CN101450991B - Method for preparing temperature and pH double responsiveness hyper branched polymer - Google Patents
Method for preparing temperature and pH double responsiveness hyper branched polymer Download PDFInfo
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- CN101450991B CN101450991B CN200810203444XA CN200810203444A CN101450991B CN 101450991 B CN101450991 B CN 101450991B CN 200810203444X A CN200810203444X A CN 200810203444XA CN 200810203444 A CN200810203444 A CN 200810203444A CN 101450991 B CN101450991 B CN 101450991B
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Abstract
The invention relates to a method for preparing temperature-pH double-responsiveness hyper-branched polymer in the technical field of chemical engineering. The method comprises the following concrete steps: a, water and oxygen of a reaction vessel are removed in the presence of argon; b, mineral-oil suspension of potassium hydride, tetrahydrofuran and extracted mineral oil are sequentially added to the reaction vessel in the presence of argon, and the amount of potassium hydride is calculated; c, dimethyl sulfoxide and triethanol amine are added in the presence of argon and stirred; d, 1,2,7,8-octane diepoxide is added, stirred for reaction and precipitated so as to obtain a crude product; e, the crude product obtained through precipitation is dissolved in methanol, added with hydrochloric acid, stirred and then added with sodium bicarbonate; and f, inorganic salt is removed through filtration, and the product is dialyzed in the methanol so as to obtain the temperature-pH double-responsiveness hyper-branched polymer. As the polymer has a highly branched molecular structure as well as a large number of terminal functional groups and cavities, the polymer can be used in the fields of drug controlled release, gene transfection, memory element switch, sensors and the like.
Description
Technical field
The present invention relates to a kind of hyperbranched polymer of chemical technology field, specifically, that relate to is the preparation method of a kind of temperature and pH double responsiveness hyper branched polymer.
Background technology
Hyperbranched polymer is the highly branched macromole of a class, has features such as unbranched entanglement, spherical appearance, inner lar nanometric cavities and a large amount of functional groups.By the structure of change hyperbranched polymer and the quantity and the type of functional group, can realize control, thereby obtain various functions its solvability, reactivity, surface adsorption, interface self-assembly, chemistry and bio-identification and electrochemistry and optical property etc.
Stimulating responsive polymer is meant self environment to external world, responds such as the slight change of temperature, pH value, electric field, light intensity etc., and a family macromolecule material of reversible volumetric change takes place.Current research to temperature sensitivity and pH responsive polymer mainly concentrates on linear polymer, graftomer and the multipolymer, research to highly-branched polymers with temperature sensitive property or pH responsiveness is less, and the hyperbranched polymer that has temperature and pH double responsiveness does not simultaneously appear in the newspapers as yet.Therefore how can enough commercialization raw materials, adopt simple method to come the highly-branched polymers of preparation temperature and pH double responsiveness, will be highly significant.
Find through literature search prior art, the method for preparing at present stimulating responsive polymer is mainly divided two kinds: a kind of is by the terminal-modified polymkeric substance response characteristic of giving to existing polymkeric substance, on the 2544th to 2550 page of " Macromolecules " (" macromole ") 2004 the 37th phase, delivered " Highly pH and Temperature Responsive MicrogelsFunctionalized with Vinylacetic Acid " (by the height pH of vinylacetic acid functionalization and the microgel of temperature response) as ToddHoare and Robert Pelton, this article author carries out functionalization by the utilization vinylacetic acid to the poly N-isopropyl acrylamide that self has temperature-responsive, and the volume that responsiveness can take place in very narrow pH scope the ionization microgel that obtains changes mutually.Another kind is directly to start with from molecular designing, and the synthetic molecules skeleton has the polymkeric substance of response characteristic.Zhifeng Jia etc. have delivered " Backbone-Thermoresponsive Hyperbranched Polyethers " (hyperbranched polyether of molecular skeleton temperature-responsive) on the 8144th to 8145 page of " Journal of American Chemistry Society " (" JACS ") 2006 the 128th phase, this article author by utilization polyvalent alcohol and epoxy monomer prepared in reaction molecular skeleton possess the hyperbranched polymer of temperature response characteristics.Because the research of hyperbranched polymer still is in the exploratory stage, the hyperbranched polymer that therefore has temperature and pH double responsiveness does not appear in the newspapers so far.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, the preparation method of a kind of temperature and pH double responsiveness hyper branched polymer is provided, by the utilization molecular designing, both had hyperbranched molecular structure, possess the macromolecular material of temperature response and pH response characteristic again simultaneously.
The present invention is achieved by the following technical solutions, the present invention with potassium hydride KH as initiator, nitrogenous polyvalent alcohol and bis-epoxy monomer utilize oxygen anion to cause proton transfer polymerization as raw material, obtain the hyperbranched polymer that molecular skeleton has temperature and pH double responsiveness.
The present invention includes following steps:
Step a: the deoxygenation that dewaters is handled to reaction vessel under argon shield;
Step b: add mineral oil suspension, the tetrahydrofuran (THF) of potassium hydride KH in argon shield downhill reaction container successively, extraction mineral oil is removed the residue tetrahydrofuran (THF), calculates the potassium hydride KH consumption;
Step c: under argon shield, in the solution that step b obtains, add dimethyl sulfoxide (DMSO) and trolamine, stir;
Steps d: add 1,2,7 in the solution that step c obtains, 8-diepoxy octane under agitation reacts, precipitation;
Step e: the crude product that precipitation is obtained is dissolved in the methyl alcohol, adds hydrochloric acid, stirs, and adds sodium bicarbonate then;
Step f: remove by filter inorganic salt, product is dialysed more than 24 hours in methyl alcohol, obtain temperature and pH double responsiveness hyper branched polymer.
Among the step b, the mineral oil suspension of described potassium hydride KH, wherein the potassium hydride KH massfraction is 30%.
Among the step c, described stirring, its time is 30 minutes.
In the steps d, described adding 1,2,7,8-diepoxy octane is meant: add greater than 0 less than 3 times to 1,2,7 of trolamine molar weight, 8-diepoxy octane.
In the steps d, react under the described stirring, its temperature is 40 ℃.
In the steps d, described precipitation is meant product is splashed in acetone and the ether mixed solution that wherein volume ratio is 1/4.
Among the step e, described adding hydrochloric acid is meant the methanol solution that adds hydrochloric acid.
Among the step e, described stirring, its time is 24 hours.
Principle of the present invention is to utilize potassium hydride KH as initiator, by itself and hydroxyl groups effect, generation can be carried out the oxygen anion of chain transfer, thereby cause the nitrogenous polyvalent alcohol and the bis-epoxy monomer that contain great amount of hydroxy group and carry out the hydridization ring-opening polymerization, thereby had the hyperbranched polymer of temperature-responsive and pH responsiveness simultaneously.The highly branched molecular structure of the double responsiveness hyper branched polymer that this reaction obtains can be measured by nuclear magnetic resonance spectrum.The temperature of hyperbranched polymer and pH double responsiveness can be measured by the alternating temperature ultraviolet spectrophotometer.And infrared spectra, gel permeation chromatography, differential scanning calorimetry, thermal weight loss etc. can be used as the assistant analysis means.
Temperature prepared in accordance with the present invention and pH double responsiveness hyper branched polymer, its simple synthetic method, controllability is good, and the raw material commercialization helps mass preparation.This polymkeric substance has good chemical stability and thermostability, and simultaneous temperature responsiveness and pH responsiveness are obvious, suits to be used as advanced materials such as drug loading and controllable release, gene transfection, smart molecule memory switch.The present invention has prepared the hyperbranched polymer of temperature and pH double responsiveness by single step reaction, by design molecular structure, adjusting material rate, not only realized the functionalization of hyperbranched polymer, and its function can adjust according to practical application request, widened the Application Areas of hyperbranched polymer.
Description of drawings
Fig. 1 is the temperature of the present invention's preparation and the nuclear magnetic spectrogram of pH double responsiveness hyper branched polymer;
Wherein: figure a, b, c be corresponding embodiment 1, example 2, the temperature of example 3 preparations and the one dimension nucleus magnetic hydrogen spectrum collection of illustrative plates of pH double responsiveness hyper branched polymer respectively.
Fig. 2 is the temperature of the present invention's preparation and the differential scanning calorimetry figure of pH double responsiveness hyper branched polymer.
Fig. 3 is the temperature of the present invention's preparation and the alternating temperature ultraviolet figure of pH double responsiveness hyper branched polymer.
Fig. 4 is the temperature of the present invention's preparation and the temperature and the pH response relation figure of pH double responsiveness hyper branched polymer.
Fig. 5 is the temperature of the present invention's preparation and the hot weightless picture of pH double responsiveness hyper branched polymer.
Embodiment
Below embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Step a: the deoxygenation that dewaters under argon shield is handled to 100 milliliters Shi Lunke bottles.
Step b: under argon shield; in the Shi Lunke bottle, add the mineral oil suspension (massfraction is 30%) of potassium hydride KH, add tetrahydrofuran (THF) then, extraction mineral oil; carry out three times in bottle no mineral oil exist, and then vacuumize and remove the residue tetrahydrofuran (THF).Calculate the potassium hydride KH consumption, the potassium hydride KH consumption is 0.2572 gram.
Step c: under argon shield, add 40 milliliters of dimethyl sulfoxide (DMSO) and 4.7913 gram trolamines in the Shi Lunke bottle, the sealing bottleneck stirred 30 minutes.
Steps d: add 4.5652 grams 1,2,7,8-diepoxy octane, 40 ℃, react under stirring, product (volume ratio is 1/4) in 500 milliliters acetone mixed solution is precipitated.
Step e: the crude product that precipitation is obtained is dissolved in 50 ml methanol, adds 50 ml methanol solution of 2 milliliters of hydrochloric acid.This solution stirring 24 hours adds sodium bicarbonate then and removes excessive hydrochloric acid.
Step f: remove by filter inorganic salt, then product is dialysed more than 24 hours in methyl alcohol, obtain temperature and pH double responsiveness hyper branched polymer.
Embodiment 2
Step a: the deoxygenation that dewaters under argon shield is handled to 100 milliliters Shi Lunke bottles.
Step b: under argon shield, add the mineral oil suspension (massfraction is 30%) of potassium hydride KH, add tetrahydrofuran (THF) then, extraction mineral oil carries out three no mineral oil existence in bottle, and then vacuumizes and remove the residue tetrahydrofuran (THF).Calculate the potassium hydride KH consumption, the potassium hydride KH consumption is 0.2095 gram.
Step c: under argon shield, add 40 milliliters of dimethyl sulfoxide (DMSO) and 3.8746 gram trolamines in bottle, the sealing bottleneck stirred 30 minutes.
Steps d: add 4.4556 grams 1,2,7,8-diepoxy octane, 40 ℃, react under stirring, product is precipitated in 500 milliliters acetone mixed solution.
Step e: the crude product that precipitation is obtained is dissolved in 50 ml methanol, adds 50 ml methanol solution of 2 milliliters of hydrochloric acid.This solution stirring 24 hours adds sodium bicarbonate then and removes excessive hydrochloric acid.
Step f: remove by filter inorganic salt, then product is dialysed more than 24 hours in methyl alcohol, obtain temperature and pH double responsiveness hyper branched polymer.
Embodiment 3
Step a: the deoxygenation that dewaters under argon shield is handled to 100 milliliters Shi Lunke bottles.
Step b: under argon shield, add the mineral oil suspension (massfraction is 30%) of potassium hydride KH, add tetrahydrofuran (THF) then, extraction mineral oil carries out three no mineral oil existence in bottle, and then vacuumizes and remove the residue tetrahydrofuran (THF).Calculate the potassium hydride KH consumption, the potassium hydride KH consumption is 0.1986 gram.
Step c: under argon shield, add 40 milliliters of dimethyl sulfoxide (DMSO) and 4.4327 gram trolamines, the sealing bottleneck stirred 30 minutes.
Steps d: add 3.5208 grams 1,2,7,8-diepoxy octane, 40 ℃, react under stirring, product is precipitated in 500 milliliters acetone mixed solution.
Step e: the crude product that precipitation is obtained is dissolved in 50 ml methanol, adds 50 ml methanol solution of 2 milliliters of hydrochloric acid then.This solution stirring 24 hours adds sodium bicarbonate then and removes excessive hydrochloric acid.
Step f: remove by filter inorganic salt, then product is dialysed more than 24 hours in methyl alcohol, obtain temperature and pH double responsiveness hyper branched polymer.
Embodiment the results are shown in accompanying drawing:
Fig. 1 a, 1b, 1c be corresponding embodiment 1, example 2, the temperature of example 3 preparations and the one dimension nucleus magnetic hydrogen spectrum collection of illustrative plates of pH double responsiveness hyper branched polymer respectively, wherein 1.2 to 1.4ppm correspondences is reaction monomers 1,2,7, hydrogen atom in the 8-diepoxy octane on the butyl, 3.16ppm corresponding is 1,2,7, hydrogen atom after the open loop of 8-diepoxy octane on the tertiary carbon, 3.47 to 3.53ppm correspondences be respectively the hydrogen atom and 1,2 of ethyl in the trolamine, 7, the hydrogen atom after the open loop of 8-diepoxy octane on the end group.
The temperature of corresponding embodiment 1 preparation of Fig. 2 and the differential scanning calorimetry spectrogram of pH double responsiveness hyper branched polymer.Occurred two-39 ℃ and-19 ℃ respectively among Fig. 2 and significantly changed steps,, illustrated in this polymkeric substance that the segment that two kinds of different chemicals are formed has independent but more approaching second-order transition temperature two glass transition intervals that should polymkeric substance.
The temperature of corresponding embodiment 1 preparation of Fig. 3 and the temperature response characteristics of pH double responsiveness hyper branched polymer.This figure shows that polymkeric substance has the phase sensibility variable in 5 ℃ of scopes, can carry out precise dose response, and does not show different response temperatures simultaneously when the concentration of aqueous solution of polymkeric substance, illustrates that its response characteristic can adjust according to the demand of practical application.
The temperature of corresponding embodiment 1,2,3 preparations of Fig. 4 and the temperature and the pH double responsiveness energy of pH double responsiveness hyper branched polymer.Between the temperature-responsive of polymkeric substance and the residing pH value clear and definite single corresponding relation is arranged,, can design and prepare the material that meets multiple requirement according to requirement of actual application.
The thermogravimetric curve that the temperature of corresponding embodiment 1 preparation of Fig. 5 and pH double-bang firecracker are answered hyperbranched polymer, curve illustrates that weightless less than 3 percent below 400 ℃ this hyperbranched polymer has good thermostability.
Claims (7)
1. the preparation method of temperature and pH double responsiveness hyper branched polymer is characterized in that, may further comprise the steps:
Step a: the deoxygenation that dewaters is handled to reaction vessel under argon shield;
Step b: add mineral oil suspension, the tetrahydrofuran (THF) of potassium hydride KH in argon shield downhill reaction container successively, extraction mineral oil calculates the potassium hydride KH consumption;
Step c: under argon shield, in the solution that step b obtains, add dimethyl sulfoxide (DMSO) and trolamine, stir;
Steps d: add 1,2,7 in the solution that step c obtains, 8-diepoxy octane under agitation reacts, and precipitates after the reaction again; Wherein: 1,2,7,8-diepoxy octane add-on is less than 3 times trolamine molar weight greater than 0;
Step e: the crude product that the steps d precipitation is obtained is dissolved in the methyl alcohol, adds hydrochloric acid, stirs, and adds sodium bicarbonate then;
Step f: remove by filter inorganic salt, product is dialysed more than 24 hours in methyl alcohol, obtain temperature and pH double responsiveness hyper branched polymer.
2. the preparation method of temperature according to claim 1 and pH double responsiveness hyper branched polymer is characterized in that, among the step b, and the mineral oil suspension of described potassium hydride KH, wherein the potassium hydride KH massfraction is 30%.
3. the preparation method of temperature according to claim 1 and pH double responsiveness hyper branched polymer is characterized in that, among the step c, and described stirring, its time is 30 minutes.
4. the preparation method of temperature according to claim 1 and pH double responsiveness hyper branched polymer is characterized in that, in the steps d, describedly under agitation reacts, and its temperature is 40 ℃.
5. the preparation method of temperature according to claim 1 and pH double responsiveness hyper branched polymer is characterized in that, in the steps d, described precipitation is meant product is splashed in acetone and the ether mixed solution that wherein the volume ratio of acetone and ether is 1/4.
6. the preparation method of temperature according to claim 1 and pH double responsiveness hyper branched polymer is characterized in that, among the step e, described adding hydrochloric acid is meant the methanol solution that adds hydrochloric acid.
7. the preparation method of temperature according to claim 1 and pH double responsiveness hyper branched polymer is characterized in that, among the step e, and described stirring, its time is 24 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005073284A2 (en) * | 2004-01-28 | 2005-08-11 | The University Of Sheffield | Hyperbranched polymers |
| CN1718609A (en) * | 2005-08-04 | 2006-01-11 | 上海交通大学 | Temperature sensitive saper branched polyether and its preparation method |
| CN101054442A (en) * | 2007-04-19 | 2007-10-17 | 上海交通大学 | Method of preparing amphiphilic superbranched polyether nano-level self-assembly body |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2005073284A2 (en) * | 2004-01-28 | 2005-08-11 | The University Of Sheffield | Hyperbranched polymers |
| CN1718609A (en) * | 2005-08-04 | 2006-01-11 | 上海交通大学 | Temperature sensitive saper branched polyether and its preparation method |
| CN101054442A (en) * | 2007-04-19 | 2007-10-17 | 上海交通大学 | Method of preparing amphiphilic superbranched polyether nano-level self-assembly body |
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