CN102127194A - Water-soluble light-sensitive luminous polymer and preparation method thereof - Google Patents
Water-soluble light-sensitive luminous polymer and preparation method thereof Download PDFInfo
- Publication number
- CN102127194A CN102127194A CN 201010585778 CN201010585778A CN102127194A CN 102127194 A CN102127194 A CN 102127194A CN 201010585778 CN201010585778 CN 201010585778 CN 201010585778 A CN201010585778 A CN 201010585778A CN 102127194 A CN102127194 A CN 102127194A
- Authority
- CN
- China
- Prior art keywords
- fluorenes
- alkyl
- polymer
- reaction
- group
- 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
Images
Abstract
The invention discloses a water-soluble light-sensitive luminous polymer and a preparation method thereof. A macroinitiator adapting to atom transfer radical polymerization (ATRP) reaction is prepared, and a flexible segment is initiated by the ATRP reaction and is modified into the polymer capable of photocrosslinking. The polymer has good luminescent properties and is a high-polymer luminescent material capable of photocrosslinking. Firstly, a water-soluble solvent (such as water, ethanol and the like) is used for coating films; then, an insoluble film is formed by virtue of heating or photocuring, thereby ensuring the environment friendliness, and lowering the manufacture cost of relevant devices.
Description
Technical field
The invention belongs to photoelectric material and organic polymer material technical field, be specifically related to a kind of luminescence polymer material and preparation method thereof.
Background technology
In recent years, along with conjugated system begins to be applied in electron device gradually, based on the organic electronic industry of conjugated system just flourish.Especially polymer luminescent material has easy processing to luminous organic material for the small molecules luminescent material, filming technology is simple and the characteristic of Heat stability is good, overcome easy crystallization of small molecule material and formation charge transfer complex and excited state and assembled the shortcoming that causes degradation, caused extensive studies interest.Many polymer luminescent materials such as polyphenyl, poly-fluorenes and Polythiophene or the like are synthesized and further investigate.The researchist finds, by the modification of luminescence polymer, can keep its good optical characteristic when improving its processing characteristics and other physical propertiess.Among the method for numerous modifications and modification luminescence polymer, synthesizing and containing the hard and soft block polymer of the luminous segmental of conjugated polymers is a kind of efficient ways.
Introduce new polymers such as water-soluble polymers and the temperature sensing polymer etc. that different soft segments can obtain difference in functionality at conjugation block polymer main chain, for new functional luminescent material design provides a kind of new channel.The introducing of this soft segment, not only can carry out modification to polymkeric substance, also can make polymkeric substance in solution and in the solid film, produce some special forms, be easy to take place structure such as spherical, polynuclear plane and laminate structure etc. that micron-scale phase separation forms the Nano/micron yardstick under suitable condition.This is caused with compact arranged characteristic by tangible chemical physical property difference and rigid chain segment trend that rigidity difference between two kinds of segments is brought.Form if these height-oriented aligned rigid segments are luminescent conjugated polymers, the compact arranged segment of this trend can show some special luminosities, and wherein some characteristic is highly suitable for organic luminescent device.Exactly because aforesaid characteristic and advantage, the block polymer of many block polymers that contain the luminescence polymer stiff chain such as Polythiophene, polyphenyl, poly-fluorenes, polyphenylacetylene support and polystyrene support is synthesized and furthers investigate.
In above-mentioned polymkeric substance, poly-fluorenes and derivative thereof are a kind of polymer luminescent materials that business development is worth that has because its good chemistry and thermostability and solid state fluorescence quantum yield efficiently have been widely used in the research of polymer light-emitting device.In character modified object to luminescence polymer, exploitation is applicable to that the polymkeric substance of different organic light emitting display manufacture crafts is very important, in the organic light-emitting device making processes, thin film-forming method and picture element manufacture craft have significant effects to its performance and cost of manufacture.At present much become membrane preparation method to be suggested and to have dropped into business development based on the device of polymer luminescent material cheaply, wherein Chang Yong technology has spray ink Printing, light/electron beam lithography, self-assembly and silk screen printing etc.
The polymkeric substance of Photocrosslinkable since its insoluble characteristic can utilize heat or photocuring to form insoluble film, as the UV photosensitive sensitive polymeric already by particularly electronic industry institute widespread use of industry member.Covering on the polymkeric substance of photosensitivity the optical etching technology that forms fine structure by illumination by lighttight mask is the main method that present semi-conductor industry is used for making the large vol unicircuit.Present sophisticated photoetching technique is incorporated into simplifies the process of making organic light emitting display in the organic light-emitting device manufacturing processed and reduce cost.
Summary of the invention
The object of the present invention is to provide a kind of water-soluble triblock polymer luminescent material and preparation method thereof, the synthetic of block polymer mainly is by obtaining a macromole evocating agent that is adapted to atom transfer controllable free-radical polymerisation (ATRP) reaction, introducing soft segment and modify the polymkeric substance that becomes Photocrosslinkable by ATRP again.
A kind of water-soluble light activated luminescence polymer has following structure:
Wherein, R is that chain length is the alkyl of random length, and alkyl chain can contain N, O atom and amido linkage; X is a water soluble group: a kind of in carboxyl, sulfonic group, phosphate, quaternary amines, the alcoxyl long-chain.The preparation method of above-mentioned water-soluble light activated luminescence polymer, adopt following steps:
(1) fluorenes is monomeric synthetic
1. anionic monomer
With 2,7-dibromo fluorenes is a template, and adding 1～2 times of amount end group under the base catalysis condition is the bromo alkyl of hydroxyl, synthetic 9 fluorenes A that two alkyl replace; A is directly carried out oxidation with potassium permanganate to hydroxyl, and getting end group is the fluorenes A of two alkyl replacements of carboxyl
1
Perhaps, in A, add the hydroxy-protecting agent methane sulfonyl chloride, and the iodination reagent sodium iodide, react through S-WAT again with 2～4 times of amounts, obtaining end group is the fluorenes A that sulfonic pair of alkyl replaces
2
Perhaps, A is placed carbon tetrabromide and triphenyl phosphorus mixing solutions, with the tributyl phosphate reaction, products therefrom reacts with bromotrimethylsilane in lutidine, souring soln, and promptly obtaining end group is the fluorenes A of two alkyl replacements of phosphate
3
2. cationic monomer
With the fluorenes is raw material, in dimethyl sulfoxide solution, under the sodium hydroxide catalysis, obtains two alkyl substituted fluorene B that end group is a dimethyl amine with the reaction of dimethyl propylene ammonium chloride, further reacts in acetum with Paraformaldehyde 96, and obtaining 2,7 is the monomers B of aldehyde radical
1
Perhaps, with 2,7-dibromo fluorenes is a raw material, the samely obtains two alkyl substituted fluorene B that end group is a dimethyl amine
2, B
2Trimethyl borate with 3 times of amounts under the catalysis of n-Butyl Lithium reacts, and it is 9 two substituted fluorene B of boric acid that hydrolysis can get 2,7
3, adding toluene, propylene glycol backflow again, it is 9 two substituted fluorene B of boric acid ester that reaction makes 2,7
4
3. neutral monomer
With two sections polyoxyethylene glycol and phosphorus tribromide reactions that have hydroxyl, obtain two sections polyoxyethylene glycol that have bromine; Then under the base catalysis condition with 2,7-dibromo fluorenes reaction obtains the fluorenes C that 9 two alcoxyl long-chains of neutral monomer replace
1
With compd A under the catalysis of n-Butyl Lithium with the reaction of the trimethyl borate of 2～4 times of amounts, obtaining 2,7 through hydrolysis be 9 couples of alkyl substituted fluorene C of boric acid
2
(2) macromole evocating agent is synthetic
2, the two boric acid esters-9 of 7-, 9 '-dialkyl group-fluorenes is monomeric synthetic
Above-mentioned couple of fluorenes monomer A, the A that alkyl replaces
1, A
2, A
3, B, B
1, B
2, B
3, B
4, C
1, C
2In any, at two (1, the 5-cyclooctadiene) nickel (Ni (COD)
2) under the catalysis, adopt bromobenzene methyl alcohol end-blocking is got the poly-fluorenes of terminal hydroxy group, then with 2-bromine isobutyryl bromine reaction, products therefrom is through precipitation and dialysis membrane filtration step by step, and obtaining end group is the poly-fluorenes macromole evocating agent of 2-bromine isobutyl-;
(3) ATRP polymerization
With the poly-fluorenes macromole evocating agent of (two) in the orthodichlorobenzene solvent; use cuprous bromide catalysis; with vinylformic acid-2-trimethylsiloxy group ethyl ester as monomer; obtain pectination luminous high polymer compound; handling the pectination high molecular polymer obtain terminal hydroxy group with concentrated hydrochloric acid then in tetrahydrofuran solution, is that solvent and methacrylic chloride react under nitrogen protection and promptly obtain subject polymer at last with the anhydrous pyridine.
The water-soluble triblock polymer that contains the Photocrosslinkable group of the present invention, wherein hard section are the poly-fluorenes of inflexible conjugate light-emitting material, the soft section vinylformic acid flexible chain for the styracin modification; Not only realized the application target of photoetching technique, and because soft segment has produced the embedding effect to luminous hard section, make that the arrangement of stiff chain is tightr, obviously improved poly-fluorenes segmental thermostability and water-soluble, combine photo-crosslinking network and block polymer two big advantages to the luminescent material modification, make that the modification of polymkeric substance is convenient, and obtain some special microscopic patterns.
Embodiment
Further specify technical scheme of the present invention below by embodiment, so that understand content of the present invention better.
Embodiment carries out according to the following steps:
(1) the poly-fluorenes macromole evocating agent of the present invention is synthetic
Synthesizing of 2,7 dibromo fluorenes (2)
Fluorenes 50.15g (128.34mmol), iron trichloride 0.325g (2.00mmol) and chloroform 200ml are joined in the 500ml two neck bottles postcooling to 0 ℃, then 13.80g (269.5mmol) liquid bromine slowly was added drop-wise in the above-mentioned mixed solution in 30 minutes, is warmed up to stir after the room temperature and spends the night.After reaction finishes mixed solution is poured in the water, the sodium hydroxide solution washing with 10%, to solution by redness become faint yellow till.With three waters of chloroform extraction, merge organic phase, use saturated common salt water washing organic phase three times, add anhydrous sodium sulfate drying, the elimination siccative boils off solvent and obtains yellow heavy-gravity liquid.With this liquid with silica gel column chromatography with the sherwood oil be obtain faint yellow solid after elutriant separates after, at methyl alcohol: acetone ratio is a recrystallization in 1: 1 the mixing solutions, obtain white solid be purified 2,7-dibromo fluorenes (2).
2,7 two bromo-9,9-two (3 '-(N, N dimethylamine) propyl group)-fluorenes (3) synthetic
2,7-dibromo fluorenes (2) and 3-dimethyl propylene amine hydrochlorate, 50% sodium hydroxide and catalyzer back flow reaction 12 hours in methyl-sulphoxide is used dichloromethane extraction, is spin-dried for solvent and gets thick product.Thick product gets white crystal 2,7 two bromo-9,9-two (3 '-(N, N dimethylamine) propyl group)-fluorenes (3) through recrystallization.
Synthesizing of vinylformic acid-2-trimethylsiloxy group ethyl ester (HEATMS)
In the 500ml round-bottomed flask, add 25ml (217.7mmol) vinylformic acid-2-hydroxyl ethyl ester, triethylamine 40ml and methylene dichloride 250ml, under nitrogen atmosphere, slowly be added dropwise to trimethylchlorosilane 30.5ml (239.5mmol) after flask put into ice-water bath and be cooled to 0 ℃, be raised to room temperature after adding, continue reaction 30 minutes.Remove by filter the salt that reaction generates then, methylene dichloride is removed in underpressure distillation, remove by filter remaining throw out once more, solution after concentrating is dissolved in the 150ml ethyl acetate, behind deionized water wash three times, add anhydrous sodium sulfate drying, boil off solvent, it is the heavy 31g productive rate 77% of product vinylformic acid-2-trimethylsiloxy group ethyl ester that underpressure distillation obtains colourless liquid.
1H?NMR(400MHz，CDCl
3，ppm)：δ6.42(dd，1H)，6.15(m，1H)，5.83(dd，1H)，4.24(t，2H)，3.83(t，2H)，0.13(s，9H)。Phenylcarbinol is end capped poly-9, and the 9-dioctyl fluorene (4, PFOH) synthetic
In glove box, with 2 of 1.2g (7.7mmol), 2 '-dipyridyl and 2g (12.8mmol) two (1, the 5-cyclooctadiene) nickel (Ni (COD)
2) join in the 100ml two neck bottles, charge into behind the nitrogen and add 1.1ml 1,5-cyclooctadiene (COD) and 10ml dry DMF and 10ml dry toluene with syringe again.This moment, solution became mazarine, this solution was inserted in 70 ℃ the oil bath stirring reaction 30 minutes.Simultaneously in another single neck flask, add 2 of 2.74g (5mmol), 7-two bromo-9,9-dioctyl fluorene solid and 0.187g (1mmol) are to bromobenzene methyl alcohol, add the 10ml dry toluene with syringe behind the vacuum nitrogen filling gas three times repeatedly behind the enclosed system, treat that two kinds of monomers dissolve fully in toluene after, with syringe this solution is transferred to and before to have been reacted in the halfhour blue mixed solution, oil bath is raised to 80 ℃ continues reaction two days.Reaction finishes postcooling to room temperature, adds 50ml THF and 2ml hydrazine hydrate, continues under the room temperature to stir one day.At last mixture is removed by filter the black insolubles, and filtrate is precipitated in 500ml methyl alcohol, filter, collect yellow solid; This solid washed in apparatus,Soxhlet's three days with methyl alcohol, discarded solution, and with remaining solid dissolving, precipitation obtains faint yellow solid 1.05g productive rate 54% in methyl alcohol once more.
1H?NMR(400MHz，CDCl
3，ppm)：δ7.81-7.85(br，2H，Ar-H)，7.65-7.71(br，4H，Ar-H))，7.61(d?0.43H，phenylend?groups)，7.48(d，0.43H，phenyl?end?groups)，4.76(s，0.43H，PhCH
2O-)，2.10(br，4H)，1.10-1.25(br，20H)，0.76-0.91(br，10H)。
Poly-fluorenes macromole evocating agent (5, PFiBr) synthetic
With phenylcarbinol end capped poly-9; 9-dioctyl fluorene (PFOH) 1.0g (0.26mmol), 3.3ml (23mmol) triethylamine and 30ml anhydrous methylene chloride join in single neck flask of 150ml; in ice-water bath, be cooled to 0 ℃; under nitrogen protection and vigorous stirring, slowly add 3.3ml (23.8mmol) 2-bromine isobutyl acylbromide again, slowly go back up to room temperature reaction after dropwising and spend the night.Wash mixture with water three times after reaction finishes, it is right to remove the salt that generates in the dereaction and excessive unreacted 2-bromine isobutyl acylbromide, adds anhydrous sodium sulfate drying again, concentrates and obtains heavy-gravity liquid.This liquid is precipitated in methyl alcohol, and obtaining end group is the poly-fluorenes macromole evocating agent of 2-bromine isobutyl-, and suction filtration is collected solid, and with a large amount of methanol wash repeatedly, drying obtains flaxen product 0.8g, productive rate 80% in 50 ℃ of vacuum drying ovens.
1H?NMR(400MHz，CDCl
3，ppm)：δ7.81-7.85(br，2H，Ar-H)，7.62-7.71(br，4H，Ar-H))，7.56(d?0.43H，phenyl?end?groups)，7.48(d，0.43H，phenyl?end?groups)，5.27(s，0.43H，PhCH
2O-)，2.10(br，4H)，1.98(s，1.30H)，1.12-1.25(br，20H)，0.75-0.91(br，10H).
13C?NMR(100MHz，CDCl
3，ppm)：δ171.6(C＝O)，151.8(fluorene?q-C)，141.8(w)，140.5(fluorene?q-C)，140.4(w)，140.0(fluorene?q-C)，139.9(w)，139.4(w)，134.3(phenylene?q-C)，128.5(phenylene?H-C)，127.4(phenylene?H-C)，126.2(fluorene?H-C)，121.5(fluorene?H-C)，120.0(fluoreneq-C)，67.4(Ph-C-O)，55.7(C(CH
3)
2)，55.4(Ph-C-Ph)，40.4(CH
2)，31.8(CH
2)，30.8(CH
3)，30.1(CH
2)，29.7(CH
2)，29.2(CH
2)，23.9(CH
2)，22.6(CH
2)，14.1(CH
3).
(2) contain the synthetic route of three block conjugated polymers of photo-crosslinking group
The synthetic PF-b-HEATMS (6) of the atom transfer controllable free-radical polymerisation that poly-fluorenes macromole evocating agent causes
Tool at 10ml props up the 8mg 0.056mmol that packs in the test tube) cuprous bromide and the poly-fluorenes macromole evocating agent of 100mg (0.0275mmol), soft rubber ball vacuumizes after airtight beyond the Great Wall, after inflated with nitrogen is repeatedly removed oxygen, add orthodichlorobenzene and vinylformic acid-2-trimethylsiloxy group ethyl ester (HEATMS) 0.135ml (0.69mmol) of 0.2ml with syringe.It is freezing to put into liquid nitrogen after this mixture mixed, after treating the liquid completely solidified, vacuumize with vacuum pump and to drain behind the air under vacuum condition this solid of dissolving and treat oxygen in the solution, freezing once more vacuumizing after discharging, so repeated multiple times is removed the oxygen in the system fully.Reaction tubes is inserted in 80 ℃ of good oil baths of preheating, and the back that stirs adds 116 μ l (0.058mmol) 1,1,4,7,10,10-hexamethyl triethyl tetramine (HEMTETA), and solution becomes clarifying deep green rapidly behind the adding HEMTETA.Mixture continued stirring reaction 24 hours, and freezing stopped reaction in liquid nitrogen adds the tetrahydrofuran (THF) dissolved dilution of 5ml then.Remove mantoquita by the aluminium sesquioxide chromatography column,, in 100ml methyl alcohol, precipitate, obtain faint yellow solid, in 50 ℃ of vacuum drying ovens, obtain the 0.11g product after the dried overnight, productive rate 81% again with solution concentration.
Triblock polymer PF-b-HEATMS (6) removes protection (7PF-b-HEA) and modified with functional group (8PF-b-CEA)
0.08g triblock polymer PF-b-HEATMS is dissolved in the mixed solution of 4ml tetrahydrofuran (THF) and 1ml methyl alcohol, drips 3 concentrated hydrochloric acids then, stirring is spent the night.Reaction after finishing boils off solvent, with a large amount of methanol wash, obtains intermediate product PF-b-HEA (7).Taking a morsel gives over to analysis and characterization, and all the other products are dissolved in the 1.5ml anhydrous pyridine, adds 0.067g (0.40mmol) cinnamyl chloride again, reacts under nitrogen protection.Mixture removes by filter the salt of generation with mixture after reaction under the lucifuge condition is spent the night, precipitation is poured into solution in the mixture of a large amount of methyl alcohol and ice then, obtains flaxen solid PF-b-CEA.Use the vacuum drying oven drying at normal temperatures, obtain flaxen product 0.1g.
Synthesizing of water-soluble polymers (9PF-b-HCEA)
In the round-bottomed flask of a 50ml, add 0.4mmol neutral polymer (8), add the dissolving of 20ml tetrahydrofuran (THF), add 0.436g monobromethane and 5ml DMSO then.Under 50 ℃,, revolve to steam and remove most of monobromethane and tetrahydrofuran (THF) this solution stirring 3 days, polymkeric substance acetone sedimentation, centrifugation, 50 ℃ of following vacuum-dryings can obtain subject polymer (9).
Description of drawings
Fig. 1 is the proton nmr spectra of PF-b-HCEA of the present invention;
The gained proton nmr spectra records at Varian Mercury Plus 400 type NMRs (400Mz), take deuterochloroform as, tetramethylsilane (TMS) is interior mark, hydrogen spectrum concentration is 5mg/ml, carbon spectrum concentration is about 20mg/ml, the about 0.5ml of volume;
Fig. 2 is the infrared spectrum of the PF-b-MEA of different heat treatment time;
For following the tracks of the conversion process of ultraviolet light cross-linking, by FFIR (FTIR), the film in the photo-crosslinking process is characterized. Detailed process is as follows: the tetrahydrofuran solution of PF-b-HCEA is added drop-wise on the bromination sylvite sheet, and to be dried rear crosslinked under the 365nm of uviol lamp wavelength, at selected its infrared spectrum of time measurement;
The small scale structures that Fig. 3 obtains for photoetching of the present invention;
PF-b-HCEA is dissolved in the oxolane, is made into the solution of 5mg/ml, 8 seconds of speed spin coating of on desk-top sol evenning machine, turning to per minute 600 then, but obtain the film of ultraviolet photolithographic after the film forming to be dried. As mask, (power is about 4mW/cm with common uv lamp with the transmission electron microscope copper mesh processed2) the about 20min of 365nm wavelength illumination (after under the uviol lamp of 300W, filtering with the optical filter of 365nm crosslinked need 2 minutes). Get place's glass substrate after crosslinked, fully clean with oxolane, the diameter that namely obtains as shown in Figure 3 is about 100 microns dots structure.
Claims (2)
1. water-soluble light activated luminescence polymer is characterized in that having following structure:
Wherein, R is that chain length is the alkyl of random length, and alkyl chain can contain N, O atom and amido linkage;
X is a water soluble group: a kind of in carboxyl, sulfonic group, phosphate, quaternary amines, the alcoxyl long-chain.
2. the preparation method of the described water-soluble light activated luminescence polymer of claim 1 is characterized in that adopting following steps:
(1) fluorenes is monomeric synthetic
1 anionic monomer
With 2,7-dibromo fluorenes is a template, and adding 1～2 times of amount end group under the base catalysis condition is the bromo alkyl of hydroxyl, synthetic 9 fluorenes A that two alkyl replace; A is directly carried out oxidation with potassium permanganate to hydroxyl, and getting end group is the fluorenes A of two alkyl replacements of carboxyl
1
Perhaps, in A, add the hydroxy-protecting agent methane sulfonyl chloride, and the iodination reagent sodium iodide, react through S-WAT again with 2～4 times of amounts, obtaining end group is the fluorenes A that sulfonic pair of alkyl replaces
2
Perhaps, A is placed carbon tetrabromide and triphenyl phosphorus mixing solutions, with the tributyl phosphate reaction, products therefrom reacts with bromotrimethylsilane in lutidine, souring soln, and promptly obtaining end group is the fluorenes A of two alkyl replacements of phosphate
3
2 cationic monomers
With the fluorenes is raw material, in dimethyl sulfoxide solution, under the sodium hydroxide catalysis, obtains two alkyl substituted fluorene B that end group is a dimethyl amine with the reaction of dimethyl propylene ammonium chloride, further reacts in acetum with Paraformaldehyde 96, and obtaining 2,7 is the monomers B of aldehyde radical
1
Perhaps, with 2,7-dibromo fluorenes is a raw material, the samely obtains two alkyl substituted fluorene B that end group is a dimethyl amine
2, B
2Trimethyl borate with 3 times of amounts under the catalysis of n-Butyl Lithium reacts, and it is 9 two substituted fluorene B of boric acid that hydrolysis can get 2,7
3, adding toluene, propylene glycol backflow again, it is 9 two substituted fluorene B of boric acid ester that reaction makes 2,7
4
3 neutral monomer
With two sections polyoxyethylene glycol and phosphorus tribromide reactions that have hydroxyl, obtain two sections polyoxyethylene glycol that have bromine; Then under the base catalysis condition with 2,7-dibromo fluorenes reaction obtains the fluorenes C that 9 two alcoxyl long-chains of neutral monomer replace
1
With compd A under the catalysis of n-Butyl Lithium with the reaction of the trimethyl borate of 2～4 times of amounts, obtaining 2,7 through hydrolysis be 9 couples of alkyl substituted fluorene C of boric acid
2
(2) macromole evocating agent is synthetic
2, the two boric acid esters-9 of 7-, 9 '-dialkyl group-fluorenes is monomeric synthetic
Above-mentioned couple of fluorenes monomer A, the A that alkyl replaces
1,A
2, A
3, B, B
1, B
2, B
3, B
4, C
1, C
2In any, at two (1, the 5-cyclooctadiene) nickel (Ni(COD)
2) under the catalysis, adopt bromobenzene methyl alcohol end-blocking is got the poly-fluorenes of terminal hydroxy group, then with 2-bromine isobutyryl bromine reaction, products therefrom is through precipitation and dialysis membrane filtration step by step, and obtaining end group is the poly-fluorenes macromole evocating agent of 2-bromine isobutyl-;
(3) ATRP polymerization
With the poly-fluorenes macromole evocating agent of (two) in the orthodichlorobenzene solvent; use cuprous bromide catalysis; with vinylformic acid-2-trimethylsiloxy group ethyl ester as monomer; obtain pectination luminous high polymer compound; handling the pectination high molecular polymer obtain terminal hydroxy group with concentrated hydrochloric acid then in tetrahydrofuran solution, is that solvent and methacrylic chloride react under nitrogen protection and promptly obtain subject polymer at last with the anhydrous pyridine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010585778 CN102127194A (en) | 2010-12-10 | 2010-12-10 | Water-soluble light-sensitive luminous polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010585778 CN102127194A (en) | 2010-12-10 | 2010-12-10 | Water-soluble light-sensitive luminous polymer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102127194A true CN102127194A (en) | 2011-07-20 |
Family
ID=44265491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010585778 Pending CN102127194A (en) | 2010-12-10 | 2010-12-10 | Water-soluble light-sensitive luminous polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102127194A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020019238A1 (en) * | 2018-07-26 | 2020-01-30 | 中认英泰检测技术有限公司 | Environmental-responsive smart sensing device and preparation method and use thereof |
| CN111514380A (en) * | 2019-02-02 | 2020-08-11 | 江苏百赛飞生物科技有限公司 | Ureteral stent and preparation method thereof |
| CN114324286A (en) * | 2022-01-07 | 2022-04-12 | 中国人民解放军军事科学院军事医学研究院 | Photosensitive cross-linking agent and application thereof |
| CN115449085A (en) * | 2022-09-12 | 2022-12-09 | 西北工业大学 | Core-shell hyperbranched polyborosiloxane red delayed fluorescent material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594314A (en) * | 2004-06-24 | 2005-03-16 | 复旦大学 | Fluorene based water soluble conjugated polymer and process for preparing same |
-
2010
- 2010-12-10 CN CN 201010585778 patent/CN102127194A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594314A (en) * | 2004-06-24 | 2005-03-16 | 复旦大学 | Fluorene based water soluble conjugated polymer and process for preparing same |
Non-Patent Citations (1)
| Title |
|---|
| 《Macromolecular Rapid Communications》 20061231 Liangliang Qiang等 Novel Photo-Crosslinkable Light-Emitting Rod/Coil Copolymers: Underlying Facile Material for Fabricating Pixelated Displays 1779-1786 1 第27卷, 2 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020019238A1 (en) * | 2018-07-26 | 2020-01-30 | 中认英泰检测技术有限公司 | Environmental-responsive smart sensing device and preparation method and use thereof |
| CN111514380A (en) * | 2019-02-02 | 2020-08-11 | 江苏百赛飞生物科技有限公司 | Ureteral stent and preparation method thereof |
| CN111514380B (en) * | 2019-02-02 | 2021-06-08 | 江苏百赛飞生物科技有限公司 | Ureteral stent and preparation method thereof |
| CN114324286A (en) * | 2022-01-07 | 2022-04-12 | 中国人民解放军军事科学院军事医学研究院 | Photosensitive cross-linking agent and application thereof |
| CN115449085A (en) * | 2022-09-12 | 2022-12-09 | 西北工业大学 | Core-shell hyperbranched polyborosiloxane red delayed fluorescent material and preparation method thereof |
| CN115449085B (en) * | 2022-09-12 | 2023-08-08 | 西北工业大学 | Core-shell hyperbranched polyborosiloxane red delay fluorescent material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI545398B (en) | Hardmask composition, method of forming patterns using the hardmask composition and semiconductor integrated circuit device including the patterns | |
| CN102127195B (en) | Photosensitive luminescent polymer and preparation method thereof | |
| TWI564659B (en) | I-line photoresist composition and method of forming fine pattern using the same | |
| WO2021031818A1 (en) | Polyvinyl thioether ester, preparation method therefor and use thereof | |
| CN107132207B (en) | It is a kind of for quickly detecting the fluorescent optical sensor and preparation method thereof of explosive, quickly detect explosive method | |
| KR20140035434A (en) | Transistors and methods for making them | |
| CN107129487B (en) | One kind can excite the preparation method and applications of sulfosalt using thioxanthone as the LED of conjugated structure | |
| WO2015133375A1 (en) | Organic thin film transistor and method for manufacturing same | |
| KR20160118340A (en) | Cross-linkable fluorinated photopolymer | |
| CN102127194A (en) | Water-soluble light-sensitive luminous polymer and preparation method thereof | |
| TWI620011B (en) | Photosensitive resin composition, manufacturing method for color filter, color filter and liquid crystal display element using the same | |
| CN105198916A (en) | Functionalized double tower-type polyhedron oligomeric silsesquioxane and preparation method thereof | |
| CN107286327A (en) | It is a kind of for fluorescent test paper of quick detection explosive and preparation method thereof, the method for quick detection explosive | |
| CN105573053B (en) | Method for producing substrate having lyophilic and lyophobic parts, use thereof and composition | |
| US20060234148A1 (en) | Pyrrole derivative and photosensitive film using the same | |
| Han et al. | Monomer stoichiometry imbalance-promoted formation of multisubstituted polynaphthalenes by palladium-catalyzed polycouplings of aryl iodides and internal diynes | |
| CN105669889B (en) | Styrene derivative-methacrylate copolymer, its preparation and its application of acid groups are produced containing light | |
| CN113121302B (en) | Monodisperse polymer with main chain containing fluorene-diacetylene structure and preparation method and application thereof | |
| CN1594314A (en) | Fluorene based water soluble conjugated polymer and process for preparing same | |
| JP6934875B2 (en) | Colorant compound and colorant material containing it | |
| CN102713756A (en) | Light-sensitive polymer composition, method for producing pattern, and electronic component | |
| KR102488388B1 (en) | Patterned cnt film-coated substrate using click reaction and manufacturing method thereof | |
| CN104144908B (en) | Spirofluorene derivative molecular glass and preparation method thereof and the application in photoetching | |
| KR100316735B1 (en) | Polyamides having carbonate group and heat-resistant photoresist composition therefrom | |
| CN102713753A (en) | Positive photosensitive resin composition, method for producing patterned cured film and electronic component |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20110720 |