CN115926156A - Preparation method of color-changing polyurea - Google Patents
Preparation method of color-changing polyurea Download PDFInfo
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- CN115926156A CN115926156A CN202211557627.8A CN202211557627A CN115926156A CN 115926156 A CN115926156 A CN 115926156A CN 202211557627 A CN202211557627 A CN 202211557627A CN 115926156 A CN115926156 A CN 115926156A
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- 229920002396 Polyurea Polymers 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 49
- 238000010992 reflux Methods 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- KYNSBQPICQTCGU-UHFFFAOYSA-N Benzopyrane Chemical compound C1=CC=C2C=CCOC2=C1 KYNSBQPICQTCGU-UHFFFAOYSA-N 0.000 claims description 39
- 230000015572 biosynthetic process Effects 0.000 claims description 35
- 238000003786 synthesis reaction Methods 0.000 claims description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 12
- FUGKCSRLAQKUHG-UHFFFAOYSA-N 5-chloro-2-hydroxybenzaldehyde Chemical compound OC1=CC=C(Cl)C=C1C=O FUGKCSRLAQKUHG-UHFFFAOYSA-N 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 11
- CBHOOMGKXCMKIR-UHFFFAOYSA-N azane;methanol Chemical compound N.OC CBHOOMGKXCMKIR-UHFFFAOYSA-N 0.000 claims description 10
- 229960001701 chloroform Drugs 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 29
- 229920000642 polymer Polymers 0.000 abstract description 11
- 239000004202 carbamide Substances 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 8
- 230000002441 reversible effect Effects 0.000 abstract description 8
- 230000032683 aging Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 25
- -1 amino compound Chemical class 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 230000008859 change Effects 0.000 description 11
- 230000003321 amplification Effects 0.000 description 10
- 238000003199 nucleic acid amplification method Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- HZOKZZNMIDZZFK-UHFFFAOYSA-N 1-(4-chlorophenyl)-1-phenylhydrazine Chemical compound C=1C=C(Cl)C=CC=1N(N)C1=CC=CC=C1 HZOKZZNMIDZZFK-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 230000000638 stimulation Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PWMWNFMRSKOCEY-UHFFFAOYSA-N 1-Phenyl-1,2-ethanediol Chemical group OCC(O)C1=CC=CC=C1 PWMWNFMRSKOCEY-UHFFFAOYSA-N 0.000 description 2
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 125000003003 spiro group Chemical group 0.000 description 2
- 230000003335 steric effect Effects 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- UOFGSWVZMUXXIY-UHFFFAOYSA-N 1,5-Diphenyl-3-thiocarbazone Chemical compound C=1C=CC=CC=1N=NC(=S)NNC1=CC=CC=C1 UOFGSWVZMUXXIY-UHFFFAOYSA-N 0.000 description 1
- YDLDGRGWTVZRNE-UHFFFAOYSA-N 1-benzyl-1-(4-chlorophenyl)hydrazine Chemical compound C=1C=C(Cl)C=CC=1N(N)CC1=CC=CC=C1 YDLDGRGWTVZRNE-UHFFFAOYSA-N 0.000 description 1
- WCQAZRJBAWCCMZ-UHFFFAOYSA-N 2,3-dihydro-1h-indole;2h-pyran Chemical compound C1OC=CC=C1.C1=CC=C2NCCC2=C1 WCQAZRJBAWCCMZ-UHFFFAOYSA-N 0.000 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- ITPCCQOGYMDBHK-UHFFFAOYSA-N 3h-benzo[f][1,2]benzoxazine;2,3-dihydro-1h-indole Chemical compound C1=CC=C2NCCC2=C1.C1=CC=CC2=C(C=CNO3)C3=CC=C21 ITPCCQOGYMDBHK-UHFFFAOYSA-N 0.000 description 1
- VCMLCMCXCRBSQO-UHFFFAOYSA-N 3h-benzo[f]chromene Chemical compound C1=CC=CC2=C(C=CCO3)C3=CC=C21 VCMLCMCXCRBSQO-UHFFFAOYSA-N 0.000 description 1
- ZMGMDXCADSRNCX-UHFFFAOYSA-N 5,6-dihydroxy-1,3-diazepan-2-one Chemical compound OC1CNC(=O)NCC1O ZMGMDXCADSRNCX-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- OYQYHJRSHHYEIG-UHFFFAOYSA-N ethyl carbamate;urea Chemical compound NC(N)=O.CCOC(N)=O OYQYHJRSHHYEIG-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- HOBCFUWDNJPFHB-UHFFFAOYSA-N indolizine Chemical compound C1=CC=CN2C=CC=C21 HOBCFUWDNJPFHB-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of color-changing polyurea, which belongs to the technical field of high polymer materials. The color-changing group changes color repeatedly, the reversible cycle number determines the long-term color-changing performance of the material, and photochemical side reaction can occur in the reversible process of C-O bond breakage to cause color-changing failure. The content of the color-changing groups is high, and the problem of color-changing failure of partial color-changing groups is avoided. The polyurea polymer prepared by the four-step reaction has the advantages that each molecular chain is connected through a urea bond, the generation of bubbles caused by the reaction with humid air is avoided, the polymer molecules are more stable, and the physical and mechanical properties are better. The reaction does not need a catalyst, the material has good aging resistance, and the service life of the material is prolonged. The defects of poor thermal stability, poor fatigue resistance and the like of the photochromic material are also overcome, and the photochromic material is easy to obtain raw materials and low in cost.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation method of color-changing polyurea.
Background
In recent years, photochromic materials have attracted more and more attention due to their extremely high potential application value, and have become an important research subject in the world. Photochromic materials have been put into practical use in the fields of photosensitive decoration, photochromic glasses, digital display and the like, and have very attractive prospects in the high and new technology fields of optical information storage, optical switches, holographic superfine development, biological probes and the like. Under the action of an external force field, the force-induced color-changing material can qualitatively judge the stress condition of the material through the change of the color of the material, the distribution of the color and the like, so that the molecular level research can be carried out on the polymer by utilizing the color-changing phenomenon.
Polyurea is an elastomeric material formed by the reaction of an isocyanate component and an amino compound component. Polyurea has excellent mechanical properties due to the high bond energy of urea, such as: high strength, high wear resistance, high impact resistance, excellent flexibility, and excellent weather resistance and chemical resistance, the coating is widely applied to the fields of corrosion prevention and protection of pipelines, buildings, energy sources, traffic, water conservancy, chemical engineering, military affairs and the like.
Therefore, if the functional advantages of the two can be combined to realize the force-photochromic polyurea, the combination of the advantages of the two can be realized, and the material can be more widely applied.
For example, chinese patent CN110537114A discloses a method for producing photochromic spectacle lenses. In an embodiment, at least one layer of the improved photochromic poly (urea-urethane) is formed by combining a photochromic material and a polyurethane prepolymer with the reaction product of a mixture of diethyltoluenediamine and one or more polyols and a catalyst. The photochromic material is selected from at least one of silver halide, dichroic metal oxide, dichroic organic dye, thermochromic compound, spiro (indoline) pyran, naphthopyran, benzopyran, dithizone, benzoxazine, spiro-oxazine, spiro (indoline) naphthooxazine, spiro-pyridobenzoxazine, anthraquinone, oxazine, indolizine, fulgide and fulgimide.
However, the prior art is directed to the photochromic effect of polyureas by the addition of photochromic materials, the polyurea starting materials being common knowledge in the art, formed by the combination of isocyanate and polyol to form a prepolymer, polyurethane prepolymer and a mixture of diethyltoluenediamine and a variety of polyols, and the reaction product of a catalyst. The reaction product has both urea bonds and urethane bonds, the urethane bonds have low reaction activity, foaming tendency and poor material performance, and the system contains a catalyst and has poor durability.
Furthermore, it is not described in the above-mentioned method for producing photochromic ophthalmic lenses how the photochromic material is combined with polyurea, i.e., physical mixing or chemical reaction? And the addition amount of the photochromic material is 0.25-2%, the combination form and addition amount of the photochromic material and polyurea determine the color change effect of the material, and the prior patent only relates to photochromic and does not mention mechanochromism.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a color-changing polyurea, wherein in the force-photochromic polyurea, the color-changing groups are intrinsic functional groups on the main chain of the polyurea molecule, each polyurea chain segment contains the color-changing groups, the color-changing groups are uniformly distributed, and the color-changing polyurea is sensitive to color change under external stimulation. The reaction does not involve polyhydric alcohol, corresponding products do not contain urethane bonds and only contain urea bonds, and the polymer is more stable and has better physical and mechanical properties.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of the color-changing polyurea comprises the following steps:
step one, synthesis of compound a
Weighing raw materials of N-R group-4-chlorophenylhydrazine, 3-methyl-2-butanone and triethylamine according to parts by weight, sequentially adding the raw materials into a three-neck flask, heating in a water bath under the protection of nitrogen, stirring for reaction, adding sodium carbonate for neutralization, and distilling to collect fractions to obtain a product a;
step two, synthesis of compound b
Sequentially adding the weighed compound a and 5-chlorosalicylaldehyde into a round-bottom flask containing a methanol solution, installing a reflux condenser tube, placing the reflux condenser tube in an ultrasonic cleaner for bath ultrasonic reflux reaction for 1-3min, filtering, drying and cooling to obtain a compound b;
step three, synthesis of compound c
Adding the compound b into a round-bottom flask, adding 10% ammonia methanol solution, placing in a water bath, stirring and refluxing for 5-10h, and distilling the redundant solvent to obtain a compound c;
step four, synthesis of compound d
And (3) preparing solid phosgene in a three-neck flask to dissolve in trichloromethane, slowly dropwise adding the compound c in the three-neck flask, stirring in a water bath for reflux reaction, and distilling redundant solvent after dropwise adding is finished to obtain the compound d color-changing polyurea.
As a further scheme of the invention, in the first step, a stirrer, a thermometer and a reflux condenser device are arranged in the three-neck flask, and 2-6 parts by weight of N-R group-4-chlorophenylhydrazine, 1-3 parts by weight of 3-methyl-2-butanone and 1-3 parts by weight of triethylamine are weighed.
As a further scheme of the invention, in the first step, under the protection of nitrogen, water bath heating at 80 ℃ and stirring reaction are carried out, then 1-3 parts of sodium carbonate are used for neutralization, and 240-320 ℃ fractions are collected through distillation to obtain the product a.
As a further scheme of the invention, the compound a is 1-5 parts of 5-chloro-1-R group-3, 3-dimethyl-2-methylene indoline, wherein the R group of the compound a is benzene and derivatives thereof.
As a further scheme of the invention, in the second step, 1-5 parts of the compound a and 1-5 parts of 5-chlorosalicylaldehyde are sequentially added into a round-bottom flask containing 30 parts of a methanol solution, a reflux condenser tube is arranged, and the round-bottom flask is placed in a 70w ultrasonic cleaner to carry out ultrasonic reflux reaction in a 70 ℃ water bath for 1-3min.
As a further embodiment of the invention, the purity of the 3-methyl-2-butanone and the purity of the 5-chlorosalicylaldehyde are both more than or equal to 98 percent.
As a further scheme of the invention, in the third step, 1-5 parts of compound b is added into a round-bottom flask, 10-50 parts of 10% ammonia methanol solution is added, and the mixture is placed in a 70 ℃ water bath and stirred for reflux.
In the fourth step, 0.5-1 part of phosgene solid is dissolved in 50 parts of trichloromethane in a three-neck flask, 4-6 parts of compound c is slowly dropped into the three-neck flask, and the mixture is stirred and refluxed in a water bath at 70 ℃ for reaction.
As a further scheme of the invention, the purity of the solid phosgene is more than or equal to 99.5 percent.
As a further embodiment of the present invention, the compound b is 5,6 '-dichloro-1-benzyl-3, 3-dimethylspiroindoline benzopyran, and the compound c is 5,6' -diamino-1-benzyl-3, 3-dimethylspiroindoline benzopyran.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the photochromic polyurea of the invention prepares the photochromic polyurea, the photochromic groups are on the main chain of polyurea molecules, and are intrinsic functional groups, each polyurea chain segment contains the photochromic groups, and the photochromic groups are uniformly distributed and are sensitive to color change under the external stimulation. The reaction does not involve polyhydric alcohol, corresponding products do not contain urethane bonds and only contain urea bonds, and the polymer is more stable and has better physical and mechanical properties.
1. According to the preparation method of the color-changing polyurea, each polyurea chain segment contains the color-changing groups, the color-changing groups are uniformly distributed, and the color-changing polyurea is sensitive to change color under external stimulation. The color-changing group changes color repeatedly, the reversible cycle number determines the long-term color-changing performance of the material, and photochemical side reaction can occur in the reversible process of C-O bond breakage to cause color-changing failure. The content of the color-changing groups is high, and the problem of color-changing invalidation of partial color-changing groups is avoided.
2. According to the polyurea polymer prepared by the four-step reaction, each molecular chain is connected through a urea bond, no polyol participates in the reaction, the corresponding product does not contain a urethane bond and only contains the urea bond, the generation of bubbles caused by the reaction with moist air is avoided, the polymer molecules are more stable, and the physical and mechanical properties are better. Moreover, no catalyst is needed in the reaction, no catalyst remains in the molecular chain, the material has good aging resistance, and the service life of the material is prolonged. The urea bond overcomes the defects of poor thermal stability, poor fatigue resistance and the like of the photochromic material;
3. the color-changing polyurea prepared by the invention has the advantages of easily available raw materials and low cost.
Detailed Description
The present invention is further described with reference to the following specific embodiments, which are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and are not intended to limit the present invention, and any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
The preparation method of the color-changing polyurea is used for preparing the force-photochromic polyurea, the color-changing group is arranged on the main chain of polyurea molecules and is an intrinsic functional group, the force-photochromic principle is that the C-O bond of a six-membered ring can generate reversible covalent bond fracture under the irradiation of ultraviolet light or stress of colorless polymer molecules to generate an open ring body, so that the open ring body has strong absorption in a visible light region to generate color, and the polymer can be reconnected into a closed ring body and the intrinsic functional group when no light is irradiated or stressed because the photoresponse is reversible, and the expression of the force-photochromic is as follows:
a preparation method of the color-changing polyurea comprises the following steps:
synthesis of Compound a: adding 2-6 parts of N-R group-4-chlorophenylhydrazine into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser device, then adding 1-3 parts of 3-methyl-2-butanone and 1-3 parts of triethylamine, heating in a water bath at 80 ℃ under the protection of nitrogen, stirring for reaction, then neutralizing with 1-3 parts of sodium carbonate, distilling and collecting fractions at 240-320 ℃ to obtain the product a.
Synthesis of Compound b: adding 1-5 parts of compound a and 1-5 parts of 5-chlorosalicylaldehyde into a round-bottom flask containing 30 parts of methanol solution in sequence, installing a reflux condenser tube, placing in a 70w ultrasonic cleaner, performing ultrasonic reflux reaction in a water bath at 70 ℃ for 1-3min, filtering, drying and cooling to obtain a compound b.
Synthesis of Compound c: adding 1-5 parts of compound b into a round-bottom flask, adding 10-50 parts of 10% ammonia methanol solution, placing in a 70 ℃ water bath, stirring and refluxing for 5-10h, and distilling the redundant solvent to obtain compound c.
Synthesis of Compound d: 0.5-1 part of solid phosgene is prepared in a three-neck flask and dissolved in 50 parts of trichloromethane, 4-6 parts of compound c is slowly dripped into the three-neck flask, the mixture is stirred in a water bath at 70 ℃ for reflux reaction, and after the dripping is finished, the redundant solvent is distilled to obtain the compound d color-changing polyurea.
The expression formula of the preparation method of the color-changing polyurea is as follows:
wherein the compound a is 1-5 parts of 5-chloro-1-R group-3, 3-dimethyl-2-methylene indoline, wherein the R group of the compound a is benzene and derivatives thereof. The compound b is 5,6 '-dichloro-1-benzyl-3, 3-dimethyl spiroindoline benzopyran, and the compound c is 5,6' -diamino-1-benzyl-3, 3-dimethyl spiroindoline benzopyran.
The technical solution of the present invention will be described in further detail with reference to specific embodiments.
Example 1
The preparation method of the color-changing polyurea provided by the embodiment of the invention comprises the following synthetic preparation processes:
synthesis of 5-chloro-1-phenyl-3, 3-dimethyl-2-methylindoline: 6 parts of N-phenyl-4-chlorophenylhydrazine, 3 parts of 3-methyl-2-butanone and 2 parts of triethylamine are added into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser device, the mixture is heated in a water bath at 80 ℃ under the protection of nitrogen and is stirred for reaction, then 2 parts of sodium carbonate is used for neutralization, and 200-280 ℃ fractions are collected through distillation. The product 5-chloro-1-phenyl-3, 3-dimethyl-2-methylene indoline is obtained.
Synthesis of 5,6' -dichloro-1-phenyl-3, 3-dimethylspiroindoline benzopyran: adding 3 parts of 5-chloro-1-phenyl-3, 3-dimethyl-2-methylene indoline and 1 part of 5-chlorosalicylaldehyde into a round-bottom flask containing 30 parts of methanol solution in sequence, installing a reflux condenser tube, placing the reflux condenser tube in a 70w ultrasonic cleaner, performing ultrasonic reflux reaction in a 70 ℃ water bath for 3min, filtering, drying and cooling to obtain 5,6' -dichloro-1-phenyl-3, 3-dimethyl spiroindoline benzopyran.
Synthesis of 5,6' -diamino-1-phenyl-3, 3-dimethyl spiroindoline benzopyran: 5,6 '-dichloro-1-phenyl-3, 3-dimethylspiroindoline benzopyran is added into a round-bottom flask, 25 parts of 10% ammonia methanol solution is added, the mixture is placed in a 70 ℃ water bath and stirred and refluxed for 10 hours, and redundant solvent is distilled to obtain 5,6' -diamino-1-phenyl-3, 3-dimethylspiroindoline benzopyran. Hydrogen nuclear magnetic resonance spectroscopy: m/z 369.18 (100.0%), 370.19 (26.3%), 371.19 (3.5%), 370.18 (1.1%), elemental analysis C,78.02; h,6.27; n,11.37; o,4.33.
Synthesis of color-changing polyurea: 1 part of solid phosgene is prepared in a three-neck flask and dissolved in 50 parts of trichloromethane, 5 parts of 5,6' -diamino-1-phenyl-3, 3-dimethyl spiroindoline benzopyran is slowly dripped into the three-neck flask, the mixture is stirred in a water bath at 70 ℃ for reflux reaction, and after the dripping is finished, the redundant solvent is distilled, thus obtaining the color-changing polyurea.
Secondly, an ultraviolet spectrometer is used for testing, the ultraviolet characteristic absorption peak of the polyurea is 565nm, the absorption peak intensity is 0.10, the absorption peak intensity is 0.85 and the amplification is 750 percent when the polyurea is illuminated, the absorption peak intensity is 0.80 and the amplification is 700 percent when the polyurea is stretched by 350 percent, and the obvious color change phenomenon exists.
Example 2
The preparation method of the color-changing polyurea provided by the embodiment of the invention comprises the following synthetic preparation processes:
synthesis of 5-chloro-1-benzyl-3, 3-dimethyl-2-methylindoline: adding 6 parts of N-benzyl-4-chlorophenylhydrazine, then adding 2 parts of 3-methyl-2-butanone and 2 parts of triethylamine into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser device, heating in a water bath at 80 ℃ under the protection of nitrogen, stirring for reaction, then neutralizing with 2 parts of sodium carbonate, and collecting 220-300 ℃ fractions through distillation. The product 5-chloro-1-benzyl-3, 3-dimethyl-2-methylene indoline is obtained.
Synthesis of 5,6' -dichloro-1-benzyl-3, 3-dimethylspiroindoline benzopyran: adding 5 parts of 5-chloro-1-benzyl-3, 3-dimethyl-2-methylindoline and 1 part of 5-chlorosalicylaldehyde into a round-bottom flask containing 30 parts of methanol solution in sequence, installing a reflux condenser tube, placing the reflux condenser tube in a 70w ultrasonic cleaner, performing ultrasonic reflux reaction in a 70 ℃ water bath for 3min, filtering, drying and cooling to obtain the 5,6' -dichloro-1-benzyl-3, 3-dimethyl spiroindoline benzopyran.
Synthesis of 5,6' -diamino-1-benzyl-3, 3-dimethyl spiroindoline benzopyran: adding 5 parts of 5,6 '-dichloro-1-benzyl-3, 3-dimethyl spiroindoline benzopyran into a round-bottom flask, adding 25 parts of 10% ammonia methanol solution, placing in a 70 ℃ water bath, stirring and refluxing for 10 hours, and distilling the redundant solvent to obtain the 5,6' -diamino-1-benzyl-3, 3-dimethyl spiroindoline benzopyran. Hydrogen nuclear magnetic resonance spectroscopy: m/z 383.20 (100.0%), 384.20 (28.2%), 385.21 (3.6%), elemental analysis C,78.30; h,6.57; n,10.96; and O,4.17.
Synthesis of color-changing polyurea: 1 part of solid phosgene is prepared in a three-neck flask and dissolved in 50 parts of trichloromethane, 4 parts of 5,6' -diamino-1-phenyl-3, 3-dimethyl spiroindoline benzopyran is slowly dripped into the three-neck flask, the mixture is stirred and refluxed in a water bath at 70 ℃ for reaction, and the surplus solvent is distilled after the dripping is finished, thus obtaining the color-changing polyurea.
Secondly, an ultraviolet spectrometer is used for testing, the ultraviolet characteristic absorption peak of the polyurea is 565nm, the absorption peak intensity is 0.10, the absorption peak intensity is 0.85 and the amplification is 750 percent when the polyurea is illuminated, the absorption peak intensity is 0.80 and the amplification is 700 percent when the polyurea is stretched by 300 percent, and the obvious color change phenomenon exists.
Example 3
The preparation method of the color-changing polyurea provided by the embodiment of the invention comprises the following synthetic preparation processes:
synthesis of 5-chloro-1, 3-trimethyl-2-methyleneindoline: 6 parts of N-phenyl-4-chlorophenylhydrazine, 3 parts of 3-methyl-2-butanone and 2 parts of triethylamine are added into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser device, the mixture is heated in a water bath at 80 ℃ under the protection of nitrogen and is stirred for reaction, then 2 parts of sodium carbonate is used for neutralization, and 200-280 ℃ fractions are collected through distillation. The product 5-chloro-1, 3-trimethyl-2-methylene indoline is obtained.
Synthesis of 5,6' -dichloro-1, 3-trimethylspiroindoline benzopyran: adding 3 parts of 5-chloro-1, 3-trimethyl-2-methylene indoline and 1 part of 5-chlorosalicylaldehyde into a round-bottom flask containing 30 parts of methanol solution in sequence, installing a reflux condenser tube, placing the reflux condenser tube in a 70w ultrasonic cleaner, performing ultrasonic reflux reaction in a 70 ℃ water bath for 3min, filtering, drying and cooling to obtain 5,6' -dichloro-1, 3-trimethyl spiroindoline benzopyran.
Synthesis of 5,6' -diamino-1, 3-trimethylspiroindoline benzopyran: 5 parts of 5,6 '-dichloro-1, 3-trimethylspiroindoline benzopyran are added into a round-bottom flask, 25 parts of 10% ammonia methanol solution are added, the mixture is placed in a 70 ℃ water bath and stirred for refluxing for 10 hours, and redundant solvent is distilled to obtain the 5,6' -diamino-1, 3-trimethylspiroindoline benzopyran. Hydrogen nuclear magnetic resonance spectroscopy: m/z 307.17 (100.0%), 308.17 (21.9%), 309.18 (2.1%), elemental analysis: c,74.24; h,6.89; n,13.67; and O,5.20.
Synthesis of polyurea: 1 part of solid phosgene is prepared in a three-neck flask and dissolved in 50 parts of trichloromethane, 5 parts of 5,6' -diamino-1, 3-trimethyl spiroindoline benzopyran is slowly dripped into the three-neck flask, the three-neck flask is stirred in a water bath at 70 ℃ for reflux reaction, and after the dripping is finished, redundant solvent is distilled to obtain the polyurea.
Secondly, an ultraviolet spectrometer is used for testing, the ultraviolet characteristic absorption peak of the polyurea is 565nm, the absorption peak intensity is 0.10, the absorption peak intensity is 0.20 and the amplification is 100% when the polyurea is illuminated, the absorption peak intensity is 0.15 and the amplification is 50% when the polyurea is stretched by 400%, and the phenomenon of color change does not occur. The spiro tertiary amine has no steric effect of benzene ring, and reacts with phosgene to generate complex and destroy color changing group.
Comparative example 1
Compared with example 1, the R group adopts methyl to replace phenyl, and the synthesis and preparation processes of the polyurea material are as follows:
synthesis of 5-chloro-1, 3-trimethyl-2-methyleneindoline: 6 parts of N-phenyl-4-chlorophenylhydrazine, 3 parts of 3-methyl-2-butanone and 2 parts of triethylamine are added into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser device, the mixture is heated in a water bath at 80 ℃ under the protection of nitrogen and is stirred for reaction, then 2 parts of sodium carbonate is used for neutralization, and 200-280 ℃ fractions are collected through distillation. The product 5-chloro-1, 3-trimethyl-2-methylene indoline is obtained.
Synthesis of 5,6' -dichloro-1, 3-trimethylspiroindoline benzopyran: 3 parts of 5-chloro-1, 3-trimethyl-2-methylene indoline and 1 part of 5-chlorosalicylaldehyde are sequentially added into a round-bottom flask containing 30 parts of methanol solution, a reflux condenser tube is arranged, the round-bottom flask is placed in a 70w ultrasonic cleaner to carry out ultrasonic reflux reaction in water bath at 70 ℃ for 3min, and the round-bottom flask is filtered, dried and cooled to obtain 5,6' -dichloro-1, 3-trimethyl spiroindoline benzopyran.
Synthesis of 5,6' -diamino-1, 3-trimethylspiroindoline benzopyran: 5 parts of 5,6 '-dichloro-1, 3-trimethylspiroindoline benzopyran are added into a round-bottom flask, 25 parts of 10% ammonia methanol solution are added, the mixture is placed in a 70 ℃ water bath and stirred for refluxing for 10 hours, and redundant solvent is distilled to obtain the 5,6' -diamino-1, 3-trimethylspiroindoline benzopyran. Hydrogen nuclear magnetic resonance spectroscopy: m/z 307.17 (100.0%), 308.17 (21.9%), 309.18 (2.1%), elemental analysis: c,74.24; h,6.89; n,13.67; and O,5.20.
Synthesis of polyurea: 1 part of solid phosgene is prepared in a three-neck flask and dissolved in 50 parts of trichloromethane, 5 parts of 5,6' -diamino-1, 3-trimethyl spiroindoline benzopyran is slowly dripped into the three-neck flask, the three-neck flask is stirred in a water bath at 70 ℃ for reflux reaction, and after the dripping is finished, redundant solvent is distilled to obtain the polyurea.
The polyurea ultraviolet characteristic absorption peak is 565nm and the absorption peak intensity is 0.10 by using an ultraviolet spectrometer, the absorption peak intensity is 0.20 and the amplification is 100 percent when the polyurea ultraviolet characteristic absorption peak is illuminated, the absorption peak intensity is 0.15 and the amplification is 50 percent when the polyurea ultraviolet characteristic absorption peak is stretched by 400 percent, and the phenomenon of color change does not occur. The spiro tertiary amine has no steric effect of benzene ring, and reacts with phosgene to generate complex and destroy color changing group.
Comparative example 2
Compared with example 1, the last step of polyurea synthesis is changed to be that solid phosgene is dripped into benzopyran, and the synthesis and preparation processes of the polyurea material are as follows:
synthesis of 5-chloro-1-phenyl-3, 3-dimethyl-2-methylindoline: adding 6 parts of N-phenyl-4-chlorophenylhydrazine, 3 parts of 3-methyl-2-butanone and 2 parts of triethylamine into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, heating in a water bath at 80 ℃ under the protection of nitrogen, stirring for reaction, neutralizing with 2 parts of sodium carbonate, and distilling to collect 200-280 ℃ fractions. The product 5-chlorine-1-phenyl-3, 3-dimethyl-2-methylene indoline is obtained.
Synthesis of 5,6' -dichloro-1-phenyl-3, 3-dimethylspiroindoline benzopyran: adding 3 parts of 5-chloro-1-phenyl-3, 3-dimethyl-2-methylene indoline and 1 part of 5-chlorosalicylaldehyde into a round-bottom flask containing 30 parts of methanol solution in sequence, installing a reflux condenser tube, placing the reflux condenser tube in a 70w ultrasonic cleaner, performing ultrasonic reflux reaction in a 70 ℃ water bath for 3min, filtering, drying and cooling to obtain 5,6' -dichloro-1-phenyl-3, 3-dimethyl spiroindoline benzopyran.
Synthesis of 5,6' -diamino-1-phenyl-3, 3-dimethyl spiroindoline benzopyran: 5,6 '-dichloro-1-phenyl-3, 3-dimethylspiroindoline benzopyran is added into a round-bottom flask, 25 parts of 10% ammonia methanol solution is added, the mixture is placed in a 70 ℃ water bath and stirred and refluxed for 10 hours, and redundant solvent is distilled to obtain 5,6' -diamino-1-phenyl-3, 3-dimethylspiroindoline benzopyran.
Hydrogen nuclear magnetic resonance spectroscopy: m/z 369.18 (100.0%), 370.19 (26.3%), 371.19 (3.5%), 370.18 (1.1%), elemental analysis C,78.02; h,6.27; n,11.37; o,4.33.
Synthesis of polyurea: weighing 5 parts of 5,6' -diamino-1-phenyl-3, 3-dimethyl spiroindoline benzopyran, placing the benzopyran into a three-neck flask, stirring and refluxing in a water bath at 70 ℃ for reaction, preparing 1 part of solid phosgene, dissolving the solid phosgene into 50 parts of trichloromethane, slowly dripping the solid phosgene into the three-neck flask, and distilling redundant solvent after dripping to obtain the polyurea. The polyurea ultraviolet characteristic absorption peak is 565nm and the absorption peak intensity is 0.10 by using an ultraviolet spectrometer, the absorption peak intensity is 0.15 and the amplification is 50% when the polyurea ultraviolet characteristic absorption peak is illuminated, the absorption peak intensity is 0.10 and the amplification is 0% when the polyurea ultraviolet characteristic absorption peak is stretched by 350%, and the phenomenon of color change does not occur. When the primary amine is excessive, small molecular cyclic urea is generated by reaction, and the color-changing group cannot be recovered due to steric hindrance, so that the color-changing group is damaged.
Compared with comparative example 1 and comparative example 2, each polyurea chain segment of examples 1-3 of the invention contains color-changing groups, and the color-changing groups are uniformly distributed and sensitive to color change under external stimulation. The color-changing group changes color repeatedly, the reversible cycle number determines the long-term color-changing performance of the material, and photochemical side reaction can occur in the reversible process of C-O bond breakage to cause color-changing failure. According to the scheme disclosed by the application document, the content of the color-changing groups is high, and the problem of color-changing failure of part of the color-changing groups is avoided.
Secondly, each molecular chain of the polyurea polymer prepared by four-step reaction is connected through a urea bond, no polyhydric alcohol participates in the reaction, the corresponding product does not contain urethane bonds and only contains urea bonds, bubbles generated by the reaction with humid air are avoided, the polymer molecules are more stable, and the physical and mechanical properties are better. Moreover, no catalyst is needed in the reaction, no catalyst remains in the molecular chain, the material has good aging resistance, and the service life of the material is prolonged. The defects of poor thermal stability, poor fatigue resistance and the like of the photochromic material are overcome.
Thirdly, the color-changing polyurea provided by the invention has the advantages of easily obtained raw materials and low cost.
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. The preparation method of the color-changing polyurea is characterized by comprising the following steps:
step one, synthesis of compound a
Weighing raw materials of N-R group-4-chlorophenylhydrazine, 3-methyl-2-butanone and triethylamine according to parts by weight, sequentially adding the raw materials into a three-neck flask, heating in a water bath under the protection of nitrogen, stirring for reaction, adding sodium carbonate for neutralization, and distilling to collect fractions to obtain a product a;
step two, synthesis of compound b
Sequentially adding the weighed compound a and 5-chlorosalicylaldehyde into a round-bottom flask containing a methanol solution, installing a reflux condenser tube, placing in an ultrasonic cleaner for ultrasonic reflux reaction in a water bath for 1-3min, filtering, drying and cooling to obtain a compound b;
step three, synthesis of compound c
Adding the compound b into a round-bottom flask, adding 10% ammonia methanol solution, placing in a water bath, stirring and refluxing for 5-10h, and distilling the redundant solvent to obtain a compound c;
step four, synthesis of compound d
And (3) preparing solid phosgene in a three-neck flask to be dissolved in trichloromethane, slowly dropwise adding the compound c in the three-neck flask, stirring in a water bath for reflux reaction, and distilling redundant solvent after dropwise adding is finished to obtain the compound d color-changing polyurea.
2. The method for preparing color-changing polyurea according to claim 1, wherein in the first step, the three-neck flask is provided with a stirrer, a thermometer and a reflux condenser device, and 2-6 parts by weight of N-R group-4-chlorophenylhydrazine, 1-3 parts by weight of 3-methyl-2-butanone and 1-3 parts by weight of triethylamine are weighed.
3. The preparation method of color-changing polyurea according to claim 2, characterized in that in the first step, under the protection of nitrogen, the reaction is carried out by heating in water bath at 80 ℃ and stirring, then the neutralization is carried out by 1-3 parts of sodium carbonate, and the fraction at 240-320 ℃ is collected by distillation to obtain the product a.
4. The method for preparing color-changing polyurea according to claim 3, wherein the compound a is 1-5 parts of 5-chloro-1-R group-3, 3-dimethyl-2-methylene indoline, wherein the R group of the compound a is benzene and derivatives thereof.
5. The method for preparing color-changing polyurea according to claim 3, wherein in the second step, 1-5 parts of the compound a and 1-5 parts of 5-chlorosalicylaldehyde are sequentially added into a round bottom flask containing 30 parts of methanol solution, a reflux condenser tube is arranged, and the mixture is placed into a 70w ultrasonic cleaner for ultrasonic reflux reaction in a water bath at 70 ℃ for 1-3min.
6. The method for preparing color-changing polyurea according to claim 5, wherein the purity of the 3-methyl-2-butanone and the purity of the 5-chlorosalicylaldehyde are both greater than or equal to 98%.
7. The method for preparing color-changing polyurea according to claim 5, wherein in the third step, 1-5 parts of compound b is added into a round-bottom flask, 10-50 parts of 10% ammonia methanol solution is added, and the mixture is placed in a water bath at 70 ℃ and stirred under reflux.
8. The method of preparing color-changing polyurea according to claim 7, wherein in the fourth step, 0.5 to 1 part of phosgene solution is prepared in a three-neck flask and dissolved in 50 parts of chloroform, 4 to 6 parts of compound c is slowly added dropwise to the three-neck flask, and the mixture is stirred in a 70 ℃ water bath and refluxed.
9. The method for preparing color-changing polyurea according to claim 8, wherein the purity of the solid phosgene is not less than 99.5%.
10. The method for preparing color-changing polyurea according to claim 7, wherein the compound b is 5,6 '-dichloro-1-benzyl-3, 3-dimethylspiroindoline benzopyran, and the compound c is 5,6' -diamino-1-benzyl-3, 3-dimethylspiroindoline benzopyran.
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