CN107686538A - A kind of conducting polymer raw material and preparation method thereof - Google Patents
A kind of conducting polymer raw material and preparation method thereof Download PDFInfo
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- CN107686538A CN107686538A CN201710767691.1A CN201710767691A CN107686538A CN 107686538 A CN107686538 A CN 107686538A CN 201710767691 A CN201710767691 A CN 201710767691A CN 107686538 A CN107686538 A CN 107686538A
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- monomer
- conducting polymer
- side chain
- raw material
- silane
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
Abstract
The invention discloses a kind of conducting polymer raw material and preparation method thereof, belong to polymer modification field, aim to provide the composite that processing characteristics is good, conductance is high, the strand of described conducting polymer includes main chain and side chain, described main chain is polyethers nitrile strand, described side chain includes the strand containing imidazole ring, and the relative molecular mass of described side chain is 500 4000, and the relative molecular mass of described main chain is more than 30000.
Description
Technical field
The present invention relates to industrial chemicals field, is specifically a kind of conducting polymer raw material and preparation method thereof.
Background technology
Conducting polymer is a kind of polymeric material for having conducting function electrical conductivity in more than 10-6S/m.Macromolecule is led
Electric material have small density, easy processing, it is corrosion-resistant, can large area film forming and electrical conductivity can be in the range of the individual order of magnitude more than ten
The features such as being adjusted, the substitute of various metals material and inorganic conductive material is can be used as, and turn into many elder generations
Enter the indispensable a kind of material of industrial department and sophisticated technology field.High polymer material is for a long time by exhausted as excellent electricity
Edge body, until 1977, the polyacetylene film of the discovery of talented people such as Japanese Hideki Shirakawa arsenic pentafluoride or I2 doping has metal
Conductive property, electrical conductivity reach 10S/m.This is first conductive high polymer material.After, poly- pyrrole is have developed in succession
Cough up, the high polymer material that polyphenylene sulfide, poly- phthalocyanine-like compound, polyaniline, polythiophene etc. can be conductive.
But the problem of low with conductance, mechanical property is inadequate is integrally presented in existing conducting polymer homopolymerization, so derivative
Go out a kind of method by Polymer-supported chain grafted branches to be modified the electric conductivity of polymer, mechanical property, still
Simultaneously grafting there is also mechanical property it is inadequate the problem of.
The content of the invention
It is an object of the invention to：By being modified to the method for polymer physics grafted branches to polymer performance：
The invention discloses a kind of conducting polymer raw material, the strand of described conducting polymer includes main chain and side chain, institute
The main chain stated is polyethers nitrile strand, and described side chain includes the strand containing imidazole ring, the average molecular of described side chain
Quality is 500-4000, and the relative molecular mass of described main chain is more than 30000, wherein the repetition list of described imidazole ring side chain
The offer monomer of member is the imidazoles monomer containing unsaturated bond, and described unsaturated bond can be that triple carbon-carbon bonds can also be carbon carbon
Double bond.
As an improvement, described offer monomer is N- vinyl imidazoles, 6-acetenyl imidazo [1,2-A] pyrazine, 3-
[2- (trimethyl silicon substrate) acetenyl]-imidazo [1,2-b] pyridazine, 3- alkynyls imidazoles [1,2-B] pyridazine, 5-acetenyl H- miaows
Azoles simultaneously [1,2-a] pyridine.
As an improvement, described side chain also includes the first side chain and the second side chain, the first described side chain repeat unit
Monomer is provided and is selected from N- vinyl imidazoles, 6-acetenyl imidazo [1,2-A] pyrazine, 3- [2- (trimethyl silicon substrate) acetylene
Base]-imidazo [1,2-b] pyridazine, 3- alkynyls imidazoles [1,2-B] pyridazine, 5-acetenyl H- imidazos [1,2-a] pyridine；
The offer monomer of the repeat unit of the second described side chain is unsaturated silane monomer.
As an improvement, described unsaturated silane is selected from triethylvinylsilane silane, three tert-butoxy vinyl silanes, three
Phenoxy group vinyl silanes, 3- chloropropyl dimethylvinylsiloxies base silane, triphenyl vinyl silane, three [(1,1- dimethyl second
Base) dioxy] vinyl silanes, two (dimethylamino) ethylene methacrylic base silanes, dimethyl (dimethylamino) vinyl silanes, diformazan
Base phenylethylene base silane, diethylmethyl vinyl silanes, dimethyl (dimethylamino) vinyl silanes, dimethyl (2- pyrroles
Piperidinyl) vinyl silanes, dimethyl divinyl silane, trivinyl silane.
The present invention discloses a kind of method for preparing conducting polymer, it is characterised in that comprises the following steps：
Step A：Unsaturated silane monomer, the heterocyclic monomer containing imidazole ring and polyethers nitrile polymer are mixed among organic solvent
Close；The weight ratio that wherein monomer weight accounts for the mixture not including solvent is 5%-50%.
Step B:Said mixture is stirred using physical method；
Step C:The initiator for accounting for polyethers nitrile polymer weight 0.01%-0.1% is added to said mixture；
Step D:Acid solution is added, adjusts the PH of mixture in 5-6;
Step E:2-10 hours are reacted at 40 DEG C -81 DEG C；
Step F：Solvent is removed, is dried.
As an improvement, unsaturated silane monomer and the mol ratio containing imidazole ring monomer are 1:10-10:1.
As an improvement, the one kind of the physical method of the step B for stirring, mechanical agitation and magnetic agitation by hand, described
Acid solution for watery hydrochloric acid, dilute sulfuric acid, concentrated hydrochloric acid, the concentrated sulfuric acid, perchloric acid, one kind of acetic acid.
As an improvement, described initiator is selected from：Benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, mistake
Aoxidize diisopropylbenzene (DIPB), isopropyl benzene hydroperoxide, TBHP, peroxidized t-butyl perbenzoate, peroxidating trimethylacetic acid uncle
Butyl ester, (methyl ethyl ketone peroxide, cyclohexanone peroxide, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate；
As an improvement, the organic solvent stated is selected from：Trifluoroacetic acid, DMSO, DMF, hexamethyl-phosphoramide, methanol, ethanol, second
Acid, trichloro ethylene, n-butanol, ether, n-butyl ether, carbon tetrachloride, hexamethylene, hexane.
The excellent effect of the present invention is that the present invention develops a kind of new graft polymers conductive material, processing characteristics
It is preferable with stability, and there is higher conductance, it can be used in the fields such as microelectronics, new energy.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Specific embodiment 1：Triethylvinylsilane silane monomer, N- vinyl imidazoles monomer and polyethers nitrile polymer are being had
Mixed among solvent；The weight ratio that wherein monomer weight accounts for the mixture not including solvent is 5%, silane monomer and miaow
The mol ratio of azoles heterocyclic monomer is 1:10, secondly carry out magnetic agitation；Add the initiator for accounting for polyethers nitrile polymer weight 0.01%
Benzoyl peroxide solution, the PH of concentrated hydrochloric acid solution adjustment mixture is added in 5-6;Secondly, reacted 2 hours at 40 DEG C；Most
After remove solvent, the conducting polymer raw material packed for standby use for being made described is dried.
Specific embodiment 2：By three tert-butoxy 6-acetenyl of vinyl silane monomer imidazo [1,2-A] pyrazine monomers
Mixed with polyethers nitrile polymer among organic solvent；Wherein monomer weight accounts for the weight ratio of the mixture not including solvent
For 50%, the mol ratio of silane monomer and imidazolyl heterocycle monomer is 10:1, secondly carry out magnetic agitation；Addition accounts for the polymerization of polyethers nitrile
The initiator lauroyl peroxide of thing weight 0.1%；Concentrated sulfuric acid solution is added, adjusts the PH of mixture in 5-6;Secondly, at 80 DEG C
Lower reaction 10 hours；Solvent is finally removed, the conducting polymer raw material packed for standby use for being made described is dried.
Specific embodiment 3：By two (dimethylamino) methyl ethylene silane monomers, 3- [2- (trimethyl silicon substrate) acetylene
Base]-imidazo [1,2-b] pyridazine monomer and polyethers nitrile polymer mix among organic solvent；Wherein monomer weight, which accounts for, does not wrap
The weight ratio for including the mixture including solvent is 20%, and the mol ratio of silane monomer and imidazolyl heterocycle monomer is 1:2, secondly carry out
Magnetic agitation；Add the initiator di-t-butyl peroxide for accounting for polyethers nitrile polymer weight 0.05%；Add acetum, adjustment
The PH of mixture is in 5-6;Secondly, reacted 4 hours at 60 DEG C；Solvent is finally removed, the conduction for being made described is dried and gathers
Compound raw material packed for standby use.
Specific embodiment 4：By dimethyl (dimethylamino) vinyl silane monomer, 3- [2- (trimethyl silicon substrate) acetylene
Base]-imidazo [1,2-b] pyridazine monomer and polyethers nitrile polymer mix among organic solvent；Wherein monomer weight, which accounts for, does not wrap
The weight ratio for including the mixture including solvent is 10%, and the mol ratio of silane monomer and imidazolyl heterocycle monomer is 1:3, secondly carry out
Magnetic agitation；Add the initiator di-t-butyl peroxide for accounting for polyethers nitrile polymer weight 0.1%；Add concentrated hydrochloric acid solution, adjustment
The PH of mixture is 6;Secondly, reacted 10 hours at 81 DEG C；Solvent is finally removed, the conducting polymer for being made described is dried
Raw material packed for standby use.
Specific embodiment 5：By 3,5-dimethylphenyl vinyl silane monomer, 6-acetenyl imidazo [1,2-A] pyrazine list
Body and polyethers nitrile polymer mix among organic solvent；Wherein monomer weight accounts for the weight of the mixture not including solvent
Than for 10%, the mol ratio of silane monomer and imidazolyl heterocycle monomer is 1:2, secondly carry out magnetic agitation；Addition accounts for the polymerization of polyethers nitrile
The initiator cumyl peroxide of thing weight 0.1%；Perchloric acid solution is added, adjusts the PH of mixture in 5-6;Secondly, 80
Reacted 4 hours at DEG C；Solvent is finally removed, the conducting polymer raw material packed for standby use for being made described is dried.
Specific embodiment 6：By two (dimethylamino) methyl ethylene silane monomers, 3- [2- (trimethyl silicon substrate) acetylene
Base]-imidazo [1,2-b] pyridazine monomer and polyethers nitrile polymer mix among organic solvent；Wherein monomer weight, which accounts for, does not wrap
The weight ratio for including the mixture including solvent is 10%, and the mol ratio of silane monomer and imidazolyl heterocycle monomer is 1:2, secondly carry out
Magnetic agitation；Add the initiator di-t-butyl peroxide for accounting for polyethers nitrile polymer weight 0.1%；Add concentrated sulfuric acid solution, adjustment
The PH of mixture is in 5-6;Secondly, reacted 8 hours at 50 DEG C；Solvent is finally removed, the conduction for being made described is dried and gathers
Compound raw material packed for standby use.
It is as follows to the performance detection of embodiment 1-6 polymer raw materials：
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
All any modification, equivalent and improvement made within principle etc., should be included in the scope of the protection.
Claims (10)
1. a kind of conducting polymer raw material, the strand of described conducting polymer includes main chain and side chain, and described main chain is
Polyethers nitrile strand, described side chain include the strand containing imidazole ring, and the relative molecular mass of described side chain is 500-
4000, the relative molecular mass of described main chain is more than 30000.
2. conducting polymer raw material according to claim 1, it is characterised in that the repeat unit of described imidazole ring side chain
Offer monomer be the imidazoles monomer containing unsaturated bond.
3. conducting polymer raw material according to claim 2, it is characterised in that described unsaturated bond is carbon-carbon double bond.
4. conducting polymer raw material according to claim 2, it is characterised in that described offer monomer is N- vinyl miaows
Azoles, 6-acetenyl imidazo [1,2-A] pyrazine, 3- [2- (trimethyl silicon substrate) acetenyl]-imidazo [1,2-b] pyridazine, 3-
Alkynyl imidazoles [1,2-B] pyridazine, 5-acetenyl H- imidazos [1,2-a] pyridine.
5. conducting polymer raw material according to claim 1, it is characterised in that described side chain also include the first side chain and
Second side chain, the offer monomer of the first described side chain repeat unit be selected from N- vinyl imidazoles, 6-acetenyl imidazo [1,
2-A] pyrazine, 3- [2- (trimethyl silicon substrate) acetenyl]-imidazo [1,2-b] pyridazine, 3- alkynyls imidazoles [1,2-B] pyridazine, 5-
Acetenyl H- imidazos [1,2-a] pyridine；
The offer monomer of the repeat unit of the second described side chain is unsaturated silane monomer.
6. conducting polymer raw material according to claim 5, it is characterised in that described unsaturated silane is selected from triethyl group
Vinyl silanes, three tert-butoxy vinyl silanes, triple phenoxyl vinyl silanes, 3- chloropropyl dimethylvinylsiloxies base silane,
Triphenyl vinyl silane, three [(1,1- dimethyl ethyls) dioxy] vinyl silanes, two (dimethylamino) methyl ethylene silicon
Alkane, dimethyl (dimethylamino) vinyl silanes, 3,5-dimethylphenyl vinyl silanes, diethylmethyl vinyl silanes, diformazan
Base (dimethylamino) vinyl silanes, dimethyl (2- pyridine radicals) vinyl silanes, dimethyl divinyl silane, trivinyl
Silane.
A kind of 7. method for preparing conducting polymer, it is characterised in that comprise the following steps：
Step A：Unsaturated silane monomer, the heterocyclic monomer containing imidazole ring and polyethers nitrile polymer are mixed among organic solvent
Close；The weight ratio that wherein monomer weight accounts for the mixture not including solvent is 5%-50%；
Step B:Said mixture is stirred using physical method；
Step C:The initiator for accounting for polyethers nitrile polymer weight 0.01%-0.1% is added to said mixture；
Step D:Acid solution is added, adjusts the PH of mixture in 5-6;
Step E:2-10 hours are reacted at 40 DEG C -81 DEG C；
Step F：Solvent is removed, is dried.
8. the method according to claim 7 for preparing conducting polymer, it is characterised in that unsaturated silane monomer and contain
The mol ratio of imidazole ring monomer is 1:10-10:1.
9. the method according to claim 8 for preparing conducting polymer, it is characterised in that the physical method of the step B
For one kind of manual stirring, mechanical agitation and magnetic agitation, described acid solution is watery hydrochloric acid, dilute sulfuric acid, concentrated hydrochloric acid, dense sulphur
Acid, perchloric acid, one kind of acetic acid.
10. the method according to claim 8 for preparing conducting polymer, it is characterised in that described initiator is selected from：Cross
BP, lauroyl peroxide, di-t-butyl peroxide, cumyl peroxide, isopropyl benzene hydroperoxide, tert-butyl group mistake
Hydrogen oxide, peroxidized t-butyl perbenzoate, peroxidating trimethylacetic acid tertiary butyl ester, (methyl ethyl ketone peroxide, cyclohexanone peroxide, mistake
Aoxidize two diisopropyl carbonates, di-cyclohexylperoxy di-carbonate；
Described organic solvent is selected from：Trifluoroacetic acid, DMSO, DMF, hexamethyl-phosphoramide, methanol, ethanol, acetic acid, three chloroethenes
Alkene, n-butanol, ether, n-butyl ether, carbon tetrachloride, hexamethylene, hexane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710767691.1A CN107686538A (en) | 2017-08-31 | 2017-08-31 | A kind of conducting polymer raw material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710767691.1A CN107686538A (en) | 2017-08-31 | 2017-08-31 | A kind of conducting polymer raw material and preparation method thereof |
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| CN107686538A true CN107686538A (en) | 2018-02-13 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513897A (en) * | 2003-04-25 | 2004-07-21 | 大连理工大学 | Polyether nitrile ketone containing phthalazine biphenyl structure and its preparation method |
| CN1916004A (en) * | 2004-08-17 | 2007-02-21 | 三星电子株式会社 | Organic-inorganic metal hybrid material and composition comprising the same |
| CN101016375A (en) * | 2007-02-05 | 2007-08-15 | 大连理工大学 | Method of preparing diazanaphthalene biphenyl type sulphonation polyarylethernitrile electrolyte film material |
-
2017
- 2017-08-31 CN CN201710767691.1A patent/CN107686538A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513897A (en) * | 2003-04-25 | 2004-07-21 | 大连理工大学 | Polyether nitrile ketone containing phthalazine biphenyl structure and its preparation method |
| CN1916004A (en) * | 2004-08-17 | 2007-02-21 | 三星电子株式会社 | Organic-inorganic metal hybrid material and composition comprising the same |
| CN101016375A (en) * | 2007-02-05 | 2007-08-15 | 大连理工大学 | Method of preparing diazanaphthalene biphenyl type sulphonation polyarylethernitrile electrolyte film material |
Non-Patent Citations (3)
| Title |
|---|
| 冯孝中: "《高分子材料》", 28 February 2007, 哈尔滨工业大学出版社 * |
| 王卉: "新型氮杂环聚醚腈砜酮耐高温胶黏剂的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 黄俐研: "聚醚腈的合成与表征[1]", 《江西师范大学学报（自然科学版）》 * |
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