CN102702536A - Synthetic method of triblock polymer - Google Patents
Synthetic method of triblock polymer Download PDFInfo
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- CN102702536A CN102702536A CN2012101480929A CN201210148092A CN102702536A CN 102702536 A CN102702536 A CN 102702536A CN 2012101480929 A CN2012101480929 A CN 2012101480929A CN 201210148092 A CN201210148092 A CN 201210148092A CN 102702536 A CN102702536 A CN 102702536A
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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, phase compatilizers and surfactants.
Description
Technical field: the invention belongs to the synthetic and preparing technical field of macromolecular material, relate to adopt ATRP, progressively polymerization and click chemistry reacting phase bonded method prepare triblock polymer.
Background technology
Segmented copolymer is to study the regular polymkeric substance of maximum, a most widely used class formation at present; It has particular 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 is used to prepare nano material (like 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 extensive and deep research.
At present; The compound method that contains the triblock polymer of urethane segment mainly concentrates on the active free radical polymerization field, normally at first synthesizes the macromole evocating agent of an active free radical polymerization, owing to the kind of the macromole evocating agent that can cause second monomer polymerization is less; Building-up process is loaded down with trivial details; Initiating activity is lower, and polymeric reaction condition is harsh, thereby has the triblock polymer MWD broad of preparation; The shortcoming that reaction conversion ratio is low makes the Modulatory character of molecular structure and designability reduce.For example; 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 with its NCO end-blocking, synthesized bromine end group ATRP initiator, under the BrCu/PMDETA catalystsystem, caused cinnamic ATRP polymerization; And studied the influence of reaction times, reaction solvent, temperature, but its MWD (M to molecular weight and MWD
w/ M
n) be 2.0-5.9, make the homogeneity of product descend (Polym Int 57:226-232 (2008)).
Calendar year 2001; Nobel laureate Sharpless proposes " Click Chemistry " notion first; Wherein research is the most sophisticated is 1 between cuprous catalytic nitrine and the alkynyl, the 3-Dipolar Cycloaddition, and it has the advantage 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 showed application prospects (Angew.Chem.Int.Ed.2001 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, combine with the active free radical polymerization existing more report of research of preparation block polymer of click chemistry reaction, but progressively polymerization and click-reaction combine report seldom, mainly concentrate on the side chain graft aspect.For example; The alkynes end group of people such as Leen Billiet through side chain carries out the Click reaction with the nitrine end group organism that has benzyl or contain fluorine element and synthesized the functionalized polyurethane material of side chain, thereby avoided traditional " protection " " to go to protect " step (Polymer 50 (2009) 3877-3886); Alkynes end group and contain fluorine atoms or the polyoxyethylated nitrine end group organism of people such as David Fournier through polyurethane foam and polyurethane film surface carries out click-reaction, and polymer surfaces has been carried out hydrophobicity and hydrophilically modified (Polymer 50 (2009) 5362-5367).
Summary of the invention
The objective of the invention is to solve that traditional active free radical polymerization prepares that efficiency of initiation is low in the block polymer process, MWD is wide, the shortcoming of severe reaction conditions, molecular structure Modulatory character difference; First progressively polymerization, active free radical polymerization are combined with the click chemistry reacting phase; Utilize nitrine end group ATRP polymkeric substance and Terminal Acetylenes based polyurethanes performed polymer to carry out 1; 3-quadripole cycloaddition reaction; Synthesize to contain on the main chain triblock polymer of triazole ring a kind of, under the reaction conditions of gentleness, prepared the triblock polymer of distribution of low molecular weight efficiently, be 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 a divalent alcohol, and B is a vulcabond, and D is an alkynes end group end-capping reagent, and E is a vinyl polymer, and n is the number of repeat unit (n >=1) that contains in the base polyurethane prepolymer for use as.
Wherein,
A is: polyoxyethylene glycol (PEG), polytetramethylene ether diol (PTMG), W 166 (PPG), polycaprolactone divalent alcohol (PCL), polycarbonate diol (PCDL), polyether silicone glycol, gather hexanodioic acid pinakon esterdiol, poly adipate succinic acid ester glycol, polyethylene glycol adipate glycol etc., and verivate separately.
B is: TDI, MDI, IPDI, HDI, HMDI, XDI, ADI and verivate separately thereof.
D is alkynol or ynamine compounds.
E is the polymkeric substance that is caused by the ATRP initiator.
The preparation method of triblock polymer of the present invention:, comprise the steps: by progressively polymerization, ATRP and the preparation of click chemistry reaction bonded
Synthesizing of step 1. nitrine end group vinyl polymer
Step 1.1. adopts atom transfer radical polymerization method, adds solvent, monomer, catalyzer successively, reaction system carry out three liquid nitrogen cool off-vacuumize-fill nitrogen-thaw cycles after; Add the ATRP polymerization starter; Wherein, monomer, initiator, catalyst molar ratio are 5-500: 1: 1, at the nitrogen atmosphere lower seal; After placing oil bath reaction certain hour, drop into termination reaction in the liquid nitrogen.An amount of THF or methylene dichloride dilution, and cross the neutral alumina chromatography column, to pour in the precipitation agent after concentrating and precipitate, redissolve concentrating and precipitating operation three times is filtered and is obtained halo end group ATRP polymkeric substance.
Step 1.2 is dissolved in step 1.1 a synthetic halo end group polymer and sodium azide among the DMF with mol ratio 1: 5-10,50-70 ℃ of lucifuge magnetic agitation reaction 24h, and spinning is the DMF solution of nitrine end group ATRP polymkeric substance.
Synthesizing of step 2. Terminal Acetylenes based polyurethanes performed polymer
Divalent alcohol joined whisking appliance is housed; In the three-necked bottle of TM,, add vulcabond in 110-120 ℃ of dehydration 2.5h; The mol ratio of vulcabond and divalent alcohol is 1.1-2: 1; 40-85 ℃ is reacted to NCO arrival theoretical value under the argon shield, adds alkynes end group end-capping reagent, and 40-85 ℃ is reacted to NCO content is zero.
Step 3. click chemistry method is synthesized triblock polymer
With the Terminal Acetylenes based polyurethanes performed polymer of the nitrine end group ATRP polymkeric substance DMF solution of step 1 preparation, step 2 preparation, catalyzer, part according to mol ratio 1-1.2: feed intake at 1: 1: 1, take a breath three times, 50-70 ℃ is reacted 24h under nitrogen protection.After DMF was removed in the vacuum decompression distillation, the neutral alumina post was crossed in the THF dilution, concentrates THF, after vacuum-drying is also purified, promptly obtained containing the triblock polymer of triazole ring.
The foregoing invention technical scheme can be represented as follows:
The said ATRP initiator end of above-mentioned preparing method's step (1) is a halogen atom, can select haloalkane, benzyl halogenide, a-bromo ester, a-halogenated ketone, a-halo nitrile etc. for use, and the verivate of above-claimed cpd.Polymerization single polymerization monomer can adopt any ATRP of carrying out polymeric vinyl monomer, like methacrylic ester, propenoate, vinylbenzene, acrylic amide, vinyl cyanide, vinyl pyridine etc.The said ATRP catalyzer of above-mentioned preparing 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.
Above-mentioned preparing method's step (3) is said, adopts the synthetic triblock polymer of click chemistry, and catalyzer is cuprous iodide, cuprous bromide, cuprous chloride, cupric chloride, copper sulfate, and part is pentamethyl-diethylenetriamine, sodium ascorbate, triethylamine etc.
Above-mentioned preparing method's step (3) is said, and method of purification is the cable-styled extraction or the selective solvent precipitator method.
Because the utilization of technique scheme, the present invention compared with prior art has advantage:
1. the present invention utilizes progressively polymerization, active free radical polymerization to combine with " Click Chemistry " to contain the triblock polymer of triazole ring, widened the realization approach of block polymer synthesis first, makes Molecular Structure Design variation more.
The present invention overcome that efficiency of initiation is low in the synthetic triblock polymer process of living polymerisation process, MWD is wide, the shortcoming of severe reaction conditions, molecular structure Modulatory character difference, reaction efficiency is high, reaction conditions is gentle, molecular weight of product narrowly distributing and easy purifying.
3. contain the urethane segment owing in the triblock polymer, and contain hydrogen bond action, thereby be a novel research field, and in biological medicine, phase solubilizing agent, tensio-active agent, there is very big potential using value in fields such as nano material.
Description of drawings
Accompanying drawing is to synthesize PS-b-PU-b-PS's among the embodiment 1
1H NMR (CDCl
3) spectrogram.
Embodiment
In order to be easy to further understand the present invention, the following example will be done further elaboration to the present invention, but embodiment of the present invention is not limited thereto.
Embodiment 1
(1) synthetic PS-Br.In the Schlenk of cleaning bottle, add stirrer, according to mol ratio 108: 192: 1: 1 added toluene, vinylbenzene, PMDETA, cuprous bromide successively.Reaction system through three liquid nitrogen cool off-vacuumize-fill nitrogen-thaw cycles after; Add a-isobutyl ethyl bromide (EBiB) with syringe; The mol ratio of vinylbenzene and a-isobutyl ethyl bromide is 192: 1; At the nitrogen atmosphere lower seal, react 2h down, termination reaction in the cold water cooling back adding liquid nitrogen in 90 ℃.After adopting THF to dilute, cross the neutral alumina column chromatography,, adopt Rotary Evaporators to concentrate THF, in a large amount of cold methyl alcohol, precipitate to remove the catalyzer that has color.Redissolve/precipitation operation three times obtains the white powder product and places 50 ℃ of dry 12h of vacuum drying oven.
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) in the flask of cleaning, successively added PS-Br and sodium azide in 1: 8 in molar ratio, add DMF (10wt%) then and make its dissolving, 60 ℃ of reactions are spent the night, and centrifugal unreacted sodium azide promptly obtains the DMF solution of nitrine end group PS.
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 whisking appliance is housed, in the three-necked bottle of TM, in 110-120 ℃ of dehydration 2.5h; Be cooled to 65 ℃; Add isofoer diisocyanate, the mol ratio of vulcabond and polyoxyethylene glycol is 2: 1, and argon shield is reacted to NCO arrival theoretical value for following 85 ℃; Add the propiolic alcohol end-blocking, 70 ℃ are reacted to NCO content is zero.
1H?NMR(CDCl
3)d?ppm：3.50-3.80(m，-CH2CH2O-of?PEG)，4.22(d，2H，-OCH2C＝CH).
(4) with the DMF solution, Terminal Acetylenes based polyurethanes performed polymer, CuBr, PMDETA of the nitrine end group PS of preparation according to mol ratio 1.1: 1: 1: 1 feeds intake, and vacuumizes-change nitrogen three times, 60 ℃ of reaction 24h under nitrogen protection.After DMF was removed in the vacuum decompression distillation, the neutral alumina post was crossed in the THF dilution, concentrates THF and vacuum-drying.Adopt the cable-styled extraction of hexanaphthene, room temperature leaves standstill the back and falls to remove supernatant liquid, after lower floor's thick liquid vacuum-drying, promptly obtains 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 the Schlenk of cleaning bottle, add stirrer, according to mol ratio 200: 200: 2: 1 added toluene, MMA, PMDETA, cuprous bromide successively.Reaction system through three liquid nitrogen cool off-vacuumize-fill nitrogen-thaw cycles after; Add the a-isobutyl ethyl bromide with syringe, the mol ratio of MMA and a-isobutyl ethyl bromide is 200: 1, at the nitrogen atmosphere lower seal; React 6h down, termination reaction in the cold water cooling back adding liquid nitrogen in 70 ℃.Employing ethanol is precipitation agent, is dissolved in THF after the filtration, crosses the neutral alumina column chromatography, to remove the catalyzer that has color, adopts Rotary Evaporators evaporate to dryness THF, obtains the white powder product and places vacuum drying oven dry.
(2) PMMA-N
3Compound method with embodiment 1.
(3) W 166 2000 is joined whisking appliance is housed, in the three-necked bottle of TM, in 110-120 ℃ of dehydration 2.5h; Be cooled to 60 ℃; Add tolylene diisocyanate, the mol ratio of tolylene diisocyanate and Macrogol 2000 is 1.5: 1, and argon shield is reacted to NCO arrival theoretical value for following 80 ℃; Add the propiolic alcohol end-blocking, 70 ℃ are reacted to NCO content is zero.
(4) remove catalyzer and part and select CuSO for use
4/ Na
Asc, other are with step (4) in the case study on implementation 1.
Embodiment 3
(1) removing initiator adopts isobutyl bromide to the nitrobenzyl ester; Catalyzer adopts cuprous bromide, and 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 ℃, and the reaction times is outside the 4h, and other are with step (1) among the embodiment 1.
(2) mol ratio except that PS-Br and sodium azide is 1: 10, and DMF is outside the 20wt%, and other are with step (2) among the embodiment 1.
(3), (4) are all with step (3), (4) among the embodiment 1.
Embodiment 4
(1), (2) PS-N
3Compound method with (1), (2) among the embodiment 1.
(3) polytetramethylene ether diol 1000 is joined whisking appliance is housed, in the three-necked bottle of TM, in 110-120 ℃ of dehydration 2.5h; Be cooled to 60 ℃, add 1, the 6-hexamethylene diisocyanate; The mol ratio of vulcabond and polytetramethylene ether diol 1000 is 1.25: 1; Argon shield is reacted to NCO arrival theoretical value for following 80 ℃, adds the propargylamine end-blocking, and 70 ℃ are reacted to NCO content is zero.
(4) except that method of purification is the mixed solvent washing of hexanaphthene and sherwood oil, all with step (4) among the embodiment 1.
Embodiment 5
(1), (2) all are same as step among the embodiment 1 (1), (2).
(3) except that end-capping reagent adopted 2-methyl-3-crotonylene-amine, other all were same as step among the embodiment 1 (3).
(4) remove catalyzer and part and select cuprous iodide/triethylamine for use, the DMF solution of nitrine end group PS, Terminal Acetylenes based polyurethanes performed polymer, CuBr, PMDETA are 1.05: 1: 1 according to mol ratio: 1 feed intake outside, all be same as step among the embodiment 1 (4).
Embodiment 6
(1) adopt the fluorobenzene ethene except that vinyl monomer, other all are same as step among the embodiment 1.
Embodiment 7
(1) remove vinyl monomer and adopt Bing Xisuandingzhi, initiator is the 2 bromopropionic acid methyl esters, and other all are same as step among the embodiment 1.
Embodiment 8
(1) removing vinyl monomer is the mix monomer of vinylbenzene and vinyl cyanide, and initiator adopts the a-bromo acid tert-butyl ester, and catalyst system adopts outside cuprous bromide/dipyridyl, and other all are same as step among the embodiment 1.
Claims (7)
1. one type of triblock polymer is characterized in that this polymkeric substance has following structure:
A is a divalent alcohol, and B is a vulcabond, and D is an alkynes end group end-capping reagent, and E is a vinyl polymer, and n is the number of repeat unit (n >=1) that contains in the base polyurethane prepolymer for use as;
Wherein,
A is: polyoxyethylene glycol (PEG), polytetramethylene ether diol (PTMG), W 166 (PPG), polycaprolactone divalent alcohol (PCL), polycarbonate diol (PCDL), polyether silicone glycol, gather hexanodioic acid pinakon esterdiol, poly adipate succinic acid ester glycol, polyethylene glycol adipate glycol etc., and verivate separately;
B is: TDI, MDI, IPDI, HDI, HMDI, XDI, diisocyanates such as ADI and verivate separately thereof;
D is alkynol or ynamine compounds;
E is by the homopolymer of ATRP initiator initiation or for containing the unitary multipolymer of different monomers.
2. the said triblock polymer of claim 1 is characterized in that: by progressively polymerization, ATRP and the preparation of click chemistry reaction bonded, comprise the steps:
Synthesizing of step 1. nitrine end group polymer
Step 1.1 adopts atom transfer radical polymerization method, adds solvent, monomer, catalyzer successively, carry out cooled with liquid nitrogen-vacuumize-fill nitrogen-thaw cycles after; Add the ATRP polymerization starter; Wherein, monomer, initiator, catalyst molar ratio are 5-500: 1: 1, at the nitrogen atmosphere lower seal; After placing oil bath reaction certain hour, drop into termination reaction in the liquid nitrogen.An amount of THF or methylene dichloride dilution, and cross the neutral alumina chromatography column, pour in the precipitation agent after concentrating and precipitate, filter the ATRP polymkeric substance that obtains halo end group vinyl monomer;
Step 1.2 is dissolved in step 1.1 a synthetic halo end group polymer and sodium azide among the DMF with mol ratio 1: 5-10, and 50-70 ℃ of lucifuge magnetic agitation reacted 24h, is the DMF solution of nitrine end group polymer.
Synthesizing of step 2 Terminal Acetylenes based polyurethanes performed polymer
Divalent alcohol joined whisking appliance is housed; In the three-necked bottle of TM,, add vulcabond in 110-120 ℃ of dehydration 2.5h; The mol ratio of vulcabond and divalent alcohol is 1.1-2: 1; 40-85 ℃ is reacted to NCO arrival theoretical value under the argon shield, adds alkynes end group end-capping reagent, and 40-85 ℃ is reacted to NCO content is zero;
Step 3 click chemistry method is synthesized triblock polymer
With the Terminal Acetylenes based polyurethanes performed polymer of the nitrine end group polymer DMF solution of step 1 preparation, step 2 preparation, catalyzer, part according to mol ratio 1-1.2: feed intake at 1: 1: 1, take a breath three times, 50-70 ℃ is reacted 24h under nitrogen protection.After DMF was removed in the vacuum decompression distillation, the neutral alumina post was crossed in the THF dilution, concentrates THF, and vacuum-drying promptly obtains the synthetic triblock polymer after also purifying.
3. the said ATRP initiator of claim 1 is characterized in that: terminally be halogen atom.Can select haloalkane, benzyl halogenide, alpha-brominated ester, α-Lu Daitong, alpha-halogen nitrile etc. for use, and the verivate of above-claimed cpd.
4. the said preparation method of claim 2 is characterized in that: can adopt any ATRP of carrying out polymeric vinyl monomer, like methacrylic ester, propenoate, vinylbenzene, acrylic amide, vinyl cyanide, vinyl pyridine etc.
5. the said preparation method of claim 2, it is characterized in that: the ATRP catalyzer can comprise transistion metal compound and its part, comprising CuBr/PMDETA, CuBr/2dNbpy, CuCl/2dNbpy, Cu (II) Br
2/ 2dNbpy, Cu (II) Br
2/ PMDETA, Cu (II) C1
2/ 2dNbpy, CuCl/Me
6TREN, Cu (II) Br
2/ Me
6TREN etc.
6. the said preparation method of claim 2; It is characterized in that: adopt the synthetic triblock polymer of Click Chemistry; The said catalyzer of step 3 is cuprous iodide, cuprous bromide, cuprous chloride, cupric chloride, copper sulfate, and part is pentamethyl-diethylenetriamine, sodium ascorbate, triethylamine etc.
7. the said preparation method of claim 2, it is characterized in that: the said method of purification of step 3 is the cable-styled extraction or the selective solvent precipitator method.
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