CN101173046A - Poly-oxosilane fluorescence polymer material with side chain containing pyrenes derivant and method for producing the same - Google Patents
Poly-oxosilane fluorescence polymer material with side chain containing pyrenes derivant and method for producing the same Download PDFInfo
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- CN101173046A CN101173046A CNA2007100929836A CN200710092983A CN101173046A CN 101173046 A CN101173046 A CN 101173046A CN A2007100929836 A CNA2007100929836 A CN A2007100929836A CN 200710092983 A CN200710092983 A CN 200710092983A CN 101173046 A CN101173046 A CN 101173046A
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Abstract
The invention relates to a polyoxy silane fluorescence high polymer material containing pyrene derivatives and a preparation method thereof. The pyrene derivatives with oxygen quenching characteristic is immobilized to polyoxy silane through hydrogenation silanization reaction to form an intrinsic polyoxy silane fluorescence high polymer material with the oxygen quenching characteristic. The structural general form is shown at right, wherein, Y is a bond bridge, which can be such groups as ester group, azo group, amide group, ether, etc.; n and m mean the amount of mild interval, n equals to 2 to 10, and m equals to 3 and 4. Compared with the prior art, the invention radically solves the problems of the thermal stability, the storing stability and uneven distribution of the fluorescence material of the pyrene fluorescence materials as the molecular probe in the pressure sensitive paint.
Description
Technical field
The present invention relates to the preparation method that a kind of side chain contains the polyoxy silane fluorescence polymer of pyrene analog derivative.
Background technology
Optics pressure sensitive paint manometric technique (Pressure Sensitive Paint abbreviates the PSP technology as) provides a revolutionary technology for the aircraft wind tunnel experiment.This technology is to utilize to be coated on that the fluorescence intensity to the stream pressure sensitive coating changes on the tested dummy vehicle surface, measures the surface pressure and the distribution thereof in tested zone with optical means.Compare with traditional manometric technique, can obtain successive pressure data on a large scale, overcome the influence of pre-buried sensor, provide cost savings and the time flying surface.The fluorescent substance that adopts in the optics pressure sensitive paint mainly contains the metallo-organic complex and the pyrene analog derivative two big classes of porphyrin class at present, generally with the solvent blending method they is dispersed in to prepare the optics pressure sensitive paint in the organosilicon polymer.
Wherein, the greatest problem that porphyrin metalloid organic complex exists is the luminous power reduction that temperature raises and makes the fluorescent substance molecule, is difficult to thermal quenching and oxygen quencher in the distinguishing tests process.Though and the pyrene analog derivative has lower temperature-sensitivity coefficient as the fluorescent substance molecule, they evaporate, distil easily in macromolecule matrix, cause the poor stability of fluorescent substance; In addition, the fluorescent substance molecule is to be dispersed in the organosilicon polymer matrix, belongs to the thermodynamic instability system, is separated easily, causes fluorescent substance skewness in matrix.When the air high speed flow was crossed flying surface, the oxygen quencher that the serious distribution of pressure interference of fluorescent substance oxygen quencher pockety meeting causes made detected fluorescence intensity distortion, caused measuring pressure and the true pressure difference is very big.
(Sensors ﹠amp such as Basu; Actuators B, 2003,94,257-266) the oxygen quencher characteristic of each class standard pyrene derivatives and their mechanism of degradations in resin have been carried out systematic research, proposed to improve stability imagination based on pyrene analog derivative pressure sensitive paint by the spread coefficient that reduces pyrene derivatives.They have synthesized a kind of new pyrene analog derivative that contains chain alkyl, stability in storage based on the pressure sensitive paint of this class pyrene derivatives increases, but its thermostability still has problems, its fluorescence intensity 15% (Sensors ﹠amp that descended under 60 ℃ and 0.1 atmospheric condition; Actuators B, 2005,104,15-22).The applicant also adopts similar methodology of organic synthesis, on the pyrene ring, introduce the alkyl of different chain length, the chain length of investigating pyrene analog derivative fluorescence molecule is to the influence based on the thermostability of the pressure sensitive paint of this class pyrene derivatives, the result shows the thermal stability problems (functional materials that does not still fundamentally solve pyrene analog derivative pressure sensitive paint, 2007,38 (5), 795-797).
So development has finely dispersed optics pressure sensitive paint and is used for wind tunnel experiment for this technology, the piezometry under particularly hypersonic has great importance.
Summary of the invention
The purpose of this invention is to provide a kind of polyoxy silane fluorescence polymer material and preparation method who contains the pyrene analog derivative, fluorescence polymer material not only has characteristics such as temperature-sensitivity coefficient, oxygen quencher coefficient be big, also has advantages such as satisfactory stability and fluorescent substance are evenly distributed.
The inventor finds through long term studies, if the fluorescence molecule is not to combine with polymkeric substance with the lower Van der Waals force of interaction force, but with the covalent bonds of big several magnitude, this will fundamentally improve the thermostability and the consistency of fluorescence and matrix, for this reason, propose the fluorescence small molecules is bonded in way in the polymer, preparation eigenmode fluorescence polymer, be the polyoxy silane fluorescence polymer that a kind of side chain contains the pyrene analog derivative, its general structure is as follows:
Wherein X is the polymerization degree, and Y is the key bridge, is ester group, azo-group, amide group or ether group, and n and m are the number of flexible spacer, n=2～10, m=3,4.
The preparation method of this fluorescence polymer material will have the pyrene analog derivative of oxygen quencher characteristic, pass through hydrosilylation reactions, be grafted on the polyoxy silane, constitute eigenmode polyoxy silane fluorescence polymer material with oxygen quencher characteristic, because the pyrene ring is connected with polymer by covalent linkage, the polyoxy silane fluorescence polymer that the synthetic side chain contains the pyrene analog derivative not only has characteristics such as temperature-sensitivity coefficient, oxygen quencher coefficient be big, also has advantages such as satisfactory stability and fluorescent substance are evenly distributed.
Its concrete steps are as follows:
(1) utilizes the reaction of pyrene analog derivative and fatty vinyl derivative, reaction between them can be esterification, azoization, amidation and become the ether reaction, their mole proportioning is 1.0～4.0, and synthetic two ends are contained two keys and pyrene ring respectively, and the centre is the pyrene analog derivative of fatty long-chain;
(2) the two key pyrene analog derivatives of end group that contain that polymethyl hydrogen siloxane and step (1) obtained are 1.0～3.0 to be dissolved in the solution by the mole proportioning, wherein polymethyl hydrogen siloxane is in Si-H, under catalyst action, react, utilize in the polymethyl hydrogen siloxane the two strong hydrosilylation reactions of end group in the silicon hydrogen base and pyrene analog derivative, the preparation side chain contains the polyoxy silane fluorescence polymer of pyrene analog derivative;
(3) add activated carbon in the reaction solution of step (2), filter, add precipitation agent again in filtrate, to remove unreacted monomer, product is faint yellow or yellow viscous liquid.
Synthetic route is as follows:
Wherein, the pyrene analog derivative in the step (1) comprises pyrene butyric acid, pyrene butanols, 1-pyrenyl-4-amino-butane; The fat vinyl derivative comprises: CH
2=CH-(CH
2)
n-COOH, CH
2=CH-(CH
2)
n-OH, CH
2=CH-(CH
2)
n-NH
2, CH
2=CH-(CH
2)
n-Br (wherein n=2～10).
The catalyzer of step (2) adopts Platinic chloride, metal platinum or dicyclopentadiene platinum chloride.Solution is toluene, tetrahydrofuran (THF) or methylene dichloride.Precipitation agent is methyl alcohol or ethanol.
In addition in step (1) with the normal hexane of normal hexane, hexanaphthene, 2: 1～2: 3 (volume ratio): the hexane of ethyl acetate, 2: 1～2: 3 (volume ratio): ethyl acetate or acetone leacheate.
Compare with compound fluorescence polymer, the eigenmode fluorescence polymer has tangible advantage: (1) fluorescence and matrix are covalent bonds, for the thermodynamically metastable fixed system, are not separated; (2) fluorescence arrives the uniform distribution of molecular level in matrix; (3) with after polymer combines, the thermostability of fluorescent substance improves, and improves the sensitivity to temperature.Adopt the eigenmode fluorescence polymer to prepare the optics pressure sensitive paint, to fundamentally solve problems such as traditional optical pressure sensitive paint thermostability and skewness, for optics pressure sensitive paint manometric technique lays a good foundation in the hypersonic piezometry of wind tunnel experiment down.
Description of drawings
Fig. 1 pyrene butyric acid certain herbaceous plants with big flowers alkene ester and side chain contain the fluorescence emission spectrum of polyoxy silane in solution of pyrene butyric acid certain herbaceous plants with big flowers alkene ester
Fig. 2 side chain contains the fluorescence emission spectrum of polyoxy solution of silane under aerobic and oxygen free condition of pyrene butyric acid certain herbaceous plants with big flowers alkene ester
Fig. 3 9-decylenic acid pyrene butyl ester and side chain contain the fluorescence emission spectrum of polyoxy silane in solution of 9-decylenic acid pyrene butyl ester
Fig. 4 side chain contains the fluorescence emission spectrum of polyoxy solution of silane under aerobic and oxygen free condition of 9-decylenic acid pyrene butyl ester
Embodiment
The performance of implementation procedure of the present invention and material is by following examples and description of drawings.
Embodiment 1: the polyoxy silane that side chain contains pyrene butyric acid certain herbaceous plants with big flowers alkene ester synthesizes
1.15g (0.4mmol) the positive certain herbaceous plants with big flowers alkene of pyrene butyric acid and 1.25g (0.8mmol)-1-alcohol is dissolved in the toluene of 50ml, places the there-necked flask of 250ml, adds the 0.4g tosic acid, is equipped with the reflux water-dividing device on the device.Above-mentioned solution reacts under reflux temperature, nitrogen protection and magnetic agitation condition, adopts tlc observing response degree, and the reaction times is generally 6h.After reaction finished, the solution cool to room temperature filtered and concentrating under reduced pressure.Concentrated solution carries out purifying with column layer chromatography silicone rubber.With normal hexane and ethyl acetate (2: 1) mixed solution is leacheate.Get pyrene butyric acid hexadecyl ester through concentrating under reduced pressure and vacuum-drying, be light yellow solid.Pyrene butyric acid certain herbaceous plants with big flowers alkene ester (DCPB), productive rate 82%,
1HNMR (CDCl
3, δ in ppm), 8.30～7.82 (9H inpyrene), 4.07 (COOCH
2), 3.37 (pyrene-CH
2), 2.18 (pyrene-CH
2-CH
2), 2.44 (CH
2COO), 1.60 (COO-CH
2-CH
2), 1.27 (CH
2-(CH
2)
5), 2.02 (CH
2-CH=CH
2), 5.80 (CH=CH
2); 4.90～5.00 (CH=CH
2).IR, 1730.02cm
-1, 1180.02cm
-1(C=O absorption peak) is at 3340cm
-1No OH absorption peak.
0.13g (2.00mmol; in Si-H) polymethyl hydrogen siloxane and 0.94g (2.19mmol) pyrene butyric acid certain herbaceous plants with big flowers alkene ester be dissolved in the toluene of 50ml; place the there-necked flask of 250ml, solution reacts 1hr under reflux temperature, nitrogen protection and magnetic agitation condition, adds the 2mg Platinic chloride.Under these conditions, continue the about 60hr of reaction.By Si-H's in the detection product
12167cm among 4.72ppm and the IR among the HNMR
-1Disappear, come controlling reaction time.Add the 1.0g activated carbon in the reaction solution, filter.The precipitation agent methanol that adds 300ml in the filtrate is to remove unreacted monomer.Product is a yellow viscous liquid.Productive rate is 80%,
1HNMR (CDCl
3, δ in ppm), 8.32～7.74 (9H in pyrene), 4.08 (COOCH
2), 3.40 (pyrene-CH
2), 2.20 (pyrene-CH
2-CH
2), 2.43 (CH
2COO), 1.52 (COO-CH
2-CH
2), 1.20 ((CH
2)
7), 0.50 (Si (CH
2)-O), 0.06 (Si (CH
2)-O).IR，(CH
2)
72926cm
-1、C＝O1735cm
-1。
Side chain contains fluorescence emission spectrum and the oxygen quencher characteristic of polyoxy silane in solution of pyrene butyric acid certain herbaceous plants with big flowers alkene ester and sees Fig. 1, Fig. 2 and table 1 respectively.
Table 1 side chain contains the oxygen quencher coefficient of polyoxy silane under different concns of pyrene butyric acid certain herbaceous plants with big flowers alkene ester
| 1.67mg/ml | 0.33mg/ml | 0.07mg/ml | 0.01mg/ml | |
| 375.5nm 394.0nm | 43％ | 49％ 43％ | 59％ 51％ | 52％ 50％ |
| 479.5nm | 51％ | 50％ | 54％ | 53％ |
The polyoxy silane that embodiment 2:(side chain contains 9-decylenic acid pyrene butyl ester synthesizes)
1.09g (0.4mmol) pyrene butanols and 1.20g (0.8mmol) 9-decylenic acid is dissolved in the toluene of 50ml, places the there-necked flask of 250ml, adds the 0.4g tosic acid, is equipped with the reflux water-dividing device on the device.Above-mentioned solution reacts under reflux temperature, nitrogen protection and magnetic agitation condition, adopts tlc observing response degree, and the reaction times is generally 6h.After reaction finished, the solution cool to room temperature filtered and concentrating under reduced pressure.Concentrated solution carries out purifying with column layer chromatography silicone rubber.With normal hexane and ethyl acetate (2: 1) mixed solution is leacheate.Get 9-decylenic acid pyrene butyl ester (PBDE) through concentrating under reduced pressure and vacuum-drying, be light yellow solid.9-decylenic acid pyrene butyl ester (PBDE), productive rate 75%.
1HNMR(CDCl
3，δin ppm)，8.19～7.76(9Hin pyrene)，3.29(pyrene-CH
2)，1.67～1.77(pyrene-CH
2-CH
2-CH
2)，4.06(CH
2OOC)，2.19(OOCCH
2)，1.19(CH
2-(CH
2)
5)，1.92(CH
2-CH＝CH
2)，5.69(C
H＝CH
2)，4.85(CH＝CH
2)。IR, 1730.0cm
-1, 1180.0cm
-1(C=O absorption peak) is at 3340cm
-1No OH absorption peak.
0.11g (2.00mmol; in Si-H) polymethyl hydrogen siloxane (PMHS) and 0.80g (1.89mmol) 9-decylenic acid pyrene butyl ester (PBDE) be dissolved in the toluene of 50ml; place the there-necked flask of 250ml; solution reacts 1hr under reflux temperature, nitrogen protection and magnetic agitation condition, add the 2mg Platinic chloride.Under these conditions, continue the about 60hr of reaction.By Si-H's in the detection product
12167cm among 4.72ppm and the IR among the HNMR
-1Disappear, come controlling reaction time.Add the 1.0g activated carbon in the reaction solution, filter.The precipitation agent methanol that adds 300ml in the filtrate is to remove unreacted monomer.Product is a yellow viscous liquid, and productive rate is 80%.
1HNMR(CDCl
3，δin ppm)，8.14～7.77(9H in pyrene)，3.25(pyrene-CH
2)，1.71～1.87(pyrene-CH
2-CH
2-CH
2)，4.05(CH
2OOC)，2.19(OOCCH
2)，1.20(CH
2-(CH
2)
6)，1.92(-CH
2-CH
2-Si-)，0.50(-Si(CH
2)-O)，0.06(-Si(CH
3)-O)。IR，(CH
2)
72926cm
-1、C＝O1735cm
-1。
Side chain contains fluorescence emission spectrum and the oxygen quencher characteristic of polyoxy silane in solution of 9-decylenic acid pyrene butyl ester and sees Fig. 3, Fig. 4 and table 2 respectively.
Table 2 side chain contains the oxygen quencher coefficient of polysiloxane fluorescence polymer under different concns of pyrene ring
| 2mg/ml | 1mg/ml | 0.2mg/ml | 0.02mg/ml | |
| 394.5nm | 17％ | 13％ | 37％ | 33％ |
| 475nm | 41％ | 40％ | 56％ | 51％ |
Claims (8)
1. a side chain contains the polyoxy silane fluorescence polymer of pyrene analog derivative, and its general structure is as follows:
Wherein, X is the polymerization degree, and Y is the key bridge, is ester group, azo-group, amide group or ether group, and n and m are the number of flexible spacer, n=2～10, m=3,4.
2. the described side chain of claim 1 contains the preparation method of the polyoxy silane fluorescence polymer material of pyrene analog derivative, it is characterized in that: it is to have the pyrene analog derivative of oxygen quencher characteristic, pass through hydrosilylation reactions, be grafted on the polyoxy silane, constitute eigenmode polyoxy silane fluorescence polymer material with oxygen quencher characteristic.
3. contain the polyoxy silane fluorescence polymer material preparation method of pyrene analog derivative as side chain as described in the claim 2, it is characterized in that the preparation method may further comprise the steps:
(1) utilizes the reaction of pyrene analog derivative and fatty vinyl derivative, reaction between them is esterification, azoization, amidation or becomes the ether reaction, their mole proportioning is 1.0～4.0, and synthetic two ends are contained two keys and pyrene ring respectively, and the centre is the pyrene analog derivative of fatty long-chain;
(2) the two key pyrene analog derivatives of end group that contain that polymethyl hydrogen siloxane and step (1) obtained are 1.0～3.0 to be dissolved in the solution by the mole proportioning, wherein polymethyl hydrogen siloxane is in Si-H, under catalyst action, react, utilize in the polymethyl hydrogen siloxane the two strong hydrosilylation reactions of end group in the silicon hydrogen base and pyrene analog derivative, the preparation side chain contains the polyoxy silane fluorescence polymer of pyrene analog derivative;
(3) in the reaction solution of step (2), add activated carbon, filter, in filtrate, add precipitation agent again, get product.
4. as polyoxy silane fluorescence polymer preparation method as described in the claim 3, it is characterized in that the pyrene analog derivative in the described step (1) comprises: pyrene butyric acid, pyrene butanols or 1-pyrenyl-4-amino-butane; The fat vinyl derivative comprises: CH
2=CH-(CH
2)
n-COOH, CH
2=CH-(CH
2)
n-OH, CH
2=CH-(CH
2)
n-NH
2, or CH
2=CH-(CH
2)
n-Br, wherein n=2～10.
5. as polyoxy silane fluorescence polymer preparation method as described in the claim 3, the catalyzer that it is characterized in that step (2) adopts Platinic chloride, metal platinum or dicyclopentadiene platinum chloride, consumption is 0.01～2.00mmol platinum catalyst/1mol polymethyl hydrogen siloxane, and polymethyl hydrogen siloxane is in Si-H.
6. as the preparation method of polyoxy silane fluorescence polymer as described in the claim 3, the solution that it is characterized in that step (2) is toluene, tetrahydrofuran (THF) or methylene dichloride.
7. as the preparation method of polyoxy silane fluorescence polymer as described in the claim 3, the precipitation agent that it is characterized in that step (2) is normal hexane, methyl alcohol, ethanol or acetone.
8. as the preparation method of polyoxy silane fluorescence polymer as described in the claim 3, it is characterized in that in step (1) with normal hexane, hexanaphthene, 2: 1～2: 3 normal hexane of volume ratio: 2: 1～2: 3 hexane of ethyl acetate or volume ratio: ethyl acetate or acetone are leacheate.
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| CN101845145B (en) * | 2009-03-26 | 2012-01-11 | 中国科学院化学研究所 | Pyrene substituted polydimethylsiloxane derivative and preparation method and application thereof |
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| CN102757781B (en) * | 2011-04-26 | 2014-03-26 | 北京化工大学 | Trapezoidal polysiloxane organic electroluminescent material with pyrene bridge base, and synthesizing method thereof |
| FR2975397A1 (en) * | 2011-05-19 | 2012-11-23 | Thales Sa | New fluorescent polymer with polysiloxane main chain useful for the preparation of a fluorescent polymer film, which is useful for detecting traces of organic compound in the gas state |
| CN102516547A (en) * | 2011-11-18 | 2012-06-27 | 西南科技大学 | Benzocyclobutene silicone oil resin and preparation method thereof |
| CN105808933A (en) * | 2016-03-03 | 2016-07-27 | 中国科学院微电子研究所 | Structure stability determining method and system for polymeric ComplexingAgent |
| CN105808933B (en) * | 2016-03-03 | 2019-03-15 | 中国科学院微电子研究所 | A kind of the structural stability judgment method and system of high molecular surfactant |
| CN110028673A (en) * | 2019-04-25 | 2019-07-19 | 济南大学 | A kind of novel pyrenyl polysiloxanes and its application |
| CN110028673B (en) * | 2019-04-25 | 2021-11-02 | 济南大学 | Pyrenyl polysiloxane and application thereof |
| CN112344861A (en) * | 2020-11-05 | 2021-02-09 | 辽宁大学 | Novel method for testing roadway surrounding rock support deformation |
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