CN102516428A - Method for preparing initiator for polyamine amphipathic block polyelectrolyte - Google Patents
Method for preparing initiator for polyamine amphipathic block polyelectrolyte Download PDFInfo
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Abstract
The invention discloses a method for preparing an initiator for polyamine amphipathic block polyelectrolyte. The method comprises the following steps of: (1) reacting 4-vinyl benzyl amine hydrochloride with di-tert-butyl carbonate to obtain 4-vinyl benzyl amine tert-butyl carbonate; and (2) subjecting the 4-vinyl benzyl amine tert-butyl carbonate to atom transfer and free radical polymerization under the initiation of benzyl chloride to obtain the initiator. The initiator prepared by the method provided by the invention can initiate the preparation of the polyamine amphipathic block polyelectrolyte and has the action of pH value regulation and self-assembly, and the assembly action is achieved by volume change arising from the formation or the dissociation of amphipathic block polyelectrolytes with different pH values and is closely related to the charge properties, the densities, the structures of molecular chains, preparation conditions and the like, of the polyelectrolytes. The pH-responsive release of drugs can be achieved by using the polyamine amphipathic block polyelectrolyte as a carrier.
Description
Technical field
The present invention relates to a kind of preparation method who is used to prepare the initiator of polyamine type amphiphilic block polyelectrolyte.
Background technology
Polyelectrolyte be contain on the class formation unit alkalescence with (or) water-soluble polymer of acid ionogen, like natural nucleic acid, protein or synthetic tackifier, soap etc.
Amphiphilic block polyelectrolyte refers generally to have at least in the amphiphilic block copolymer one section to be polyelectrolyte; Have the characteristic of polyelectrolyte, segmented copolymer and tensio-active agent concurrently; Extensive use is arranged; Can be used as emulsifying agent, flocculation agent, viscosity modifier, medicine controlled release carrier, single or multiple lift LB film, liquid crystal elastic body etc.Many natural macromoleculars (like protein, DNA) all are amphipathic compounds, and its physiological process can be studied as model compound through the synthetic amphiphilic polymer.Polyelectrolyte segmented copolymer with obvious wetting ability difference can be self-assembled into micella in the aqueous solution.Because its charge characteristic; With neutral is that the segmented copolymer of unionization is compared; Amphipathic block polyelectrolyte not only can be in selective solvent; Can also be self-assembled into the aggregate of different shapes such as style group bunch, spherical, vesica through the pH value of regulating surrounding medium, the structure of aggregate is controlled by hydrogen bond, static, reactive force such as hydrophobic.These aggregates not only can prepare nano material as template; And because aggregates such as vesica have the lar nanometric cavities structure; Its covering amount is more many greatly than solid spherical micelle, at aspects such as drug release, biologically active substance coatings good prospects for application is arranged.
Be incorporated into polymkeric substance to amido; Particularly in the segmented copolymer of compound with regular structure; The polyamine type amphiphilic block polyelectrolyte that obtains, the same with small molecule amine have a series of biological performance, in the biological physiology process, plays important effect; And the chain structure of polymkeric substance helps the performance of the stable and functional group of amido, can be applicable to fields such as enzyme and cell fixation, tissue regeneration engineering; Therefore need provide a kind of initiator preparation method who is used to prepare polyamine type amphiphilic block polyelectrolyte significant.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who is used to prepare the initiator of polyamine type amphiphilic block polyelectrolyte.
Be used to prepare the preparation method of the initiator of polyamine type amphiphilic block polyelectrolyte shown in the formula (a), comprise the steps:
In the formula, when n is number-average degree of polymerization, be the number between 10～100;
(1) 4-vinyl benzyl amine hydrochlorate and di-tert-butyl dicarbonic acid ester react and obtain 4-vinyl benzylamine tertiary butyl carbonic ether;
(2) 4-vinyl benzylamine tertiary butyl carbonic ether obtains initiator shown in the formula (a) through atom transition free radical polymerization reaction under the initiation of benzyl chlorine.
Among the above-mentioned preparation method, in the formula (a), when n is number-average degree of polymerization, specifically can be 59.
Among the above-mentioned preparation method, the temperature of atom transition free radical polymerization reaction is 120 ℃～130 ℃ described in the step (2), specifically can be 130 ℃; The time of said atom transition free radical polymerization reaction is 15 hours～25 hours, specifically can be 24 hours.
Among the above-mentioned preparation method, atom transition free radical polymerization reaction carries out under inert atmosphere described in the step (2), like nitrogen or argon gas.
Among the above-mentioned preparation method, the solvent of atom transition free radical polymerization reaction can be N described in the step (2), and dinethylformamide, promotor can be cuprous chloride and 2,2 '-dipyridyl.
Among the above-mentioned preparation method, 4-vinyl benzylamine tertiary butyl carbonic ether, cuprous chloride and 2 in the step (2), the molfraction ratio of 2 '-dipyridyl can be (96～99.92): (0.03～1): (0.04～3) specifically can be 96: 1: 3.
Among the above-mentioned preparation method; 4-vinyl benzylamine tertiary butyl carbonic ether, benzyl chlorine, cuprous chloride and 2 in the step (2); The ratio of quality and the number of copies of the solvent of the total mass of 2 '-dipyridyl and the reaction of said atom transferred free radical can be (75～18): (25～82) specifically can be 54: 46.
Among the above-mentioned preparation method, the molar content that the middle benzyl chlorine of step (2) accounts for 4-vinyl benzylamine tertiary butyl carbonic ether can be 0.5%～1%, specifically can be 0.91%.
The initiator of method preparation provided by the invention can be used for causing the polyelectrolyte of polyamine type amphiphilic block shown in the preparation formula (b),
In the formula (b), when m is number-average degree of polymerization, being 64～525 natural number, when n is number-average degree of polymerization, is the number between 10～100, specifically can be 59.
The number-average molecular weight of above-mentioned polyelectrolyte can be 1.6 * 10
4～6.5 * 10
4G/mol; Weight-average molecular weight can be 2.2 * 10
4～7.7 * 10
4G/mol.
The number-average molecular weight of above-mentioned polyelectrolyte specifically can be 16635g/mol; Weight-average molecular weight specifically can be 22291g/mol.
The number-average molecular weight of above-mentioned polyelectrolyte specifically can be 20277g/mol; Weight-average molecular weight specifically can be 27577g/mol.
The number-average molecular weight of above-mentioned polyelectrolyte specifically can be 22711g/mol; Weight-average molecular weight specifically can be 32721g/mol.
The number-average molecular weight of above-mentioned polyelectrolyte specifically can be 64607g/mol; Weight-average molecular weight specifically can be 77528g/mol.
When the initiator of method preparation provided by the invention prepares the polyelectrolyte of polyamine type amphiphilic block shown in the above-mentioned formula (b), can carry out according to the method that comprises the steps:
(1) vinylbenzene obtains gathering shown in the formula (c) 4-vinyl benzylamine tertiary butyl carbonic ether-block-PS through atom transition free radical polymerization reaction under the initiation of initiator shown in the formula (a); The definition cotype (b) of m and n in the formula (c);
(2) gather 4-vinyl benzylamine tertiary butyl carbonic ether-block-PS shown in the formula (c) and promptly get the polyelectrolyte of polyamine type amphiphilic block shown in the formula (b) through the deprotection reaction of amino.
Among the above-mentioned preparation method, the temperature of atom transition free radical polymerization reaction can be 120 ℃～130 ℃ described in the step (1), specifically can be 130 ℃; The time of said atom transition free radical polymerization reaction is 15 hours～25 hours, specifically can be 15 hours or 24 hours.
Among the above-mentioned preparation method, atom transition free radical polymerization reaction can carry out under inert atmosphere described in the step (1), like nitrogen or argon gas.
Among the above-mentioned preparation method, the solvent of atom transition free radical polymerization reaction can be N described in the step (1), and dinethylformamide, promotor can be cuprous chloride and 2,2 '-dipyridyl.
Among the above-mentioned preparation method; Vinylbenzene, cuprous chloride and 2 in the step (1); The molfraction ratio of 2 '-dipyridyl can be (96～99.92): (0.03～1): (0.04～3) specifically can be 98.8: 0.5: 0.7,99: 0.3: 0.7,99.4: 0.2: 0.4 or 99.92: 0.03: 0.04.
Among the above-mentioned preparation method; Initiator, cuprous chloride and 2 shown in vinylbenzene, the formula (a) in the step (1); The ratio of quality and the number of copies of the solvent of the total mass of 2 '-dipyridyl and said atom transferred free radical reaction is (75～18): (25～82) specifically can be and specifically can be 18: 82,24: 76,29: 71 or 75: 25.
Among the above-mentioned preparation method, it is 0.006%～0.92% that initiator shown in step (1) Chinese style (a) accounts for cinnamic molar content, specifically can be 0.006%, 0.43%, 0.61% or 0.92%.
Among the above-mentioned preparation method, deprotection reaction amino described in the step (2) can carry out in the hydrochloric acid aqueous isopropanol.
The initiator of method preparation provided by the invention can cause preparation polyamine type amphiphilic block polyelectrolyte; It has pH value regulation and control self-assembly behavior; This assembly behavior is to realize through the volume change that amphiphilic block polyelectrolyte forms when the different pH or disassociation is caused, and is closely related with the structure of the charge property of polyelectrolyte, density, molecular chain, preparation condition etc.Do carrier with polyamine type amphiphilic block polyelectrolyte; The pH response that can realize medicine discharges; For example cancer cell has higher metabolic speed and slightly acidic enchylema with respect to normal cell; The particle that pH is responsive can optionally dissociate in cancer cell as pharmaceutical carrier and discharge medicine, thereby reaches better result of treatment.
Description of drawings
Fig. 1 is the monomeric nuclear magnetic spectrogram of 4-vinyl benzyl amine hydrochlorate (4-VBAHS).
Fig. 2 is the monomeric infrared spectrum of 4-vinyl benzyl amine hydrochlorate (4-VBAHS).
Fig. 3 is the monomeric nuclear magnetic spectrogram of 4-vinyl benzylamine tertiary butyl carbonic ether (4-VBA-Boc).
Fig. 4 is for gathering 4-vinyl benzylamine tertiary butyl carbonic ether P (4-VBA-Boc)
59The GPC spectrogram of-Cl.
Fig. 5 is for gathering 4-vinyl benzylamine tertiary butyl carbonic ether P (4-VBA-Boc)
59-Cl, gather 4-vinyl benzylamine tertiary butyl carbonic ether-block-PS P (4-VBA-Boc)
59-b-PS
525With gather 4-vinyl benzyl amine hydrochlorate-block-PS P (4-VBAHS)
59-b-PS
525Nuclear magnetic spectrogram.
Fig. 6 is for gathering 4-vinyl benzylamine tertiary butyl carbonic ether-block-PS P (4-VBA-Boc)
59-b-PS
525With gather 4-vinyl benzyl amine hydrochlorate-block-PS P (4-VBAHS)
59-b-PS
525Infrared spectrum.
Fig. 7 is for gathering 4-vinyl benzylamine tertiary butyl carbonic ether-block-PS P (4-VBA-Boc)
59-b-PS
525With gather 4-vinyl benzyl amine hydrochlorate-block-PS P (4-VBAHS)
59-b-PS
525Thermogravimetric curve.
Fig. 8 is for gathering 4-vinyl benzylamine tertiary butyl carbonic ether-block-PS P (4-VBA-Boc)
59-b-PS
525With gather 4-vinyl benzyl amine hydrochlorate-block-PS P (4-VBAHS)
59-b-PS
525Differential scanning calorimetric curve.
Fig. 9 is for gathering 4-vinyl benzyl amine hydrochlorate-block-PS P (4-VBAHS)
59-b-PS
525At mixed solvent THF/H
2Assembling morphology among the O (v/v=3) under the different pH changes, and the form when wherein Fig. 9 (A) be pH=4 is schemed (B) and (C) form when being pH=5, the form when Fig. 9 (D) is pH=6, the form when Fig. 9 (E) is pH=7, the form when Fig. 9 (F) is pH=8.
Figure 10 is for gathering 4-vinyl benzyl amine hydrochlorate-block-PS P (4-VBAHS)
59-b-PS
525Molecular model, and at mixed solvent THF/H
2The two-dimensional representation of the assembling morphology among the O (v/v=3) under the different pH.
Embodiment
Employed experimental technique is ordinary method like no specified otherwise among the following embodiment.
Used material, reagent etc. like no specified otherwise, all can obtain from commercial sources among the following embodiment.
Gather 4-vinyl benzylamine tertiary butyl carbonic ether P (4-VBA-Boc) shown in embodiment 1, the formula (d)
59The preparation of-Cl
(1) preparation of 4-vinyl benzyl amine hydrochlorate (4-VBAHS)
With 4-vinyl benzyl chloride (ACROS; 90%) and sodium azide (Zhejiang Dongyang City triumphant bright special reagent ltd) add 20mL N, in the dinethylformamide (Tianjin chemical reagent one factory), 47 ℃ of reaction 24h after-filtration residual solid; Filtrating is revolved dried after washing; The yellow liquid that obtains is splashed in the THF (Dihua worker ltd is won in Tianjin), and 0 ℃ slowly adds triphenylphosphine (ACROS, 99%).Drip concentrated hydrochloric acid (Yantai three and chemical reagent ltd) behind the reaction 24h to pH=5-6.Suction filtration obtains yellow powder powder 4-vinyl benzyl amine hydrochlorate monomer, and its structural formula is suc as formula shown in (e), productive rate 89%; Wherein the mol ratio of 4-vinyl benzyl chloride and sodium azide, triphenylphosphine is 1.3: 2.6: 1, and reactant and N, the mass ratio of dinethylformamide are 44: 56, and the mass ratio of reactant and THF is 24: 76.
Monomeric nuclear-magnetism of 4-vinyl benzyl amine hydrochlorate and infrared spectrum are as depicted in figs. 1 and 2 respectively, and ultimate analysis is as shown in table 1.
The ultimate analysis experimental value of table 1 4-vinyl benzyl amine hydrochlorate and theoretical value contrast
(2) preparation of 4-vinyl benzylamine tertiary butyl carbonic ether (4-VBA-Boc)
4-vinyl benzyl amine hydrochlorate and triethylamine (Tianjin section close europeanized reagent development centre) are dissolved in THF; 0 ℃ of tetrahydrofuran solution to mixed solution and dripping di-tert-butyl dicarbonic acid ester (ACROS, 99%), room temperature reaction 24 hours; Product separates through post; Obtain white solid 4-vinyl benzylamine tertiary butyl carbonic ether (4-VBA-Boc) monomer, its structural formula is suc as formula shown in (f), and productive rate is 96%; Wherein the mol ratio of 4-vinyl benzyl amine hydrochlorate and di-tert-butyl dicarbonic acid ester is 1: 2, and the mass ratio of reactant and triethylamine is 33: 67, and the mass ratio of reactant and THF is 6: 94.
Monomeric nuclear magnetic spectrogram of 4-vinyl benzylamine tertiary butyl carbonic ether (4-VBA-Boc) and results of elemental analyses are respectively shown in Fig. 3 and table 2.
The ultimate analysis experimental value of table 2 4-vinyl benzylamine tertiary butyl carbonic ether and theoretical value contrast
(3) gather 4-vinyl benzylamine tertiary butyl carbonic ether P (4-VBA-Boc) shown in the formula (d)
59The preparation of-Cl
Cut open to the peace that is connected with nitrogen and to add 2.005g (8.605mmol) 4-vinyl benzylamine tertiary butyl carbonate monomer, catalyzer 0.012g (0.121mmol) cuprous chloride (Tianjin extensively becomes chemical reagent ltd) and 0.037g (0.237mmol) 2 in the bottle; 2 '-dipyridyl (Shanghai moisten prompt chemical reagent ltd) and 8mL N; Dinethylformamide; Place 130 ℃ of oil baths; Squeeze into 9 μ L (0.078mmol) Benzyl Chlorides (Taixing, Tianjin chemical reagent work) that logical nitrogen is handled, sealed reaction after 24 hours with reaction solution with THF dilution back through aluminum oxide (Chemical Reagent Co., Ltd., Sinopharm Group) chromatography column to remove catalyzer, pour in a large amount of anhydrous methanols (Tianjin chemical reagent two factories) after effluent concentrates and precipitate; Filter and vacuum-drying, obtain macromole evocating agent and gather 4-vinyl benzylamine tertiary butyl carbonic ether P (4-VBA-Boc)
59-Cl, its structural formula be suc as formula shown in (g), reaction yield 66.93%; Wherein 4-vinyl benzylamine tertiary butyl carbonic ether and cuprous chloride and 2; The mol ratio of 2 '-dipyridyl is 96: 1: 3; Reactant (4-vinyl benzylamine tertiary butyl carbonic ether, cuprous chloride and 2; The total mass of 2 '-dipyridyl) and N, the mass ratio of dinethylformamide is 54: 46, and the add-on of initiator Benzyl Chloride is that the molar content of reaction monomers 4-vinyl benzylamine tertiary butyl carbonic ether is 0.91%.
Initiator P (4-VBA-Boc)
59The number-average molecular weight of-Cl
Be 13674g/mol, weight-average molecular weight
Be 16728g/mol, all characterize through GPC, as shown in table 3; Its GPC spectrogram and nuclear magnetic spectrogram are respectively shown in Fig. 4 and Fig. 5 A.
(1) gathers 4-vinyl benzylamine tertiary butyl carbonic ether-block-PS (P (4-VBA-Boc) shown in the formula (h)
59-b-PS
64) preparation
Cut open to the peace of logical nitrogen respectively and add macromole evocating agent P (4-VBA-Boc) in the bottle
59-Cl, CuCl, 2,2 '-dipyridyl and DMF place 130 ℃ of oil baths; Add the vinylbenzene that logical nitrogen is handled; Sealed reaction 24 hours, with THF dilution back through alumina chromatographic column to remove catalyzer, pour in a large amount of anhydrous methanols after effluent concentrates and precipitate; Filter and vacuum-drying, obtain gathering shown in the formula (h) 4-vinyl benzylamine tertiary butyl carbonic ether-block-PS P (4-VBA-Boc)
59-b-PS
64, productive rate 66.66%; Wherein vinylbenzene and cuprous chloride, 2, the mol ratio of 2 '-dipyridyl is 98.8: 0.5: 0.7, reactant (P (4-VBA-Boc)
59-Cl, CuCl, 2,2 '-dipyridyl and cinnamic total mass) and N, the mass ratio of dinethylformamide is 18: 82, initiator P (4-VBA-Boc)
59It is 0.92% that the add-on of-Cl accounts for the cinnamic molar content of reaction monomers.
P (4-VBA-Boc)
59-b-PS
64Number-average molecular weight
Be 20393g/mol, weight-average molecular weight
Be 27337g/mol, all characterize (is standard with the PS) through GPC, as shown in table 3, its GPC spectrogram such as Fig. 4.
(2) gather 4-vinyl benzyl amine hydrochlorate-block-PS (P (4-VBAHS) shown in the formula (g)
59-b-PS
64) preparation
With P (4-VBA-Boc)
59-b-PS
64Be dissolved in Virahol (Qingdao Marine Chemical Co., Ltd.) solution of the concentrated hydrochloric acid of 3mol/L; 50 ℃ of stirring reactions are poured in a large amount of methyl alcohol after 2 hours and are precipitated; Filter and vacuum-drying; Promptly obtain gathering shown in the formula (d) 4-vinyl benzyl amine hydrochlorate-block-PS, wherein segmented copolymer (P (4-VBA-Boc)
59-b-PS
64) with the mass ratio of concentrated hydrochloric acid be 1: 99.
(1) gathers 4-vinyl benzylamine tertiary butyl carbonic ether-block-PS (P (4-VBA-Boc) shown in the formula (j)
59-b-PS
99) preparation
Cut open to the peace of logical nitrogen respectively and add macromole evocating agent P (4-VBA-Boc) in the bottle
59-Cl, CuCl, 2,2 '-dipyridyl and DMF place 130 ℃ of oil baths; Add the vinylbenzene that logical nitrogen is handled; Sealed reaction 24 hours, with THF dilution back through alumina chromatographic column to remove catalyzer, pour in a large amount of anhydrous methanols after effluent concentrates and precipitate; Filter and vacuum-drying, obtain gathering shown in the formula (j) 4-vinyl benzylamine tertiary butyl carbonic ether-block-PS P (4-VBA-Boc)
59-b-PS
99, productive rate 66.17%; Wherein vinylbenzene and cuprous chloride, 2, the mol ratio of 2 '-dipyridyl is 99.0: 0.3: 0.7, reactant (P (4-VBA-Boc)
59-Cl, CuCl, 2,2 '-dipyridyl and cinnamic total mass) and N, the mass ratio of dinethylformamide is 24: 76, initiator P (4-VBA-Boc)
59It is 0.61% that the add-on of-Cl accounts for the cinnamic molar content of reaction monomers.
P (4-VBA-Boc)
59-b-PS
99Number-average molecular weight
Be 24022g/mol, weight-average molecular weight
Be 32670g/mol, all characterize (is standard with the PS) through GPC, as shown in table 3, its GPC spectrogram such as Fig. 4.
(2) gather 4-vinyl benzyl amine hydrochlorate-block-PS (P (4-VBAHS) shown in the formula (i)
59-b-PS
99) preparation
With P (4-VBA-Boc)
59-b-PS
64Be dissolved in Virahol (Qingdao Marine Chemical Co., Ltd.) solution of the concentrated hydrochloric acid of 3mol/L; 50 ℃ of stirring reactions are poured in a large amount of methyl alcohol after 2 hours and are precipitated; Filter and vacuum-drying; Promptly obtain gathering shown in the formula (d) 4-vinyl benzyl amine hydrochlorate-block-PS, wherein segmented copolymer (P (4-VBA-Boc)
59-b-PS
99) with the mass ratio of concentrated hydrochloric acid be 2: 98.
(1) gathers 4-vinyl benzylamine tertiary butyl carbonic ether-block-PS (P (4-VBA-Boc) shown in the formula (l)
59-b-PS
132) preparation
Cut open to the peace of logical nitrogen respectively and add macromole evocating agent P (4-VBA-Boc) in the bottle
59-Cl, CuCl, 2,2 '-dipyridyl and DMF place 130 ℃ of oil baths; Add the vinylbenzene that logical nitrogen is handled; Sealed reaction 24 hours, with THF dilution back through alumina chromatographic column to remove catalyzer, pour in a large amount of anhydrous methanols after effluent concentrates and precipitate; Filter and vacuum-drying, obtain gathering shown in the formula (l) 4-vinyl benzylamine tertiary butyl carbonic ether-block-PS P (4-VBA-Boc)
59-b-PS
132, productive rate 62.90%; Wherein vinylbenzene and cuprous chloride, 2, the mol ratio of 2 '-dipyridyl is 99.4: 0.2: 0.4, reactant (P (4-VBA-Boc)
59-Cl, CuCl, 2,2 '-dipyridyl and cinnamic total mass) and N, the mass ratio of dinethylformamide is 29: 71, initiator P (4-VBA-Boc)
59It is 0.43% that the add-on of-Cl accounts for the cinnamic molar content of reaction monomers.
P (4-VBA-Boc)
59-b-PS
132Number-average molecular weight
Be 27475g/mol, weight-average molecular weight
Be 37916g/mol, all characterize (is standard with the PS) through GPC, as shown in table 3, its GPC spectrogram such as Fig. 4.
(2) gather 4-vinyl benzyl amine hydrochlorate-block-PS (P (4-VBAHS) shown in the formula (k)
59-b-PS
132) preparation
With P (4-VBA-Boc)
59-b-PS
132Be dissolved in Virahol (Qingdao Marine Chemical Co., Ltd.) solution of the concentrated hydrochloric acid of 3mol/L; 50 ℃ of stirring reactions are poured in a large amount of methyl alcohol after 2 hours and are precipitated; Filter and vacuum-drying; Promptly obtain gathering shown in the formula (d) 4-vinyl benzyl amine hydrochlorate-block-PS, wherein segmented copolymer (P (4-VBA-Boc)
59-b-PS
132) with the mass ratio of concentrated hydrochloric acid be 3: 97.
(1) gathers 4-vinyl benzylamine tertiary butyl carbonic ether-block-PS (P (4-VBA-Boc) shown in the formula (n)
59-b-PS
525) preparation
Cut open to the peace of logical nitrogen respectively and add macromole evocating agent P (4-VBA-Boc) in the bottle
59-Cl, CuCl, 2,2 '-dipyridyl and DMF place 130 ℃ of oil baths; Add the vinylbenzene that logical nitrogen is handled; Sealed reaction 24 hours, with THF dilution back through alumina chromatographic column to remove catalyzer, pour in a large amount of anhydrous methanols after effluent concentrates and precipitate; Filter and vacuum-drying, obtain gathering shown in the formula (n) 4-vinyl benzylamine tertiary butyl carbonic ether-block-PS P (4-VBA-Boc)
59-b-PS
525, productive rate 59.71%; Wherein vinylbenzene and cuprous chloride, 2, the mol ratio of 2 '-dipyridyl is 99.92: 0.03: 0.05, reactant (P (4-VBA-Boc)
59-Cl, CuCl, 2,2 '-dipyridyl and cinnamic total mass) and N, the mass ratio of dinethylformamide is 75: 25, initiator P (4-VBA-Boc)
59It is 0.006% that the add-on of-Cl accounts for the cinnamic molar content of reaction monomers.
P (4-VBA-Boc)
59-b-PS
525Number-average molecular weight
Be 68384g/mol, weight-average molecular weight
Be 82061g/mol, all characterize (is standard with the PS) through GPC, as shown in table 3, its GPC spectrogram, nuclear magnetic spectrogram, infrared spectrum, thermogravimetric curve and differential scanning calorimetric curve are seen Fig. 4, Fig. 5 B, Fig. 6 A, Fig. 7 and shown in Figure 8 respectively.
(2) gather 4-vinyl benzyl amine hydrochlorate-block-PS (P (4-VBAHS) shown in the formula (m)
59-b-PS
525) preparation
With P (4-VBA-Boc)
59-b-PS
525Be dissolved in Virahol (Qingdao Marine Chemical Co., Ltd.) solution of the concentrated hydrochloric acid of 3mol/L; 50 ℃ of stirring reactions are poured in a large amount of methyl alcohol after 2 hours and are precipitated; Filter and vacuum-drying, promptly obtain gathering shown in the formula (m) 4-vinyl benzyl amine hydrochlorate-block-PS P (4-VBAHS)
59-b-PS
525, wherein the mass ratio of segmented copolymer and concentrated hydrochloric acid is 5: 95; Its nuclear magnetic spectrogram, infrared spectrum, thermogravimetric curve and differential scanning calorimetric curve are respectively like Fig. 5 C, Fig. 6 B, Fig. 7 and shown in Figure 8.
The P (4-VBA-Boc) that table 1GPC characterizes
59The structural parameter that gather 4-vinyl benzylamine tertiary butyl carbonic ether-block-PS of-Cl and embodiment 2-5 preparation
A is P (4-VBA-Boc)
59-Cl and respectively gather the polymerization degree of gathering 4-vinyl benzylamine tertiary butyl carbonate blocks in 4-vinyl benzylamine tertiary butyl carbonic ether-block-PS;
B is for respectively gathering the polymerization degree of polystyrene block in 4-vinyl benzylamine tertiary butyl carbonic ether-block-PS.
Gather 4-vinyl benzyl amine hydrochlorate-block-PS P (4-VBAHS) shown in embodiment 6, the pH regulation and control following formulas (m)
59-b-PS
525The research of the accumulation shape in mixed solvent
PH is 4 o'clock; P (4-VBAHS) segmental electric density is very big; Bigger electrostatic repulsion makes segmented copolymer be assembled into nucleocapsid structure; Wherein polyelectrolyte part is owing to be in the bigger mixed solvent of polarity and unfold state and become shell, and the vinylbenzene segment is arranged parallel to each other and interchain takes place assembles and form nuclear, and nucleocapsid structure integral body is style group bunch (Fig. 9 A); When pH increased to 5, P (4-VBAHS) segmental effective charge density reduced, and chain is interior and interchain has caused aggregate curvature to become big with the formation of the hydrogen bond action between free amino and protonated amido tridimensional network, and (Fig. 9 B and 9C) appears in the vesica form.
PH is between 6 and 7 the time; More amine groups occurs with the form of free amino in P (4-VBAHS) segment; The repulsive interaction of electric charge spherical reversed phase micelle occurred to the decisive action forfeiture of aggregate form in the solution, the PS segment stretches becomes shell; Free amido quantity increases with pH on P (4-VBAHS) segment; In the chain and interchain form the tridimensional network reach with the hydrogen bond action between free amino and protonated amido and increase, form micella nuclear, so the radius of reversed phase micelle increases (Fig. 9 D and 9E) with the increase of pH; PH is 8 o'clock, because free amino content is far more than protonated amido, hydrogen bond quantity reduces, and has observed the nucleocapsid micellar and has disintegrated, and still tangling each other between molecular chain is random floc sedimentation shape (Fig. 9 F).
Therefore according to above-mentioned Research Hypothesis the molecular model of segmented copolymer of initiator preparation of method preparation provided by the invention, and the two-dimensional representation (shown in figure 10) of its assembling morphology that drawn.
Claims (8)
1. be used to prepare the preparation method of the initiator of polyamine type amphiphilic block polyelectrolyte shown in the formula (a), comprise the steps:
In the formula, when n is number-average degree of polymerization, be the number between 10～100;
(1) 4-vinyl benzyl amine hydrochlorate and di-tert-butyl dicarbonic acid ester react and obtain 4-vinyl benzylamine tertiary butyl carbonic ether;
(2) 4-vinyl benzylamine tertiary butyl carbonic ether obtains initiator shown in the formula (a) through atom transition free radical polymerization reaction under the initiation of benzyl chlorine.
2. method according to claim 1 is characterized in that: in the formula (a), when n is number-average degree of polymerization, be 59.
3. method according to claim 1 and 2 is characterized in that: the temperature of atom transition free radical polymerization reaction described in the step (2) is 120 ℃～130 ℃; The time of said atom transition free radical polymerization reaction is 15 hours～25 hours.
4. according to arbitrary described method among the claim 1-3, it is characterized in that: atom transition free radical polymerization reaction carries out under inert atmosphere described in the step (2).
5. according to arbitrary described method among the claim 1-4, it is characterized in that: the solvent of atom transition free radical polymerization reaction is N described in the step (2), and dinethylformamide, promotor are cuprous chloride and 2,2 '-dipyridyl.
6. method according to claim 5 is characterized in that: 4-vinyl benzylamine tertiary butyl carbonic ether, cuprous chloride and 2 in the step (2), the molfraction of 2 '-dipyridyl is than being (96～99.92): (0.03～1): (0.04～3).
7. according to claim 5 or 6 described methods; It is characterized in that: 4-vinyl benzylamine tertiary butyl carbonic ether, benzyl chlorine, cuprous chloride and 2 in the step (2), the ratio of quality and the number of copies of the solvent of the total mass of 2 '-dipyridyl and the reaction of said atom transferred free radical is (75～18): (25～82).
8. according to arbitrary described method among the claim 1-7, it is characterized in that: the molar content that the middle benzyl chlorine of step (2) accounts for 4-vinyl benzylamine tertiary butyl carbonic ether is 0.5%～1%.
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| EP1493756A1 (en) * | 2002-04-08 | 2005-01-05 | Kaneka Corporation | Vinyl polymers and processes for producing the same |
| US20050079148A1 (en) * | 2001-10-04 | 2005-04-14 | Fitzhugh Anthony L. | Highly cross-linked, extremely hydrophobic nitric oxide-releasing polymers and methods for their manufacture and use |
| CN101864048A (en) * | 2010-05-28 | 2010-10-20 | 中国科学院长春应用化学研究所 | Method for preparing block type polyelectrolyte |
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| US20050079148A1 (en) * | 2001-10-04 | 2005-04-14 | Fitzhugh Anthony L. | Highly cross-linked, extremely hydrophobic nitric oxide-releasing polymers and methods for their manufacture and use |
| EP1493756A1 (en) * | 2002-04-08 | 2005-01-05 | Kaneka Corporation | Vinyl polymers and processes for producing the same |
| CN101864048A (en) * | 2010-05-28 | 2010-10-20 | 中国科学院长春应用化学研究所 | Method for preparing block type polyelectrolyte |
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