CN1919970A - Preparation method of multi-metal oxygen cluster organic/inorganic hybridization liquid crystal material - Google Patents
Preparation method of multi-metal oxygen cluster organic/inorganic hybridization liquid crystal material Download PDFInfo
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- CN1919970A CN1919970A CN 200610017146 CN200610017146A CN1919970A CN 1919970 A CN1919970 A CN 1919970A CN 200610017146 CN200610017146 CN 200610017146 CN 200610017146 A CN200610017146 A CN 200610017146A CN 1919970 A CN1919970 A CN 1919970A
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Abstract
The invention relates the preparing method for liquid crystal material with metal oxygen cluster organic/inorganic hybridization. The method comprises the following steps: synthesizing cationic surface active agent with dielectric crystal group; surface active agent static electricity coating metal oxygen cluster. The character of the method is that the surface of compound expresses thermal liquid crystal behavior. The hybridization material made by the method has functional properties of metal oxygen cluster and aeolotropy and response property of liquid crystal molecule. The method can be used to make the liquid crystal material with functional properties.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of utilization and contain the cats product of mesomorphic group, coat the inorganic multi-metal oxygen cluster that has negative charge by electrostatic interaction and form mixture, and then preparation contains the method for multi-metal oxygen cluster hybrid liquid crystal material.
Background technology
Liquid crystal material has the crystalline anisotropy, and the mobile and faint to external world electricity of liquid, magnetic field is characteristics such as responsiveness fast, and this also is that liquid crystal is used as the principal element that display material uses.Liquid-crystal display grows out of nothing, and is shown to colored the demonstration from monochrome, during trials and hardships experienced 40 years of development courses.Liquid-crystal display have zero radiation, low power consuming, heat radiation little, show that character is sharp keen, picture does not stablely glimmer, slim advantage such as light and handy, the main flow that has become IT industry circle is at present selected.In addition, it also is widely used in a plurality of fields such as clock and watch, counter, instrument, pocket colour TV, large flat demonstration, notebook computer, industry and military indicating meter.Yet, along with progressively going deep into of practice and improving constantly of understanding, it is found that liquid-crystal display also exists many weak points, as comparing with traditional indicating meter, polaroid in the liquid-crystal display and color filter plate have had a strong impact on the angular field of view of indicating meter, and contrast gradient and display brightness are not high.Improving the visual range of liquid-crystal display and the method for display brightness is to select the liquid crystal cell of not being with polaroid and color filter plate in indicating meter for use, and this just requires to develop the fluorescent type liquid crystal material with good luminous performance.
Multi-metal oxygen cluster claims polyoxometallate or polyacid again, is the inorganic clusters compound of the definite nano-scale of a class formation.It has numerous moietys and rich and varied topological framework, and the huge applications potentiality that show in fields such as catalysis, proton conduction, magnetic and optics.For over 100 years more than a hundred years, the multi-metal oxygen cluster chemistry has all been obtained considerable progress in theoretical and practical application.
Consider the good optical functional performance of multi-metal oxygen cluster, we are incorporated into inorganic multi-metal oxygen cluster in the organic lcd system in expectation, and development contains the functional hybrid liquid crystal material of multi-metal oxygen cluster.In recent years, utilize organic molecule and inorganic metal ion successfully to synthesize the hybridization liquid crystal material of metal ion by the noncovalent interaction people, this provides useful inspiration for the functional liquid crystal material that preparation contains multi-metal oxygen cluster.In the world latest report several methods that metal ion are incorporated into the liquid crystal system by noncovalent interaction, its thinking mainly contains two kinds, the one, the organic molecule with liquid crystal liquid crystal property is combined by coordination with metal ion, utilize the organic lcd molecule to induce the liquid crystal behavior that shows mixture; The 2nd, the organic molecule that does not have liquid crystal liquid crystal property is combined by coordination with metal ion, make the mixture of formation have liquid crystal liquid crystal property.Though these methods can be incorporated into metal ion in the liquid crystal system,, and then limit the range of application of this hybridization liquid crystal material because the coordination of organic ligand can influence the original photoluminescent property of metal ion.Multi-metal oxygen cluster has good optical, and combine with organic molecule not can cancellation himself fluorescence.Therefore, a kind of preparation method who contains multi-metal oxygen cluster hybrid liquid crystal material of exploitation is very necessary.
Summary of the invention
The purpose of this invention is to provide the method that a kind of preparation contains the hybrid liquid crystal material of multi-metal oxygen cluster.This method is simple to operate, and generally is applicable to common multi-metal oxygen cluster system.
Embodiment of the present invention are: the at first synthetic cats product that contains mesomorphic group, utilize this tensio-active agent to coat multi-metal oxygen cluster by electrostatic interaction again, and induce the mixture of formation to show the thermotropic liquid crystal behavior.
The present invention includes following technological step: cats product synthetic that contains mesomorphic group; Utilize this cats product static to coat electronegative multi-metal oxygen cluster and make mixture with thermotropic liquid crystal.
1) contains cats product synthetic of mesomorphic group
The cats product basic structure that contains mesomorphic group that this patent relates to is made of the hydrophilic head of quaternary ammonium salt cationic, hydrophobic alkyl chain interval, inflexible biphenyl (perhaps nitrogen benzide) mesomorphic group and terminal flexible alkyl chains.
(general formula is (CH to contain the quaternary ammonium salt cationic surfactant of mesomorphic group
3)
2N
+[(CH
2)
mCH
3] [(CH
2)
mMES (CH
2)
nCH
3] or (CH
3)
2N
+[(CH
2)
mMES (CH
2)
nCH
3]
2(5≤n≤11,8≤m≤12) synthetic is the haloalkane [X (CH by containing mesomorphic group
2)
aMES (CH
2)
bCH
3] and tertiary amine [(CH
3)
2N (CH
2)
cCH
3] (X=Cl or Br, MES can be biphenyl or nitrogen benzide mesomorphic group, 8≤a≤12,5≤b≤11,8≤c≤12) here quaterisation or contain the haloalkane and the secondary amine [(CH of mesomorphic group
3)
2NH] carry out two-step reaction quaternized realization.
General molecular formula: (CH
3)
2N
+[(CH
2)
mCH
3] [(CH
2)
mMES (CH
2)
nCH
3], (CH
3)
2N
+[(CH
2)
mMES (CH
2)
nCH
3]
2The tensio-active agent of (5≤n≤11,8≤m≤12) all is fit to this patent, and (concrete synthetic method can reference Chem.Commun.2005,3785-3787).Haloalkane and final surfactant structure formula are as follows:
X(CH
2)m-O-MES-O-(CH
2)
nCH
3
The haloalkane general formula is: [X (CH
2)
aMES (CH
2)
bCH
3]
The tensio-active agent general formula is: (CH
3)
2N
+[(CH
2)
mMES (CH
2)
nCH
3]
2
The tensio-active agent general formula is: (CH
3)
2N
+[(CH
2)
mCH
3] [(CH
2)
mMES (CH
2)
nCH
3]
X=Cl wherein, Br;
2) tensio-active agent static coating multi-metal oxygen cluster anions prepares the liquid crystal liquid crystal property mixture
The synthetic method of multi-metal oxygen cluster has had a lot of bibliographical informations, and the part multi-metal oxygen cluster commercially produces, and therefore will directly use as raw material in this patent.Multi-metal oxygen cluster is of a great variety, and function is different, for example has magnetic, catalysis, functional performance such as luminous.The multi-metal oxygen cluster Na that selects for use in this patent
3PW
12O
40, Na
4SiW
12O
40, H
3PW
12O
40Deng having catalytic, Na
9EuW
10O
36, K
11[Eu (PW
11O
39)
2], K
13[Eu (SiW
11O
39)
2], K
15[Eu (BW
11O
39)
2] wait and have fluorescence.In actual applications, the multi-metal oxygen cluster that can select as required to have the difference in functionality characteristic coats.On method for coating, because used tensio-active agent is soluble in as in chloroform and the dichloromethane solvent among the present invention, the mode that can adopt the aqueous solution-organic solvent (water/oil) two-phase to coat.
It is with multi-metal oxygen cluster to be coated (10-30 mg/ml) soluble in water that water/oily two-phase coats, and the temperature that keeps the aqueous solution is at 40-50 degree centigrade.The cats product that will contain mesomorphic group in addition is dissolved in (0.02-0.07mol/L) in the chloroform, and keeps chloroform phase temperature at 30-40 degree centigrade.Control the two consumption, make the total charge number of multi-metal oxygen cluster equal or be slightly larger than the total charge number (1: 0.9-1.0) of tensio-active agent.Under whipped state, with surfactant soln dropwise (1.0-1.3 ml/min) join in the aqueous solution of multi-metal oxygen cluster.After continuing to stir 4 to 5 hours under the 40-50 degrees celsius, tell organic phase with separating funnel.Organic phase washes with water 2 to 3 times again, (add-on is the 20-40% of previous reaction system gross weight to add anhydrous magnesium sulfate, except the embodiment 2-11) dry 30-60 minute after-filtration, solvent evaporated obtains containing the multi-metal oxygen cluster mixture that the mesomorphic group cats product coats.
The present invention adopts the cats product static that contains mesomorphic group to coat functional multi-metal oxygen cluster, and then utilizes the liquid crystal liquid crystal property of cats product to induce mixture to show the thermotropic liquid crystal behavior.By this method multi-metal oxygen cluster and liquid crystal system are organically combined the hybrid material that obtains having concurrently the functional and organic molecule liquid crystal liquid crystal property of multi-metal oxygen cluster.The hybrid material that makes by this method has the anisotropy and the responsiveness of the functional performance and the liquid crystal molecule of multi-metal oxygen cluster concurrently.This in addition method can generally be suitable for for common multi-metal oxygen cluster, therefore can be used for preparing the liquid crystal material with functional performance.
Description of drawings
Fig. 1: the preparation process synoptic diagram of multi-metal oxygen cluster hybrid liquid crystal material
Fig. 2: Na
9EuW
10O
36, tensio-active agent (CH
3)
2N
+[(CH
2)
10Biphenyl (CH
2)
7CH
3]
2(S1) with mixture (S1)
9EuW
10O
36Infrared spectra
Fig. 3: S1 and mixture (S1)
9EuW
10O
36Proton nmr spectra
Fig. 4: (S1)
9EuW
10O
36The differential scanning calorimetry curve of mixture
Fig. 5: (S1)
9EuW
10O
36The polarizing microscope photo that mixture obtains in process of cooling
Fig. 6: (S1)
9EuW
10O
36The alternating temperature X-ray diffraction curve of mixture in process of cooling
As shown in Figure 1, the cationic surfactant embedding multi-metal oxygen cluster compound that contains mesomorphic group has been described, Form the process schematic diagram of liquid crystal liquid crystal property organic/inorganic composite. Wherein, a represents to contain the work of mesomorphic group cationic surface The property agent, circular portion is the cation head, with positive charge, rectangle part is the rigidity mesomorphic group; B represents many Metal oxygen cluster, surperficial counter ion counterionsl gegenions dissociate and fully with negative electrical charge in water; C represents that static coats rear formation Compound
As shown in Figure 2, multi-metal oxygen cluster Na has been described9EuW
10O
36, the cationic surfactant S1 that contains biphenyl group of embodiment 1-1 preparation and coating gained compound (S1)9EuW
10O
36Infrared spectrum. Wherein, A is Na9EuW
10O
36Infrared spectrum: the infrared absorption band at 945 wave number places belongs to Na among the figure9EuW
10O
36W-Od eigen vibration pattern, the infrared absorption band at 841 and 777 wave number places belongs to Na9EuW
10O
36 W-Oc-W eigen vibration pattern. B is the infrared spectrum of surfactant S1: high wave number place (2600 among the figure-3000) infrared absorption peak is the feature stretching vibration pattern of alkyl chain methyl and methylene in the surfactant. The absorption band at 1606,1500 wave number places is the skeletal vibration of phenyl ring in the surfactant. The suction at 1394 wave number places Receiving bands of a spectrum is and quaternary ammonium (N+) the scissoring vibration pattern of the methyl that links to each other. The absorption band at 1247 wave number places is fragrant fat The vibration mode of fat ether: phenyl ring-O-C. C forms compound (S1) for coating9EuW
10O
36Infrared spectrum. Logical Crossing contrast can find namely to have in the compound characteristic infrared Absorption Spectroscopy of S1 to exist again Na9EuW
10O
36Characteristic absorption band, the coating of this explanation S1 success Na9EuW
10O
36Become compound (S1)9EuW
10O
36。
As shown in Figure 3, be S1 and compound (S1)9EuW
10O
36Proton nmr spectra. Wherein, a is S1 Proton nmr spectra: two groups of doublets of high chemical shift (6.9-7.5ppm) are in the surfactant among the figure The nuclear-magnetism vibrational spectra of hydrogen atom on the cyclohexyl biphenyl; The triplet of chemical shift at the 4ppm place is the methylene that links to each other with oxygen The eigen vibration of hydrogen atom spectrum in the base; With quaternary ammonium N+The eigen vibration pattern of hydrogen respectively in the methyl that links to each other and the methylene What be chemical shift at the triplet at 3.5ppm place and 3.36ppm place is unimodal. Other methylene in the surfactant The vibrational spectra of base then appears at low chemical shift district (1.94-1.1ppm); The chemical shift of hydrogen is in the terminal methyl group 0.88ppm the triplet of locating. In conjunction with the result of above NMR spectrum and infrared spectrum, we determine synthetic Target surface activating agent S1. B is (S1)9EuW
10O
36Proton nmr spectra. Can find compound by contrast The feature hydrogen of S1 quaternary ammonium head place's methyl and methylene spectrum obviously broadens in the thing, this explanation S1 and Na9EuW
10O
36Between exist strong electrostatic interaction.
As shown in Figure 4, be (S1)9EuW
10O
36The differential scanning calorimetry curve of compound. Wherein, a is The heat branch that the thermal analysis curve of compound in first time cooling procedure, b are compounds in second time heating process Analyse curve. Compound (S1) as we can see from the figure9EuW
10O
36When heating and cooling, have a plurality of phase transition process. In cooling procedure, 185 degrees centigrade the heat of transformation of locating is littler and 121 degrees centigrade of heat of transformations of locating are bigger, and The phase transformation of compound has invertibity in the heating and cooling process. Locating bigger heat of transformation correspondence at 121 degrees centigrade Compound is from more orderly solid-state transformation to unordered liquid crystal state, and 185 degrees centigrade are located the littler heat of transformation pair Answering compound from unordered liquid crystal state to the transformation fully unordered liquid state.
As shown in Figure 5, be (S1)9EuW
10O
36The petrographic microscope photo that compound obtains in cooling procedure. Polarisation photo when a is compound from isotropy attitude liquid cools to 170 degree centigrade among the figure, b is that compound is cold Polarisation photo during but to 100 degrees centigrade. Can see that compound exists significantly two in the time of 170 degrees centigrade Refraction effect, and show typical liquid crystal state texture. And in the time of 100 degrees centigrade, compound is by liquid crystal Attitude changes into orderly solid-state. The result shows that compound has the thermotropic liquid crystal behavior.
As shown in Figure 6, be compound (S1)9EuW
10O
36Alternating temperature X-ray diffraction experiment. Wherein, a is compound The diffraction curve of thing when 30 degrees centigrade of room temperatures, b is the diffraction curve of compound in the time of 100 degrees centigrade, c is The diffraction curve of compound when 170 degrees centigrade of room temperatures. Can find that from figure compound is in the time of 170 degrees centigrade Exist unordered smectic liquid crystal attitude.
Embodiment
Following embodiment is that the present invention is further elaborated, does not limit the invention and do not represent according to this.
1, contain the synthetic of mesomorphic group cats product
Reaction principle: utilize 1, the substitution reaction of n-saturated dihalide (8≤n≤12) and phenolic hydroxyl group make the haloalkane that contains mesomorphic group, then with contain the haloalkane of mesomorphic group and the quaterisation of tertiary amine (embodiment 1-5) or with quaternized (the embodiment 1-1 of secondary amine two-step reaction, 2,3,4,6) realize various the synthetic of different alkyl chain length and the tensio-active agent that contains different mesomorphic groups that have.
Organic solvent used in the experiment is analytical pure, and water is secondary water; It is the SILVER REAGENT column layer chromatography silicone rubber that post separates used silica gel: model is gross porosity ZCX-II, and granularity is the 100-200 order; Post separates used chromatography column specification: internal diameter is 4.5 centimetres, and length is 50 centimetres and has the glass column that gathers the tetrafluoro pipe valve; It is that above-mentioned chromatographic silica gel is inserted chromatography column as stationary phase that post separates the equipment of purifying, and mixture to be separated is injected from the chromatography column upper end, with selected eluent flushing, collects elutriant respectively then.
Embodiment 1-1:
N, two [10-(4 '-Xin alkoxyl group-4-xenyl) alkoxyl group in the last of the ten Heavenly stems] brometo de amonios of N-dimethyl (abbreviation S1) synthesizes
With 6 gram (33mmol) 4,4-dihydroxybiphenyl, 5.79 gram (30mmol) n-bromooctanes, 5 gram K
2CO
3(36mmol) join in 110 milliliters of acetone solns.Mixture reflux 24 hours under agitation condition.Reaction is poured solution in the water into after finishing, and with dilute hydrochloric acid regulator solution pH value to slightly acidic.Collect solid, carry out post separation (chromatography column specification: internal diameter=4.5 centimetre, length=50 centimetre with the chloroform give developping agent; Used silica gel is a column layer chromatography silicone rubber, and gross porosity type, granularity are the 100-200 order).Get solid 4 '-Xin alkoxyl group-4-xenol, productive rate 44-50%.
Get 3.99 gram (13.4mmol) previous step gained solids, 4 '-Xin oxygen alkane-4-xenol and be dissolved in 120 milliliters of acetone, and to wherein adding 4.82 gram (16.06mmol) 1,10-dibromo-decane, 2.82 gram (20mmol) K
2CO
3After about 24 hours of the mixture heating up stirring and refluxing, rotary evaporation removes and desolvates.The gained solid is dissolved in chloroform, filters.Tell organic phase and wash with water 2-3 time, use anhydrous magnesium sulfate drying then, filter thick product.Post separate to be purified, with chloroform and sherwood oil (v/v=1: mixed solvent 3) is made eluent, product 4-(10-bromodecane oxygen base)-4 '-Xin alkoxyl group biphenyl, productive rate is 60-65%.
The dimethylamine agueous solution (mass percent is 33%) that takes by weighing 1.01 gram (1.93mmol) 4-(10-bromodecane oxygen base)-4 '-Xin alkoxyl group biphenyl and 2.4 grams (9.65mmol) is dissolved in 100 milliliters of ethanol.The mixture stirring and refluxing is removed after 24 hours and is desolvated, and the gained solid is dissolved in the chloroform.Filtration washes with water 2-3 time after telling organic phase, with anhydrous magnesium sulfate drying (0.4 gram), filter thick product.Post separate to be purified, with chloroform and methyl alcohol (v/v=12: mixed solvent 1) is made eluent, product N, N-dimethyl-10-(4 '-Xin alkoxyl group-4-xenyl) alkoxylamine in the last of the ten Heavenly stems, productive rate is 84-90%.
With 0.481 gram (1mmol) product N, N-dimethyl-10-(4 '-Xin alkoxyl group-4-xenyl) alkoxylamine in the last of the ten Heavenly stems and 0.62 gram (1.2mmol) product 4-(10-bromodecane oxygen base)-4 '-Xin alkoxyl group biphenyl are dissolved in 105 milliliters of ethanol mixture stirring and refluxing 24 hours.Rotary evaporation removes and desolvates, and solid is dissolved in the chloroform.Tell organic phase and wash with water 2-3 time, with 0.3 gram anhydrous magnesium sulfate drying, filter thick product.Post separate to be purified, with chloroform and methyl alcohol (v/v=10: mixed solvent 1) is washed release agent, final tensio-active agent S1, productive rate is 80-84%.
Embodiment 1-2:
N, N-dimethyl two [10-(4 '-last of the ten Heavenly stems alkoxyl group-4-xenyl) alkoxyl group in the last of the ten Heavenly stems] brometo de amonio synthetic
With 6 gram (33mmol) 4,4 '-dihydroxybiphenyl, 6.64 gram (30mmol) n-bromodecanes, 5 gram K
2CO
3(36mmol) join in 110 milliliters of acetone solns.Mixture reflux 24 hours under agitation condition.Reaction is poured solution in the water into after finishing, and with dilute hydrochloric acid regulator solution pH value to slightly acidic.Collect solid, carry out post with the chloroform give eluent and separate.Solid 4 '-last of the ten Heavenly stems alkoxyl group-4-xenol, productive rate 44-50%.
Get 4.37 gram alkoxyl group in (13.4mmol) 4 '-last of the ten Heavenly stems-4-xenols and be dissolved in 120 milliliters of acetone, and to wherein adding 4.82 gram (16.06mmol) 1,10-dibromo-decane, 2.82 gram (20mmol) K
2CO
3After about 24 hours of the mixture heating up stirring and refluxing, rotary evaporation removes and desolvates.The gained solid is dissolved in chloroform, filters.Organic phase washes with water 2-3 time, then with 1.8 gram anhydrous magnesium sulfate dryings, filter thick product.Post separate to be purified, with chloroform and sherwood oil (v/v=1: mixed solvent 3) is made eluent, product 4-(10-bromodecane oxygen base) alkoxyl group biphenyl in-4 '-last of the ten Heavenly stems, productive rate is 60-65%.
The dimethylamine agueous solution (mass percent is 33%) that takes by weighing 1.05 gram (1.93mmol) 4-(10-bromodecane oxygen base) alkoxyl group biphenyl in-4 '-last of the ten Heavenly stems and 2.4 grams (9.65mmol) is dissolved in 105 milliliters of ethanol.The mixture stirring and refluxing is removed after 24 hours and is desolvated, and the gained solid is dissolved in the chloroform.Filtration washes with water 2-3 time after telling organic phase, with 0.75 gram anhydrous magnesium sulfate drying, filter thick product.Post separate to be purified, with chloroform and methyl alcohol (v/v=12: mixed solvent 1) is made eluent, product N, N-dimethyl-10-(4 '-last of the ten Heavenly stems alkoxyl group-4-xenyl) alkoxylamine in the last of the ten Heavenly stems, productive rate is 84-90%.
With 0.51 gram (1mmol) product N, N-dimethyl-10-(4 '-last of the ten Heavenly stems alkoxyl group-4-xenyl) alkoxylamine in the last of the ten Heavenly stems and 0.65 gram (1.2mmol) product 4-(10-bromodecane oxygen base) alkoxyl group biphenyl in-4 '-last of the ten Heavenly stems are dissolved in 120 milliliters of ethanol mixture stirring and refluxing 24 hours.Rotary evaporation removes and desolvates, and solid is dissolved in the chloroform.Tell organic phase and wash with water 2-3 time, with 0.3 gram anhydrous magnesium sulfate drying, filter thick product.Post separate to be purified, with chloroform and methyl alcohol (v/v=10: mixed solvent 1) is made eluent, final tensio-active agent N, N-dimethyl two [10-(4 '-last of the ten Heavenly stems alkoxyl group-4-xenyl) alkoxyl group in the last of the ten Heavenly stems] brometo de amonio, productive rate is 80-84%.
Embodiment 1-3:
N, two [10-(4 '-dodecyloxy-4-xenyl) alkoxyl group in the last of the ten Heavenly stems] brometo de amonios of N-dimethyl synthetic
With 6 gram (33mmol) 4,4 '-dihydroxybiphenyl, 7.47 gram (30mmol) n-bromododecanes, 5 gram K
2CO
3(36mmol) join in 110 milliliters of acetone solns.Mixture reflux 24 hours under agitation condition.Reaction is poured solution in the water into after finishing, and with dilute hydrochloric acid regulator solution pH value to slightly acidic.Collect solid, carry out post with the chloroform give eluent and separate.Get solid 4 '-dodecyloxy-4-xenol, productive rate 44-50%.
Get 4.74 gram (13.4mmol) 4 '-dodecyloxy-4-xenols and be dissolved in 120 milliliters of acetone, and to wherein adding 4.82 gram (16.06mmol) 1,10-dibromo-decane, 2.82 gram (20mmol) K
2CO
3After about 24 hours of the mixture heating up stirring and refluxing, rotary evaporation removes and desolvates.The gained solid is dissolved in chloroform, filters.Organic phase washes with water 2-3 time, then with 2 gram anhydrous magnesium sulfate dryings, filter thick product.Post separate to be purified, with chloroform and sherwood oil (v/v=1: mixed solvent 3) is made eluent, product 4-(10-bromodecane oxygen base)-4 '-dodecyloxy biphenyl, productive rate is 60-65%.
The dimethylamine agueous solution (mass percent is 33%) that takes by weighing 1.11 gram (1.93mmol) 4-(10-bromodecane oxygen base)-4 '-dodecyloxy biphenyl and 2.4 grams (9.65mmol) is dissolved in 105 milliliters of ethanol.The mixture stirring and refluxing is removed after 24 hours and is desolvated, and the gained solid is dissolved in the chloroform.Filtration washes with water 2-3 time after telling organic phase, with 0.8 gram anhydrous magnesium sulfate drying, filter thick product.Post separate to be purified, with chloroform and methyl alcohol (v/v=12: mixed solvent 1) is made eluent, product N, N-dimethyl-10-(4 '-dodecyloxy-4-xenyl) alkoxylamine in the last of the ten Heavenly stems, productive rate is 84-90%.
With 0.54 gram (1mmol) product N, N-dimethyl-10-(4 '-dodecyloxy-4-xenyl) alkoxylamine in the last of the ten Heavenly stems and 0.69 gram (1.2mmol) product 4-(10-bromodecane oxygen base)-4 '-dodecyloxy biphenyl are dissolved in 120 milliliters of ethanol mixture stirring and refluxing 24 hours.Rotary evaporation removes and desolvates, and solid is dissolved in the chloroform.Tell organic phase and wash with water 2-3 time, with 0.3 gram anhydrous magnesium sulfate drying, filter thick product.Post separate to be purified, with chloroform and methyl alcohol (v/v=10: mixed solvent 1) is made eluent, final tensio-active agent N, two [10-(4 '-dodecyloxy-4-xenyl) alkoxyl group in the last of the ten Heavenly stems] brometo de amonios of N-dimethyl, productive rate is 80-84%.
Embodiment 1-4:
N, two [10-(4 '-own alkoxyl group-4-xenyl) alkoxyl group in the last of the ten Heavenly stems] brometo de amonios of N-dimethyl synthetic
With 6 gram (33mmol) 4,4-dihydroxybiphenyl, 4.95 gram (30mmol) n-bromo hexanes, 5 gram K
2CO
3(36mmol) join in 110 milliliters of acetone solns.Mixture reflux 24 hours under agitation condition.Reaction is poured solution in the water into after finishing, and with dilute hydrochloric acid regulator solution pH value to slightly acidic.Collect solid, carry out post with the chloroform give eluent and separate.Get solid 4 '-own alkoxyl group-4-xenol, productive rate 44-50%.
Get 3.62 gram (13.4mmol) 4 '-own alkoxyl group-4-xenols and be dissolved in 120 milliliters of acetone, and to wherein adding 4.82 gram (16.06mmol) 1,10-dibromo-decane, 2.82 gram (20mmol) K
2CO
3After about 24 hours of the mixture heating up stirring and refluxing, rotary evaporation removes and desolvates.The gained solid is dissolved in chloroform, filters.Organic phase washes with water 2-3 time, then with 1.9 gram anhydrous magnesium sulfate dryings, filter thick product.Post separate to be purified, with chloroform and sherwood oil (v/v=1: mixed solvent 3) is made eluent, product 4-(10-bromodecane oxygen base)-4 '-own alkoxyl group biphenyl, productive rate is 60-65%.
The dimethylamine agueous solution (mass percent is 33%) that takes by weighing 0.95 gram (1.93mmol) 4-(10-bromodecane oxygen base)-4 '-own alkoxyl group biphenyl and 2.4 grams (9.65mmol) is dissolved in 105 milliliters of ethanol.The mixture stirring and refluxing is removed after 24 hours and is desolvated, and the gained solid is dissolved in the chloroform.Filtration washes with water 2-3 time after telling organic phase, with 0.8 gram anhydrous magnesium sulfate drying, filter thick product.Post separate to be purified, with chloroform and methyl alcohol (v/v=12: mixed solvent 1) is made eluent, product N, N-dimethyl-10-(4 '-own alkoxyl group-4-xenyl) alkoxylamine in the last of the ten Heavenly stems, productive rate is 84-90%.
With 0.45 gram (1mmol) product N, N-dimethyl-10-(4 '-own alkoxyl group-4-xenyl) alkoxylamine in the last of the ten Heavenly stems and 0.59 gram (1.2mmol) product 4-(10-bromodecane oxygen base)-4 '-own alkoxyl group biphenyl are dissolved in 120 milliliters of ethanol mixture stirring and refluxing 24 hours.Rotary evaporation removes and desolvates, and solid is dissolved in the chloroform.Tell organic phase and wash with water 2-3 time, with 0.38 gram anhydrous magnesium sulfate drying, filter thick product.Post separate to be purified, with chloroform and methyl alcohol (v/v=10: mixed solvent 1) is made eluent, final tensio-active agent N, two [10-(4 '-own alkoxyl group-4-xenyl) alkoxyl group in the last of the ten Heavenly stems] brometo de amonios of N-dimethyl, productive rate is 80-84%.
Embodiment 1-5:
N, N-dimethyl dodecyl 12-(4 '-Xin alkoxyl group-4-azobenzene) dodecyloxy brometo de amonio synthetic
4-acetaminophenol 8 grams (53mmol) are dissolved in 150 milliliters of acetone, add the 1-bromooctane of 11.2 grams (58mmol) and the K of 7.7 grams (56mmol) in this solution
2CO
3After about 24 hours of the mixture heating up stirring and refluxing, in reaction mixture impouring water, wait to precipitate and separate out after-filtration in a large number and wash solid with water.The gained solid is dissolved in few ethanol of trying one's best to clarification.Then, adding water to precipitation in ethanolic soln separates out.Filter gained solid 4-acetamido-4 '-dodecyloxy benzene and be directly used in down-go on foot reaction.
(6.5 grams are 20mmol) in the mixing solutions of water-soluble and hydrochloric acid (volume ratio is 6: 1) for previous step gained solid 4-acetamido-4 '-dodecyloxy benzene.Above-mentioned solution stirring refluxed about 10 hours, after reaction finishes solution was cooled to room temperature and with NaOH solution was transferred to weakly alkaline (pH=8), filtered the gained precipitation and washed with water 2-3 time.Directly be dissolved in behind the solid drying in the acetone soln that contains concentrated hydrochloric acid and water, cryosel is bathed and is cooled to 0-5 degree centigrade.15mL is dissolved with NaNO
2(1.66 grams, aqueous solution 24mmol) dropwise joins in the above-mentioned acetone soln, and temperature remains on below 5 degrees centigrade in the whole process.Drip the back and continue stir about half an hour, filter, the gained diazonium salt solution is kept at during cryosel bathes.Take by weighing 2.26 gram (24mmol) phenol, 1.28 gram (32mmol) NaOH, 10 gram (100mmol) Na
2CO
3Soluble in water, cryosel is bathed and is cooled to 5 degrees centigrade.Under violent stirring, above-mentioned diazonium salt solution is dropwise added, maintain the temperature at below 5 degrees centigrade.Drip off the back and continue reaction 2 hours, add hydrochloric acid conditioning solution pH to 6-7.With reaction soln filtration, dry, rotation evaporate to dryness.Thick product carries out post with the chloroform give eluent to be separated, and gets pure product 4 '-octane oxygen alkane-4-hydroxyazobenzene, and productive rate is 60-65%.
Get 2.2 gram (6.7mmol) above products therefrom 4 '-octane oxygen alkane-4-hydroxyazobenzenes and be dissolved in 110 milliliters of acetone, and to wherein adding 3.76 gram (11.5mmol) 1, the K of 12-dibromo-dodecane and the new porphyrize of 2.82 grams (20mmol)
2CO
3, about 24 hours of mixture stirring and refluxing.Reaction end after-filtration is collected filtrate, and post separates purifies, and the mixed solvent flushing with sherwood oil and chloroform (volume ratio is 2: 1) gets product 4-(12-bromododecane oxygen base)-4 '-Xin alkoxyl group nitrogen benzide, and productive rate is 70-75%.
Get 2.47 gram (4.78mmol) 4-(12-bromododecane oxygen base)-4 '-Xin alkoxyl group nitrogen benzides, 0.85 gram (3.98mmol) N, N-dimethyl lauryl amine, mixed dissolution are in 120 milliliters of ethanol, and 80-85 degree centigrade was refluxed 24 hours under whipped state.Rotary evaporation removes and desolvates, and solid is dissolved in the chloroform.Tell organic phase and wash with water 2-3 time, with 1 gram anhydrous magnesium sulfate drying, filter thick product.Post separate to be purified, with chloroform and methyl alcohol (v/v=10: mixed solvent 1) is made eluent, final tensio-active agent N, N-dimethyl dodecyl 12-(4 '-Xin alkoxyl group-4-azobenzene) dodecyloxy brometo de amonio, productive rate 80-85%.
Embodiment 1-6:
N, two [12-(the 4 '-Xin alkoxyl group-4-azobenzene) dodecyloxy] brometo de amonios of N-dimethyl synthetic
The dimethylamine agueous solution (mass percent is 33%) that takes by weighing 0.5 gram (0.87mmol) 4-(12-bromododecane oxygen base)-4 '-Xin alkoxyl group nitrogen benzide and 0.62 gram (2.5mmol) is dissolved in 100 milliliters of ethanol.The mixture stirring and refluxing is removed after 24 hours and is desolvated, and the gained solid is dissolved in the chloroform.Organic phase washes with water 2-3 time, uses anhydrous magnesium sulfate drying then, filter thick product.Post separate to be purified, with chloroform and methyl alcohol (v/v=15: mixed solvent 1) is made eluent, N, N-dimethyl-12-(4 '-Xin alkoxyl group-4-azobenzene) dodecyloxy amine, productive rate is 84-90%.
With 0.3 gram (0.56mmol) product 4-(12-N, N dimethyl dodecyloxy)-4 '-Xin alkoxyl group nitrogen benzide and 0.42 gram (0.73mmol) 4-(12-bromododecane oxygen base)-4 '-octane oxyalkyl nitrogen benzide are dissolved in 110 milliliters of ethanol mixture stirring and refluxing 24 hours.Rotary evaporation removes and desolvates, and solid is dissolved in the chloroform.Tell organic phase and wash with water 2-3 time, with 0.28 gram anhydrous magnesium sulfate drying, filter thick product.Post separate to be purified, with chloroform and methyl alcohol (v/v=10: mixed solvent 1) is washed release agent, final tensio-active agent N, two [12-(4 '-Xin alkoxyl group-4-azobenzene) the ten dioxy alkane] brometo de amonios of N-dimethyl, productive rate is 80-85%.
2, contain of the coating of the quaternary cationics of mesomorphic group to multi-metal oxygen cluster
Reaction principle: multi-metal oxygen cluster its surperficial counter ion in the aqueous solution dissociate, and form the cluster anions that has negative charge.Contain the mesomorphic group cats product therewith cluster ion form stable organic/inorganic composite by electrostatic interaction, this mixture can be dissolved in the organic solvents such as chloroform or methylene dichloride.
Multi-metal oxygen cluster is commercial medicine or synthetic with reference to existing document.Wherein, Na
3PW
12O
40, Na
4SiW
12O
40And H
3PW
12O
40Buy from the Beijing Chemical Plant; K
11[Eu (PW
11O
39)
2] 13H
2O, K
13[Eu (SiW
11O
39)
2] 20H
2O, K
15[Eu (BW
11O
39)
2] 16H
2O is synthetic with reference to J.Chem.Soc.A 1971,1836; Na
9[EuW
10O
36] 32H
2O is with reference to Bull.Chem.Soc.Jpn.1993, and 66,444 is synthetic.Other common multi-metal oxygen cluster also all is fit to this patent.
Embodiment 2-1:
N, two [10-(4 '-Xin alkoxyl group-4-xenyl) alkoxyl group in the last of the ten Heavenly stems] brometo de amonios (S1) of N-dimethyl coat Na
9[EuW
10O
36] 32H
2O
Get 2.98 gram S1 (being 2.94mmol) and be dissolved in 40 milliliters of chloroforms, 1.24 gram Na
9[EuW
10O
36] 32H
2O (being 0.37mmol) is dissolved in 100 ml waters.Maintain the temperature at 40-50 degree centigrade, the chloroformic solution of S1 is dropwise joined Na
9EuW
10O
36The aqueous solution in, tensio-active agent S1 and Na
9EuW
10O
36Charge ratio be 8: 1.Dripping the back continues to stir 4-5 hour.Afterwards, separate organic phase and add 1 gram anhydrous magnesium sulfate drying.Remove by filter organic solvent, the vacuum-drying of gained white solid, productive rate 74-80%.
Embodiment 2-2:
N, two [10-(4 '-Xin alkoxyl group-4-xenyl) alkoxyl group in the last of the ten Heavenly stems] brometo de amonios (S1) of N-dimethyl coat K
11[Eu (PW
11O
39)
2] 13H
2O
Get 2.08 gram S1 (being 2.04mmol) and be dissolved in 40 milliliters of chloroforms, 1.26 gram K
11[Eu (PW
11O
39)
2] 13H
2O (being 0.20mmol) is dissolved in 100 ml waters.S1 and K
11[Eu (PW
11O
39)
2] 13H
2The charge ratio of O is 10: 1.Maintain the temperature at 40-50 degree centigrade, the chloroformic solution of S1 is dropwise joined K
11[Eu (PW
11O
39)
2] .13H
2In the aqueous solution of O.Dripping the back continues to stir 4-5 hour.Afterwards, separate organic phase and add 0.8 the gram anhydrous magnesium sulfate drying.Remove by filter organic solvent, the vacuum-drying of gained white solid, productive rate 73-78%.
Embodiment 2-3:
N, two [10-(4 '-Xin alkoxyl group-4-xenyl) alkoxyl group in the last of the ten Heavenly stems] brometo de amonios (S1) of N-dimethyl coat K
13[Eu (SiW
11O
39)
2] 20H
2O
Get 2.35 gram S1 (being 2.31mmol) and be dissolved in 45 milliliters of chloroforms, 1.23 gram K
13[Eu (SiW
11O
39)
2] 20H
2O (being 0.19mmol) is dissolved in 100 ml waters.S1 and K
13[Eu (SiW
11O
39)
2] 20H
2The charge ratio of O is 12: 1.Maintain the temperature at 40-50 degree centigrade, the chloroformic solution of S1 is dropwise joined K
13[Eu (SiW
11O
39)
2] 20H
2In the aqueous solution of O.Dripping the back continues to stir 4-5 hour.Afterwards, separate organic phase and add 0.9 gram anhydrous magnesium sulfate drying.Remove by filter organic solvent, the vacuum-drying of gained white solid, productive rate 73-81%.
Embodiment 2-4:
N, two [10-(4 '-Xin alkoxyl group-4-xenyl) alkoxyl group in the last of the ten Heavenly stems] brometo de amonios (S1) of N-dimethyl coat K
15[Eu (BW
11O
39)
2] 16H
2O
Get 2.76 gram S1 (being 2.71mmol) and be dissolved in 50 milliliters of chloroforms, 1.43 gram K
15[Eu (BW
11O
39)
2] 16H
2O (being 0.23mmol) is dissolved in 100 ml waters.S1 and K
15[Eu (BW
11O
39)
2] 16H
2The charge ratio of O is 12: 1.Maintain the temperature at 40-50 degree centigrade, the chloroformic solution of S1 is dropwise joined K
15[Eu (BW
11O
39)
2] 16H
2In the aqueous solution of O.Dripping the back continues to stir 4-5 hour.Afterwards, separate organic phase also with 1.2 gram anhydrous magnesium sulfate dryings.Remove by filter organic solvent, the vacuum-drying of gained white solid, productive rate 74-80%.
Embodiment 2-5:
N, two [10-(4 '-own alkoxyl group-4-xenyl) alkoxyl group in the last of the ten Heavenly stems] brometo de amonios of N-dimethyl coat K
15[Eu (BW
11O
39)
2] 16H
2O
Get 1.76 gram N, two [10-(4 '-own alkoxyl group-4-xenyl) alkoxyl group in the last of the ten Heavenly stems] brometo de amonios (being 1.79mmol) of N-dimethyl are dissolved in 35 milliliters of chloroforms, 0.95 gram K
15[Eu (BW
11O
39)
2] 16H
2O (being 0.15mmol) is dissolved in 100 ml waters.Tensio-active agent and K
15[Eu (BW
11O
39)
2] 16H
2The charge ratio of O is 12: 1.Maintain the temperature at 40-50 degree centigrade, with N, the chloroformic solution of two [10-(4 '-own alkoxyl group-4-xenyl) alkoxyl group in the last of the ten Heavenly stems] brometo de amonios of N-dimethyl dropwise joins K
15[Eu (BW
11O
39)
2] 16H
2In the aqueous solution of O.Dripping the back continues to stir 4-5 hour.Afterwards, separate organic phase and add 0.75 gram anhydrous magnesium sulfate drying.Remove by filter organic solvent, the vacuum-drying of gained white solid, productive rate 73-79%.
Embodiment 2-6:
N, N-dimethyl two [10-(4 '-last of the ten Heavenly stems alkoxyl group-4-xenyl) alkoxyl group in the last of the ten Heavenly stems] brometo de amonio coats K
15[Eu (BW
11O
39)
2] 16H
2O
Get 1.96 gram N, N-dimethyl two [10-(4 '-last of the ten Heavenly stems alkoxyl group-4-xenyl) alkoxyl group in the last of the ten Heavenly stems] brometo de amonio (being 1.83mmol) is dissolved in 35 milliliters of chloroforms 0.95 gram K
15[Eu (BW
11O
39)
2] 16H
2O (being 0.15mmol) is dissolved in 100 ml waters.Tensio-active agent and K
15[Eu (BW
11O
39)
2] 16H
2The charge ratio of O is 12: 1.Maintain the temperature at 40-50 degree centigrade, with N, the chloroformic solution of N-dimethyl two [10-(4 '-last of the ten Heavenly stems alkoxyl group-4-xenyl) alkoxyl group in the last of the ten Heavenly stems] brometo de amonio dropwise joins K
15[Eu (BW
11O
39)
2] 16H
2In the aqueous solution of O.Dripping the back continues to stir 4-5 hour.Afterwards, separate organic phase and add 0.8 gram anhydrous magnesium sulfate drying.Remove by filter organic solvent, the vacuum-drying of gained white solid, productive rate 71-78%.
Embodiment 2-7
N, two [10-(4 '-dodecyloxy-4-xenyl) alkoxyl group in the last of the ten Heavenly stems] brometo de amonios of N-dimethyl coat K
15[Eu (BW
11O
39)
2] 16H
2O
Get 3.22 gram N, two [10-(4 '-dodecyloxy-4-xenyl) alkoxyl group in the last of the ten Heavenly stems] brometo de amonios (being 2.81mmol) of N-dimethyl are dissolved in 50 milliliters of chloroforms, 1.46 gram K
15[Eu (BW
11O
39)
2] (being 0.23mmol) be dissolved in 110 ml waters.Tensio-active agent and K
15[Eu (BW
11O
39)
2] 16H
2The charge ratio of O is 12: 1.Maintain the temperature at 40-50 degree centigrade, with N, the chloroformic solution of two [10-(4 '-dodecyloxy-4-xenyl) alkoxyl group in the last of the ten Heavenly stems] brometo de amonios of N-dimethyl dropwise joins K
15[Eu (BW
11O
39)
2] the aqueous solution in.Dripping the back continues to stir 4-5 hour.Afterwards, separate organic phase and add 1 gram anhydrous magnesium sulfate drying.Remove by filter organic solvent, the vacuum-drying of gained white solid, productive rate 72-79%.
Embodiment 2-8
N, N-dimethyl dodecyl 12-(4 '-octyloxy-4-azobenzene) dodecyloxy brometo de amonio coats Na
9[EuW
10O
36] 32H
2O
Get 3.23 gram N, N-dimethyl dodecyl 12-(4 '-octyloxy-4-azobenzene) dodecyloxy brometo de amonio (being 4.10mmol) is dissolved in 40 milliliters of chloroforms, 1.71 gram Na
9EuW
10O
36(being 0.51mmol) is dissolved in 100 ml waters.Tensio-active agent and Na
9[EuW
10O
36] 32H
2The charge ratio of O is 8: 1.Maintain the temperature at 40-50 degree centigrade, with N, the chloroformic solution of N-dimethyl dodecyl 12-(4 '-octyloxy-4-azobenzene) dodecyloxy brometo de amonio dropwise joins Na
9EuW
10O
36The aqueous solution in.Dripping the back continues to stir 4-5 hour.Afterwards, separate organic phase and add 1.3 gram anhydrous magnesium sulfate dryings.Remove by filter organic solvent, the vacuum-drying of gained yellow solid, productive rate 70-80%.
Embodiment 2-9
N, N-dimethyl dodecyl 12-(4 '-octyloxy-4-azobenzene) dodecyloxy brometo de amonio coats Na
3PW
12O
40
Get 2.21 gram N, N-dimethyl dodecyl 12-(4 '-octyloxy-4-azobenzene) dodecyloxy brometo de amonio (being 2.8mmol) is dissolved in 45 milliliters of chloroforms, 2.82 gram Na
3PW
12O
40(being 0.93mmol) is dissolved in 90 ml waters.Tensio-active agent and Na
3PW
12O
40Charge ratio be 3: 1.Maintain the temperature at 40-50 degree centigrade, with N, the chloroformic solution of N-dimethyl dodecyl 12-(4 '-octyloxy-4-azobenzene) dodecyloxy brometo de amonio dropwise joins Na
3PW
12O
40The aqueous solution in.Dripping the back continues to stir 4-5 hour.Afterwards, separate organic phase and add 1.2 gram anhydrous magnesium sulfate dryings.Remove by filter organic solvent, the vacuum-drying of gained yellow solid, productive rate 71-76%.
Embodiment 2-10
N, N-dimethyl dodecyl 12-(4 '-octyloxy-4-azobenzene) dodecyloxy brometo de amonio coats Na
4SiW
12O
40
Get 1.85 gram N, N-dimethyl dodecyl 12-(4 '-octyloxy-4-azobenzene) dodecyloxy brometo de amonio (being 2.35mmol) is dissolved in 30 milliliters of chloroforms, 2.01 gram Na
4SiW
12O
40(being 0.59mmol) is dissolved in 90 ml waters.Tensio-active agent and Na
4SiW
12O
40Charge ratio be 4: 1.Maintain the temperature at 40-50 degree centigrade, with N, the chloroformic solution of N-dimethyl dodecyl 12-(4 '-octyloxy-4-azobenzene) dodecyloxy brometo de amonio dropwise joins Na
4SiW
12O
40The aqueous solution in.Dripping the back continues to stir 4-5 hour.Afterwards, separate organic phase and add 1 gram anhydrous magnesium sulfate drying.Remove by filter organic solvent, the vacuum-drying of gained yellow solid, productive rate 73-77%.
Embodiment 2-11
N, two [12-(4 '-octyloxy-4-azobenzene) the ten dioxy alkane] brometo de amonios of N-dimethyl coat H
3PW
12O
40
Get 2.34 gram N, two [12-(4 '-octyloxy-4-azobenzene) dodecyloxy] brometo de amonios (being 2.04mmol) of N-dimethyl are dissolved in 40 milliliters of chloroforms, 2.2 gram H
3PW
12O
40(being 0.68mmol) is dissolved in 80 ml waters.Tensio-active agent and H
3PW
12O
40Charge ratio be 3: 1.Maintain the temperature at 40-50 degree centigrade, with N, the chloroformic solution of two [12-(4 '-octyloxy-4-azobenzene) dodecyloxy] brometo de amonios of N-dimethyl dropwise joins H
3PW
12O
40The aqueous solution in.Dripping the back continues to stir 4-5 hour.Afterwards, separate organic phase and remove organic solvent (not adding siccative), the vacuum-drying of gained red solid, productive rate 71-78%.
Claims (4)
1, the preparation method of multi-metal oxygen cluster hybrid liquid crystal material, comprise that the synthetic and cats product that contains the mesomorphic group cats product that is suitable for coating multi-metal oxygen cluster carries out static to multi-metal oxygen cluster and coats two steps, it is characterized in that:
(1) be suitable for coating multi-metal oxygen cluster contain the mesomorphic group cats product synthetic be to carry out the quaternized realization of two-step reaction by haloalkane and the tertiary amine that contains mesomorphic group or the haloalkane that contains mesomorphic group and secondary amine;
(2) containing mesomorphic group cats product static coats multi-metal oxygen cluster to prepare the liquid crystal liquid crystal property mixture be to realize by the method that the organic and inorganic two-phase coats: multi-metal oxygen cluster that at first will be to be coated is soluble in water, concentration is the 10-30 mg/ml, and the temperature that keeps the aqueous solution is at 40-50 degree centigrade;
The cats product that will contain mesomorphic group in addition is dissolved in the chloroform, concentration is 0.02-0.07mol/L, control the two consumption, making the ratio of the total charge number of the total charge number of multi-metal oxygen cluster and tensio-active agent is 1: 0.9-1: 1, under whipped state, the chloroformic solution of the tensio-active agent speed with the 1.0-1.3 ml/min is added drop-wise in the multi-metal oxygen cluster aqueous solution; Maintain the temperature under the 40-50 degrees celsius, continue to stir after 4-5 hour and tell organic phase with separating funnel, organic phase washes with water 2-3 time again, the anhydrous sodium sulfate drying 30-60 minute after-filtration that adds reaction system gross weight 20-40% then, solvent evaporated promptly obtains containing the multi-metal oxygen cluster mixture that the mesomorphic group cats product coats.
2, the preparation method who contains the hybrid liquid crystal material of multi-metal oxygen cluster as claimed in claim 1, it is characterized in that: institute's synthetic surfactant basic structure is made of the hydrophilic head of quaternary ammonium salt cationic, hydrophobic alkyl chain interval, rigidity nitrogen benzide or biphenyl mesomorphic group and end alkyl chain, its structural formula is as follows
Or
5≤n≤11,8≤m≤12 wherein, MES is
Or
3, the preparation method who contains the hybrid liquid crystal material of multi-metal oxygen cluster as claimed in claim 1, it is characterized in that: the cats product that contains mesomorphic group is N, two [10-(4 '-own alkoxyl group-4-xenyl) alkoxyl group in the last of the ten Heavenly stems] brometo de amonios of N-dimethyl, N, two [10-(4 '-Xin alkoxyl group-4-xenyl) alkoxyl group in the last of the ten Heavenly stems] brometo de amonios of N-dimethyl, N, N-dimethyl two [10-(4 '-last of the ten Heavenly stems alkoxyl group-4-xenyl) alkoxyl group in the last of the ten Heavenly stems] brometo de amonio, N, two [10-(4 '-dodecyloxy-4-xenyl) alkoxyl group in the last of the ten Heavenly stems] brometo de amonios of N-dimethyl, N, two [12-(4 '-Xin alkoxyl group-4-azobenzene) dodecyloxy] brometo de amonio and the N of N-dimethyl, N-dimethyl dodecyl 12-(4 '-Xin alkoxyl group-4-azobenzene) dodecyloxy brometo de amonio.
4, the preparation method who contains the hybrid liquid crystal material of multi-metal oxygen cluster as claimed in claim 1, it is characterized in that: multi-metal oxygen cluster to be coated is: the Na with photoluminescence
9EuW
10O
36, K
13[Eu (SiW
11O
39)
2], K
15[Eu (BW
11O
39)
2] or K
11[Eu (PW
11O
39)
2], have the H of catalytic
3PW
12O
40Or Na
3PW
12O
40Na
4SiW
12O
40
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