CN108727606A - The method that graphene oxide is grafted low molecule aromatic polymer manufacture liquid crystal polymer - Google Patents

The method that graphene oxide is grafted low molecule aromatic polymer manufacture liquid crystal polymer Download PDF

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Publication number
CN108727606A
CN108727606A CN201810383224.3A CN201810383224A CN108727606A CN 108727606 A CN108727606 A CN 108727606A CN 201810383224 A CN201810383224 A CN 201810383224A CN 108727606 A CN108727606 A CN 108727606A
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liquid crystal
graphene oxide
catalyst
low molecule
crystal polymer
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石振东
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Wuyi University
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Wuyi University
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/001Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38Polymers
    • C09K19/3804Polymers with mesogenic groups in the main chain
    • C09K19/3809Polyesters; Polyester derivatives, e.g. polyamides

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention belongs to graphene oxide technical field and disclose graphene oxide grafting low molecule aromatic polymer manufacture liquid crystal polymer method, include the following steps:1) light base acid monomers, heteroaromatic diacid monomer, aromatic series diphenol monomer and acetic acid are fitted over and is reacted 2-6 hour in 120-150 degrees Celsius in the presence of catalyst A, obtain second phthalein oxo-compound and the mixture of diacid monomer, preparation epoxy group liquid crystal;2) under the conditions of inert gas, 220-330 DEG C, by in step 1) second phthalein oxo-compound and diacid monomer carry out cruel exchange reaction 1-4h in the presence of catalyst B and generate oligomer, then oligomer is carried out to negative pressure of vacuum preparation functional graphene oxide mixed solution under solid-state or molten state;It 3) will be in epoxy group liquid crystal grafted graphene oxide compound.The present invention can avoid damage to the liquid crystal property of macromolecular while assigning strand preferably flexibility, and assign liquid crystal polymer excellent mobile performance and mechanical property.

Description

The method that graphene oxide is grafted low molecule aromatic polymer manufacture liquid crystal polymer
Technical field
Present invention relates particularly to the methods that graphene oxide grafting low molecule aromatic polymer manufactures liquid crystal polymer, belong to Graphene oxide technical field.
Background technology
The liquid crystal state existence form important and universal as substance, the meaning of own profound and abundant intension.Liquid crystal is high Molecule is started late relative to liquid crystalline small molecules, and it is larger can to study space.Liquid crystal polymer is also known as liquid crystal polymer, is with liquid The polymer of brilliant property combines small molecule liquid crystal and polymer in different ways, be synthesis liquid crystal polymer it is simple and Practical method.Liquid crystal polymer is divided into two major classes, i.e., using rigid primitive as the backbone chain type of polymer backbone components and with it Side chain type as side group.The former polymerize by condensation polymerization or gradually obtains, and the latter is obtained by addition polymerization or chain polymerization It arrives.It can get the backbone chain type rigid chain liquid crystal polymer that can serve as high-strength material by condensation polymerization, obtained by addition polymerization It must possibly serve for the side chain type flexible chain liquid crystal polymer of photoelectric respone material.
Graphene oxide, it is a kind of by graphite prepared under the conditions of strong oxidizing property containing hydroxyl, epoxy group and carboxyl Monolithic layer carbon material is widely used in many fields in past 5 years, such as composite material, energy and material, sensor, thin Membrane material, Flied emission transistor material and technical field of biological material.Due to there are a large amount of oxygen-containing functional group, graphene oxide can be with Chemical modification graphene oxide is prepared by covalent bond chemical modification or non-covalent bond chemical modification.Chemical modification graphite oxide Alkene is because be provided simultaneously with the performance of graphene oxide and decorative material, it is possible to preferably apply in above-mentioned field.? Field of compound material is prepared, chemical modification graphene oxide especially can be better with polymer-modified graphene oxide It is dispersed in corresponding polymeric matrix, increases the compatibility of filler and matrix, improve the mechanical property of composite material.Currently, Graphene oxide has been used as filler to be used in many polymeric matrixs, for example, polystyrene, polymethyl methacrylate, Polyvinyl alcohol, polypropylene, polyurethane, polyester and makrolon.
By method physically or chemically, both the above substance is combined, can make a variety of materials in performance Learn from other's strong points to offset one's weaknesses, meets a variety of different requirements better than former composition material.Therefore, graphene is grafted low molecule aromatic polymer system The research of liquid making polycrystalline macromolecule has great importance.
Invention content
The technical problem to be solved in the present invention overcomes existing defect, provides graphene oxide grafting low molecule fragrance polymerization The method that object manufactures liquid crystal polymer, heteroaromatic diacid monomer have the ability for forming liquid crystal, are a kind of mesomorphic group, function There is about 150 degree of angle with molecular skeleton plane in group, can have after heteroaromatic diacid monomer is introduced liquid crystal polymer strand The linear regularity for imitating regulatory molecule chain can avoid damage to the liquid crystal liquid crystal property of macromolecular while assigning strand preferably flexibility Can, and assign liquid crystal polymer excellent mobile performance and mechanical property, it can effectively solve the problems in background technology.
In order to solve the above technical problem, the present invention provides the following technical solutions:
The method that the present invention provides graphene oxide grafting low molecule aromatic polymer manufacture liquid crystal polymer, including it is as follows Step:
1) by light base acid monomers, heteroaromatic diacid monomer, aromatic series diphenol monomer and acetic acid fit in the presence of catalyst A in 120-150 degrees Celsius is reacted 2-6 hours, and second phthalein oxo-compound and the mixture of diacid monomer are obtained, and prepares epoxy group liquid crystal;
2) under the conditions of inert gas, 220-330 DEG C, by step 1) second phthalein oxo-compound and diacid monomer urging Cruel exchange reaction 1-4h is carried out in the presence of agent B and generates oligomer, then oligomer is subjected to vacuum under solid-state or molten state and is born The standby functional graphene oxide mixed solution of compacting;
3) by epoxy group liquid crystal grafted graphene oxide compound to get to epoxy group liquid crystal grafted graphene oxide Close object.
As a preferred technical solution of the present invention, the acetic acid in step 1) is matched and the ratio between the amount of substance through base For 1-1.5:1.
As a preferred technical solution of the present invention, the catalyst A in step 1) is p-methyl benzenesulfonic acid or sulphur Acid, the quality of catalyst are the 0.Ol-0.5wt% of starting monomer gross mass.
As a preferred technical solution of the present invention, the inert gas in step 2) is nitrogen or hydrogen.
As a preferred technical solution of the present invention, the catalyst B in step 2) is magnesium acetate, zinc acetate, vinegar Sour sodium, potassium acetate or acetic acid bore in any one.
As a preferred technical solution of the present invention, the dosage of the catalyst B in step 2) is that starting monomer is total The 0.01-1wt% of quality.
The advantageous effect that is reached of the present invention is:Graphene oxide is grafted low molecule aromatic polymer and manufactures liquid crystal polymer Method, heteroaromatic diacid monomer, which has, forms the ability of liquid crystal, is a kind of mesomorphic group, functional group and molecular skeleton plane In the presence of about 150 degree of angle, by heteroaromatic diacid monomer introduce after liquid crystal polymer strand can Effective Regulation strand line Property regularity, assign strand it is preferably flexible while can avoid damage to the liquid crystal property of macromolecular, and assign liquid crystal height Molecule excellent mobile performance and mechanical property, in terms of mobility improvement and enhancing that general-purpose plastics can be used for.
Specific implementation mode
Hereinafter, preferred embodiments of the present invention will be described, it should be understood that preferred embodiment described herein is only used In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment:The method of graphene oxide grafting low molecule aromatic polymer manufacture liquid crystal polymer of the present invention, including Following steps:
1) by light base acid monomers, heteroaromatic diacid monomer, aromatic series diphenol monomer and acetic acid fit in the presence of catalyst A in 120-150 degrees Celsius is reacted 2-6 hours, and second phthalein oxo-compound and the mixture of diacid monomer are obtained, and prepares epoxy group liquid crystal;
2) under the conditions of inert gas, 220-330 DEG C, by step 1) second phthalein oxo-compound and diacid monomer urging Cruel exchange reaction 1-4h is carried out in the presence of agent B and generates oligomer, then oligomer is subjected to vacuum under solid-state or molten state and is born The standby functional graphene oxide mixed solution of compacting;
3) by epoxy group liquid crystal grafted graphene oxide compound to get to epoxy group liquid crystal grafted graphene oxide Close object.
Further, it is 1-1.5 that the acetic acid in step 1), which is matched with the ratio between the amount of substance through base,:1.
Further, the catalyst A in step 1) is p-methyl benzenesulfonic acid or sulfuric acid, and the quality of catalyst is raw material The 0.Ol-0.5wt% of monomer gross mass.
Further, the inert gas in step 2) is nitrogen or hydrogen.
Further, the catalyst B in step 2) is during magnesium acetate, zinc acetate, sodium acetate, potassium acetate or acetic acid bore Any one.
Further, the dosage of the catalyst B in step 2) is the 0.01-1wt% of starting monomer gross mass.
It should be noted that the present invention is the side that graphene oxide is grafted that low molecule aromatic polymer manufactures liquid crystal polymer Method, when work, heteroaromatic diacid monomer has the ability for forming liquid crystal, is a kind of mesomorphic group, functional group and molecular skeleton There is about 150 degree of angle in plane, heteroaromatic diacid monomer is introduced can Effective Regulation strand after liquid crystal polymer strand Linear regularity, assign strand it is preferably flexible while can avoid damage to the liquid crystal property of macromolecular, and assign liquid Polycrystalline macromolecule excellent mobile performance and mechanical property, in terms of mobility improvement and enhancing that general-purpose plastics can be used for.
Finally it should be noted that:The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features. All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in the present invention's Within protection domain.

Claims (6)

1. the method that graphene oxide is grafted low molecule aromatic polymer manufacture liquid crystal polymer, which is characterized in that including as follows Step:
1) light base acid monomers, heteroaromatic diacid monomer, aromatic series diphenol monomer and acetic acid are fitted in the presence of catalyst A in 120- 150 degrees Celsius are reacted 2-6 hours, and second phthalein oxo-compound and the mixture of diacid monomer are obtained, and prepare epoxy group liquid crystal;
2) under the conditions of inert gas, 220-330 DEG C, by step 1) second phthalein oxo-compound and diacid monomer in catalyst Cruel exchange reaction 1-4h is carried out in the presence of B and generates oligomer, then oligomer is subjected to negative pressure of vacuum system under solid-state or molten state Standby functional graphene oxide mixed solution;
3) by epoxy group liquid crystal grafted graphene oxide compound to get to epoxy group liquid crystal grafted graphene oxide chemical combination Object.
2. the method for graphene oxide grafting low molecule aromatic polymer manufacture liquid crystal polymer according to claim 1, It is characterized in that, it is 1-1.5 that the acetic acid in step 1), which is matched with the ratio between the amount of substance through base,:1.
3. the method for graphene oxide grafting low molecule aromatic polymer manufacture liquid crystal polymer according to claim 1, It is characterized in that, the catalyst A in step 1) is p-methyl benzenesulfonic acid or sulfuric acid, the quality of catalyst is that starting monomer is total The 0.Ol-0.5wt% of quality.
4. the method for graphene oxide grafting low molecule aromatic polymer manufacture liquid crystal polymer according to claim 1, It is characterized in that, the inert gas in step 2) is nitrogen or hydrogen.
5. the method for graphene oxide grafting low molecule aromatic polymer manufacture liquid crystal polymer according to claim 1, It is characterized in that, the catalyst B in step 2) is arbitrary in magnesium acetate, zinc acetate, sodium acetate, potassium acetate or acetic acid brill It is a kind of.
6. the method for graphene oxide grafting low molecule aromatic polymer manufacture liquid crystal polymer according to claim 1, It is characterized in that, the dosage of the catalyst B in step 2) is the 0.01-1wt% of starting monomer gross mass.
CN201810383224.3A 2018-04-26 2018-04-26 The method that graphene oxide is grafted low molecule aromatic polymer manufacture liquid crystal polymer Pending CN108727606A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110333612A (en) * 2019-07-04 2019-10-15 湘潭大学 A method of multiple response smart window is prepared by the carbon nanotube that liquid crystal polymer is modified

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106519200A (en) * 2016-10-25 2017-03-22 中原工学院 Aromatic heterocyclic liquid crystal high-molecular polymer and preparation method thereof
CN107033880A (en) * 2017-05-16 2017-08-11 中原工学院 The preparation method and applications of graphene doping hetero-aromatic ring liquid crystal high-molecular luminous material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106519200A (en) * 2016-10-25 2017-03-22 中原工学院 Aromatic heterocyclic liquid crystal high-molecular polymer and preparation method thereof
CN107033880A (en) * 2017-05-16 2017-08-11 中原工学院 The preparation method and applications of graphene doping hetero-aromatic ring liquid crystal high-molecular luminous material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110333612A (en) * 2019-07-04 2019-10-15 湘潭大学 A method of multiple response smart window is prepared by the carbon nanotube that liquid crystal polymer is modified
CN110333612B (en) * 2019-07-04 2021-10-01 湘潭大学 Method for preparing multi-response intelligent window through liquid crystal polymer modified carbon nano tube

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