CN103965506A - Preparation method of porous azo polyurethane material - Google Patents
Preparation method of porous azo polyurethane material Download PDFInfo
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- CN103965506A CN103965506A CN201410232427.4A CN201410232427A CN103965506A CN 103965506 A CN103965506 A CN 103965506A CN 201410232427 A CN201410232427 A CN 201410232427A CN 103965506 A CN103965506 A CN 103965506A
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- azo
- urethane
- porous material
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- freezing
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- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 229920002635 polyurethane Polymers 0.000 title abstract description 47
- 239000004814 polyurethane Substances 0.000 title abstract description 47
- 239000000463 material Substances 0.000 title abstract description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 230000008014 freezing Effects 0.000 claims abstract description 26
- 238000007710 freezing Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002425 crystallisation Methods 0.000 claims abstract description 16
- 230000008025 crystallization Effects 0.000 claims abstract description 16
- 238000007789 sealing Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000000967 suction filtration Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- RWGTZMRRJYJMNP-UHFFFAOYSA-N CCOC(=O)NN=NNC(=O)OCC Chemical compound CCOC(=O)NN=NNC(=O)OCC RWGTZMRRJYJMNP-UHFFFAOYSA-N 0.000 claims description 80
- 239000011148 porous material Substances 0.000 claims description 57
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000000746 purification Methods 0.000 claims description 18
- 230000006698 induction Effects 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- BKHLYUZOCOAYBB-UHFFFAOYSA-N OCCC=1C(=C(C(=C(C1)N=NC1=C(C=CC=C1)C)C)N)[N+](=O)[O-] Chemical compound OCCC=1C(=C(C(=C(C1)N=NC1=C(C=CC=C1)C)C)N)[N+](=O)[O-] BKHLYUZOCOAYBB-UHFFFAOYSA-N 0.000 claims description 10
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 4
- BQFCCCIRTOLPEF-UHFFFAOYSA-N chembl1976978 Chemical compound CC1=CC=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 BQFCCCIRTOLPEF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 17
- 238000005406 washing Methods 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 230000001939 inductive effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 23
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 18
- 239000000178 monomer Substances 0.000 description 17
- 230000001413 cellular effect Effects 0.000 description 16
- 150000002009 diols Chemical class 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 12
- 239000007788 liquid Substances 0.000 description 9
- 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 description 8
- 238000013019 agitation Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 8
- 150000002513 isocyanates Chemical class 0.000 description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 238000002336 sorption--desorption measurement Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920006264 polyurethane film Polymers 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- -1 timber Substances 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Abstract
The invention discloses a porous azo polyurethane material and a preparation method thereof. The method comprises the following steps of (1) preparing azo polyurethane; and (2) inducing the azo polyurethane obtained in the step (1) to prepare the porous azo polyurethane material by crystallization: weighting 1 part by mass of azo polyurethane obtained in the step (1), placing azo polyurethane into a vessel, adding 15-30 parts by mass of dimethyl sulfoxide into the vessel, heating to 80-100 DEG C, cooling to room temperature after completely dissolving azo polyurethane, then, sealing the vessel, freezing the vessel at the temperature of 20 DEG C below zero to 3 DEG C for 1-4 days, washing a sample by using water with the temperature of 3-20 DEG C, next, carrying out suction filtration and drying to obtain the porous azo polyurethane material, wherein the sample is obtained through freezing. The porous azo polyurethane material prepared by using the method disclosed by the invention is provided with micro-level and nano-level holes and has gas adsorbability; and in addition, the adsorption quantity can be regulated through changing the mass ratio of azo polyurethane to dimethyl sulfoxide, the crystallization temperature, the crystallization time and the washing temperature.
Description
Technical field
The present invention relates to macromolecular material and preparation method thereof technical field, particularly a kind of preparation method of azo urethane porous material.
Background technology
Urethane is the abbreviation of polyurethane(s), it is a kind of novel organic polymer material, be described as " the fifth-largest plastics ", because its remarkable performance is widely used in various fields, relate to light industry, chemical industry, electronics, weaving, medical treatment, building, building materials, automobile etc.
Urethane is a kind of block polymer, can be by regulating composition, the proportioning of different blocks to synthesize mechanics excellent performance, bio-medical material that biocompatibility is good.In polyurethane backbone, introduce the synthetic azo urethane of azo group, also give urethane certain optical activity.
The cellular polyurethane material property being comprised of a large amount of minute apertures and urethane hole wall channels and collaterals is good, compare with other porous plastics, urethane porous material has that density is low, odorless, ventilative, heat insulating ability is good, ageing-resistant, to advantages such as metal, timber, Glass lamp adhesivity are good.The physical property in hole has larger impact such as pore size, distribution etc. to the application of porous material.All these are the strong preparation process that depends on utilized porous material again.And the porous material using value with optically active azo urethane is higher, the preparation method of azo urethane porous material is not yet disclosed in prior art.
The Refrigeration Technique of doing template by ice crystal in recent years can be used for the preparation of porous material, but the method is only applicable to water-soluble or dispersibles the material in water.Cellular polyurethane material of the prior art mostly is cellular polyurethane film or the porous polyurethane sheet of preparing by foaming technique, and cellular polyurethane film or porous polyurethane sheet are often grade, and preparation method is complicated.If application publication number is for the patent of invention of " CN 101735475 A " discloses a kind of hydrophilic porous urethane carrier preparation method, carry out in accordance with the following steps: 1) configuration concentration is 5 ~ 40% with negatively charged ion or cationic polyurethane-modified dose; 2), by urethane soaking at room temperature 0.3 ~ 1 h in above-mentioned properties-correcting agent of foaming, stir; 3) the cellular polyurethane liquid that soaks properties-correcting agent is carried out separated with cellular polyurethane; 4) cellular polyurethane of modification is dry at room temperature or 80 ℃, obtain the cellular polyurethane water treatment carrier of modification.
Summary of the invention
In order to make up above deficiency, the invention provides a kind of short-cut method of preparing azo urethane porous material by Refrigeration Technique.
Technical scheme of the present invention is:.
A preparation method for azo urethane porous material, comprises the following steps:
1) preparation of azo urethane
Get N, N-two (2-hydroxyethyl) amino-2,2 '-dimethyl-4 '-nitro-azo benzo dissolves with solvent orange 2 A; 4, the 4 '-diphenylmethanediisocyanate that waits amount of substance is scattered in solvent B and heating; In the time of 65 ~ 80 ℃, to 4, in 4 '-diphenylmethanediisocyanate solution, dropwise drip N, N-two (2-hydroxyethyl) amino-2,2 '-dimethyl-4 '-nitro-azo benzole soln, dropwise rear continuation reaction 3 ~ 4 h, adopt the protection of protection gas in reaction process, purifying after completion of the reaction and being dried obtains azo urethane;
2) azo urethane porous material is prepared in crystallization induction
The azo urethane that takes 1 mass parts step 1) gained is put into container, and to the methyl-sulphoxide that adds 15 ~ 30 mass parts in described container, be heated to 80 ~ 100 ℃, after being dissolved completely, described azo urethane is cooled to room temperature, then by described container sealing and be positioned over-20 ~ 3 ℃ freezing 1 ~ 4 day, the water of 3 ~ 20 ℃ of freezing gained sample employings is washed, then suction filtration, the dry azo urethane porous material that to obtain.
Preferably, described solvent orange 2 A and solvent B are anhydrous DMF.
Preferably, N in step 1), N-two (2-hydroxyethyl) amino-2, the rate of addition of 2 '-dimethyl-4 '-nitroazobenzene is 2 ~ 3 seconds/.
Preferably, the purification concrete operations described in step 1) are: rotary evaporation solution after completion of the reaction, the reaction solution after concentrated is poured into water, and form precipitation, filter, adopt methanol wash precipitation, then the drying precipitated azo urethane that must purify at 80 ℃.
As preferably, step 2) the azo urethane that takes 1 mass parts step 1) gained in is put into container, and to the methyl-sulphoxide that adds 20 mass parts in described container.
As preferred version, step 2) in be cooled to room temperature after described azo urethane is dissolved completely, then by described container sealing and be positioned at-20 ℃ freezing 2 days.
Step 2) in, adopt the water of 3 ℃ to wash freezing gained solid.
Beneficial effect of the present invention is:
1) the dibasic alcohol monomer that contains azo group is introduced in polymkeric substance, given this urethane and there is ultraviolet light response.
2) the azo urethane porous material that prepared by the inventive method has gas adsorbability, can regulate and control by changing mass ratio, Tc, crystallization time and the washing temperature etc. of azo urethane and methyl-sulphoxide the physical properties in hole and then regulation and control adsorptive capacity.
3) the azo urethane porous material that prepared by the inventive method contains the hole of macropore and mesoporous two kinds of yardsticks simultaneously.
4) be different from the drilling of common induction phase partition method, the crystallization induction drilling method that the inventive method is used does not have particular requirement to polymer morphology, not only can prepare azo Polyurethane Porous Membranes, can prepare azo urethane voluminous powder yet.
5) Tc of using in the inventive method is 3 ~-20 ℃, does not need special cold condition to process.
6) what in the inventive method, remove that dimethyl sulfoxide (DMSO) adopts is that water is got method express developed, avoided lyophilize except dimethyl sulfoxide (DMSO) bring consuming time for a long time, easy residual problem.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the scanning electron microscope (SEM) photograph of the azo urethane porous material of embodiment 1 preparation;
Fig. 2 is the scanning electron microscope (SEM) photograph of the azo urethane porous material of embodiment 2 preparations;
Fig. 3 is the scanning electron microscope (SEM) photograph of the azo urethane porous material of embodiment 3 preparations;
Fig. 4 is the azo urethane porous material nitrogen adsorption desorption situation comparison diagram of embodiment 1,2,3 preparations, wherein 20/1,15/1,30/1 represents respectively embodiment 1, embodiment 2, embodiment 3 gained azo urethane porous materials;
Fig. 5 is the scanning electron microscope (SEM) photograph of the azo urethane porous material of embodiment 4 preparations;
Fig. 6 is the nitrogen adsorption desorption situation map of the azo urethane porous material of embodiment 4 preparations;
Fig. 7 is the scanning electron microscope (SEM) photograph of the azo urethane porous material of embodiment 5 preparations;
Fig. 8 is the scanning electron microscope (SEM) photograph of the azo urethane porous material of embodiment 6 preparations;
Fig. 9 is the azo urethane porous material nitrogen adsorption situation comparison diagram of embodiment 5,6 preparations;
Figure 10 is the scanning electron microscope (SEM) photograph of the azo urethane porous material of embodiment 7 preparations;
Figure 11 is the nitrogen adsorption situation map of the azo urethane porous material of embodiment 7 preparations;
Figure 12 is the ultraviolet-visible light spectrogram of DMF solution of the azo urethane of 0.03mg/L, is specially before ultraviolet lighting, the absorbancy comparison diagram of azo polyurethane solution after illumination 0.5h, 1h, 3h, 5h;
Figure 13 is step 2 in embodiment 1) the thermogravimetic analysis (TGA) figure of the azo urethane that obtains.
Embodiment
Below the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment
Embodiment 1
A kind of azo urethane porous material and preparation method thereof, comprises the following steps:
1) azo urethane is synthetic
Take 0.5 gram 4,4 '-diphenylmethanediisocyanate, is scattered in 100 milliliters of there-necked flasks with 15 milliliters of DMFs (DMF).Take 0.716 gram of N, N-two (2-hydroxyethyl) amino-2,2 '-dimethyl-4 '-nitroazobenzene (diol monomer) is dissolved in 30 milliliters of DMF, seals standby.At 70 ℃, to slowly dripping diol monomer solution (2 ~ 3 seconds one) in isocyanate solution, dropwise rear continuation isothermal reaction 3 ~ 4 hours.In reaction process, use magnetic agitation and argon shield.
Reaction equation is:
2) purification of azo urethane
The polyurethane solution that step 1) is obtained revolves to steam removes partial solvent, by polyurethane solution be concentrated to thick after, join in 200 ml waters and form precipitation, filter and collect filter residue and by methanol wash 2 ~ 3 times, after filtering, collect filter residue, 80 ℃ are dry.
3) crystallization induction
Take 0.5 gram of step 2) products therefrom, at 80 ~ 100 ℃, be dissolved in 10 grams of dimethyl sulfoxide (DMSO), after dissolving completely, it is cooled to room temperature sealing.Gained urethane/dimethyl sulphoxide solution is positioned in-20 ℃ of environment freezing, freezing time is 2 days.
4) purification of azo cellular polyurethane material
Step 3) gained sample is rinsed with a large amount of 3 ℃ of water, obtain suspension liquid.After suction filtration, gained filter residue is dried, drying temperature is 80 ℃.Dry gained sample is nitrogen benzide urethane porous material.
Embodiment 2
A kind of azo urethane porous material and preparation method thereof, comprises the following steps:
1) azo urethane is synthetic
Take 0.5 gram 4,4 '-diphenylmethanediisocyanate, is scattered in 100 milliliters of there-necked flasks with 15 milliliters of DMFs (DMF).Take 0.716 gram of N, N-two (2-hydroxyethyl) amino-2,2 '-dimethyl-4 '-nitroazobenzene (diol monomer) is dissolved in 30 milliliters of DMF, seals standby.At 70 ℃, to slowly dripping diol monomer solution (2 ~ 3 seconds one) in isocyanate solution, dropwise rear continuation isothermal reaction 3 ~ 4 hours.In reaction process, use magnetic agitation and argon shield.
2) purification of azo urethane
The polyurethane solution that step 1) is obtained revolves to steam removes partial solvent, by polyurethane solution be concentrated to thick after, join in 200 ml waters and form precipitation, filter and collect filter residue and by methanol wash 2 ~ 3 times, after filtering, collect filter residue, 80 ℃ are dry.
3) crystallization induction
Take 0.5 gram of step 2) products therefrom, at 80 ~ 100 ℃, be dissolved in 7.5 grams of dimethyl sulfoxide (DMSO), after dissolving completely, it is cooled to room temperature sealing.Gained urethane/dimethyl sulphoxide solution is positioned in-20 ℃ of environment freezing, freezing time is 2 days.
4) purification of azo cellular polyurethane material
Step 3) gained sample is rinsed with a large amount of 3 ℃ of water, obtain suspension liquid.After suction filtration, gained filter residue is dried, drying temperature is 80 ℃.Dry gained sample is nitrogen benzide urethane porous material.
Embodiment 3
A kind of azo urethane porous material and preparation method thereof, comprises the following steps:
1) azo urethane is synthetic
Take 0.5 gram 4,4 '-diphenylmethanediisocyanate, is scattered in 100 milliliters of there-necked flasks with 15 milliliters of DMFs (DMF).Take 0.716 gram of N, N-two (2-hydroxyethyl) amino-2,2 '-dimethyl-4 '-nitroazobenzene (diol monomer) is dissolved in 30 milliliters of DMF, seals standby.At 70 ℃, to slowly dripping diol monomer solution (2 ~ 3 seconds one) in isocyanate solution, dropwise rear continuation isothermal reaction 3 ~ 4 hours.In reaction process, use magnetic agitation and argon shield.
2) purification of azo urethane
The polyurethane solution that step 1) is obtained revolves to steam removes partial solvent, by polyurethane solution be concentrated to thick after, join in 200 ml waters and form precipitation, filter and collect filter residue and by methanol wash 2 ~ 3 times, after filtering, collect filter residue, 80 ℃ are dry.
3) crystallization induction
Take 0.5 gram of step 2) products therefrom, at 80 ~ 100 ℃, be dissolved in 15 grams of dimethyl sulfoxide (DMSO), after dissolving completely, it is cooled to room temperature sealing.Gained urethane/dimethyl sulphoxide solution is positioned in-20 ℃ of environment freezing, freezing time is 2 days.
4) purification of azo cellular polyurethane material
Step 3) gained sample is rinsed with a large amount of 3 ℃ of water, obtain suspension liquid.After suction filtration, gained filter residue is dried, drying temperature is 80 ℃.Dry gained sample is nitrogen benzide urethane porous material.
Embodiment 4
A kind of azo urethane porous material and preparation method thereof, comprises the following steps:
1) azo urethane is synthetic
Take 0.5 gram 4,4 '-diphenylmethanediisocyanate, is scattered in 100 milliliters of there-necked flasks with 15 milliliters of DMFs (DMF).Take 0.716 gram of N, N-two (2-hydroxyethyl) amino-2,2 '-dimethyl-4 '-nitroazobenzene (diol monomer) is dissolved in 35 milliliters of DMF, seals standby.At 70 ℃, to slowly dripping diol monomer solution (2 ~ 3 seconds one) in isocyanate solution, dropwise rear continuation isothermal reaction 3 ~ 4 hours.In reaction process, use magnetic agitation and nitrogen protection.
2) purification of azo urethane
The polyurethane solution that step 1) is obtained revolves to steam removes partial solvent, by polyurethane solution be concentrated to thick after, join in 200 ml waters and form precipitation, filter and collect filter residue and by methanol wash 2 ~ 3 times, after filtering, collect filter residue, 80 ℃ are dry.
3) crystallization induction
Take 0.5 gram of step 2) products therefrom, at 80 ~ 100 ℃, be dissolved in 10 grams of dimethyl sulfoxide (DMSO), after dissolving completely, it is cooled to room temperature sealing.Gained urethane/dimethyl sulphoxide solution is positioned in 3 ℃ of environment freezing, freezing time is 2 days.
4) purification of azo cellular polyurethane material
Step 3) gained sample is rinsed with a large amount of 3 ℃ of water, obtain suspension liquid.After suction filtration, gained filter residue is dried, drying temperature is 80 ℃.Dry gained sample is nitrogen benzide urethane porous material.
Embodiment 5
A kind of azo urethane porous material and preparation method thereof, comprises the following steps:
1) azo urethane is synthetic
Take 0.5 gram 4,4 '-diphenylmethanediisocyanate, is scattered in 100 milliliters of there-necked flasks with 15 milliliters of DMFs (DMF).Take 0.716 gram of N, N-two (2-hydroxyethyl) amino-2,2 '-dimethyl-4 '-nitroazobenzene (diol monomer) is dissolved in 30 milliliters of DMF, seals standby.At 70 ℃, to slowly dripping diol monomer solution (2 ~ 3 seconds one) in isocyanate solution, dropwise rear continuation isothermal reaction 3 ~ 4 hours.In reaction process, use magnetic agitation and argon shield.
2) purification of azo urethane
The polyurethane solution that step 1) is obtained revolves to steam removes partial solvent, by polyurethane solution be concentrated to thick after, join in 200 ml waters and form precipitation, filter and collect filter residue and by methanol wash 2 ~ 3 times, after filtering, collect filter residue, 80 ℃ are dry.
3) crystallization induction
Take 0.5 gram of step 2) products therefrom, at 80 ~ 100 ℃, be dissolved in 10 grams of dimethyl sulfoxide (DMSO), after dissolving completely, it is cooled to room temperature sealing.Gained urethane/dimethyl sulphoxide solution is positioned in-20 ℃ of environment freezing, freezing time is 24 hours.
4) purification of azo cellular polyurethane material
Step 3) gained sample is rinsed with a large amount of 3 ℃ of water, obtain suspension liquid.After suction filtration, gained filter residue is dried, drying temperature is 80 ℃.Dry gained sample is nitrogen benzide urethane porous material.
Embodiment 6
A kind of azo urethane porous material and preparation method thereof, comprises the following steps:
1) azo urethane is synthetic
Take 0.5 gram 4,4 '-diphenylmethanediisocyanate, is scattered in 100 milliliters of there-necked flasks with 15 milliliters of DMFs (DMF).Take 0.716 gram of N, N-two (2-hydroxyethyl) amino-2,2 '-dimethyl-4 '-nitroazobenzene (diol monomer) is dissolved in 30 milliliters of DMF, seals standby.At 70 ℃, to slowly dripping diol monomer solution (2 ~ 3 seconds one) in isocyanate solution, dropwise rear continuation isothermal reaction 3 ~ 4 hours.In reaction process, use magnetic agitation and argon shield.
2) purification of azo urethane
The polyurethane solution that step 1) is obtained revolves to steam removes partial solvent, by polyurethane solution be concentrated to thick after, join in 200 ml waters and form precipitation, filter and collect filter residue and by methanol wash 2 ~ 3 times, after filtering, collect filter residue, 80 ℃ are dry.
3) crystallization induction
Take 0.5 gram of step 2) products therefrom, at 80 ~ 100 ℃, be dissolved in 10 grams of dimethyl sulfoxide (DMSO), after dissolving completely, it is cooled to room temperature sealing.Gained urethane/dimethyl sulphoxide solution is positioned in-20 ℃ of environment freezing, freezing time is 4 days.
4) purification of azo cellular polyurethane material
Step 3) gained sample is rinsed with a large amount of 3 ℃ of water, obtain suspension liquid.After suction filtration, gained filter residue is dried, drying temperature is 80 ℃.Dry gained sample is nitrogen benzide urethane porous material.
Embodiment 7
A kind of azo urethane porous material and preparation method thereof, comprises the following steps:
1) azo urethane is synthetic
Take 0.5 gram 4,4 '-diphenylmethanediisocyanate, is scattered in 100 milliliters of there-necked flasks with 15 milliliters of DMFs (DMF).Take 0.716 gram of N, N-two (2-hydroxyethyl) amino-2,2 '-dimethyl-4 '-nitroazobenzene (diol monomer) is dissolved in 30 milliliters of DMF, seals standby.At 70 ℃, to slowly dripping diol monomer solution (2 ~ 3 seconds one) in isocyanate solution, dropwise rear continuation isothermal reaction 3 ~ 4 hours.In reaction process, use magnetic agitation and argon shield.
2) purification of azo urethane
The polyurethane solution that step 1) is obtained revolves to steam removes partial solvent, by polyurethane solution be concentrated to thick after, join in 200 ml waters and form precipitation, filter and collect filter residue and by methanol wash 2 ~ 3 times, after filtering, collect filter residue, 80 ℃ are dry.
3) crystallization induction
Take 0.5 gram of step 2) products therefrom, at 80 ~ 100 ℃, be dissolved in 10 grams of dimethyl sulfoxide (DMSO), after dissolving completely, it is cooled to room temperature sealing.Gained urethane/dimethyl sulphoxide solution is positioned in-20 ℃ of environment freezing, freezing time is 2 days.
4) purification of azo cellular polyurethane material
Step 3) gained sample is rinsed with a large amount of 20 ℃ of water, obtain suspension liquid.After suction filtration, gained filter residue is dried, drying temperature is 80 ℃.Dry gained sample is nitrogen benzide urethane porous material.
Embodiment 8
A kind of azo urethane porous material and preparation method thereof, comprises the following steps:
1) azo urethane is synthetic
Take 0.5 gram 4,4 '-diphenylmethanediisocyanate, is scattered in 100 milliliters of there-necked flasks with 15 milliliters of DMFs (DMF).Take 0.716 gram of N, N-two (2-hydroxyethyl) amino-2,2 '-dimethyl-4 '-nitroazobenzene (diol monomer) is dissolved in 30 milliliters of DMF, seals standby.At 70 ℃, to slowly dripping diol monomer solution (2 ~ 3 seconds one) in isocyanate solution, dropwise rear continuation isothermal reaction 3 ~ 4 hours.In reaction process, use magnetic agitation and argon shield.
2) purification of azo urethane
The polyurethane solution that step 1) is obtained revolves to steam removes partial solvent, by polyurethane solution be concentrated to thick after, join in 200 ml waters and form precipitation, filter and collect filter residue and by methanol wash 2 ~ 3 times, after filtering, collect filter residue, 80 ℃ are dry.
3) crystallization induction
Take 0.5 gram of step 2) products therefrom, at 80 ~ 100 ℃, be dissolved in 10 grams of dimethyl sulfoxide (DMSO), after dissolving completely, it is cooled to room temperature sealing.Gained urethane/dimethyl sulphoxide solution is positioned in-10 ℃ of environment freezing, freezing time is 2 days.
4) purification of azo cellular polyurethane material
Step 3) gained sample is rinsed with a large amount of 10 ℃ of water, obtain suspension liquid.After suction filtration, gained filter residue is dried, drying temperature is 80 ℃.Dry gained sample is nitrogen benzide urethane porous material.
The azo urethane porous material that above each embodiment is obtained all carries out the aptitude tests of nitrogen adsorption desorption and surface topography test.The nitrogen adsorption desorption aptitude tests of azo urethane porous material adopt TriStar 3020 ratio surface area instruments to measure; Adopt the surface topography of each azo urethane porous material of Quanta 200 scanning electron microscope tests.
From the nitrogen adsorption desorption ability of the azo urethane porous material of each embodiment, analyze, the hole that comprises macropore and mesoporous two kinds of yardsticks in azo urethane porous material prepared by the inventive method, and can regulate and control by changing mass ratio, Tc, crystallization time and the washing temperature etc. of azo urethane and methyl-sulphoxide the physical properties in hole and then regulation and control adsorptive capacity.
Claims (7)
1. a preparation method for azo urethane porous material, is characterized in that, comprises the following steps:
1) preparation of azo urethane
Get N, N-two (2-hydroxyethyl) amino-2,2 '-dimethyl-4 '-nitro-azo benzo dissolves with solvent orange 2 A; 4, the 4 '-diphenylmethanediisocyanate that waits amount of substance is scattered in solvent B and heating; In the time of 65 ~ 80 ℃, to 4, in 4 '-diphenylmethanediisocyanate solution, dropwise drip N, N-two (2-hydroxyethyl) amino-2,2 '-dimethyl-4 '-nitro-azo benzole soln, dropwise rear continuation reaction 3 ~ 4 h, adopt the protection of protection gas in reaction process, purifying after completion of the reaction and being dried obtains azo urethane;
2) azo urethane porous material is prepared in crystallization induction
The azo urethane that takes 1 mass parts step 1) gained is put into container, and to the methyl-sulphoxide that adds 15 ~ 30 mass parts in described container, be heated to 80 ~ 100 ℃, after being dissolved completely, described azo urethane is cooled to room temperature, then by described container sealing and be positioned over-20 ~ 3 ℃ freezing 1 ~ 4 day, the water of 3 ~ 20 ℃ of freezing gained sample employings is washed, then suction filtration, the dry azo urethane porous material that to obtain.
2. the preparation method of azo urethane porous material as claimed in claim 1, is characterized in that: described solvent orange 2 A and solvent B are anhydrous DMF.
3. the preparation method of azo urethane porous material as claimed in claim 1, is characterized in that: N in step 1), N-two (2-hydroxyethyl) is amino-2, the rate of addition of 2 '-dimethyl-4 '-nitroazobenzene be 2 ~ 3 seconds/drip.
4. the preparation method of azo urethane porous material as claimed in claim 1, it is characterized in that, purification concrete operations described in step 1) are: rotary evaporation solution after completion of the reaction, reaction solution after concentrated is poured into water, form precipitation, filter, adopt methanol wash precipitation, then the drying precipitated azo urethane that must purify at 80 ℃.
5. the preparation method of azo urethane porous material as claimed in claim 1, is characterized in that: step 2) in take 1 mass parts step 1) gained azo urethane put into container, and to the methyl-sulphoxide that adds 20 mass parts in described container.
6. the preparation method of the azo urethane porous material as described in claim 1 or 5, is characterized in that: step 2) in be cooled to room temperature after described azo urethane is dissolved completely, then by described container sealing and be positioned at-20 ℃ freezing 2 days.
7. the preparation method of the azo urethane porous material as described in claim 1 or 5, is characterized in that: step 2) in adopt the water of 3 ℃ to wash freezing gained solid.
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| CN109535361A (en) * | 2018-11-12 | 2019-03-29 | 中山大学 | A kind of ultraviolet light irradiation mechanical response aqueous polyurethane and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107652682A (en) * | 2017-09-26 | 2018-02-02 | 成都新柯力化工科技有限公司 | A kind of method that vibration-damping foamed rubber is prepared under the conditions of cold cure |
| CN109535361A (en) * | 2018-11-12 | 2019-03-29 | 中山大学 | A kind of ultraviolet light irradiation mechanical response aqueous polyurethane and preparation method thereof |
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