CN115386081A - 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
- Publication number
- CN115386081A CN115386081A CN202211067198.6A CN202211067198A CN115386081A CN 115386081 A CN115386081 A CN 115386081A CN 202211067198 A CN202211067198 A CN 202211067198A CN 115386081 A CN115386081 A CN 115386081A
- Authority
- CN
- China
- Prior art keywords
- nonlinear optical
- order nonlinear
- chromophore
- optical polymer
- polymer material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/12—Diazo compounds, i.e. compounds having the free valencies of >N2 groups attached to the same carbon atom
- C07C245/14—Diazo compounds, i.e. compounds having the free valencies of >N2 groups attached to the same carbon atom having diazo groups bound to acyclic carbon atoms of a carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 chromophore and azide functionalized chromophore as thermal crosslinking monomers to prepare a second-order nonlinear optical polymer network structure:
the invention utilizes maleimide functionalized chromophores in combination with azide functionalized chromophores for the preparation of bis via in situ thermal crosslinkingThe order nonlinear optical polymer material has simple monomer synthesis operation, short reaction time, mild condition, simple in-situ heat crosslinking mode to form a second order nonlinear optical polymer network structure in the polarization heating process, and the d of the second order nonlinear optical polymer network structure is measured by an in-situ second harmonic generation method 33 The value is as high as 222pm/V, T 80％ The temperature reaches 99.7 ℃, and the second-order nonlinear optical coefficient of the non-resonance enhancement part related to the light transmission reaches 49pm/V, which is the highest value of azobenzene second-order nonlinear optical polymers.
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 through in-situ thermal crosslinking reaction.
Background
In order to replace the commercialized inorganic crystal material, the organic second-order nonlinear optical material must meet the requirements of practical application, and must simultaneously achieve the following conditions: sufficiently large macroscopic second-order nonlinear optical effect value (d) 33 ) Good stability (T) 80％ ) And as low optical losses as possible. In fact, if only a specific index is aimed at, the research results in the early century can meet most requirements, and even the most difficult "macroscopic nonlinear optical effect large enough" has been greatly developed. It is difficult to satisfy these three requirements at the same time. The reason for this is that three points of practical use are not isolated but closely related and mutually restricted: (1) The macroscopic second-order nonlinear optical effect of the polarizing film can be improved by improving the hyperpolarizability of the chromophore molecule, but the chromophore absorption wavelength is also red-shifted, so that the propagation loss of light is increased; (2) Increasing the dipole moment of the chromophore increases the electrostatic interaction between chromophore molecules, resulting in a decrease in the degree of orientational ordering, and ultimately potentially a decrease in the macroscopic second-order nonlinear optical effect of the polarizing film; (3) Increasing the chromophore content can theoretically improve the macroscopic second-order nonlinear optical effect of the polarizing film, but the electrostatic interaction between chromophore molecules can also be enhanced, and the improvement of the macroscopic second-order nonlinear optical coefficient is inhibited; (4) The improvement of the glass transition temperature of the polymer has a very important significance for improving the orientation stability of the polarizing film, but the material with high glass transition temperature has a very strict requirement on the polarizing condition and is often difficult to polarize. These constraints are summarized by scientists as conflicting "non-linearity" and "stability" and conflicting "non-linearity" and "light transmission".
Among the various chromophores, the azobenzene chromophore isSimple synthetic steps and excellent photo-thermal stability are often used as building units of second-order nonlinear optical materials, and the same contradiction exists among second-order nonlinear optical materials based on azobenzene chromophore: azobenzene chromophore polymer with good stability 33 The values tend not to be high; and has a higher d 33 The azobenzene chromophore dendrimer has poor stability; regardless of the dendrimer or polymer, the second-order nonlinear optical coefficient d of the non-resonance-enhanced part reflecting the optical transparency of the material 33(∞) There has been no significant increase.
In conclusion, it is necessary to design and synthesize azobenzene second-order nonlinear optical material with balanced "nonlinearity-stability-light transmittance".
Disclosure of Invention
The invention aims to provide a method for constructing a second-order nonlinear optical polymer material by in-situ thermal crosslinking reaction, which has the advantages of simple monomer synthesis operation, short reaction time and mild conditions, and can construct a second-order nonlinear optical polymer network structure by in-situ thermal crosslinking reaction under the solvent-free condition.
The scheme adopted by the invention for realizing the purpose is as follows: a method for constructing a second-order nonlinear optical polymer material by in-situ thermal crosslinking reaction takes maleimide functionalized chromophore and azide functionalized chromophore as thermal crosslinking monomers to prepare a second-order nonlinear optical polymer network structure:
wherein MA is a maleimide functional group; r 1 And R 2 Are second order nonlinear optical molecules; m is a maleimide functional group at R 1 The number of functionalisations on the molecule; n is-N 3 Functional group at R 2 Number of functionalisations on the molecule.
Preferably, said R is 1 ,R 2 The chromophores are selected from D-pi-A donor-acceptor electron-withdrawing structures, and can be the same or different.
Preferably, said R is 1 ,R 2 Each of the azo chromophore, FTC chromophore, CLD chromophore and DANS chromophore may be the same or different.
Further, when R is 1 ,R 2 When the azo chromophore is selected from azo chromophores, the azo chromophore is nitroazobenzene or sulfuryl azobenzene chromophore.
The sulfuryl azobenzene is further applied to the scheme as a spacer chromophore, so that the d can be further improved 33 Value sum T 80％ The optical transparency is improved on the basis of the above.
Preferably, said R is 1 ,R 2 Is a single chromophore molecule or a multichromophore molecule.
Preferably, m.gtoreq.2, n.gtoreq.2.
Preferably, said R is 1 -mMA is prepared by esterification of hydroxyl-containing chromophore molecules with maleimide alkylcarboxylic acids.
Further, the maleimide alkyl carboxylic acid is selected from at least one of maleimide propionic acid, maleimide butyric acid and maleimide caproic acid.
Preferably, said R is 2 -nN 3 Substituted with an azidation reagent for halogenated chromophore molecules or for p-toluenesulfonate-containing chromophore molecules.
Further, the azidation reagent is selected from the group consisting of sodium azide, trimethylsilyl azide, diphenyl phosphorazidate, tributyltin azide, and tetrabutylammonium azide.
Preferably, said R is 1 -mMA with R 2 -nN 3 Dissolving the mixture in a solvent to prepare a solution, coating the solution on the surface of a conductive substrate, drying the solution to form a film, and polarizing the film at a certain temperature to obtain the second-order nonlinear optical polymer material.
With two-component monomers R 1 -mMA with R 2 -nN 3 The doped spin coating film is formed, and the second-order nonlinear optical polymer film is formed through in-situ polarization thermal crosslinking, so that the operation is simpler and more convenient compared with the complicated synthesis and difficult purification process of the conventional polymer.
Preferably, the solvent is any one of tetrahydrofuran, dichloromethane, trichloromethane and acetone, and R is 1 -mMA with 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 polarization process temperature is 25-150 ℃.
The polarization voltage is 7000-8000V, the polarization distance is 5-10mm, and the heating rate is 5-10 deg.C/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, has simple monomer synthesis operation, short reaction time and mild condition, and forms a second-order nonlinear optical polymer reticular structure 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 is measured by an in-situ second harmonic generation method to obtain d 33 The value is as high as 222pm/V, T 80％ The temperature reaches 99.7 ℃, and the second-order nonlinear optical coefficient of the non-resonance enhancement part related to the light transmission reaches 49pm/V, which is the highest value of azobenzene second-order nonlinear optical polymers. Exhibit a higher d than pre-heated films, i.e., films crosslinked or polymerized prior to polarization 33 The values, however, are almost identical in thermal stability. Illustrating the necessity of an in situ polarized thermal crosslinking process.
The method is simple and convenient to synthesize and operate, constructs the azobenzene second-order nonlinear optical material with balanced nonlinearity-stability-light transmittance, and is suitable for wide application.
Drawings
FIG. 1 is an IR spectrum (1 a) of each of the doped monomers and IR spectra (1 b) of the doped films of examples 1-4 before and after heating;
FIG. 2 shows the solubility test of the polarized products of examples 1-4.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
In the following examples, compounds are named: the compounds are subsequently designated by abbreviations, in the case of T3MA, "T" here denotes the chromophore triton (no other notation defaults to the azo chromophore), "MA" denotes the maleimide functionality and "3" denotes the MA functionalization number; TS2N similar thereto 3 "T" herein denotes a chromophore of three colors, "S" denotes a chromophore type of sulfuryl azobenzene chromophore, "N" denotes a chromophore of three colors 3 "represents an azido functional group," 2 "represents N 3 The amount of functionalization. For the single chromophore, with N2N 3 For example, "N" indicates that the chromophore type is nitroazobenzene chromophore, "2N 3 "in accordance with the foregoing, and similar F2MA for example," F "represents the chromophore type as FTC chromophore," 2MA "is in accordance with the foregoing.
Example 1:
synthesis of T3 MA:
the reaction formula is as follows:
the method comprises the following specific steps: a magneton was placed in a Schlenk flask, and Compound 1 (300.0mg, 0.61mmol), compound 2 (816.0mg, 1.81mmol), and CuSO were weighed into the flask 4 ·5H 2 O (60.5mg, 0.24mmol), vcNa (359.0 mg, 1.81mmol), after weighing, rapidly plugging a saline plug and evacuating the gas several times; adding 40mL of tetrahydrofuran and 6mL of water into another eggplant-shaped bottle, placing the bottle under ultrasonic, exhausting for 10-15min, taking 10mL of mixed solvent under the aeration state after the ultrasonic is stopped, injecting the mixed solvent into a Schlenk bottle under the aeration state, reacting for 3-4h at 30 ℃, and monitoring the reaction process by TLC. After the reaction is finished, adding 100mL of water into the reaction solution to quench the reaction, extracting 3-4 times with 50mL of DCM each time, combining organic phases, washing 3-4 times with saturated salt water, drying with anhydrous sodium sulfate, removing the solvent by rotary evaporation, carrying out column chromatography on the obtained crude product, rapidly eluting and recovering the raw material with eluent DCM: EA =3, and then carrying out gradient elution with EtOH: EA =1The product T3OH (555mg, 66%) was a colored solid. 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.
A Schlenk bottle was filled with magnetons, T3OH (100.0mg, 0.07mmol), compound 3 (50.0mg, 0.30mmol), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) (41.0mg, 0.22mmol), 4-dimethylaminopyridine p-toluenesulfonate (DPTS) (10.0mg, 0.03mmol) were weighed and added rapidly because EDC is very hygroscopic, after that, a saline stopper was rapidly added and the gas was evacuated several times, ultra-dry DCM was injected in the gas-vented state, and the reaction was carried out at room temperature for 2-3h, with TLC monitoring every 0.5 h. After the reaction was complete, 100mL of water was added and extracted with 50 mL/time of DCM until the aqueous phase was essentially colorless, the combined organic phases were washed 3-4 times with saturated brine, the organic phase was dried over anhydrous sodium sulfate and the solvent was dried by column chromatography, and the product T3MA was obtained as a red solid by flash elution with DCM eluent: etOH =30 (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 The synthesis of (2):
the reaction formula is as follows:
the method comprises the following specific steps:
weighing acceptor nitroaniline (1.0 eq), placing into a reaction tube, completely dissolving fluoboric acid as little as possible, placing the reaction tube at 0 deg.C, stirring, and dissolving NaNO with ice water as little as possible after about 10min 2 The solution is dripped into the reaction tube, and the solution is continuously stirred for 3 to 4 hours at the temperature of 0 ℃ after dripping. The 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 after the addition was completed, and the progress of the reaction was monitored by TLC. After the reaction is finished, 100mL of water is added for quenching, DCM is used for extraction, organic phases are combined, anhydrous sodium sulfate is used for drying, the solvent is removed through rotary evaporation, and the crude product is separated through column chromatography to obtain 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 THF is used as a solvent to prepare the solution with the concentration of 25mg/mL (the concentration is generally controlled to be 20-40mg/mL,this example prefers 25 mg/mL) of solution, and the solution prepared is filtered using a 0.22 micron filter. Placing the ITO glass on an objective table of a spin coater, enabling the non-conducting surface to face upwards, taking 80 microlitres of solution by a liquid transfer gun, and quickly starting spin coating after dripping. And (3) glue homogenizing: the first stage has 1000rpm and 18s of time; the second stage rotation speed is 1500rpm, the time is 60s, and no time interval exists between the two stages. And carrying out vacuum drying at 25 ℃ for 8h, carrying out polarization, heating at 110 ℃ for 1 h, carrying out polarization on the other group at 1064nm laser system, and carrying out polarization and testing on the obtained film by adopting an in-situ Second Harmonic Generation (SHG) testing system. The corona polarization conditions were: 7000V high voltage direct current power supply, the 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 were: 7000V high voltage direct current power supply, the polarization distance is 8mm. The test process is as follows: polarization curve and optimum polarization temperature T of film under applied voltage and temperature rise test e The heating rate is 5 ℃/min, and the temperature is increased from room temperature to the optimal polarization temperature (the optimal polarization temperature is generally less than or equal to 150 ℃, and the temperature is increased to the corresponding optimal polarization temperature according to the requirement); keeping the polarization voltage, cooling to room temperature, removing the polarization voltage, heating, and testing its depolarization curve and attenuation temperature T 80％ The temperature rise rate is 5 ℃/min. Parallel conditions were as follows: at least 3 films are tested on the same sample, each film takes at least 3 groups of values, and the number of the film thickness samples of the same film is at least more than 6 times.
The test results are given in table 1 below:
a an optimal polarization temperature; b the thickness of the film; c the uv-vis absorption maximum wavelength of the film; d measuring NLO coefficient by SHG; e calculating a second-order nonlinear optical effect of the non-resonance enhancement part by using dual energy and a model; f sequence parameter Φ =1-a 1 /A 0 Wherein A is 1 And A 0 When the film is after and before poling at lambda respectively max Absorbance of (d); g d 33 the temperature at which the value decayed to 80% of the initial value.
As can be seen from the data in Table 1 above, the preheating of the film (T3 MA/N2N) 3 preheated) film not preheated (T3 MA/N2N) 3 ) Shows a higher d 33 Value, and T 80％ The difference is small, which shows that the stability of the two is basically consistent. I.e. the thermal crosslinking is also completely carried out simultaneously during the in situ poling process. Comparing the optimal polarization temperature and sequence parameters of the two can also find that the unheated group is easier to polarize and presents better polarization effect.
Example 2:
synthesis of T3 MA:
the same as in example 1.
S2N 3 The synthesis of (2):
the reaction formula is as follows:
the method comprises the following specific steps:
weighing receptor sulfuryl aniline (1.0 eq), placing into a reaction tube, dissolving fluoboric acid as little as possible, placing the reaction tube at 0 deg.C, stirring, and dissolving NaNO with ice water as little as possible after about 10min 2 The solution is dripped into the reaction tube, and the solution is continuously stirred for 3 to 4 hours at the temperature of 0 ℃ after dripping. The 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 after the addition was completed, and the progress of the reaction was monitored by TLC. After the reaction is finished, 100mL of water is added for quenching, DCM is used for extraction, organic phases are combined and dried by anhydrous sodium sulfate, the solvent is removed by rotary evaporation, and a crude product is separated by column chromatography to obtain 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 preparation steps and the test process of the second-order nonlinear optical polymer material are the same as those of example 1, and the results are shown in table 2:
a an optimum polarization temperature; b the thickness of the film; c the uv-vis absorption maximum wavelength of the film; d measuring NLO coefficient by SHG; e calculating a second-order nonlinear optical effect of the non-resonance enhancement part by using dual energy and a model; f sequence parameter Φ =1-a 1 /A 0 Wherein A is 1 And A 0 When the film is at lambda after and before poling max Absorbance of (b); g d 33 the temperature at which the value decayed to 80% of the initial value.
The information obtained from the data in Table 2 is substantially the same as in example one, and comparison of the two examples shows that S2N 3 Is added so that d of the film 33 Value sum T 80％ Both rise slightly. Embodying the superiority of the spacing chromophore strategy.
Example 3:
synthesis of T3 MA:
the same as in example 1.
T2N 3 The synthesis of (2):
the reaction formula is as follows:
the method comprises the following specific steps:
a magneton was placed in a Schlenk flask, and the compound N2N was weighed into the flask 3 (300.0 mg, 0.79mmol), compound 4 (982.0 mg, 2.37mmol), cuSO 4 ·5H 2 O (78.9mg, 0.32mmol), vcNa (468.9mg, 2.37mmol), after weighing, rapidly plugging a saline plug and evacuating the air for several times; another eggplant is takenAdding 20mL of tetrahydrofuran and 3mL of water into the flask, placing the flask under ultrasonic to exhaust for 10-15min, taking 12mL of mixed solvent under an aeration state after the ultrasonic is stopped, injecting the mixed solvent into a Schlenk flask under the aeration state, reacting for 3-4h at 30 ℃, and monitoring the reaction process by TLC. After the reaction, 100mL of water is added into the reaction liquid, 1,4,7, 10-tetraazacyclododecane is added into the reaction liquid to complex copper ions in the reaction liquid, DCM 50mL is used for extracting for 3-4 times, organic phases are combined, saturated salt water is used for washing for 3-4 times, then the organic phases are dried by anhydrous sodium sulfate, the solvent is removed by rotary evaporation, and the crude product is subjected to column chromatography to obtain a red solid product T2Cl (697 mg, 73%). 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).
Weighing T2Cl (500.0 mg, 0.41mmol) in a reaction bottle, placing magnetons in the reaction bottle, adding 5mL of DMF, and stirring at room temperature; naN scale 3 (58.6mg, 0.90mmol) are added into a reaction bottle in batches, the temperature is raised to 70 ℃ after the addition, a bottle mouth is plugged with a drying tube for reaction for 5-6h, and the reaction progress is monitored by TLC. After the reaction was complete, 100mL of water was added and extracted with 50 mL/time DCM until the aqueous phase had essentially no apparent colour, the organic phases were combined and washed 3-4 times with saturated brine, the organic phase was dried over anhydrous sodium sulphate and spin dried, the crude product was subjected to column chromatography and eluted rapidly with the eluent DCM: EA =10 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 preparation steps and the test process of the second-order nonlinear optical polymer material are the same as those of example 1, and the results are shown in table 3:
a an optimal polarization temperature; b the thickness of the film; c the uv-vis absorption maximum wavelength of the film; d measuring NLO coefficient by SHG; e calculating a second-order nonlinear optical effect of the non-resonance enhancement part by using dual energy and a model; f order parameter Φ =1-a 1 /A 0 Wherein A is 1 And A 0 When the film is after and before poling at lambda respectively max Absorbance of (b); g d 33 the temperature at which the value decayed to 80% of the initial value.
Similarly, the information obtained from the data in Table 3 is substantially the same as that of examples one and two, and comparison of the three examples shows that T2N is 3 Does not allow the film to exhibit better second order nonlinear optical properties.
Example 4:
synthesis of T3 MA:
the same as in example 1.
TS2N 3 The synthesis of (2):
the reaction formula is as follows:
the method comprises the following specific steps:
a Schlenk flask was charged with magneton, into which was weighed compound S2N 3 (300.0 mg,0.7 mmol), compound 5 (971.0 mg,2.1 mmol), cuSO 4 ·5H 2 O (70.0 mg, 0.28mmol), vcNa (416.0 mg,2.1 mmol), which is called immediately after completion, a stopper of saline was added and the gas was evacuated several times; adding 20mL tetrahydrofuran and 3mL water into another eggplant-shaped bottle, placing under ultrasound, exhausting for 10-15min, and venting after ultrasound is stopped13mL of the mixed solvent was taken out and poured into a Schlenk flask in a vented state, and the reaction was carried out at 30 ℃ for 3 to 4 hours with TLC monitoring. After the reaction, 100mL of water was added to the reaction mixture, and 50mL of DCM was used for each extraction 3-4 times, the resulting organic phase was washed with saturated brine 3-4 times, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation, and the resulting crude product was subjected to column chromatography to give TS2Br (738mg, 78%) as a red solid. 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).
Weighing TS2Br (500.0 mg, 0.37mmol) in a reaction bottle, placing magnetons, adding DMF, and stirring at room temperature; naN scale 3 (52.7 mg, 0.81mmol) and added into a reaction bottle in batches, after the addition, the temperature is raised to 70 ℃, a drying tube is plugged at the bottle mouth for reaction for 5 to 6 hours, and the reaction progress is monitored by TLC. After the reaction is finished, adding 100mL of water into a reaction bottle, extracting with 50 mL/time of DCM (DCM) until the water phase has no obvious color basically, combining organic phases, washing with saturated saline for 3-4 times, drying the organic phase by anhydrous sodium sulfate, and carrying out spin drying on the crude product, and quickly eluting with eluent DCM: EA =10 by column chromatography to obtain 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 preparation steps and the test process of the second-order nonlinear optical polymer material are the same as those of example 1, and the results are shown in table 4:
a optimal polarization temperature; b the thickness of the film; c the uv-vis absorption maximum wavelength of the film; d measuring NLO coefficient by SHG; e calculating the second-order nonlinear optical effect of the non-resonance enhancement part by using dual energy and a model; f sequence parameter Φ =1-a 1 /A 0 Wherein A is 1 And A 0 When the film is at lambda after and before poling max Absorbance of (b); g d 33 the temperature at which the value decays to 80% of the initial value.
The information obtained from the data in the table is basically consistent with the first, second and third examples, and the comparison of the fourth example shows that TS2N 3 Is added to greatly improve d while not changing the stability of the film 33 The value is obtained. And d is 33(∞) The highest values based on azobenzene chromophore polymers were achieved.
FIG. 1 shows the IR spectra (1 a) of each of the doped monomers and the IR spectra (1 b) of the doped films before and after heating in examples 1-4, which demonstrate the in situ thermal crosslinking process: as can be seen from FIG. 1 (a), T3MA shows a distinct characteristic peak for the hydrocarbon of the maleimide double bond, while T2N 3 And TS2N 3 A distinct azide characteristic stretching vibration peak is shown. After the two-component doping, as shown in fig. 1 (b), the two characteristic peaks remain before heating and disappear after heating, indicating that the azide and maleimide cross-linking reaction 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 shows a marked solvent resistance compared to that before heating.
Example 5:
this example relates to the doping of FTC and azo chromophores, where the absorption maximum wavelength, order parameter and d of the film 33(∞) The meaning of the physical quantity related to the maximum absorption wavelength is not so great, and the summary is not carried out.
Synthesis of F2 MA:
in a Schlenk flask, magnetons are placed, weighed in F2OH (495.0mg, 1.0eq)After weighing maleimidyl propionic acid (314.5mg, 2.5eq), EDC (336.2mg, 2.3eq), and DPTS (95.3mg, 0.4eq), the mixture was dissolved in dry dichloromethane, and the reaction was carried out at room temperature in the dark by plugging a drying tube. After the reaction was complete, 100mL of water was added and extracted with 50 mL/time of DCM until the aqueous phase had essentially no apparent colour, the combined organic phases were washed 3-4 times with saturated brine, the organic phase was dried over anhydrous sodium sulphate and the solvent was spun dry and separated by column chromatography, eluting rapidly with DCM eluent: etOH = 30. 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 The synthesis of (2):
the same as in example 1.
The preparation steps and the testing process of the second-order nonlinear optical polymer material are the same as those of example 1, and the results are shown in Table 5,
a an optimum polarization temperature; b the thickness of the film; c measuring NLO coefficient by SHG; d d 33 the temperature at which the value decayed to 80% of the initial value.
As can be seen from the data in the table, although FTC doped film d 33 Value is not high, but T thereof 80％ The temperature is up to 143 ℃, which is greatly improved compared with the pure azo chromophore.
Example 6:
this example relates to the doping of FTC and azo chromophores, where the absorption maximum wavelength, order parameter and d of the film 33(∞) And the meaning of the physical quantity related to the maximum absorption wavelength is not large, and the summary is not summarized.
Synthesis of F2 MA:
the same as in example 5.
S2N 3 The synthesis of (2):
the same as in example 2.
The preparation steps and the testing process of the second-order nonlinear optical polymer material are the same as those of example 1, and the results are shown in Table 6,
a an optimum polarization temperature; b the thickness of the film; c measuring NLO coefficient by SHG; d d 33 the temperature at which the value decays to 80% of the initial value.
As can be seen from the data in the table, the doped film d 33 The value is still not high, but is somewhat elevated compared to example 5, and its T 80％ The temperature is maintained at 143 ℃, and is greatly improved compared with a pure azo chromophore.
Meanwhile, the doped monomers of examples 1 to 4 were subjected to corresponding second-order nonlinear optical property tests, and the results are shown in table 7:
the data results in Table 7 show the d of the non-preheated films compared to all monomers 33 And T 80％ The values are obviously improved, and the advantages of in-situ polarized heat crosslinking are reflected.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (10)
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 1 And R 2 Are second order nonlinear optical molecules; m is a maleimide functional group at R 1 The number of functionalizations on the molecule; n is-N 3 Functional group at R 2 Number of functionalisations on the molecule.
2. The method for constructing a second-order nonlinear optical polymer material through in-situ thermal crosslinking reaction according to claim 1, wherein: the R is 1 ,R 2 The chromophores are selected from D-pi-A donor-acceptor electron-withdrawing structures, and can be the same or different.
3. The method for constructing a second-order nonlinear optical polymer material through in-situ thermal crosslinking according to claim 2, wherein: the R is 1 ,R 2 Each of the azo chromophore, FTC chromophore, CLD chromophore and DANS chromophore may be the same or different.
4. The method for constructing a second-order nonlinear optical polymer material through in-situ thermal crosslinking according to claim 1, wherein: the R is 1 ,R 2 Is a single chromophore molecule or a multichromophore molecule.
5. The method for constructing a second-order nonlinear optical polymer material through in-situ thermal crosslinking according to claim 1, wherein: m is more than or equal to 2, n is more than or equal to 2.
6. The in situ thermal crosslinking reaction of claim 1 to construct a second order nonlinearityA method of making an optical polymeric material, characterized by: the R is 1 -mMA is prepared by esterification of hydroxyl-containing chromophore molecules with maleimide alkylcarboxylic acids.
7. The method for constructing a second-order nonlinear optical polymer material through in-situ thermal crosslinking reaction according to claim 1, wherein: the R is 2 -nN 3 Substituted with an azidation reagent for halogenated chromophore molecules or for p-toluenesulfonate-containing chromophore molecules.
8. The method for constructing a second-order nonlinear optical polymer material through in-situ thermal crosslinking according to claim 1, wherein: subjecting said R to 1 -mMA with R 2 -nN 3 Dissolving the mixture in a solvent to prepare a solution, coating the solution on the surface of a conductive substrate, drying the solution to form a film, and polarizing the film at a certain temperature to obtain the second-order nonlinear optical polymer material.
9. The method for constructing a second-order nonlinear optical polymer material according to claim 8, wherein the method comprises the following steps: the solvent is any one of tetrahydrofuran, dichloromethane, trichloromethane and acetone, and R is 1 -mMA with R 2 -nN 3 Mixing according to the stoichiometric ratio to prepare a solution with the total concentration of 20-40 mg/mL.
10. The method for constructing a second-order nonlinear optical polymer material according to claim 8, wherein the method comprises the following steps: the temperature of the polarization process is 25-150 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211067198.6A CN115386081B (en) | 2022-09-01 | 2022-09-01 | Method for constructing second-order nonlinear optical polymer material through in-situ thermal crosslinking reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211067198.6A CN115386081B (en) | 2022-09-01 | 2022-09-01 | Method for constructing second-order nonlinear optical polymer material through in-situ thermal crosslinking reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115386081A true CN115386081A (en) | 2022-11-25 |
| CN115386081B CN115386081B (en) | 2023-07-28 |
Family
ID=84125139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211067198.6A Active CN115386081B (en) | 2022-09-01 | 2022-09-01 | Method for constructing second-order nonlinear optical polymer material through in-situ thermal crosslinking reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115386081B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0602654A1 (en) * | 1992-12-18 | 1994-06-22 | ENICHEM S.p.A. | Efficient electron-donating groups for nonlinear optical applictions |
| US5371173A (en) * | 1992-11-25 | 1994-12-06 | Northwestern University | Poled polymeric nonlinear optical materials |
| US5395556A (en) * | 1990-12-12 | 1995-03-07 | Enichem S.P.A. | Tricyanovinyl substitution process for NLO polymers |
| US5834575A (en) * | 1996-11-13 | 1998-11-10 | Hitachi Chemical Company, Ltd. | Compounds and polymers, resin compositions, nonlinear optical element and nonlinear optical devices, and production process therefor |
| CN1226978A (en) * | 1997-05-27 | 1999-08-25 | 克拉瑞特国际有限公司 | Composition for antireflection or light absorption film and compounds for use in the same |
| CN1942826A (en) * | 2004-03-25 | 2007-04-04 | Az电子材料美国公司 | Positive-working photoimageable bottom antireflective coating |
| CN102281904A (en) * | 2008-11-20 | 2011-12-14 | 通用电气医疗集团股份有限公司 | Dye conjugate imaging agents |
| CN104583857A (en) * | 2012-08-22 | 2015-04-29 | 旭硝子株式会社 | Prepolymer, curable material, coating composition, non-linear optical material, optical waveguide and light control device |
| CN104974151A (en) * | 2014-04-14 | 2015-10-14 | 中国科学院理化技术研究所 | Organic second-order nonlinear optical chromophore containing azide group, synthetic method and application thereof |
| CN110591079A (en) * | 2018-06-13 | 2019-12-20 | 厦门赛诺邦格生物科技股份有限公司 | Preparation method of monofunctional nonlinear polyethylene glycol |
-
2022
- 2022-09-01 CN CN202211067198.6A patent/CN115386081B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5395556A (en) * | 1990-12-12 | 1995-03-07 | Enichem S.P.A. | Tricyanovinyl substitution process for NLO polymers |
| US5371173A (en) * | 1992-11-25 | 1994-12-06 | Northwestern University | Poled polymeric nonlinear optical materials |
| EP0602654A1 (en) * | 1992-12-18 | 1994-06-22 | ENICHEM S.p.A. | Efficient electron-donating groups for nonlinear optical applictions |
| US5834575A (en) * | 1996-11-13 | 1998-11-10 | Hitachi Chemical Company, Ltd. | Compounds and polymers, resin compositions, nonlinear optical element and nonlinear optical devices, and production process therefor |
| CN1226978A (en) * | 1997-05-27 | 1999-08-25 | 克拉瑞特国际有限公司 | Composition for antireflection or light absorption film and compounds for use in the same |
| CN1942826A (en) * | 2004-03-25 | 2007-04-04 | Az电子材料美国公司 | Positive-working photoimageable bottom antireflective coating |
| CN102879999A (en) * | 2004-03-25 | 2013-01-16 | Az电子材料美国公司 | Positive-working photoimageable bottom antireflective coating |
| CN102281904A (en) * | 2008-11-20 | 2011-12-14 | 通用电气医疗集团股份有限公司 | Dye conjugate imaging agents |
| CN104583857A (en) * | 2012-08-22 | 2015-04-29 | 旭硝子株式会社 | Prepolymer, curable material, coating composition, non-linear optical material, optical waveguide and light control device |
| CN104974151A (en) * | 2014-04-14 | 2015-10-14 | 中国科学院理化技术研究所 | Organic second-order nonlinear optical chromophore containing azide group, synthetic method and application thereof |
| CN110591079A (en) * | 2018-06-13 | 2019-12-20 | 厦门赛诺邦格生物科技股份有限公司 | Preparation method of monofunctional nonlinear polyethylene glycol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115386081B (en) | 2023-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101671250B (en) | Norbornene monomer, polynorbornene derivative, liquid crystal photoalignment film containing the same and liquid crystal display containing the same | |
| Wang et al. | Multi-stimuli responsive supramolecular gels based on a D–π–A structural cyanostilbene derivative with aggregation induced emission properties | |
| CN104558004B (en) | Organic second order non-linear optical chromophore and preparation method and use with D π A structures | |
| CN104974151B (en) | Organic second order non-linear optical chromophore and its synthetic method and application containing azido group | |
| Sun et al. | Design, synthesis, and properties of nonlinear optical chromophores based on a verbenone bridge with a novel dendritic acceptor | |
| CN109438459B (en) | Organic second-order nonlinear optical chromophore and synthetic method and application thereof | |
| CN107216320A (en) | A kind of organic second order non-linear optical chromophore and preparation method and use with double donor structures | |
| Zang et al. | A TCBD-based AB 2-type second-order nonlinear optical hyperbranched polymer prepared by a facile click-type postfunctionalization | |
| TWI701320B (en) | Liquid crystal composition | |
| Lin et al. | Six-branched chromophores with isolation groups: synthesis and enhanced optical nonlinearity | |
| Koeckelberghs et al. | Synthesis and properties of chiral helical chromophore-functionalised polybinaphthalenes for second-order nonlinear optical applications | |
| Cui et al. | An indanone-based alkoxysilane dye with second order nonlinear optical properties | |
| Sung et al. | Thermal stability of NLO sol—gel networks with reactive chromophores | |
| CN116854652A (en) | Self-crosslinking organic electro-optical molecular glass material and preparation method and application thereof | |
| CN115386081A (en) | Method for constructing second-order nonlinear optical polymer material through in-situ thermal crosslinking reaction | |
| Hao et al. | Short-conjugated zwitterionic cyanopyridinium chromophores: Synthesis, crystal structure, and linear/nonlinear optical properties | |
| JP2020507816A (en) | Liquid crystal alignment composition, method for producing liquid crystal alignment film using the same, and liquid crystal alignment film using the same | |
| KR20190099415A (en) | A mixture, a polymer, an optical film, an optically anisotropic body, a polarizing plate, a display device and an antireflection film, and a method of producing the mixture | |
| CN114957313B (en) | Siloxane-bridged tetraphenyl ethylene derivatives, process for their preparation and their use | |
| CN104293356B (en) | A kind of liquid crystalline cpd is as high birefringence rate liquid crystal material or improving the application in liquid crystal host degree of birefringence | |
| CN111944513B (en) | Low-driving voltage electrochromic material based on quinacridone and preparation method thereof | |
| CN112079831B (en) | Quinacridone-thiophene derivative and preparation method and application thereof | |
| CN112250881B (en) | Alkyl chain bridged terpyridyl iron coordination polymer electrochromic material | |
| CN111116793B (en) | Heat crosslinking functionalized triphenylamine polymer and preparation method and application thereof | |
| CN114656433A (en) | Thioisoprophorone bridge modified double-donor organic optical nonlinear chromophore and synthetic method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |