CN101973878B - Liquid crystal compound containing dicyclohexyl as well as preparation method and application thereof - Google Patents
Liquid crystal compound containing dicyclohexyl as well as preparation method and application thereof Download PDFInfo
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 50
- 150000001875 compounds Chemical class 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 23
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 239000003960 organic solvent Substances 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 238000001953 recrystallisation Methods 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- NPSSWQJHYLDCNV-UHFFFAOYSA-N prop-2-enoic acid;hydrochloride Chemical compound Cl.OC(=O)C=C NPSSWQJHYLDCNV-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004965 chloroalkyl group Chemical group 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 abstract description 5
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 238000004891 communication Methods 0.000 abstract description 3
- 230000010287 polarization Effects 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 229920005570 flexible polymer Polymers 0.000 abstract description 2
- 239000004566 building material Substances 0.000 abstract 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical compound C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 abstract 1
- 238000012856 packing Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 23
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 8
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- -1 organic compound cholesteryl benzoate Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000005267 main chain polymer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000005264 High molar mass liquid crystal Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000005266 side chain polymer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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Abstract
The invention discloses a liquid crystal compound containing dicyclohexyl as well as a preparation method and application thereof. The structural general formula of the liquid crystal compound is shown in the formula I, wherein n is an integer from 1 to 5, and m is an integer from 2 to 6; and -(CH2)m- and -CnH2n+1 are linear chain alkyl groups. The dicyclohexane macromolecular liquid crystal compound intermediate provided by the invention comprises a dicyclohexyl rigid frame and double-bond groups which can be polymerized to form a flexible polymer repeating unit. The frame does not comprise a pi-electron system of benzene rings, the charge density distribution is reduced, the polarization is weakened, and cyclohexane rings are mutually stacked in a staggered mode to form compact packing, thus the clearing point of the liquid crystal phase can be improved. Compared with the aromatic ring liquid crystal with the similar structure, the liquid crystal of the invention has lower viscosity, better stability and hardly andy ultraviolet absorption. The liquid crystal compound of the invention is a good liquid crystal function material and can be used for many fields of building materials, anti-counterfeiting materials, optical communication materials, new optical materials and the like. Formula I is shown in the specification.
Description
Technical field
The present invention relates to a kind of liquid crystalline cpd that contains dicyclohexyl and preparation method thereof and application.
Background technology
1888, Austrian scientist F.Reinitzer synthesized a kind of special organic compound cholesteryl benzoate, when its solid crystals is heated to 145 ℃, just is melt into liquid, and is only muddy, and is transparent during all pure materials fusings.If when continuing to be heated to 175 ℃, as if it is again fusing, becomes as clear as crystal liquid.This clarified liq cools off a little, and muddiness is appeared again again existing.Roentgen Lehmann is defined as the crystalline state fluid with it after this material is furtherd investigate, and crystal (Fliessende kristalle), namely said liquid crystal today (liquid crystal) flow.Development through decades, especially nearly two during the last ten years, the liquid crystal theory is constantly perfect, and the liquid crystal science has also obtained many important development, and research field spreads all over the every subjects such as liquid crystal optics, molecular physics, Liquid Crystal, liquid crystal molecule spectrum, Liquid Crystalline Biomacromolecules.
High molecule liquid crystal is to have a base polymer that is similar to the low molecular weight liquid crystal ordered structure, and they present the distinctive flowability of liquid crystal and anisotropy in molten state or solution.Find in to the molten research process that causes the type Liquid Crystalline Polymeric Materials, some high molecule liquid crystal demonstrates the function of biological tissue in specific solvent, and this is for synthesized membrane and make it to have biological activity possibility is provided; In the research process to the thermotropic Liquid Crystalline Polymeric Materials, find, because the existence of liquid crystal phase in the polymkeric substance, the various synthon that can obtain superstrength, ultra high modulus, thermostability are high and mechanical property is good, this has caused the huge interest of people to macromolecular compound liquid crystal state structure more.Along with to the deepening continuously of such investigation of materials, the matrix material that is obtained by the liquid crystal state polymkeric substance has been widely used in a plurality of fields such as aerospace material, material of construction, anti-fake material, optical communication material and novel optical material.
Liquid Crystalline Polymeric Materials is divided into compound three classes of main chain polymer, side chain polymer and main chain side chain usually according to its structure.The constructional feature of main chain polymer liquid crystal is that polymer repeat unit is the rigid backbone with mesomorphic phase structure, as shown in Figure 1; The constructional feature of side chain high molecule liquid crystal is that the repeating unit of polymkeric substance is flexible, has the rigid backbone of mesomorphic phase structure on the side chain of molecule, as shown in Figure 2; The constructional feature of main chain side chain composite polymer liquid crystal is all to have the rigid backbone with mesomorphic phase structure on the side chain of polymer repeat unit and polymer molecule, as shown in Figure 3.
In the application process of liquid crystal, in order to satisfy all-environment requirement, various Secretaries have been proposed liquid crystal material.Early stage high molecule liquid crystal has in the rigid backbone of mesomorphic phase structure and usually all contains benzene ring structure, contains a large conjugated system in the benzene ring structure, and UV-light is had stronger absorption, has therefore affected the stability of material; Along with going deep into of research, cyclohexane ring is more and more introduced in the rigid backbone, and behind the phenyl ring that replaces with cyclohexane ring in the liquid crystal, the π-electron system reduces or disappears, charge density distribution reduces, polarization weakens, and cyclohexane ring is interlaced stacks, and forms tightly packed, cause the liquid crystal clearing point to increase, the aromatic ring class mesomorphic phase specific viscosity of such liquid crystal and structural similitude is lower, and does not almost have uv-absorbing, and stability is better.
Summary of the invention
The purpose of this invention is to provide a kind of liquid crystalline cpd that contains dicyclohexyl and preparation method thereof.
Liquid crystalline cpd provided by the present invention, its general structure are suc as formula the compound shown in (I):
(formula I)
Among the formula I, n is the integer of 1-5, and m is the integer of 2-6;-(CH
2)
m-and-C
nH
2n+1Be straight chained alkyl.
The preparation method of formula I compound provided by the present invention comprises the steps:
1) in inert atmosphere, alkyl dicyclohexyl shown in formula II alcohol and the chloro alkyl alcohol shown in the formula III or bromo alkyl alcohol are reacted under the condition that sodium hydride (NaH) exists, obtain the 4-hydroxyl-alkoxyl group-4 ' shown in the formula IV-alkyl-bis cyclohexane;
2) in inert atmosphere, the acrylate chloride shown in the 4-hydroxyl-alkoxyl group-4 ' shown in the formula IV-alkyl-bis cyclohexane and the formula V is reacted, obtain the compound shown in the formula I;
(formula II) (formula III)
(formula IV) (formula V)
In the described structural formula, n is the integer of 1-5, and m is the integer of 2-6;-(CH
2)
m-and-C
nH
2n+1Be straight chained alkyl.
Aforesaid method step 1) reaction described in is carried out in organic solvent, and described organic solvent specifically can be tetrahydrofuran (THF), ether or dioxane.
Step 1) in the described reaction, the alkyl dicyclohexyl alcohol shown in the formula II can be (1-2) with the mol ratio of chloro alkyl alcohol shown in the formula III or bromo alkyl alcohol: (1-2), such as 1: 1,1: 1.5,1: 2,1.5: 1 or 2: 1; The temperature of reaction of described reaction is 50-60 ℃, and the reaction times is 1-24 hour.
The method also can be included in step 2) front to step 1) the formula IV compound that obtains carries out the step of purifying, method is as follows: step 1) described in after reaction finishes, in the reaction solution that contains formula IV compound, add entry, the separated and collected organic solvent layer, washing, dried over sodium sulfate is steamed except described organic solvent, the solid that obtains sherwood oil recrystallization namely obtains the formula IV compound behind the purifying.
Aforesaid method step 2) reaction described in is also carried out in organic solvent, and described organic solvent is benzene or toluene.
Step 2) in the described reaction, the mol ratio of the acrylate chloride shown in the 4-hydroxyl-alkoxyl group-4 ' shown in the formula IV-alkyl-bis cyclohexane and the formula V can be 1: (1-2), such as 1: 1,1: 1.5,1: 2; The temperature of reaction of described reaction is 60-90 ℃, and the reaction times is 3-10 hour.
Method of the present invention also can comprise the step of formula I compound being carried out purifying, method is as follows: step 2) described in after reaction finishes, in the reaction solution that contains formula I compound, add entry, the separated and collected organic solvent layer, washing, dried over sodium sulfate is steamed except described organic solvent, the solid that obtains sherwood oil recrystallization namely obtains the formula I compound behind the purifying.
Inert atmosphere is nitrogen atmosphere described in the inventive method.
Another object of the present invention provides the purposes of compound shown in the formula (I).
The purposes of compound shown in the formula provided by the present invention (I) is that this compound is as the application of liquid crystal material.
In addition, can also formula (I) compound be monomer (or performed polymer) preparation high molecule liquid crystal compound.
Dicyclic hexane high molecule liquid crystal compound intermediate provided by the invention, have the two key groups and the dicyclohexyl rigid backbone that can polymerization form the flexible polymer repeating unit, this skeleton is without the π-electron system of phenyl ring, charge density distribution reduces, polarization weakens, and cyclohexane ring is interlaced to be stacked, form tightly packed, can improve the clearing point of mesomorphic phase, the aromatic ring class mesomorphic phase specific viscosity of such liquid crystal and structural similitude is lower, and does not almost have uv-absorbing, and stability is better, be a kind of good liquid crystal functional materials, can be used for material of construction, anti-fake material, a plurality of fields such as optical communication material and novel optical material.
Description of drawings
Fig. 1 is the structure iron of main chain polymer liquid crystal.
Fig. 2 is the structure iron of side chain high molecule liquid crystal.
Fig. 3 is the structure iron of main chain side chain composite polymer liquid crystal.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.
Experimental technique among the following embodiment if no special instructions, is ordinary method.Used test materials if no special instructions, is and purchases available from conventional reagent shop.
The preparation of embodiment 1,2-((4 '-methyl-dicyclohexyl)-4-oxygen base) ethyl-acrylate (m=2 among the formula I, the compound of n=1)
1) preparation of 4-hydroxyl-oxyethyl group-4 '-methyl-bis cyclohexane
In the 250ML there-necked flask; under the nitrogen protection; 2.4 gram (0.1mol) sodium hydrides are dissolved in the 100ml tetrahydrofuran (THF) (THF); again methyl bicycle hexyl alcohol 19.6 grams (0.1mol) are added in the reaction flask, stirred 0.5 hour, drip 12.1 gram (0.15mol) 2-chloro-ethanol; dropwise and stirred 1 hour; refluxed 6 hours at 60 ℃, after the cooling, add 50ml water; isolate the THF layer; washing THF layer, dried over sodium sulfate steams THF; the solid that obtains 50ml sherwood oil recrystallization; obtain white solid 14.9 grams, be 4-hydroxyl-oxyethyl group-4 '-methyl-bis cyclohexane, yield 62%.
2) preparation of 2-((4 '-methyl-dicyclohexyl)-4-oxygen base) ethyl-acrylate
In the 250ML there-necked flask; under the nitrogen protection; adding above-mentioned 24 gram (0.1mol) 4-hydroxyl-oxyethyl group-4 '-methyl-bis cyclohexanes adds in the reaction flask and 100ml benzene; stirred 0.5 hour; drip 9.05 gram (0.1mol) acrylate chlorides, dropwise, refluxed 4 hours at 80 ℃; after the cooling; add 50ml water, isolate the benzene layer, washing; dried over sodium sulfate; steam benzene, the solid that obtains obtains white solid 26.5 grams with 100ml sherwood oil recrystallization; be 2-((4 '-methyl-dicyclohexyl)-4-oxygen base) ethyl-acrylate, yield 90%.
This product structure appraising datum is as follows:
IR：3090，3025，2975，2960，2920，2860，，1730，1635，1470，，1300，1150，990，910，725；
MS：294(M+)，240，223，196，179，165
HNMR：0.96(3H)，1.27～1.70(19H)，2.79(1H)，3.65(2H)，4.27(2H)，5.80(1H)，6.05(1H)，6.43(1H)
By the said determination result as can be known, this compound structure is correct.
The DSC data are as follows:
DSC:T
C-N(fusing point) 41 ℃
Viscosity: 23mm
2S
Measure dielectric anisotropy (Δ ε) and the specific refractory power anisotropy (Δ n) of 2-((4 '-methyl-dicyclohexyl)-4-oxygen base) ethyl-acrylate liquid crystalline cpd.
Take TEB110 (being purchased from Shijiazhuang Yongshenghuaqing Liquid Crystal Co., Ltd) as the parent mixed liquid crystal, 2-((4 '-methyl-dicyclohexyl)-4-oxygen base) ethyl-acrylate liquid crystalline cpd is pressed 5% (w/w, mass ratio) is dissolved among the TEB 110, under the condition of 20 ℃ and 1KHz, test the ε of 2-((4 '-methyl-dicyclohexyl)-4-oxygen base) ethyl-acrylate liquid crystalline cpd with capacitance method || and ε ⊥, and calculate the Δ ε of this liquid crystal compound, thereby calculate the ε of pure 2-((4 '-methyl-dicyclohexyl)-4-oxygen base) ethyl-acrylate liquid crystalline cpd || and ε ⊥, and calculate the Δ ε of this liquid crystalline cpd, test result is listed in the table 1.
Utilize Abbe refractometer, measure ne and the no of above-mentioned liquid crystal compound, and calculate the Δ ε of this liquid crystal compound.Thereby calculate ne and the no of this pure liquid crystalline cpd, and calculate the Δ n of this liquid crystalline cpd, test result is listed in the table 1.
Wherein, the method for calculation of Δ ε and Δ n are as follows:
The parameter ε of parent liquid crystal TEB110 (B) || (B), ε ⊥ (B) and Δ ε (B) see Table 1, liquid crystalline cpd (A) is dissolved among the parent liquid crystal TEB110 by 5% (W/W), under the condition of 20 ℃ and 1KHz, test the ε of this liquid crystal compound with capacitance method || and ε ⊥, and calculate the Δ ε of this liquid crystal compound, Δ ε=ε ||-ε ⊥.
According to the additivity of liquid crystalline cpd dielectric anisotropy, calculate ε || (A), ε ⊥ (A), Δ ε (A)
ε||＝ε||(A)×5％+ε||(B)×95％ ε||(A)＝[ε||-ε||(B)×95％]/5％
ε⊥＝ε⊥(A)×5％+ε⊥(B)×95％ ε⊥(A)＝[ε⊥×5％+ε⊥(B)×95％]/5％
Δε(A)＝ε||(A)-ε⊥(A)
The parameter ne (B) of parent liquid crystal TEB110 (B), no (B) and Δ n (B) see Table 1, liquid crystalline cpd (A) is dissolved among the parent liquid crystal TEB110 by 5% (W/W), utilize Abbe refractometer to measure ne, the no of liquid crystal compound, and calculate the Δ n of this liquid crystal compound, Δ n=ne-no.
According to the anisotropic additivity of liquid crystalline cpd specific refractory power, calculate ne (A), no (A) and Δ n (A)
ne＝ne(A)×5％+ne(B)×95％ ne(A)＝[ne-ne(B)×95％]/5％
no＝no(A)×5％+no(B)×95％ no(A)＝[no×5％+no(B)×95％]/5％
Δn(A)＝ne(A)-no(A)
The measurement result of table 12-((4 '-methyl-dicyclohexyl)-4-oxygen base) ethyl-acrylate liquid crystalline cpd
| ne | no | Δn | ε|| | ε⊥ | Δε | |
| TEB110(B) | 1.640 | 1.503 | 0.137 | 14.6 | 6.0 | 8.6 |
| Mixture | 1.635 | 1.502 | 0.132 | 14.11 | 5.86 | 8.25 |
| A | 1.541 | 1.499 | 0.042 | 4.76 | 3.18 | 1.58 |
The preparation of embodiment 2,3-((4 '-methyl-dicyclohexyl)-4-oxygen base) propyl group-acrylate (m=3 among the formula I, the compound of n=1)
1) preparation of 4-hydroxyl-propoxy--4 '-methyl-bis cyclohexane
In the 250ML there-necked flask; under the nitrogen protection; 2.4 gram (0.1mol) sodium hydrides are dissolved in the 100ml ether; again methyl bicycle hexyl alcohol 19.6 grams (0.1mol) are added in the reaction flask, stirred 0.5 hour, drip 25 gram (0.2mol) 3-bromo-propyl alcohol; dropwise and stirred 1 hour; refluxed 6 hours at 55 ℃, after the cooling, add 50ml water; isolate the THF layer; washing, dried over sodium sulfate steams THF; the solid that obtains 50ml sherwood oil recrystallization; obtain 19.2 gram white solids, be 4-hydroxyl-propoxy--4 '-methyl-bis cyclohexane, yield 75%.
2) preparation of 3-((4 '-methyl-dicyclohexyl)-4-oxygen base) propyl group-acrylate
In the 250ML there-necked flask; under the nitrogen protection; add above-mentioned 25.6 gram (0.1mol) 4-hydroxyl-propoxy--4 '-methyl-bis cyclohexane and 100ml toluene; stirred 1 hour; drip 13.58 gram (0.15mol) acrylate chlorides, dropwise and stirred 5 hours, refluxed 4 hours at 90 ℃; after the cooling; add 100ml water, isolate toluene layer, washing; dried over sodium sulfate; steam toluene, the solid that obtains obtains white solid 29.3 grams with 100lL sherwood oil recrystallization; be 3-((4 '-methyl-dicyclohexyl)-4-oxygen base) propyl group-acrylate, yield 95%.
This product structure appraising datum is as follows:
IR：3090，3020，2980，2960，2920，2860，，1735，1635，1470，，1300，1150，990，900
MS：308(M+)，255，237，196，179，165；
HNMR：0.97(3H)，1.27～1.70(19H)，1.86(2H)，2.79(1H)，3.37(2H)，4.20(2H)，5.80(1H)，6.05(1H)，6.43(1H)
By the said determination result as can be known, this compound structure is correct.
The DSC data are as follows:
DSC:T
C-N(fusing point) 46 ℃
Viscosity: 25mm
2S
Adopt Δ n and the Δ ε of method mensuration 3-((4 '-methyl-the dicyclohexyl)-4-oxygen base) propyl group-acrylate liquid crystalline cpd identical with embodiment 1.Data are as follows: Δ n:0.038, Δ ε: 1.39.
Claims (10)
1. general structure is suc as formula the compound shown in (I):
(formula I)
Wherein, n is the integer of 1-5, and m is the integer of 2-6;-(CH
2)
m-and-C
nH
2n+1Be straight chained alkyl.
2. compound according to claim 1, it is characterized in that: the compound shown in the described formula (I) is following 1) or 2) in compound:
1) m=2 in the formula (I), the compound of n=1;
2) m=3 in the formula (I), the compound of n=1.
3. prepare the method for the described compound of claim 1, comprise the steps:
1) in inert atmosphere, the alcohol of the alkyl dicyclohexyl shown in the formula II and the chloro alkyl alcohol shown in the formula III or bromo alkyl alcohol are reacted under the condition that sodium hydride exists, obtain the 4-hydroxyl-alkoxyl group-4 ' shown in the formula IV-alkyl-bis cyclohexane;
2) in inert atmosphere, the acrylate chloride shown in the 4-hydroxyl-alkoxyl group-4 ' shown in the formula IV-alkyl-bis cyclohexane and the formula V is reacted, obtain the compound shown in the formula I;
(formula II) (formula III)
(formula IV) (formula V)
Among described formula II, formula III and the formula IV, n is the integer of 1-5, and m is the integer of 2-6;-(CH
2)
m-and-C
nH
2n+1Be straight chained alkyl.
4. method according to claim 3 is characterized in that: step 1) in the described reaction, the alkyl dicyclohexyl alcohol shown in the formula II is (1-2) with the mol ratio of chloro alkyl alcohol shown in the formula III or bromo alkyl alcohol: (1-2); The temperature of reaction of described reaction is 50-60 ℃, and the reaction times is 1-24 hour;
Step 1) reaction described in is carried out in organic solvent, and described organic solvent is tetrahydrofuran (THF), ether or dioxane; Described inert atmosphere is nitrogen atmosphere.
5. method according to claim 4, it is characterized in that: described method also is included in step 2) front to step 1) the formula IV compound that obtains carries out the step of purifying, method is as follows: step 1) described in after reaction finishes, in the reaction solution that contains formula IV compound, add entry, separated and collected organic solvent layer, washing, dried over sodium sulfate, steam except described organic solvent, the solid that obtains sherwood oil recrystallization namely obtains the formula IV compound behind the purifying.
6. each described method is characterized in that: step 2 according to claim 3-5) in the described reaction, the mol ratio of the acrylate chloride shown in the 4-hydroxyl-alkoxyl group-4 ' shown in the formula IV-alkyl-bis cyclohexane and the formula V is 1:(1-2); The temperature of reaction of described reaction is 60-90 ℃, and the reaction times is 3-10 hour.
7. method according to claim 6 is characterized in that: step 2) described reaction carries out in organic solvent, and described organic solvent is benzene or toluene; Described inert atmosphere is nitrogen atmosphere.
8. method according to claim 7, it is characterized in that: described method also comprises step 2) the formula I compound that obtains carries out the step of purifying, method is as follows: step 2) described in after reaction finishes, in the reaction solution that contains formula I compound, add entry, separated and collected organic solvent layer, washing, dried over sodium sulfate, steam except described organic solvent, the solid that obtains sherwood oil recrystallization namely obtains the formula I compound behind the purifying.
9. claim 1 or 2 described compounds are as the application of liquid crystal material.
10. claim 1 or the 2 described compounds application in preparation high molecule liquid crystal compound.
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