CN115820265B - High-flexibility liquid crystal polymer and preparation method thereof - Google Patents
High-flexibility liquid crystal polymer and preparation method thereof Download PDFInfo
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- CN115820265B CN115820265B CN202211528153.4A CN202211528153A CN115820265B CN 115820265 B CN115820265 B CN 115820265B CN 202211528153 A CN202211528153 A CN 202211528153A CN 115820265 B CN115820265 B CN 115820265B
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- 229920000106 Liquid crystal polymer Polymers 0.000 title claims abstract description 51
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical group C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 claims abstract description 42
- 235000012000 cholesterol Nutrition 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims description 94
- 238000006243 chemical reaction Methods 0.000 claims description 69
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 34
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 30
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 30
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims description 18
- 229960002479 isosorbide Drugs 0.000 claims description 18
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 18
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 14
- 229920002307 Dextran Polymers 0.000 claims description 12
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 12
- LEAQUNCACNBDEV-ZHACJKMWSA-N (e)-undec-1-en-1-ol Chemical compound CCCCCCCCC\C=C\O LEAQUNCACNBDEV-ZHACJKMWSA-N 0.000 claims description 10
- 229910001923 silver oxide Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- GIEMHYCMBGELGY-UHFFFAOYSA-N 10-undecen-1-ol Chemical compound OCCCCCCCCCC=C GIEMHYCMBGELGY-UHFFFAOYSA-N 0.000 claims description 3
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000009477 glass transition Effects 0.000 abstract description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 36
- 239000000047 product Substances 0.000 description 29
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 24
- 239000012043 crude product Substances 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 239000004973 liquid crystal related substance Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 3
- 229920001503 Glucan Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008268 response to external stimulus Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Steroid Compounds (AREA)
Abstract
The application relates to a high-flexibility liquid crystal polymer and a preparation method thereof, belonging to the technical field of high-molecular compounds; the side chain terminal of the liquid crystal polymer has chiral units, so that the glass transition temperature of the liquid crystal polymer can be reduced, and the flexibility of the liquid crystal polymer is further improved. Meanwhile, the structure of the liquid crystal polymer contains cholesterol units, so that the glass transition temperature can be reduced, the flexibility of the liquid crystal polymer is improved, and the problem of poor flexibility of the conventional liquid crystal polymer is solved.
Description
Technical Field
The application relates to the technical field of high molecular compounds, in particular to a high-flexibility liquid crystal polymer and a preparation method thereof.
Background
Liquid crystal polymers are found and applied in the nineteenth century, and the liquid crystal polymers are used as a special response material, and can generate different response signals under different environments such as light, electricity, magnetism and the like, so that materials with the properties of both the polymers and the liquid crystals can be prepared by combining the liquid crystal materials and the high polymer materials, and the liquid crystal materials are applied to various fields such as displays, sensors and the like.
The liquid crystal polymer is provided with a side chain type liquid crystal polymer and a main chain liquid crystal polymer, the side chain type liquid crystal polymer is different from the main chain liquid crystal polymer, the flexible main chain only plays a role of connecting mesogenic units, the property of the flexible main chain is mainly determined by mesogenic units at the side chain position, the influence of the main chain of the polymer is small, but the phase transition temperature of the material and the response to external stimulus can still be influenced by changing the flexibility of the main chain.
In recent years, side chain liquid crystals have been developed toward the supramolecular structure. Self-assembly is realized through non-covalent interactions such as hydrogen bonds, ionic dipoles, charge transfer and the like, so that liquid crystal molecules are ordered. However, the flexibility of the current liquid crystal polymers is still poor.
Disclosure of Invention
The application provides a high-flexibility liquid crystal polymer and a preparation method thereof, which are used for solving the problem of poor flexibility of the existing liquid crystal polymer.
In a first aspect, the present application provides a highly flexible liquid crystalline polymer having the formula:
Wherein, X 1 is:
wherein Y is:
X 2 is:
X 3 is:
d. m and n are each independently selected from positive integers.
In a second aspect, the present application provides a method for preparing a highly flexible liquid crystalline polymer, the method comprising:
Obtaining a first monomer, a second monomer and a third monomer;
Mixing a first monomer, a second monomer and a third monomer to obtain a mixture to be reacted;
mixing the mixture to be reacted, N-dimethylformamide and ammonia sulfate for reaction to obtain a liquid crystal polymer; wherein the chemical formula of the first monomer is:
the chemical formula of the second monomer is:
wherein Y is:
The chemical formula of the third monomer is:
as an alternative embodiment, the method for preparing the first monomer includes:
mixing dextran and acetic anhydride to react to obtain a first intermediate compound;
Mixing the first intermediate compound, acetic acid and hydrogen bromide to react to obtain a second intermediate compound;
And mixing the second intermediate compound, silver oxide and undecenol with chloroform to react to obtain a first monomer.
As an alternative embodiment, the molar ratio of the acetic anhydride to the dextran is not less than 7.
As an alternative embodiment, the molar ratio of the first intermediate compound to the hydrogen bromide is not less than 7.
As an alternative embodiment, the molar ratio of undecylenic alcohol to second intermediate compound is (1-3): 0.5-1.5.
As an alternative embodiment, the method for preparing the second monomer includes:
and mixing cholesterol and 4- (ethoxy acrylate) benzoyl chloride to react to obtain a second monomer.
As an alternative embodiment, the molar ratio of cholesterol to 4- (ethoxy acrylate) benzoyl chloride is (1-3): 0.5-1.5.
As an alternative embodiment, the method for preparing the third monomer includes:
mixing isosorbide, hydroquinone, acryloyl chloride and triethylamine to react to obtain a third monomer; wherein, the mole ratio of the isosorbide to the acryloyl chloride is 1:1.
As an alternative embodiment, the molar ratio of the first monomer, the second monomer and the third monomer is 1:5:1.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
The liquid crystal polymer provided by the embodiment of the application has chiral units at the tail ends of the side chains, so that the glass transition temperature of the liquid crystal polymer can be reduced, and the flexibility of the liquid crystal polymer is further improved. Meanwhile, the structure of the liquid crystal polymer contains cholesterol units, so that the glass transition temperature can be reduced, the flexibility of the liquid crystal polymer is improved, and the problem of poor flexibility of the conventional liquid crystal polymer is solved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the application or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to a person skilled in the art that other drawings can be obtained from these drawings without inventive effort.
Fig. 1 is a flowchart of a method according to an embodiment of the present application.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present application are commercially available or may be prepared by existing methods.
The embodiment of the application provides a high-flexibility liquid crystal polymer, which has the following chemical formula:
Wherein, X 1 is:
wherein Y is:
X 2 is:
X 3 is:
As shown in fig. 1, based on a general inventive concept, an embodiment of the present application further provides a method for preparing a liquid crystal polymer with high flexibility, the method comprising:
s1, obtaining a first monomer, a second monomer and a third monomer;
in some embodiments, the method of preparing the first monomer comprises:
s1.1, mixing dextran and acetic anhydride to react to obtain a first intermediate compound;
Specifically, in this example, 100g of dextran was dissolved in 300ml of water, 200ml of acetic anhydride was added, and 20ml of 1mol sodium hydroxide solution was reacted at 37 degrees celsius overnight to remove water, to give a first intermediate compound.
The content of acetic anhydride is excessive, so that the hydroxyl groups of the glucan can react with the acetic anhydride, and further, the molar ratio of the acetic anhydride to the glucan is not less than 7. For example, dextran: the molar ratio of acetic anhydride was 1:7.
S2.2, carrying out a mixed reaction on the first intermediate compound, acetic acid and hydrogen bromide to obtain a second intermediate compound;
Specifically, in this example, 0.1mol of the first intermediate compound was added to 300ml of water, 5ml of acetic acid and 0.015mol of hydrogen bromide were added, and the mixture was lyophilized to give a second intermediate compound.
The hydrogen bromide content is small, and further, the molar ratio of the first intermediate compound to the hydrogen bromide is not less than 7. For example, the molar ratio of the first intermediate compound to hydrogen bromide is 7:1.
S1.3, mixing the second intermediate compound, silver oxide and undecenol with chloroform for reaction to obtain a first monomer.
Specifically, in this example, 0.1mol of the second intermediate compound was dissolved in 100ml of chloroform, 0.1g of silver oxide was added as a catalyst, and 0.2mol of undecenol was added to react overnight at 37 ℃.
Further, the molar ratio of the undecylenic alcohol to the second intermediate compound is (1-3): 0.5-1.5. Preferably, undecenol: the molar ratio of the second intermediate compound was 2:1.
The reaction process for the preparation of the first monomer is as follows:
in some embodiments, the method of preparing the second monomer comprises:
s1.4, mixing cholesterol and 4- (ethoxy acrylate) benzoyl chloride to react, and obtaining a second monomer.
Specifically, in this example, 38g of cholesterol was added to a reaction flask, and then 40 ml of pyridine was added to a temperature of 80 degrees celsius to dissolve the cholesterol. 0.05mol of 4- (ethoxy acrylate) benzoyl chloride in a 10% pyridine solution was added to the reaction flask at a rate of one drop per 10 seconds and reacted at 37 degrees celsius for 24 hours. And (3) distilling under reduced pressure to remove pyridine after the reaction is finished, and separating out the reacted component product through acid to obtain a white product. The crude product obtained was recrystallized from isopropanol to give the second monomer.
Further, the mole ratio of cholesterol to 4- (ethoxyacrylate) benzoyl chloride is (1-3): 0.5-1.5. Preferably, the molar ratio of cholesterol to 4- (ethoxy acrylate) benzoyl chloride is 2:1.
The reaction process for the preparation of the second monomer is as follows:
Wherein Y is
In some embodiments, the method of preparing the third monomer comprises:
S1.5, mixing isosorbide, hydroquinone, acryloyl chloride and triethylamine to react, and obtaining a third monomer.
Specifically, in this example, 15g of isosorbide and 0.5g of hydroquinone were put into a reaction flask, and the isosorbide and hydroquinone were dissolved with chloroform. After the mixture was sufficiently dissolved, 10g of acryloyl chloride and 0.5g of triethylamine were added thereto, and the mixture was reacted at room temperature for 24 hours. And after the reaction is finished, cooling the product to zero ℃, separating out a crude product, recrystallizing the crude product by using isopropanol, and drying to obtain a third monomer.
Further, the molar ratio of isosorbide to acryloyl chloride is 1:1.
The reaction process for the preparation of the second monomer is as follows:
s2, mixing the first monomer, the second monomer and the third monomer to obtain a mixture to be reacted;
In some embodiments, the first monomer, second monomer, and third monomer are in a molar ratio of 1:5:1.
S3, mixing the mixture to be reacted, N-dimethylformamide and ammonia sulfate for reaction to obtain a liquid crystal polymer;
Specifically, in this example, a certain amount of the first monomer, the second monomer and the third monomer are weighed into a reaction bottle, 30mL of N, N-dimethylformamide is added, 39 mg of ammonia persulfate is added, the reaction environment is filled with nitrogen, the reaction is carried out for 48 hours at 60 ℃, the reaction is cooled to room temperature, and after the crude product is separated out, acetone is used for recrystallization and drying, the product is obtained.
The reaction process of the mixing reaction is as follows:
Wherein, X 1 is:
wherein Y is:
X 2 is:
X 3 is:
d. m and n are each independently selected from positive integers.
The addition of chiral monomers (first and third monomers) not only reduces the cost of synthesis, but also lowers the glass transition temperature of the liquid crystal polymer, and lower glass transition temperature and cost provide the possibility for its application. The addition of the second monomer increases the stability of the liquid crystal polymer.
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. The experimental procedures, which are not specified in the following examples, are generally determined according to national standards. If the corresponding national standard does not exist, the method is carried out according to the general international standard, the conventional condition or the condition recommended by the manufacturer.
Example 1
A method for preparing a highly flexible liquid crystalline polymer, the method comprising:
(a) First monomer Synthesis
100G of dextran was dissolved in 300ml of water, 200ml of acetic anhydride was added, 20ml of 1mol of sodium hydroxide solution was reacted at 37 degrees celsius overnight to remove water, to obtain a first intermediate compound, 0.1mol of the first intermediate compound was added to 300ml of water, 5ml of acetic acid and 0.015mol of hydrogen bromide were added to freeze-dry to obtain a second intermediate compound, 0.1mol of the second intermediate compound was dissolved in 100ml of chloroform, 0.1g of silver oxide was added as a catalyst, and 0.2mol of undecenol was added to react at 37 degrees celsius overnight.
(B) Synthesis of the second monomer
38G of cholesterol was added to the reaction flask, and 40 ml of pyridine was then added to 80 degrees celsius to dissolve the cholesterol. 0.05mol of 4- (ethoxy acrylate) benzoyl chloride in a 10% pyridine solution was added to the reaction flask at a rate of one drop per 10 seconds and reacted at 37 degrees celsius for 24 hours. And (3) distilling under reduced pressure to remove pyridine after the reaction is finished, and separating out the reacted component product through acid to obtain a white product. The crude product obtained was recrystallized from isopropanol.
(C) Synthesis of third monomer
15G of isosorbide and 0.5g of hydroquinone were put into a reaction flask, and the isosorbide and hydroquinone were dissolved with chloroform. After the mixture was sufficiently dissolved, 10g of acryloyl chloride and 0.5g of triethylamine were added thereto, and the mixture was reacted at room temperature for 24 hours. And after the reaction is finished, cooling the product to zero ℃, separating out a crude product, recrystallizing the crude product by using isopropanol, and drying to obtain the product.
(D) Synthesis of liquid crystal high molecular polymer
1Mol of first monomer, 5mol of second monomer and 1mol of third monomer are weighed into a reaction bottle, 500mL of N, N-dimethylformamide is added, 500 mg of ammonia persulfate is added, the reaction environment is filled with nitrogen, the reaction is carried out for 48 hours at 60 ℃, after the reaction is ended, the reaction is cooled to room temperature, the crude product is separated out, and then the product is obtained after the acetone is recrystallized and dried.
Example 2
A method for preparing a highly flexible liquid crystalline polymer, the method comprising:
(a) First monomer Synthesis
120G of dextran was dissolved in 310ml of water, 220ml of acetic anhydride was added, 22ml of 1mol of sodium hydroxide solution was reacted at 37 degrees celsius overnight to remove water, to obtain a first intermediate compound, 0.11mol of the first intermediate compound was added to 300ml of water, 5ml of acetic acid and 0.015mol of hydrogen bromide were added to freeze-dry to obtain a second intermediate compound, 0.11mol of the second intermediate compound was dissolved in 100ml of chloroform, 0.12g of silver oxide was added as a catalyst, and 0.2mol of undecenol was added to react overnight at 37 degrees celsius.
(B) Synthesis of the second monomer
40G of cholesterol was added to the reaction flask, and 45 ml of pyridine was then added to 80 degrees celsius to dissolve the cholesterol. 0.05mol of 4- (ethoxy acrylate) benzoyl chloride in a 10% pyridine solution was added to the reaction flask at a rate of one drop per 10 seconds and reacted at 37 degrees celsius for 24 hours. And (3) distilling under reduced pressure to remove pyridine after the reaction is finished, and separating out the reacted component product through acid to obtain a white product. The crude product obtained was recrystallized from isopropanol.
(C) Synthesis of third monomer
18G of isosorbide and 0.6g of hydroquinone were put into a reaction flask, and the isosorbide and hydroquinone were dissolved with chloroform. After the mixture was sufficiently dissolved, 10g of acryloyl chloride and 0.5g of triethylamine were added thereto, and the mixture was reacted at room temperature for 24 hours. And after the reaction is finished, cooling the product to zero ℃, separating out a crude product, recrystallizing the crude product by using isopropanol, and drying to obtain the product.
(D) Synthesis of liquid crystal high molecular polymer
1.1Mol of the first monomer, 5mol of the second monomer and 1mol of the third monomer are weighed into a reaction bottle, 500mL of N, N-dimethylformamide is added, 500 mg of ammonia persulfate is added, the reaction environment is filled with nitrogen, the reaction is carried out for 48 hours at 60 ℃, after the reaction is ended, the reaction is cooled to room temperature, the crude product is separated out, and then the product is obtained after the acetone recrystallization and drying are carried out.
Example 3
A method for preparing a highly flexible liquid crystalline polymer, the method comprising:
(a) First monomer Synthesis
140G of dextran was dissolved in 300ml of water, 200ml of acetic anhydride was added, 20ml of 1mol of sodium hydroxide solution was reacted at 37 degrees celsius overnight to remove water, to obtain a first intermediate compound, 0.1mol of the first intermediate compound was added to 300ml of water, 5ml of acetic acid and 0.015mol of hydrogen bromide were added to freeze-dry to obtain a second intermediate compound, 0.1mol of the second intermediate compound was dissolved in 100ml of chloroform, 0.1g of silver oxide was added as a catalyst, and 0.21mol of undecenol was added to react at 37 degrees celsius overnight.
(B) Synthesis of the second monomer
38G of cholesterol was added to the reaction flask, and 40 ml of pyridine was then added to 80 degrees celsius to dissolve the cholesterol. 0.05mol of 4- (ethoxy acrylate) benzoyl chloride in a 10% pyridine solution was added to the reaction flask at a rate of one drop per 10 seconds and reacted at 37 degrees celsius for 24 hours. And (3) distilling under reduced pressure to remove pyridine after the reaction is finished, and separating out the reacted component product through acid to obtain a white product. The crude product obtained was recrystallized from isopropanol.
(C) Synthesis of third monomer
15G of isosorbide and 0.5g of hydroquinone were put into a reaction flask, and the isosorbide and hydroquinone were dissolved with chloroform. After the mixture was sufficiently dissolved, 10g of acryloyl chloride and 0.5g of triethylamine were added thereto, and the mixture was reacted at room temperature for 24 hours. And after the reaction is finished, cooling the product to zero ℃, separating out a crude product, recrystallizing the crude product by using isopropanol, and drying to obtain the product.
(D) Synthesis of liquid crystal high molecular polymer
1.2Mol of the first monomer, 5mol of the second monomer and 1mol of the third monomer are weighed into a reaction bottle, 500mL of N, N-dimethylformamide is added, 500 mg of ammonia persulfate is added, the reaction environment is filled with nitrogen, the reaction is carried out for 48 hours at 60 ℃, after the reaction is ended, the reaction is cooled to room temperature, the crude product is separated out, and then the product is obtained after the acetone recrystallization and drying are carried out.
Example 4
A method for preparing a highly flexible liquid crystalline polymer, the method comprising:
(a) First monomer Synthesis
100G of dextran was dissolved in 300ml of water, 200ml of acetic anhydride was added, 20ml of 1mol of sodium hydroxide solution was reacted at 37 degrees celsius overnight to remove water, to obtain a first intermediate compound, 0.1mol of the first intermediate compound was added to 300ml of water, 5ml of acetic acid and 0.015mol of hydrogen bromide were added to freeze-dry to obtain a second intermediate compound, 0.1mol of the second intermediate compound was dissolved in 100ml of chloroform, 0.1g of silver oxide was added as a catalyst, and 0.2mol of undecenol was added to react at 37 degrees celsius overnight.
(B) Synthesis of the second monomer
38G of cholesterol was added to the reaction flask, and 40 ml of pyridine was then added to 80 degrees celsius to dissolve the cholesterol. 0.05mol of 4- (ethoxy acrylate) benzoyl chloride in a 10% pyridine solution was added to the reaction flask at a rate of one drop per 10 seconds and reacted at 37 degrees celsius for 24 hours. And (3) distilling under reduced pressure to remove pyridine after the reaction is finished, and separating out the reacted component product through acid to obtain a white product. The crude product obtained was recrystallized from isopropanol.
(C) Synthesis of third monomer
15G of isosorbide and 0.5g of hydroquinone were put into a reaction flask, and the isosorbide and hydroquinone were dissolved with chloroform. After the mixture was sufficiently dissolved, 10g of acryloyl chloride and 0.5g of triethylamine were added thereto, and the mixture was reacted at room temperature for 24 hours. And after the reaction is finished, cooling the product to zero ℃, separating out a crude product, recrystallizing the crude product by using isopropanol, and drying to obtain the product.
(D) Synthesis of liquid crystal high molecular polymer
1.3Mol of the first monomer, 5mol of the second monomer and 1mol of the third monomer are weighed into a reaction bottle, 500mL of N, N-dimethylformamide is added, 500 mg of ammonia persulfate is added, the reaction environment is filled with nitrogen, the reaction is carried out for 48 hours at 60 ℃, after the reaction is ended, the reaction is cooled to room temperature, the crude product is separated out, and then the product is obtained after the acetone recrystallization and drying are carried out.
Example 5
A method for preparing a highly flexible liquid crystalline polymer, the method comprising:
(a) First monomer Synthesis
100G of dextran was dissolved in 300ml of water, 200ml of acetic anhydride was added, 20ml of 1mol of sodium hydroxide solution was reacted at 37 degrees celsius overnight to remove water, to obtain a first intermediate compound, 0.1mol of the first intermediate compound was added to 300ml of water, 5ml of acetic acid and 0.015mol of hydrogen bromide were added to freeze-dry to obtain a second intermediate compound, 0.1mol of the second intermediate compound was dissolved in 100ml of chloroform, 0.1g of silver oxide was added as a catalyst, and 0.2mol of undecenol was added to react at 37 degrees celsius overnight.
(B) Synthesis of the second monomer
38G of cholesterol was added to the reaction flask, and 40 ml of pyridine was then added to 80 degrees celsius to dissolve the cholesterol. 0.05mol of 4- (ethoxy acrylate) benzoyl chloride in a 10% pyridine solution was added to the reaction flask at a rate of one drop per 10 seconds and reacted at 37 degrees celsius for 24 hours. And (3) distilling under reduced pressure to remove pyridine after the reaction is finished, and separating out the reacted component product through acid to obtain a white product. The crude product obtained was recrystallized from isopropanol.
(C) Synthesis of third monomer
15G of isosorbide and 0.5g of hydroquinone were put into a reaction flask, and the isosorbide and hydroquinone were dissolved with chloroform. After the mixture was sufficiently dissolved, 10g of acryloyl chloride and 0.5g of triethylamine were added thereto, and the mixture was reacted at room temperature for 24 hours. And after the reaction is finished, cooling the product to zero ℃, separating out a crude product, recrystallizing the crude product by using isopropanol, and drying to obtain the product.
(D) Synthesis of liquid crystal high molecular polymer
1.4Mol of the first monomer, 5mol of the second monomer and 1mol of the third monomer are weighed into a reaction bottle, 500mL of N, N-dimethylformamide is added, 500 mg of ammonia persulfate is added, the reaction environment is filled with nitrogen, the reaction is carried out for 48 hours at 60 ℃, after the reaction is ended, the reaction is cooled to room temperature, the crude product is separated out, and then the product is obtained after the acetone recrystallization and drying are carried out.
The properties of the materials prepared in examples 1 to 5 were analyzed, and the results are shown in the following table:
| glass transition temperature | Clearing point | |
| Example 1 | 89 | 250 |
| Example 2 | 78 | 246 |
| Example 3 | 65 | 235 |
| Example 4 | 60 | 221 |
| Example 5 | 58 | 210 |
As can be seen from the above table, the glass transition temperature decreases with increasing content of the first monomer, thereby improving the flexibility of the liquid crystal polymer, and the clearing point decreases with increasing content of the first monomer.
Various embodiments of the application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1,2,3, 4,5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In the present application, unless otherwise specified, terms such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present specification, the terms "include", "comprising" and the like mean "including but not limited to". Relational terms such as "first" and "second", and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Herein, "and/or" describing an association relationship of an association object means that there may be three relationships, for example, a and/or B, may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. Herein, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one" or the like refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
The foregoing is only a specific embodiment of the application to enable those skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A highly flexible liquid crystalline polymer characterized by the chemical formula:
Wherein, X 1 is:
Wherein Y is:
、
X 2 is:
、
X 3 is:
D, m and n are each independently selected from positive integers.
2. A method for preparing a highly flexible liquid crystalline polymer, the method comprising:
Obtaining a first monomer, a second monomer and a third monomer;
Mixing a first monomer, a second monomer and a third monomer to obtain a mixture to be reacted;
Mixing the mixture to be reacted, N-dimethylformamide and ammonia sulfate for reaction to obtain a liquid crystal polymer;
wherein the chemical formula of the first monomer is:
、
the chemical formula of the second monomer is:
Wherein Y is:
The chemical formula of the third monomer is:
。
3. the method for preparing a highly flexible liquid crystal polymer according to claim 2, wherein the method for preparing the first monomer comprises:
mixing dextran and acetic anhydride to react to obtain a first intermediate compound;
Mixing the first intermediate compound, acetic acid and hydrogen bromide to react to obtain a second intermediate compound;
And mixing the second intermediate compound, silver oxide and undecenol with chloroform to react to obtain a first monomer.
4. A method of producing a highly flexible liquid crystalline polymer as claimed in claim 3, wherein the molar ratio of said acetic anhydride to said dextran is not less than 7.
5. A method for producing a highly flexible liquid crystalline polymer as claimed in claim 3, wherein the molar ratio of said first intermediate compound to said hydrogen bromide is not less than 7.
6. A process for preparing a highly flexible liquid-crystalline polymer according to claim 3, wherein the molar ratio of undecylenic alcohol to the second intermediate compound is from (1 to 3): from (0.5 to 1.5).
7. The method for preparing a highly flexible liquid crystal polymer according to claim 2, wherein the method for preparing the second monomer comprises:
and mixing cholesterol and 4- (ethoxy acrylate) benzoyl chloride to react to obtain a second monomer.
8. The method for preparing a highly flexible liquid crystalline polymer according to claim 7, wherein the molar ratio of cholesterol to 4- (ethoxy acrylate) benzoyl chloride is (1-3): 0.5-1.5.
9. The method for preparing a highly flexible liquid crystal polymer according to claim 2, wherein the method for preparing the third monomer comprises:
mixing isosorbide, hydroquinone, acryloyl chloride and triethylamine to react to obtain a third monomer; wherein, the mole ratio of the isosorbide to the acryloyl chloride is 1:1.
10. The method for preparing a highly flexible liquid crystal polymer according to claim 9, wherein the molar ratio of the first monomer, the second monomer and the third monomer is 1:5:1.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5676878A (en) * | 1993-04-06 | 1997-10-14 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Liquid crystal polymers |
| JP2001316428A (en) * | 2000-05-10 | 2001-11-13 | Nitto Denko Corp | Branched cholesteric liquid crystal polymer |
| CN107077037A (en) * | 2014-08-20 | 2017-08-18 | 三星电子株式会社 | Display device and for this manufacture method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5676878A (en) * | 1993-04-06 | 1997-10-14 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Liquid crystal polymers |
| JP2001316428A (en) * | 2000-05-10 | 2001-11-13 | Nitto Denko Corp | Branched cholesteric liquid crystal polymer |
| CN107077037A (en) * | 2014-08-20 | 2017-08-18 | 三星电子株式会社 | Display device and for this manufacture method |
Non-Patent Citations (1)
| Title |
|---|
| 新型液晶高分子聚合物的合成与表征;陶旭晨，李磊;《纺织学报》;20110131;第32卷(第1期);20-24页 * |
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