CN110041279A - A kind of conjugation diamine monomer and its synthetic method - Google Patents
A kind of conjugation diamine monomer and its synthetic method Download PDFInfo
- Publication number
- CN110041279A CN110041279A CN201910406288.5A CN201910406288A CN110041279A CN 110041279 A CN110041279 A CN 110041279A CN 201910406288 A CN201910406288 A CN 201910406288A CN 110041279 A CN110041279 A CN 110041279A
- Authority
- CN
- China
- Prior art keywords
- solution
- diamine monomer
- conjugation
- solvent
- dissolved
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/48—Two nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
The invention discloses a kind of conjugation diamine monomer and its synthetic methods.The molecular formula of the diamine monomer is as follows:
Description
Technical field
The present invention relates to organic chemical synthesis technical fields, in particular to a kind of synthetic method for being conjugated diamine monomer.
Background technique
Late 1970s, Heeger have found that the conductivity of metal magnitude can be achieved by adulterating for polyacetylene, break
Polymer can only do the traditional concept of insulator, cause people to the research interest of conjugated polymer material.So far, conjugation is poly-
Object is closed as the important a member of organic semi-conductor, is all widely used in light, electrical domain.2017, Chen project was combined into
2,4- diamino -6- phenyl -1,3,5-triazines out, and with 2,4- diamino -6- phenyl -1,3,5-triazines and Pyromellitic Acid two
Acid anhydride synthesis of polyimides, discovery synthesis of polyimides have electro-chemical activity (Ziyu Li, Kaichang Kou, Jiaoqiang
Zhang, Yu Zhang, Yiqun Wang, Chen Pan.Solubility, electrochemical behavior and
thermal stability of polyimides synthesized from 1,3,5-triazine-based diamine
[J].Journal of Materials Science Materials in Electronics,2017,28(8):6079-
6087.).It is well known that polyimides is a kind of insulating materials, but the polyimides synthesized herein has electro-chemical activity, I
Guess be due to its structure be conjugated structure, form the big pi bond of delocalization.
108640881 A of patent CN is it is found that using 2, bis- chloro-6-phenyls of 4- -1,3,5-triazines and 4,4 '-diamino two
Phenylmethane can synthesize a kind of new diamine monomer, but since it does not have conjugated structure can not be as synthesis semi-conductor polyimide
Material, application field has certain limitations.
Summary of the invention
In order to solve the above technical problem, the present invention provides a kind of conjugation diamine monomer and its synthetic methods.The diamines list
Body has conjugation triazine structure, and the later period by design, is expected to synthesize a kind of semiconductor polyamides of novel covalent triazine structure
Imines, and this polyimide material is intrinsic semiconductor organic material, can reduce difficulty of processing to a certain extent.
The present invention is using bis- chloro-6-phenyl -1,3,5- triazine of 2,4- and 4,4 '-diamino -2,2 '-dimethyl diphenyl conduct
Material synthesis goes out a kind of new conjugation diamine monomer.The present invention is reached by screening catalyst and proportion optimizing accelerates dissolution instead
Object is answered to improve the purpose of reaction rate, when sodium carbonate is used only as catalyst, the reaction time is longer, when being added to sodium hydroxide
Later, the reaction time shortens, and improves reaction rate.In the screening of catalyst proportion, sodium carbonate and hydrogen-oxygen have been separately verified
The mass ratio for changing sodium is the solubility of 1:9,3:7,5:5,7:3 and 9:1 in a solvent, the experimental results showed that working as sodium carbonate and hydrogen-oxygen
When the mass ratio for changing sodium is 9:1, catalyst can dissolve completely.In entire reaction process, H is had2O is generated, therefore toluene is added
As dehydrating agent, reaction process can be accelerated, the ratio of two kinds of solvents is got by theoretical calculation.The raw material that the present invention uses
4,4 '-diamino -2,2 '-dimethyl diphenyls are different from the raw material in 108640881 A of patent CN, 4,4 '-diamino -2, and 2 ' -
Dimethyl diphenyl has had conjugated structure, is innovated on this basis, and triazine radical is introduced, and synthesizes a kind of new gather for the later period
Acid imide material provides diamines raw material.The polyimide material can be expected to apply in microelectronics, solar battery, light-emitting diodes
Pipe etc..
Technical solution provided by the invention is as follows:
A kind of conjugation diamine monomer, molecular formula are as follows:
Another object of the present invention is to provide the preparation method of above-mentioned conjugation diamine monomer, comprising the following steps:
(1) by 4,4 '-diamino -2,2 '-dimethyl diphenyls and catalyst are dissolved in solvent A, are heated to reflux complete to solid
Fully dissolved obtains solution I；
(2) 2,4-, bis- chloro-6-phenyls -1,3,5-triazines is dissolved in solvent A and obtains solution II, solution II is added dropwise to
In solution I, solution III sufficiently is obtained after reflux；
(3) solution III is poured into ice water, stands to solution and is layered, there is solid precipitation in lower layer, filters, obtained solid
Column Chromatographic purification is carried out, target product conjugation diamine monomer is obtained.
Upper that is stated catalyst and is made of sodium carbonate and sodium hydroxide, and the mass ratio of the two is 9:1.
Above-mentioned solvent A is the mixture of Isosorbide-5-Nitrae-dioxane and toluene, and the volume ratio of the two is 3:1.
Bis- chloro-6-phenyl -1,3,5- triazine of 2,4- and 4,4 '-diamino -2,2 '-dimethyl diphenyl in above-mentioned steps (1)
Molar ratio be 1:4~1:8.
Return time is 2~6h in above-mentioned steps (2).
Purification is the mixture of ethyl acetate and petroleum ether with eluant, eluent in above-mentioned steps (3), and the volume ratio of the two is 1:
1。
Synthesis path is as follows:
In addition to this, the present invention also provides above-mentioned conjugation diamine monomers has partly leading for covalent triazine structure in synthesis
Application in body polyimides.
Beneficial effects of the present invention:
(1) using 4,4 '-diamino -2,2 '-dimethyl diphenyl and bis- chloro-6-phenyl -1,3,5- triazine of 2,4- as anti-
Raw material is answered, the pi-conjugated structure of large-scale p- being capable of forming after synthesis, the diamine monomer of the structure can be used in synthesizing semiconductor
Polyimides；
(2) selection of catalyst and rational proportion can accelerate the solution rate of raw material, improve reaction rate；
(3) toluene serves not only as solvent in the reaction, is alternatively arranged as dehydrating agent, improves reaction rate；
(4) the conjugation diamine monomer prepared by can be used as the raw material of synthesis semi-conductor polyimide, have biggish application
Prospect and biggish potentiality；
(5) new route of synthesis of conjugate diamine monomer is provided, the synthesis for being conjugated diamine monomer has biggish reference
Value.
Detailed description of the invention
Fig. 1 is differential scanning calorimeter (DSC) curve graph of Examples 1 to 3 synthesis of conjugate diamine monomer；
Fig. 2 is Examples 1 to 3 synthesis of conjugate diamine monomer1H-NMR spectrum；
Fig. 3 is the infrared spectrogram of Examples 1 to 3 synthesis of conjugate diamine monomer, 3368.0cm in figure-1And 1593.17cm-1For primary amine N-H characteristic absorption peak, 1243.53cm-1And 1170.59cm-1For primary amine C-N stretching vibration absworption peak,
1398.47cm-1And 1300.41cm-1For secondary amine C-N stretching vibration absworption peak, 1541.66cm-1For the absorption of phenyl ring skeletal vibration
Peak, 1484.24cm-1For triazine ring characteristic absorption peak 697.79cm-1And 776.32cm-1For the monosubstituted absorption peak of phenyl ring,
818.85cm-1And 862.88cm-1Replace absorption peak for phenyl ring 1,2,4- tri-.
Specific embodiment
The present invention is further described combined with specific embodiments below, and the contents of the present invention are completely without being limited thereto.
Embodiment 1
1) glass apparatus to be used in experiment is all cleaned up into rear drying for standby, mechanical stirring bar, nitrogen is being housed
First it is added 4,4 '-diamino -2 in the 250mL three-necked flask of gas shielded device, 2 '-dimethyl diphenyls (3.3966g,
16.0mmol), catalyst (0.7624g sodium carbonate, 0.0847g sodium hydroxide) and 10mL mixed organic solvents Isosorbide-5-Nitrae-dioxane
With toluene (volume ratio 3:1), it is heated to reflux to solid and dissolves, obtain mixed solution；
2) 2,4-, bis- chloro-6-phenyls -1,3,5-triazines (0.9000g, 4.0mmol) is dissolved in 20mL mixed organic solvents
Isosorbide-5-Nitrae-dioxane and toluene (volume ratio 3:1) solution are added in reaction flask by constant pressure funnel, to sufficiently flow back
2h obtains mixed reaction solution；
3) reaction solution is poured into 60mL ice water, after standing a period of time, solution layering, upper layer is clear solution, lower layer
There is solid precipitation, filter, obtained solid carries out column Chromatographic purification, with volume ratio VEthyl acetate: VPetroleum ether=1:1 is eluant, eluent, is obtained
Target product is conjugated diamine monomer 1.3736g, yield 59.76%.
Embodiment 2
1) glass apparatus to be used in experiment is all cleaned up into rear drying for standby, mechanical stirring bar, nitrogen is being housed
First it is added 4,4 '-diamino -2 in the 250mL three-necked flask of gas shielded device, 2 '-dimethyl diphenyls (5.0949g,
24.0mmol), catalyst (1.5249g sodium carbonate, 0.1694g sodium hydroxide) and 10mL mixed organic solvents Isosorbide-5-Nitrae-dioxane
With toluene (volume ratio 3:1), it is heated to reflux to solid and dissolves, obtain mixed solution；
2) 2,4-, bis- chloro-6-phenyls -1,3,5-triazines (0.9000g, 4.0mmol) is dissolved in 20mL mixed organic solvents
Solution is added in reaction flask by constant pressure funnel, is then sufficiently returned by Isosorbide-5-Nitrae-dioxane and toluene (volume ratio 3:1)
4h is flowed, mixed reaction solution is obtained；
3) reaction solution is poured into 60mL ice water, after standing a period of time, solution layering, upper layer is clear solution, lower layer
There is solid precipitation, filter, obtained solid carries out column Chromatographic purification, with volume ratio VEthyl acetate: VPetroleum ether=1:1 is eluant, eluent, is obtained
Target product is conjugated diamine monomer 1.4510g, yield 63.13%.
Embodiment 3
1) glass apparatus to be used in experiment is all cleaned up into rear drying for standby, mechanical stirring bar, nitrogen is being housed
First it is added 4,4 '-diamino -2 in the 250mL three-necked flask of gas shielded device, 2 '-dimethyl diphenyls (6.7933g,
32.0mmol), catalyst (1.1437g sodium carbonate, 0.1270g sodium hydroxide) and 10mL mixed organic solvents Isosorbide-5-Nitrae-dioxane
With toluene (volume ratio 3:1), it is heated to reflux to solid and dissolves, obtain mixed solution；
2) 2,4-, bis- chloro-6-phenyls -1,3,5-triazines (0.9000g, 4.0mmol) is dissolved in 20mL1,4- dioxy six
Solution is added in reaction flask by constant pressure funnel for ring, and then sufficiently reflux 6h, obtains mixed reaction solution；
3) reaction solution is poured into 60mL ice water, after standing a period of time, solution layering, upper layer is clear solution, lower layer
There is solid precipitation, filter, obtained solid carries out column Chromatographic purification, with volume ratio VEthyl acetate: VPetroleum ether=1:1 is eluant, eluent, is obtained
Target product is conjugated diamine monomer 1.7953g, yield 78.11%.
Embodiment 4
1, differential scanning calorimeter is tested
Fig. 1 is differential scanning calorimeter (DSC) curve graph that diamine monomer is conjugated synthesized by Examples 1 to 3, Cong Tuzhong
It can
To find out its fusing point for 223.68 DEG C；
2, structural characterization
Fig. 2 is Examples 1 to 3 synthesis of conjugate diamine monomer1H-NMR spectrum.It as can be seen from the figure is secondary amino group at 10
Hydrogen signal peak, is primary amino group hydrogen signal peak at 1, is respectively methyl hydrogen signal peak at 4 and at 7, remaining is phenyl ring hydrogen signal peak.
Fig. 3 is the infrared spectrogram of Examples 1 to 3 synthesis of conjugate diamine monomer.As can be seen from the figure: 3368.0cm-1
And 1593.17cm-1For primary amine N-H characteristic absorption peak, 1243.53cm-1And 1170.59cm-1For primary amine C-N stretching vibration absorption
Peak, 1398.47cm-1And 1300.41cm-1For secondary amine C-N stretching vibration absworption peak, 1541.66cm-1For the suction of phenyl ring skeletal vibration
Receive peak, 1484.24cm-1For triazine ring characteristic absorption peak 697.79cm-1And 776.32cm-1For the monosubstituted absorption peak of phenyl ring,
818.85cm-1And 862.88cm-1Replace absorption peak for phenyl ring 1,2,4- tri-.
Prove that target product has successfully synthesized by the structural characterization of above two means.
The foregoing is only a preferred embodiment of the present invention, but the scope of protection of the invention be not limited thereto,
Any modification that anyone skilled in the art is made in the technical scope disclosed by the present invention, equivalent replacement and
Improve etc., it should be included within the protection scope of invention.
Claims (8)
1. a kind of conjugation diamine monomer, molecular formula are as follows:
2. a kind of preparation method of conjugation diamine monomer described in claim 1, which comprises the following steps:
(1) by 4,4 '-diamino -2,2 '-dimethyl diphenyls and catalyst are dissolved in solvent A, are heated to reflux completely molten to solid
Solution, obtains solution I；
(2) 2,4-, bis- chloro-6-phenyls -1,3,5-triazines is dissolved in solvent A and obtains solution II, solution II is added dropwise to solution
In I, solution III sufficiently is obtained after reflux；
(3) solution III is poured into ice water, stands to solution and is layered, there is solid precipitation in lower layer, filters, and obtained solid carries out
Column Chromatographic purification obtains target product conjugation diamine monomer.
3. according to the method described in claim 2, it is characterized by: the catalyst is made of sodium carbonate and sodium hydroxide, two
The mass ratio of person is 9:1.
4. according to the method described in claim 2, it is characterized by: the solvent A is the mixing of Isosorbide-5-Nitrae-dioxane and toluene
Object, the volume ratio of the two are 3:1.
5. according to the method described in claim 2, it is characterized by: 2,4-, bis- chloro-6-phenyl -1,3,5- in the step (1)
Triazine and 4,4 '-diamino -2,2 '-dimethyl diphenyl molar ratio are 1:4~1:8.
6. according to the method described in claim 2, it is characterized by: return time is 2~6h in the step (2).
7. according to the method described in claim 2, it is characterized by: in the step (3) purification with eluant, eluent be ethyl acetate
With the mixture of petroleum ether, the volume ratio of the two is 1:1.
8. conjugation diamine monomer answering in the semi-conductor polyimide that synthesis has conjugation triazine structure described in claim 1
With.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910406288.5A CN110041279B (en) | 2019-05-15 | 2019-05-15 | Conjugated diamine monomer and synthesis method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910406288.5A CN110041279B (en) | 2019-05-15 | 2019-05-15 | Conjugated diamine monomer and synthesis method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110041279A true CN110041279A (en) | 2019-07-23 |
| CN110041279B CN110041279B (en) | 2021-03-23 |
Family
ID=67282232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910406288.5A Active CN110041279B (en) | 2019-05-15 | 2019-05-15 | Conjugated diamine monomer and synthesis method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110041279B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997003642A1 (en) * | 1995-07-22 | 1997-02-06 | Ciba Specialty Chemicals Holding Inc. | Sunscreen compositions |
| CN106883215A (en) * | 2017-01-24 | 2017-06-23 | 瑞声科技（南京）有限公司 | Triaizine compounds and luminescent device |
| CN108640881A (en) * | 2018-04-26 | 2018-10-12 | 江汉大学 | A kind of diamine monomer and its synthetic method |
-
2019
- 2019-05-15 CN CN201910406288.5A patent/CN110041279B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997003642A1 (en) * | 1995-07-22 | 1997-02-06 | Ciba Specialty Chemicals Holding Inc. | Sunscreen compositions |
| CN106883215A (en) * | 2017-01-24 | 2017-06-23 | 瑞声科技（南京）有限公司 | Triaizine compounds and luminescent device |
| CN108640881A (en) * | 2018-04-26 | 2018-10-12 | 江汉大学 | A kind of diamine monomer and its synthetic method |
Non-Patent Citations (1)
| Title |
|---|
| ZIYU LI等: "Solubility, electrochemical behavior and thermal stability of polyimides synthesized from 1,3,5-triazine-based diamine", 《MATER ELECTRON》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110041279B (en) | 2021-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Thermally reversible cross-linked polyamides and thermo-responsive gels by means of Diels–Alder reaction | |
| WO2018166242A1 (en) | Method for preparing polyimide film having low dielectric constant and high fracture toughness | |
| CN103881091B (en) | A kind of preparation method of the polyimide containing carborane structure | |
| CN105566127B (en) | A kind of Triamine monomer and its preparation method and application | |
| CN104447869B (en) | It is a kind of containing DOPO and the asymmetric bismaleimide of molecular structure, preparation method and in the application prepared in compound resin | |
| CN103922989B (en) | Pyrrole radicals aromatic diamines of phthalonitrile structure and its preparation method and application | |
| TW200827405A (en) | Composition comprising bismaleimide oligomer and preparation method thereof | |
| EP3131951B1 (en) | Hydroxide-stable ionenes | |
| CN104448311A (en) | Polyimide based on 2,3,6,7-triptycene tetracarboxylic dianhydride and preparation method of polyimide | |
| CN103044348A (en) | Benzoxazine resin containing sulfonic group, and preparation method and application thereof | |
| CN105037383A (en) | High-purity ptyltetracid dianhydride and synthesis method thereof, and polyimides synthesized on basis of ptyltetracid dianhydride | |
| CN102382300B (en) | Watersoluble sulfonated polyamide and preparation method of the same | |
| CN108864137A (en) | A kind of acceptor compound, preparation method, purposes and the photovoltaic cell containing it | |
| Wang et al. | Isomeric dicyclic polymers via atom transfer radical polymerization and atom transfer radical coupling cyclization | |
| CN108640881A (en) | A kind of diamine monomer and its synthetic method | |
| CN110041279A (en) | A kind of conjugation diamine monomer and its synthetic method | |
| EP1754739A1 (en) | Deuterated polyimides and derivatives thereof | |
| Schroot et al. | Hydrophilic Poly (naphthalene diimide)‐Based Acceptor–Photosensitizer Dyads: Toward Water‐Processible Modular Photoredox‐Active Architectures | |
| Nagamani et al. | Synthesis and characterization of phenol‐based biaryl proton conducting polymers | |
| CN106543174A (en) | A kind of synthesis containing ether and the fluorene structured diacid monomer of phenodiazine and its polybenzimidazoles | |
| Wang et al. | Investigation of bismaleimide containing naphthalene unit. II. Thermal behavior and properties of polymer | |
| CN114634619B (en) | Polyimide, preparation method thereof and gas separation membrane | |
| CN109438343A (en) | Diamine compound, Kapton and flexible display apparatus | |
| CN102532532B (en) | Thioether-containing semi-aromatic polyamide and preparation method thereof | |
| CN109535139A (en) | One kind is containing two compound anhydride of carbazole and its synthetic method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |