CN101619124A - Comb-shaped polymer containing carbazole lateral chain and preparation method thereof - Google Patents
Comb-shaped polymer containing carbazole lateral chain and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a comb-shaped polymer containing a carbazole lateral chain and a preparation method thereof. The preparation method comprises the following steps: taking potassium tertbutoxide as an initiator, carrying out anion ring opening polymerization on 4-glycidyl-2, 2, 6 and 6-4-methyl oxidation piperidinol (GTEMPO) monomers and preparing a macro molecule TEMPO reagent PGTEMPO; taking the PGEMPO as an adjustment and control reagent, polymerizing N-(4-vinylbenzyl)-carbazole under the initiation of the initiator and preparing the comb-shaped polymer PGTEMPO-g-PVBK taking polyether as a main chain and polymer with a carbazole structure as a lateral chain. The research on VBK polymerization behavior shows the characteristics of typical activity/controlled radical polymerization. The optical, thermal and electrical properties of the prepared comb-shaped polymer are researched. The ultraviolet absorption, the fluorescence intensity and the oxidation-reduction potential of comb-shaped polymers with different molecular weights display good regularity.
Description
Technical field
The present invention relates in a kind of organic electronic devices hole transport or luminescent material efficiently, be specifically related to a kind of comb-shaped polymer that contains carbazole lateral chain.
Background technology
Carbazole structure has caused the interest of material educational circles owing to it has performances such as good hole transport and electroluminescent.After the photoconductive phenomenon of the back polyvinyl carbazole that mixes was found, the polymkeric substance that contains carbazole group had caused people's extensive interest.This base polymer is used as in a lot of functional materials, for example: light-guide material, light refraction material, electroluminescent device, programmable optical communication material, data storage, chemical light transmitter, nonlinear optical material, surface relief grating, blue light emitting material and Hologram Storage etc.
Contriver place seminar has reported and has successfully carried out N-by the living free radical polymerization polymerization technique (activity/controllable free-radical polymerisation of 4-vinyl benzyl carbazole is (referring to Zhang W, Yan Y, Zhou N, Cheng Z, Zhu J, Xia C, Zhu X, Eur.Polym.J., 2008,44,3300-3305).Polymerization result has shown tangible living features: molecular weight and transformation efficiency are linear and remain narrower molecular weight distribution, can also carry out successfully chain extension to vinylbenzene simultaneously.By the investigation of polymers soln is found that the fluorescence intensity of polymkeric substance can change along with the change of chromophore concentration in the polymkeric substance, when the concentration of carbazole group reaches 8 * 10
-5Reach maximum value during mol/L.Simultaneously, the fluorescent emission of polystyrene carbazole can be by methacrylic ester (MA) quencher.
But, in the above-mentioned prior art, be linear polymer, do not see the report that the carbazole of pectination method for producing polymer is arranged; And highest occupied molecular orbital(HOMO) of described polymkeric substance (HOMO) and lowest unoccupied molecular orbital (LUMO) and edge energy are not found to increase along with the increase of polymericular weight.
Summary of the invention
The object of the invention provides a kind of comb-shaped polymer that contains carbazole lateral chain.
For achieving the above object, the concrete technical scheme of the present invention is, a kind of comb-shaped polymer that contains carbazole lateral chain, described comb-shaped polymer are PGTEMPO-g-PVBK, and its chemical structural formula is as follows:
The molecular weight of described comb-shaped polymer is 6000～30000, m=1～42, n=10～25.
In the technique scheme, described comb-shaped polymer is to contain 2,2,6, and the polyethers PGTEMPO of 6-tetramethyl-oxidation piperidines alcohol (TEMPO) structure is a main chain, is side chain to contain N-(4-vinyl benzyl)-carbazole (VBK) structural polymer.
The chemical structural formula of described polyethers PGTEMPO is as follows:
The chemical structural formula of described N-(4-vinyl benzyl)-carbazole is as follows:
The method for preparing above-mentioned comb-shaped polymer may further comprise the steps:
(1) with the potassium tert.-butoxide initiator, to 4-glycidyl-2,2,6,6-tetramethyl-oxidation piperidines alcohol (GTEMPO) monomer carries out anionic ring-opening polymerization, poly-(the 4-glycidyl-2 of preparation macromole TEMPO reagent, 2,6,6-tetramethyl-oxidation piperidines alcohol) (PGTEMPO);
(2) with poly-(4-glycidyl-2,2,6,6-tetramethyl-oxidation piperidines alcohol) as regulation and control reagent, be reductive agent, under initiator causes with the ascorbic acid usp/bp, carry out the polymerization of N-(4-vinyl benzyl)-carbazole (VBK), obtain comb-shaped polymer PGTEMPO-g-PVBK.
In the technique scheme step (1), 4-glycidyl-2,2,6, the mol ratio of the pure and mild potassium tert.-butoxide of 6-tetramethyl-oxidation piperidines is 30～150: 1, polymeric reaction temperature is at 55～70 ℃.
In the technique scheme, but method reference (the Suga T for preparing macromole TEMPO reagent PGTEMPO, Yoshimura K, Nishide H, Macromol.Symp., 2006,245-246,416-422), can obtain the PGTEMPO (n=10～25) of different polymerization degree by controlled polymerization time and monomer and ratio of initiator; N-(4-vinyl benzyl)-carbazole (VBK) but preparation method's reference (Cho YS, Kim SW, Ihn CS, Lee JS.Polymer 2001; 42:7611-6.).
In the technique scheme step (2), the mol ratio of VBK, initiator, reductive agent and PGTEMPO is 30～200: 1: 1.3: 1.3, the polymerization temperature of described polyreaction is 123～135 ℃, and polymerization time is 8～15 hours, can control the value of m by the controlled polymerization time.
In the technique scheme, described initiator is benzoyl peroxide BPO.
In the technique scheme, step (1) and described being reflected in the inert atmosphere of step (2) are carried out, and described inert atmosphere is nitrogen atmosphere or argon gas atmosphere.
In the technique scheme step (2), the solvent that polyreaction adopts is selected from: chlorine benzene,toluene,xylene, methyl-phenoxide, N, a kind of in dinethylformamide, N,N-dimethylacetamide or the methyl-sulphoxide.
Further in the technical scheme, step (2) products therefrom system is dissolved in solvent, and uses methyl alcohol to precipitate, after the separate vacuum drying, obtain the comb-shaped polymer PGTEMPO-g-PVBK of purifying as precipitation agent.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1, among the present invention, PGTEMPO is owing to contain activated TEMPO structure fragment, can be used as macromole TEMPO reagent, effectively carry out the controllable free-radical polymerisation of styrene monomer, can obtain a series of comb-shaped polymer PGTEMPO-g-PVBK with different molecular weight by the molecular weight of change macromole TEMPO reagent and the proportioning of VBK monomer and TEMPO reagent;
2, uv-absorbing, fluorescence intensity and the redox potential of the comb-shaped polymer PGTEMPO-g-PVBK of different molecular weight demonstrate good regularity, and for example: 1. along with the increase of the polymerization degree, uv-absorbing intensity decreases; 2. under the situation of carbazole group concentration unanimity, the comb-shaped polymer fluorescence intensity strengthens along with the increase of the polymerization degree; 3. the HOMO of polymkeric substance, LUMO and edge energy all increase along with the increase of polymericular weight.
Description of drawings
Fig. 1. 4-glycidyl-2,2,6 among the embodiment one, the synthetic route of 6-tetramethyl-oxidation piperidines alcohol (GTEMPO);
Fig. 2. the synthetic route of N-among the embodiment three (4-vinyl benzyl)-carbazole (VBK);
Fig. 3. the synthetic route of comb-shaped polymer in embodiment four～11 (PGTEMPO-g-PVBK);
Fig. 4. monomer concentration semilog ln ([M] among the embodiment 13
0/ [M]) with the polymerization time graph of a relation;
Fig. 5. Mn of polymkeric substance (GPC) and PDI are with transformation efficiency variation relation figure among the embodiment 13;
Fig. 6. the ultraviolet-visible absorption spectroscopy figure of the polymkeric substance of monomer among the embodiment 14 (VBK) and different molecular weight;
Fig. 7. the fluorescent emission spectrogram of the polymkeric substance of monomer among the embodiment 14 (VBK) and different molecular weight;
Fig. 8 (a). the DSC collection of illustrative plates of the comb-shaped polymer of different molecular weight among the embodiment 15;
Fig. 8 (b). the TGA collection of illustrative plates of the comb-shaped polymer of different molecular weight among the embodiment 15;
Fig. 9. polyethers and different molecular weight comb-shaped polymer are at CHCl among the embodiment 16
3Potential ph diagram ph in the solution;
Figure 10. different molecular weight PVBK polymkeric substance is at CHCl among the embodiment 16
3Potential ph diagram ph in the solution.
Embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Raw material: 4-hydroxyl-2,2,6,6-tetramethyl-oxidation piperidines alcohol (98%; Chemical plant, Wuxi City Fuan, the Wuxi) behind the normal hexane recrystallization, use; Benzoyl peroxide (BPO; Aldrich) through the dehydrated alcohol recrystallization; P-chloromethyl styrene (Aldrich; 90%) is untreated and directly uses; Carbazole (analytical pure), ascorbic acid usp/bp (VC; 99.7%), NaOH (analytical pure), N, dinethylformamide (DMF; Analytical pure), chloroform (CHCl
3Analytical pure) and tetrahydrofuran (THF) (THF; Analytical pure) all is Shanghai chemical reagents corporation product, handles by standard method before using.
Embodiment one, 4-glycidyl-2,2,6,6-tetramethyl-oxidation piperidines alcohol (GTEMPO) synthetic
Monomer 4-glycidyl-2,2,6, the synthetic route of 6-tetramethyl-oxidation piperidines alcohol (GTEMPO) is as Fig. 1. shown in.
Epoxy chloropropane (10mL, 120mmol) and tetra-n-butyl ammonium bromide (1.5g 4.6mmol) joins sodium hydroxide (16mL, 50wt%) in the solution, stirred 10 minutes 4-hydroxyl-2 under the room temperature, 2,6, and 6-tetramethyl-oxidation piperidines alcohol (4.12g, 24mmol), join in the 30mL tetrahydrofuran (THF), pour into then in the above mixing solutions, at room temperature stir 12 hours after, pour in about 50mL frozen water and use ethyl acetate extraction again.With the anhydrous MgSO of extraction liquid
4Dry.Thick product can obtain after the Rotary drying, then by (sherwood oil: ethyl acetate=8: 1) cross the silica gel pillar, use the normal hexane recrystallization afterwards again, obtain containing the TEMPO monomer (GTEMPO) of epoxy at last, productive rate is about 80% with developping agent.By purity that HPLC surveys is that 98% GTEMPO results of elemental analyses is: C
12H
22NO
3(%): C, 63.13; H, 9.71; N, 6.14.Found (%): C, 62.52; H, 9.63; N, 5.71.
Embodiment two, the anionic ring-opening polymerization of monomer GTEMPO
The anionic ring-opening polymerization of monomer GTEMPO is as follows: the reaction flask of 25mL dried by the fire 24 hours down at 100 ℃, was evacuated to room temperature, dropped to-20 ℃ again; With GTEMPO (0.556g, 2mmol), potassium tert.-butoxide (40L, 0.04mmol) and 2mLTHF under the argon gas state, join in the reactor, 60 ℃ of following stirring reactions 24 hours.Then, Dropwise 5 mLTHF dissolve polymer in polymerization reactor precipitates polymers soln in about 200mL normal hexane, obtain polymkeric substance through suction filtration, and is refining by twice dissolution precipitation again, obtains orange solids at last and is polymer P GTEMPO.
Embodiment three, N-(4-vinyl benzyl)-carbazole (VBK) synthetic
According to document (Wei Zhang, Yuefang Yan, Nianchen Zhou, ZhenpingCheng, Jian Zhu, Chunmei Xia, Xiulin Zhu.Eur Polym J 2008; 44:3300.) synthetic N-(4-vinyl benzyl)-carbazole (VBK) (as Fig. 2 .).
Carbazole (8.4g, 50mmol) and NaOH (2g 50mmol) joins among the 100mL DMF and stirs, and (7.6g 50mmol), adds back stirring at room 24h to drip p-chloromethyl styrene under the room temperature.Reaction solution is poured in the big water gaging, and filtration will obtain crude product, obtain white crystalline thing (productive rate 85%) by acetone recrystallization.
1H NMR (DMSO-d
6) (PPm): d 5.71 (1H, CH
2=CH), 5.17 (1H, CH
2=CH), 5.64 (2H, CH
2), 6.64 (1H, CH
2=CH), 7.34,7.12,8.17,7.42,7.19,7.62 (12H, Ar-H) .Element.Anal.:Calcd for C
21H
17N (%): C, 89.01; H, 6.05; N, 4.94.Found (%): C, 88.69; H, 6.11; N, the 5.15. liquid phase shows that purity is 98.5%.
Embodiment four～11, the polymerization of N-(4-vinyl benzyl)-carbazole (VBK)
Typically polymerization process is as shown in Figure 3:
(1) VBK, BPO, PGTEMPO, VC are dissolved in DMF and join in the exsiccant ampere bottle, the logical argon gas of this ampere bottle 20 minutes to get rid of oxygen wherein, is sealed, and put into 123 ℃ oil bath polymerization;
(2) after the predetermined reaction times, frozen water is put in its taking-up, opened and seal, reaction solution is dissolved among the THF, solution precipitates in methyl alcohol, suction filtration, vacuum-drying get final product required polymkeric substance, transformation efficiency is measured in weighing.
The sign of table 1. different molecular weight graft copolymer (PGTEMPO-g-PVBK)
a: polymerizing condition is 123 ℃ and reacted 8 hours down;
b: the reaction times is 15 hours.
Embodiment 12, the preparation of N-(4-vinyl benzyl)-carbazole (VBK) homopolymer (PVBK):
VBK, BPO, 2,2,6,6-tetramethyl-oxidation piperidines (TEMPO), VC (mol ratio [VBK]
0: [BPO]
0: [TEMPO]
0: [VC]
0=150: 1: 1.3: 1.3) be dissolved in DMF and join in the exsiccant ampere bottle, the logical argon gas of this ampere bottle 20 minutes to get rid of oxygen wherein, is sealed, and put into 123 ℃ oil bath polymerization.Respectively after the polymerization through 8 hours and 15 hours, frozen water is put in its taking-up, open and seal, reaction solution is dissolved among the THF, and solution precipitates in methyl alcohol, suction filtration, vacuum-drying get final product required polymkeric substance, weighing is measured transformation efficiency and is respectively 55.3% and 82.1%, and its molecular weight is respectively 4700 and 8200, and molecular weight distribution is respectively 1.33 and 1.36.
Embodiment 13, polymerization kinetics research:
With PGTEMPO (M
n=4080, PDI=1.35) be macromole TEMPO reagent, proportioning is [VBK]
0: [BPO]
0: [PGTEMPO]
0: [VC]=130: 1: 1.3: 1.3, [VBK]
0=0.5mol/L.The result is as shown in Figure 4: in the polymerization process, and monomer concentration semilog ln ([M]
0/ [M]) linear with polymerization time, show that increasing number of free radical in the polymerization process remains unchanged substantially.By the GPC test, the molecular weight of polymkeric substance and transformation efficiency also linear (Fig. 5), this point also meets the characteristics of active free radical polymerization.
Embodiment 14, the spectral response curve of PGTEMPO-g-PVBK
The polymkeric substance of carbazolyl-containing group is a kind of well behaved photic electro-conductive material, and the spectral signature of the polymkeric substance that obtains is investigated, and wherein the concentration of carbazole group is 5 * 10
-5M.
Fig. 6 has shown the ultraviolet-visible absorption spectroscopy of monomer VBK and polymer P GTEMPO-g-PVBK.Monomer and polymkeric substance 294,331 and 345nm absorption peak is all arranged, wherein also as can be seen, along with the increase of the polymerization degree, absorption intensity decreases, and mainly is because the result that acts on each other of carbazole chromophoric group.
Fig. 7 as can be seen comb-shaped polymer with λ
ExUnder the ultraviolet excitation of=294nm, it demonstrates stronger fluorescent emission at 350nm and 365nm under room temperature condition in DMF solution.The fluorescent emission of these positions, main rigid structure owing to carbazole group.A little less than the fluorescence intensity ratio monomer of polymkeric substance, mainly be because the VBK after the polymerization is relative more weak electron deficiency system.In VBK homopolymerization system and N-ethyl-3-vinylcarbazole system similar conclusion is arranged also.It can also be seen that from Fig. 7 under the situation of carbazole group concentration unanimity, the comb-shaped polymer fluorescence intensity strengthens along with the increase of the polymerization degree.
Wherein, PGTEMPO-g-PVBK-1:M
N (GPC)=10230g/mol, PDI=1.84; PGTEMPO-g-PVBK-2:M
N (GPC)=13700g/mol, PDI=1.84PGTEMPO-g-PVBK-3:M
N (GPC)=17860g/mol, PDI=1.87.
Embodiment 15, the thermal characteristics of polymkeric substance
By dynamic differential scanning (DSC) and thermal weight loss (TGA) test, the polymkeric substance thermal characteristics is characterized.Result such as Fig. 8 and table 2.Macromole TEMPO polymkeric substance (PGTEMPO-1～3) molecular weight is respectively 4080,4740 and at 5010 o'clock, its second-order transition temperature (T
g) be respectively 15.4,22.7 and 25.3 ℃, heat decomposition temperature (T
d) be respectively 285.9,294.4 and 306 ℃.After connecting VBK, the second-order transition temperature of these comb-shaped polymers all increases: obtain molecular weight and be respectively 10230 and 17860 PGTEMPO-g-PVBK-1 and the T of PGTEMPO-g-PVBK-3 after meeting VBK on the PGTEMPO-3
gBe respectively 74.2 and 94.1 ℃; The molecular weight that meets the PGTEMPO-g-PVBK-2 of VBK on PGTEMPO-2 is 13700 T
gIt is 81.5 ℃.This shows that the introducing of VBK can improve the T of polymkeric substance
g, this also is because the rigid structure of carbazole group is caused.The introducing of carbazole group has also improved the thermostability of polymkeric substance.Fig. 8 as seen, wherein the TGA curve display of comb-shaped polymer PGTEMPO-g-PVBK goes out two heat decomposition temperatures, one is the decomposition temperature of main chain PGTEMPO, probably at 218 ℃; Another then is the decomposition temperature of PVBK, the T of the PVBK chain of different polymerization degree
dProbably at 388～398 ℃.Curiously, the heat decomposition temperature of PGTEMPO chain in comb-shaped polymer low than in homopolymer.
Second-order transition temperature (the T of table 2. differing molecular weight polymers
g) and heat decomposition temperature (T
d).
| Polymkeric substance | ??M n，GPC | ??PDI | ??T g/℃ | ??T d/℃ |
| ??PGTEMPO-1 a | ??4080 | ??1.35 | ??15.4 | ??285.9 |
| ??PGTEMPO-2 a | ??4740 | ??1.59 | ??22.7 | ??294.4 |
| ??PGTEMPO-3 a | ??5010 | ??1.59 | ??25.3 | ??306.0 |
| ??PGTEMPO-g-PVBK-1 b | ??10230 | ??1.84 | ??74.2 | ??218.8，388.9 |
| ??PGTEMPO-g-PVBK-2 c | ??13700 | ??1.84 | ??81.5 | ??218.5，397.6 |
| ??PGTEMPO-g-PVBK-3 b | ??17860 | ??1.87 | ??94.1 | ??218.5，392.7 |
a: three polymkeric substance are in same temperature of reaction, and same reaction ratio obtained with the different reaction times;
b: polymkeric substance is to be macro-TEMPO reagent with PGTEMPO-3;
c: polymkeric substance is to be macro-TEMPO reagent with PGTEMPO-2.
Embodiment 16, the electrochemical behavior of polymkeric substance
By cyclic voltammetry the electrochemical behavior of polymkeric substance is investigated.Actual conditions is: with (n-Bu) of 0.1M
4NPF
6As supporting electrolyte, use three-electrode system (working electrode is platinum filament, and Ag/AgCl (0.1M) is as reference electrode, and counter electrode is a silver electrode), scanning speed is 50mVs under the room temperature
-1The result is as Fig. 9. and shown in the table 3..PGTEMPO (M
N (GPC)=4740g/mol, reversible redox electromotive force PDI=1.59) is respectively 0.62V and 0.45V.Comb-shaped polymer has also shown the reversible redox effect.PGTEMPO-g-PVBK-1, the oxidation potential of PGTEMPO-g-PVBK-2 and PGTEMPO-g-PVBK-3 is respectively 0.50,0.54 and 0.59V.The size of oxidation voltage can be considered to weigh the standard of polymer architecture electron donation size.Its recovery voltage is respectively 0.46,0.48 and 0.55V.Can calculate highest occupied molecular orbital(HOMO) (HOMO) energy level [37] of polymer materials by oxidation potential.HOMO＝E
onset ox+4.8-E
Foc
Here, E
FocBe the voltage of ferrocene vs.Ag/AgCl.After tested, E in the body series
Foc=0.247V.Absorption edge by the polymkeric substance ultraviolet-visible absorption spectroscopy (is seen Fig. 9, polyethers (PGTEMPO, M
N (GPC)=4740g/mol is PDI=1.59) with different molecular weight comb-shaped polymer (PGTEMPO-g-PVBK-1:M
N (GPC)=10230g/mol, PDI=1.84; PGTEMPO-g-PVBK-2:M
N (GPC)=13700g/mol, PDI=1.84; PGTEMPO-g-PVBK-3:M
N (GPC)=17860g/mol is PDI=1.87) at CHCl
3Potential ph diagram ph in the solution.The concentration of carbazole group is 5 * 10
-4M is with (n-Bu)
4NPF
6) be supporting electrolyte, concentration is 0.1M), to the energy gap (E of polymer materials
g) estimate.Can calculate lowest unocccupied molecular orbital (LUMO) energy level of polymer materials by the numerical value of HOMO and energy gap.Utilize the polymkeric substance HOMO of this method estimation, LUMO and energy gap are as shown in table 3.The HOMO of three comb-shaped polymers is respectively 5.015,5.036 and 5.094eV; LUMO is respectively 1.148,1.506 and 1.559eV.The energy gap of HOMO and LUMO is approximately 3.53eV.Therefore these polymkeric substance all have higher H OMO energy level, help the positive interpolar hole transport with ITO, thereby can be used as in the organic electronic devices hole transport or luminescent material efficiently.In addition, the result also shows the HOMO of polymkeric substance, and LUMO and edge energy all increase along with the increase of polymericular weight, illustrates that these performance perameters can control by the molecular weight of telomerized polymer, and this will be its big advantage as the electron device raw material.
And as can be seen from Figure 10, the correlation parameter of corresponding VBK homopolymer is but irrelevant with molecular weight.
The electromotive force of table 3. comb-shaped polymer and energy level
| Polymkeric substance | Molecular weight | ??[E onset ox] a(V) | ??HOMO b(eV) | ??LUMO c(eV) | ??E g d(eV) |
| ??PGTEMPO-g-PVBK-1 | ??10230 | ??0.462 | ??5.015 | ??1.489 | ??3.526 |
| ??PGTEMPO-g-PVBK-2 | ??13700 | ??0.483 | ??5.036 | ??1.506 | ??3.530 |
| ??PGTEMPO-g-PVBK-3 | ??17860 | ??0.541 | ??5.094 | ??1.559 | ??3.535 |
a: the oxidation potential of cyclic voltammetry;
b: highest occupied molecular orbital(HOMO) (HOMO) is calculated by oxidation potential;
c: lowest unocccupied molecular orbital (LUMO) energy level is calculated by highest occupied molecular orbital(HOMO) (HOMO) energy level and energy gap;
d: by being with that uv-visible absorption spectra calculates.
Claims (9)
1. a comb-shaped polymer that contains carbazole lateral chain is characterized in that, described comb-shaped polymer is PGTEMPO-g-PVBK, and its chemical structural formula is as follows:
The molecular weight of described comb-shaped polymer is 6000～30000, m=1～42, n=10～25.
2. prepare the method for the described comb-shaped polymer of claim 1, it is characterized in that, may further comprise the steps:
(1) be initiator with the potassium tert.-butoxide, to 4-glycidyl-2,2,6,6-tetramethyl-oxidation piperidines alcohol monomer carries out anionic ring-opening polymerization, preparation macromole TEMPO reagent poly-(4-glycidyl-2,2,6,6-tetramethyl-oxidation piperidines alcohol);
(2) with poly-(4-glycidyl-2,2,6,6-tetramethyl-oxidation piperidines alcohol) as regulation and control reagent, be reductive agent, under initiator causes with the ascorbic acid usp/bp, carry out the polymerization of N-(4-vinyl benzyl)-carbazole, obtain comb-shaped polymer PGTEMPO-g-PVBK.
3. method according to claim 2 is characterized in that, in the step (1), and 4-glycidyl-2,2,6, the mol ratio of the pure and mild potassium tert.-butoxide of 6-tetramethyl-oxidation piperidines is 30～150: 1, polymeric reaction temperature is at 55～70 ℃.
4. method according to claim 2 is characterized in that, in the step (2), the mol ratio of VBK, initiator, reductive agent and PGTEMPO is 30～200: 1: 1.3: 1.3.
5. method according to claim 2 is characterized in that, in the step (2), the polymerization temperature of described polyreaction is 123～135 ℃, and polymerization time is 8～15h.
6. method according to claim 2 is characterized in that, described initiator is a benzoyl peroxide.
7. method according to claim 2 is characterized in that, step (1) and described being reflected in the inert atmosphere of step (2) are carried out, and described inert atmosphere is nitrogen atmosphere or argon gas atmosphere.
8. method according to claim 2 is characterized in that, in the step (2), the solvent of polyreaction is selected from: chlorine benzene,toluene,xylene, methyl-phenoxide, N, a kind of in dinethylformamide, N,N-dimethylacetamide or the methyl-sulphoxide.
9. method according to claim 2 is characterized in that, step (2) products therefrom system is dissolved in solvent, and uses methyl alcohol to precipitate as precipitation agent, after the separate vacuum drying, obtains the comb-shaped polymer PGTEMPO-g-PVBK of purifying.
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| CN110305308A (en) * | 2019-06-24 | 2019-10-08 | 万华化学（宁波）容威聚氨酯有限公司 | A kind of polyether polyol and preparation method thereof, a kind of hard polyurethane foam |
| CN112940227A (en) * | 2021-02-01 | 2021-06-11 | 浙江工业大学 | Polycarbazole with side chain containing TEMPO and preparation method and application thereof |
| CN112940227B (en) * | 2021-02-01 | 2022-09-23 | 浙江工业大学 | Polycarbazole with side chain containing TEMPO and preparation method and application thereof |
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