CN103387663B - Prepare the method for end group containing the amphipathic nature block polymer of sulfydryl - Google Patents
Prepare the method for end group containing the amphipathic nature block polymer of sulfydryl Download PDFInfo
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- CN103387663B CN103387663B CN201310323564.4A CN201310323564A CN103387663B CN 103387663 B CN103387663 B CN 103387663B CN 201310323564 A CN201310323564 A CN 201310323564A CN 103387663 B CN103387663 B CN 103387663B
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Abstract
The present invention relates to a kind of method prepared end group and contain the amphipathic nature block polymer of sulfydryl, it is characterized by employing following steps: 1) be initiator with poly glycol monomethyl ether, be solvent with tetrahydrofuran (THF), use naphthalene potassium to be initiator, with active anionic polymerization method ring-opening polymerization butylene oxide ring, synthesizing amphipathic segmented copolymer PEO-b-PBO, wherein the mol ratio of initiator and initiator and oxetane monomers is 1:1 ~ 1.1:15 ~ 33; 2) react with 3,3 '-two sulphur two propionyl chlorides and amphipathic nature block polymer PEO-b-PBO, generate the amphipathic nature block polymer PEO-b-PBO-SS containing disulfide linkage; 3) by dithiothreitol (DTT) in tetrahydrofuran (THF), under nitrogen protection, 20 ~ 35 DEG C of reduction containing the amphipathic nature block polymer PEO-b-PBO-SS of disulfide linkage, obtain the amphipathic nature block polymer PEO-b-PBO-SH of end group containing sulfydryl.The molecular weight of the target compound that the present invention obtains is controlled, narrow molecular weight distribution, is got final product the solvability of control objectives thing by the add-on and monomer conversion regulating oleophylic monomer.
Description
Technical field
The present invention relates to a kind of method prepared end group and contain the amphipathic nature block polymer of sulfydryl, belong to macromolecule synthesising technology field.
Background technology
Polymkeric substance containing sulfydryl has unique oxidation-reduction quality, and can assemble on the surface of gold or silver and quantum dot, therefore, this kind of material has caused the interest of numerous investigator in the field such as biological medicine and nano science.
Amphipathic nature block polymer PEO-b-PBO is the molecules surfactant of a class non-ionic type, is with a wide range of applications.If sulfydryl on its end group band, amphipathic metal nanoparticle is prepared in the effect of the amphiphilic surfactant PEO-b-PBO-SH and nanometer gold or nanometer silver that end group then can be utilized to contain sulfydryl, again because its surface-active action, the emulsifying agent of letex polymerization can be used as further, prepare polymer-coated metal nanoparticle, there is very important application prospect.Not yet find at present to prepare the technology report of end group containing the amphipathic nature block polymer PEO-b-PBO-SH of sulfydryl.
Summary of the invention
The object of this invention is to provide a kind ofly to solve the problem, technique simply prepares the method for end group containing the amphipathic nature block polymer of sulfydryl.Its technology contents is:
A kind of method prepared end group and contain the amphipathic nature block polymer of sulfydryl, it is characterized by employing following steps: 1) be initiator with poly glycol monomethyl ether, be solvent with tetrahydrofuran (THF), use naphthalene potassium to be initiator, with active anionic polymerization method ring-opening polymerization butylene oxide ring, synthesizing amphipathic segmented copolymer PEO-b-PBO, wherein the mol ratio of initiator and initiator and oxetane monomers is 1:1 ~ 1.1:15 ~ 33; 2) react with 3,3 '-two sulphur two propionyl chlorides and amphipathic nature block polymer PEO-b-PBO, generate the amphipathic nature block polymer PEO-b-PBO-SS containing disulfide linkage; 3) by dithiothreitol (DTT) in tetrahydrofuran (THF), under nitrogen protection, 20 ~ 35 DEG C of reduction containing the amphipathic nature block polymer PEO-b-PBO-SS of disulfide linkage, obtain the amphipathic nature block polymer PEO-b-PBO-SH of end group containing sulfydryl.
Described prepares the method for end group containing the amphipathic nature block polymer of sulfydryl, step 1) in, react and carry out in ampoule, before reaction the ampoule that initiator and solvent are housed carried out successively liquid nitrogen freezing-vacuumize-warm up-Tong argon gas, repeatedly after three times, seal in argon atmospher; Light green is titrated to naphthalene potassium initiator, then butylene oxide ring is added, magnetic agitation, after 20 ~ 35 DEG C of reaction 12 ~ 24h, move in 50 DEG C of water-baths and react 12 ~ 24h, then after being warming up to 70 DEG C of reaction 4h, add the mixed solution termination reaction of hydrochloric acid and methyl alcohol, wherein the volume ratio of hydrochloric acid and methyl alcohol is 1:100 ~ 1000, and the add-on of mixed solution is that the mol ratio of methyl alcohol and initiator is not less than 10; Then mixed solution in ampoule is added dropwise in the cold diethyl ether of 10 ~ 15 times of volumes and precipitates, then suction filtration, freeze-drying, obtained amphipathic nature block polymer PEO-b-PBO.
Described prepares the method for end group containing the amphipathic nature block polymer of sulfydryl, step 2) in, obtain light yellow liquid 3 with 3,3 '-two thiodipropionic acids and sulfur oxychloride back flow reaction, 3 '-two sulphur two propionyl chloride, both mol ratios are 1:7 ~ 10; Then under the catalysis of triethylamine, by 3,3 '-two sulphur two propionyl chloride and amphipathic nature block polymer PEO-b-PBO ice bath stirring reaction 24h, triethylamine and 3, the mol ratio of 3 '-two sulphur two propionyl chloride and amphipathic nature block polymer PEO-b-PBO is 1:1:0.2 ~ 0.25, obtains the segmented copolymer PEO-b-PBO-SS containing disulfide linkage.
Described prepares the method for end group containing the amphipathic nature block polymer of sulfydryl, step 3) in, dithiothreitol (DTT) is 5 ~ 10:1 with the mol ratio of the amphipathic nature block polymer PEO-b-PBO-SS containing disulfide linkage.
Compared with prior art, its advantage is in the present invention:
1, the end group adopting this method to obtain is controlled containing the molecular weight of the amphipathic nature block polymer PEO-b-PBO-SH of sulfydryl, narrow molecular weight distribution.
2, add-on and monomer conversion by regulating oleophylic monomer get final product the solvability of control objectives thing, this segmented copolymer can be utilized very easily as stablizer, in all kinds of SOLVENTS, prepare metal nanoparticle.
Accompanying drawing explanation
Fig. 1 is the nuclear magnetic spectrogram of the amphipathic nature block polymer PEO-b-PBO obtained in the embodiment of the present invention 1;
Fig. 2 is the GPC spectrogram of the amphipathic nature block polymer PEO-b-PBO obtained in the embodiment of the present invention 1;
Fig. 3 is that in the embodiment of the present invention 3, end group contains the amphipathic nature block polymer PEO-b-PBO-SH of sulfydryl and the GPC spectrogram of precursor thereof.
Embodiment
Embodiment 1, adopts following steps:
(1) prepared by amphipathic nature block polymer PEO-b-PBO: take poly glycol monomethyl ether (Mn=1100) 5g dry in advance, with newly steam tetrahydrofuran (THF) 25mL and together join in ampoule, ampoule is carried out successively liquid nitrogen freezing-vacuumize-warm up-Tong argon gas, repeatedly after three times, seal in argon atmospher.Instillation 11.36ml concentration is that the naphthalene potassium solution of 0.4mol/l is to light green, then oxetane monomers 6mL is injected, magnetic agitation, 20 DEG C of reactions moved in 50 DEG C of water-baths after 12 hours reacts 12 hours, be warming up to 70 DEG C of reactions 4 hours again, by the degassed mixed solution termination reaction of 1ml hydrochloric acid and methyl alcohol, wherein the volume ratio of hydrochloric acid and methyl alcohol is 1:100; Be added dropwise to by mixed solution in ampoule in the cold diethyl ether of 10 times of volumes and precipitate, suction filtration, products therefrom uses tetrahydrofuran (THF)/cold diethyl ether dissolution/precipitation three times again, then filters, freeze-drying, obtains amphipathic nature block polymer PEO-b-PBO.
(2) containing the preparation of the amphipathic nature block polymer PEO-b-PBO-SS of disulfide linkage: get 4.2g3,3 '-two thiodipropionic acid and 10mL sulfur oxychloride are placed in the there-necked flask with prolong, 74 DEG C of back flow reaction 6 hours, the thionyl chloride that pressure reducing and steaming is excessive, obtain light yellow liquid 3,3 '-two sulphur two propionyl chloride; Get dry amphipathic nature block polymer PEO-b-PBO1.8g and be placed in 100mL there-necked flask, first add the tetrahydrofuran (THF) that the triethylamine of 0.45g and 30mL newly steam, ice bath stirs, then adds 1.089g3,3 '-two sulphur two propionyl chloride, reaction 24h, filter, concentrated filtrate, then precipitate with the normal hexane of 10 times of volumes, then use tetrahydrofuran (THF)/normal hexane dissolution/precipitation three times repeatedly, freeze-drying must containing the amphipathic nature block polymer PEO-b-PBO-SS of disulfide linkage.
(3) end group is containing the preparation of the amphipathic nature block polymer PEO-b-PBO-SH of sulfydryl: get the amphipathic nature block polymer PEO-b-PBO-SS of 1.5g containing disulfide linkage; be dissolved in 10mL tetrahydrofuran (THF); add 0.548g dithiothreitol (DTT); the lower 20 DEG C of stirring reactions of nitrogen protection 24 hours; concentrated, precipitation, suction filtration; then use tetrahydrofuran (THF)/normal hexane dissolution/precipitation three times repeatedly, freeze-drying obtains the amphipathic nature block polymer PEO-b-PBO-SH of end group containing sulfydryl.
Fig. 1 is the nuclear magnetic spectrogram of the amphipathic nature block polymer PEO-b-PBO obtained in embodiment 1, Fig. 2 is the GPC spectrogram of the amphipathic nature block polymer PEO-b-PBO obtained in embodiment 1, eluent is THF, and flow velocity is 1mL/min, and detector is refractive index detector; Test is known, gained end group containing sulfydryl segmented copolymer consist of PEO
25-b-PBO
11-SH, number-average molecular weight is 1990, and molecular weight distributing index is 1.12, and product can directly be dissolved in water.Embodiment 2, adopts following steps:
(1) prepared by amphipathic nature block polymer PEO-b-PBO: take poly glycol monomethyl ether (Mn=1100) 5g dry in advance, with newly steam tetrahydrofuran (THF) 25mL and together join in ampoule, ampoule is carried out successively liquid nitrogen freezing-vacuumize-warm up-Tong argon gas, repeatedly after three times, seal in argon atmospher.Instillation 12.5ml concentration is that the naphthalene potassium solution of 0.4mol/l is to light green, then oxetane monomers 6mL is injected, magnetic agitation, 35 DEG C of reactions moved in 50 DEG C of water-baths after 24 hours reacts 24 hours, be warming up to 70 DEG C of reactions 4 hours again, by the degassed mixed solution termination reaction of 1ml hydrochloric acid and methyl alcohol, wherein the volume ratio of hydrochloric acid and methyl alcohol is 1:1000; Be added dropwise to by mixed solution in ampoule in the cold diethyl ether of 15 times of volumes and precipitate, suction filtration, products therefrom uses tetrahydrofuran (THF)/cold diethyl ether dissolution/precipitation three times again, then filters, freeze-drying, obtains amphipathic nature block polymer PEO-b-PBO.
(2) containing the preparation of the amphipathic nature block polymer PEO-b-PBO-SS of disulfide linkage: the preparation of 3,3 '-two sulphur two propionyl chloride is with embodiment 1,3, and the mol ratio of 3 '-two thiodipropionic acid and sulfur oxychloride is 1:10; Get dry amphipathic nature block polymer PEO-b-PBO4.2g and be placed in 100mL there-necked flask, first add the tetrahydrofuran (THF) that the triethylamine of 0.854g and 30mL newly steam, ice bath stirs, then adds 2.08g3,3 '-two sulphur two propionyl chloride, reaction 24h, filter, concentrated filtrate, then precipitate with the normal hexane of 10 times of volumes, then use tetrahydrofuran (THF)/normal hexane dissolution/precipitation three times repeatedly, freeze-drying must containing the amphipathic nature block polymer PEO-b-PBO-SS of disulfide linkage.
(3) end group is containing the preparation of the amphipathic nature block polymer PEO-b-PBO-SH of sulfydryl: get the amphipathic nature block polymer PEO-b-PBO-SS of 4g containing disulfide linkage; be dissolved in 10mL tetrahydrofuran (THF); add 2.19g dithiothreitol (DTT); the lower 35 DEG C of stirring reactions of nitrogen protection 24 hours; concentrated, precipitation, suction filtration; then use tetrahydrofuran (THF)/normal hexane dissolution/precipitation three times repeatedly, freeze-drying obtains the amphipathic nature block polymer PEO-b-PBO-SH of end group containing sulfydryl.
Test is known: gained end group containing sulfydryl segmented copolymer consist of PEO
25-b-PBO
22-SH, number-average molecular weight is 2690, and molecular weight distributing index is 1.08, and product can be dissolved in tetrahydrofuran (THF), ethanol organic solvent, but can not directly be dissolved in water.
Embodiment 3, adopts following steps:
(1) prepared by amphipathic nature block polymer PEO-b-PBO: take poly glycol monomethyl ether (Mn=2000) 5g dry in advance, with newly steam tetrahydrofuran (THF) 25mL and together join in ampoule, ampoule is carried out successively liquid nitrogen freezing-vacuumize-warm up-Tong argon gas, repeatedly after three times, seal in argon atmospher.Instillation 6.25ml concentration is that the naphthalene potassium solution of 0.4mol/l is to light green, then oxetane monomers 6mL is injected, magnetic agitation, 25 DEG C of reactions moved in 50 DEG C of water-baths after 18 hours reacts 24 hours, be warming up to 70 DEG C of reactions 4 hours again, by the degassed mixed solution termination reaction of 1ml hydrochloric acid and methyl alcohol, wherein the volume ratio of hydrochloric acid and methyl alcohol is 1:500; Be added dropwise to by mixed solution in ampoule in the cold diethyl ether of 12 times of volumes and precipitate, suction filtration, products therefrom uses tetrahydrofuran (THF)/cold diethyl ether dissolution/precipitation three times again, then filters, freeze-drying, obtains amphipathic nature block polymer PEO-b-PBO.
(2) containing the preparation of the amphipathic nature block polymer PEO-b-PBO-SS of disulfide linkage: the preparation of 3,3 '-two sulphur two propionyl chloride is with embodiment 1,3, and the mol ratio of 3 '-two thiodipropionic acid and sulfur oxychloride is 1:8; Get dry amphipathic nature block polymer PEO-b-PBO4.2g and be placed in 100mL there-necked flask, first add the tetrahydrofuran (THF) that the triethylamine of 0.61g and 30mL newly steam, ice bath stirs, then adds 1.48g3,3 '-two sulphur two propionyl chloride, reaction 24h, filter, concentrated filtrate, then precipitate with the normal hexane of 10 times of volumes, then use tetrahydrofuran (THF)/normal hexane dissolution/precipitation three times repeatedly, freeze-drying must containing the amphipathic nature block polymer PEO-b-PBO-SS of disulfide linkage.
(3) end group is containing the preparation of the amphipathic nature block polymer PEO-b-PBO-SH of sulfydryl: get the amphipathic nature block polymer PEO-b-PBO-SS of 4g containing disulfide linkage; be dissolved in 10mL tetrahydrofuran (THF); add 1.73g dithiothreitol (DTT); the lower 35 DEG C of stirring reactions of nitrogen protection 24 hours; concentrated, precipitation, suction filtration; then use tetrahydrofuran (THF)/normal hexane dissolution/precipitation three times repeatedly, freeze-drying obtains the amphipathic nature block polymer PEO-b-PBO-SH of end group containing sulfydryl.
Fig. 3 is that in embodiment 3, end group is containing the amphipathic nature block polymer PEO-b-PBO-SH of sulfydryl and the GPC spectrogram of precursor thereof, and eluent is DMF, and flow velocity is 1mL/min, and detector is refractive index detector.Test is known: test know, gained end group containing sulfydryl segmented copolymer consist of PEO
45-b-PBO
11-SH, number-average molecular weight is 2850, and molecular weight distributing index is 1.08, and product can directly be dissolved in water, and micelle-forming concentration is 0.833g/L.
Claims (1)
1. prepare the method for end group containing the amphipathic nature block polymer of sulfydryl for one kind, it is characterized by employing following steps: 1) be initiator with poly glycol monomethyl ether, be solvent with tetrahydrofuran (THF), be initiator with naphthalene potassium, with active anionic polymerization method ring-opening polymerization butylene oxide ring, synthesizing amphipathic segmented copolymer PEO-b-PBO, wherein the mol ratio of initiator and initiator and oxetane monomers is 1:1 ~ 1.1:15 ~ 33, reaction is carried out in ampoule, before reaction the ampoule that initiator and solvent are housed carried out successively liquid nitrogen freezing-vacuumize-warm up-Tong argon gas, repeatedly after three times, seal in argon atmospher, light green is titrated to naphthalene potassium initiator, then butylene oxide ring is added, magnetic agitation, after 20 ~ 35 DEG C of reaction 12 ~ 24h, move in 50 DEG C of water-baths and react 12 ~ 24h, then after being warming up to 70 DEG C of reaction 4h, add the mixed solution termination reaction of hydrochloric acid and methyl alcohol, wherein the volume ratio of hydrochloric acid and methyl alcohol is 1:100 ~ 1000, and the add-on of mixed solution is that the mol ratio of methyl alcohol and initiator is not less than 10, then mixed solution in ampoule is added dropwise in the cold diethyl ether of 10 ~ 15 times of volumes and precipitates, then suction filtration, freeze-drying, obtained amphipathic nature block polymer PEO-b-PBO, 2) with 3,3 '-two sulphur two propionyl chloride and amphipathic nature block polymer PEO-b-PBO react, generate the amphipathic nature block polymer PEO-b-PBO-SS containing disulfide linkage, wherein use 3,3 '-two thiodipropionic acid and sulfur oxychloride back flow reaction obtain light yellow liquid 3,3 '-two sulphur two propionyl chloride, both mol ratios are 1:7 ~ 10, then under the catalysis of triethylamine, by 3,3 '-two sulphur two propionyl chloride and amphipathic nature block polymer PEO-b-PBO ice bath stirring reaction 24h, triethylamine and 3, the mol ratio of 3 '-two sulphur two propionyl chloride and amphipathic nature block polymer PEO-b-PBO is 1:1:0.2 ~ 0.25, obtains the segmented copolymer PEO-b-PBO-SS containing disulfide linkage, 3) by dithiothreitol (DTT) in tetrahydrofuran (THF), under nitrogen protection, 20 ~ 35 DEG C of reduction are containing the amphipathic nature block polymer PEO-b-PBO-SS of disulfide linkage, dithiothreitol (DTT) is 5 ~ 10:1 with the mol ratio of the amphipathic nature block polymer PEO-b-PBO-SS containing disulfide linkage, obtains the amphipathic nature block polymer PEO-b-PBO-SH of end group containing sulfydryl.
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| CN101056936A (en) * | 2004-11-10 | 2007-10-17 | 陶氏环球技术公司 | Amphiphilic block copolymer-toughened epoxy resins and powder coatings made therefrom |
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| CN101353475B (en) * | 2008-09-09 | 2011-03-16 | 北京科技大学 | Preparation of aquagel material having thermal sensitivity and reactivity |
| CN102348757A (en) * | 2009-03-09 | 2012-02-08 | 陶氏环球技术有限责任公司 | Thermosettable composition containing combination of amphiphilic block copolymer and polyol and thermoset product therefrom |
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