CN102181054A - Method for preparing hyperbranched polymer through dual click chemistry - Google Patents
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Abstract
The invention discloses a method for preparing a hyperbranched polymer through dual click chemistry. The method comprises the following steps of: 1) adding one mole of bis(thiol) compound, 0.1 to 10 moles of solvent, 0.05 to 2 moles of base catalyst, and 0.9 to 1.1 moles of compound containing alkynyl and alkenyl into a reactor sequentially under the protection of nitrogen, performing sulfydryl-alkene addition reaction at the temperature of between 10 and 40 DEG C for 0.5 to 24 hours, and performing reduced pressure evaporation to remove the solvent; and 2) dissolving the product obtained in the step 1) in 0.25 to 10 moles of solvent under the protection of nitrogen, adding 0.005 to 0.05 mole of photosensitive radical initiator or thermosensitive radical initiator, irradiating by ultraviolet light or heating at the temperature of between 40 and 90 DEG C to produce radical, performing sulfydryl-alkene addition polymerization reaction for 0.5 to 24 hours, and precipitating, separating and drying to obtain the hyperbranched polymer. The method has the advantages of no need of complex AB2 monomer synthesis and purification steps, high speed and efficiency, convenience, wide application range and the like. The obtained hyperbranched polymer containing a large amount of thioether bonds has wide application prospect in the fields of biomedical carriers, high-performance materials, additives and the like.
Description
Technical field
The present invention relates to a kind of method of double-click on chemical preparation hyperbranched polymer, particularly contain the synthetic method of the hyperbranched polymer of thioether and alkynyl.
Background technology
Since the eighties in last century, hyperbranched polymer (Hyperbranched polymers) has caused people's research interest more and more widely.It is the highly branched macromole with triaxial ellipsoid shape three-dimensional arrangement of a class, with dendrimer (Dendrimers) and be called highly-branched polymers.Compare with linear polymer, it has the character of many uniquenesses, such as: high resolution, low viscosity, inner branching skeleton, internal cavities, binding site, a large amount of terminal functionality etc.Compare with dendrimer, its synthetic method is easier, also makes molecular designing more changeable.The continuous development of synthetic aspect has promoted its application in fields such as processing aid, coating, medical carrier, metal nano catalyzer templates.And these achievements obtain require it conversely in a hurry synthetic to gentle, fast, high yield and development in enormous quantities.The synthetic method of developing the hyperbranched polymer of more optimizing is a research focus in the last few years.Though constantly there is new progress to be in the news, but still have critical difficult point to need to break through: the monomer coupling strategy of 1, having reported makes people can use business-like unsymmetrical monomer to come the synthesis of super branched polymkeric substance by traditional polycondensation method, representing the much progress on the synthesis strategy, but the chemical reaction of being reported is limited, synthetic hyperbranched polymer kind remains to be expanded, yet there are no report (the Gao et al. for preparing hyperbranched poly thioether alkynes with this strategy
Prog. Polym. Sci.2004,
29, 183); That 2, has reported passes through to use AB with single click chemistry (click chemistry) reaction
2Or A
2+ B
3Method is used to prepare hyperbranched polymer, has represented the innovation on the synthetic technology, but still has the problem on the certain methods, as: low (the Perrier et al. of loaded down with trivial details and comprehensive yield be bought, be synthesized to used monomer can not commercialization
J. Am. Chem. Soc.2009,
131, 18075), easy gel etc.Up to the present, how to utilize quick, easy, the high yield of click chemistry to prepare hyperbranched polymer and remain a great problem.
Summary of the invention
The objective of the invention is to overcome the existing deficiency of hyperbranched polymer on synthetic method, a kind of method of double-click on chemical preparation hyperbranched polymer is provided.
The step of the method for double-click on chemical preparation hyperbranched polymer is as follows:
1) under the nitrogen protection, in reactor, add 1 mole two mercaptan compounds successively, 0.1-10 mole solvent, 0.05 ~ 2 mol alkali catalyzer, 0.9 ~ 1.1 mole the compound that contains alkynyl and thiazolinyl is in 10
oC ~ 40
oCarried out sulfydryl-alkene addition reaction under the C 0.5 ~ 24 hour, solvent removed by evaporation at reduced pressure;
2) under the nitrogen protection, the step 1) products therefrom is dissolved in 0.25 ~ 10 mole of solvent, adds 0.005 ~ 0.05 mole photosensitive radical initiator or temperature-sensitive radical initiator, by ultraviolet light irradiation or 40
oC ~ 90
oC adds the thermogenesis free radical, carries out sulfydryl-alkynes polyaddition reaction 0.5 ~ 24 hour, obtains hyperbranched polymer through precipitation, separation, drying.
Described two mercaptan compounds are selected from 1,4-succinimide mercaptans, 1,6-ethanthiol, 1, hot two mercaptan, 3 of 8-, 6-two oxa-s-1,8-octane two mercaptan, two (2-mercaptoethyl) ether, two (3-thiohydracrylic acid) butyleneglycol, 2,3-dimercapto-1-propyl alcohol or 1, the 4-DTT.
Described solvent is selected from water, methyl alcohol, ethanol, Virahol, toluene, benzene, chloroform, methylene dichloride, tetrahydrofuran (THF), diox, hexane, ether, ethyl acetate, N, dinethylformamide, N,N-dimethylacetamide or N-Methyl pyrrolidone.
Described alkali is selected from sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, potassium tert.-butoxide, triethylamine, Tri-n-Propylamine, tri-n-butylamine, diisopropyl ethyl amine, Tetramethyl Ethylene Diamine or five methyl diethylentriamine.
The described compound that contains alkynyl and thiazolinyl is selected from vinylformic acid propynyl ester, ethyl acetylene acrylate, Ba Dousuan propynyl ester, styracin propynyl ester, methacrylic acid propynyl ester, maleic acid list propynyl ester, the single propynyl ester of FUMARIC ACID TECH GRADE, N-proyl acrylamide, N-proyl-Methacrylamide or N-proyl maleinamide.
Described photosensitive radical initiator is selected from st-yrax dme, 1-hydroxy-cyclohexyl phenyl ketone or methyl benzoylformate.
Described temperature-sensitive radical initiator is selected from Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo dicyano valeric acid, azo-bis-iso-dimethyl, 2,2'-azo two (4-methoxy-2,4-methyl pentane nitrile), benzoyl peroxides, Potassium Persulphate or ammonium persulphate.
The present invention adopts the strategy of brand-new double-click on chemical reaction coupling, uses sulfydryl-alkene addition and sulfydryl-alkynes addition click chemistry reaction continuously, obtains to contain the polymkeric substance of a large amount of thioether bonds and alkynyl, and the molecular weight of product and the degree of branching are higher and adjustable.This preparation method and traditional method relatively have tangible advantage, as: utilize the efficient characteristics fast of click chemistry, need not loaded down with trivial details AB
2Monomer synthesizes with purification step, technology is easy, suitable monomers is extensive, operation is simple, controllability strong, repeatability is high, yield is high.The hyperbranched polymer that contains a large amount of thioether bonds of gained will have a wide range of applications in fields such as biological medicine carrier, high-performance multifunctional material, additives.
Description of drawings
Fig. 1 is with ethanthiol and vinylformic acid propynyl ester synthetic hyperbranched polymer among the present invention
1The H nmr spectrum has shown the signal (1.3 ~ 1.6 ppm) of hydrocarbon proton in the signal (2.5 ~ 3.0 ppm) of the hydrocarbon proton that tangible thioether bond connects and the ethanthiol.
Fig. 2 be among the present invention with 3,6-two oxa-s-1,8-octane two mercaptan and methacrylic acid propynyl ester synthetic hyperbranched polymer
1The H nmr spectrum has shown the signal (3.5 ~ 3.7 ppm) of the hydrocarbon proton that the signal (2.5 ~ 3.0 ppm) of the hydrocarbon proton that tangible thioether bond connects is connected with ether-oxygen bond.
Fig. 3 is with 3, and 6-two oxa-s-1,8-octane two mercaptan and methacrylic acid propynyl ester are the GPC curve of raw material institute synthetic hyperbranched polymer.
Embodiment
We's ratio juris is can supply the polymeric presoma with sulfydryl-alkene reaction is efficiently synthetic, implements the hyperbranched polymer that radical polymerization obtains containing a large amount of thioether bonds with sulfydryl-alkyne reaction again.
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1:
Step 1) under the nitrogen protection, adds ethanthiol (3.01 g, 20 mmol) successively in reactor, ethyl acetate (17.62 g, 200 mmol), and triethylamine (1.01 g, 10 mmol), vinylformic acid propynyl ester (2.20 g, 20 mmol) is 30
oC reacted 5 hours down, and reduction vaporization is removed ethyl acetate and triethylamine;
Step 2), under the nitrogen protection, the step 1) products therefrom is dissolved in the 20 mL toluene, adds the temperature-sensitive radical initiator Diisopropyl azodicarboxylate (131.3 mg) of 4 mol%, 65
o C polyreaction 3 hours, (number-average molecular weight is 7200 to obtain hyperbranched polymer through methanol extraction, separation, drying; Weight-average molecular weight is 104800; The degree of branching 0.76).
Embodiment 2:
Step 1) under the nitrogen protection, adds ethanthiol (3.01 g, 20 mmol) successively in reactor, ethyl acetate (17.62 g, 200 mmol), and triethylamine (4.04 g, 40 mmol), vinylformic acid propynyl ester (2.20 g, 20 mmol) is 10
oC reacted 5 hours down, and reduction vaporization is removed ethyl acetate and triethylamine;
Step 2), under the nitrogen protection, the step 1) products therefrom is dissolved in the 20 mL toluene, adds the temperature-sensitive radical initiator Diisopropyl azodicarboxylate (131.3 mg) of 4 mol%, 65
o C polyreaction 3 hours obtains hyperbranched polymer through methanol extraction, separation, drying.
Embodiment 3:
Step 1) under the nitrogen protection, adds ethanthiol (3.01 g, 20 mmol) successively in reactor, ethyl acetate (0.17g, 2 mmol), and triethylamine (1.23 g, 22 mmol), vinylformic acid propynyl ester (2.20 g, 20 mmol) is 40
oC reacted 0.5 hour down, and reduction vaporization is removed ethyl acetate and triethylamine;
Step 2), under the nitrogen protection, the step 1) products therefrom is dissolved in the 20 mL toluene, adds the temperature-sensitive radical initiator Diisopropyl azodicarboxylate (131.3 mg) of 4 mol%, 65
o C polyreaction 3 hours obtains hyperbranched polymer through methanol extraction, separation, drying.
Embodiment 4:
Step 1) under the nitrogen protection, adds ethanthiol (3.01 g, 20 mmol) successively in reactor; tetrahydrofuran (THF) (14.42 g, 200 mmol), diisopropyl ethyl amine (1.29 g, 10 mmol); vinylformic acid propynyl ester (2.42 g, 22 mmol) is 40
oC reacted 0.5 hour down, and reduction vaporization is removed ethyl acetate and triethylamine;
Step 2), under the nitrogen protection, the step 1) products therefrom is dissolved in the 20 mL toluene, adds the temperature-sensitive radical initiator Diisopropyl azodicarboxylate (131.3 mg) of 4 mol%, 65
o C polyreaction 3 hours obtains hyperbranched polymer through methanol extraction, separation, drying.
Embodiment 5:
Step 1) under the nitrogen protection, adds ethanthiol (3.01 g, 20 mmol) successively in reactor; methylene dichloride (17.0 g, 200 mmol), TBAH (0.259 g, 1 mmol); vinylformic acid propynyl ester (1.98 g, 18 mmol) is 30
oC reacted 5 hours down, and with a little dilute hydrochloric acid neutralization, then washing, drying, methylene dichloride is removed in evaporation;
Step 2), under the nitrogen protection, the step 1) products therefrom is dissolved in the 20 mL toluene, adds the temperature-sensitive radical initiator Diisopropyl azodicarboxylate (131.3 mg) of 4 mol%, 65
o C polyreaction 3 hours obtains hyperbranched polymer through methanol extraction, separation, drying.
Embodiment 6:
Step 1) under the nitrogen protection, adds ethanthiol (3.01 g, 20 mmol) successively in reactor, ethyl acetate (17.62 g, 200 mmol), and triethylamine (1.01 g, 10 mmol), vinylformic acid propynyl ester (2.20 g, 20 mmol) is 30
oC reacted 5 hours down, and reduction vaporization is removed ethyl acetate and triethylamine;
Step 2), under the nitrogen protection, the step 1) products therefrom is dissolved in the 20 mL benzene, adds the temperature-sensitive radical initiator Diisopropyl azodicarboxylate (164mg) of 5 mol%, 75
o C polyreaction 10 minutes obtains hyperbranched polymer through methanol extraction, separation, drying.
Embodiment 7:
Step 1) under the nitrogen protection, adds ethanthiol (3.01 g, 20 mmol) successively in reactor, ethyl acetate (17.62 g, 200 mmol), and triethylamine (1.01 g, 10 mmol), vinylformic acid propynyl ester (2.20 g, 20 mmol) is 30
oC reacted 5 hours down, and reduction vaporization is removed ethyl acetate and triethylamine;
Step 2), under the nitrogen protection, the step 1) products therefrom is dissolved in the 20 mL toluene, adds the temperature-sensitive radical initiator 2 of 2 mol%, 2'-azo two (4-methoxy-2,4-methyl pentane nitrile) (124 mg) is 40
o C polyreaction 5 hours obtains hyperbranched polymer through methanol extraction, separation, drying.
Embodiment 8:
Step 1) under the nitrogen protection, adds ethanthiol (3.01 g, 20 mmol) successively in reactor, ethyl acetate (17.62 g, 200 mmol), and triethylamine (1.01 g, 10 mmol), vinylformic acid propynyl ester (2.20 g, 20 mmol) is 30
oC reacted 5 hours down, and reduction vaporization is removed ethyl acetate and triethylamine;
Step 2), under the nitrogen protection, the step 1) products therefrom is dissolved in the 20 mL toluene, adds the temperature-sensitive radical initiator Diisopropyl azodicarboxylate (97 mg) of 2 mol%, 90
o C polyreaction 10 minutes obtains hyperbranched polymer through methanol extraction, separation, drying.
Embodiment 9:
Step 1) under the nitrogen protection, adds ethanthiol (3.01 g, 20 mmol) successively in reactor, ethyl acetate (17.62 g, 200 mmol), and triethylamine (1.01 g, 10 mmol), vinylformic acid propynyl ester (2.20 g, 20 mmol) is 30
oC reacted 5 hours down, and reduction vaporization is removed ethyl acetate and triethylamine;
Step 2); under the nitrogen protection, the step 1) products therefrom is dissolved in the 20 mL toluene, adds the photosensitive radical initiator st-yrax dme (25.6 mg) of 0.5 mol%; through ultraviolet light irradiation 20 minutes, obtain hyperbranched polymer through methanol extraction, separation, drying.
Embodiment 10:
Step 1) under the nitrogen protection, adds ethanthiol (3.01 g, 20 mmol) successively in reactor, ethyl acetate (17.62 g, 200 mmol), and triethylamine (1.01 g, 10 mmol), vinylformic acid propynyl ester (2.20 g, 20 mmol) is 30
oC reacted 5 hours down, and reduction vaporization is removed ethyl acetate and triethylamine;
Step 2); under the nitrogen protection, the step 1) products therefrom is dissolved in the 20 mL toluene, adds the temperature-sensitive radical initiator Diisopropyl azodicarboxylate (256 mg) of 5 mol%; process ultraviolet light irradiation 20 minutes obtains hyperbranched polymer through methanol extraction, separation, drying.
Embodiment 11:
Step 1) under the nitrogen protection, adds ethanthiol (3.01 g, 20 mmol) successively in reactor, ethyl acetate (17.62 g, 200 mmol), and triethylamine (1.01 g, 10 mmol), vinylformic acid propynyl ester (2.20 g, 20 mmol) is 30
oC reacted 5 hours down, and reduction vaporization is removed ethyl acetate and triethylamine;
Step 2), under the nitrogen protection, the step 1) products therefrom is dissolved in the 20 mL toluene, adds the temperature-sensitive radical initiator Diisopropyl azodicarboxylate (66 mg) of 2 mol%, 75
oC polyreaction 24 hours obtains hyperbranched polymer through methanol extraction, separation, drying.
Embodiment 12:
Step 1) under the nitrogen protection, adds 3 successively in reactor, 6-two oxa-s-1,8-octane two mercaptan (3.64 g; 20 mmol), ethyl acetate (17.62 g, 200 mmol), triethylamine (1.01 g; 10 mmol), vinylformic acid propynyl ester (2.20 g, 20 mmol) is 30
oC reacted 5 hours down, and reduction vaporization is removed ethyl acetate and triethylamine;
Step 2), under the nitrogen protection, the step 1) products therefrom is dissolved in the 20 mL toluene, adds the temperature-sensitive radical initiator Diisopropyl azodicarboxylate (131.3 mg) of 4 mol%, 65
o C polyreaction 3 hours, (number-average molecular weight is 6300 to obtain hyperbranched polymer through ethanol sedimentation, separation, drying; Weight-average molecular weight is 19300; The degree of branching is 0.83).
Embodiment 13:
Step 1) under the nitrogen protection, adds ethanthiol (3.01 g, 20 mmol) successively in reactor, ethyl acetate (17.62 g, 200 mmol), and triethylamine (1.01 g, 10 mmol), vinylformic acid propynyl ester (2.20 g, 20 mmol) is 30
oC reacted 5 hours down, and reduction vaporization is removed ethyl acetate and triethylamine;
Step 2), under the nitrogen protection, the step 1) products therefrom is dissolved in the 20 mL toluene, adds the temperature-sensitive radical initiator Diisopropyl azodicarboxylate (131.3 mg) of 4 mol%, 65
o C polyreaction 1 hour obtains hyperbranched polymer through methanol extraction, separation, drying.
Embodiment 14:
Step 1) under the nitrogen protection, adds the ethanthiol of 1 mol successively in reactor, the ethyl acetate of 0.1 mol, and the triethylamine of 0.05 mol, the vinylformic acid propynyl ester of 0.9 mol is 10
oC reacted 0.5 hour down, and reduction vaporization is removed ethyl acetate and triethylamine;
Step 2), under the nitrogen protection, the step 1) products therefrom is dissolved in the 0.25 mol benzene; the photosensitive radical initiator st-yrax dme (131.3 mg) that adds 0.5 mol%; by ultraviolet light irradiation, polyreaction 0.5 hour obtains hyperbranched polymer through methanol extraction, separation, drying.
Embodiment 15:
Step 1) under the nitrogen protection, adds the ethanthiol of 1 mol successively in reactor, the ethyl acetate of 0.1 mol, and the triethylamine of 0.05 mol, the vinylformic acid propynyl ester of 0.9 mol is 10
oC reacted 0.5 hour down, and reduction vaporization is removed ethyl acetate and triethylamine;
Step 2), under the nitrogen protection, the step 1) products therefrom is dissolved in the 0.25 mol benzene, adds 2 of 0.5 mol%, 2'-azo two (4-methoxy-2,4-methyl pentane nitrile) is 40
oPolyreaction is 0.5 hour under the C, obtains hyperbranched polymer through methanol extraction, separation, drying.
Embodiment 16:
Step 1) under the nitrogen protection, adds the ethanthiol of 1 mol successively in reactor, 10 mol tetrahydrofuran (THF)s, and the triethylamine of 2 mol (1.01 g, 10 mmol), the vinylformic acid propynyl ester of 1.1 mol is 40
oC reacted 24 hours down, and reduction vaporization is removed ethyl acetate and triethylamine;
Step 2), under the nitrogen protection, with 1) the step products therefrom is dissolved in the 10 mol toluene; the photosensitive radical initiator st-yrax dme that adds 5 mol%; by ultraviolet light irradiation, polyreaction 24 hours obtains hyperbranched polymer through methanol extraction, separation, drying.
Embodiment 17:
Step 1) under the nitrogen protection, adds the ethanthiol of 1 mol successively in reactor, the methylene dichloride of 10 mol, and the triethylamine of 2 mol, the vinylformic acid propynyl ester of 1.1 mol is 40
oC reacted 24 hours down, and reduction vaporization is removed ethyl acetate and triethylamine;
Step 2), under the nitrogen protection, the step 1) products therefrom is dissolved in the 10 mol toluene, adds the temperature-sensitive radical initiator benzoyl peroxide of 5 mol%, 90
oC polyreaction 24 hours obtains hyperbranched polymer through methanol extraction, separation, drying.
Claims (7)
1. the method for a double-click on chemical preparation hyperbranched polymer is characterized in that its step is as follows:
1) under the nitrogen protection, in reactor, add 1 mole two mercaptan compounds successively, 0.1 ~ 10 mole of solvent, 0.05 ~ 2 mol alkali catalyzer, 0.9 ~ 1.1 mole the compound that contains alkynyl and thiazolinyl is in 10
oC ~ 40
oCarried out sulfydryl-alkene addition reaction under the C 0.5 ~ 24 hour, solvent removed by evaporation at reduced pressure;
2) under the nitrogen protection, the step 1) products therefrom is dissolved in 0.25 ~ 10 mole of solvent, adds 0.005 ~ 0.05 mole photosensitive radical initiator or temperature-sensitive radical initiator, by ultraviolet light irradiation or 40
oC ~ 90
oC adds the thermogenesis free radical, carries out sulfydryl-alkynes polyaddition reaction 0.5 ~ 24 hour, obtains hyperbranched polymer through precipitation, separation, drying.
2. the method for a kind of double-click on chemical preparation hyperbranched polymer according to claim 1, it is characterized in that described two mercaptan compounds are selected from 1,4-succinimide mercaptans, 1,6-ethanthiol, 1, hot two mercaptan, 3 of 8-, 6-two oxa-s-1,8-octane two mercaptan, two (2-mercaptoethyl) ether, two (3-thiohydracrylic acid) butyleneglycol, 2,3-dimercapto-1-propyl alcohol or 1, the 4-DTT.
3. the method for a kind of double-click on chemical preparation hyperbranched polymer according to claim 1, it is characterized in that described solvent is selected from water, methyl alcohol, ethanol, Virahol, toluene, benzene, chloroform, methylene dichloride, tetrahydrofuran (THF), diox, hexane, ether, ethyl acetate, N, dinethylformamide, N,N-dimethylacetamide or N-Methyl pyrrolidone.
4. the method for a kind of double-click on chemical preparation hyperbranched polymer according to claim 1 is characterized in that described alkali is selected from sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, potassium tert.-butoxide, triethylamine, Tri-n-Propylamine, tri-n-butylamine, diisopropyl ethyl amine, Tetramethyl Ethylene Diamine or five methyl diethylentriamine.
5. the method for a kind of double-click on chemical preparation hyperbranched polymer according to claim 1 is characterized in that the described compound that contains alkynyl and thiazolinyl is selected from vinylformic acid propynyl ester, ethyl acetylene acrylate, Ba Dousuan propynyl ester, styracin propynyl ester, methacrylic acid propynyl ester, maleic acid list propynyl ester, the single propynyl ester of FUMARIC ACID TECH GRADE, N-proyl acrylamide, N-proyl-Methacrylamide or N-proyl maleinamide.
6. the method for a kind of double-click on chemical preparation hyperbranched polymer according to claim 1 is characterized in that described photosensitive radical initiator is selected from st-yrax dme, 1-hydroxy-cyclohexyl phenyl ketone or methyl benzoylformate.
7. the method for a kind of double-click on chemical preparation hyperbranched polymer according to claim 1, it is characterized in that described temperature-sensitive radical initiator is selected from Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo dicyano valeric acid, azo-bis-iso-dimethyl, 2,2'-azo two (4-methoxy-2,4-methyl pentane nitrile), benzoyl peroxides, Potassium Persulphate or ammonium persulphate.
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