CN102702536B - Synthetic method of triblock polymer - Google Patents
Synthetic method of triblock polymer Download PDFInfo
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- CN102702536B CN102702536B CN201210148092.9A CN201210148092A CN102702536B CN 102702536 B CN102702536 B CN 102702536B CN 201210148092 A CN201210148092 A CN 201210148092A CN 102702536 B CN102702536 B CN 102702536B
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Abstract
The invention belongs to the technical field of synthesis and preparation of polymer materials, and discloses a synthetic method of triblock polymer, wherein stepwise polymerization (SGB), atom transfer radical polymerization (ATRP) and click chemistry method are combined at first; and 1, 3-dipolar cycloaddition reaction is performed to polymer with azido terminal group and polyurethane prepolymer with alkynyl terminal group to successfully synthesize triblock polymer containing triazole ring. The synthesis method provided by the invention overcomes the defects in traditional block polymer synthesis that reaction conditions are strict, molecular weight distribution is controlled difficultly, and selectable classes of monomers are less, and has the advantages of high conversion rate, mild reaction conditions, narrow molecular weight distribution and strong controllability. The triblock polymer provided by the invention has potential application in ways of medicine slow release, solubilizers and surfactants.
Description
Technical field: the invention belongs to synthesis of polymer material and preparing technical field, relate to and adopt atom transfer radical polymerization, method that progressively polymerization is combined with click chemistry reacting phase to prepare triblock polymer.
Background technology
Segmented copolymer is current most study, the regular polymkeric substance of a most widely used class formation, it has unique structure and performance, it not only has a wide range of applications at aspects such as biomaterial, engineering materials, thermoplastic elastomer, tackiness agent, additive, coating, but also for the preparation of nano material (as LB film, nano dot or nano-tube array), photonic crystal, inorganic mesoporous molecular sieve etc.In recent years, investigators have synthesized many different types of triblock polymers, and its physicochemical property have been carried out to extensive and deep research.
At present, the synthetic method of the triblock polymer that contains urethane segment mainly concentrates on active free radical polymerization field, the normally macromole evocating agent of a first synthetic active free radical polymerization, less owing to can causing the kind of macromole evocating agent of the second monomer polymerization, building-up process is loaded down with trivial details, initiating activity is lower, polymeric reaction condition harshness, thereby the triblock polymer molecular weight distribution with preparation is wider, the shortcoming that reaction conversion ratio is low, reduces the Modulatory character of molecular structure and designability.For example, the people such as Hemant Verma have reported employing PTMG and TDI is that raw material has synthesized base polyurethane prepolymer for use as, and with ethylene bromohyrin by its NCO end-blocking, synthesize bromine end group ATRP initiator, under BrCu/PMDETA catalyst system, cause cinnamic ATRP polymerization, and studied reaction times, reaction solvent, the impact of temperature on molecular weight and molecular weight distribution, but its molecular weight distribution (M
w/ M
n) be 2.0-5.9, make the homogeneity decline (Polym Int 57:226-232 (2008)) of product.
Calendar year 2001, nobel laureate Sharpless proposes " Click Chemistry " concept first, between the nitrine of what wherein research was the most ripe is cuprous catalysis and alkynyl 1,3-Dipolar Cycloaddition, it has advantages of high-level efficiency, highly selective, reaction conditions gentleness, no coupling product." Click Chemistry " caused the very big concern of the researcher of functionalization of polymers and macromolecular structure design field, and show application prospect (Angew.Chem.Int.Ed.2001 widely at aspects such as DNA, self-assembly, finishing, supramolecular chemistry, dendrimer, functional polymer, colloidal nanoparticles, combinatorial chemistry, proteomics, biological coupling technology and biological medicines, 40,2004-2021).
Up to now, click chemistry reaction combines with active free radical polymerization and prepares the existing more report of research of block polymer, but progressively polymerization reports little with the combination of click-reaction, mainly concentrates on side chain graft aspect.For example, the people such as Leen Billiet are by the alkynes end group of side chain with benzyl or carry out Click reaction containing the nitrine end group organism of fluorine element and synthesized the functionalized polyurethane material of side chain, thereby have avoided traditional " protection " " to go to protect " step (Polymer 50 (2009) 3877-3886); The alkynes end group of the people such as David Fournier by polyurethane foam and polyurethane film surface and contain fluorine atoms or polyoxyethylated nitrine end group organism carry out click-reaction, and polymer surfaces has been carried out to hydrophobicity and hydrophilically modified (Polymer 50 (2009) 5362-5367).
Summary of the invention
The object of the invention is to solve traditional active free radical polymerization, to prepare in block polymer process efficiency of initiation low, molecular weight distribution is wide, severe reaction conditions, the shortcoming that molecular structure Modulatory character is poor, first by progressively polymerization, active free radical polymerization is combined with click chemistry reacting phase, utilize nitrine end group ATRP polymkeric substance and end alkynyl radical base polyurethane prepolymer for use as to carry out 1, 3-quadripole cycloaddition reaction, synthesize to contain on main chain the triblock polymer of triazole ring a kind of, under gentle reaction conditions, prepare efficiently the triblock polymer of distribution of low molecular weight, for the synthetic method that a convenient and efficient is provided of distribution of low molecular weight block polymer.
Triblock polymer of the present invention, is characterized in that this polymkeric substance has following structure:
Wherein A is dibasic alcohol, and B is vulcabond, and D is alkynes end group end-capping reagent, and E is vinyl polymer, and n is the number of repeat unit (n >=1) containing in base polyurethane prepolymer for use as.
Wherein,
A is: polyoxyethylene glycol (PEG), polytetramethylene ether diol (PTMG), polypropylene glycol (PPG), polycaprolactone dibasic alcohol (PCL), polycarbonate diol (PCDL), polyether silicone glycol, polyhexamethylene adipate glycol, polybutylene glyool adipate, polyethylene glycol adipate glycol etc., and derivative separately.
B is: TDI, MDI, IPDI, HDI, HMDI, XDI, ADI and separately derivative.
D is alkynol or ynamine compounds.
E is the polymkeric substance being caused by ATRP initiator.
The preparation method of triblock polymer of the present invention: prepared by progressively polymerization, atom transfer radical polymerization and click chemistry reaction bonded, comprise the steps:
Synthesizing of step 1. nitrine end group vinyl polymer
Step 1.1. adopts atom transfer radical polymerization method, add successively solvent, monomer, catalyzer, reaction system is carried out three cooled with liquid nitrogen-vacuumize-fill after nitrogen-thaw cycles, add ATRP polymerization starter, wherein, monomer, initiator, catalyst molar ratio are 5-500: 1: 1, at nitrogen atmosphere lower seal, be placed in oil bath and react after certain hour, drop into termination reaction in liquid nitrogen.Appropriate tetrahydrofuran (THF) or methylene dichloride dilution, and cross neutral alumina chromatography column, after concentrating, to pour in precipitation agent and precipitate, redissolve concentrating and precipitating operation three times, filters and obtains halo end group ATRP polymkeric substance.
Step 1.2 is dissolved in the halo end group polymer of step 1.1 synthesized and sodium azide in DMF with mol ratio 1: 5-10,50-70 DEG C of lucifuge magnetic agitation reaction 24h, and centrifugation, is the DMF solution of nitrine end group ATRP polymkeric substance.
Synthesizing of step 2. end alkynyl radical base polyurethane prepolymer for use as
Dibasic alcohol is joined agitator is housed; in the three-necked bottle of thermometer; in 110-120 DEG C of dehydration 2.5h; add vulcabond; the mol ratio of vulcabond and dibasic alcohol is 1.1-2: 1; under argon shield, 40-85 DEG C is reacted to NCO and arrives after theoretical value, adds alkynes end group end-capping reagent, 40-85 DEG C react to NCO content be zero.
Step 3. click chemistry method is synthesized triblock polymer
Nitrine end group ATRP polymkeric substance DMF solution prepared by step 1, end alkynyl radical base polyurethane prepolymer for use as prepared by step 2, catalyzer, part are according to mol ratio 1-1.2: feed intake at 1: 1: 1, take a breath three times, 50-70 DEG C of reaction 24h under nitrogen protection.Vacuum decompression distillation is removed after DMF, and THF dilution, crosses neutral alumina column, concentrated THF, and vacuum-drying obtain the triblock polymer containing triazole ring after also purifying.
Foregoing invention technical scheme can be expressed as follows:
The described ATRP initiator of above-mentioned preparation method's step (1) end is halogen atom, can select haloalkane, benzyl halide compound, a-brominated esters, a-halogenated ketone, a-halo nitrile etc., and the derivative of above-claimed cpd.Polymerization single polymerization monomer can adopt the vinyl monomer of any ATRP of carrying out polymerization, as methacrylic ester, acrylate, vinylbenzene, acrylamide, vinyl cyanide, vinyl pyridine etc.The described ATRP catalyzer of above-mentioned preparation method's step (1) can comprise transistion metal compound and its part, comprising CuBr/PMDETA, and CuBr/2dNbpy, CuCl/2dNbpy, Cu (II) Br
2/ 2dNbpy, Cu (II) Br
2/ PMDETA, Cu (II) Cl
2/ 2dNbpy, CuCl/Me
6tREN, Cu (II) Br
2/ Me
6tREN etc.
Described in above-mentioned preparation method's step (3), adopt the synthetic triblock polymer of click chemistry, catalyzer is cuprous iodide, cuprous bromide, cuprous chloride, cupric chloride, copper sulfate, and part is pentamethyl-diethylenetriamine, sodium ascorbate, triethylamine etc.
Described in above-mentioned preparation method's step (3), method of purification is soxhlet extraction or the selective solvent precipitator method.
Due to the utilization of technique scheme, the present invention compared with prior art has following advantages:
1. the present invention utilizes progressively polymerization, active free radical polymerization to combine containing the triblock polymer of triazole ring with " Click Chemistry " first, has widened the approach that realizes of block polymer synthesis, makes the Molecular Structure Design can be more diversified.
The present invention overcome that in the synthetic triblock polymer process of living polymerisation process, efficiency of initiation is low, molecular weight distribution is wide, severe reaction conditions, the poor shortcoming of molecular structure Modulatory character, reaction efficiency is high, reaction conditions is gentle, molecular weight of product narrowly distributing and easy purifying.
3. owing to containing urethane segment in triblock polymer, and contain hydrogen bond action, because of but a novel research field, and in biological medicine, phase solubilizing agent, tensio-active agent, there is very large potential using value in the fields such as nano material.
Brief description of the drawings
Accompanying drawing is in embodiment 1, to synthesize PS-b-PU-b-PS's
1h NMR (CDCl
3) spectrogram.
Embodiment
Understand the present invention for ease of further, the present invention is further elaborated for the following example, but embodiments of the present invention are not limited to this.
Embodiment 1
(1) synthetic PS-Br.In clean Schlenk bottle, add stirrer, according to mol ratio 108: 192: 1: 1 adds toluene, vinylbenzene, PMDETA, cuprous bromide successively.Reaction system is by three cooled with liquid nitrogen-vacuumize-fill after nitrogen-thaw cycles, add a-isobutyl ethyl bromide (EBiB) with syringe, the mol ratio of vinylbenzene and a-isobutyl ethyl bromide is 192: 1, at nitrogen atmosphere lower seal, at 90 DEG C, react 2h, after cold water cooling, add termination reaction in liquid nitrogen.After adopting tetrahydrofuran (THF) to dilute, cross neutral alumina column chromatography, be with coloured catalyzer to remove, adopt the concentrated tetrahydrofuran (THF) of Rotary Evaporators, in a large amount of cold methyl alcohol, precipitate.Redissolve/precipitation operation three times, obtains white powder product and is placed in the dry 12h of 50 DEG C of vacuum drying ovens.
1H?NMR(CDCl
3)d?ppm：0.7-0.99(m，9H，-C(CH
3)
2-PS，CH
3CH
2O-)，1.20-2.15(m，3H，-CH
2CH-ofPS)，3.44-3.63(m，2H，CH
3CH
2O-)，4.41-4.52(m，1H，-CH(Ph)-Br)，6.30-7.30(m，5H，C
6H
5?of?PS)；Mn＝2000g/mol，PDI＝1.07.
(2) within 1: 8 in molar ratio in clean flask, successively add PS-Br and sodium azide, then add DMF (10wt%) that it is dissolved, 60 DEG C of reactions are spent the night, and centrifugal unreacted sodium azide obtains the DMF solution of nitrine end group polystyrene.
1H?NMR(CDCl
3)d?ppm：0.7-0.99(m，9H，-C(CH
3)
2-PS，CH
3CH
2O-)，1.20-2.15(m，3H，-CH
2CH-of?PS)，3.44-3.63(m，2H，CH
3CH
2O-)，3.95(m，1H，-CH(Ph)-Br)，6.30-7.30(m，5H，C
6H
5?of?PS)；Mn＝2000g/mol，PDI＝1.07.
(3) Macrogol 4000 is joined agitator is housed; in the three-necked bottle of thermometer; in 110-120 DEG C of dehydration 2.5h; be cooled to 65 DEG C; add isofoer diisocyanate, the mol ratio of vulcabond and polyoxyethylene glycol is 2: 1, and lower 85 DEG C of argon shield is reacted to NCO and arrived after theoretical value; add propiolic alcohol end-blocking, 70 DEG C react to NCO content be zero.
1H?NMR(CDCl
3)d?ppm：3.50-3.80(m，-CH2CH2O-of?PEG)，4.22(d，2H，-OCH2C＝CH).
(4) by the DMF solution, end alkynyl radical base polyurethane prepolymer for use as, CuBr, PMDETA of the nitrine end group polystyrene of preparation according to mol ratio 1.1: 1: 1: 1 feeds intake, and vacuumizes-change nitrogen three times, 60 DEG C of reaction 24h under nitrogen protection.Vacuum decompression distillation is removed after DMF, and THF dilution, crosses neutral alumina column, concentrated THF vacuum-drying.Adopt hexanaphthene soxhlet extraction, after room temperature leaves standstill, fall except supernatant liquid, by after lower floor's thick liquid vacuum-drying, obtain synthetic PS-b-PU-b-PS triblock polymer.
1H?NMR(CDCl
3)d?ppm：6.30-7.30(m，5H，C
6H
5?of?PS)，3.50-3.80(m，-CH2CH2O-of?PEG)，4.62(m，2H，-CH
2CH
2OCH
2-triazole?ring).
Mn＝8400g/mol，PDI＝1.20.
Embodiment 2
(1) synthetic PMMA-Br.In clean Schlenk bottle, add stirrer, according to mol ratio 200: 200: 2: 1 adds toluene, MMA, PMDETA, cuprous bromide successively.Reaction system is by three cooled with liquid nitrogen-vacuumize-fill after nitrogen-thaw cycles, add a-isobutyl ethyl bromide with syringe, the mol ratio of MMA and a-isobutyl ethyl bromide is 200: 1, at nitrogen atmosphere lower seal, at 70 DEG C, react 6h, after cold water cooling, add termination reaction in liquid nitrogen.Employing ethanol is precipitation agent, is dissolved in tetrahydrofuran (THF) after filtration, crosses neutral alumina column chromatography, is with coloured catalyzer to remove, and adopts Rotary Evaporators evaporate to dryness THF, and obtaining white powder product, to be placed in vacuum drying oven dry.
(2) PMMA-N
3synthetic method with embodiment 1.
(3) polypropylene glycol 2000 is joined agitator is housed; in the three-necked bottle of thermometer; in 110-120 DEG C of dehydration 2.5h; be cooled to 60 DEG C; add tolylene diisocyanate, the mol ratio of tolylene diisocyanate and Macrogol 2000 is 1.5: 1, and lower 80 DEG C of argon shield is reacted to NCO and arrived after theoretical value; add propiolic alcohol end-blocking, 70 DEG C react to NCO content be zero.
(4) remove catalyzer and part and select CuSO
4/ Na
asc, other are with step (4) in case study on implementation 1.
Embodiment 3
(1) except initiator adopts isobutyl bromide to p-Nitrobenzyl, catalyzer adopts cuprous bromide, part adopts dipyridyl, initiator: catalyzer: part: St=1: 1: 2: 200, the volume ratio of toluene and St is 1: 1, temperature of reaction is 110 DEG C, and the reaction times is outside 4h, and other are with step (1) in embodiment 1.
(2) except the mol ratio of PS-Br and sodium azide is 1: 10, DMF is outside 20wt%, and other are with step (2) in embodiment 1.
(3), (4) are all with step (3), (4) in embodiment 1.
Embodiment 4
(1), (2) PS-N
3synthetic method with (1), (2) in embodiment 1.
(3) polytetramethylene ether diol 1000 is joined agitator is housed; in the three-necked bottle of thermometer; in 110-120 DEG C of dehydration 2.5h; be cooled to 60 DEG C, add 1,6-hexamethylene diisocyanate; the mol ratio of vulcabond and polytetramethylene ether diol 1000 is 1.25: 1; lower 80 DEG C of argon shield is reacted to NCO and is arrived after theoretical value, adds propargylamine end-blocking, 70 DEG C react to NCO content be zero.
(4) except method of purification is the mixed solvent washing of hexanaphthene and sherwood oil, all with step (4) in embodiment 1.
Embodiment 5
(1), (2) are all same as step in embodiment 1 (1), (2).
(3) except end-capping reagent adopts 2-methyl-3-crotonylene-amine, other are all same as step in embodiment 1 (3).
(4) remove catalyzer and part and select cuprous iodide/triethylamine, the DMF solution of nitrine end group polystyrene, end alkynyl radical base polyurethane prepolymer for use as, CuBr, PMDETA are 1.05: 1: 1 according to mol ratio: 1 feed intake outside, be all same as step in embodiment 1 (4).
Embodiment 6
(1) except vinyl monomer adopts pfluorostyrene, other are all same as step in embodiment 1.
Embodiment 7
(1) except vinyl monomer adopts butyl acrylate, initiator is 2 bromopropionic acid methyl esters, and other are all same as step in embodiment 1.
Embodiment 8
(1) except vinyl monomer is the mix monomer of vinylbenzene and vinyl cyanide, initiator adopts the a-bromo acid tert-butyl ester, and catalyst system adopts outside cuprous bromide/dipyridyl, and other are all same as step in embodiment 1.
Claims (7)
1. a triblock polymer, is characterized in that this polymkeric substance has following structure:
A is dibasic alcohol, and B is vulcabond, and D is alkynes end group end-capping reagent, and E is vinyl polymer, and n is the number of repeat unit containing in base polyurethane prepolymer for use as, n >=1;
Wherein,
A is: polyoxyethylene glycol (PEG), polytetramethylene ether diol (PTMG), polypropylene glycol (PPG), polycaprolactone dibasic alcohol (PCL), polycarbonate diol (PCDL), polyether silicone glycol, polyhexamethylene adipate glycol, polybutylene glyool adipate, polyethylene glycol adipate glycol;
B is: tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), isophorone diisocyanate (IPDI), 1,6-hexamethylene diisocyanate (HDI), dicyclohexyl methane diisocyanate (HMDI), xylylene diisocyanate (XDI);
D is alkynol or ynamine compound;
E is the homopolymer by the initiation of atom transfer radical polymerization (ATRP) initiator or the multipolymer for containing different monomers unit.
2. triblock polymer described in claim 1, is characterized in that: prepared by progressively polymerization, atom transfer radical polymerization and click chemistry reaction bonded, comprise the steps:
Synthesizing of step 1. nitrine end group polymer
Step 1.1 adopts atom transfer radical polymerization method, add successively solvent, monomer, catalyzer, carry out cooled with liquid nitrogen-vacuumize-fill after nitrogen-thaw cycles, add ATRP polymerization starter, wherein, monomer, initiator, catalyst molar ratio are 5-500: 1: 1, at nitrogen atmosphere lower seal, being placed in oil bath reacts after certain hour, drop into termination reaction in liquid nitrogen, appropriate tetrahydrofuran (THF) or methylene dichloride dilution, and cross neutral alumina chromatography column, after concentrated, pour in precipitation agent and precipitate, filter the ATRP polymkeric substance that obtains halo end group vinyl monomer;
Step 1.2 is dissolved in the halo end group polymer of step 1.1 synthesized and sodium azide in DMF with mol ratio 1: 5-10, and 50-70 DEG C of lucifuge magnetic agitation reacted 24h, is the DMF solution of nitrine end group polymer;
Synthesizing of step 2 end alkynyl radical base polyurethane prepolymer for use as
Dibasic alcohol is joined agitator is housed, in the three-necked bottle of thermometer, in 110-120 DEG C of dehydration 2.5h, add vulcabond, the mol ratio of vulcabond and dibasic alcohol is 1.1-2: 1, under argon shield, 40-85 DEG C is reacted to NCO and arrives after theoretical value, adds alkynes end group end-capping reagent, 40-85 DEG C react to NCO content be zero;
Step 3 click chemistry method is synthesized triblock polymer
Nitrine end group polymer DMF solution prepared by step 1, end alkynyl radical base polyurethane prepolymer for use as prepared by step 2, catalyzer, part are according to mol ratio 1-1.2: feed intake at 1: 1: 1, take a breath three times, 50-70 DEG C of reaction 24h under nitrogen protection; Vacuum decompression distillation is removed after DMF, and THF dilution, crosses neutral alumina column, concentrated THF, and vacuum-drying obtain synthetic triblock polymer after also purifying.
3. triblock polymer described in claim 1, is characterized in that: ATRP initiator end is halogen atom, can select haloalkane, benzyl halide compound, alpha-brominated ester, α-halogenatedketone, alpha-halogen nitrile.
4. triblock polymer described in claim 2, is characterized in that: can adopt the vinyl monomer that can carry out ATRP polymerization, comprise methacrylic ester, acrylate, vinylbenzene, acrylamide, vinyl cyanide, vinyl pyridine, pfluorostyrene.
5. triblock polymer described in claim 2, is characterized in that: the catalyzer in step 1.1 in ATRP polymerization can comprise transistion metal compound and its part, comprising CuBr/PMDETA, and CuBr/2dNbpy, CuCl/2dNbpy, Cu (II) Br
2/ 2dNbpy, Cu (II) Br
2/ PMDETA, Cu (II) Cl
2/ 2dNbpy, CuCl/Me
6tREN, Cu (II) Br
2/ Me
6tREN.
6. triblock polymer described in claim 2, it is characterized in that: adopt the synthetic triblock polymer of click chemistry (Click Chemistry), described in step 3, catalyzer is cuprous iodide, cuprous bromide, cuprous chloride, cupric chloride, copper sulfate, and part is pentamethyl-diethylenetriamine, sodium ascorbate, triethylamine.
7. triblock polymer described in claim 2, is characterized in that: described in step 3, method of purification is soxhlet extraction or the selective solvent precipitator method.
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| CN113072696A (en) * | 2021-04-28 | 2021-07-06 | 河南农业大学 | Preparation method of linear-annular reversible topological structure polymer |
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