CN109503815A - A kind of method and the conjugated polythiofuran preparing conjugated polythiofuran by one step of elemental sulfur - Google Patents
A kind of method and the conjugated polythiofuran preparing conjugated polythiofuran by one step of elemental sulfur Download PDFInfo
- Publication number
- CN109503815A CN109503815A CN201811418543.XA CN201811418543A CN109503815A CN 109503815 A CN109503815 A CN 109503815A CN 201811418543 A CN201811418543 A CN 201811418543A CN 109503815 A CN109503815 A CN 109503815A
- Authority
- CN
- China
- Prior art keywords
- conjugated
- polythiofuran
- formula
- elemental sulfur
- conjugated polythiofuran
- 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.)
- Pending
Links
Classifications
-
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/18—Definition of the polymer structure conjugated
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
- C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention belongs to sulfur-bearing organic polymer preparation technical fields, disclose a kind of method and the conjugated polythiofuran that conjugated polythiofuran is prepared by one step of elemental sulfur.The method are as follows: in a solvent, activation alkynes monomer and elemental sulfur are reacted under highly basic effect, dilutes, precipitates, it is dry, obtain conjugated polythiofuran；The activation alkynes monomer is the binary acetylene compound of binary acetylenic ketone or alkynes ester compounds or non-ester ketone.Method of the invention is simple, and polymerization reaction yield is high, and product is easily separated；3,4 conjugated polythiofurans for being located at main chain had both can be obtained in this method, and 2,5 conjugated polythiofurans for being located at main chain also can be obtained；The conjugated polythiofuran of preparation conjugated structure rich in, thermal stability and refraction index with higher.Prepared conjugated polythiofuran has potential application in fields such as photovoltaic cell, chemical anti-pass sensor, nerve probe and biosensors.
Description
Technical field
The invention belongs to sulfur-bearing organic polymer preparation technical fields, and in particular to one kind is total by the preparation of one step of elemental sulfur
The method of yoke polythiophene and the conjugated polythiofuran.
Background technique
With the appearance of most simple conjugated polymer polyacetylene in 1997, the conjugated polymer based on heterocyclic compound (is led
Electric polymer) field be constantly extended, including to some heterocycles such as polypyrrole, polycarbazole, polythiophene, poly- furans polymerize
The research of object.Wherein, polythiophene is widely used in organic electroluminescence hair due to preferable electric conductivity, thermal stability and dissolubility
In the fields such as optical device, solar battery, fluorescence detection.The synthetic method of polythiophene includes electrochemistry, metal coupling, oxygen at present
Some synthetic methods such as change, light-initiated, acid catalysis.These methods are substantially is reacted with raw material containing thiphene ring
, and most methods is needed using special catalyst, develops the milder aggregation strategy of reaction condition to polythiophene more
Add to be widely applied and have very important significance.
Ideal polymerization reaction is since cheap and easily-available raw material, and elemental sulfur is as member abundant the third-largest in ore
Element, it is cheap, simple and easy to get, it is that can be used as the desirable feedstock for preparing conjugated polythiofuran.The present invention directly utilizes elemental sulfur
The preparation for carrying out conjugated polythiofuran, avoids the use of thiophene derivant and catalyst, economic and environment-friendly, simple height in the process
Effect, production application further for conjugated polythiofuran are of great significance.In addition, prepared conjugated polythiofuran is in light
There is potential application in the fields such as volt battery, chemical anti-pass sensor, nerve probe and biosensor.
Summary of the invention
In order to solve the disadvantage that the above prior art and deficiency, the primary purpose of the present invention is that providing one kind passes through simple substance
The method that one step of sulphur prepares conjugated polythiofuran.
Another object of the present invention is to provide conjugated polythiofurans prepared by the above method.
The object of the invention is achieved through the following technical solutions:
A method of conjugated polythiofuran is prepared by one step of elemental sulfur, comprising the following steps:
In a solvent, activation alkynes monomer and elemental sulfur are reacted in the presence of highly basic, is diluted, precipitated, it is dry, it obtains
Conjugated polythiofuran.
The structure of the activation alkynes monomer is formula (IV), formula (V) or formula (VI):
R1、R4For identical or different organic group, R2、R3For identical or different organic group.Preferably, R1、R4Choosing
From any one in following structural formula 1~19；R2、R3Any one in following structural formula 20~33；R5Selected from following
There is any one in the structural formula 34~37 of greater activity；
M, the integer that p, q, r are 1~20；It * is junction.
The highly basic is potassium hydroxide, sodium hydroxide, more than one in sodium methoxide, preferably potassium hydroxide.
The temperature of the reaction be room temperature~100 DEG C, preferably 80 DEG C；Reaction time is 20min~6h, preferably
30min；The reaction is to carry out under inert gas protection.
The activation alkynes monomer: molar ratio=1:(0.5~3 of highly basic), preferably 1:1.5；
The activation alkynes monomer: molar ratio=1:(1~5 of elemental sulfur monomer), preferably 1:3；
The concentration of the activation alkynes monomer in a solvent is 0.1~0.5mol/L, preferably 0.3mol/L.
The preferred sublimed sulfur of the elemental sulfur；The potassium hydroxide is analysis pure cerium hydroxide potassium powder；The solvent is normal
The organic solvent of rule, such as: toluene, dimethyl sulfoxide (DMSO), n,N-Dimethylformamide (DMF), n,N-dimethylacetamide
(DMAc), Isosorbide-5-Nitrae-dioxane etc., preferably DMSO.
The precipitating reagent that the precipitating is selected is ether.
When being precipitated, reaction mother liquor be added to the mode in precipitating reagent be added dropwise (speed of dropwise addition be 1~3 drop/
Second), and reaction mother liquor is first diluted with n,N-Dimethylformamide before being added in precipitating reagent, dilution carried out later
Filter.
When the structure of binary activation alkynes monomer is formula (IV), formula (V) or formula (VI), the structure of the conjugated polythiofuran is logical
Formula is formula (I), formula (II) or formula (III):
In formula (I)~(III), the integer that n is 2~200, R1、R4For identical or different organic group, R2、R3It is identical
Or different organic group.Preferably, R1、R4Any one in structure above 1~19；R2、R3Selected from above structure
Any one in formula 20~33；R5Any one in the above-mentioned structural formula 34~37 for having greater activity.
Prepared conjugated polythiofuran is in fields such as photovoltaic cell, chemical anti-pass sensor, nerve probe and biosensors
There is potential application.
It is formula (VII), formula that the present invention, which prepares reaction equation involved in the method for conjugated polythiofuran by one step of elemental sulfur,
(VIII) or formula (Ⅸ):
Compared with prior art, preparation method of the invention and obtained product have the following advantages that and the utility model has the advantages that
(1) monomer used in polymerization of the present invention is easy to get, and polymerization reaction yield is high (up to 99%), polymer
Molecular weight is high (weight average molecular weight is 0.5~70,000), and Atom economy is high, and the preferable refraction index of film forming is higher；
(2) polymerization of the present invention does not need any catalyst, only needs alkaline condition existing for potassium hydroxide, directly
It connects using elemental sulfur as reactant, synthesizes a series of conjugated polythiofurans using activation alkine compounds；
(3) polymerization reaction of the present invention can carry out at room temperature, and obtain good result；
(4) conjugated polythiofuran prepared by the present invention can be 3,4 positioned at main chain, is also possible to 2,5 and is located at main chain
Polythiophene.
Detailed description of the invention
Fig. 1 is that carbon of the obtained conjugated polythiofuran of embodiment 1 in deuterated dimethyl sulfoxide composes nuclear magnetic spectrogram；
Fig. 2 is the thermogravimetric analysis figure for the conjugated polythiofuran that Examples 1 to 4 obtains；
Fig. 3 is the refractive index curve that the conjugated polythiofuran film that Examples 1 to 4 obtains changes with wavelength.
Specific embodiment
Further specific detailed description, but implementation of the invention is made to the present invention with attached drawing combined with specific embodiments below
Mode is without being limited thereto, for not specifically specified technological parameter, can refer to routine techniques progress.
Embodiment 1
A method of activation alkynes and elemental sulfur polymerization prepare conjugated polythiofuran, and steps are as follows:
(1) under inert gas protection, 90.0mg binary acetylenic ketone compound 1a and 19.0mg sublimed sulfur is added to
It is dissolved in the DMSO of 0.67mL, KOH is added, binary acetylenic ketone: molar ratio=1:1.5 of highly basic is warming up to 80 DEG C, is stirred to react
30min；
(2) it is cooled to room temperature after having reacted, with 4mL DMF diluting reaction mother liquor, then is added dropwise that (speed of dropwise addition is 2
Drop/sec) precipitated into 100mL diethyl ether solution, sediment is collected, dry (dry temperature is 40 DEG C) obtains to constant weight
Conjugated polythiofuran.The products collection efficiency of the present embodiment is 98%, weight average molecular weight 61800g/mol, PDI 4.12.
The binary acetylenic ketone compound 1a of the present embodiment according to document (Chao Zheng, Haiqin Deng, Zujin Zhao,
Anjun Qin,Rongrong Hu,and Ben Zhong Tang Multicomponent Tandem Reactions and
Polymerizations of Alkynes,Carbonyl Chlorides,and Thiols.Macromolecules,2015,
48,1941-1951.) disclosed in method preparation.
A kind of conjugated polythiofuran of the present embodiment has the structural formula of P1:
Reaction equation involved in the present embodiment is as follows:
Carbon spectrum nuclear magnetic spectrogram of the conjugated polythiofuran P1 of the present embodiment in deuterated chloroform is as shown in Figure 1.It can from Fig. 1
Out, the solvent peak of deuterated chloroform is located at 77.16ppm, is in addition to this appearance of carbon atom in polythiophene, wherein
It is the characteristic peak of carbonyl in polymer P 1 at 192.2ppm.The thermogravimetric analysis figure of the polythiophene P1 of the present embodiment and its film with
Wavelength and change refractive index curve difference it is as shown in Figures 2 and 3.
Embodiment 2
A method of activation alkynes and elemental sulfur polymerization prepare conjugated polythiofuran, and steps are as follows:
(1) under inert gas protection, 118mg binary acetylenic ketone compound 1b and 19.0mg sublimed sulfur is added to 0.67mL
DMSO in dissolve, be added KOH, binary acetylenic ketone: molar ratio=1:1.5 of highly basic is warming up to 80 DEG C, is stirred to react 30min；
(2) it is cooled to room temperature after having reacted, with 4mL DMF diluting reaction mother liquor, then is added dropwise that (speed of dropwise addition is 2
Drop/sec) precipitated into 100mL diethyl ether solution, sediment is collected, dry (dry temperature is 40 DEG C) obtains to constant weight
Conjugated polythiofuran.The products collection efficiency of the present embodiment is 75%, weight average molecular weight 33500g/mol, PDI 2.82.
A kind of structural formula of the conjugated polythiofuran P2 of the present embodiment:
Reaction equation involved in the present embodiment is as follows:
The refractive index curve that the thermogravimetric analysis figure of the polythiophene P2 of the present embodiment and its film change with wavelength is respectively such as
Shown in Fig. 2 and 3.
Embodiment 3
A method of activation alkynes and elemental sulfur polymerization prepare conjugated polythiofuran, and steps are as follows:
(1) under inert gas protection, 100mg binary acetylenic ketone compound 1c and 19.0mg sublimed sulfur is added to 0.67mL
DMSO in dissolve, be added KOH, binary acetylenic ketone: molar ratio=1:1.5 of highly basic is warming up to 80 DEG C, is stirred to react 30min；
(2) it is cooled to room temperature after having reacted, with 4mL DMF diluting reaction mother liquor, then is added dropwise that (speed of dropwise addition is 2
Drop/sec) precipitated into 100mL diethyl ether solution, sediment is collected, dry (dry temperature is 40 DEG C) obtains to constant weight
Conjugated polythiofuran.The products collection efficiency of the present embodiment is 48%, weight average molecular weight 9500g/mol, PDI 1.45.
A kind of structural formula of the conjugated polythiofuran P3 of the present embodiment:
Reaction equation involved in the present embodiment is as follows:
The refractive index curve that the thermogravimetric analysis figure of the polythiophene P3 of the present embodiment and its film change with wavelength is respectively such as
Shown in Fig. 2 and 3.
Embodiment 4
A method of activation alkynes and elemental sulfur polymerization prepare conjugated polythiofuran, and steps are as follows:
(1) under inert gas protection, 113mg binary acetylenic ketone compound 1d and 19.0mg sublimed sulfur is added to 0.67mL
DMSO in dissolve, be added KOH, binary acetylenic ketone: molar ratio=1:1.5 of highly basic is warming up to 80 DEG C, is stirred to react 30min；
(2) it is cooled to room temperature after having reacted, with 4mL DMF diluting reaction mother liquor, then is added dropwise that (speed of dropwise addition is 2
Drop/sec) precipitated into 100mL diethyl ether solution, sediment is collected, dry (dry temperature is 40 DEG C) obtains to constant weight
Conjugated polythiofuran.The products collection efficiency of the present embodiment is 87%, weight average molecular weight 6200g/mol, PDI 1.26.
A kind of structural formula of the conjugated polythiofuran P4 of the present embodiment:
Reaction equation involved in the present embodiment is as follows:
The refractive index curve that the thermogravimetric analysis figure of the polythiophene P4 of the present embodiment and its film change with wavelength is respectively such as
Shown in Fig. 2 and 3.
The above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be to the present invention
Embodiment restriction.For those of ordinary skill in the art, it can also make on the basis of the above description
Other various forms of variations or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all of the invention
Made any modifications, equivalent replacements, and improvements etc., should be included in the protection of the claims in the present invention within spirit and principle
Within the scope of.
Claims (9)
1. a kind of method for preparing conjugated polythiofuran by one step of elemental sulfur, it is characterised in that: the following steps are included:
In a solvent, activation alkynes monomer and elemental sulfur are reacted in the presence of highly basic, is diluted, precipitated, it is dry, it is conjugated
Polythiophene；
The structure of the activation alkynes monomer is formula (IV), formula (V) or formula (VI):
When the structure of the activation alkynes monomer is formula (IV), formula (V) or formula (VI), the general structure of the conjugated polythiofuran is
Formula (I), formula (II) or formula (III):
In formula (I)~(VI), the integer that n is 2~200, R1、R4For identical or different organic group, R2、R3It is identical or different
Organic group.
2. the method for preparing conjugated polythiofuran by one step of elemental sulfur according to claim 1, it is characterised in that: R1、R4It is selected from
Any one in following structural formula 1~19；R2、R3Any one in following structural formula 20~33；R5Selected from following knot
Any one in structure formula 34~37；
M, the integer that p, q, r are 1~20；It * is junction.
3. the method for preparing conjugated polythiofuran by one step of elemental sulfur according to claim 1, it is characterised in that: the highly basic
For more than one in potassium hydroxide, sodium hydroxide, sodium methoxide.
4. the method for preparing conjugated polythiofuran by one step of elemental sulfur according to claim 3, it is characterised in that: the highly basic
For potassium hydroxide.
5. the method for preparing conjugated polythiofuran by one step of elemental sulfur according to claim 1, it is characterised in that: the reaction
Temperature be room temperature~100 DEG C；Reaction time is 20min~6h；The reaction is to carry out under inert gas protection.
6. the method for preparing conjugated polythiofuran by one step of elemental sulfur according to claim 1, it is characterised in that: the activation
Alkynes monomer: molar ratio=1:(0.5~3 of highly basic)；
The activation alkynes monomer: molar ratio=1:(1~5 of elemental sulfur monomer).
7. the method for preparing conjugated polythiofuran by one step of elemental sulfur according to claim 1, it is characterised in that: the activation
The concentration of alkynes monomer in a solvent is 0.1~0.5mol/L；
The elemental sulfur is sublimed sulfur；The solvent is toluene, dimethyl sulfoxide, N,N-dimethylformamide, N, N- diformazan
More than one in yl acetamide, 1,4- dioxane；
The precipitating reagent that the precipitating is selected is ether.
8. a kind of conjugated polythiofuran obtained by any one of claim 1~7 the method.
9. the application of conjugated polythiofuran according to claim 8, it is characterised in that: the conjugated polythiofuran photovoltaic cell,
Application in chemical anti-pass sensor, nerve probe and biosensor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811418543.XA CN109503815A (en) | 2018-11-26 | 2018-11-26 | A kind of method and the conjugated polythiofuran preparing conjugated polythiofuran by one step of elemental sulfur |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811418543.XA CN109503815A (en) | 2018-11-26 | 2018-11-26 | A kind of method and the conjugated polythiofuran preparing conjugated polythiofuran by one step of elemental sulfur |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109503815A true CN109503815A (en) | 2019-03-22 |
Family
ID=65750630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811418543.XA Pending CN109503815A (en) | 2018-11-26 | 2018-11-26 | A kind of method and the conjugated polythiofuran preparing conjugated polythiofuran by one step of elemental sulfur |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109503815A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790927A (en) * | 2019-11-07 | 2020-02-14 | 华南理工大学 | Poly-1, 4, 5-substituted triazole and preparation method and application thereof |
| CN112225899A (en) * | 2020-09-22 | 2021-01-15 | 华南理工大学 | Method for preparing poly-1, 4-dithiine and polythiophene through polymerization of elemental sulfur and active internal alkyne under temperature regulation and control, mutual conversion and application |
| CN112442008A (en) * | 2020-09-22 | 2021-03-05 | 华南理工大学 | Method for preparing 1, 4-dithiine and thiophene compounds by regulating elemental sulfur and active internal alkyne at temperature and conversion reaction of compound |
| CN113388105A (en) * | 2021-04-25 | 2021-09-14 | 香港科技大学深圳研究院 | Polyquinolinazine compound and preparation method and application thereof |
-
2018
- 2018-11-26 CN CN201811418543.XA patent/CN109503815A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790927A (en) * | 2019-11-07 | 2020-02-14 | 华南理工大学 | Poly-1, 4, 5-substituted triazole and preparation method and application thereof |
| CN110790927B (en) * | 2019-11-07 | 2021-09-21 | 华南理工大学 | Poly-1, 4, 5-substituted triazole and preparation method and application thereof |
| CN112225899A (en) * | 2020-09-22 | 2021-01-15 | 华南理工大学 | Method for preparing poly-1, 4-dithiine and polythiophene through polymerization of elemental sulfur and active internal alkyne under temperature regulation and control, mutual conversion and application |
| CN112442008A (en) * | 2020-09-22 | 2021-03-05 | 华南理工大学 | Method for preparing 1, 4-dithiine and thiophene compounds by regulating elemental sulfur and active internal alkyne at temperature and conversion reaction of compound |
| CN112442008B (en) * | 2020-09-22 | 2022-05-27 | 华南理工大学 | Method for preparing 1, 4-dithiine and thiophene compounds by regulating elemental sulfur and active internal alkyne at temperature and conversion reaction of compound |
| CN113388105A (en) * | 2021-04-25 | 2021-09-14 | 香港科技大学深圳研究院 | Polyquinolinazine compound and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109503815A (en) | A kind of method and the conjugated polythiofuran preparing conjugated polythiofuran by one step of elemental sulfur | |
| CN109553778B (en) | Method for preparing polyselenuride/polyselenocylamide by multicomponent polymerization of elemental selenium, isonitrile/alkyne and amine | |
| CN107236128A (en) | The multicomponent polymerization of a kind of isonitrile, sulphur and amine prepares the method for polythiourea and the application of the polythiourea | |
| CN110407714A (en) | Hindered phenol and the compound difunctional antioxidant of amide groups intramolecular and its synthetic method | |
| CN113292721B (en) | Polythiourea compound and preparation method and application thereof | |
| CN103407992B (en) | Method for preparing hydrophilic temperature and pH dual-sensitive graphene through thiol-ene click chemistry method | |
| CN102850340B (en) | One class have the narrowband gap conjugated polymer of taxis or oligopolymer, and preparation method thereof | |
| CN105001419B (en) | Alkyne, sulfur and amine multi-component polymerization method for preparing poly-thioamide | |
| CN113265051B (en) | Method for preparing polymer with controllable sulfur and/or selenium sequence by one-pot method and product thereof | |
| CN109796581B (en) | Narrow-band conjugated polymer containing low polyethylene glycol side chain structure and preparation method and application thereof | |
| CN106832257B (en) | A kind of polyallyl ethers compound and the preparation method and application thereof | |
| CN104130421B (en) | Method for preparing diselenide polymer | |
| CN105618139B (en) | A kind of ligocellulose degradation's method based on molybdenum multi-metal oxygen hydrochlorate | |
| CN107325284A (en) | A kind of hyperbranched poly phenyl triazole formic acid esters and preparation method and application | |
| CN114316265B (en) | Polythiourea compound and preparation method and application thereof | |
| CN106243351B (en) | No metal catalytic multicomponent polymerization preparation sequence controllable linear/hyper-branched polymer and method and application | |
| CN103467742B (en) | Polyvinylene sulfide and preparation method thereof | |
| CN104558541A (en) | Alkyne-ketone intermediate based conjugated high-molecular polymer as well as preparation method and application thereof | |
| CN101778835A (en) | Method for production of purified ammonium salt of fluorinated bis-sulfonylimide | |
| CN106279677B (en) | Rich in heteroatomic phosphine amidine quasi polymer and prepares the multicomponent polymerization of the polymer and apply | |
| CN101503513B (en) | Preparation of conductive polymers based bisulfide | |
| CN111592521A (en) | Amino acid group S-carboxyl internal cyclic anhydride and functionalized poly-thioester and preparation method thereof | |
| CN110343242A (en) | Photochromic hyperbranched azopolyamide of one kind and preparation method thereof | |
| CN105418930A (en) | Preparation method of water-soluble polyaniline | |
| CN107641197B (en) | It is a kind of using carbon dioxide and 7-oxa-bicyclo[4.1.0 as the copolyreaction catalyst of monomer |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190322 |
|
| RJ01 | Rejection of invention patent application after publication |