CN115386081B - Method for constructing second-order nonlinear optical polymer material through in-situ thermal crosslinking reaction - Google Patents
Method for constructing second-order nonlinear optical polymer material through in-situ thermal crosslinking reaction Download PDFInfo
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Abstract
The invention relates to the technical field of material science, in particular to a method for constructing a second-order nonlinear optical polymer material by in-situ thermal crosslinking reaction, which takes maleimide functionalized chromophores and azide functionalized chromophores as thermal crosslinking monomers to prepare a second-order nonlinear optical polymer network structure:the invention prepares the second-order nonlinear optical polymer material by utilizing maleimide functionalized chromophore and azide functionalized chromophore through in-situ thermal crosslinking, has simple monomer synthesis operation, short reaction time, mild condition and simple in-situ thermal crosslinking mode in the polarization heating process to form a second-order nonlinear optical polymer network structure, and d is measured by an in-situ second harmonic generation method 33 Up to 222pm/V, T 80％ The temperature reaches 99.7 ℃, the second-order nonlinear optical coefficient of the non-resonance enhancement part related to the light transmittance reaches 49pm/V, and the non-resonance enhancement part is the highest value of the azobenzene second-order nonlinear optical polymer.
Description
Technical Field
The invention relates to the technical field of material science, in particular to a method for constructing a second-order nonlinear optical polymer material by an in-situ thermal crosslinking reaction.
Background
To replace the commercialized inorganic crystal materials, the organic second-order nonlinear optical materials meet the requirements of practical applications, and must simultaneously meet the following conditions: a macroscopic second order nonlinear optical effect value (d 33 ) Good stability (T 80％ ) And as low optical losses as possible. In fact, if only for a specific index, the research results at the beginning of this century can meet most of the requirements, even the most difficult to meetThere has also been great progress in "large enough macroscopic nonlinear optical effects". But meeting these three requirements at the same time is very difficult. The reason for this is that the three-point requirements of the practicality are not isolated, but closely related and mutually restricted: (1) Increasing the hyperpolarizability of the chromophore molecules can increase the macroscopic second-order nonlinear optical effect of the polarized film, but can also lead to the red shift of the absorption wavelength of the chromophore, thereby increasing the propagation loss of light; (2) Increasing the dipole moment of the chromophore increases the electrostatic interaction between the chromophore molecules, and as a result, the degree of orientation ordering is reduced, and finally, the macroscopic second-order nonlinear optical effect of the polarized film is possibly reduced; (3) Increasing the content of the chromophore can theoretically improve the macroscopic second-order nonlinear optical effect of the polarized film, but simultaneously the electrostatic interaction among the chromophore molecules can be enhanced, and the improvement of the macroscopic second-order nonlinear optical coefficient is suppressed; (4) Increasing the glass transition temperature of a polymer is of great importance for increasing the orientation stability of a polarized film, but such materials with high glass transition temperature are very demanding in terms of polarization conditions and often difficult to polarize. These interrelationships are summarized by scientists as contradictions between "nonlinearity" and "stability" and between "nonlinearity" and "light transmittance".
Among the numerous chromophores, azobenzene chromophores are often used as building blocks for second-order nonlinear optical materials due to simple synthesis steps and excellent photo-thermal stability, and the same contradiction exists for second-order nonlinear optical materials based on azobenzene chromophores: azobenzene chromophore polymer d with better stability 33 The value is often not high; with a higher d 33 The stability of the azobenzene chromophore dendrimer is poor; regardless of the dendrimer or polymer, the second order nonlinear optical coefficient d of the non-resonance enhanced portion of the optical transparency of the material can be reflected 33(∞) There has been no significant rise.
In summary, it is necessary to design and synthesize the azobenzene second order nonlinear optical material with the balance of nonlinear-stability-light transmittance.
Disclosure of Invention
The invention aims to provide a method for constructing a second-order nonlinear optical polymer material by an in-situ thermal crosslinking reaction, which has the advantages of simple monomer synthesis operation, short reaction time and mild condition, and can construct a second-order nonlinear optical polymer network structure by the in-situ thermal crosslinking reaction under the condition of no solvent.
The scheme adopted by the invention for achieving the purpose is as follows: a method for constructing a second-order nonlinear optical polymer material by in-situ thermal crosslinking reaction uses maleimide functionalized chromophores and azide functionalized chromophores as thermal crosslinking monomers to prepare a second-order nonlinear optical polymer network structure:
wherein MA is a maleimide functional group; r is R 1 And R is 2 Are second-order nonlinear optical molecules; m is maleimide functional group in R 1 Number of functionalization on the molecule; n is-N 3 Functional group at R 2 Number of functionalization on the molecule.
Preferably, said R 1 ,R 2 Any one of chromophores selected from D-pi-A donor-acceptor electron-withdrawing structures can be the same or different.
Preferably, said R 1 ,R 2 Any one of azo chromophore, FTC chromophore, CLD chromophore and DANS chromophore can be the same or different.
Further, when R 1 ,R 2 When the azo chromophore is respectively selected from azo chromophores, the azo chromophore is nitroazobenzene or sulfonyl azobenzene chromophore.
Further applying the sulfonyl azobenzene as a spacing chromophore to the scheme can further improve d 33 Value sum T 80％ On the basis of which improvement of optical transparency is achieved.
Preferably, said R 1 ,R 2 Is a single chromophore molecule or a multichromophore molecule.
Preferably, m is equal to or greater than 2 and n is equal to or greater than 2.
Preferably, said R 1 -mMA is prepared by esterification of a hydroxyl-containing chromophore molecule with a maleimide alkyl carboxylic acid.
Further, the maleimide alkyl carboxylic acid is at least one selected from maleimide propionic acid, maleimide butyric acid and maleimide caproic acid.
Preferably, said R 2 -nN 3 The preparation is carried out by substituting halogenated chromophore molecule or p-toluenesulfonate-containing chromophore molecule with azide reagent.
Further, the azide reagent is selected from the group consisting of sodium azide, trimethylsilane azide, diphenyl azide phosphate, tributyltin azide, and tetrabutylammonium azide.
Preferably, said R is 1 -mMA and R 2 -nN 3 Dissolving in a solvent to prepare a solution, coating the solution on the surface of a conductive substrate, drying to form a film, and polarizing at a certain temperature to obtain the second-order nonlinear optical polymer material.
In a two-component monomer R 1 -mMA and R 2 -nN 3 Doping spin coating to form a film, and forming a second-order nonlinear optical polymer film through in-situ polarization thermal crosslinking, wherein compared with the complicated synthesis and difficult purification process of the conventional polymer, the method is simpler and more convenient to operate.
Preferably, the solvent is any one of tetrahydrofuran, dichloromethane, chloroform and acetone, R is as follows 1 -mMA and R 2 -nN 3 Mixing according to the stoichiometric ratio to prepare a solution with the total concentration of 20-40 mg/mL.
Preferably, the temperature of the polarization process is 25-150 ℃.
The polarization voltage is 7000-8000V, the polarization distance is 5-10mm, and the heating rate is 5-10 ℃/min.
The invention has the following advantages and beneficial effects:
the method utilizes maleimide functionalized chromophore and azide functionalized chromophore to prepare the second-order nonlinear optical polymer material through in-situ thermal crosslinking, and the monomer synthesis operation is simple, the reaction time is short, the condition is mild, and a second-order nonlinear optical polymer network structure is formed in a simple in-situ thermal crosslinking mode in the polarization heating process.
The second order nonlinear optical polymer network structure prepared by the method of the invention is measured by an in-situ second harmonic generation method 33 Up to 222pm/V, T 80％ The temperature reaches 99.7 ℃, the second-order nonlinear optical coefficient of the non-resonance enhancement part related to the light transmittance reaches 49pm/V, and the non-resonance enhancement part is the highest value of the azobenzene second-order nonlinear optical polymer. Exhibits a higher d than a preheated film, i.e., a film crosslinked or polymerized prior to polarization 33 Values, but the thermal stability of both are nearly identical. The necessity of an in situ polarized thermal crosslinking process is illustrated.
The method of the invention has simple and convenient synthesis and operation, builds the azobenzene second order nonlinear optical material balanced by nonlinear-stability-light transmittance, and is suitable for wide application.
Drawings
FIG. 1 shows the IR spectrum (1 a) of each of the doped monomers and the IR spectrum (1 b) of the doped film before and after heating in examples 1 to 4;
FIG. 2 is a solubility test of the products of examples 1-4 after polarization.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrative of the present invention, but the contents of the present invention are not limited to the following examples only.
In the following examples, the compounds are named: the compounds are subsequently named by abbreviations, taking T3MA as an example, "T" here representing a triple chromophore (no other remarks are made as azo chromophores), "MA" representing a maleimide function and "3" representing the number of MA functionalities; similar to TS2N 3 "T" herein means a triple chromophore, "S" means that the chromophore type is a sulfone azobenzene chromophore, "N 3 "represents an azide functional group," 2 "represents N 3 Number of functionalizations. For mono-chromophores, in N2N 3 For example, "N" means that the chromophore type is a nitroazobenzene chromophore, "2N 3 "in accordance with the foregoing, and the likeAs an example of F2MA, "F" represents a chromophore of the type FTC and "2MA" is consistent with the foregoing.
Example 1:
synthesis of T3 MA:
the reaction formula is:
the method comprises the following specific steps: put magneton in Schlenk flask, put compound 1 (300.0 mg,0.61 mmol), compound 2 (816.0 mg,1.81 mmol), cuSO 4 ·5H 2 O (60.5 mg,0.24 mmol), vcNa (359.0 mg,1.81 mmol), and Bi Xunsu stoppered saline plugs and vented several times; another eggplant type bottle is taken, 40mL of tetrahydrofuran and 6mL of water are added into the eggplant type bottle, the eggplant type bottle is placed under ultrasonic exhaust for 10-15min, 10mL of mixed solvent is taken under an aeration state after ultrasonic stopping and injected into a Schlenk bottle under the aeration state, the reaction is carried out for 3-4h at 30 ℃, and TLC monitors the reaction progress. After the reaction is finished, 100mL of water is added into the reaction liquid to quench the reaction, 50mL of DCM is used for extraction for 3 to 4 times each time, the combined organic phases are washed with saturated common salt water for 3 to 4 times, then the combined organic phases are dried with anhydrous sodium sulfate, the solvent is removed by rotary evaporation, the obtained crude product is subjected to column chromatography, the raw materials are quickly eluted and recovered by using a leaching agent DCM: EA=3:1, and then the gradient elution is carried out by using EtOH: EA=1:30, so that a red solid product T3OH (55mg, 66%) is obtained. 1 H NMR (400MHz,CDCl 3 ,298K),δ(TMS,ppm):7.84-7.67(m,12H,-ArH),7.62-7.52(m,3H,-ArH), 7.27(s,2H,-ArH),6.66(d,J＝8.8Hz,4H,-ArH),6.49(d,J＝8.8Hz,2H,-ArH),4.35(t,J＝6.0 Hz,4H,-CH 2 -),4.18-4.04(m,6H,-CH 2 -),3.71(t,J＝6.0Hz,4H,-CH 2 -),3.66-3.59(m,6H, -CH 2 -),3.43(q,J＝7.1Hz,4H,-CH 2 -),3.33(t,J＝7.8Hz,4H,-CH 2 -),2.93(t,J＝7.1Hz,4H, -CH 2 -),2.19(p,J＝6.4Hz,4H,-CH 2 -),1.87(p,J＝6.2Hz,2H,-CH 2 -),1.67-1.52(m,12H, -CH 2 -),1.47-1.32(m,10H,-CH 2 -),1.19(t,J＝6.9Hz,6H,-CH 3 ). 13 C NMR(100MHz,CDCl 3 , 298K),δ(ppm):154.7,151.2,147.7,147.1,143.8,126.4,125.9,122.5,117.2,116.6,116.1,111.6, 111.1,109.2,69.8,68.5,62.5,62.4,51.1,50.6,47.3,45.4,32.7,32.6,29.0,28.3,27.4,26.8,26.0, 25.6,21.8,12.4.
In a Schlenk flask was placed a magnet, T3OH (100.0 mg,0.07 mmol), compound 3 (50.0 mg,0.30 mmol), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) (41.0 mg,0.22 mmol), 4-dimethylaminopyridine p-toluenesulfonate (DPTS) (10.0 mg,0.03 mmol) was weighed and added quickly since EDC was very water absorbing, a plug of Bi Xunsu plug of brine was added and aerated several times, ultra dry DCM was injected under aeration, and the reaction was allowed to react at ambient temperature for 2-3h every 0.5 h TLC to monitor the course of the reaction. After completion of the reaction, 100mL of water was added and extracted 50 mL/time with DCM until the aqueous phase was substantially clear, the combined organic phases were washed 3-4 times with saturated brine, the organic phases were dried over anhydrous sodium sulfate and the solvent was dried by spin-drying, and separated by column chromatography eluting rapidly with eluent DCM: etoh=30:1 to give the product T3MA as a red solid (109 mg, 82%). 1 H NMR(400MHz,CDCl 3 ,298K),δ(TMS,ppm):7.88-7.72(m,12H,-ArH),7.65-7.55 (m,3H,-ArH),7.27(s,2H,-ArH),6.73-6.53(m,12H,-ArH),4.38(t,J＝6.0Hz,4H,-CH 2 -),4.19 (t,J＝6.4Hz,2H,-CH 2 -),4.13(t,J＝6.3Hz,4H,-CH 2 -),4.05(t,J＝6.6Hz,6H,-CH 2 -), 3.84-3.69(m,10H,-CH 2 -),3.45(q,J＝7.1Hz,4H,-CH 2 -),3.35(t,J＝7.8Hz,4H,-CH 2 -),2.94(t, J＝7.1Hz,4H,-CH 2 -),2.66-2.54(m,6H,-CH 2 -),2.22(p,J＝6.7Hz,4H,-CH 2 -),1.91(p,J＝6.5 Hz,2H,-CH 2 -),1.69-1.51(m,12H,-CH 2 -),1.51-1.34(m,10H,-CH 2 -),1.21(t,J＝7.0Hz,6H, -CH 3 ). 13 C NMR(100MHz,CDCl 3 ,298K),δ(ppm):170.8,170.3,154.8,151.2,147.8,147.2, 147.2,143.9,134.2,134.1,126.4,126.0,122.3,117.3,116.6,111.7,111.1,109.2,68.6,64.8,64.7, 51.2,50.5,47.2,45.4,33.6,32.9,28.8,28.4,28.4,27.5,26.7,25.7,25.7,25.6,21.8,12.4.
N2N 3 Is synthesized by the following steps:
the reaction formula is:
the method comprises the following specific steps:
weighing nitroaniline receptor (1.0 eq), placing into a reaction tube, completely dissolving with as little fluoboric acid as possible, placing the reaction tube at 0deg.C, stirring, and dissolving NaNO with as little ice water as possible after about 10min 2 The solution is dripped into a reaction tube, and the dripping is continued to be stirred for 3-4 hours at the temperature of 0 ℃. Donor aniline (1.1 eq) dissolved in ice THF was added dropwise to the reaction tube, and the reaction was continued at 0 ℃ for 3-4h, with TLC monitoring the progress of the reaction. After the reaction was completed, 100mL of water was added to quench and extract with DCM, the combined organic phases were dried over anhydrous sodium sulfate and the solvent was removed by rotary evaporation, and the crude product was separated by column chromatography to give a red solid product. 1 H NMR(400MHz, CDCl 3 ,298K),δ(TMS,ppm):8.39-8.25(m,2H,-ArH),7.99-7.87(m,4H,-ArH),6.87-6.75(m, 2H,-ArH),3.80-3.64(m,4H,-CH 2 -),3.59(t,J＝6.0Hz,4H,-CH 2 -). 13 C NMR(100MHz,CDCl 3 , 298K),δ(ppm):156.4,150.0,147.7,144.5,126.2,124.7,122.8,111.9,50.7,48.8.
The preparation method of the second-order nonlinear optical polymer material comprises the following steps:
weighing corresponding mass of T3MA and N2N according to stoichiometric ratio of chemical reaction 3 And THF was used as a solvent to prepare a solution having a concentration of 25mg/mL (generally, the concentration is controlled to be 20-40mg/mL, and 25mg/mL is preferable in this example), and the prepared solution was filtered using a 0.22 μm filter membrane. The ITO glass is placed on a stage of a spin coater with a non-conductive surface facing upwards, 80 microliters of solution is taken by a pipette and dropped on the stage, and spin coating is started rapidly after the dropping. And (3) a glue homogenizing process: the first stage rotates at 1000rpm for 18s; the second stage rotates at 1500rpm for 60s without interval. Thus, a uniform transparent film was obtained, one group was dried in vacuo at 25 ℃ for 8 hours and then polarized, the other group was heated at 110 ℃ for 1 hour after film formation, and the polarization was performed on a 1064nm laser system, and the resulting film was polarized and tested using an in situ Second Harmonic Generation (SHG) test system. The corona polarization conditions are: 7000V high-voltage direct current power supply, polarization distance is 8mm. .
The second-order nonlinear optical effect test process comprises the following steps:
the resulting films were tested on a 1064nm laser system using an in situ Second Harmonic Generation (SHG) test system. The corona polarization conditions are: 7000V high-voltage direct current power supply, polarization distance is 8mm. The testing process comprises the following steps: polarization curve and optimal polarization temperature T of voltage-applied and temperature-rising test film e The temperature rising rate is 5 ℃/min, and the temperature is raised from room temperature to the optimal polarization temperature (the optimal polarization temperature is generally less than or equal to 150 ℃ and is heated to the corresponding optimal polarization temperature according to the need); maintaining the polarization voltage, cooling to room temperature, and then heating up to test the depolarization curve and attenuation temperature T 80％ The temperature rising rate is 5 ℃/min. Parallel conditions: at least 3 films are tested by the same sample, each film takes at least 3 groups of values, and the film thickness sampling number of the same film is at least more than 6 times.
The test results are shown in Table 1 below:
a optimum polarization temperature; b film thickness; c the ultraviolet-visible maximum absorption wavelength of the film; d the SHG measures NLO coefficient; e second-order nonlinear optical effects of the non-resonance enhancement part calculated by using the dual energy and the model; f sequence parameter Φ=1-a 1 /A 0 Wherein A is 1 And A 0 The film being at lambda after and before polarisation respectively max Absorbance at; g d 33 the value decays to a temperature of 80% of the initial value.
As can be seen from the data in Table 1 above, the film was preheated (T3 MA/N2N 3 Compared with the preheated film (T3 MA/N2N) 3 ) Shows a higher d 33 Value, and T 80％ The difference is smaller, which indicates that the stability of the two materials is basically consistent. I.e. the thermal crosslinking also proceeds completely simultaneously during in situ polarization. Comparing the optimal polarization temperature and sequence parameters of the two can also find that the unheated group is easier to polarize and shows better polarization effect.
Example 2:
synthesis of T3 MA:
as in example 1.
S2N 3 Is synthesized by the following steps:
the reaction formula is:
the method comprises the following specific steps:
weighing acceptor sulfonyl aniline (1.0 eq), placing into a reaction tube, completely dissolving as little fluoboric acid as possible, placing the reaction tube at 0deg.C, stirring, and dissolving NaNO with as little ice water as possible after about 10min 2 The solution is dripped into a reaction tube, and the dripping is continued to be stirred for 3-4 hours at the temperature of 0 ℃. Donor aniline (1.1 eq) dissolved in ice THF was added dropwise to the reaction tube, and the reaction was continued at 0 ℃ for 3-4h, with TLC monitoring the progress of the reaction. After the reaction was completed, 100mL of water was added to quench and extract with DCM, the combined organic phases were dried over anhydrous sodium sulfate and the solvent was removed by rotary evaporation, and the crude product was separated by column chromatography to give a red solid product. 1 H NMR(400MHz, CDCl 3 ,298K),δ(TMS,ppm):8.09-7.83(m,6H,-ArH),6.81(d,J＝8.8Hz,2H,-ArH),3.71(t,J ＝6.0Hz,4H,-CH 2 -),3.58(t,J＝6.0Hz,4H,-CH 2 -),3.15(q,J＝7.2Hz,2H,-CH 2 -),1.30(t,J＝ 7.2Hz,3H,-CH 3 ). 13 C NMR(100MHz,CDCl 3 ,298K),δ(ppm):156.1,149.7,144.4,138.2, 129.3,126.0,122.8,111.8,50.7,50.7,48.7,7.4.
The procedure for preparing the second order nonlinear optical polymer material and testing the second order nonlinear optical effect is the same as in example 1, and the results are shown in table 2:
a optimum polarization temperature; b film thickness; c the ultraviolet-visible maximum absorption wavelength of the film; d the SHG measures NLO coefficient; e second-order nonlinear optical effects of the non-resonance enhancement part calculated by using the dual energy and the model; f sequence parameter Φ=1-a 1 /A 0 Wherein A is 1 And A 0 The film being at lambda after and before polarisation respectively max Absorbance at; g d 33 the value decays to a temperature of 80% of the initial value.
The information obtained from the data in Table 2 is substantially the same as in example one, comparing the two to find S2N 3 Is added so that d of the film 33 Value sum T 80％ Are slightly raised. The superiority of the interval chromophore strategy is reflected.
Example 3:
synthesis of T3 MA:
as in example 1.
T2N 3 Is synthesized by the following steps:
the reaction formula is:
the method comprises the following specific steps:
put magneton in Schlenk flask, and put compound N2N into it 3 (300.0 mg,0.79 mmol), compound 4 (982.0 mg,2.37mmol), cuSO 4 ·5H 2 O (78.9 mg,0.32 mmol), vcNa (468.9 mg,2.37 mmol), weighing Bi Xunsu stoppered saline plug and pumping in air several times; another eggplant type bottle is taken, 20mL of tetrahydrofuran and 3mL of water are added into the eggplant type bottle, the eggplant type bottle is placed under ultrasonic exhaust for 10-15min, 12mL of mixed solvent is taken under an aeration state after ultrasonic stopping and injected into a Schlenk bottle under the aeration state, the reaction is carried out for 3-4h at 30 ℃, and TLC monitors the reaction progress. After the reaction was completed, 100mL of water was added to the reaction solution and 1,4,7, 10-tetraazacyclododecane was added to complex copper ions therein and extracted 3 to 4 times with 50mL of DCM each time, the combined organic phases were washed 3 to 4 times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation, and the crude product was subjected to column chromatography to give T2Cl (697 mg, 73%) as a red solid. 1 H NMR(400MHz,CDCl 3 ,298K),δ(TMS,ppm):8.26(d,J＝8.8Hz, 2H),7.90-7.81(m,8H),7.79-7.74(m,4H),7.63(d,J＝8.8Hz,2H),7.24(s,2H),6.79-6.69(m, 4H),6.59-6.49(m,2H),4.38(t,J＝6.0Hz,4H),4.13(t,J＝6.4Hz,4H),3.82-3.62(m,12H),3.53 (q,J＝7.2Hz,4H),2.96(t,J＝7.2Hz,4H),2.24(p,J＝6.8Hz,4H),1.24(t,J＝6.8Hz,6H).
T2Cl (500.0 mg,0.41 mmol) was weighed into a reaction flask, the magneton was placed in, DMF 5mL was added and stirred at room temperature; naN is called 3 (58.6 mg,0.90 mmol) and added in portions to a reaction flask, the temperature was raised to 70℃after the addition, the flask was stoppered and the tube was dried for 5-6h, and TLC monitored the progress of the reaction. After the reaction is completed, 100mL of water is added and 50 mL/time of DCM is used for extraction until the water phase has no obvious color basically, the organic phases are combined and washed 3 to 4 times with saturated saline water, the organic phases are dried with anhydrous sodium sulfate and spin-dried, the crude product is subjected to column chromatography, and the eluent DCM: EA=10:1 is used for quick elution, thus obtaining a red solid product T2N 3 (471mg, 94％)。 1 H NMR(400MHz,CDCl 3 ,298K),δ(TMS,ppm):8.30-8.21(m,2H),7.90-7.79(m,8H, -ArH),7.78-7.72(m,4H,-ArH),7.62(d,J＝8.8Hz,2H,-ArH),7.23(s,2H,-ArH),6.76(d,J＝ 8.4Hz,4H,-ArH),6.54(d,J＝8.4Hz,2H,-ArH),4.38(s,4H,-CH 2 -),4.13(t,J＝6.0Hz,4H, -CH 2 -),3.73(t,J＝6.0Hz,4H,-CH 2 -),3.64-3.46(m,12H,-CH 2 -),2.96(t,J＝7.2Hz,4H,-CH 2 -), 2.24(p,J＝6.8Hz,4H,-CH 2 -),1.25(t,J＝6.8Hz,6H,-CH 3 ). 13 C NMR(100MHz,CDCl 3 ,298 K),δ(ppm):155.0,150.6,148.1,147.2,126.3,126.0,124.6,122.9,122.4,117.4,116.6,111.7, 111.5,109.22,68.5,51.2,49.6,48.9,47.3,45.9,28.3,21.8,12.3.
The procedure for preparing the second order nonlinear optical polymer material and testing the second order nonlinear optical effect is the same as in example 1, and the results are shown in table 3:
a optimum polarization temperature; b film thickness; c the ultraviolet-visible maximum absorption wavelength of the film; d the SHG measures NLO coefficient; e second-order nonlinear optical effects of the non-resonance enhancement part calculated by using the dual energy and the model; f sequence parameter Φ=1-a 1 /A 0 Wherein A is 1 And A 0 Respectively at the time of film polarizationPost and pre-polarization at lambda max Absorbance at; g d 33 the value decays to a temperature of 80% of the initial value.
Also, the information obtained from the data in Table 3 is substantially identical to those of examples one and two, and it was found in comparative examples three that T2N 3 The addition of (c) does not allow the film to exhibit better second order nonlinear optical properties.
Example 4:
synthesis of T3 MA:
as in example 1.
TS2N 3 Is synthesized by the following steps:
the reaction formula is:
the method comprises the following specific steps:
put magneton in Schlenk flask and weigh compound S2N into it 3 (300.0 mg,0.7 mmol), compound 5 (971.0 mg,2.1 mmol), cuSO 4 ·5H 2 O (70.0 mg,0.28 mmol), vcNa (416.0 mg,2.1 mmol), just after completion, the saline plug was stoppered and vented several times; another eggplant type bottle is taken, 20mL of tetrahydrofuran and 3mL of water are added into the eggplant type bottle, the eggplant type bottle is placed under ultrasonic exhaust for 10-15min, 13mL of mixed solvent is taken under an aeration state after ultrasonic stopping, the mixed solvent is injected into a Schlenk bottle under the aeration state, and the reaction is monitored by TLC in the middle of 3-4h at 30 ℃. After the reaction was completed, 100mL of water was added to the reaction mixture, extraction was performed 3 to 4 times with 50mL of DCM, the obtained organic phase was washed 3 to 4 times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation, and the obtained crude product was subjected to column chromatography to give a red solid product TS2Br (738 mg, 78%). 1 H NMR(400MHz,CDCl 3 , 298K),δ(TMS,ppm):8.05-7.97(m,4H),7.96-7.88(m,14H),7.22(s,2H),6.78-6.69(m,6H), 4.44(t,J＝6.0Hz,4H),3.80(t,J＝7.6Hz,4H),3.73(t,J＝6.0Hz,4H),3.58-3.47(m,8H), 3.21-3.11(m,6H),2.83(t,J＝7.2Hz,4H),2.14-2.04(m,4H),1.32-1.25(m,9H).
TS2Br (500.0 mg,0.37 mmol) was weighed into a reaction flask, the magneton was placed in, DMF was added and stirred at room temperature; naN is called 3 (52.7 mg,0.81 mmol) and added in portionsAdding the mixture into a reaction bottle, heating to 70 ℃ after adding, adding a plug drying tube into a bottle mouth for reaction for 5-6h, and monitoring the reaction progress by TLC. After the reaction is completed, 100mL of water is added into a reaction bottle, 50mL of DCM is used for extraction until the water phase has no obvious color basically, the organic phases are combined, the organic phases are washed with saturated common salt water for 3 to 4 times, anhydrous sodium sulfate is used for drying the organic phases, the organic phases are dried by spin drying, the crude product is subjected to column chromatography, and the eluent DCM is used for eluting with EA=10:1 quickly, thus obtaining a red solid product TS2N 3 (420 mg,89％)。 1 H NMR(400MHz,CDCl 3 ,298K),δ(TMS,ppm):8.03-7.96(m,4H,-ArH), 7.96-7.86(m,14H,-ArH),7.22(s,2H,-ArH),6.80-6.74(m,4H,-ArH),6.74-6.68(m,2H,-ArH), 4.43(t,J＝6.0Hz,4H,-CH 2 -),3.73(t,J＝6.0Hz,4H,-CH 2 -),3.64-3.50(m,12H,-CH 2 -), 3.20-3.11(m,6H,-CH 2 -),2.82(t,J＝7.2Hz,4H,-CH 2 -),2.13-2.02(m,4H,-CH 2 -),1.34-1.22(m, 9H,-CH 3 ). 13 C NMR(100MHz,CDCl 3 ,298K),δ(ppm):156.3,155.9,150.7,146.3,143.8,138.3, 129.3,129.0,126.2,123.0,122.8,122.3,112.0,111.5,47.2,45.9,23.7,22.6,12.3,7.5.
The procedure for preparing the second order nonlinear optical polymer material and testing the second order nonlinear optical effect is the same as in example 1, and the results are shown in table 4:
a optimal polarization temperature; b film thickness; c the ultraviolet-visible maximum absorption wavelength of the film; d the SHG measures NLO coefficient; e second-order nonlinear optical effects of the non-resonance enhancement part calculated by using the dual energy and the model; f sequence parameter Φ=1-a 1 /A 0 Wherein A is 1 And A 0 The film being at lambda after and before polarisation respectively max Absorbance at; g d 33 the value decays to a temperature of 80% of the initial value.
The information obtained from the data in the table is substantially identical to those of examples one, two and three, and the comparative example found TS2N 3 Is added without changing the stability of the filmGreatly promote d 33 Values. And d 33(∞) The highest value based on azobenzene chromophore polymer is reached.
FIG. 1 shows the IR spectrum (1 a) of each of the doped monomers and the IR spectrum (1 b) of the doped films before and after heating in examples 1 to 4, which demonstrates the above-mentioned in-situ thermal crosslinking process: as can be seen from FIG. 1 (a), T3MA shows a distinct hydrocarbon characteristic peak of maleimide double bond, while T2N 3 And TS2N 3 A distinct azide characteristic stretching vibration peak is exhibited. After the two-component doping, as in fig. 1 (b), the two characteristic peaks remain before heating, but disappear after heating, indicating that the cross-linking reaction of azide and maleimide occurs during heating. FIG. 2 shows the solubility test of the polarized products of examples 1-4, from which it can be seen that the polymer network formed by crosslinking exhibits significant solvent resistance properties compared to that before heating.
Example 5:
this example relates to the doping of FTC and azo chromophores, wherein the film has a maximum absorption wavelength, order parameters and d 33(∞) The meaning of the physical quantity related to the maximum absorption wavelength is not great, and the summary is not performed.
Synthesis of F2 MA:
in a Schlenk flask, a magneton was placed, F2OH (495.0 mg,1.0 eq) and Mareimide propionic acid (314.5 mg,2.5 eq), EDC (336.2 mg,2.3 eq) were weighed out, DPTS (95.3 mg,0.4 eq) was dissolved in dry dichloromethane, and the desiccated tube was stoppered at ambient temperature. After completion of the reaction, 100mL of water was added and extracted with 50 mL/time DCM until the aqueous phase was substantially clear, the combined organic phases were washed 3-4 times with saturated brine, dried over anhydrous sodium sulfate and the solvent was spun-dried, and separated by column chromatography eluting rapidly with eluent DCM: etoh=30:1 to give the product F2MA as a red solid (651.0 mg, 90%). 1 H NMR(400MHz,CDCl 3 ,298K)δ9.05(d,J＝15.6Hz,1H),7.92(d,J＝1.2Hz,1H),7.40(d, J＝8.4Hz,2H),7.26(s,1H),7.16-6.91(m,2H),6.75-6.64(m,7H),4.44(t,J＝7.2Hz,2H),4.26 (t,J＝6.4Hz,2H),4.07(t,J＝6.4Hz,2H),3.82(td,J＝7.2,1.2Hz,4H),3.61(t,J＝6.4Hz,2H), 3.46(q,J＝7.2Hz,2H),2.64(td,J＝7.2,3.2Hz,4H),2.05-1.93(m,2H),1.83(s,6H),1.61(d,J ＝2.4Hz,2H),1.47–1.33(m,J＝3.2,2.4Hz,4H),1.21(t,J＝7.2Hz,3H).
N2N 3 Is synthesized by the following steps:
as in example 1.
The procedure for preparing the second order nonlinear optical polymer material and testing the second order nonlinear optical effect is the same as in example 1, and the results are shown in table 5,
a optimum polarization temperature; b film thickness; c the SHG measures NLO coefficient; d d 33 the value decays to a temperature of 80% of the initial value.
As can be seen from the data in the table, although the FTC doped film d 33 The value is not high, but T 80％ Up to 143 c, a great improvement over the pure azo chromophores.
Example 6:
this example relates to the doping of FTC and azo chromophores, wherein the film has a maximum absorption wavelength, order parameters and d 33(∞) The meaning of the physical quantity related to the maximum absorption wavelength is not great, and the summary is not performed.
Synthesis of F2 MA:
same as in example 5.
S2N 3 Is synthesized by the following steps:
as in example 2.
The procedure for preparing the second order nonlinear optical polymer material and testing the second order nonlinear optical effect is the same as in example 1, and the results are shown in table 6,
a optimum polarization temperature; b film thickness; c the SHG measures NLO coefficient; d d 33 the value decays to a temperature of 80% of the initial value.
Watch with a watchAs can be seen from the data, the doped film d 33 The value is still not high but there is a certain increase compared to example 5, and T is 80％ Maintaining at 143 deg.c results in great improvement over pure azo chromophore.
Meanwhile, the corresponding second-order nonlinear optical performance test is carried out on the doping monomers of the examples 1-4, and the results are shown in Table 7:
the data in Table 7 shows that the film without preheating is d compared to all monomers 33 And T 80％ The values are obviously improved, and the advantages of in-situ polarized thermal crosslinking are reflected.
While the invention has been described with respect to the preferred embodiments, it will be understood that the invention is not limited thereto, but is capable of modification and variation without departing from the spirit of the invention, as will be apparent to those skilled in the art.
Claims (7)
1. A method for constructing a second-order nonlinear optical polymer material by in-situ thermal crosslinking reaction is characterized by comprising the following steps: preparing a second-order nonlinear optical polymer network structure by taking a maleimide functionalized chromophore and an azide functionalized chromophore as thermal crosslinking monomers:
，
wherein MA is a maleimide functional group; r is R 1 And R is 2 Are second-order nonlinear optical molecules; m is maleimide functional group in R 1 Number of functionalization on the molecule; n is-N 3 Functional group at R 2 Number of functionalization on the molecule;
the R is 1 Any one selected from azo chromophores, R 2 Any one selected from azo chromophore or FTC chromophoreOr R is the same or different 2 Any one selected from azo chromophores, R 1 Any one selected from azo chromophore and FTC chromophore can be the same or different;
the m is more than 2, n is more than or equal to 2, or m is more than or equal to 2, n is more than or equal to 2.
2. The method for constructing a second order nonlinear optical polymer material by in-situ thermal crosslinking reaction according to claim 1, wherein the method comprises the following steps: the R is 1 ，R 2 Is a single chromophore molecule or a multichromophore molecule.
3. The method for constructing a second order nonlinear optical polymer material by in-situ thermal crosslinking reaction according to claim 1, wherein the method comprises the following steps: the R is 1 -mMA is prepared by esterification of a hydroxyl-containing chromophore molecule with a maleimide alkyl carboxylic acid.
4. The method for constructing a second order nonlinear optical polymer material by in-situ thermal crosslinking reaction according to claim 1, wherein the method comprises the following steps: the R is 2 -nN 3 The preparation is carried out by substituting halogenated chromophore molecule or p-toluenesulfonate-containing chromophore molecule with azide reagent.
5. The method for constructing a second order nonlinear optical polymer material by in-situ thermal crosslinking reaction according to claim 1, wherein the method comprises the following steps: subjecting the R to 1 -mMA and R 2 -nN 3 Dissolving in a solvent to prepare a solution, coating the solution on the surface of a conductive substrate, drying to form a film, and polarizing at a certain temperature to obtain the second-order nonlinear optical polymer material.
6. The method for constructing a second order nonlinear optical polymer material by in situ thermal crosslinking reaction according to claim 5, wherein the method comprises the following steps: the solvent is any one of tetrahydrofuran, dichloromethane, chloroform and acetone, R is selected from the group consisting of 1 -mMA and R 2 -nN 3 According to the stoichiometric ratio of the chemical reactionsMixing and preparing into solution with total concentration of 20-40 mg/mL.
7. The method for constructing a second order nonlinear optical polymer material by in situ thermal crosslinking reaction according to claim 5, wherein the method comprises the following steps: the temperature of the polarization process is 25-150 DEG C o C。
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