is beta-cyclodextrin.
5. method according to claim 3, it is characterized in that: in step 3, described isocyanic ester is hexamethylene diisocyanate.
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| CN108484800A (en) * | 2018-03-27 | 2018-09-04 | 广西大学 | A kind of micro-or nano size beta cyclo dextrin polymer powder and its preparation method and application |
| CN113307945A (en) * | 2021-06-01 | 2021-08-27 | 西南石油大学 | Ultraviolet self-healing polyurea material and preparation method thereof |
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| CN113307945A (en) * | 2021-06-01 | 2021-08-27 | 西南石油大学 | Ultraviolet self-healing polyurea material and preparation method thereof |
| CN113307945B (en) * | 2021-06-01 | 2021-12-14 | 西南石油大学 | Ultraviolet self-healing polyurea material and preparation method thereof |
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