CN106366135A - Preparation method for spiroheterocyclic molecule electronic material - Google Patents
Preparation method for spiroheterocyclic molecule electronic material Download PDFInfo
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- CN106366135A CN106366135A CN201610636469.3A CN201610636469A CN106366135A CN 106366135 A CN106366135 A CN 106366135A CN 201610636469 A CN201610636469 A CN 201610636469A CN 106366135 A CN106366135 A CN 106366135A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G99/00—Subject matter not provided for in other groups of this subclass
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- C—CHEMISTRY; METALLURGY
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- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P21/00—Preparation of peptides or proteins
- C12P21/06—Preparation of peptides or proteins produced by the hydrolysis of a peptide bond, e.g. hydrolysate products
Abstract
The invention relates to a preparation method for a spiroheterocyclic molecule electronic material, belonging to the technical field of preparation of electronic materials. The preparation method comprises the following steps: subjecting substances like silk fibroin and a tris(hydroxymethyl)aminomethane solution to mixing and heating; then adding trypsin for hydrolysis; carrying out heating, centrifugation and drying so as to obtain crude silk peptide; mixing the crude silk peptide with acetone and carrying out ultrasonic vibration; then mixing a mixture obtained in the previous step with substances like sodium hydroxide and toluene under stirring and carrying out standing; separately adding carbon disulfide and isoamyl iodide and successively carrying out stirring, heating and centrifugation; and drying a precipitate at a lower layer so as to obtain the spiroheterocyclic molecule electronic material. The spiroheterocyclic molecule electronic material prepared in the invention has a melting point of more than 320 DEG C, high thermal stability, good film forming ability, and is uniform in film formation and widely applicable to microelectonic devices and molecule electronic devices.
Description
Technical field
The present invention relates to a kind of preparation method of spiroheterocyclic molecule electronic material, belong to electronic material preparing technical field.
Background technology
The performance of organic molecule material depends primarily on the structure of molecule itself and the property of functional group.Many structures are special
Different organic molecule material can control and modify light, electricity, magnetic signal, and some of which has been able to replace inorganic semiconductor and gold
Belong to material to be used for making multiple electronic devices, such as: electric memory, field-effect transistor, organic conducting wire, display device and electricity
Container etc., application prospect is boundless.
The advantage of organic electronic material is effect small volume, be readily available, cheap, but the one-tenth of most material
Film properties and heat stability are poor, which limits the practical application of these materials.In organic molecule, specific functional group has
Specific character, such as cyano group (- cn) are typical electron-withdrawing groups, and alkylthio group (- sr) is typically to push away electronics base, alkylthio group
Carry out conjugation with cyano group and connect it is possible to composition has the construction unit pushing away suction (push-pull) electric function, if by 2
Alkylthio group and 2 cyano group carry out conjugation and connect, and can also strengthen this pushing away electrophilic function.But, many has this knot
The organic molecule of structure is often difficult to practical application because fusing point is relatively low.
Content of the invention
The technical problem to be solved: for existing organic electronic material filming performance and heat stability
Can be poor, limit the problem of its practical application, the materials such as fibroin albumen, tricarboxylic aminomethane solution are entered by the present invention first
Row Hybrid Heating, adds trypsin and is hydrolyzed, heated, centrifugation and drying, obtains crude product silk peptide, then by it
Mix with acetone, after sonic oscillation, stand after being stirred with materials such as sodium hydroxide, toluene, finally add two sulfur respectively
Change carbon, iodo isopentane, be stirred heating, centrifugation, the lower sediment obtaining is dried, you can obtain spiroheterocyclic molecule
Electronic material.Preferably, thermal stability is high, can be widely applied to for the spiroheterocyclic molecule electronic material filming performance of present invention preparation
In microelectronic component and molecular electronic device.
For solving above-mentioned technical problem, the technical solution used in the present invention is:
(1) count by weight, weigh 10～15 parts of fibroin albumens and 45～50 parts of mass concentration 10% 3 carboxymethylaminos respectively
Dichloromethane, 5～10 parts of 0.3mol/l hydrochloric acid solutions are placed in beaker, stirring mixing be placed at 37 DEG C heating in water bath 25～
30min；
(2), after the completion for the treatment of heating in water bath, account for the trypsin of fibroin albumen quality 10% to adding in beaker, to be added after the completion of,
At 37 DEG C, heating in water bath 6～8h is hydrolyzed, and after the completion of waiting to hydrolyze, continues intensification and is heated to 80～85 DEG C, subsequently insulation adds
Hot 10～15min, then centrifugation 10～15min under 10000～11000r/min, collect lower sediment lyophilization 6
～8h, is prepared into crude product silk peptide；
(3) 1:10 in mass ratio, the crude product silk peptide of above-mentioned preparation is mixed with acetone stirring, sonic oscillation under 200～330w
10～15min, is prepared into silk peptide dispersion liquid, subsequently counts by weight, weigh respectively 55～60 parts of silk peptide dispersion liquids, 10～15
Part sodium hydroxide, 25～30 parts of toluene, 3～5 parts of Cyanoacetyl-Cyacetazid are placed in there-necked flask, and stirring mixing juxtaposition stands 10 at room temperature
～15min；
(4), after the completion of waiting to stand, in there-necked flask, add the Carbon bisulfide identical in quality with Cyanoacetyl-Cyacetazid, stir mixing 25～
After 30min, continue there-necked flask is added with the iodo isopentane of Carbon bisulfide quality 10%, stirring mixing is placed in 65～70 DEG C
Lower heating in water bath 6～8h, subsequently staticly settles 6～8h, in 1000～1200r/min centrifugation 10～15min, collects lower floor
Precipitation is placed at 65～70 DEG C being dried 6～8h, you can be prepared into a kind of spiroheterocyclic molecule electronic material.
The spiroheterocyclic molecule electronic material of present invention preparation obtains yield and reaches more than 89%, and internal is in spirane structure shape, melts
Point is more than 320 DEG C.
Compared with additive method, Advantageous Effects are the present invention:
(1) the spiroheterocyclic molecule electronic material fusing point of present invention preparation is more than 320 DEG C, has higher thermal stability；
(2) preferably, film forming uniformly, can be widely applied to microelectronics to the spiroheterocyclic molecule electronic material filming performance of present invention preparation
In device and molecular electronic device；
(3) preparation process of the present invention is simple, required low cost.
Specific embodiment
Count by weight first, weigh 10～15 parts of fibroin albumens and 45～50 parts of mass concentration 10% tricarboxylic first respectively
Base aminomethane solution, 5～10 parts of 0.3mol/l hydrochloric acid solutions are placed in beaker, and stirring mixing is placed in heating in water bath at 37 DEG C
25～30min；After the completion for the treatment of heating in water bath, account for the trypsin of fibroin albumen quality 10% to adding in beaker, to be added complete
Afterwards, at 37 DEG C, heating in water bath 6～8h is hydrolyzed, and after the completion of waiting to hydrolyze, continues intensification and is heated to 80～85 DEG C, be subsequently incubated
Heating 10～15min, then centrifugation 10～15min under 10000～11000r/min, collect lower sediment lyophilization
6～8h, is prepared into crude product silk peptide；1:10 in mass ratio again, the crude product silk peptide of above-mentioned preparation is mixed with acetone stirring, 200
Sonic oscillation 10～15min under～330w, is prepared into silk peptide dispersion liquid, subsequently counts by weight, weighs 55～60 parts respectively
Silk peptide dispersion liquid, 10～15 parts of sodium hydroxide, 25～30 parts of toluene, 3～5 parts of Cyanoacetyl-Cyacetazid are placed in there-necked flask, stirring mixing
Juxtaposition stands 10～15min at room temperature；After the completion of waiting to stand, add two sulfur identical in quality with Cyanoacetyl-Cyacetazid in there-necked flask
Change carbon, after stirring mixing 25～30min, continue there-necked flask is added with the iodo isopentane of Carbon bisulfide quality 10%, stirring is mixed
Merge and be placed in heating in water bath 6～8h at 65～70 DEG C, subsequently staticly settle 6～8h, in 1000～1200r/min centrifugation 10
～15min, collects lower sediment and is placed at 65～70 DEG C being dried 6～8h, you can be prepared into a kind of spiroheterocyclic molecular electronic material
Material.
Example 1
Count by weight first, weigh 15 parts of fibroin albumens respectively molten with 50 parts of mass concentrations 10% tricarboxylic aminomethane
Liquid, 10 parts of 0.3mol/l hydrochloric acid solutions are placed in beaker, and stirring mixing is placed in heating in water bath 30min at 37 DEG C；Treat that water-bath adds
After the completion of heat, account for the trypsin of fibroin albumen quality 10% to adding in beaker, to be added after the completion of, water-bath at 37 DEG C adds
Hot 8h is hydrolyzed, and after the completion of waiting to hydrolyze, continues intensification and is heated to 85 DEG C, subsequent Heat preservation 15min, then in 11000r/min
Lower centrifugation 15min, collects lower sediment lyophilization 8h, is prepared into crude product silk peptide；1:10 in mass ratio again, will be above-mentioned
The crude product silk peptide of preparation is mixed with acetone stirring, and sonic oscillation 15min under 330w is prepared into silk peptide dispersion liquid, subsequently presses weight
Amount number meter, weighs 60 parts of silk peptide dispersion liquids, 15 parts of sodium hydroxide, 30 parts of toluene, 5 parts of Cyanoacetyl-Cyacetazid respectively and is placed in there-necked flask
In, stirring mixing juxtaposition stands 15min at room temperature；After the completion of waiting to stand, add and Cyanoacetyl-Cyacetazid quality phase in there-necked flask
Same Carbon bisulfide, after stirring mixing 30min, continues there-necked flask is added with the iodo isopentane of Carbon bisulfide quality 10%, stirs
Mix mixing and be placed in heating in water bath 8h at 70 DEG C, subsequently staticly settle 8h, in 1200r/min centrifugation 15min, collect lower floor
Precipitation is placed in 8h being dried at 70 DEG C, you can be prepared into a kind of spiroheterocyclic molecule electronic material.After testing, the spiral shell of present invention preparation
Heterocyclic molecular electronic material obtains yield and reaches 90%, and internal is in spirane structure shape, and fusing point is 330 DEG C.
Example 2
Count by weight first, weigh 10 parts of fibroin albumens respectively molten with 45 parts of mass concentrations 10% tricarboxylic aminomethane
Liquid, 5 parts of 0.3mol/l hydrochloric acid solutions are placed in beaker, and stirring mixing is placed in heating in water bath 25min at 37 DEG C；Treat heating in water bath
After the completion of, account for the trypsin of fibroin albumen quality 10% to adding in beaker, to be added after the completion of, heating in water bath at 37 DEG C
6h is hydrolyzed, and after the completion of waiting to hydrolyze, continues intensification and is heated to 80 DEG C, subsequent Heat preservation 10min, then under 10000r/min
Centrifugation 10min, collects lower sediment lyophilization 6h, is prepared into crude product silk peptide；1:10 in mass ratio again, by above-mentioned system
Standby crude product silk peptide is mixed with acetone stirring, and sonic oscillation 10min under 200w is prepared into silk peptide dispersion liquid, subsequently by weight
Number meter, weighs 55 parts of silk peptide dispersion liquids, 10 parts of sodium hydroxide, 25 parts of toluene, 3 parts of Cyanoacetyl-Cyacetazid respectively and is placed in there-necked flask,
Stirring mixing juxtaposition stands 10min at room temperature；After the completion of waiting to stand, add identical in quality with Cyanoacetyl-Cyacetazid in there-necked flask
Carbon bisulfide, after stirring mixing 25min, continues there-necked flask is added with the iodo isopentane of Carbon bisulfide quality 10%, stirring is mixed
Merge and be placed in heating in water bath 6h at 65 DEG C, subsequently staticly settle 6h, in 1000r/min centrifugation 10min, collect lower sediment
It is placed in 6h being dried at 65 DEG C, you can be prepared into a kind of spiroheterocyclic molecule electronic material.After testing, the spiroheterocyclic of present invention preparation
Molecule electronic material obtains yield and reaches 91%, and internal is in spirane structure shape, and fusing point is 325 DEG C.
Example 3
Count by weight first, weigh 12 parts of fibroin albumens respectively molten with 47 parts of mass concentrations 10% tricarboxylic aminomethane
Liquid, 7 parts of 0.3mol/l hydrochloric acid solutions are placed in beaker, and stirring mixing is placed in heating in water bath 27min at 37 DEG C；Treat heating in water bath
After the completion of, account for the trypsin of fibroin albumen quality 10% to adding in beaker, to be added after the completion of, heating in water bath at 37 DEG C
7h is hydrolyzed, and after the completion of waiting to hydrolyze, continues intensification and is heated to 82 DEG C, subsequent Heat preservation 12min, then under 11500r/min
Centrifugation 12min, collects lower sediment lyophilization 7h, is prepared into crude product silk peptide；1:10 in mass ratio again, by above-mentioned system
Standby crude product silk peptide is mixed with acetone stirring, and sonic oscillation 12min under 250w is prepared into silk peptide dispersion liquid, subsequently by weight
Number meter, weighs 57 parts of silk peptide dispersion liquids, 12 parts of sodium hydroxide, 27 parts of toluene, 4 parts of Cyanoacetyl-Cyacetazid respectively and is placed in there-necked flask,
Stirring mixing juxtaposition stands 12min at room temperature；After the completion of waiting to stand, add identical in quality with Cyanoacetyl-Cyacetazid in there-necked flask
Carbon bisulfide, after stirring mixing 27min, continues there-necked flask is added with the iodo isopentane of Carbon bisulfide quality 10%, stirring is mixed
Merge and be placed in heating in water bath 7h at 67 DEG C, subsequently staticly settle 7h, in 1100r/min centrifugation 12min, collect lower sediment
It is placed in 7h being dried at 67 DEG C, you can be prepared into a kind of spiroheterocyclic molecule electronic material.After testing, the spiroheterocyclic of present invention preparation
Molecule electronic material obtains yield and reaches more than 92%, and internal is in spirane structure shape, and fusing point is 330 DEG C.
Claims (1)
1. a kind of preparation method of spiroheterocyclic molecule electronic material is it is characterised in that concrete preparation process is:
(1) count by weight, weigh 10～15 parts of fibroin albumens and 45～50 parts of mass concentration 10% 3 carboxymethylaminos respectively
Dichloromethane, 5～10 parts of 0.3mol/l hydrochloric acid solutions are placed in beaker, stirring mixing be placed at 37 DEG C heating in water bath 25～
30min；
(2), after the completion for the treatment of heating in water bath, account for the trypsin of fibroin albumen quality 10% to adding in beaker, to be added after the completion of,
At 37 DEG C, heating in water bath 6～8h is hydrolyzed, and after the completion of waiting to hydrolyze, continues intensification and is heated to 80～85 DEG C, subsequently insulation adds
Hot 10～15min, then centrifugation 10～15min under 10000～11000r/min, collect lower sediment lyophilization 6
～8h, is prepared into crude product silk peptide；
(3) 1:10 in mass ratio, the crude product silk peptide of above-mentioned preparation is mixed with acetone stirring, sonic oscillation under 200～330w
10～15min, is prepared into silk peptide dispersion liquid, subsequently counts by weight, weigh respectively 55～60 parts of silk peptide dispersion liquids, 10～15
Part sodium hydroxide, 25～30 parts of toluene, 3～5 parts of Cyanoacetyl-Cyacetazid are placed in there-necked flask, and stirring mixing juxtaposition stands 10 at room temperature
～15min；
(4), after the completion of waiting to stand, in there-necked flask, add the Carbon bisulfide identical in quality with Cyanoacetyl-Cyacetazid, stir mixing 25～
After 30min, continue there-necked flask is added with the iodo isopentane of Carbon bisulfide quality 10%, stirring mixing is placed in 65～70 DEG C
Lower heating in water bath 6～8h, subsequently staticly settles 6～8h, in 1000～1200r/min centrifugation 10～15min, collects lower floor
Precipitation is placed at 65～70 DEG C being dried 6～8h, you can be prepared into a kind of spiroheterocyclic molecule electronic material.
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| CN201610636469.3A CN106366135A (en) | 2016-08-05 | 2016-08-05 | Preparation method for spiroheterocyclic molecule electronic material |
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| CN201610636469.3A CN106366135A (en) | 2016-08-05 | 2016-08-05 | Preparation method for spiroheterocyclic molecule electronic material |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1310182A (en) * | 2001-02-20 | 2001-08-29 | 复旦大学 | Organic electronic material and its preparation |
| CN1344719A (en) * | 2001-10-11 | 2002-04-17 | 复旦大学 | Organic electronic material with thiowhorl structure and its prepn |
| CN101163712A (en) * | 2004-07-31 | 2008-04-16 | 生物高级株式会社 | Silk peptide improving neuroprotective and neurofunctional effects and a method of its preparation |
| CN102020696A (en) * | 2009-09-23 | 2011-04-20 | 吾儿得伟有限公司 | Production method for silk peptide |
| CN103897021A (en) * | 2013-02-04 | 2014-07-02 | 中国科学院上海有机化学研究所 | Silk peptide as well as preparation method and application thereof |
-
2016
- 2016-08-05 CN CN201610636469.3A patent/CN106366135A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1310182A (en) * | 2001-02-20 | 2001-08-29 | 复旦大学 | Organic electronic material and its preparation |
| CN1344719A (en) * | 2001-10-11 | 2002-04-17 | 复旦大学 | Organic electronic material with thiowhorl structure and its prepn |
| CN101163712A (en) * | 2004-07-31 | 2008-04-16 | 生物高级株式会社 | Silk peptide improving neuroprotective and neurofunctional effects and a method of its preparation |
| CN102020696A (en) * | 2009-09-23 | 2011-04-20 | 吾儿得伟有限公司 | Production method for silk peptide |
| CN103897021A (en) * | 2013-02-04 | 2014-07-02 | 中国科学院上海有机化学研究所 | Silk peptide as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 王蜀，等: "基于自组装的丝素蛋白材料应用研究进展", 《蚕学通讯》 * |
| 邓连霞，等: "蚕丝的综合利用概述", 《北方蚕业》 * |
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Application publication date: 20170201 |
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