CN111718487B - Preparation method of click-modified polysiloxane side chain liquid crystal polymer - Google Patents

Preparation method of click-modified polysiloxane side chain liquid crystal polymer Download PDF

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CN111718487B
CN111718487B CN202010600976.8A CN202010600976A CN111718487B CN 111718487 B CN111718487 B CN 111718487B CN 202010600976 A CN202010600976 A CN 202010600976A CN 111718487 B CN111718487 B CN 111718487B
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洪希杭
王冬
王慧东
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Wuhan Yuhong Technology Co ltd
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Abstract

The invention discloses a preparation method of a click-modified polysiloxane side chain liquid crystal polymer, which comprises the steps of firstly preparing p-alkenyloxybenzoic acid by adopting microwave irradiation, preparing 4-allyloxybenzoyl chloride and a liquid crystal monomer by adopting an ultraviolet and laser irradiation combined technology, then preparing p-iodoallyloxybenzene and p- (dibutylamino) phenylacetylene by utilizing a reflux reaction, synthesizing a polysiloxane side chain liquid crystal polymer white solid by the substances under the combined action of ultraviolet, laser and microwave according to a hydrosilylation reaction principle, and then preparing the click-modified polysiloxane side chain liquid crystal polymer by carrying out triple bond modification and click chemical modification. The technology makes full use of the chemical energy of microwave, ultraviolet and laser to synthesize the material and chemically modify the precise point position, can overcome the defects of insufficient product purity, difficult removal of the catalyst and the like, obtains the liquid crystal polymer material with excellent performance, and provides a feasible technical route for the rapid control synthesis and the industrial production of the material.

Description

Preparation method of click-modified polysiloxane side chain liquid crystal polymer
[ technical field ]: the invention belongs to the field of organic material synthesis, and particularly relates to a preparation method of a click-modified polysiloxane side chain liquid crystal polymer.
[ technical background ]: a liquid crystal high-molecular polymer integrates the anisotropy of liquid crystal and the mechanical property of polymer, has the characteristics of good processability, optical anisotropy, dielectric anisotropy and the like, and is widely applied to the fields of photoelectricity, biology, high-strength and high-modulus fibers, plastic engineering and the like (Yao W, Gao Y, Yuan X, et al. Synthesis and self-assembly fibers based on the polysiloxane backbone [ J ]. J.Mater.Chem.C,2016,4(7):1425 and 1440.).
The polysiloxane side chain liquid crystal polymer is a liquid crystal polymer material formed by taking polysiloxane oligomers or Polymers as a main chain and suspending liquid crystal micromolecule units on side chains, and a large number of theoretical and experimental results show that the small-molecule liquid crystal units have great freedom to obtain the optimal arrangement with the lowest energy in the process of synthesizing the polysiloxane side chain liquid crystal polymer because the bond energy of Si-O bonds is lower than that of C-C bonds, so that the obtained polymer has lower glass transition temperature and wider liquid crystal phase temperature range (Zhang L Y, Yao W H, Gao Y Z, et al.
At present, polysiloxane side chain liquid crystal polymers are generally obtained by grafting alkenyl liquid crystalline monomers onto hydrogen-containing silicone oil through a traditional hydrosilylation reaction, and the method has two technical difficulties to be overcome: firstly, how to completely remove noble metal platinum used in the synthesis process in subsequent purification; secondly, the target product is actually a mixture of the Ma addition product and the anti-Ma addition product, and the structure and performance characterization of a single product (rebuke drijin, Chen satellite, Zhu Sheng Bo, etc.. the synthesis and performance research of polysiloxane side chain cholesterol ester liquid crystal polymer [ J]Application chemical, 2019,048(003): 517-520). Aiming at the problem, the invention provides a preparation method of a click-modified polysiloxane side chain liquid crystal polymer, which utilizes microwave irradiation, ultraviolet and Nd: YAG (Neodymium-doped yttrium aluminum garnet, Nd: Y)3Al5O12) The synthesis technology utilizes the chemical energy of microwave, ultraviolet and laser to synthesize materials and chemically modify precise point positions, thereby overcoming the defects of insufficient product purity and the like and obtaining the liquid crystal polymer material with excellent performance; meanwhile, the technical route has the advantages of simple operation, concentrated reaction energy, easy industrialization of operation and the like, has bright application prospect, and provides a new idea for rapid synthesis and product purification of materials of the same type.
[ summary of the invention ]: the invention aims to provide a preparation method of a click-modified polysiloxane side chain liquid crystal polymer, which comprises the steps of firstly preparing p-alkenyloxybenzoic acid by adopting a microwave irradiation method, then respectively preparing 4-allyloxybenzoyl chloride and a liquid crystal monomer by utilizing ultraviolet and Nd-YAG solid pulse laser combined technology, then preparing p-iodoallyloxybenzene and p- (dibutylamino) phenylacetylene by utilizing a reflux reaction, further synthesizing white polysiloxane side chain liquid crystal polymer solid by utilizing the substances under the combination of laser, ultraviolet and microwave according to the principle of hydrosilylation reaction, then carrying out triple bond modification and click chemical modification to prepare the click-modified polysiloxane side chain liquid crystal polymer, wherein the polysiloxane side chain liquid crystal polymer can adjust the performance of the polysiloxane side chain liquid crystal polymer by adjusting the length of a carbon chain in a spacer, the structure of the side chain liquid crystal monomer and the grafting molar ratio of a click modification part, the obtained substance can be used in the fields of photoelectricity, biology, plastic engineering and the like, and the synthetic method also provides a feasible technical route for the rapid control synthesis and the industrial production of the polysiloxane side chain liquid crystal polymer.
[ technical solution of the present invention ]:
the invention relates to a preparation method of a click-modified polysiloxane side chain liquid crystal polymer, which has the following structural general formula:
Figure GDA0003271644060000031
wherein: m, p and q are integers more than or equal to 3, and n is an integer between 0 and 16;
r is selected from
Figure GDA0003271644060000032
In the above-mentioned manner, the first and second substrates are,
one of the used liquid crystal monomers is cholesteryl p-alkenyloxybenzoate, and the structural formula is as follows:
Figure GDA0003271644060000033
the other liquid crystal monomer is p-alkenyloxy benzoic acid alcohol ester, and the structural formula is as follows:
Figure GDA0003271644060000034
wherein R is
Figure GDA0003271644060000035
One of (1);
M2
the click modification moiety used has the general structural formula:
Figure GDA0003271644060000041
a preparation method of a click-modified polysiloxane side chain liquid crystal polymer comprises the following steps of carrying out hydrosilylation on polymethyl hydrogen-containing silicone oil, p-alkenyloxy benzoic acid cholesterol ester and/or p-alkenyloxy benzoic acid alcohol ester and p-iodoallyloxy benzene, reacting with p- (dibutylamino) phenyl acetylene, and finally carrying out click reaction with 7,7,8, 8-tetracyano-p-quinodimethane, tetracyanoethylene, 2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanoquinodimethane, wherein the preparation steps are specifically as follows:
step one, preparation of p-alkenyloxy benzoic acid
Putting a mixture of 0.001-0.100 mol of ethyl p-hydroxybenzoate, 0.001-0.100 mol of alkene bromide, 0.001-0.100 mol of solid potassium carbonate and 100-500 mL of acetone into a 100-1000 mL flask, then moving the flask into a normal-pressure reflux microwave reactor with ultraviolet and Nd, YAG solid pulse laser, and only starting microwave energy, wherein the microwave power is 500-1000W, the frequency is 2450MHz, the heating temperature is 25-200 ℃, the heating time is 1-36 h, reflux condensation is carried out during microwave heating, when the temperature in the microwave reactor exceeds a preset temperature, the microwave generator is closed to reduce the temperature, when the temperature is lower than the preset temperature, the microwave generator is opened to increase the temperature, and a reflux condensing device is started in the reaction process; after the microwave is finished, filtering the obtained product, carrying out rotary evaporation at the speed of 80-100 r/min at the temperature of 30 ℃ until acetone is removed, adding 100-300 mL of diethyl ether into the product, adding 100mL of distilled water, stirring for 5-10 min, standing for layering, separating an ether layer from a distilled water layer, extracting the ether layer twice by using 50-200 mL of 5-30% NaOH aqueous solution, evaporating the diethyl ether at the temperature of 35-40 ℃, adding the obtained residue into 300mL of ethanol containing 30g of KOH according to the mass ratio of 1:2, boiling until the residue is dissolved, cooling the solution to room temperature, stirring the solution at the speed of 100-2000 r/min, simultaneously adding 6mol/L of hydrochloric acid solution, adjusting the pH value to be 1-2, filtering the obtained product to obtain a crude product, stirring and washing the filtered solid phase substance by using 300mL of distilled water for 30min, adding the washed product into ethanol which is heated and stirred under reflux at the temperature of 80 ℃, until the product is not dissolved any more, quickly cooling the product in a refrigerator at 5 ℃ for 10-30 min, filtering the mixture to obtain white needle crystals, and drying the crystal product at 30-60 ℃ for 12-72 h in vacuum to obtain p-alkenyloxy benzoic acid;
step two, preparation of 4-allyloxybenzoyl chloride
Adding the white needle-shaped crystal obtained in the step one and 5-30 mL of thionyl chloride into a 20-100 mL flask with a hydrogen chloride absorber, transferring the flask into a normal-pressure reflux microwave reactor with ultraviolet and Nd-YAG solid pulse laser, starting ultraviolet light and laser irradiation on the flask, wherein the ultraviolet wavelength is 190-400 nm, and the power is 5mW/cm2～15W/cm2The laser wavelength of Nd-YAG solid pulse laser is 1.06 mu m, the pulse width is 1.2ms, the spot diameter is 0.2-6 mm, and the steps are repeatedFrequency of 2-40 Hz, power density of 1.0X 106W/cm2The light spot of the laser focus is 1-3 mm below the liquid level, the irradiation time is 0.1-20 h, the irradiation temperature is 20-200 ℃, the mixture is stirred at the speed of 200-2000 r/min in the irradiation process, reflux condensation is carried out during heating, then the solution is taken out, and the excessive thionyl chloride is removed by reduced pressure distillation for 10min under the conditions of-0.09 MPa and 40 ℃, so as to obtain 4-allyloxybenzoyl chloride;
step three, preparation of liquid crystal monomer p-alkenyloxy benzoic acid cholesterol ester
Dissolving the obtained 4-allyloxybenzoyl chloride in 1-50 mL of dry dichloromethane, adding 0.01-1.00 mmol of cholesterol and 1-20 mL of pyridine into 50-200 mL of dry dichloromethane, dropwise adding the 4-allyloxybenzoyl chloride solution into a dichloromethane cold liquid containing cholesterol and pyridine, transferring the mixed liquid into a normal-pressure microwave reactor with reflux of ultraviolet and Nd: YAG solid pulse laser, and only starting ultraviolet light and laser to irradiate the flask, wherein the ultraviolet wavelength is 190-400 nm, and the power is 5mW/cm2～15W/cm2The Nd is YAG solid pulse laser wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.2-6 mm, repetition frequency 2-40 Hz, power density 1.0 x 106W/cm2A light spot of a laser focus is 1-3 mm below a liquid level, the irradiation time is 0.1-10 h, the irradiation temperature is 20-200 ℃, the mixture is stirred at the speed of 200-2000 r/min and is subjected to reflux condensation simultaneously in the irradiation process, then the solution is taken out, 100-500 mL of ethanol is added into the filtrate to precipitate a crude product, the crude product is recrystallized from the ethanol, and the obtained white powder product is dried in a vacuum drying oven at the temperature of 50-80 ℃ for 6-72 h to obtain the p-alkenyloxy benzoic acid cholesterol ester;
step four, preparation of liquid crystal monomer p-alkenyloxy benzoic alcohol ester
Dissolving the 4-allyloxybenzoyl chloride obtained in the second step in 5-20 mL of dry dichloromethane, dripping the solution into a cold solution containing 0.01-0.20 mol of R-OH and 3-20 mL of pyridine in 100mL of dichloromethane, transferring the mixture into a flask, transferring the flask into a microwave reactor with ultraviolet and Nd, YAG solid pulse laser and normal pressure backflow, only opening the flask for ultraviolet light and laser irradiation,wherein the ultraviolet wavelength is 190-400 nm, and the power is 5mW/cm2～15W/cm2YAG solid pulse laser wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.2mm, repetition frequency 20Hz, power density 1.0 × 106W/cm2The method comprises the following steps of (1) enabling a light spot of a laser focus to be 2mm below a liquid level, enabling the irradiation time to be 4-10 hours, enabling the irradiation temperature to be 20-50 ℃, stirring a mixture at a speed of 200-2000 r/min in the irradiation process, simultaneously carrying out reflux condensation, then taking out a solution, adding 300mL of ethanol into a filtrate to precipitate a crude product, recrystallizing the crude product from the ethanol, and drying an obtained white powder product in a vacuum drying oven at the temperature of 50-80 ℃ for 12-48 hours to obtain p-alkenyloxy benzoic acid alcohol ester;
step five, preparation of p-iodoallyloxybenzene
Dissolving 0.01-0.10 mol of p-iodophenol in 10-100 mL of acetonitrile, stirring for 5-10 min, then placing in a 30-300 mL flask, adding 0.01-0.10 mol of 3-bromopropylene and 0.01-0.10 mol of potassium carbonate, heating to 85 ℃, stirring at 100-2000 r/min, carrying out water bath heat preservation reflux reaction for 1-5 h, carrying out centrifugal separation after reaction to remove solids, carrying out rotary evaporation for 10-300 min at the speed of-0.09 MPa, the temperature of 40-80 ℃ and the speed of 80-100 r/min to remove excess solvent, and then carrying out silica gel column chromatography purification by taking a mixture of dichloromethane and petroleum ether with the volume ratio of 1:2 as an eluent to obtain iodine p-allyloxybenzene;
step six, preparation of p- (dibutylamino) phenylacetylene
Dissolving 5-100 mmol of para-iodoaniline and 5-100 mmol of bromobutane or iodomethane in 10-200 mL of N, N-dimethylformamide, adding 5-100 mmol of potassium carbonate and 5-100 mmol of potassium iodide, placing the mixture in a 40KHz ultrasonic cleaning instrument for ultrasonic oscillation for 20-40 min, introducing argon gas for removing oxygen at 0.1-2L/min, carrying out water bath reflux reaction on a 20-500 mL flask containing the mixture at 80-150 ℃ for 15-24 h, plugging a reflux condenser tube opening with a rubber plug, carrying out suction filtration after the reaction to remove solids, extracting with 30-300 mL of water and 30-300 mL of dichloromethane to remove N, N-dimethylformamide, rotary evaporating at-0.09 MPa, 25-50 deg.C and 90r/min for 10-200 min to remove excessive solvent, then, using a mixture of dichloromethane and petroleum ether with a volume ratio of 1:6 as eluent to carry out silica gel column chromatography purification, thus obtaining a p- (dibutylamino) phenylacetylene product; dissolving 0.001-0.100 mol of product in 50-100 mL of mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, introducing argon gas at 0.1-2L/min, ultrasonically deoxidizing at 40KHz for 30min, then adding 0.001-0.100 mol of trimethylsilyl acetylene TMSA, 0.1-1.0 mmol of bis (triphenylphosphine) palladium dichloride and 0.1-1.0 mmol of cuprous iodide, stirring in a 100-300 mL flask containing the mixture at a speed of 100-2000 r/min, carrying out a water bath reflux reaction at 25-60 ℃ for 8-12 h, plugging a reflux condenser pipe orifice with a rubber plug, carrying out suction filtration after the reaction to remove solids, carrying out vacuum evaporation at a speed of-0.09 MPa, 40-80 ℃ and 80-100 r/min for 30min to remove more solvent, and then carrying out silica gel column chromatography purification by taking a mixture of dichloromethane and petroleum ether in a volume ratio of 1:6 as eluent to obtain yellow liquid; dissolving 0.001-0.100 mol of the product and 0.001-0.100 mol of potassium carbonate in 30-100 mL of a mixed solution of tetrahydrofuran and absolute ethyl alcohol with a volume ratio of 7:3, transferring the mixed solution into a 50-300 mL flask, stirring the mixture in the flask at 100-2000 r/min, carrying out reflux reaction at room temperature for 2-10 h, stopping the reaction, carrying out suction filtration to remove solids, carrying out rotary evaporation at a vacuum degree of-0.09 MPa, a temperature of 40-80 ℃ and a rotating speed of 80-100 r/min for 20-60 min to remove the solvent, and carrying out dichloromethane column chromatography purification to obtain a yellow oily liquid;
step seven, 4-ethynyl-N, N-hexacosanylaniline preparation
Dissolving 5-100 mmol of p-iodoaniline and 5-100 mmol of 1-bromohexadecane in 10-200 mLN, N-dimethylformamide, then adding 5-100 mmol of potassium carbonate and 5-100 mmol of potassium iodide, placing the mixture in a 40KHz ultrasonic cleaning instrument for ultrasonic oscillation for 20-40 min, introducing argon gas for removing oxygen at 0.1-2L/min, carrying out water bath reflux reaction on a 20-500 mL flask containing the mixture at 80-150 ℃ for 15-24 h, plugging a reflux condenser tube opening with a rubber plug, carrying out suction filtration after the reaction to remove solids, extracting with 30-300 mL of water and 30-300 mL of dichloromethane to remove N, N-dimethylformamide, rotary evaporating at-0.09 MPa, 25-50 deg.C and 90r/min for 10-200 min to remove excessive solvent, then, using a mixture of dichloromethane and petroleum ether with a volume ratio of 1:6 as an eluent to carry out silica gel column chromatography purification, thus obtaining a product; dissolving 0.001-0.100 mol of the product in 50-100 mL of mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, introducing argon gas at 0.1-2L/min, ultrasonically deoxidizing at 40KHz for 30min, then adding 0.001-0.100 mol of trimethylsilyl acetylene TMSA, 0.1-1.0 mmol of bis (triphenylphosphine) palladium dichloride and 0.2mmol of cuprous iodide, stirring in a 100-300 mL flask containing the mixture at a speed of 100-2000 r/min, carrying out reflux reaction in a water bath at 25-60 ℃ for 8-12 h, plugging a reflux condenser pipe orifice with a rubber plug, carrying out suction filtration after the reaction to remove solids, carrying out vacuum rotary evaporation for 30min at a speed of-0.09 MPa, 40-80 ℃ and 80-100 r/min to remove more solvent, and then carrying out silica gel column chromatography purification by using a mixture of dichloromethane and petroleum ether in a volume ratio of 1:6 as an eluent to obtain yellow liquid; dissolving 0.001-0.100 mol of product and 0.001-0.100 mol of potassium carbonate in 30-100 mL of a mixture of tetrahydrofuran and absolute ethyl alcohol with a volume ratio of 7:3, transferring the mixture into a 50-300 mL flask, stirring the mixture in the flask at 100-2000 r/min, carrying out reflux reaction at room temperature for 2-10 h, stopping the reaction, carrying out suction filtration to remove solids, carrying out rotary evaporation at a vacuum degree of-0.09 MPa, a temperature of 40-80 ℃ and a rotating speed of 80-100 r/min for 20-60 min to remove the solvent, and carrying out dichloromethane column chromatography purification to obtain a yellow oily liquid;
step eight, preparing white solid of polysiloxane side chain liquid crystal polymer by hydrosilylation reaction
Adding 0.10-5.00 mmol of liquid crystal monomer p-alkenyloxy cholesteryl benzoate, 0.10-5.00 mmol of p-iodoallyloxy benzene and 10-10 ppm of platinum catalyst into a flask for reaction, adding the mixture into 10-50 mL of toluene, evacuating the flask through a double-row pipe and filling nitrogen, discharging oxygen in the flask, transferring the flask into a normal-pressure belt reflux microwave reactor with ultraviolet and Nd: YAG solid pulse laser, and irradiating the solution with Nd: YAG solid pulse laser, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.2-6 mm in spot diameter, 2-40 Hz in repetition frequency and 1.0 multiplied by 10 Hz in power density6W/cm2The light spot of the laser focus is 1-3 mm below the liquid level, and the irradiation time is 0.1-24 h; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 190-400 nm, and the intensity is 5mW/cm2～15W/cm2The irradiation time is 0.1-24 h; by laser and ultraviolet irradiationSimultaneously, synchronously starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 300-1000W, the microwave time is 0.1-24 h, the heating temperature is 25-100 ℃, the microwave generator is closed to cool when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is opened to heat when the temperature is lower than the set temperature, reflux condensation is started, and the mouth of a reflux condenser pipe is plugged by a rubber plug to prevent air from entering; after the reaction is finished, adding 200-500 mg of polymethylhydrosilicone oil PMHS under the condition of keeping vacuum, and irradiating the solution by Nd-YAG solid pulse laser, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.2-6 mm in spot diameter, 2-40 Hz in repetition frequency and 1.0 multiplied by 10 in power density6W/cm2The light spot of the laser focus is 1-3 mm below the liquid level, and the irradiation time is 0.1-24 h; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 190-400 nm, and the power is 5mW/cm2～15W/cm2The irradiation time is 0.1-24 h; simultaneously carrying out laser and ultraviolet irradiation, synchronously starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 300-1000W, the microwave time is 0.1-24 h, the heating temperature is 60-100 ℃, when the temperature in the microwave reactor exceeds a set temperature, a microwave generator is closed to reduce the temperature, and when the temperature in the microwave reactor is lower than the set temperature, the microwave generator is opened to increase the temperature; after the reaction is finished, taking out the reaction liquid, cooling the reaction liquid to room temperature, dropwise adding the reaction liquid into 20-500 mL of methanol under the condition of mechanical stirring at 100-1000 r/min, centrifugally separating at 7000r/min, re-dissolving the solid phase substance into 20-500 mL of chloroform, precipitating with 20-500 mL of methanol to remove unreacted raw materials, and drying at 70-80 ℃ for 6-72 hours to obtain white solid of the polysiloxane side chain liquid crystal polymer;
step nine, preparation of polysiloxane side chain liquid crystal polymer modified by triple bond
Dissolving 50-150 mg of liquid crystal polymer prepared by hydrosilylation reaction and 0.10-1.00 mmol of p- (dibutylamino) phenylacetylene or 4-ethynyl-N, N-hexacosanylaniline in 5-30 mL of triethylamine and tetrahydrofuran solution with a volume ratio of 1:1, introducing 0.1-2L/min of argon, ultrasonically deoxidizing for 30min under the condition of 40KHz, adding 0.1-1.0 mmol of bis (triphenylphosphine) palladium dichloride and 0.1-1.0 mmol of cuprous iodide, stirring at 100-2000 r/min, refluxing and reacting in water bath at 40 ℃ for 5-20 h, centrifugally separating at 7000r/min to remove solids, dropwise adding the liquid product into 100-500 mL of methanol solution under stirring at a rotating speed of 100-2000 r/min, centrifugally separating at 7000r/min, redissolving the precipitate in 100-500 mL of trichloromethane, precipitating with 20-500 mL of methanol to remove unreacted raw materials, obtaining polysiloxane side chain liquid crystal polymer modified by triple bonds;
step ten, click reaction preparation of click-modified polysiloxane side chain liquid crystal polymer
And (4) adding the polysiloxane side chain liquid crystal polymer obtained in the step nine into 5-50 mL of methanol, adding a click chemistry modified micromolecule monomer into the other 5-50 mL of methanol, and mixing the two solutions to prepare the click modified polysiloxane side chain liquid crystal polymer through click reaction.
In the preparation of the p-alkenyloxybenzoic acid, the p-alkenyloxybenzoic acid is obtained by reacting ethyl p-hydroxybenzoate with allyl bromide.
In the preparation of the p-alkenyloxybenzoic acid, the alkene bromine is one or any combination of two or more than two of 3-bromine-1-propylene, 5-bromine-1-pentene and 13-bromine-1-tridecene.
In the preparation of the liquid crystal polymer by the hydrosilylation reaction, when the polymethyl hydrogen-containing silicone oil reacts with two liquid crystal monomers, one of the two liquid crystal monomers is 0, but not both of the two liquid crystal monomers are 0.
In the preparation of the liquid crystal monomer-p-alkenyloxy benzoic acid cholesterol ester, the p-alkenyloxy benzoic acid cholesterol ester is obtained by esterifying p-alkenyloxy benzoic acid and cholesterol.
In the preparation of the liquid crystalline monomer p-alkenyloxy benzoic alcohol ester, the p-alkenyloxy benzoic alcohol ester is obtained by esterifying p-alkenyloxy benzoic acid and R-OH, wherein R is selected from
Figure GDA0003271644060000091
One kind of (1).
The solvent used in the polysiloxane side chain liquid crystal polymer prepared by click modification is dichloromethane, and the small molecular monomer is one, two or more of 7,7,8, 8-tetracyanoquinodimethane, tetracyanoethylene, 2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanoquinodimethane, wherein the dichloromethane is 5-30 mL, the 7,7,8, 8-tetracyanoterephthalquinodimethane is 10-100 mg, the 2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanoquinodimethane is 10-100 mg, and the tetracyanoethylene is 1-50 mg.
The polysiloxane side chain liquid crystal polymer prepared by click modification has a polysiloxane main chain, has good surface energy, mechanical and thermal stability, and can graft side chains with different properties through hydrosilylation reaction, so that the polysiloxane side chain liquid crystal polymer shows liquid crystallinity and nonlinear optical effect.
According to the polysiloxane side chain liquid crystal polymer prepared by click modification, the grafted side chain is a chiral compound named as p-alkenyloxy benzoic acid cholesterol ester, wherein m is an integer larger than 3, so that linear polysiloxane can show liquid crystallinity.
According to the linear polysiloxane displaying liquid crystallinity, the grafted side chain is a compound of substitution termination of achiral different polar groups, and the introduction of the side chain can achieve that the polysiloxane side chain liquid crystal polymer has different phase structures, wherein p is an integer larger than or equal to 3, and different polar groups are cyano-group, methoxy-group and phenyl-group structures.
According to the linear polysiloxane for displaying the nonlinear optical effect, the grafted side chain of the linear polysiloxane is an organic conjugated group modified by click chemistry, and the linear polysiloxane has a good chromophore structure for an acceptor after click modification, so that the linear polysiloxane displays good third-order nonlinear optical effect, wherein q is an integer larger than or equal to 3, and n is an integer from 0 to 16.
[ advantages and effects of the invention ]: the invention provides a preparation method of a click-modified polysiloxane side chain liquid crystal polymer, which has the following advantages and beneficial effects: 1. through sulfydryl-vinyl click reaction, polymethyl hydrogen-containing silicone oil is used as a main chain, a liquid crystal monomer is grafted to the main chain under the combined catalysis of ultraviolet light, laser and microwave to synthesize polysiloxane side chain liquid crystal polymer, microwave irradiation, ultraviolet and laser technical means are selectively or intensively comprehensively applied in the synthesis process, the obtained product is uniform and high in purity, the catalyst is easy to remove, the microwave heating reaction rate is high, the temperature hysteresis effect is avoided, the ultraviolet irradiation energy temperature is reduced, the laser energy is concentrated and pollution is avoided, and the technical foundation is laid for further exploring the structure and performance of subsequent products; 2. by changing the use types of the liquid crystal monomers and the grafting molar ratio of the two liquid crystal monomers, the polysiloxane side chain liquid crystal polymer structure can be adjusted, so that the polysiloxane side chain liquid crystal polymer structure has different properties, and guarantee and power are provided for promoting the application of the materials in the fields of liquid crystal displays, biological medicines and the like.
[ description of drawings ]:
FIG. 1 is a reaction scheme of the synthesis of polysiloxane side chain liquid crystalline polymers according to the present invention
FIG. 2 is a schematic view of the structure of a combined laser, UV and microwave apparatus used in the present invention (with reflux condenser)
FIG. 3 is a schematic diagram showing the structure of the laser, UV and microwave combination apparatus used in the present invention (glass four-port connecting tube, one of which is connected to a flask, and the other three ports are connected to a reflux condenser, a stirring paddle, a separating funnel, an argon tube or for evacuation and evacuation as required)
[ detailed description ] embodiments
In order to clearly illustrate the technical features of the present invention, the following detailed description of the present invention is provided with reference to the accompanying drawings.
Example 1: preparation of click-modified polysiloxane side chain liquid crystal polymer sample 1
Where m is 3, p is 3, q is 3, n is 1, and R is
Figure GDA0003271644060000111
X, y, z is 0:0:100, X is 7,7,8, 8-tetracyanoquinodimethane, a specific synthesis method of polysiloxane side chain liquid crystal polymer sample 1 is described, and a specific synthesis scheme is shown in fig. 1:
step one, preparation of p-iodoallyloxybenzene (M3): dissolving 0.025mol of p-iodophenol in 50mL of acetonitrile, stirring for 10min, then placing the mixture in a 100mL flask, adding 0.03mol of 3-bromopropylene and 0.03mol of potassium carbonate, heating to 85 ℃, stirring at 300r/min, carrying out reflux reaction for 3h under the condition of water bath heat preservation, carrying out centrifugal separation after reaction to remove solids, carrying out rotary evaporation for 30min at the temperature of 60 ℃ and the speed of 90r/min under the pressure of-0.09 MPa to remove redundant solvent, and then carrying out silica gel column chromatography purification by taking a mixture of dichloromethane and petroleum ether with the volume ratio of 1:2 as an eluent to obtain the p-iodoallyloxybenzene.
Step two, preparation of p- (dibutylamino) phenylacetylene (M4): dissolving 20mmol of p-iodoaniline and 80mmol of iodomethane in 65mL of N, N-dimethylformamide, adding 60mmol of potassium carbonate and 60mmol of potassium iodide, placing in a 40KHz ultrasonic cleaner, ultrasonically oscillating for 30min, introducing argon gas for removing oxygen at 1L/min, carrying out water bath reflux reaction for 20h at 120 ℃ in a 150mL flask filled with the mixture, plugging a reflux condenser tube orifice with a rubber plug, carrying out suction filtration to remove solids after the reaction, extracting with 200mL of water and 200mL of dichloromethane to remove N, N-dimethylformamide, carrying out rotary evaporation for 100min at the speed of-0.09 MPa, 30 ℃ and 90r/min to remove excessive solvent, and then carrying out silica gel column chromatography purification by using a mixture of dichloromethane and petroleum ether as eluent at the volume ratio of 1:6 to obtain the p- (dibutylamino) phenylacetylene (M4). Dissolving 0.002mol of the product in 80mL of mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, introducing argon gas for 1L/min, ultrasonically deoxidizing for 30min at 40KHz, then adding 0.003mol of trimethylsilyl acetylene TMSA, 0.2mmol of bis-triphenylphosphine palladium dichloride and 0.2mmol of cuprous iodide, stirring in a 150mL flask filled with the mixture at a speed of 300r/min, refluxing in a water bath at 40 ℃ for 10h, plugging a reflux condenser pipe orifice with a rubber plug, filtering to remove solids after reaction, carrying out vacuum rotary evaporation for 30min at a speed of-0.09 MPa, 60 ℃ and 90r/min to remove more solvent, and then carrying out silica gel column chromatography purification by taking a mixture of dichloromethane and petroleum ether as eluent in a volume ratio of 1:6 to obtain yellow liquid. Dissolving the product 0.005mol and 0.005mol of potassium carbonate in 50mL of mixed solution of tetrahydrofuran and absolute ethyl alcohol with the volume ratio of 7:3, transferring the mixed solution into a 100mL flask, stirring the mixture in the flask at 300r/min, carrying out reflux reaction at room temperature for 3h, stopping the reaction, carrying out suction filtration to remove solids, carrying out vacuum rotary evaporation for 30min at the vacuum degree of-0.09 MPa and the temperature of 50 ℃ and the rotating speed of 90r/min to remove the solvent, and carrying out dichloromethane column chromatography purification to obtain the product.
Step three, preparing white solid of polysiloxane side chain liquid crystal polymer: adding 0.22mmol of p-iodoallyloxybenzene and 50ppm of platinum catalyst into a flask, dissolving in 20mL of toluene, evacuating the mixture through a double-row pipe, filling nitrogen, removing oxygen, transferring the mixture into a normal-pressure belt reflux microwave reactor with ultraviolet and Nd: YAG solid pulse laser, and irradiating the solution with the Nd: YAG solid pulse laser, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.2mm in spot diameter, 20Hz in repetition frequency, 1.0X 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level, and the irradiation time is 0.2 h; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the intensity is 5mW/cm2The irradiation time is 0.2 h; simultaneously carrying out laser and ultraviolet irradiation, synchronously starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 600W, the microwave time is 0.2h, the heating temperature is 60 ℃, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to cool, when the temperature is lower than the set temperature, the microwave generator is opened to heat, reflux condensation is started, and the mouth of a reflux condensation pipe is blocked by a rubber plug, so that air is prevented from entering; after the reaction is finished, 275.2mg of polymethyl hydrogen silicone oil PMHS is added under the condition of keeping vacuum, and Nd: YAG solid pulse laser is used for irradiating the solution, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.2-6 mm in spot diameter, 20Hz in repetition frequency and 1.0 multiplied by 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level, and the irradiation time is 8 h; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the power is 5mW/cm2The irradiation time is 8 h; simultaneously performing laser and ultraviolet irradiation, synchronously starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 800W, the microwave time is 8h, the heating temperature is 80 ℃, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, and when the temperature is lower than the set temperature, the microwave generator is opened to increase the temperature; after the reaction, the reaction mixture was taken out and cooled to room temperature, and was added dropwise to 300mL of methanol under mechanical stirring at 300r/min, 7000r/min was centrifuged, and the solid phase was redissolvedAfter dissolving in 300mL of chloroform and precipitating with 300mL of methanol to remove unreacted materials, the resulting product was dried at 70 ℃ for 72 hours, i.e., a white solid of polysiloxane side chain liquid crystalline polymer.
Step four, preparing the polysiloxane side chain liquid crystal polymer modified by triple bonds: 79mg of white solid product of polysiloxane side chain liquid crystal polymer and 0.22mmol of p- (dibutylamino) phenylacetylene (M4) are dissolved in 10mL of triethylamine and tetrahydrofuran solution with the volume ratio of 1:1, then argon is introduced at 1L/min, ultrasonic deoxygenation is carried out for 30min under the condition of 40KHz, 0.2mmol of bis (triphenylphosphine) palladium dichloride and 0.2mmol of cuprous iodide are added, stirring is carried out at 200r/min, reflux reaction is carried out for 12h at 40 ℃, centrifugal separation is carried out at 7000r/min to remove solid, the liquid product is dropwise added into 300mL of methanol solution under stirring at the rotating speed of 300r/min, centrifugal separation is carried out at 7000r/min, the precipitate is re-dissolved in 200mL of trichloromethane, and then 200mL of methanol is used for precipitation to remove unreacted raw materials, thus obtaining the triple bond modified polysiloxane side chain liquid crystal polymer.
Step five, preparing click-modified polysiloxane side chain liquid crystal polymer through click reaction: and (3) dissolving the product obtained in the fourth step in 10mL of dichloromethane, and adding 45mg of 7,7,8, 8-tetracyanoterephthalquinodimethane into another 10mL of dichloromethane solution to prepare a liquid crystal polymer sample 1 with a click-modified polysiloxane side chain through a click reaction, wherein the yield is 90%.
The obtained white solid sample 1 of polysiloxane side chain liquid crystal polymer has no liquid crystal phase state and good nonlinear optical characteristics.
Example 2: preparation of click-modified polysiloxane side chain liquid crystal polymer sample 2
Where m is 3, p is 3, q is 3, n is 4, and R is
Figure GDA0003271644060000131
X: y: z ═ 0:98:2, X is 2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanoquinodimethane as an example, a specific synthesis method of polysiloxane side chain liquid crystal polymer sample 2 is described, and a specific synthesis scheme is shown in fig. 1:
step one, preparation of p-alkenyloxy benzoic acid: putting a mixture of 0.01mol of ethyl p-hydroxybenzoate, 0.015mol of 3-bromo-1-propylene, 0.01mol of solid potassium carbonate and 250mL of acetone into a 500mL flask, then moving the flask into a microwave reactor with ultraviolet and Nd, YAG solid pulse laser and normal pressure and backflow, and only starting microwave energy, wherein the microwave power is 650W, the frequency is 2450MHz, boiling and heating are carried out for 24 hours, the microwave heating process is accompanied with backflow, when the temperature in the microwave reactor exceeds a set temperature, a microwave generator is closed to cool, when the temperature is lower than the set temperature, the microwave generator is opened to heat, and a backflow condensing device is started in the reaction process; after the microwave is finished, filtering the obtained product, carrying out rotary evaporation at the speed of 90r/min at the temperature of 30 ℃ until acetone is removed, adding 200mL of diethyl ether into the product, adding 100mL of distilled water, stirring for 5min, standing for layering, separating an diethyl ether layer from a distilled water layer, extracting the diethyl ether layer twice by using 100mL of 10% NaOH aqueous solution, evaporating the diethyl ether at the temperature of 40 ℃, putting the obtained residue into 300mL of a mixture of ethanol containing 30g of KOH and water in a mass ratio of 1:2, boiling until the residue is dissolved, cooling the solution to room temperature, stirring the solution at the speed of 300r/min, adding 6mol/L hydrochloric acid solution, adjusting the pH to 2, filtering the obtained product to obtain a crude product, stirring and washing the filtered solid phase by using 300mL of distilled water for 30min, adding the washed product into ethanol which is heated, refluxed and stirred at the temperature of 80 ℃, and (3) rapidly cooling the product in a refrigerator at 5 ℃ for 10min until the product is not dissolved any more, filtering the mixture to obtain white needle-shaped crystals, and drying the crystal product at 40 ℃ for 48h in vacuum to obtain the p-alkenyloxybenzoic acid.
Step two, preparation of 4-allyloxybenzoyl chloride: adding 0.05mol of white needle-shaped crystal obtained in the step one and 10mL of thionyl chloride into a 30mL flask provided with a hydrogen chloride absorber, transferring the flask into a normal-pressure reflux microwave reactor with ultraviolet and Nd: YAG solid pulse laser, starting ultraviolet light and laser irradiation on the flask, wherein the ultraviolet wavelength is 365nm, and the power is 300mW/cm2YAG solid pulse laser wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.2mm, repetition frequency 20Hz, power density 1.0 × 106W/cm2The light spot of the laser focus is 2mm below the liquid level, the irradiation time is 6h, the irradiation temperature is 40 ℃, the mixture is stirred at the speed of 300r/min in the irradiation process,the solution was then taken out while heating with reflux condensation and distilled under reduced pressure at-0.09 MPa at 40 ℃ for 10min to remove excess thionyl chloride, yielding 4-allyloxybenzoyl chloride.
Step three, synthesizing a liquid crystal monomer (M2) through an esterification reaction: 4-allyloxybenzoyl chloride was dissolved in 10mL of dry dichloromethane and added dropwise to a cold solution of 100mL of dichloromethane containing 0.06mol of p-hydroxybenzonitrile and 8mL of pyridine, transferred into an atmospheric pressure microwave reactor with reflux of UV and laser, and the flask was irradiated with UV light and laser, wherein the UV wavelength was 365nm and the power was 300mW/cm2YAG solid pulse laser wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.2mm, repetition frequency 20Hz, power density 1.0 × 106W/cm2The light spot of the laser focus is 2mm below the liquid level, the irradiation time is 6h, the irradiation temperature is 40 ℃, the mixture is stirred at the speed of 300r/min in the irradiation process, the precipitate is removed by filtration, 300mL of ethanol is added into the filtrate to precipitate a crude product, the crude product is recrystallized from the ethanol, and the obtained white powder product is dried in a vacuum drying oven at the temperature of 70 ℃ for 24h to obtain the liquid crystal monomer M2.
Step four, preparation of p-iodoallyloxybenzene (M3): dissolving 0.025mol of p-iodophenol in 50mL of acetonitrile, then placing the solution in a 100mL flask, adding 0.03mol of 3-bromopropylene and 3.5g of potassium carbonate, heating the solution to 85 ℃, stirring the solution at 300r/min, carrying out reflux reaction for 2h under the condition of water bath heat preservation, filtering the reaction solution to remove solids, carrying out rotary evaporation for 30min under the conditions of-0.09 MPa and 60 ℃ to remove redundant solvent, and then carrying out silica gel column chromatography purification by using a mixture of dichloromethane and petroleum ether in a volume ratio of 1:2 as an eluent to obtain a white product of p-iodoallyloxybenzene M3.
Step five, preparation of p- (dibutylamino) phenylacetylene (M4): dissolving 20mmol of p-iodoaniline and 80mmol of bromobutane in 65mL of N, N-dimethylformamide, then adding 60mmol of potassium carbonate and 60mmol of potassium iodide, introducing argon gas for 30min at 1L/min in an ultrasonic cleaning instrument to remove oxygen, carrying out water bath reflux reaction on a 150mL flask filled with the mixture for 20h at 120 ℃, plugging a reflux condenser tube orifice with a rubber plug, carrying out suction filtration to remove solids after the reaction, extracting with 200mL of water to remove N, N-dimethylformamide, carrying out rotary evaporation for 30min at the speed of-0.09 MPa, 40 ℃ and 90r/min to remove redundant solvent, and then carrying out silica gel column chromatography by using a mixture of dichloromethane and petroleum ether with the volume ratio of 1:6 as eluent to obtain a p- (dibutylamino) phenylacetylene product; dissolving 0.002mol of product in 80mL of mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, introducing argon gas for 1L/min, carrying out ultrasonic deoxidization for 30min at 40KHz, adding 0.003mol of trimethylsilyl acetylene TMSA, 0.2mmol of bis (triphenylphosphine) palladium dichloride and 0.2mmol of cuprous iodide, stirring in a 150mL flask containing the mixture at a speed of 300r/min, carrying out reflux reaction for 10h in a water bath at 40 ℃, plugging a reflux condenser pipe orifice with a rubber plug, carrying out suction filtration after the reaction to remove solids, carrying out vacuum rotary evaporation for 30min at a speed of-0.09 MPa, 60 ℃ and 90r/min to remove more solvent, and then using a mixture of dichloromethane and petroleum ether in a volume ratio of 1:6 as an eluent to carry out silica gel column chromatography purification to obtain yellow liquid; dissolving 0.005mol of the product and 0.005mol of potassium carbonate in 50mL of a mixture of tetrahydrofuran and absolute ethyl alcohol with the volume ratio of 7:3, transferring the mixture into a 100mL flask, stirring the mixture in the flask at 300r/min, carrying out reflux reaction at room temperature for 3h, stopping the reaction, carrying out suction filtration to remove solids, carrying out rotary evaporation at-0.09 MPa and 50 ℃ for 30min to remove redundant solvent, and carrying out dichloromethane column chromatography to obtain a yellow oily liquid.
Step six, polysiloxane side chain liquid crystal polymer white solid: adding 2.156mmol 4-cyanophenyl 4- (allyloxy) benzoate, 0.044mmol p-iodoallyloxy benzene and 60ppm platinum catalyst into a flask, dissolving in 20mL toluene, evacuating and filling nitrogen through a double-row pipe, removing oxygen, transferring into an atmospheric pressure belt reflux microwave reactor with ultraviolet and Nd: YAG solid pulse laser, and irradiating the solution with Nd: YAG solid pulse laser, wherein the laser parameters are 1.06 μm in wavelength, 1.2ms in pulse width, 0.2mm in spot diameter, 20Hz in repetition frequency, 1.0 × 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level, and the irradiation time is 0.5 h; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the intensity is 5mW/cm2The irradiation time is 0.5 h; simultaneously, the laser and the ultraviolet irradiation synchronously start the microwave heating, the microwave frequency is 2450MHz, the microwave power is 650W, and the microwave heating is startedThe time is 0.5h, the heating temperature is 60 ℃, when the temperature in the microwave reactor exceeds the set temperature, the microwave generator is closed to reduce the temperature, when the temperature in the microwave reactor is lower than the set temperature, the microwave generator is opened to increase the temperature, reflux condensation is started, and the opening of a reflux condensation pipe is blocked by a rubber plug, so that air is prevented from entering; after the reaction is finished, 275.2mg of polymethylhydrosilicone oil PMHS is added under the condition of keeping vacuum, and then Nd: YAG solid pulse laser is used for irradiating the solution, wherein the laser parameters are that the wavelength is 1.06 mu m, the pulse width is 1.2ms, the spot diameter is 0.2mm, the repetition frequency is 20Hz, and the power density is 1.0 multiplied by 106W/cm2The light spot of the laser focus is 2mm below the liquid level, and the irradiation time is 8 h; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the intensity is 5mW/cm2The irradiation time is 8 h; simultaneously performing laser and ultraviolet irradiation, synchronously starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 650W, the microwave time is 8h, the heating temperature is 80 ℃, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, and when the temperature is lower than the set temperature, the microwave generator is opened to increase the temperature; after the reaction is finished, taking out the reaction liquid, cooling the reaction liquid to room temperature, dropwise adding the reaction liquid into 300mL of methanol under the mechanical stirring condition of 300r/min, carrying out suction filtration and precipitation, re-dissolving the solid phase substance into 300mL of chloroform, then precipitating with 300mL of methanol to remove unreacted raw materials, carrying out 7000r/min centrifugal separation, and drying at 80 ℃ for 48 hours to obtain the white solid of the polysiloxane side chain liquid crystal polymer.
Step seven, preparing the polysiloxane side chain liquid crystal polymer modified by triple bonds: dissolving 839mg and 0.044mmol of p- (dibutylamino) phenylacetylene in the sixth step in 10mL of triethylamine and tetrahydrofuran solution with a volume ratio of 1:1, introducing argon gas at 1L/min, ultrasonically removing oxygen for 30min under the condition of 40KHz, adding 0.2mmol of bis (triphenylphosphine) palladium dichloride and 0.2mmol of cuprous iodide, stirring at 300r/min, refluxing in water bath at 40 ℃ for 12h, centrifugally separating at 7000r/min to remove solids, dropwise adding the liquid product into 300mL of methanol solution under stirring at the rotating speed of 300r/min, centrifugally separating at 7000r/min, redissolving the precipitate in 300mL of trichloromethane, and precipitating with 300mL of methanol to remove unreacted raw materials to obtain the triple bond modified polysiloxane side chain liquid crystal polymer.
Step eight, click reaction preparation of click-modified polysiloxane side chain liquid crystal polymer
And (3) dissolving the product obtained in the step seven in 10mL of dichloromethane, then dissolving 13mg of 2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanoquinodimethane in another 10mL of dichloromethane, and mixing the two solutions to obtain the click-modified polysiloxane side chain liquid crystal polymer sample 2 with the yield of 89%.
The liquid crystal phase state of the obtained white solid sample 2 of the polysiloxane side chain liquid crystal polymer is smectic phase A, and the nonlinear optical property is good.
Example 3: preparation of click-modified polysiloxane side chain liquid crystal polymer sample 3
Where m is 3, p is 3, q is 3, n is 4, and R is
Figure GDA0003271644060000161
X, y, z is 98:0:2, X is tetracyanoethylene, and a specific synthesis method of polysiloxane side chain liquid crystal polymer sample 3 is described, and a specific synthesis scheme is shown in fig. 1:
step one, preparation of p-alkenyloxy benzoic acid: putting a mixture of 0.01mol of ethyl p-hydroxybenzoate, 0.015mol of 3-bromo-1-propylene, 0.01mol of solid potassium carbonate and 250mL of acetone into a 500mL flask, then moving the flask into a microwave reactor with ultraviolet and Nd, YAG solid pulse laser and normal pressure and backflow, and only starting microwave energy, wherein the microwave power is 650W, the frequency is 2450MHz, boiling and heating are carried out for 24 hours, the microwave heating process is accompanied with backflow, when the temperature in the microwave reactor exceeds a set temperature, a microwave generator is closed to cool, when the temperature is lower than the set temperature, the microwave generator is opened to heat, and a backflow condensing device is started in the reaction process; after the microwave is finished, filtering the obtained product, carrying out rotary evaporation at the speed of 90r/min at the temperature of 30 ℃ until acetone is removed, adding 200mL of diethyl ether into the product, adding 100mL of distilled water, stirring for 5min, standing for layering, separating an diethyl ether layer from a distilled water layer, extracting the diethyl ether layer twice by using 100mL of 10% NaOH aqueous solution, evaporating the diethyl ether at the temperature of 40 ℃, putting the obtained residue into 300mL of a mixture of ethanol containing 30g of KOH and water in a mass ratio of 1:2, boiling until the residue is dissolved, cooling the solution to room temperature, stirring the solution at the speed of 300r/min, adding 6mol/L hydrochloric acid solution, adjusting the pH to 2, filtering the obtained product to obtain a crude product, stirring and washing the filtered solid phase by using 300mL of distilled water for 30min, adding the washed product into ethanol which is heated, refluxed and stirred at the temperature of 80 ℃, and (3) rapidly cooling the product in a refrigerator at 5 ℃ for 30min until the product is not dissolved any more, filtering the mixture to obtain white needle-shaped crystals, and drying the crystal product at 40 ℃ for 48h in vacuum to obtain the p-alkenyloxybenzoic acid.
Step two, preparation of 4-allyloxybenzoyl chloride: adding 0.05mol of white needle-shaped crystal obtained in the step one and 10mL of thionyl chloride into a 30mL flask provided with a hydrogen chloride absorber, transferring the flask into a normal-pressure reflux microwave reactor with ultraviolet and Nd: YAG solid pulse laser, starting ultraviolet light and laser irradiation on the flask, wherein the ultraviolet wavelength is 365nm, and the power is 300mW/cm2YAG solid pulse laser wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.2mm, repetition frequency 20Hz, power density 1.0 × 106W/cm2The light spot of the laser focus is 2mm below the liquid level, the irradiation time is 6h, the irradiation temperature is 40 ℃, the mixture is stirred at the speed of 300r/min in the irradiation process, reflux condensation is carried out during heating, then the solution is taken out, and the excessive thionyl chloride is removed by reduced pressure distillation for 10min under the conditions of-0.09 MPa and 40 ℃, so as to obtain the 4-allyloxybenzoyl chloride.
Step three, synthesizing a liquid crystal monomer (M1) through an esterification reaction: 4-allyloxybenzoyl chloride was dissolved in 10mL of dry dichloromethane and added dropwise to a cold solution of 100mL of dichloromethane containing 0.06mol of cholesterol and 8mL of pyridine, transferred to an atmospheric pressure reflux microwave reactor with UV and laser, and the flask was irradiated with UV light and laser while turning on the UV light irradiation at 365nm, 300mW/cm power2YAG solid pulse laser wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.2mm, repetition frequency 20Hz, power density 1.0 × 106W/cm2The light spot of the laser focus is 2mm below the liquid level, the irradiation time is 6h, the temperature is 40 ℃, after the reaction, the mixture is stirred at the speed of 300r/min in the irradiation process, the precipitate is removed by filtration after the reaction, 300mL of ethyl is added into the filtrateThe crude product was precipitated with alcohol and recrystallized from ethanol to give a white powder product, which was dried in a vacuum oven at 70 ℃ for 24 hours to give liquid crystalline monomer M1.
Step four, preparation of p-iodoallyloxybenzene (M3): dissolving 0.025mol of p-iodophenol in 50mL of acetonitrile, then placing the solution in a 100mL flask, adding 0.03mol of 3-bromopropylene and 3.5g of potassium carbonate, heating the solution to 85 ℃, stirring the solution at 300r/min, carrying out reflux reaction for 2h under the condition of water bath heat preservation, filtering the reaction solution to remove solids, carrying out rotary evaporation for 30min under the conditions of-0.09 MPa and 60 ℃ to remove redundant solvent, and then carrying out silica gel column chromatography purification by using a mixture of dichloromethane and petroleum ether in a volume ratio of 1:2 as an eluent to obtain a white product of p-iodoallyloxybenzene M3.
Step five, preparation of p- (dibutylamino) phenylacetylene (M4): dissolving 20mmol of p-iodoaniline and 80mmol of bromobutane in 65mL of N, N-dimethylformamide, then adding 60mmol of potassium carbonate and 60mmol of potassium iodide, introducing argon gas for 30min at 1L/min in an ultrasonic cleaning instrument to remove oxygen, carrying out water bath reflux reaction on a 150mL flask filled with the mixture for 20h at 120 ℃, plugging a reflux condenser tube orifice with a rubber plug, carrying out suction filtration to remove solids after the reaction, extracting with 200mL of water to remove N, N-dimethylformamide, carrying out rotary evaporation for 30min at the speed of-0.09 MPa, 40 ℃ and 90r/min to remove redundant solvent, and then carrying out silica gel column chromatography by using a mixture of dichloromethane and petroleum ether with the volume ratio of 1:6 as eluent to obtain a p- (dibutylamino) phenylacetylene product; dissolving 0.002mol of product in 80mL of mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, introducing argon gas for 1L/min, carrying out ultrasonic deoxidization for 30min at 40KHz, adding 0.003mol of trimethylsilyl acetylene TMSA, 0.2mmol of bis (triphenylphosphine) palladium dichloride and 0.2mmol of cuprous iodide, stirring in a 150mL flask containing the mixture at a speed of 300r/min, carrying out reflux reaction for 10h in a water bath at 40 ℃, plugging a reflux condenser pipe orifice with a rubber plug, carrying out suction filtration after the reaction to remove solids, carrying out vacuum rotary evaporation for 30min at a speed of-0.09 MPa, 60 ℃ and 90r/min to remove more solvent, and then using a mixture of dichloromethane and petroleum ether in a volume ratio of 1:6 as an eluent to carry out silica gel column chromatography purification to obtain yellow liquid; dissolving 0.005mol of the product and 0.005mol of potassium carbonate in 50mL of a mixture of tetrahydrofuran and absolute ethyl alcohol with the volume ratio of 7:3, transferring the mixture into a 100mL flask, stirring the mixture in the flask at 300r/min, carrying out reflux reaction at room temperature for 3h, stopping the reaction, carrying out suction filtration to remove a solid, carrying out rotary evaporation at-0.09 MPa and 50 ℃ for 30min to remove an excessive solvent, removing the solvent, and carrying out dichloromethane column chromatography to obtain a yellow oily liquid.
Step six, polysiloxane side chain liquid crystal polymer white solid: adding 2.156mmol of 4-allyloxybenzoic acid cholesteryl ester, 0.044mmol of p-iodoallyloxybenzene and 50ppm of platinum catalyst into a flask, dissolving in 20mL of toluene, evacuating and filling nitrogen through a double-row pipe, removing oxygen, transferring into a normal-pressure belt reflux microwave reactor with ultraviolet and Nd-YAG solid pulse laser, and irradiating the solution with Nd-YAG solid pulse laser, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.2mm in spot diameter, 20Hz in repetition frequency and 1.0X 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level, and the irradiation time is 0.5 h; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the intensity is 5mW/cm2The irradiation time is 0.5 h; simultaneously carrying out laser and ultraviolet irradiation, synchronously starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 650W, the microwave time is 0.5h, the heating temperature is 60 ℃, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to cool, when the temperature is lower than the set temperature, the microwave generator is opened to heat, reflux condensation is started, and the mouth of a reflux condensation pipe is blocked by a rubber plug, so that air is prevented from entering; after the reaction is finished, 275.2mg of polymethylhydrosilicone oil PMHS is added under the condition of keeping vacuum, and then Nd: YAG solid pulse laser is used for irradiating the solution, wherein the laser parameters are that the wavelength is 1.06 mu m, the pulse width is 1.2ms, the spot diameter is 0.2mm, the repetition frequency is 20Hz, and the power density is 1.0 multiplied by 106W/cm2The light spot of the laser focus is 2mm below the liquid level, and the irradiation time is 8 h; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the intensity is 5mW/cm2The irradiation time is 8 h; simultaneously performing laser and ultraviolet irradiation, synchronously starting microwave heating with microwave frequency of 2450MHz, microwave power of 650W and microwave time of 8h, heating temperature of 80 deg.C, and microwave reactor with temperature higher than the set temperatureWhen the temperature is lower than the set temperature, the microwave generator is turned on to heat up; after the reaction is finished, taking out the reaction liquid, cooling the reaction liquid to room temperature, dropwise adding the reaction liquid into 300mL of methanol under the mechanical stirring condition of 300r/min, carrying out suction filtration and precipitation, re-dissolving the solid phase substance into 300mL of chloroform, then precipitating with 300mL of methanol to remove unreacted raw materials, carrying out 7000r/min centrifugal separation, and drying at 80 ℃ for 48 hours to obtain the white solid of the polysiloxane side chain liquid crystal polymer.
Step seven, preparing the polysiloxane side chain liquid crystal polymer modified by triple bonds: 1.3525g of the product obtained in the sixth step and 0.044mmol of p- (dibutylamino) phenylacetylene are dissolved in 10mL of triethylamine and tetrahydrofuran solution with the volume ratio of 1:1, then argon is introduced at 1L/min, ultrasonic deoxygenation is carried out for 30min under the condition of 40KHz, 0.2mmol of bis (triphenylphosphine) palladium dichloride and 0.2mmol of cuprous iodide are added, stirring is carried out at 300r/min, water bath reflux reaction is carried out at 40 ℃ for 12h, centrifugal separation is carried out at 7000r/min to remove solid, liquid product is dropwise added into 300mL of methanol solution under stirring at the rotating speed of 300r/min, centrifugal separation is carried out at 7000r/min, the precipitate is redissolved in 300mL of trichloromethane, and then 300mL of methanol is used for precipitation to remove unreacted raw materials, thus obtaining the triple bond modified polysiloxane side chain liquid crystal polymer.
Step eight, preparing click-modified polysiloxane side chain liquid crystal polymer through click reaction: and dissolving the product obtained in the seventh step in 10mL of dichloromethane, and then dissolving 6mg of tetracyanoethylene in another 10mL of dichloromethane to obtain a click-modified polysiloxane side chain liquid crystal polymer sample 3 with a yield of 88%.
The liquid crystal phase state of the obtained white solid sample 3 of the polysiloxane side chain liquid crystal polymer is smectic phase A, and the nonlinear optical property is good.
Example 4: preparation of click-modified polysiloxane side chain liquid crystal polymer sample 4
Where m is 3, p is 3, q is 3, n is 16, and R is
Figure GDA0003271644060000201
X, y, z 49:49:2, X tetracyanoethylenetetracyanoethylene as an example, polysiloxane side chain liquid crystalline polymers are introducedA specific synthesis method of sample 4, scheme 1 for synthesis:
step one, preparation of p-alkenyloxy benzoic acid: putting a mixture of 0.01mol of ethyl p-hydroxybenzoate, 0.015mol of 3-bromo-1-propylene, 0.01mol of solid potassium carbonate and 250mL of acetone into a 500mL flask, then moving the flask into a microwave reactor with ultraviolet and Nd, YAG solid pulse laser and normal pressure and backflow, and only starting microwave energy, wherein the microwave power is 600W, the frequency is 2450MHz, boiling and heating are carried out for 24 hours, the microwave heating process is accompanied with backflow, when the temperature in the microwave reactor exceeds a set temperature, a microwave generator is closed to cool, when the temperature is lower than the set temperature, the microwave generator is opened to heat, and a backflow condensing device is started in the reaction process; after the microwave is finished, filtering the obtained product, carrying out rotary evaporation at the speed of 90r/min at the temperature of 30 ℃ until acetone is removed, adding 200mL of diethyl ether into the product, adding 100mL of distilled water, stirring for 5min, standing for layering, separating an diethyl ether layer from a distilled water layer, extracting the diethyl ether layer twice by using 100mL of 10% NaOH aqueous solution, evaporating the diethyl ether at the temperature of 40 ℃, putting the obtained residue into 300mL of a mixture of ethanol containing 30g of KOH and water in a mass ratio of 1:2, boiling until the residue is dissolved, cooling the solution to room temperature, stirring the solution at the speed of 300r/min, adding 6mol/L hydrochloric acid solution, adjusting the pH to 2, filtering the obtained product to obtain a crude product, stirring and washing the filtered solid phase by using 300mL of distilled water for 30min, adding the washed product into ethanol which is heated, refluxed and stirred at the temperature of 80 ℃, and (3) putting the product into a refrigerator at 5 ℃ for rapid cooling for 25min until the product is not dissolved any more, filtering the mixture to obtain white needle-shaped crystals, and drying the crystal product at 40 ℃ for 48h in vacuum to obtain the p-alkenyloxybenzoic acid.
Step two, preparation of 4-allyloxybenzoyl chloride: adding 0.05mol of white needle-shaped crystal obtained in the step one and 10mL of thionyl chloride into a 30mL flask provided with a hydrogen chloride absorber, transferring the flask into a normal-pressure reflux microwave reactor with ultraviolet and Nd: YAG solid pulse laser, starting ultraviolet light and laser irradiation on the flask, wherein the ultraviolet wavelength is 365nm, and the power is 300mW/cm2YAG solid pulse laser wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.2mm, repetition frequency 20Hz, power density 1.0X 106W/cm2The light spot of the laser focus is 2mm below the liquid level, the irradiation time is 6h, the irradiation temperature is 40 ℃, the mixture is stirred at the speed of 300r/min in the irradiation process, reflux condensation is carried out during heating, then the solution is taken out, and the excessive thionyl chloride is removed by reduced pressure distillation for 10min under the conditions of-0.09 MPa and 40 ℃, so as to obtain the 4-allyloxybenzoyl chloride.
Step three, synthesizing a liquid crystal monomer (M1) through an esterification reaction: 4-allyloxybenzoyl chloride was dissolved in 10mL of dry dichloromethane and added dropwise to a cold solution of 100mL of dichloromethane containing 0.06mol of cholesterol and 8mL of pyridine, transferred to an atmospheric pressure reflux microwave reactor with UV and laser, and the flask was irradiated with UV light and laser while turning on the UV light irradiation at 365nm, 300mW/cm power2YAG solid pulse laser wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.2mm, repetition frequency 20Hz, power density 1.0 × 106W/cm2The light spot of the laser focus is 2mm below the liquid level, the irradiation time is 6h, the irradiation temperature is 40 ℃, the mixture is stirred at the speed of 300r/min in the irradiation process, the precipitate is removed by filtration, 300mL of ethanol is added into the filtrate to precipitate a crude product, the crude product is recrystallized from the ethanol, and the obtained white powder product is dried in a vacuum drying oven at the temperature of 70 ℃ for 24h to obtain the liquid crystal monomer M1.
Step four, synthesizing a liquid crystal monomer (M2) through an esterification reaction: 4-allyloxybenzoyl chloride was dissolved in 10mL of dry dichloromethane and added dropwise to a cold solution of 100mL of dichloromethane containing 0.06mol of p-hydroxybenzonitrile and 8mL of pyridine, transferred into an atmospheric pressure microwave reactor with reflux of UV and laser, and the flask was irradiated with UV light and laser, wherein the UV wavelength was 365nm and the power was 300mW/cm2YAG solid pulse laser wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.2mm, repetition frequency 20Hz, power density 1.0 × 106W/cm2The light spot of the laser focus is 2mm below the liquid level, the irradiation time is 6h, the irradiation temperature is 40 ℃, the mixture is stirred at the speed of 300r/min in the reaction, the precipitate is removed by filtration, 300mL of ethanol is added into the filtrate to precipitate the crude product, the crude product is recrystallized from the ethanol, and the obtained white powder product is dried in a vacuum drying oven at the temperature of 70 DEG CThen dried for 24h to obtain the liquid crystal monomer M2.
Step five, preparation of p-iodoallyloxybenzene (M3): dissolving 0.025mol of p-iodophenol in 50mL of acetonitrile, then placing the solution in a 100mL flask, adding 0.03mol of 3-bromopropylene and 3.5g of potassium carbonate, heating the solution to 85 ℃, stirring the solution at 300r/min, carrying out reflux reaction for 2h under the condition of water bath heat preservation, filtering the reaction solution to remove solids, carrying out rotary evaporation for 30min under the conditions of-0.09 MPa and 60 ℃ to remove redundant solvent, and then carrying out silica gel column chromatography purification by using a mixture of dichloromethane and petroleum ether in a volume ratio of 1:2 as an eluent to obtain a white product of p-iodoallyloxybenzene M3.
Step six, preparation of 4-ethynyl-N, N-hexacosanylaniline (M4): dissolving 20mmol of p-iodoaniline and 80mmol of 1-bromohexadecane in 65mLN, N-dimethylformamide, then adding 60mmol of potassium carbonate and 60mmol of potassium iodide, introducing argon gas for 30min at 1L/min in an ultrasonic cleaning instrument to remove oxygen, carrying out water bath reflux reaction for 20h in a 150mL flask filled with the mixture at 120 ℃, plugging a reflux condenser tube orifice with a rubber plug, carrying out suction filtration to remove solids after the reaction, extracting with 200mL of water to remove N, N-dimethylformamide, carrying out rotary evaporation for 30min at the speed of-0.09 MPa, 40 ℃ and 90r/min to remove redundant solvent, and then carrying out silica gel column chromatography purification by taking a mixture of dichloromethane and petroleum ether as an eluent with the volume ratio of 1:6 to obtain 4-ethynyl-N, N-hexacosanylaniline; dissolving 0.002mol of the product in 80mL of mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, introducing argon gas into 1L/min, ultrasonically deoxidizing for 30min at 40KHz, then adding 0.003mol of trimethylsilyl acetylene TMSA, 0.2mmol of bis (triphenylphosphine) palladium dichloride and 0.2mmol of cuprous iodide, stirring in a 150mL flask containing the mixture at a speed of 300r/min, refluxing in a water bath at 40 ℃ for 10h, plugging a reflux condenser pipe orifice with a rubber plug, removing solids by suction filtration after reaction, carrying out vacuum rotary evaporation for 30min at a speed of-0.09 MPa, 60 ℃ and 90r/min to remove more solvents, and then using a mixture of dichloromethane and petroleum ether in a volume ratio of 1:6 as an eluent to carry out silica gel column chromatography purification to obtain yellow liquid; dissolving 0.005mol of the product and 0.005mol of potassium carbonate in 50mL of a mixture of tetrahydrofuran and absolute ethyl alcohol with the volume ratio of 7:3, transferring the mixture into a 100mL flask, stirring the mixture in the flask at 300r/min, carrying out reflux reaction at room temperature for 3h, stopping the reaction, carrying out suction filtration to remove a solid, carrying out rotary evaporation at-0.09 MPa and 50 ℃ for 30min to remove excessive solvent, removing the solvent, and carrying out dichloromethane column chromatography to obtain a yellow oily liquid.
Step seven, polysiloxane side chain liquid crystal polymer white solid: adding 1.078mmol of 4-allyloxybenzoic acid cholesteryl ester, 1.078mmol of 4-methoxyphenyl 4- (allyloxy) benzoate, 0.044mmol of p-iodoallyloxybenzene and 50ppm of platinum catalyst into a flask, dissolving in 20mL of toluene, evacuating the mixture through a double-row pipe, filling nitrogen, discharging oxygen, transferring the mixture into an atmospheric pressure belt reflux microwave reactor with ultraviolet and Nd: YAG solid pulse laser, and irradiating the solution with Nd: YAG solid pulse laser, wherein the laser parameters are 1.06 μm in wavelength, 1.2ms in pulse width, 0.2mm in spot diameter, 20Hz in repetition frequency and 1.0 × 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level, and the irradiation time is 0.5 h; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the intensity is 5mW/cm2The irradiation time is 0.5 h; simultaneously carrying out laser and ultraviolet irradiation, synchronously starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 650W, the microwave time is 0.5h, the heating temperature is 60 ℃, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to cool, when the temperature is lower than the set temperature, the microwave generator is opened to heat, reflux condensation is started, and the mouth of a reflux condensation pipe is blocked by a rubber plug, so that air is prevented from entering; after the reaction is finished, 275.2mg of polymethylhydrosilicone oil PMHS is added under the condition of keeping vacuum, and then Nd: YAG solid pulse laser is used for irradiating the solution, wherein the laser parameters are that the wavelength is 1.06 mu m, the pulse width is 1.2ms, the spot diameter is 0.2mm, the repetition frequency is 20Hz, and the power density is 1.0 multiplied by 106W/cm2The light spot of the laser focus is 2mm below the liquid level, and the irradiation time is 8 h; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the intensity is 5mW/cm2The irradiation time is 8 h; simultaneously performing laser and ultraviolet irradiation, synchronously starting microwave heating with microwave frequency of 2450MHz and microwave power of 650W for 8h at 80 deg.C, closing microwave generator to cool when the temperature in the microwave reactor exceeds a predetermined temperature,when the temperature is lower than the set temperature, the microwave generator is turned on to heat up; after the reaction is finished, taking out the reaction liquid, cooling the reaction liquid to room temperature, dropwise adding the reaction liquid into 300mL of methanol under the mechanical stirring condition of 300r/min, carrying out suction filtration and precipitation, re-dissolving the solid phase substance into 300mL of chloroform, then precipitating with 300mL of methanol to remove unreacted raw materials, carrying out 7000r/min centrifugal separation, and drying at 80 ℃ for 48 hours to obtain the white solid of the polysiloxane side chain liquid crystal polymer.
Step eight, preparing the polysiloxane side chain liquid crystal polymer modified by triple bonds: dissolving 1g of the product obtained in the seventh step and 0.044mmol of 4-ethynyl-N, N-hexacosanylaniline in 10mL of triethylamine and tetrahydrofuran solution with the volume ratio of 1:1, introducing argon gas at 1L/min, carrying out ultrasonic deoxidization for 30min under the condition of 40KHz, adding 0.2mmol of bis-triphenylphosphine palladium dichloride and 0.2mmol of cuprous iodide, stirring at 300r/min, carrying out reflux reaction at 40 ℃ in a water bath for 12h, centrifuging at 7000r/min to remove solids, dropwise adding the liquid product into 300mL of methanol solution with stirring at the rotating speed of 300r/min, centrifuging at 7000r/min, redissolving the precipitate in 300mL of trichloromethane, and precipitating with 300mL of methanol to remove unreacted raw materials to obtain the three-bond modified polysiloxane side chain liquid crystal polymer.
Step nine, preparing click-modified polysiloxane side chain liquid crystal polymer through click reaction: and (3) dissolving the product obtained in the step eight in 10mL of dichloromethane, dissolving 6mg of tetracyanoethylene in another 10mL of dichloromethane, and mixing the two solutions to obtain a click-modified polysiloxane side chain liquid crystal polymer sample 4 with the yield of 87%.
The liquid crystal phase state of the obtained white solid sample 4 of the polysiloxane side chain liquid crystal polymer is a single-layer or double-layer smectic phase A, and the nonlinear optical property is good.
Example 5: preparation of click-modified polysiloxane side chain liquid crystal polymer sample 5
Where m is 3, p is 3, q is 3, n is 4, and R is
Figure GDA0003271644060000231
X: y: z ═ 18:80:2, and X is tetracyanoethylene as an example, polysiloxane side chain liquid crystalline polymer sample 5 was introducedThe specific synthesis method of (1), the specific synthesis scheme is shown in fig. 1:
step one, preparation of p-alkenyloxy benzoic acid: putting a mixture of 0.01mol of ethyl p-hydroxybenzoate, 0.015mol of 3-bromo-1-propylene, 0.01mol of solid potassium carbonate and 250mL of acetone into a 500mL flask, then moving the flask into a microwave reactor with ultraviolet and Nd, YAG solid pulse laser and normal pressure and backflow, and only starting microwave energy, wherein the microwave power is 650W, the frequency is 2450MHz, boiling and heating are carried out for 24 hours, the microwave heating process is accompanied with backflow, when the temperature in the microwave reactor exceeds a set temperature, a microwave generator is closed to cool, when the temperature is lower than the set temperature, the microwave generator is opened to heat, and a backflow condensing device is started in the reaction process; after the microwave is finished, filtering the obtained product, carrying out rotary evaporation at the speed of 90r/min at the temperature of 30 ℃ until acetone is removed, adding 200mL of diethyl ether into the product, adding 100mL of distilled water, stirring for 5min, standing for layering, separating an diethyl ether layer from a distilled water layer, extracting the diethyl ether layer twice by using 100mL of 10% NaOH aqueous solution, evaporating the diethyl ether at the temperature of 40 ℃, putting the obtained residue into 300mL of a mixture of ethanol containing 30g of KOH and water in a mass ratio of 1:2, boiling until the residue is dissolved, cooling the solution to room temperature, stirring the solution at the speed of 300r/min, adding 6mol/L hydrochloric acid solution, adjusting the pH to 2, filtering the obtained product to obtain a crude product, stirring and washing the filtered solid phase by using 300mL of distilled water for 30min, adding the washed product into ethanol which is heated, refluxed and stirred at the temperature of 80 ℃, and (3) rapidly cooling the product in a refrigerator at 5 ℃ for 30min until the product is not dissolved any more, filtering the mixture to obtain white needle-shaped crystals, and drying the crystal product at 40 ℃ for 48h in vacuum to obtain the p-alkenyloxybenzoic acid.
Step two, preparation of 4-allyloxybenzoyl chloride: adding 0.05mol of white needle-shaped crystal obtained in the step one and 10mL of thionyl chloride into a 30mL flask provided with a hydrogen chloride absorber, transferring the flask into a normal-pressure reflux microwave reactor with ultraviolet and Nd: YAG solid pulse laser, starting ultraviolet light and laser irradiation on the flask, wherein the ultraviolet wavelength is 365nm, and the power is 300mW/cm2The laser wavelength of Nd-YAG solid pulse laser is 1.06 μm, the pulse width is 1.2ms, the spot diameter is 0.2mm, the repetition frequency is 20Hz,power density 1.0X 106W/cm2The light spot of the laser focus is 2mm below the liquid level, the irradiation time is 6h, the irradiation temperature is 40 ℃, the mixture is stirred at the speed of 300r/min in the irradiation process, reflux condensation is carried out during heating, then the solution is taken out, and the excessive thionyl chloride is removed by reduced pressure distillation for 10min under the conditions of-0.09 MPa and 40 ℃, so as to obtain the 4-allyloxybenzoyl chloride.
Step three, synthesizing a liquid crystal monomer (M1) through an esterification reaction: 4-allyloxybenzoyl chloride was dissolved in 10mL of dry dichloromethane and added dropwise to a cold solution of 100mL of dichloromethane containing 0.06mol of cholesterol and 8mL of pyridine, transferred to an atmospheric pressure reflux microwave reactor with UV and laser, and the flask was irradiated with UV light and laser while turning on the UV light irradiation at 365nm, 300mW/cm power2YAG solid pulse laser wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.2mm, repetition frequency 20Hz, power density 1.0 × 106W/cm2And (2) keeping the light spot of the laser focus below the liquid level for 2mm, irradiating for 6h at 40 ℃, stirring the mixture at the speed of 300r/min during the irradiation, filtering to remove precipitates after the reaction, adding 300mL of ethanol into the filtrate to precipitate a crude product, recrystallizing from the ethanol, and drying the obtained white powder product in a vacuum drying oven at 70 ℃ for 24h to obtain the liquid crystal monomer M1.
Step four, synthesizing a liquid crystal monomer (M2) through an esterification reaction: 4-allyloxybenzoyl chloride was dissolved in 10mL of dry dichloromethane, added dropwise to a cold solution of 100mL of dichloromethane containing 0.06mol of p-hydroxyanisole and 8mL of pyridine, transferred into an atmospheric pressure reflux microwave reactor with UV and laser, and the flask was irradiated with UV and laser light with a UV wavelength of 365nm and a power of 300mW/cm2YAG solid pulse laser wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.2mm, repetition frequency 20Hz, power density 1.0 × 106W/cm2The light spot of the laser focus is 2mm below the liquid level, the irradiation time is 6h, the irradiation temperature is 40 ℃, the mixture is stirred at the speed of 300r/min in the irradiation process, the precipitate is removed by filtration, 300mL of ethanol is added into the filtrate to precipitate the crude product, the crude product is recrystallized from the ethanol, and the obtained white powder product is subjected to vacuum filtration at the temperature of 70 DEG CAnd drying in an air drying oven for 24 hours to obtain the liquid crystal monomer M2.
Step five, preparation of p-iodoallyloxybenzene (M3): dissolving 0.025mol of p-iodophenol in 50mL of acetonitrile, then placing the solution in a 100mL flask, adding 0.03mol of 3-bromopropylene and 3.5g of potassium carbonate, heating the solution to 85 ℃, stirring the solution at 300r/min, carrying out reflux reaction for 2h under the condition of water bath heat preservation, filtering the reaction solution to remove solids, carrying out rotary evaporation for 30min under the conditions of-0.09 MPa and 60 ℃ to remove redundant solvent, and then carrying out silica gel column chromatography purification by using a mixture of dichloromethane and petroleum ether in a volume ratio of 1:2 as an eluent to obtain a white product of p-iodoallyloxybenzene M3.
Step six, preparation of p- (dibutylamino) phenylacetylene (M4): dissolving 20mmol of p-iodoaniline and 80mmol of bromobutane in 65mLN, N-dimethylformamide, then adding 60mmol of potassium carbonate and 60mmol of potassium iodide, introducing argon gas for 30min at 1L/min in an ultrasonic cleaning instrument to remove oxygen, carrying out water bath reflux reaction on a 150mL flask filled with the mixture for 20h at 120 ℃, plugging a reflux condenser tube orifice with a rubber plug, carrying out suction filtration to remove solids after the reaction, extracting with 200mL of water to remove N, N-dimethylformamide, carrying out rotary evaporation for 30min at the speed of-0.09 MPa, 40 ℃ and 90r/min to remove redundant solvent, and then carrying out silica gel column chromatography purification by taking a mixture of dichloromethane and petroleum ether as eluent with the volume ratio of 1:6 to obtain a p- (dibutylamino) phenylacetylene product; dissolving 0.002mol of product in 80mL of mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, introducing argon gas for 1L/min, carrying out ultrasonic deoxidization for 30min at 40KHz, adding 0.003mol of trimethylsilyl acetylene TMSA, 0.2mmol of bis (triphenylphosphine) palladium dichloride and 0.2mmol of cuprous iodide, stirring in a 150mL flask containing the mixture at a speed of 300r/min, carrying out reflux reaction for 10h in a water bath at 40 ℃, plugging a reflux condenser pipe orifice with a rubber plug, carrying out suction filtration after the reaction to remove solids, carrying out vacuum rotary evaporation for 30min at a speed of-0.09 MPa, 60 ℃ and 90r/min to remove more solvent, and then using a mixture of dichloromethane and petroleum ether in a volume ratio of 1:6 as an eluent to carry out silica gel column chromatography purification to obtain yellow liquid; dissolving 0.005mol of the product and 0.005mol of potassium carbonate in 50mL of a mixture of tetrahydrofuran and absolute ethyl alcohol with the volume ratio of 7:3, transferring the mixture into a 100mL flask, stirring the mixture in the flask at 300r/min, carrying out reflux reaction at room temperature for 3h, stopping the reaction, carrying out suction filtration to remove solids, carrying out rotary evaporation at-0.09 MPa and 50 ℃ for 30min to remove excessive solvent, removing the solvent, and carrying out dichloromethane column chromatography to obtain a yellow oily liquid.
Step seven, polysiloxane side chain liquid crystal polymer white solid: adding 0.396mmol of 4-allyloxybenzoic acid cholesteryl ester, 1.76mmol of 4-methoxyphenyl 4- (allyloxy) benzoate, 0.044mmol of p-iodoallyloxybenzene and 60ppm of platinum catalyst into a flask, dissolving in 20mL of toluene, evacuating the mixture through a double-row pipe, filling nitrogen, discharging oxygen, transferring the mixture into an atmospheric pressure belt reflux microwave reactor with ultraviolet and Nd: YAG solid pulse laser, and irradiating the solution with Nd: YAG solid pulse laser, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.2mm in spot diameter, 20Hz in repetition frequency and 1.0X 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level, and the irradiation time is 0.5 h; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the intensity is 5mW/cm2The irradiation time is 0.5 h; simultaneously carrying out laser and ultraviolet irradiation, synchronously starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 650W, the microwave time is 0.5h, the heating temperature is 60 ℃, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to cool, when the temperature is lower than the set temperature, the microwave generator is opened to heat, reflux condensation is started, and the mouth of a reflux condensation pipe is blocked by a rubber plug, so that air is prevented from entering; after the reaction is finished, 275.2mg of polymethylhydrosilicone oil PMHS is added under the condition of keeping vacuum, and then Nd: YAG solid pulse laser is used for irradiating the solution, wherein the laser parameters are that the wavelength is 1.06 mu m, the pulse width is 1.2ms, the spot diameter is 0.2mm, the repetition frequency is 20Hz, and the power density is 1.0 multiplied by 106W/cm2The light spot of the laser focus is 2mm below the liquid level, and the irradiation time is 8 h; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the intensity is 5mW/cm2The irradiation time is 8 h; simultaneously performing laser and ultraviolet irradiation, synchronously starting microwave heating with microwave frequency of 2450MHz, microwave power of 650W and microwave time of 8h, heating temperature of 80 deg.C, and stopping microwave generator to lower temperature when the temperature in the microwave reactor exceeds a predetermined temperatureWhen the temperature is lower than the set temperature, the microwave generator is turned on to heat up; after the reaction is finished, taking out the reaction liquid, cooling the reaction liquid to room temperature, dropwise adding the reaction liquid into 300mL of methanol under the mechanical stirring condition of 300r/min, carrying out suction filtration and precipitation, re-dissolving the solid phase substance into 300mL of chloroform, then precipitating with 300mL of methanol to remove unreacted raw materials, carrying out 7000r/min centrifugal separation, and drying at 80 ℃ for 48 hours to obtain the white solid of the polysiloxane side chain liquid crystal polymer.
Step eight, preparing the polysiloxane side chain liquid crystal polymer modified by triple bonds: and dissolving 467mg and 0.044mmol of p- (dibutylamino) phenylacetylene in the seventh step in 10mL of triethylamine and tetrahydrofuran solution with the volume ratio of 1:1, introducing argon gas at 1L/min, ultrasonically removing oxygen for 30min under the condition of 40KHz, adding 0.2mmol of bis (triphenylphosphine) palladium dichloride and 0.2mmol of cuprous iodide, stirring at 300r/min, refluxing and reacting at 40 ℃ in a water bath for 12h, centrifugally separating at 7000r/min to remove solids, dropwise adding the liquid product into 300mL of methanol solution under the stirring of 300r/min, centrifugally separating at 7000r/min, redissolving the precipitate in 300mL of trichloromethane, and precipitating with 300mL of methanol to remove unreacted raw materials to obtain the triple bond modified polysiloxane side chain liquid crystal polymer.
Step nine, preparing click-modified polysiloxane side chain liquid crystal polymer through click reaction: and (3) dissolving the product obtained in the step eight in 10mL of dichloromethane, dissolving 6mg of tetracyanoethylene in another 10mL of dichloromethane, and mixing the two solutions to obtain the click-modified polysiloxane side chain liquid crystal polymer sample 5 with the yield of 88%.
The liquid crystal phase state of the obtained white solid sample 5 of the polysiloxane side chain liquid crystal polymer is a low-temperature smectic E phase, a high-temperature monolayer smectic A phase and good nonlinear optical characteristics.
Example 6: preparation of click-modified polysiloxane side chain liquid crystal polymer sample 6
Where m is 3, p is 3, q is 3, n is 4, and R is
Figure GDA0003271644060000271
X: y: z 80:18:2, X tetracyanoethylene for example, polysiloxane side chain liquid crystals are describedA specific synthesis method of the polymer sample 6, wherein the specific synthesis scheme is shown in fig. 1:
step one, preparation of p-alkenyloxy benzoic acid: putting a mixture of 0.01mol of ethyl p-hydroxybenzoate, 0.015mol of 3-bromo-1-propylene, 0.01mol of solid potassium carbonate and 250mL of acetone into a 500mL flask, then moving the flask into a microwave reactor with ultraviolet and Nd, YAG solid pulse laser and normal pressure and backflow, and only starting microwave energy, wherein the microwave power is 650W, the frequency is 2450MHz, boiling and heating are carried out for 24 hours, the microwave heating process is accompanied with backflow, when the temperature in the microwave reactor exceeds a set temperature, a microwave generator is closed to cool, when the temperature is lower than the set temperature, the microwave generator is opened to heat, and a backflow condensing device is started in the reaction process; after the microwave is finished, filtering the obtained product, carrying out rotary evaporation at the speed of 90r/min at the temperature of 30 ℃ until acetone is removed, adding 200mL of diethyl ether into the product, adding 100mL of distilled water, stirring for 10min, standing for layering, separating an diethyl ether layer from a distilled water layer, extracting the diethyl ether layer twice by using 100mL of 10% NaOH aqueous solution, evaporating the diethyl ether at the temperature of 40 ℃, putting the obtained residue into 300mL of a mixture of ethanol containing 30g of KOH and water in a mass ratio of 1:2, boiling until the residue is dissolved, cooling the solution to room temperature, stirring the solution at the speed of 300r/min, adding 6mol/L hydrochloric acid solution, adjusting the pH to 2, filtering the obtained product to obtain a crude product, stirring and washing the filtered solid phase by using 300mL of distilled water for 30min, adding the washed product into ethanol which is heated, refluxed and stirred at the temperature of 80 ℃, and (3) rapidly cooling the product in a refrigerator at 5 ℃ for 30min until the product is not dissolved any more, filtering the mixture to obtain white needle-shaped crystals, and drying the crystal product at 40 ℃ for 48h in vacuum to obtain the p-alkenyloxybenzoic acid.
Step two, preparation of 4-allyloxybenzoyl chloride: adding 0.05mol of white needle-shaped crystal obtained in the step one and 10mL of thionyl chloride into a 30mL flask provided with a hydrogen chloride absorber, transferring the flask into a normal-pressure reflux microwave reactor with ultraviolet and Nd: YAG solid pulse laser, starting ultraviolet light and laser irradiation on the flask, wherein the ultraviolet wavelength is 365nm, and the power is 300mW/cm2Nd is YAG solid pulse laser wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.2mm, weightComplex frequency 20Hz, power density 1.0X 106W/cm2The light spot of the laser focus is 2mm below the liquid level, the irradiation time is 6h, the irradiation temperature is 40 ℃, the mixture is stirred at the speed of 300r/min in the irradiation process, and reflux condensation is carried out during heating; then the solution was taken out and distilled under reduced pressure at-0.09 MPa and 40 ℃ for 10min to remove excess thionyl chloride, yielding 4-allyloxybenzoyl chloride.
Step three, synthesizing a liquid crystal monomer (M1) through an esterification reaction: 4-allyloxybenzoyl chloride was dissolved in 10mL of dry dichloromethane and added dropwise to a cold solution of 100mL of dichloromethane containing 0.06mol of cholesterol and 8mL of pyridine, transferred to an atmospheric pressure reflux microwave reactor with UV and laser, and the flask was irradiated with UV light and laser while turning on the UV light irradiation at 365nm, 300mW/cm power2YAG solid pulse laser wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.2mm, repetition frequency 20Hz, power density 1.0 × 106W/cm2The light spot of the laser focus is 2mm below the liquid level, the irradiation time is 6h, the irradiation temperature is 40 ℃, the mixture is stirred at the speed of 300r/min in the irradiation process, the precipitate is removed by filtration, 300mL of ethanol is added into the filtrate to precipitate a crude product, the crude product is recrystallized from the ethanol, and the obtained white powder product is dried in a vacuum drying oven at the temperature of 70 ℃ for 24h to obtain the liquid crystal monomer M1.
Step four, synthesizing a liquid crystal monomer (M2) through an esterification reaction: 4-allyloxybenzoyl chloride was dissolved in 10mL of dry dichloromethane, added dropwise to a cold solution of 100mL of dichloromethane containing 0.06mol of p-hydroxyanisole and 8mL of pyridine, transferred into an atmospheric pressure reflux microwave reactor with UV and laser, and the flask was irradiated with UV and laser light with a UV wavelength of 365nm and a power of 300mW/cm2YAG solid pulse laser wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.2mm, repetition frequency 20Hz, power density 1.0 × 106W/cm2The laser focus spot was 2mm below the liquid level, the irradiation time was 6h, the irradiation temperature was 40 ℃, the mixture was stirred at 300r/min during the irradiation, the precipitate was removed by filtration, 300mL ethanol was added to the filtrate to precipitate the crude product, and recrystallization from ethanol gave a white powder product at 70 ℃Drying in a vacuum drying oven at the temperature of 24 hours to obtain the liquid crystal monomer M2.
Step five, preparation of p-iodoallyloxybenzene (M3): dissolving 0.025mol of p-iodophenol in 50mL of acetonitrile, then placing the solution in a 100mL flask, adding 0.03mol of 3-bromopropylene and 3.5g of potassium carbonate, heating the solution to 85 ℃, stirring the solution at 300r/min, carrying out reflux reaction for 2h under the condition of water bath heat preservation, filtering the reaction product to remove solids, carrying out rotary evaporation for 30min at the temperature of 60 ℃ under the pressure of-0.09 MPa to remove redundant solvent, and then carrying out silica gel column chromatography purification by using a mixture of dichloromethane and petroleum ether in a volume ratio of 1:2 as an eluent to obtain a white product of p-iodoallyloxybenzene M3.
Step six, preparation of p- (dibutylamino) phenylacetylene (M4): dissolving 20mmol of p-iodoaniline and 80mmol of bromobutane in 65mLN, N-dimethylformamide, then adding 60mmol of potassium carbonate and 60mmol of potassium iodide, introducing argon gas for 30min at 1L/min in an ultrasonic cleaner to remove oxygen, carrying out water bath reflux reaction on a 150mL flask containing the mixture for 20h at 120 ℃, plugging a reflux condenser tube orifice with a rubber plug, carrying out suction filtration to remove solids after reaction, extracting with 200mL of water to remove N, N-dimethylformamide, carrying out rotary evaporation for 30min at the speed of-0.09 MPa, 40 ℃ and 90r/min to remove redundant solvent, and then carrying out silica gel column chromatography purification by taking a mixture of dichloromethane and petroleum ether as eluent with the volume ratio of 1:6 to obtain a product; introducing argon into 80mL of a mixed solution of triethylamine and tetrahydrofuran with the volume ratio of 1:1 of 0.002mol, simultaneously carrying out ultrasonic deoxidization for 30min at 40KHz for 1L/min, then adding 0.003mol of trimethylsilyl acetylene TMSA, 0.2mmol of bis-triphenylphosphine palladium dichloride and 0.2mmol of cuprous iodide, stirring in a 150mL flask filled with the mixture at the speed of 300r/min, carrying out water bath reflux reaction for 10h at 40 ℃, plugging a reflux condenser pipe orifice with a rubber plug, carrying out suction filtration to remove solids after reaction, carrying out vacuum rotary evaporation for 30min at the speed of-0.09 MPa, 60 ℃ and 90r/min to remove more solvents, and then carrying out silica gel column chromatography purification by taking a mixture of dichloromethane and petroleum ether with the volume ratio of 1:6 as an eluent to obtain yellow liquid; dissolving 0.005mol of the product and 0.005mol of potassium carbonate in 50mL of a mixture of tetrahydrofuran and absolute ethyl alcohol with the volume ratio of 7:3, transferring the mixture into a 100mL flask, stirring the mixture in the flask at 300r/min, carrying out reflux reaction at room temperature for 3h, stopping the reaction, carrying out suction filtration to remove solids, carrying out rotary evaporation at-0.09 MPa and 50 ℃ for 30min to remove excessive solvent, removing the solvent, and carrying out dichloromethane column chromatography to obtain a yellow oily liquid.
Step seven, polysiloxane side chain liquid crystal polymer white solid: adding 1.76mmol of 4-allyloxybenzoic acid cholesteryl ester, 0.396mmol of 4-allyloxybenzoic acid 4-methoxyphenol ester, 0.044mmol of p-iodoallyloxybenzene and 60ppm of platinum catalyst into a flask, dissolving in 20mL of toluene, evacuating the mixture through a double-row pipe, filling nitrogen, discharging oxygen, transferring the mixture into a normal-pressure belt reflux microwave reactor with ultraviolet and Nd: YAG solid pulse laser, and irradiating the solution with Nd: YAG solid pulse laser, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.2mm in spot diameter, 20Hz in repetition frequency and 1.0X 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level, and the irradiation time is 0.5 h; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the intensity is 5mW/cm2The irradiation time is 0.5 h; simultaneously carrying out laser and ultraviolet irradiation, synchronously starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 650W, the microwave time is 0.5h, the heating temperature is 60 ℃, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to cool, when the temperature is lower than the set temperature, the microwave generator is opened to heat, reflux condensation is started, and the mouth of a reflux condensation pipe is blocked by a rubber plug, so that air is prevented from entering; after the reaction is finished, 275.2mg of polymethylhydrosilicone oil PMHS is added under the condition of keeping vacuum, and then Nd: YAG solid pulse laser is used for irradiating the solution, wherein the laser parameters are that the wavelength is 1.06 mu m, the pulse width is 1.2ms, the spot diameter is 0.2mm, the repetition frequency is 20Hz, and the power density is 1.0 multiplied by 106W/cm2The light spot of the laser focus is 2mm below the liquid level, and the irradiation time is 8 h; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the intensity is 5mW/cm2The irradiation time is 8 h; simultaneously performing laser and ultraviolet irradiation, synchronously starting microwave heating with microwave frequency of 2450MHz, microwave power of 650W and microwave time of 8h, heating temperature of 80 deg.C, turning off microwave generator when the temperature in the microwave reactor exceeds a predetermined temperature, cooling, and turning on microwave generator when the temperature is lower than the predetermined temperatureHeating the microwave generator; after the reaction is finished, taking out the reaction liquid, cooling the reaction liquid to room temperature, dropwise adding the reaction liquid into 300mL of methanol under the mechanical stirring condition of 300r/min, carrying out suction filtration and precipitation, re-dissolving the solid phase substance into 300mL of chloroform, then precipitating with 300mL of methanol to remove unreacted raw materials, carrying out 7000r/min centrifugal separation, and drying at 80 ℃ for 48 hours to obtain the white solid of the polysiloxane side chain liquid crystal polymer.
Step eight, preparing the polysiloxane side chain liquid crystal polymer modified by triple bonds: and (2) dissolving 630mg and 0.044mmol of p- (dibutylamino) phenylacetylene obtained in the seventh step in 10mL of triethylamine and tetrahydrofuran solution with the volume ratio of 1:1, introducing argon gas at 1L/min, ultrasonically removing oxygen for 30min under the condition of 40KHz, adding 0.2mmol of bis (triphenylphosphine) palladium dichloride and 0.2mmol of cuprous iodide, stirring at 300r/min, carrying out reflux reaction at 40 ℃ in a water bath for 12h, centrifugally separating at 7000r/min to remove solids, dropwise adding the liquid product into 300mL of methanol solution under stirring at the rotating speed of 300r/min, centrifugally separating at 7000r/min, redissolving the precipitate in 300mL of trichloromethane, and precipitating with 300mL of methanol to remove unreacted raw materials to obtain the triple bond modified polysiloxane side chain liquid crystal polymer.
Step nine, click reaction preparation of click-modified polysiloxane side chain liquid crystal polymer
And (3) dissolving the product obtained in the step eight in 10mL of dichloromethane, dissolving 6mg of tetracyanoethylene in another 10mL of dichloromethane, and mixing the two solutions to obtain the click-modified polysiloxane side chain liquid crystal polymer sample 6 with the yield of 86%.
The liquid crystal phase of the obtained white solid sample 6 of polysiloxane side chain liquid crystal polymer is changed from a double-layer smectic A phase when the temperature is raised, and the nonlinear optical property is good.
Example 7: preparation of click-modified polysiloxane side chain liquid crystal polymer sample 7
Where m is 5, p is 5, q is 5, and R is
Figure GDA0003271644060000311
X, y, z is 100:0:0, X is tetracyanoethylene, sample polysiloxane side chain liquid crystal polymer is introduced7, scheme 1:
step one, preparation of p-alkenyloxy benzoic acid: putting a mixture of 0.01mol of ethyl p-hydroxybenzoate, 0.015mol of 5-bromo-1-pentene, 0.01mol of solid potassium carbonate and 250mL of acetone into a 500mL flask, then moving the flask into a normal-pressure microwave reactor with ultraviolet and Nd, YAG solid pulse laser, and only starting microwave energy, wherein the microwave power is 650W, the frequency is 2450MHz, boiling and heating are carried out for 24 hours, the microwave heating process is accompanied with reflux, when the temperature in the microwave reactor exceeds a set temperature, a microwave generator is closed to cool, when the temperature is lower than the set temperature, the microwave generator is opened to heat, and a reflux condensing device is started in the reaction process; after the microwave is finished, filtering the obtained product, carrying out rotary evaporation at the speed of 90r/min at the temperature of 30 ℃ until acetone is removed, adding 200mL of diethyl ether into the product, adding 100mL of distilled water, stirring for 5min, standing for layering, separating an diethyl ether layer from a distilled water layer, extracting the diethyl ether layer twice by using 100mL of 10% NaOH aqueous solution, evaporating the diethyl ether at the temperature of 40 ℃, putting the obtained residue into 300mL of a mixture of ethanol containing 30g of KOH and water in a mass ratio of 1:2, boiling until the residue is dissolved, cooling the solution to room temperature, stirring the solution at the speed of 300r/min, adding 6mol/L hydrochloric acid solution, adjusting the pH to 2, filtering the obtained product to obtain a crude product, stirring and washing the filtered solid phase by using 300mL of distilled water for 30min, adding the washed product into ethanol which is heated, refluxed and stirred at the temperature of 80 ℃, and (3) rapidly cooling the product in a refrigerator at 5 ℃ for 30min until the product is not dissolved any more, filtering the mixture to obtain white needle-shaped crystals, and drying the crystal product at 40 ℃ for 48h in vacuum to obtain the p-alkenyloxybenzoic acid.
Step two, preparation of 4-allyloxybenzoyl chloride: adding 0.05mol of white needle-shaped crystal obtained in the step one and 10mL of thionyl chloride into a 30mL flask provided with a hydrogen chloride absorber, transferring the flask into a normal-pressure reflux microwave reactor with ultraviolet and Nd: YAG solid pulse laser, starting ultraviolet light and laser irradiation on the flask, wherein the ultraviolet wavelength is 365nm, and the power is 300mW/cm2The laser wavelength of Nd-YAG solid pulse laser is 1.06 μm, the pulse width is 1.2ms, the spot diameter is 0.2mm, the repetition frequency is 20Hz,power density 1.0X 106W/cm2The light spot of the laser focus is 2mm below the liquid level, the irradiation time is 6h, the irradiation temperature is 40 ℃, the mixture is stirred at the speed of 300r/min in the irradiation process, and reflux condensation is carried out during heating; then the solution was taken out and distilled under reduced pressure at-0.09 MPa and 40 ℃ for 10min to remove excess thionyl chloride, yielding 4-allyloxybenzoyl chloride.
Step three, synthesizing a liquid crystal monomer (M1) through an esterification reaction: 4-allyloxybenzoyl chloride was dissolved in 10mL of dry dichloromethane and added dropwise to a cold solution of 100mL of dichloromethane containing 0.06mol of cholesterol and 8mL of pyridine, transferred to an atmospheric pressure reflux microwave reactor with UV and laser, and the flask was irradiated with UV light and laser while turning on the UV light irradiation at 365nm, 300mW/cm power2YAG solid pulse laser wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.2mm, repetition frequency 20Hz, power density 1.0 × 106W/cm2The light spot of the laser focus is 2mm below the liquid level, the irradiation time is 6h, the irradiation temperature is 40 ℃, the mixture is stirred at the speed of 300r/min in the irradiation process, the precipitate is removed by filtration, 300mL of ethanol is added into the filtrate to precipitate a crude product, the crude product is recrystallized from the ethanol, and the obtained white powder product is dried in a vacuum drying oven at the temperature of 70 ℃ for 24h to obtain the liquid crystal monomer M1.
Step four, polysiloxane side chain liquid crystal polymer white solid: adding 2.2mmol 4-allyl amyl oxy benzoic acid cholesteryl ester and 60ppm platinum catalyst into a flask, dissolving in 20mL toluene, evacuating the flask through a double-row pipe, charging nitrogen gas to remove oxygen, transferring into a normal pressure belt reflux microwave reactor with ultraviolet and Nd: YAG solid pulse laser, irradiating the solution with Nd: YAG solid pulse laser, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.2mm in spot diameter, 20Hz in repetition frequency, 1.0X 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level, and the irradiation time is 0.5 h; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the intensity is 8mW/cm2The irradiation time is 0.5 h; simultaneously, the laser and the ultraviolet irradiation synchronously start the microwave heating, the microwave frequency is 2450MHz, and the microwave power is 650W, microwave time is 0.5h, heating temperature is 60 ℃, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, when the temperature in the microwave reactor is lower than the set temperature, the microwave generator is opened to increase the temperature, reflux condensation is started, and the opening of a reflux condensation pipe is blocked by a rubber plug to prevent air from entering; after the reaction is finished, 275.2mg of polymethylhydrosilicone oil PMHS is added under the condition of keeping vacuum, and then Nd: YAG solid pulse laser is used for irradiating the solution, wherein the laser parameters are that the wavelength is 1.06 mu m, the pulse width is 1.2ms, the spot diameter is 0.2mm, the repetition frequency is 20Hz, and the power density is 1.0 multiplied by 106W/cm2The light spot of the laser focus is 2mm below the liquid level, and the irradiation time is 8 h; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the intensity is 8mW/cm2The irradiation time is 8 h; simultaneously performing laser and ultraviolet irradiation, synchronously starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 650W, the microwave time is 8h, the heating temperature is 80 ℃, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, and when the temperature is lower than the set temperature, the microwave generator is opened to increase the temperature; after the reaction is finished, taking out the reaction liquid, cooling the reaction liquid to room temperature, dropwise adding the reaction liquid into 300mL of methanol under the mechanical stirring condition of 300r/min, carrying out suction filtration and precipitation, re-dissolving a solid phase substance into 300mL of chloroform, then precipitating with 300mL of methanol to remove unreacted raw materials, carrying out 7000r/min centrifugal separation, and drying at 80 ℃ for 48 hours to obtain a white solid sample 7 of the polysiloxane side chain liquid crystal polymer, wherein the yield is 88%.
The liquid crystal phase state of the obtained white solid sample 7 of polysiloxane side chain liquid crystal polymer is smectic phase A, and the nonlinear optical property is poor.
Example 8: preparation of white solid sample 8 of polysiloxane side chain liquid crystalline Polymer
Where m is 5, p is 5, q is 5, and R is
Figure GDA0003271644060000331
X, y, z is 0:100:0, X is 7,7,8, 8-tetracyanoquinodimethane, a specific synthesis method of polysiloxane side chain liquid crystal polymer sample 8 is described, and a specific synthesis scheme is shown in fig. 1:
step one, preparation of p-alkenyloxy benzoic acid: putting a mixture of 0.01mol of ethyl p-hydroxybenzoate, 0.015mol of 5-bromo-1-pentene, 0.01mol of solid potassium carbonate and 250mL of acetone into a 500mL flask, then moving the flask into a normal-pressure microwave reactor with ultraviolet and Nd, YAG solid pulse laser, and only starting microwave energy, wherein the microwave power is 650W, the frequency is 2450MHz, boiling and heating are carried out for 24 hours, the microwave heating process is accompanied with reflux, when the temperature in the microwave reactor exceeds a set temperature, a microwave generator is closed to cool, when the temperature is lower than the set temperature, the microwave generator is opened to heat, and a reflux condensing device is started in the reaction process; after the microwave is finished, filtering the obtained product, carrying out rotary evaporation at the speed of 90r/min at the temperature of 30 ℃ until acetone is removed, adding 200mL of diethyl ether into the product, adding 100mL of distilled water, stirring for 5min, standing for layering, separating an diethyl ether layer from a distilled water layer, extracting the diethyl ether layer twice by using 100mL of 10% NaOH aqueous solution, evaporating the diethyl ether at the temperature of 40 ℃, putting the obtained residue into 300mL of a mixture of ethanol containing 30g of KOH and water in a mass ratio of 1:2, boiling until the residue is dissolved, cooling the solution to room temperature, stirring the solution at the speed of 300r/min, adding 6mol/L hydrochloric acid solution, adjusting the pH to 2, filtering the obtained product to obtain a crude product, stirring and washing the filtered solid phase by using 300mL of distilled water for 30min, adding the washed product into ethanol which is heated, refluxed and stirred at the temperature of 80 ℃, and (3) rapidly cooling the product in a refrigerator at 5 ℃ for 30min until the product is not dissolved any more, filtering the mixture to obtain white needle-shaped crystals, and drying the crystal product at 40 ℃ for 48h in vacuum to obtain the p-alkenyloxybenzoic acid.
Step two, preparation of 4-allyloxybenzoyl chloride: adding 0.05mol of white needle-shaped crystal obtained in the step one and 10mL of thionyl chloride into a 30mL flask provided with a hydrogen chloride absorber, transferring the flask into a normal-pressure reflux microwave reactor with ultraviolet and Nd: YAG solid pulse laser, starting ultraviolet light and laser irradiation on the flask, wherein the ultraviolet wavelength is 365nm, and the power is 300mW/cm2YAG solid pulse laser wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.2mm, repetition frequency 20Hz, power density 1.0 × 106W/cm2The light spot of the laser focus is 2mm below the liquid level, and the irradiation time is 6h, irradiating at 40 ℃, stirring the mixture at the speed of 300r/min during the irradiation, and heating while carrying out reflux condensation; then the solution was taken out and distilled under reduced pressure at-0.09 MPa and 40 ℃ for 10min to remove excess thionyl chloride, yielding 4-allyloxybenzoyl chloride.
Step three, synthesizing a liquid crystal monomer (M2) through an esterification reaction: 4-allyloxybenzoyl chloride was dissolved in 10mL of dry dichloromethane and added dropwise to a cold solution of 100mL of dichloromethane containing 0.06mol of p-hydroxybenzonitrile and 8mL of pyridine, transferred into an atmospheric pressure microwave reactor with reflux of UV and laser, and the flask was irradiated with UV light and laser, wherein the UV wavelength was 365nm and the power was 300mW/cm2YAG solid pulse laser wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.2mm, repetition frequency 20Hz, power density 1.0 × 106W/cm2The light spot of the laser focus is 2mm below the liquid level, the irradiation time is 6h, the irradiation temperature is 40 ℃, the mixture is stirred at the speed of 300r/min in the irradiation process, the precipitate is removed by filtration, 300mL of ethanol is added into the filtrate to precipitate a crude product, the crude product is recrystallized from the ethanol, and the obtained white powder product is dried in a vacuum drying oven at the temperature of 70 ℃ for 24h to obtain the liquid crystal monomer M2.
Step four, polysiloxane side chain liquid crystal polymer white solid: adding 2.2mmol of 4-allyloxybenzoic acid 4-cyanophenol ester and 60ppm of platinum catalyst into a flask, dissolving in 20mL of toluene, evacuating the mixture through a double-row pipe, filling nitrogen, discharging oxygen, transferring the mixture into a normal-pressure belt reflux microwave reactor with ultraviolet and Nd-YAG solid pulse laser, and irradiating the solution with the Nd-YAG solid pulse laser, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.2mm in spot diameter, 20Hz in repetition frequency and 1.0X 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level, and the irradiation time is 0.5 h; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the intensity is 8mW/cm2The irradiation time is 0.5 h; simultaneously, the laser and the ultraviolet irradiation are simultaneously started, the microwave heating is started, the microwave frequency is 2450MHz, the microwave power is 650W, the microwave time is 0.5h, the heating temperature is 60 ℃, and the microwave reactor is closed when the temperature in the microwave reactor exceeds the set temperatureWhen the temperature of the microwave generator is reduced and is lower than the set temperature, the microwave generator is opened to heat, reflux condensation is started, and the opening of a reflux condenser pipe is blocked by a rubber plug, so that air is prevented from entering; after the reaction is finished, 275.2mg of polymethylhydrosilicone oil PMHS is added under the condition of keeping vacuum, and then Nd: YAG solid pulse laser is used for irradiating the solution, wherein the laser parameters are that the wavelength is 1.06 mu m, the pulse width is 1.2ms, the spot diameter is 0.2mm, the repetition frequency is 20Hz, and the power density is 1.0 multiplied by 106W/cm2The light spot of the laser focus is 2mm below the liquid level, and the irradiation time is 8 h; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the intensity is 10mW/cm2The irradiation time is 8 h; simultaneously performing laser and ultraviolet irradiation, synchronously starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 650W, the microwave time is 8h, the heating temperature is 80 ℃, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, and when the temperature is lower than the set temperature, the microwave generator is opened to increase the temperature; after the reaction is finished, taking out the reaction liquid, cooling the reaction liquid to room temperature, dropwise adding the reaction liquid into 300mL of methanol under the condition of mechanical stirring at 300r/min, carrying out suction filtration and precipitation, re-dissolving a solid phase substance into 300mL of trichloromethane, then precipitating with 300mL of methanol to remove unreacted raw materials, and drying at 80 ℃ for 48 hours to obtain a white solid sample 8 of the polysiloxane side chain liquid crystal polymer, wherein the yield is 86%.
The liquid crystal phase state of the obtained white solid sample 8 of polysiloxane side chain liquid crystal polymer is smectic phase A, and the nonlinear optical property is poor.
Example 9: preparation of white solid sample 9 of polysiloxane side chain liquid crystalline Polymer
Where m is 5, p is 5, q is 5, and R is
Figure GDA0003271644060000351
X, y, z is 50:50:0, X is 7,7,8, 8-tetracyanoquinodimethane, a specific synthesis method of polysiloxane side chain liquid crystal polymer sample 9 is described, and a specific synthesis scheme is shown in fig. 1:
step one, preparation of p-alkenyloxy benzoic acid: putting a mixture of 0.01mol of ethyl p-hydroxybenzoate, 0.015mol of 5-bromo-1-pentene, 0.01mol of solid potassium carbonate and 250mL of acetone into a 500mL flask, then moving the flask into a normal-pressure microwave reactor with ultraviolet and Nd, YAG solid pulse laser, and only starting microwave energy, wherein the microwave power is 650W, the frequency is 2450MHz, boiling and heating are carried out for 24 hours, the microwave heating process is accompanied with reflux, when the temperature in the microwave reactor exceeds a set temperature, a microwave generator is closed to cool, when the temperature is lower than the set temperature, the microwave generator is opened to heat, and a reflux condensing device is started in the reaction process; after the microwave is finished, filtering the obtained product, carrying out rotary evaporation at the speed of 90r/min at the temperature of 30 ℃ until acetone is removed, adding 200mL of diethyl ether into the product, adding 100mL of distilled water, stirring for 10min, standing for layering, separating an diethyl ether layer from a distilled water layer, extracting the diethyl ether layer twice by using 100mL of 10% NaOH aqueous solution, evaporating the diethyl ether at the temperature of 40 ℃, putting the obtained residue into 300mL of a mixture of ethanol containing 30g of KOH and water in a mass ratio of 1:2, boiling until the residue is dissolved, cooling the solution to room temperature, stirring the solution at the speed of 300r/min, adding 6mol/L hydrochloric acid solution, adjusting the pH to 2, filtering the obtained product to obtain a crude product, stirring and washing the filtered solid phase by using 300mL of distilled water for 30min, adding the washed product into ethanol which is heated, refluxed and stirred at the temperature of 80 ℃, and (3) rapidly cooling the product in a refrigerator at 5 ℃ for 30min until the product is not dissolved any more, filtering the mixture to obtain white needle-shaped crystals, and drying the crystal product at 40 ℃ for 48h in vacuum to obtain the p-alkenyloxybenzoic acid.
Step two, preparation of 4-allyloxybenzoyl chloride: adding 0.05mol of white needle-shaped crystal obtained in the step one and 10mL of thionyl chloride into a 30mL flask provided with a hydrogen chloride absorber, transferring the flask into a normal-pressure reflux microwave reactor with ultraviolet and Nd: YAG solid pulse laser, starting ultraviolet light and laser irradiation on the flask, wherein the ultraviolet wavelength is 365nm, and the power is 300mW/cm2YAG solid pulse laser wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.2mm, repetition frequency 20Hz, power density 1.0 × 106W/cm2The light spot of the laser focus is 2mm below the liquid level, the irradiation time is 6h, the irradiation temperature is 40 ℃, the mixture is stirred at the speed of 300r/min in the irradiation process, and reflux condensation is carried out during heating; then taking outDistilling the solution at-0.09 MPa and 40 deg.C under reduced pressure for 10min to remove excess thionyl chloride to obtain 4-allyloxybenzoyl chloride.
Step three, synthesizing a liquid crystal monomer (M1) through an esterification reaction: 4-allyloxybenzoyl chloride was dissolved in 10mL of dry dichloromethane and added dropwise to a cold solution of 100mL dichloromethane containing 0.05mol cholesterol and 8mL pyridine, transferred to an atmospheric pressure reflux microwave reactor with UV and laser, and the flask was irradiated with UV light and laser while turning on the UV light irradiation at 365nm, 300mW/cm power2YAG solid pulse laser wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.2mm, repetition frequency 20Hz, power density 1.0 × 106W/cm2The light spot of the laser focus is 2mm below the liquid level, the irradiation time is 6h, the irradiation temperature is 40 ℃, the mixture is stirred at the speed of 300r/min in the irradiation process, the precipitate is removed by filtration, 300mL of ethanol is added into the filtrate to precipitate a crude product, the crude product is recrystallized from the ethanol, and the obtained white powder product is dried in a vacuum drying oven at the temperature of 70 ℃ for 24h to obtain the liquid crystal monomer M1.
Step four, synthesizing a liquid crystal monomer (M2) through an esterification reaction: 4-allyloxybenzoyl chloride was dissolved in 10mL of dry dichloromethane and added dropwise to a cold solution of 100mL of dichloromethane containing 0.06mol of 4-phenylphenol and 8mL of pyridine, transferred into an atmospheric pressure reflux microwave reactor with UV and laser irradiation at 365nm and 300mW/cm power, and the flask was opened to UV and laser irradiation2YAG solid pulse laser wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.2mm, repetition frequency 20Hz, power density 1.0 × 106W/cm2The light spot of the laser focus is 2mm below the liquid level, the irradiation time is 6h, the irradiation temperature is 40 ℃, the mixture is stirred at the speed of 300r/min in the irradiation process, the precipitate is removed by filtration, 300mL of ethanol is added into the filtrate to precipitate a crude product, the crude product is recrystallized from the ethanol, and the obtained white powder product is dried in a vacuum drying oven at the temperature of 70 ℃ for 24h to obtain the liquid crystal monomer M2.
Step five, polysiloxane side chain liquid crystal polymer white solid: 1.1mmol of 4-pentenyloxybenzoic acid cholesteryl ester and 1.1mmol of [1,1' -biphenyl were added to the flask]Dissolving 4-yl 4- (allyloxy) benzoate and 60ppm platinum catalyst in 20mL toluene, evacuating through double-row pipe, charging nitrogen gas to remove oxygen, transferring into normal pressure belt reflux microwave reactor with ultraviolet and Nd: YAG solid pulse laser, irradiating the solution with Nd: YAG solid pulse laser with laser parameters of 1.06 μm wavelength, 1.2ms pulse width, 0.2mm spot diameter, 20Hz repetition frequency and 1.0 × 10 power density6W/cm2The light spot of the laser focus is 2mm below the liquid level, and the irradiation time is 0.5 h; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the intensity is 8mW/cm2The irradiation time is 0.5 h; simultaneously carrying out laser and ultraviolet irradiation, synchronously starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 650W, the microwave time is 0.5h, the heating temperature is 60 ℃, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to cool, when the temperature is lower than the set temperature, the microwave generator is opened to heat, reflux condensation is started, and the mouth of a reflux condensation pipe is blocked by a rubber plug, so that air is prevented from entering; after the reaction is finished, 275.2mg of polymethylhydrosilicone oil PMHS is added under the condition of keeping vacuum, and then Nd: YAG solid pulse laser is used for irradiating the solution, wherein the laser parameters are that the wavelength is 1.06 mu m, the pulse width is 1.2ms, the spot diameter is 0.2mm, the repetition frequency is 20Hz, and the power density is 1.0 multiplied by 106W/cm2The light spot of the laser focus is 2mm below the liquid level, and the irradiation time is 8 h; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 365nm, and the intensity is 10mW/cm2The irradiation time is 8 h; simultaneously performing laser and ultraviolet irradiation, synchronously starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 650W, the microwave time is 8h, the heating temperature is 80 ℃, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, and when the temperature is lower than the set temperature, the microwave generator is opened to increase the temperature; after the reaction is finished, taking out the reaction liquid, cooling the reaction liquid to room temperature, dropwise adding the reaction liquid into 300mL of methanol under the condition of mechanical stirring at 300r/min, carrying out suction filtration and precipitation, re-dissolving the solid phase substance into 300mL of trichloromethane, then precipitating with 300mL of methanol to remove unreacted raw materials, and drying at 80 ℃ for 48 hours to obtain the white solid sample 9 of the polysiloxane side chain liquid crystal polymer, wherein the yield is 85 percent。
The liquid crystal phase state of the obtained white solid sample 9 of polysiloxane side chain liquid crystal polymer is smectic phase A, and the nonlinear optical property is poor.
TABLE 1 summary of the performance test results for the polysiloxane side chain liquid crystalline polymer samples prepared in each example
Examples Liquid crystal phase Non-linear optical characteristics
1 Is free of Good effect
2 Smectic A phase Good effect
3 Smectic A phase Good effect
4 Single or double smectic A phases Good effect
5 Low temperature smectic E phase, high temperature monolayer smectic A phase Good effect
6 The double layer changes into single layer smectic A phase at the time of temperature rise Good effect
7 Smectic A phase Difference (D)
8 Smectic A phase Difference (D)
9 Smectic A phase Difference (D)

Claims (5)

1. A preparation method of a click-modified polysiloxane side chain liquid crystal polymer is disclosed, wherein the structural general formula of the polysiloxane side chain liquid crystal polymer is as follows:
Figure FDA0003271644050000011
wherein: m, p and q are integers more than or equal to 3, and n is an integer between 0 and 16;
r is selected from
Figure FDA0003271644050000012
In the above-mentioned manner, the first and second substrates are,
one of the used liquid crystal monomers is cholesteryl p-alkenyloxybenzoate, and the structural formula is as follows:
Figure FDA0003271644050000013
the other liquid crystal monomer is p-alkenyloxy benzoic acid alcohol ester, and the structural formula is as follows:
Figure FDA0003271644050000021
wherein R is
Figure FDA0003271644050000022
One of (1);
the click modification moiety used has the general structural formula:
Figure FDA0003271644050000023
a preparation method of a click-modified polysiloxane side chain liquid crystal polymer comprises the following steps of carrying out hydrosilylation on polymethyl hydrogen-containing silicone oil, p-alkenyloxy benzoic acid cholesterol ester and/or p-alkenyloxy benzoic acid alcohol ester and p-iodoallyloxy benzene, reacting with p- (dibutylamino) phenyl acetylene, and finally carrying out click reaction with 7,7,8, 8-tetracyano-p-quinodimethane, tetracyanoethylene, 2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanoquinodimethane, wherein the preparation steps are specifically as follows:
step one, preparation of p-alkenyloxy benzoic acid
Putting a mixture of 0.001-0.100 mol of ethyl p-hydroxybenzoate, 0.001-0.100 mol of alkene bromide, 0.001-0.100 mol of solid potassium carbonate and 100-500 mL of acetone into a 100-1000 mL flask, then moving the flask into a normal-pressure reflux microwave reactor with ultraviolet and Nd, YAG solid pulse laser, and only starting microwave energy, wherein the microwave power is 500-1000W, the frequency is 2450MHz, the heating temperature is 25-200 ℃, the heating time is 1-36 h, reflux condensation is carried out during microwave heating, when the temperature in the microwave reactor exceeds a preset temperature, the microwave generator is closed to reduce the temperature, when the temperature is lower than the preset temperature, the microwave generator is opened to increase the temperature, and a reflux condensing device is started in the reaction process; after the microwave is finished, filtering the obtained product, carrying out rotary evaporation at the speed of 80-100 r/min at the temperature of 30 ℃ until acetone is removed, adding 100-300 mL of diethyl ether into the product, adding 100mL of distilled water, stirring for 5-10 min, standing for layering, separating an ether layer from a distilled water layer, extracting the ether layer twice by using 50-200 mL of 5-30% NaOH aqueous solution, evaporating the diethyl ether at the temperature of 35-40 ℃, adding the obtained residue into 300mL of ethanol containing 30g of KOH according to the mass ratio of 1:2, boiling until the residue is dissolved, cooling the solution to room temperature, stirring the solution at the speed of 100-2000 r/min, simultaneously adding 6mol/L of hydrochloric acid solution, adjusting the pH value to be 1-2, filtering the obtained product to obtain a crude product, stirring and washing the filtered solid phase substance by using 300mL of distilled water for 30min, adding the washed product into ethanol which is heated and stirred under reflux at the temperature of 80 ℃, until the product is not dissolved any more, quickly cooling the product in a refrigerator at 5 ℃ for 10-30 min, filtering the mixture to obtain white needle crystals, and drying the crystal product at 30-60 ℃ for 12-72 h in vacuum to obtain p-alkenyloxy benzoic acid;
step two, preparation of 4-allyloxybenzoyl chloride
Adding the white needle-shaped crystal obtained in the step one and 5-30 mL of thionyl chloride into a 20-100 mL flask with a hydrogen chloride absorber, transferring the flask into a normal-pressure reflux microwave reactor with ultraviolet and Nd-YAG solid pulse laser, starting ultraviolet light and laser irradiation on the flask, wherein the ultraviolet wavelength is 190-400 nm, and the power is 5mW/cm2～15W/cm2The Nd is YAG solid pulse laser wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.2-6 mm, repetition frequency 2-40 Hz, power density 1.0 x 106W/cm2The light spot of the laser focus is 1-3 mm below the liquid level, the irradiation time is 0.1-20 h, the irradiation temperature is 20-200 ℃, the mixture is stirred at the speed of 200-2000 r/min in the irradiation process, reflux condensation is carried out during heating, then the solution is taken out, and the excessive thionyl chloride is removed by reduced pressure distillation for 10min under the conditions of-0.09 MPa and 40 ℃, so as to obtain 4-allyloxybenzoyl chloride;
step three, preparation of liquid crystal monomer p-alkenyloxy benzoic acid cholesterol ester
Dissolving the obtained 4-allyloxybenzoyl chloride in 1-50 mL of dry dichloromethane, adding 0.01-1.00 mmol of cholesterol and 1-20 mL of pyridine into 50-200 mL of dry dichloromethane, and dropwise adding the 4-allyloxybenzoyl chloride solutionAdding the mixed solution into dichloromethane cold liquid containing cholesterol and pyridine, transferring the mixed solution into a normal-pressure reflux microwave reactor with ultraviolet and Nd-YAG solid pulse laser, and only starting ultraviolet light and laser to irradiate the flask, wherein the ultraviolet wavelength is 190-400 nm, and the power is 5mW/cm2～15W/cm2The Nd is YAG solid pulse laser wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.2-6 mm, repetition frequency 2-40 Hz, power density 1.0 x 106W/cm2A light spot of a laser focus is 1-3 mm below a liquid level, the irradiation time is 0.1-10 h, the irradiation temperature is 20-200 ℃, the mixture is stirred at the speed of 200-2000 r/min and is subjected to reflux condensation simultaneously in the irradiation process, then the solution is taken out, 100-500 mL of ethanol is added into the filtrate to precipitate a crude product, the crude product is recrystallized from the ethanol, and the obtained white powder product is dried in a vacuum drying oven at the temperature of 50-80 ℃ for 6-72 h to obtain the p-alkenyloxy benzoic acid cholesterol ester;
step four, preparation of liquid crystal monomer p-alkenyloxy benzoic alcohol ester
Dissolving the 4-allyloxybenzoyl chloride obtained in the second step in 5-20 mL of dry dichloromethane, dripping the solution into a cold solution containing 0.01-0.20 mol of R-OH and 3-20 mL of pyridine in 100mL of dichloromethane, transferring the mixture into a flask, transferring the flask into a microwave reactor with ultraviolet, Nd and YAG solid pulse laser and normal pressure backflow, and only starting ultraviolet light and laser to irradiate the flask, wherein the ultraviolet wavelength is 190-400 nm, and the power is 5mW/cm2～15W/cm2YAG solid pulse laser wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.2mm, repetition frequency 20Hz, power density 1.0 × 106W/cm2The method comprises the following steps of (1) enabling a light spot of a laser focus to be 2mm below a liquid level, enabling the irradiation time to be 4-10 hours, enabling the irradiation temperature to be 20-50 ℃, stirring a mixture at a speed of 200-2000 r/min in the irradiation process, simultaneously carrying out reflux condensation, then taking out a solution, adding 300mL of ethanol into a filtrate to precipitate a crude product, recrystallizing the crude product from the ethanol, and drying an obtained white powder product in a vacuum drying oven at the temperature of 50-80 ℃ for 12-48 hours to obtain p-alkenyloxy benzoic acid alcohol ester;
step five, preparation of p-iodoallyloxybenzene
Dissolving 0.01-0.10 mol of p-iodophenol in 10-100 mL of acetonitrile, stirring for 5-10 min, then placing the mixture in a 30-300 mL flask, adding 0.01-0.10 mol of 3-bromopropylene and 0.01-0.10 mol of potassium carbonate, heating to 85 ℃, stirring at 100-2000 r/min, carrying out water bath heat preservation reflux reaction for 1-5 h, carrying out centrifugal separation after reaction to remove solids, carrying out rotary evaporation for 10-300 min at the speed of-0.09 MPa, the temperature of 40-80 ℃ and the speed of 80-100 r/min to remove excess solvent, and then using a mixture of dichloromethane and petroleum ether in a volume ratio of 1:2 as an eluent to carry out silica gel column chromatography purification to obtain p-iodoallyloxybenzene;
step six, preparation of p- (dibutylamino) phenylacetylene
Dissolving 5-100 mmol of para-iodoaniline and 5-100 mmol of bromobutane or iodomethane in 10-200 mL of N, N-dimethylformamide, adding 5-100 mmol of potassium carbonate and 5-100 mmol of potassium iodide, placing the mixture in a 40KHz ultrasonic cleaning instrument for ultrasonic oscillation for 20-40 min, introducing argon gas for removing oxygen at 0.1-2L/min, carrying out water bath reflux reaction on a 20-500 mL flask containing the mixture at 80-150 ℃ for 15-24 h, plugging a reflux condenser tube opening with a rubber plug, carrying out suction filtration after the reaction to remove solids, extracting with 30-300 mL of water and 30-300 mL of dichloromethane to remove N, N-dimethylformamide, rotary evaporating at-0.09 MPa, 25-50 deg.C and 90r/min for 10-200 min to remove excessive solvent, then, using a mixture of dichloromethane and petroleum ether with a volume ratio of 1:6 as eluent to carry out silica gel column chromatography purification, thus obtaining a p- (dibutylamino) phenylacetylene product; dissolving 0.001-0.100 mol of product in 50-100 mL of mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, introducing argon gas at 0.1-2L/min, ultrasonically deoxidizing at 40KHz for 30min, then adding 0.001-0.100 mol of trimethylsilyl acetylene TMSA, 0.1-1.0 mmol of bis (triphenylphosphine) palladium dichloride and 0.1-1.0 mmol of cuprous iodide, stirring in a 100-300 mL flask containing the mixture at a speed of 100-2000 r/min, carrying out a water bath reflux reaction at 25-60 ℃ for 8-12 h, plugging a reflux condenser pipe orifice with a rubber plug, carrying out suction filtration after the reaction to remove solids, carrying out vacuum evaporation at a speed of-0.09 MPa, 40-80 ℃ and 80-100 r/min for 30min to remove more solvent, and then carrying out silica gel column chromatography purification by taking a mixture of dichloromethane and petroleum ether in a volume ratio of 1:6 as eluent to obtain yellow liquid; dissolving 0.001-0.100 mol of the product and 0.001-0.100 mol of potassium carbonate in 30-100 mL of a mixed solution of tetrahydrofuran and absolute ethyl alcohol with a volume ratio of 7:3, transferring the mixed solution into a 50-300 mL flask, stirring the mixture in the flask at 100-2000 r/min, carrying out reflux reaction at room temperature for 2-10 h, stopping the reaction, carrying out suction filtration to remove solids, carrying out rotary evaporation at a vacuum degree of-0.09 MPa, a temperature of 40-80 ℃ and a rotating speed of 80-100 r/min for 20-60 min to remove the solvent, and carrying out dichloromethane column chromatography purification to obtain a yellow oily liquid;
step seven, 4-ethynyl-N, N-hexacosanylaniline preparation
Dissolving 5-100 mmol of p-iodoaniline and 5-100 mmol of 1-bromohexadecane in 10-200 mLN, N-dimethylformamide, then adding 5-100 mmol of potassium carbonate and 5-100 mmol of potassium iodide, placing the mixture in a 40KHz ultrasonic cleaning instrument for ultrasonic oscillation for 20-40 min, introducing argon gas for removing oxygen at 0.1-2L/min, carrying out water bath reflux reaction on a 20-500 mL flask containing the mixture at 80-150 ℃ for 15-24 h, plugging a reflux condenser tube opening with a rubber plug, carrying out suction filtration after the reaction to remove solids, extracting with 30-300 mL of water and 30-300 mL of dichloromethane to remove N, N-dimethylformamide, rotary evaporating at-0.09 MPa, 25-50 deg.C and 90r/min for 10-200 min to remove excessive solvent, then, using a mixture of dichloromethane and petroleum ether with a volume ratio of 1:6 as an eluent to carry out silica gel column chromatography purification, thus obtaining a product; dissolving 0.001-0.100 mol of the product in 50-100 mL of mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, introducing argon gas at 0.1-2L/min, ultrasonically deoxidizing at 40KHz for 30min, then adding 0.001-0.100 mol of trimethylsilyl acetylene TMSA, 0.1-1.0 mmol of bis (triphenylphosphine) palladium dichloride and 0.2mmol of cuprous iodide, stirring in a 100-300 mL flask containing the mixture at a speed of 100-2000 r/min, carrying out reflux reaction in a water bath at 25-60 ℃ for 8-12 h, plugging a reflux condenser pipe orifice with a rubber plug, carrying out suction filtration after the reaction to remove solids, carrying out vacuum rotary evaporation for 30min at a speed of-0.09 MPa, 40-80 ℃ and 80-100 r/min to remove more solvent, and then carrying out silica gel column chromatography purification by using a mixture of dichloromethane and petroleum ether in a volume ratio of 1:6 as an eluent to obtain yellow liquid; dissolving 0.001-0.100 mol of product and 0.001-0.100 mol of potassium carbonate in 30-100 mL of a mixture of tetrahydrofuran and absolute ethyl alcohol with a volume ratio of 7:3, transferring the mixture into a 50-300 mL flask, stirring the mixture in the flask at 100-2000 r/min, carrying out reflux reaction at room temperature for 2-10 h, stopping the reaction, carrying out suction filtration to remove solids, carrying out rotary evaporation at a vacuum degree of-0.09 MPa, a temperature of 40-80 ℃ and a rotating speed of 80-100 r/min for 20-60 min to remove the solvent, and carrying out dichloromethane column chromatography purification to obtain a yellow oily liquid;
step eight, preparing white solid of polysiloxane side chain liquid crystal polymer by hydrosilylation reaction
Adding 0.10-5.00 mmol of liquid crystal monomer p-alkenyloxy cholesteryl benzoate, 0.10-5.00 mmol of p-iodoallyloxy benzene and 10-10 ppm of platinum catalyst into a flask for reaction, adding the mixture into 10-50 mL of toluene, evacuating the flask through a double-row pipe and filling nitrogen, discharging oxygen in the flask, transferring the flask into a normal-pressure belt reflux microwave reactor with ultraviolet and Nd: YAG solid pulse laser, and irradiating the solution with Nd: YAG solid pulse laser, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.2-6 mm in spot diameter, 2-40 Hz in repetition frequency and 1.0 multiplied by 10 Hz in power density6W/cm2The light spot of the laser focus is 1-3 mm below the liquid level, and the irradiation time is 0.1-24 h; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of ultraviolet light is 190-400 nm, and the intensity is 5mW/cm2～15W/cm2The irradiation time is 0.1-24 h; simultaneously carrying out laser and ultraviolet irradiation, synchronously starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 300-1000W, the microwave time is 0.1-24 h, the heating temperature is 25-100 ℃, when the temperature in the microwave reactor exceeds a set temperature, the microwave generator is closed to reduce the temperature, when the temperature is lower than the set temperature, the microwave generator is opened to increase the temperature, reflux condensation is started, and the orifice of the reflux condensation pipe is blocked by a rubber plug, so that air is prevented from entering; after the reaction is finished, adding 200-500 mg of polymethylhydrosilicone oil PMHS under the condition of keeping vacuum, and irradiating the solution by Nd-YAG solid pulse laser, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.2-6 mm in spot diameter, 2-40 Hz in repetition frequency and 1.0 multiplied by 10 in power density6W/cm2The light spot of the laser focus is 1-3 mm below the liquid level, and the irradiation time is 0.1-24 h; in the laser irradiation process, simultaneously starting an ultraviolet lamp for irradiation, wherein the wavelength of the ultraviolet light is 190400nm and power of 5mW/cm2～15W/cm2The irradiation time is 0.1-24 h; simultaneously carrying out laser and ultraviolet irradiation, synchronously starting microwave heating, wherein the microwave frequency is 2450MHz, the microwave power is 300-1000W, the microwave time is 0.1-24 h, the heating temperature is 60-100 ℃, when the temperature in the microwave reactor exceeds a set temperature, a microwave generator is closed to reduce the temperature, and when the temperature in the microwave reactor is lower than the set temperature, the microwave generator is opened to increase the temperature; after the reaction is finished, taking out the reaction liquid, cooling the reaction liquid to room temperature, dropwise adding the reaction liquid into 20-500 mL of methanol under the condition of mechanical stirring at 100-1000 r/min, centrifugally separating at 7000r/min, re-dissolving the solid phase substance into 20-500 mL of chloroform, precipitating with 20-500 mL of methanol to remove unreacted raw materials, and drying at 70-80 ℃ for 6-72 hours to obtain white solid of the polysiloxane side chain liquid crystal polymer;
step nine, preparation of polysiloxane side chain liquid crystal polymer modified by triple bond
Dissolving 50-150 mg of liquid crystal polymer prepared by hydrosilylation reaction and 0.10-1.00 mmol of p- (dibutylamino) phenylacetylene or 4-ethynyl-N, N-hexacosanylaniline in 5-30 mL of triethylamine and tetrahydrofuran solution with a volume ratio of 1:1, introducing 0.1-2L/min of argon, ultrasonically deoxidizing for 30min under the condition of 40KHz, adding 0.1-1.0 mmol of bis (triphenylphosphine) palladium dichloride and 0.1-1.0 mmol of cuprous iodide, stirring at 100-2000 r/min, refluxing and reacting in water bath at 40 ℃ for 5-20 h, centrifugally separating at 7000r/min to remove solids, dropwise adding the liquid product into 100-500 mL of methanol solution under stirring at a rotating speed of 100-2000 r/min, centrifugally separating at 7000r/min, redissolving the precipitate in 100-500 mL of trichloromethane, precipitating with 20-500 mL of methanol to remove unreacted raw materials, obtaining polysiloxane side chain liquid crystal polymer modified by triple bonds;
step ten, click reaction preparation of click-modified polysiloxane side chain liquid crystal polymer
And (4) adding the polysiloxane side chain liquid crystal polymer obtained in the step nine into 5-50 mL of methanol, adding a click chemistry modified micromolecule monomer into the other 5-50 mL of methanol, and mixing the two solutions to prepare the click modified polysiloxane side chain liquid crystal polymer through click reaction.
2. The method for preparing a click-modified polysiloxane side chain liquid crystal polymer according to claim 1, wherein: in the preparation of the p-alkenyloxybenzoic acid, the alkene bromine is one or any combination of two or more than two of 3-bromine-1-propylene, 5-bromine-1-pentene and 13-bromine-1-tridecene.
3. The method for preparing a click-modified polysiloxane side chain liquid crystal polymer according to claim 1, wherein: in the preparation of the liquid crystal polymer by the hydrosilylation reaction, when the polymethyl hydrogen-containing silicone oil reacts with two liquid crystal monomers, the two liquid crystal monomers are added, and the two liquid crystal monomers cannot be 0 at the same time.
4. The method for preparing a click-modified polysiloxane side chain liquid crystal polymer according to claim 1, wherein: in the preparation of the liquid crystalline monomer p-alkenyloxy benzoic alcohol ester, the p-alkenyloxy benzoic alcohol ester is obtained by esterifying p-alkenyloxy benzoic acid and R-OH, wherein R is selected from
Figure FDA0003271644050000071
One kind of (1).
5. The method for preparing a click-modified polysiloxane side chain liquid crystal polymer according to claim 1, wherein: the solvent used in the polysiloxane side chain liquid crystal polymer prepared by click modification is dichloromethane, and the small molecular monomer is one, two or more of 7,7,8, 8-tetracyanoquinodimethane, tetracyanoethylene, 2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanoquinodimethane, wherein the dichloromethane is 5-30 mL, the 7,7,8, 8-tetracyanoterephthalquinodimethane is 10-100 mg, the 2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanoquinodimethane is 10-100 mg, and the tetracyanoethylene is 1-50 mg.
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