CN104558427B - Preparation method of ring brush polymer containing polystyrene main chain - Google Patents
Preparation method of ring brush polymer containing polystyrene main chain Download PDFInfo
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Abstract
The invention discloses a preparation method of a ring brush polymer containing a polystyrene main chain. Particularly, the method comprises the following steps: (1) synthesizing linear polystyrene; (2) carrying out azidation of the linear polystyrene; (3) carrying out ring-closure reaction; (4) carrying out benzyl bromination of annular polystyrene; and (5) synthesizing the annular polystyrene. According to the preparation method, the ATRP reaction, CuAAC reaction and Woh1-Ziegler reaction are perfectly combined for the first time; the grafting density of the polymer is controlled by controlling the feeding ratio of reaction materials; the grafting length is controlled by controlling the reaction time; a series of ring brush polymers containing the polystyrene main chain are successfully prepared; and the controllability of the preparation method of the ring brush polymer is fundamentally achieved.
Description
Technical field
The invention belongs to macromolecule synthesising technology field, and in particular to a kind of main chain contains the ring brush of polystyrene structure
The preparation method of polymer.
Background technology
Cyclic polymer is the polymer that a class has special topological structure, because it does not have end-group structure, so and line
Property polymer phase than showing many special properties, for example bigger refraction index, higher glass transition temperature, bigger
Density, less hydrodynamic size, lower intrinsic viscosity etc..Cyclic polymer relies on its special performance advantage,
The field such as materialogy, supermolecule and self assembly, biological medicine is applied well, and its synthetic method just causes many researchs
The interest of person.
So far, the synthetic method of cyclic polymer is broadly divided into two big class：One is ring expansion method, and two is closed loop method.Phase
For ring expansion method, closed loop method is more suitable for multiple types monomer, and the molecular weight and molecualr weight distribution of cyclic polymer is also more
Be easily controlled, therefore suffer from the favor of many research workers, be prepare in prior art cyclic polymer it is indispensable one
The technology of kind.
Along with the research and development of synthetic method, colourful ring topologies also are exploited out, for example Ke
Tadpole shape, splayed, beading, ring brush etc..For ring brush polymer, synthetic method of the prior art mainly can be with
It is divided into following two big class：The first kind is " Graft through ", and its core is first to prepare the monomer with polymer long-chain, so
Again these macromonomer polymerizations are formed into ring brush polymer afterwards；Equations of The Second Kind is " Graft onto " and " Graft from ",
The former is first synthesis of cyclic polymer, then clicks on by polymer chain by efficient " Click " method, forms ring brush and gathers
Compound；The latter is first synthesis of cyclic polymer, and monomer slowly " extends " again from the main chain of cyclic polymer goes out, so as to be formed
Ring brush polymer.In order to further improve the performance of polymer, it may be considered that the grafting density of regulation and control ring brush polymer, this
It is a kind of method of great potential, but for " Graft through " method, it is obviously difficult to accomplish this point.Cause
This, seeks suitable approach to realize the Modulatory character of ring brush polymer grafting density from " Graft from " method, is
At present most of research workers need the difficult problem captured.
The content of the invention
For above-mentioned situation, the present invention plans ATRP（ATRP）Reaction, CuAAC reactions（Monovalence copper
The alkynyl of catalysis/azido Dipolar Cycloaddition）, Wohl-Ziegler react this three's perfect adaptation, by control reaction
The rate of charge of material prepares a series of polymerizations of the ring brush containing polystyrene backbone controlling the grafting density of polymer
Thing.
In order to achieve the above object, the present invention is first with AGET-ATRP（Electronic activation regeneration-atom transferred free radical
Polymerization）Method prepares linear polystyrene, recycles CuAAC reactions to prepare annular polystyrene, followed by Wohl-
Ziegler reactions introduce bromine atoms on the cinnamic benzyl position of repetitive of cyclic polymer, form three-level halogen initiator,
Trigger monomer polymerization again, controls the reaction time, prepares a series of ring brush polystyrene.
Specifically, the invention provides a kind of preparation method of the ring brush polymer containing polystyrene backbone, its
Comprise the steps：
1）Synthetic molecular weight is the linear polystyrene of 4300 ~ 5300g/mol：
By styrene（St）, initiator, mantoquita, part, reducing agent and solvent methyl phenyl ethers anisole be added in reaction vessel, in 80
~ 120 DEG C react 4 ~ 6 hours, obtain linear polystyrene, wherein the styrene, initiator, mantoquita, part and reducing agent it
Between mol ratio be 600 ~ 800:7~8:2~4:6~8:4~6；
2）The Azide of linear polystyrene：
By step 1）In the linear polystyrene, sodium azide and the solvent N,N-dimethylformamide that obtain（DMF）Add
To in reaction vessel, react 20 ~ 30 hours in 20 ~ 30 DEG C, Azide linear polystyrene is obtained, wherein the linear polyphenyl second
Mol ratio between alkene and sodium azide is 1:10~25；
3）Ring-closure reaction：
Solvent toluene is added in reaction vessel, inert gas overnight deoxygenation is passed through, under normal temperature by reducing agent, part and
Cuprous salt is added in reaction vessel, after reaction solution is warmed up to 60 DEG C, then the step 2 that will be dissolved in advance in toluene）In
To Azide linear polystyrene be slowly added in reaction vessel, time control between 20 ~ 40 hours, during sample introduction
Temperature control is at 50 ~ 70 DEG C and is continually fed into inert gas, and sample introduction continues to react 20 ~ 30 hours after terminating, and obtains ring-type polyphenyl
Ethene, wherein the Azide linear polystyrene, the mol ratio between cuprous salt, part and reducing agent are 1:50:75:50~
100；
4）The benzyl position bromo of annular polystyrene：
By step 3）In the annular polystyrene, N- brominated imides, radical initiator and the solvent carbon tetrachloride that obtain
（CCl4）In being added to reaction vessel, stir 0.5 ~ 1 hour at 20 ~ 25 DEG C, heating reflux reaction 6 ~ 10 hours obtains bromo
Annular polystyrene, wherein repetitive in the annular polystyrene, between N- brominated imides and radical initiator
Mol ratio be 1:0.3~0.8:0.2~0.6；
5）The synthesis of ring brush polystyrene：
With step 4）In the bromo annular polystyrene that obtains as macromole evocating agent, by macromole evocating agent, cuprous
Salt, styrene, part and solvent methyl phenyl ethers anisole are added in reaction vessel, using after the process of inert gas anaerobic that reaction vessel is close
Envelope, reacts 1 ~ 8 day in 90 ~ 110 DEG C, ring brush polystyrene is obtained, wherein the macromole evocating agent, styrene, cuprous salt
Mol ratio and part between is 1:50~200:1:1.
Further, step 1）Described in initiator be selected from 2- isobutyl bromide alkynes propyl ester, 2- isobutyl bromide alkynes butyl esters, 2- bromines
Any one in propionic acid alkynes propyl ester, preferred 2- isobutyl bromides alkynes propyl ester（PBiB）, the initiator belongs to three-level halogen initiator.
Further, step 1）Described in any one of mantoquita in copper bromide, copper chloride, the cupric iodide, preferred bromine
Change copper（CuBr2）.
Further, step 1）Described in mol ratio between styrene, initiator, mantoquita, part and reducing agent be
700:7:2:6:4。
Further, step 1）Described in react temperature be 90 DEG C, the time be 5 hours.
Further, step 2）Described in mol ratio between linear polystyrene and sodium azide be 1:20.
Further, step 2）Described in react temperature be 25 DEG C, the time be 24 hours.
Further, step 3）Described in Azide linear polystyrene, between cuprous salt, part and reducing agent mole
Than for 1:50:75:50.
Further, step 3）Described in during sample introduction temperature control at 60 DEG C, sample introduction continues to react 24 little after terminating
When.
Further, step 4）Described in N- brominated imides it is sub- selected from N-bromosuccinimide, N- bromos glutaryl
Any one in amine, N- bromo adipimides, preferred N-bromosuccinimide（NBS）.
Further, step 4）Described in radical initiator be selected from azodiisobutyronitrile, ABVN, azo two
Any one in isobutyl dimethyl phthalate, preferred azodiisobutyronitrile（AIBN）.
Further, step 4）Described in repetitive in annular polystyrene, N- brominated imides and free radical draw
It is 1 to send out the mol ratio between agent:0.3:0.2.
Further, step 4）Described in react time be 10 hours.
Further, step 5）Described in mol ratio between macromole evocating agent, styrene, cuprous salt and part be 1:
100:1:1。
Further, step 5）Described in react temperature be 90 DEG C.
Further, step 1）With step 3）Described in reducing agent selected from ascorbic acid, stannous 2-ethylhexoate, phenol,
Any one in triethylamine, preferred ascorbic acid（VC）.
Further, step 1）, step 3）With step 5）Described in part be selected from N, N, N ', N ', N "-pentamethyl divinyl
Triamine, 2, any one in 2 '-bipyridyl, three (2- dimethylaminoethyls) amine, tripropylene glycol methyl ether acetate, preferred N, N,
N ', N ', N "-pentamethyl-diethylenetriamine（PMDETA）.
Further, step 3）With step 5）Described in any one of inert gas in nitrogen, helium, the neon,
It is preferred that nitrogen.
Further, step 3）With step 5）Described in cuprous salt in cuprous bromide, stannous chloride, the cuprous iodide
Any one, preferred cuprous bromide（CuBr）.
Further, purification step is can be carried out after completing per single step reaction in said method, to obtain purity
Higher product, the purification step includes（But it is not limited to）Chromatography, dissolution/precipitation partition method, filtration method etc..
Due to the enforcement of above-mentioned technical proposal, the present invention has compared with prior art following advantages：
（1）The present invention first combines three kinds of methods of ATRP, CuAAC, Wohl-Ziegler reaction, by polyphenyl
Halogen atom is introduced on the benzyl position of ethene, continues to cause styrene monomer polymerization as three-level halogen initiator, so as to pass through
The mode of " Graft from " successfully prepares ring brush polystyrene, and to prepare ring brush polymer a kind of new side is provided
Method；
（2）When the present invention introduces bromine atoms on the benzyl position of the repetitive of annular polystyrene, used is
NBS/AIBN/CCl4System, can adjust polymer by adjusting repeating styrene units, the ratio between NBS, AIBN
Grafting density, so as to control the side chains number of later stage ring brush polymer, realizes Modulatory character；
（3）The present invention employs AGET-ATRP methods in linear polymer process is prepared, simple and convenient without the need for deoxygenation,
A large amount of synthesis of suitable polymer；
（4）The present invention employs CuAAC methods preparing cyclic polymer, with reaction condition it is gentle, reaction rate is fast,
The distinguishing feature such as selective high, yield is high, disposable, is that a kind of indispensable skill of cyclic polymer is prepared in prior art
Art.
Description of the drawings
Fig. 1 is the synthetic route chart of annular polystyrene in embodiment 1.
Fig. 2 is linear polystyrene（l-PS）Proton nmr spectra.
Fig. 3 is linear polystyrene（l-PS）, Azide linear polystyrene（l -PS-N3）And annular polystyrene
（c-PS）Proton nmr spectra（Locally）.
Fig. 4 is annular polystyrene（c-PS）Mass spectrogram.
Fig. 5 is the bromo and the synthetic route of the middle ring brush polystyrene of embodiment 3 of annular polystyrene in embodiment 2
Figure.
Fig. 6 is the GPC elution curve figures of ring brush polystyrene under the differential responses time.
Fig. 7 is the dynamic curve diagram that macromole evocating agent causes styrene polymerization.
Specific embodiment
Below in conjunction with specific embodiments further description is made to the present invention with accompanying drawing.
Chemical reagent：
Styrene, 99%, Chemical Reagent Co., Ltd., Sinopharm Group is processed using vacuum distillation is front done；
Propilolic alcohol, 97%, Aldrich；
2- bromine isobutyl acylbromides, 98%, Aldrich；
Triethylamine, 98%, Aldrich is used after molecular sieve drying；
Copper bromide, 98.5%, Chemical Reagent Co., Ltd., Sinopharm Group；
N, N, N ', N ', N "-pentamethyl-diethylenetriamine, 99%, An Naiji, processed using vacuum distillation is front done；
Ascorbic acid, 99.7%, Chemical Reagent Co., Ltd., Sinopharm Group；
Methyl phenyl ethers anisole, 98%, Chemical Reagent Co., Ltd., Sinopharm Group uses after molecular sieve drying；
Sodium azide, 98%, Aldrich；
DMF, 99.5%, Chinasun Specialty Products Co., Ltd；
Cuprous bromide, 98.5%, Chemical Reagent Co., Ltd., Sinopharm Group, after glacial acetic acid and ethanol are refined and is vacuum dried
Use；
Toluene, 99.5%, Chinasun Specialty Products Co., Ltd；
N-bromosuccinimide, 99%, lark waffle Technology Co., Ltd.；
Azodiisobutyronitrile, chemical pure, the factory of Shanghai reagent four, using front recrystallization twice；
Carbon tetrachloride, 99.5%, Chinasun Specialty Products Co., Ltd；
Tetrahydrofuran, 99.5%, Nanjing Chemistry Reagent Co., Ltd.；
Dichloromethane, 99.5%, Chinasun Specialty Products Co., Ltd；
Sodium carbonate, 99.8%, Chemical Reagent Co., Ltd., Sinopharm Group；
Anhydrous sodium sulfate, 98%, Chemical Reagent Co., Ltd., Sinopharm Group；
Salt, salt industry Group Co., Ltd of Jiangsu Province；
Methyl alcohol, analyzes pure, Chinasun Specialty Products Co., Ltd.
Tester and condition：
Gel permeation chromatography（GPC）：Determined using Waters1515 gel permeation chrommatographs, using differential refraction detector
（RI2414）, the molecular weight ranges of HR1, HR2 and HR4 pillar are 100-500000g/mol, and with THF as mobile phase, flow velocity is
1.0mL/min, is tested at 30 DEG C, and polymer molecular weight is demarcated with polystyrene standards；
Proton nmr spectra（1H-NMR）：Using Bruker 300MHz nuclear magnetic resonance spectrometers, with CDCl3For solvent, TMS is internal standard,
Determine under room temperature；
MALDI-TOF-MS（MALDI-TOF）：Using Bruker Ultraflex-III
MS spectrometer mass spectrographs, with DCTB as matrix；
Elementary analysis（EA）：Determined using EA1110-CHNO-S microanalysers.
Embodiment 1：Annular polystyrene（c-PS）Synthesis（Concrete synthetic route is as shown in Figure 1）.
By 5.6g（0.1mol）Propilolic alcohol, 100mL dichloromethane solvents are added in 250mL three-neck flasks, are added
12.2g（0.12mol）Triethylamine, makes it be cooled to 0 ~ 5 DEG C with ice-water bath, then by 27.6g（0.12mol）2- bromine isobutyl acylbromides
In being slowly dropped to reaction bulb, stirring 30min is dripped, remove ice-water bath reaction 12h, suction filtration, filtrate water, saturated sodium carbonate
Solution, saturated aqueous common salt are respectively washed once, then use anhydrous sodium sulfate drying 2h, are concentrated to give crude product, then Jing vacuum distillations, are obtained
10.2g final product PBiB, yield：50%.
By 9.06g（87.0mmol）St、178.4mg（0.87mmol）PBiB、55.8mg（0.25mmol）CuBr2、
130.0mg（0.75mmol）PMDETA、87.5mg（0.5mmol）VC and 10mL methyl phenyl ethers anisoles are added in 25mL Schlenk bottles,
5h is reacted in 90 DEG C of oil bath pan.After reactant is with THF dissolvings, mantoquita is removed by neutral alumina column, again with methanol is sunk
Form sediment and suction filtration, vacuum tank is dried 24h, finally gives the linear polystyrene of 3.04g white powders（l-PS）, oozed by gel
The number-average molecular weight that thoroughly chromatogram GPC is measuredMN=5000, molecular weight distribution PDI=1.10, by the equal molecule of the calculated number of nuclear-magnetism
AmountMN=4700, its proton nmr spectra is as shown in Figure 2.
By 1g（0.21mmol）l-PS、276mg（4.2mmol）NaN3It is added in 25mL round-bottomed flasks with 20mL DMF,
24h is reacted in 25 DEG C of oil bath pan.After reactant is with THF dissolvings, Azide reagenl is removed by neutral alumina column, then used
Methanol extraction and suction filtration, vacuum tank is dried 24h, finally gives the Azide linear polystyrene of 0.94g white powders（l -
PS-N3）, the number-average molecular weight measured by gel permeation chromatography GPCMN=5000, molecular weight distribution PDI=1.09, by nuclear-magnetism meter
The number-average molecular weight for obtainingMN=4700, from the figure 3, it may be seen that product azide is successfully obtained.In the process, polymer
And NaN3There is efficient Click reactions in DMF, so as to the halogen atom of end is converted into into azido.
800mL toluene is added in 1000mL three-neck flasks, nitrogen atmosphere overnight deoxygenation is passed through, successively will under normal temperature
281.0mg（1.60mmol）VC、414.8mg（2.40mmol）PMDETA and 228mgCuBr（1.60mmol）It is added to 1000mL
In three-neck flask, then by 150mg（0.032mmol）l -PS-N3In being dissolved in 20mL toluene, slowly noted by micro-injection pump
In being mapped to 1000mL three-neck flasks, sample introduction speed be 0.6mL/h, during sample introduction temperature control at 60 DEG C, one in course of reaction
Lead directly to into nitrogen, sample introduction continues to react 24h after terminating.Reactant liquor removed by silicagel column and concentrated after mantoquita, again with methanol precipitation
And suction filtration, vacuum tank is dried 24h, finally gives the annular polystyrene of 135.4mg white powders（c-PS）, oozed by gel
The number-average molecular weight that thoroughly chromatogram GPC is measuredMN=3800, molecular weight distribution PDI=1.08, by the equal molecule of the calculated number of nuclear-magnetism
AmountMN=4700, from the figure 3, it may be seen that linear polymer is successfully obtained.In the process, the alkynyl of polymer one end with it is another
There is efficient Click reactions in the azido at end, form the 1,2,3-triazoles fragment for closed loop.
Embodiment 2：The bromo of annular polystyrene（Reaction scheme is referring to Fig. 5）.
By 300mg（Repetitive 2.88mmol）c-PS、153.8mg（0.86mmol）NBS、94.58mg（0.58mmol）
AIBN and 50mL CCl4In adding 100mL round-bottomed flasks, stirring at normal temperature 30min is heated to 80 DEG C of back flow reactions overnight.Will be anti-
Liquid suction filtration is answered, float wadding thing on removing upper strata, and filtrate is repeatedly washed with 0.1M hypo solutions and water, used after organic phase is concentrated
Methanol extraction and suction filtration, then with THF dissolvings, methanol extraction and suction filtration, 24h is vacuum dried, obtain 238.0mg yellow powders
Bromo annular polystyrene（c-PS-Br）.NBS/AIBN/CCl is used during this4System, can be by adjusting styrene weight
Bromine content during again the ratio of unit and NBS, AIBN is to adjust polymer, so as to control the side chain number of most terminal ring brush polymer
Mesh, reaches the purpose of control polymer grafting density.The bromine content of polymer is calculated by elementary analysis, concrete condition referring to
Table 1, reaction scheme is referring to Fig. 5.
Embodiment 3：Bromo annular polystyrene causes St polymerizations as macromole evocating agent（Reaction scheme is referring to Fig. 5）.
Successively by 10.31mg（0.087mmol）Bromo annular polystyrene macromole evocating agent, 12.45mg
（0.087mmol）Cuprous bromide, 0.9060g（8.7mmol）Styrene monomer, 15.08（0.087mmol）PMDETA parts are added
In the ampoule bottle of 5mL, methyl phenyl ethers anisole is solvent, at low temperature extraction gas several times after, the tube sealing under anaerobic atmosphere.After tube sealing
Ampoule bottle is placed in 90 DEG C of heating mantles, is reacted by the predetermined time（1-8 days）.After reaction terminates, cooled down with cold water immediately
Tube sealing, to open and dissolve content with tetrahydrofuran after tube sealing, overnight places in the methyl alcohol for pouring 250mL into, suction filtration, dries, and obtains
The ring brush polystyrene of different side chain lengths.This process needs strict deoxygenation, can be by adjusting during reaction in polymerization process
Between controlling the molecular weight of polymer, concrete condition is its corresponding dynamic curve diagram referring to Fig. 6 and Biao 2, Fig. 7.
Claims (10)
1. a kind of preparation method of the ring brush polymer containing polystyrene backbone, it comprises the steps：
1）Synthetic molecular weight is the linear polystyrene of 4300 ~ 5300g/mol：
Styrene, initiator, mantoquita, part, reducing agent and solvent methyl phenyl ethers anisole are added in reaction vessel, it is anti-in 80 ~ 120 DEG C
Answer 4 ~ 6 hours, obtain linear polystyrene, wherein the styrene, between initiator, mantoquita, part and reducing agent mole
Than for 600 ~ 800:7~8:2~4:6~8:4~6；
2）The Azide of linear polystyrene：
By step 1）In the linear polystyrene, sodium azide and the solvent N,N-dimethylformamide that obtain be added to reaction vessel
In, react 20 ~ 30 hours in 20 ~ 30 DEG C, Azide linear polystyrene is obtained, wherein the linear polystyrene and Azide
Mol ratio between sodium is 1:10~25；
3）Ring-closure reaction：
Solvent toluene is added in reaction vessel, inert gas overnight deoxygenation is passed through, by reducing agent, part and cuprous under normal temperature
Salt is added in reaction vessel, after reaction solution is warmed up to 60 DEG C, then the step 2 that will be dissolved in advance in toluene）In obtain
Azide linear polystyrene is slowly added in reaction vessel, time control between 20 ~ 40 hours, temperature during sample introduction
Control is at 50 ~ 70 DEG C and is continually fed into inert gas, and sample introduction continues to react 20 ~ 30 hours after terminating, and obtains annular polystyrene,
Wherein described Azide linear polystyrene, the mol ratio between cuprous salt, part and reducing agent are 1:50:75:50~100；
4）The benzyl position bromo of annular polystyrene：
By step 3）In the annular polystyrene that obtains, N- brominated imides, radical initiator and solvent carbon tetrachloride add
To in reaction vessel, stir 0.5 ~ 1 hour at 20 ~ 25 DEG C, heating reflux reaction 6 ~ 10 hours obtains bromo ring-type polyphenyl second
Alkene, wherein the repetitive in the annular polystyrene, the mol ratio between N- brominated imides and radical initiator are
1:0.3~0.8:0.2~0.6；
5）The synthesis of ring brush polystyrene：
With step 4）In the bromo annular polystyrene that obtains as macromole evocating agent, by macromole evocating agent, cuprous salt, benzene
Ethene, part and solvent methyl phenyl ethers anisole are added in reaction vessel, are sealed reaction vessel after being processed using inert gas anaerobic, in
90 ~ 110 DEG C are reacted 1 ~ 8 day, ring brush polystyrene are obtained, wherein the macromole evocating agent, styrene, cuprous salt and part
Between mol ratio be 1:50~200:1:1.
2. preparation method according to claim 1, it is characterised in that step 1）Described in initiator be selected from 2- isobutyl bromides
Any one in alkynes propyl ester, 2- isobutyl bromide alkynes butyl esters, 2 bromopropionic acid alkynes propyl ester, the mantoquita selected from copper bromide, copper chloride,
Any one in cupric iodide, the part be selected from N, N, N ', N ', N ' '-pentamethyl-diethylenetriamine, 2,2 '-bipyridyl, three
Any one in (2- dimethylaminoethyls) amine, tripropylene glycol methyl ether acetate, the reducing agent is selected from ascorbic acid, 2- second
Any one in base caproic acid stannous, phenol, triethylamine.
3. preparation method according to claim 1, it is characterised in that step 1）Described in styrene, initiator, mantoquita,
Mol ratio between part and reducing agent is 700:7:2:6:4.
4. preparation method according to claim 1, it is characterised in that step 2）Described in linear polystyrene and Azide
Mol ratio between sodium is 1:20.
5. preparation method according to claim 1, it is characterised in that step 3）Described in inert gas be selected from nitrogen, helium
Any one in gas, neon, the reducing agent is any in ascorbic acid, stannous 2-ethylhexoate, phenol, triethylamine
One kind, the part be selected from N, N, N ', N ', N ' '-pentamethyl-diethylenetriamine, 2,2 '-bipyridyl, three (2- dimethylamino second
Base) amine, any one in tripropylene glycol methyl ether acetate, the cuprous salt is selected from cuprous bromide, stannous chloride, cuprous iodide
In any one.
6. preparation method according to claim 1, it is characterised in that step 3）Described in Azide linear polystyrene,
Mol ratio between cuprous salt, part and reducing agent is 1:50:75:50.
7. preparation method according to claim 1, it is characterised in that step 4）Described in N- brominated imides be selected from N- bromines
For any one in succinimide, N- bromo glutarimides, N- bromo adipimides, the radical initiator choosing
Any one from azodiisobutyronitrile, ABVN, azo-bis-iso-dimethyl.
8. preparation method according to claim 1, it is characterised in that step 4）Described in repetition in annular polystyrene
Mol ratio between unit, N- brominated imides and radical initiator is 1:0.3:0.2.
9. preparation method according to claim 1, it is characterised in that step 5）Described in cuprous salt selected from cuprous bromide,
Any one in stannous chloride, cuprous iodide, the part be selected from N, N, N ', N ', N ' '-pentamethyl-diethylenetriamine, 2,
Any one in 2 '-bipyridyl, three (2- dimethylaminoethyls) amine, tripropylene glycol methyl ether acetate, the inert gas choosing
Any one from nitrogen, helium, neon.
10. preparation method according to claim 1, it is characterised in that step 5）Described in macromole evocating agent, benzene second
Mol ratio between alkene, cuprous salt and part is 1:100:1:1.
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| CN108178806A (en) * | 2018-02-01 | 2018-06-19 | 苏州大学 | The amidation method of polymer ends |
| CN108239278B (en) * | 2018-02-01 | 2021-01-26 | 苏州大学 | Process for preparing amide-linked polymers |
| CN108976426B (en) * | 2018-06-26 | 2020-09-25 | 南通纺织丝绸产业技术研究院 | High-grafting-density ring comb polymer and preparation method thereof |
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| CN102585052A (en) * | 2012-03-07 | 2012-07-18 | 苏州大学 | Method and device for preparing annular polymer |
| CN103242470A (en) * | 2012-12-14 | 2013-08-14 | 苏州大学 | Polymer containing azobenzene circlet on side chain and preparation method thereof |
| CN103864984A (en) * | 2012-12-14 | 2014-06-18 | 苏州大学 | Cyclic amphiphilic random copolymer containing azobenzene at its side chain and synthesis method thereof |
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