CN103193956A - Preparation and application of grafting-type optical azo polyurethane thermo-optic material - Google Patents
Preparation and application of grafting-type optical azo polyurethane thermo-optic material Download PDFInfo
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- CN103193956A CN103193956A CN2013101175973A CN201310117597A CN103193956A CN 103193956 A CN103193956 A CN 103193956A CN 2013101175973 A CN2013101175973 A CN 2013101175973A CN 201310117597 A CN201310117597 A CN 201310117597A CN 103193956 A CN103193956 A CN 103193956A
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Abstract
The invention belongs to the field of synthesis of a polymer material, relates to preparation of optical azobenzene and polyurethane compounds, and particularly relates to a preparation and application of a grafting-type optical azo polyurethane thermo-optic material. The preparation comprises the steps of: polymerizing azobenzene-4-nitryl-3,5-dyhydroxy azobenzene (NDAB) containing two hydroxys, and isophorone diisocyanate (IPDI) under the effect of a catalyst, then reacting with (R)-3-chorine-1,2-propylene glycol to prepare the grafting-type optical azo polyurethane thermo-optic material. The material disclosed by the invention is simple in preparation method, even in molecular weight distribution of a polymer and smooth in film surface; the polymer has asymmetry of center by a chirality group contained in a molecule; the non-linear performance of the azobenzene polymer is improved; the thermal-optical property and the thermal stability of the azo polyurethane material are enhanced; and the possibility is provided for development of a novel digital thermal-optical switch with low drive power.
Description
Technical field
The invention belongs to the synthesis of polymer material field, relate to optically-active azobenzene and Polyurethane compound, particularly a kind of preparation and application of graft type optically-active azo urethane thermoluminescent material.
Background technology
In recent years, fragrant azobenzene polymer thermoluminescent material becomes the research focus.The aromatic series azobenzene polymer can show liquid crystal liquid crystal property, optically nonlinearity and various response characteristics to light, so azobenzene polymer is the advanced function material with extensive use.The azobenzene polymer of wherein introducing chiral radicals has shown better performance, as good memory function, photoelectric properties and thermostability etc.
At present, the research of different azobenzene polymer constituent structure and optical characteristics separately thereof mainly is divided into Subjective and Objective doping type and graft type azobenzene polymer.From processing condition, the preparation technology of doping type film is simple, become the mechanical property of film good, but the distribution of dyestuff in film owe evenly, behind the film drying, dyestuff is separated out; System compares with nitrogen benzide doping aggressiveness, it is homogeneous system at molecular level that azo-functional group is grafted on the polymer macromolecule that obtains the azo side group on the polymer macromolecule, can improve the skewness of azoic dyestuff in film and the shortcoming of separating out, improve the character of film significantly.
A kind of synthetic and sign, XI AN JIAOTONG UNIVERSITY Subject Index, 2002.10,36 (10): 1024-1027 of azoic dyestuff grafted polyurethane.Reported the microscopic appearance of azoic dyestuff grafted polyurethane film (HSANB/PU) and azoic dyestuff and methyl methacrylate (PMMA) blend film (HSANB/ PMMA), with scanning electron microscope (SEM) and transmission electron microscope (TEM) scanning HSANB/ PMMA blend film and HSANB/PU graft copolymer film, scanned photograph shows HSANB/ PMMA blend film, a large amount of ball of string shape materials are arranged in the SEM photo, and generation is separated; For HSANB/ PU graft copolymer film, film surface is very even, level and smooth in the TEM photo, and dyestuff and PU are homogeneous phases.Two kinds of films are carried out heat analysis, the TGA spectrogram shows, pure HSANB dyestuff is since 200 ℃ of extensive decomposition, and HSANB/ PU multipolymer just begins extensive decomposition up to 260 ℃, decomposition temperature has improved 60 ℃ than pure dye, and visible graft copolymerization can significantly improve the thermostability of azoic dyestuff.
Synthetic and the research of ethyl cellulose grafting azobenzene polymer, functional materials, 2007,4(38): 583-585.Reported the molecular weight distribution test to ethyl cellulose graft type azobenzene polymer, the GPC curve is unimodally to show that this graft type molecular weight distribution is even, and the molecular weight distributing index numerical value of graft type polymkeric substance shows that this polyreaction has activity/controlled characteristics; Reported also in the article that for general graft type polymkeric substance its higher grafting density makes repulsive interaction enhancing between side chain, thereby caused main chain appearance ductility to a certain degree.
Summary of the invention
The invention discloses a kind of preparation method with graft type optically-active azo polyurethane material of good thermo-optical property and thermostability, be with the nitrogen benzide 4-nitro-3 that contains two hydroxyls, 5-dihydroxyl nitrogen benzide (NDAB) and isophorone diisocyanate (IPDI) polymerization under catalyst action, with (R)-3-chloro-1,2-propylene glycol prepared in reaction goes out graft type optically-active azo urethane thermoluminescent material then.
Preparation process of the present invention comprises:
A, in the there-necked flask that agitator, reflux condensing tube are housed, with 4-nitro-3,5-dihydroxyl nitrogen benzide (NDAB) and isophorone diisocyanate (IPDI) are dissolved in N, among the N '-dimethyl formamide (DMF), wherein, the mass ratio of described NDAB and DMF is 1:25 ~ 1:100, preferred 1:58; The mass ratio of described IPDI and DMF is 1:20 ~ 1:100, preferred 1:34;
B, in reaction system, drip catalyzer, 80 ~ 85 ℃ are stirred 2 ~ 4h in nitrogen atmosphere, wherein, described catalyzer can be a kind of in triethylenediamine, dibutyl tin dilaurate or the dimethylethanolamine, preferred dibutyl tin dilaurate, its consumption is 0.3 ~ 0.9% of NDAB and IPDI total mass;
C, continuation add (R)-3-chloro-1, and the 2-propylene glycol stirs, wherein, described (R)-3-chloro-1,2-propylene glycol and IPDI mass ratio are 1:1 ~ 1:4, preferred 1:2;
D, be warming up to behind 85 ℃ of reaction 3 ~ 4h with methanol wash three times, filter 50 ~ 60 ℃ of following vacuum-drying 48 ~ 72h.
The mensuration of opticity and thermo-optical coeffecient sees embodiment for details.
The present invention obtains novel optically-active azo polyurethane material, have higher thermo-optical coeffecient (
Dn/dT), than organic materials such as polystyrene (1.23 * 10
4 ℃-1) and polymethylmethacrylate (1.20 * 10
4℃
-1) big; Compare with inorganic materials, as borosilicate glass (4.1 * 10
6 ℃-1), zinc silicate glass (5.5 * 10
6 ℃-1) and silica glass (10.8 * 10
6 ℃-1) etc., be more than 10 times of its thermo-optical coeffecient; This material provides possibility for the new digital thermo-optical switch that development has low driving power.
In the used reagent of the present invention, isophorone diisocyanate (IPDI) is provided by the broad chemical industry in Shanghai company limited; (R)-and 3-chloro-1, the 2-propylene glycol is provided by Shanghai Adamas reagent company limited; N, N '-dimethyl formamide (DMF), hydrochloric acid, methyl alcohol, dibutyl tin laurate (T-12), triethylenediamine, dimethylethanolamine is provided by Chemical Reagent Co., Ltd., Sinopharm Group.Above reagent is analytical pure.
Beneficial effect
Preparation method of the present invention is easy, and molecular weight distribution is even, and film surface is level and smooth; The chiral radicals that contains in the molecule makes polymkeric substance have non-centrosymmetric feature, has improved the non-linear behaviour of azobenzene polymer; Strengthened thermo-optical property and the thermostability of nitrogen benzide polyurethane material, the new digital thermo-optical switch that has low driving power for development provides possibility.
Embodiment
The present invention is described in detail below in conjunction with embodiment, so that those skilled in the art understand the present invention better, but the present invention is not limited to following examples.
Embodiment 1
In the 250mL there-necked flask of stirring, reflux condensing tube is housed, 4-nitro-3 with 1.605g, 5-dihydroxyl nitrogen benzide (NDAB) and 2.823g isophorone diisocyanate (IPDI) are dissolved in the N of 75.9g, N '-dimethyl formamide (DMF), and add 1 ~ 2 of dibutyl tin laurate (T-12) as catalyzer, 80 ℃ of following stirring reaction 4h in nitrogen atmosphere; The R-3-chloro-1 that adds 1.412g again, the 2-propylene glycol is warming up to 85 ℃ and continues to use methanol wash three times behind the reaction 3h, filters, and 50 ℃ of following vacuum-drying 72h obtain henna chirality azo polyurethane material (CAZOPU-1).
Embodiment 2
In the 250mL there-necked flask of stirring, reflux condensing tube is housed, 4-nitro-3 with 1.05g, 5-dihydroxyl nitrogen benzide (NDAB) and 1.475g isophorone diisocyanate (IPDI) are dissolved in the N of 47.44g, N '-dimethyl formamide (DMF), and add 1 ~ 2 of dibutyl tin laurate (T-12) as catalyzer, 80 ℃ of following stirring reaction 4h in nitrogen atmosphere; The R-3-chloro-1 that adds 1.105g again, the 2-propylene glycol is warming up to 85 ℃ and continues to use methanol wash three times behind the reaction 4h, filters, and 50 ℃ of following vacuum-drying 72h obtain henna chirality azo polyurethane material (CAZOPU-2).
Embodiment 3
In the 250mL there-necked flask of stirring, reflux condensing tube is housed, 4-nitro-3 with 1.305g, 5-dihydroxyl nitrogen benzide (NDAB) and 1.937g isophorone diisocyanate (IPDI) are dissolved in the N of 77.79g, N '-dimethyl formamide (DMF), and add 1 ~ 2 of triethylenediamine as catalyzer, 80 ℃ of following stirring reaction 3h in nitrogen atmosphere; The R-3-chloro-1 that adds 1.291g again, the 2-propylene glycol is warming up to 85 ℃ and continues to use methanol wash three times behind the reaction 3h, filters, and 60 ℃ of following vacuum-drying 72h obtain henna chirality azo polyurethane material (CAZOPU-3).
Embodiment 4
In the 250mL there-necked flask of stirring, reflux condensing tube is housed, 4-nitro-3 with 1.305g, 5-dihydroxyl nitrogen benzide (NDAB) and 2.223g isophorone diisocyanate (IPDI) are dissolved in the N of 73.94g, N '-dimethyl formamide (DMF), and add 1 ~ 2 of dibutyl tin laurate (T-12) as catalyzer, 80 ℃ of following stirring reaction 4h in nitrogen atmosphere; The R-3-chloro-1 that adds 1.105g again, the 2-propylene glycol is warming up to 85 ℃ and continues to use methanol wash three times behind the reaction 3h, filters, and 50 ℃ of following vacuum-drying 48h obtain henna chirality azo polyurethane material (CAZOPU-4).
Embodiment 5
In the 250mL there-necked flask of stirring, reflux condensing tube is housed, 4-nitro-3 with 0.910g, 5-dihydroxyl nitrogen benzide (NDAB) and 1.635g isophorone diisocyanate (IPDI) are dissolved in the N of 80.06g, N '-dimethyl formamide (DMF), and add 1 ~ 2 of dimethylethanolamine as catalyzer, 85 ℃ of following stirring reaction 2h in nitrogen atmosphere; The R-chlorine 3-chloro-1 that adds 0.550g again, the 2-propylene glycol is warming up to 85 ℃ and continues to use methanol wash three times behind the reaction 3h, filters, and 60 ℃ of following vacuum-drying 72h obtain henna chirality azo polyurethane material (CAZOPU-5).
Embodiment 6
In the 250mL there-necked flask of stirring, reflux condensing tube is housed, 4-nitro-3 with 1.079g, 5-dihydroxyl nitrogen benzide (NDAB) and 1.5g isophorone diisocyanate (IPDI) are dissolved in the N of 55.06g, N '-dimethyl formamide (DMF), and add 1 ~ 2 of dibutyl tin laurate (T-12) as catalyzer, 80 ℃ of following stirring reaction 4h in nitrogen atmosphere; The R-3-chloro-1 that adds 0.835g again, the 2-propylene glycol is warming up to 85 ℃ and continues to use methanol wash three times behind the reaction 4h, filters, and 60 ℃ of following vacuum-drying 48h obtain henna chirality azo polyurethane material (CAZOPU-6).
Experimental technique:
1. get proper C AZOPU-1, CAZOPU-2, CAZOPU-3, CAZOPU-4, CAZOPU-5 and CAZOPU-6 sample, be dissolved in N respectively, in N '-dimethyl formamide, being mixed with concentration is 2.5 * 10
-4The solution of g/mL.Adopt the opticity of automatic polarimeter working sample solution, its specific rotation is respectively+11.6 ° ,+12.2 ° ,+12.3 ° ,+12.6 ° ,+11.5 ° and+11.8 °, illustrate that the optically-active azo polyurethane material that obtains has opticity.
2. get proper C AZOPU-1, CAZOPU-2, CAZOPU-3, CAZOPU-4, CAZOPU-5 and CAZOPU-6 sample, be dissolved in N respectively, in N '-dimethyl formamide, be mixed with the solution that concentration is 0.5g/mL, it is spun on the quartz plate, in 25 ℃ of following vacuum-drying 72h.Adopt the optical waveguides survey meter to test its specific refractory power under differing temps, carry out one-variable linear regression, obtain thermo-optical coeffecient dn/dT, as following table:
The present invention obtains novel optically-active azo polyurethane material, have higher thermo-optical coeffecient (
Dn/dT), than organic materials such as polystyrene (1.23 * 10
4 ℃-1) and polymethylmethacrylate (1.20 * 10
4℃
-1) big; Compare with inorganic materials, as borosilicate glass (4.1 * 10
6 ℃-1), zinc silicate glass (5.5 * 10
6 ℃-1) and silica glass (10.8 * 10
6 ℃-1) etc., be more than 10 times of its thermo-optical coeffecient; This material provides possibility for the new digital thermo-optical switch that development has low driving power.
The above only is embodiments of the invention; be not so limit claim of the present invention; every equivalent structure or equivalent flow process conversion that utilizes specification sheets of the present invention to do, or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.
Claims (7)
1. the preparation of a graft type optically-active azo urethane thermoluminescent material, it is characterized in that, with the nitrogen benzide 4-nitro-3 that contains two hydroxyls, 5-dihydroxyl nitrogen benzide (NDAB) and isophorone diisocyanate (IPDI) polymerization under catalyst action, with (R)-3-chloro-1,2-propylene glycol prepared in reaction goes out graft type optically-active azo urethane thermoluminescent material then.
2. the preparation of graft type optically-active azo urethane thermoluminescent material according to claim 1 is characterized in that described preparation comprises the steps:
A, in the there-necked flask that agitator, reflux condensing tube are housed, with 4-nitro-3,5-dihydroxyl nitrogen benzide (NDAB) and isophorone diisocyanate (IPDI) are dissolved in N, among the N '-dimethyl formamide (DMF), wherein, the mass ratio of described NDAB and DMF is 1:25 ~ 1:100, and the mass ratio of described IPDI and DMF is 1:20 ~ 1:100;
B, in reaction system, drip catalyzer, 80 ~ 85 ℃ are stirred 2 ~ 4h in nitrogen atmosphere, wherein, described catalyzer can be a kind of in triethylenediamine, dibutyl tin dilaurate or the dimethylethanolamine, and its consumption is 0.3 ~ 0.9% of NDAB and IPDI total mass;
C, continuation add (R)-3-chloro-1, and the 2-propylene glycol stirs, wherein, described (R)-3-chloro-1,2-propylene glycol and IPDI mass ratio are 1:1 ~ 1:4;
D, be warming up to behind 85 ℃ of reaction 3 ~ 4h with methanol wash three times, filter 50 ~ 60 ℃ of following vacuum-drying 48 ~ 72h.
3. the preparation of graft type optically-active azo urethane thermoluminescent material according to claim 2 is characterized in that, the mass ratio 1:58 of NDAB and DMF in the described steps A, and the mass ratio of described IPDI and DMF is 1:34.
4. the preparation of graft type optically-active azo urethane thermoluminescent material according to claim 2 is characterized in that, catalyzer is dibutyl tin dilaurate (T-12) among the described step B.
5. the preparation of graft type optically-active azo urethane thermoluminescent material according to claim 2 is characterized in that, (R)-3-chloro-1 among the described step C, and the mass ratio of 2-propylene glycol and IPDI is 1:2.
6. according to the arbitrary described graft type optically-active azo urethane thermoluminescent material for preparing of claim 1 ~ 5.
7. according to the prepared graft type optically-active of claim 6 azo urethane thermoluminescent material, it is characterized in that, be applied to low driving power digital thermal photoswitch.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103804624A (en) * | 2014-01-21 | 2014-05-21 | 江苏大学 | Preparation method of optical-rotation azo polyurethane/graphite oxide-doped composite thermo-optical material and application thereof |
| CN103965506A (en) * | 2014-05-29 | 2014-08-06 | 齐鲁工业大学 | Preparation method of porous azo polyurethane material |
| CN106750090A (en) * | 2016-11-28 | 2017-05-31 | 江南大学 | A kind of preparation method of the variable hydrophobic polyurethane of photoresponse |
| CN107337780A (en) * | 2017-07-20 | 2017-11-10 | 深圳大学 | A kind of preparation method for the shape memory elastic body that light heat double-bang firecracker is answered |
| CN107868201A (en) * | 2017-12-04 | 2018-04-03 | 电子科技大学 | A kind of chiral azobenzene polymer and its manufacture method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102786659A (en) * | 2012-08-17 | 2012-11-21 | 江苏大学 | Preparation method and application of chirality azo polyurethane thermal-optic material |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786659A (en) * | 2012-08-17 | 2012-11-21 | 江苏大学 | Preparation method and application of chirality azo polyurethane thermal-optic material |
Non-Patent Citations (1)
| Title |
|---|
| FEIYAN YE ET. AL,: "Preparation and thermo-optic switch properties based on chiral azobenzene-containing polyurethane", 《OPTICS & LASER TECHNOLOGY》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103804624A (en) * | 2014-01-21 | 2014-05-21 | 江苏大学 | Preparation method of optical-rotation azo polyurethane/graphite oxide-doped composite thermo-optical material and application thereof |
| CN103804624B (en) * | 2014-01-21 | 2015-10-28 | 江苏大学 | The preparation method of a kind of optically-active azo polyurethane/graphite oxide doping type compound thermal luminescent material and application thereof |
| CN103965506A (en) * | 2014-05-29 | 2014-08-06 | 齐鲁工业大学 | Preparation method of porous azo polyurethane material |
| CN103965506B (en) * | 2014-05-29 | 2016-06-08 | 齐鲁工业大学 | The preparation method of azo polyurethane porous material |
| CN106750090A (en) * | 2016-11-28 | 2017-05-31 | 江南大学 | A kind of preparation method of the variable hydrophobic polyurethane of photoresponse |
| CN107337780A (en) * | 2017-07-20 | 2017-11-10 | 深圳大学 | A kind of preparation method for the shape memory elastic body that light heat double-bang firecracker is answered |
| CN107868201A (en) * | 2017-12-04 | 2018-04-03 | 电子科技大学 | A kind of chiral azobenzene polymer and its manufacture method |
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