CN101724157B - Synthesis method of macromolecular vesicles with pH response performance under alkaline condition - Google Patents
Synthesis method of macromolecular vesicles with pH response performance under alkaline condition Download PDFInfo
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- 238000001308 synthesis method Methods 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229920001600 hydrophobic polymer Polymers 0.000 claims abstract description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 15
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000001338 self-assembly Methods 0.000 claims abstract description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 98
- 239000008367 deionised water Substances 0.000 claims description 44
- 229910021641 deionized water Inorganic materials 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 125000003368 amide group Chemical group 0.000 claims description 32
- 229920000642 polymer Polymers 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 24
- IRQWEODKXLDORP-UHFFFAOYSA-N 4-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=C)C=C1 IRQWEODKXLDORP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 20
- 239000007795 chemical reaction product Substances 0.000 claims description 18
- 238000000710 polymer precipitation Methods 0.000 claims description 18
- 238000001291 vacuum drying Methods 0.000 claims description 18
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 16
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 claims description 8
- 229960003151 mercaptamine Drugs 0.000 claims description 8
- 239000006184 cosolvent Substances 0.000 claims description 7
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- 238000010189 synthetic method Methods 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 6
- 230000003993 interaction Effects 0.000 abstract description 5
- 239000012046 mixed solvent Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 229920000578 graft copolymer Polymers 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 229920002554 vinyl polymer Polymers 0.000 description 12
- 238000005303 weighing Methods 0.000 description 10
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 4
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 239000000592 Artificial Cell Substances 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
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Abstract
The invention relates to a method for synthesizing a macromolecular vesicle with pH response performance under alkaline conditions, which specifically comprises the steps of taking a hydrophilic macromolecular chain segment taking amino as a terminal group and a hydrophobic macromolecular chain segment with a carboxyl group on a main chain as materials, forming an amphiphilic supermolecule graft polymer by utilizing the interaction of the amino and the carboxyl, and then preparing the macromolecular vesicle by self-assembly in a mixed solvent containing water. The shell layer of the formed macromolecular vesicle is composed of hydrophobic polymers containing carboxyl groups, and the hydrophobic carboxyl groups can be protonated into hydrophilic groups under alkaline conditions, so that the macromolecular vesicle is disintegrated. Therefore, the macromolecular vesicles have pH response performance under alkaline conditions, and the pH response range is 6-9.
Description
Technical field
The present invention relates to a kind of synthetic method that under alkaline condition, has the macromolecular vesicles of pH response performance, specifically be that to utilize with the amido be that the hydrophobic polymer chain section that has carboxylic group on the hydrophilic high mol segment of end group and the main chain is a material, utilize the interaction of amido and carboxyl to form amphiphilic supramolecule graft type polymkeric substance, the self-assembly in aqueous mixed solvent prepares macromolecular vesicles then.
Background technology
In recent years, macromolecular vesicles is in the packing of slow releasing pharmaceutical, the simulation of artificial cell, and there is very big potential using value in fields such as macromolecular coating protection of active bio and pigment carrier.And the macromolecular vesicles with pH response performance has great application prospect especially in medicine sustained release field.At present, macromolecular vesicles mainly is by having the amphiphilic polymer of special block structure, as block polymer (Journal of Polymer Science:Part B:Polymer Physics, 2004,42,923～938) and graftomer (Journal of the American Chemical Society, 2006,128,2168～2169) self-assembly in mixed solvent prepares.Yet block polymer mainly is by anionoid polymerization (Chemical Reviews, 2001 at present, 101,3747～3792), atom transfer radical polymerization (Chemical Reviews, 2001,101,2921～2990), radical transfer radical polymerization (Journal of the American Chemical Society, 1983,105,5706～5708) etc. means realize.These synthesising method reacting condition harshnesses, complex process.And graftomer is synthetic also comparatively complicated, radical reaction (Nature on the end group of certain polymkeric substance of general using (side chain) and another polymkeric substance (main chain), 1995,373,49～52) gained also can form side chain by the group initiated polymerization on the main chain and obtain (Langmuir, 2002,18,8641～8646).The general character of above method all is the different block structure of form connection with covalent linkage.The present invention then utilizes the supramolecule interaction that different blocks is coupled together and obtains the supramolecule graftomer, specifically be that to utilize with the amido be that the hydrophobic polymer chain section that has carboxylic group on the hydrophilic high mol segment of end group and the main chain is a material, utilize the interaction of amido and carboxyl to form amphipathic stem-grafting type polymkeric substance, in aqueous mixed solvent, utilize the self-assembly synthetic macromolecule vesica of above-mentioned supramolecule graftomer then.It is worthy of note that these all polymkeric substance (being the hydrophobic polymer that has carboxylic group on the hydrophilic polymer of end group and the main chain with the amido) obtain by common radical polymerization, need not to use the polymerization means of above-mentioned complexity.Because contain carboxylic group in this vesica, this group can be ionized under alkaline condition, thereby makes vesica have the pH responding ability.
Summary of the invention
The purpose of this invention is to provide a kind of method that under alkaline condition, has the macromolecular vesicles of pH response performance of simply synthesizing.
The synthetic method that has the macromolecular vesicles of pH response performance under alkaline condition of the present invention is divided into two big steps, and the first step is the synthetic polymer presoma, promptly is the hydrophobic polymer that has carboxylic group on the hydrophilic polymer of end group and the main chain with the amido; Second step utilized the self-assembly in solvent of above-mentioned presoma to obtain macromolecular vesicles.
The first step, polymer precursor synthetic.
(1) be hydrophilic polymer synthetic of end group with the amido: get a certain amount of hydrophilic monomer and be dissolved in the dioxane, making the quality percentage composition of hydrophilic monomer in dioxane is between 5～25%; Adding then is the initiator benzoyl peroxide (BPO) of hydrophilic monomer molar content 0.1～5%, and adding is the mercaptoethylamine of hydrophilic monomer molar content 5～15%; Air in 15～40 minutes eliminating reaction vessels of logical rare gas element (as nitrogen), closed reaction vessel is in 60～90 ℃ of reactions 10～24 hours down; After reaction finished, adding was that the sherwood oil of 5～10 times of volumes of above-mentioned reaction product comes out polymer precipitation vacuum-drying.
Described hydrophilic monomer is selected from a kind of in N-N-isopropylacrylamide, N-n-methylolacrylamide, the N-vinyl pyrrolidone or greater than more than one mixture.
(2) have hydrophobic polymer synthetic of carboxylic group on the main chain: get a certain amount of 4-vinyl benzoic acid and be dissolved in the dimethyl sulfoxide (DMSO), adding then is the initiator benzoyl peroxide (BPO) of 4-vinyl benzoic acid molar content 0.1～5%, and wherein the quality percentage composition of 4-vinyl benzoic acid in dimethyl sulfoxide (DMSO) is between 5～25%; Or
The mixture of getting a certain amount of 4-vinyl benzoic acid and other hydrophobic monomer is dissolved in the dimethyl sulfoxide (DMSO), add then is the initiator benzoyl peroxide (BPO) of 4-vinyl benzoic acid and other hydrophobic monomer mixture molar content 0.1～5%, wherein 4-vinyl benzoic acid and other hydrophobic monomer quality percentage composition in dimethyl sulfoxide (DMSO) is between 5～25%, and the mol ratio of other hydrophobic monomer and 4-vinyl benzoic acid is between 1:100～1:1;
Air in 15～40 minutes eliminating reaction vessels of logical rare gas element (as nitrogen), closed reaction vessel is in 60～90 ℃ of reactions 10～24 hours down; After reaction finished, adding was that the deionized water of 5～10 times of volumes of above-mentioned reaction product comes out polymer precipitation vacuum-drying.
Described other hydrophobic monomer is selected from a kind of in vinylbenzene, methyl methacrylate, methyl acrylate, the butyl acrylate.
Second step, utilize the self-assembly in solvent of above-mentioned presoma to obtain macromolecular vesicles, step is as follows:
(1) will be that the hydrophobic polymer that has carboxyl on the hydrophilic polymer of end group and the main chain mixes with the amido, obtaining mixture of polymers, wherein is that the mass ratio that has the hydrophobic polymer of carboxyl on the hydrophilic polymer of end group and the main chain is between 1:5～3:1 with the amido;
(2) in the mixture of polymers that step (1) obtains, add a certain amount of cosolvent, making with the amido is the hydrophobic polymer dissolving that has carboxyl on the hydrophilic polymer of end group and the main chain, and to make the mass concentration of mixture of polymers in cosolvent be between 0.05～6%, and preferred mass concentration is 1%;
(3) in the polymers soln of step (2) preparation, dropwise add deionized water, and vigorous stirring, between 20～90%, and continue to stir 3～8 hours until the volume content of deionized water; Adding in above-mentioned polymers soln then is the deionized water of 5～10 times of its volumes, finally obtains containing the solution of macromolecular vesicles.
Described cosolvent is selected from N, dinethylformamide (DMF), tetrahydrofuran (THF) (THF), a kind of in the dimethyl sulfoxide (DMSO) (DMSO) or greater than more than one mixture.
The macromolecular vesicles of above-mentioned formation is made up of the hydrophobic polymer of carboxyl group owing to its shell, and hydrophobic carboxylic group can be made macromolecular vesicles disintegrate by the protonated hydrophilic radical that becomes under alkaline condition.Thereby above-mentioned macromolecular vesicles has the pH response performance under alkaline condition, and its pH responding range is 6～9.
The present invention compares with traditional method, need not to use the polymerization technique of various complexity.The present invention forms the supramolecule graftomer with the end amido of hydrophilic polymer and the ionic interaction of carboxyl, and self-assembly obtains macromolecular vesicles in aqueous mixed solvent then.And this macromolecular vesicles is because the existence of carboxyl has the pH response performance under alkaline condition.Therefore, the invention provides a kind of simple economy ground and synthesize the scheme that under alkaline condition, has the macromolecular vesicles of pH response performance.
Description of drawings
Fig. 1. be the transmission electron microscope photo of the prepared macromolecular vesicles of embodiment 1.
Fig. 2. be the transmission electron microscope photo of the prepared macromolecular vesicles of embodiment 2.
Fig. 3. be the pH response curve of the prepared macromolecular vesicles of embodiment 2, ordinate is the solution transmitance, and X-coordinate is the pH value.
Embodiment
Embodiment 1.
Getting 11.3g N-N-isopropylacrylamide is dissolved in the 100g dioxane.In system, add BPO0.242g, and add mercaptoethylamine 1.16g.Logical nitrogen is after 20 minutes, and closed reaction vessel reacted 24 hours down in 80 ℃.After reaction finished, adding was that the sherwood oil of 8 times of volumes of above-mentioned reaction product comes out polymer precipitation, and obtaining after the vacuum-drying with the amido is the poly N-isopropyl acrylamide of end group.
Getting the 14.8g4-vinyl benzoic acid is dissolved in the 100g dimethyl sulfoxide (DMSO).In system, add BPO0.242g.Logical nitrogen is after 20 minutes, and closed reaction vessel reacted 15 hours down in 80 ℃.After reaction finished, adding was that the deionized water of 8 times of volumes of above-mentioned reaction product comes out polymer precipitation, obtained poly-4-vinyl benzoic acid after the vacuum-drying.
Take by weighing poly N-isopropyl acrylamide and the poly-4-vinyl benzoic acid of 0.2g that 0.1g is end group with the amido, add 30ml DMSO, make its dissolving.Dropwise add deionized water in above-mentioned DMSO solution, and vigorous stirring,, continue to stir after 3 hours 30% until the volume content of deionized water, adding in above-mentioned polymers soln is the deionized water of 6 times of its volumes.Finally obtain containing the solution of the macromolecular vesicles of the about 200nm of size.Its electromicroscopic photograph as shown in Figure 1.
Embodiment 2.
Getting 11.1g N-vinyl pyrrolidone is dissolved in the 90g dioxane.In system, add BPO0.242g, and add mercaptoethylamine 0.77g.Logical nitrogen is after 20 minutes, and closed reaction vessel reacted 24 hours down in 80 ℃.After reaction finished, adding was that the sherwood oil of 10 times of volumes of above-mentioned reaction product comes out polymer precipitation, and obtaining after the vacuum-drying with the amido is the poly-N-vinyl pyrrolidone of end group.
The hydrophobic polymer that has carboxylic group on the main chain is with embodiment 1.
Take by weighing poly-N-vinyl pyrrolidone and the poly-4-vinyl benzoic acid of 0.3g that 0.1g is end group with the amido, add 40ml DMF, make its dissolving.Dropwise add deionized water in above-mentioned DMF solution, and vigorous stirring,, continue to stir after 3 hours 25% until the volume content of deionized water, adding in above-mentioned polymers soln is the deionized water of 5 times of its volumes.Finally obtain containing the solution of the macromolecular vesicles of the about 300nm of size.Its electromicroscopic photograph as shown in Figure 2, its pH response curve is as shown in Figure 3.
Embodiment 3.
Getting 11.1g N-vinyl pyrrolidone is dissolved in the 210.9g dioxane.In system, add BPO0.0242g, and add mercaptoethylamine 0.385g.Logical nitrogen is after 20 minutes, and closed reaction vessel reacted 24 hours down in 80 ℃.After reaction finished, adding was that the sherwood oil of 5 times of volumes of above-mentioned reaction product comes out polymer precipitation, and obtaining after the vacuum-drying with the amido is the poly-N-vinyl pyrrolidone of end group.
Getting the 14.8g4-vinyl benzoic acid is dissolved in the 281.2g dimethyl sulfoxide (DMSO).In system, add BPO0.0242g.Logical nitrogen is after 20 minutes, and closed reaction vessel reacted 15 hours down in 80 ℃.After reaction finished, adding was that the deionized water of 10 times of volumes of above-mentioned reaction product comes out polymer precipitation, obtained poly-4-vinyl benzoic acid after the vacuum-drying.
Take by weighing poly-N-vinyl pyrrolidone and the poly-4-vinyl benzoic acid of 0.5g that 0.1g is end group with the amido, add 60ml DMF, make its dissolving.Dropwise add deionized water in above-mentioned DMF solution, and vigorous stirring,, continue to stir after 3 hours 25% until the volume content of deionized water, adding in above-mentioned polymers soln is the deionized water of 8 times of its volumes.Finally obtain containing the solution of the macromolecular vesicles of the about 650nm of size.
Embodiment 4.
Getting 11.1g N-vinyl pyrrolidone is dissolved in the 33.3g dioxane.In system, add BPO1.21g, and add mercaptoethylamine 1.38g.Logical nitrogen is after 20 minutes, and closed reaction vessel reacted 24 hours down in 80 ℃.After reaction finished, adding was that the sherwood oil of 10 times of volumes of above-mentioned reaction product comes out polymer precipitation, and obtaining after the vacuum-drying with the amido is the poly-N-vinyl pyrrolidone of end group.
Getting the 14.8g4-vinyl benzoic acid is dissolved in the 44.4g dimethyl sulfoxide (DMSO).In system, add BPO1.21g.Logical nitrogen is after 20 minutes, and closed reaction vessel reacted 16 hours down in 80 ℃.After reaction finished, adding was that the deionized water of 5 times of volumes of above-mentioned reaction product comes out polymer precipitation, obtained poly-4-vinyl benzoic acid after the vacuum-drying.
Take by weighing poly-N-vinyl pyrrolidone and the poly-4-vinyl benzoic acid of 0.15g that 0.45g is end group with the amido, add 60ml DMF, make its dissolving.Dropwise add deionized water in above-mentioned DMF solution, and vigorous stirring,, continue to stir after 3 hours 25% until the volume content of deionized water, adding in above-mentioned polymers soln is the deionized water of 5 times of its volumes.Finally obtain containing the solution of the macromolecular vesicles of the about 60nm of size.
Embodiment 5.
The hydrophilic polymer that with amino is end group is with embodiment 1.
Get the 14.8g4-vinyl benzoic acid and 2.6g vinylbenzene is dissolved in the 100g dimethyl sulfoxide (DMSO).In system, add BPO0.303g.Logical nitrogen is after 20 minutes, and closed reaction vessel reacted 15 hours down in 80 ℃.After reaction finished, adding was that the deionized water of 10 times of volumes of above-mentioned reaction product comes out polymer precipitation, is gathered (4-vinyl benzoic acid-co-vinylbenzene) after the vacuum-drying.
Take by weighing poly N-isopropyl acrylamide and 0.2g poly-(4-vinyl benzoic acid-co-vinylbenzene) that 0.1g is end group with the amido, add 30ml DMF, make its dissolving.Dropwise add deionized water in above-mentioned DMF solution, and vigorous stirring,, continue to stir after 3 hours 40% until the volume content of deionized water, adding in above-mentioned polymers soln is the deionized water of 6 times of its volumes.Finally obtain containing the solution of the macromolecular vesicles of the about 250nm of size.
Embodiment 6.
The hydrophilic polymer that with amino is end group is with embodiment 2.
Get the 14.8g4-vinyl benzoic acid and the 4.26g butyl acrylate is dissolved in the 100g dimethyl sulfoxide (DMSO).In system, add BPO0.323g.Logical nitrogen is after 20 minutes, and closed reaction vessel reacted 15 hours down in 80 ℃.After reaction finished, adding was that the deionized water of 5 times of volumes of above-mentioned reaction product comes out polymer precipitation, is gathered (4-vinyl benzoic acid-co-butyl acrylate) after the vacuum-drying.
Take by weighing poly-N-vinyl pyrrolidone and 0.15g poly-(4-vinyl benzoic acid-co-butyl acrylate) that 0.15g is end group with the amido, add 20ml DMSO, make its dissolving.Dropwise add deionized water in above-mentioned DMSO solution, and vigorous stirring,, continue to stir after 3 hours 20% until the volume content of deionized water, adding in above-mentioned polymers soln is the deionized water of 6 times of its volumes.Finally obtain containing the solution of the macromolecular vesicles of the about 100nm of size.
Embodiment 7.
Getting 10.1g N-n-methylolacrylamide is dissolved in the 80g dioxane.In system, add BPO0.242g, and add mercaptoethylamine 1.16g.Logical nitrogen is after 20 minutes, and closed reaction vessel reacted 24 hours down in 80 ℃.After reaction finished, adding was that the sherwood oil of 10 times of volumes of above-mentioned reaction product comes out polymer precipitation, and obtaining after the vacuum-drying with the amido is the poly-N-n-methylolacrylamide of end group.
Get the 14.8g4-vinyl benzoic acid and the 2.86g methyl acrylate is dissolved in the 100g dimethyl sulfoxide (DMSO).In system, add BPO0.323g.Logical nitrogen is after 20 minutes, and closed reaction vessel reacted 15 hours down in 80 ℃.After reaction finished, adding was that the deionized water of 9 times of volumes of above-mentioned reaction product comes out polymer precipitation, is gathered (4-vinyl benzoic acid-co-methyl acrylate) after the vacuum-drying.
Take by weighing N-n-methylolacrylamide and 0.2g poly-(4-vinyl benzoic acid-co-methyl acrylate) that 0.1g is end group with the amido, add 20ml DMSO, make its dissolving.Dropwise add deionized water in above-mentioned DMSO solution, and vigorous stirring,, continue to stir after 3 hours 20% until the volume content of deionized water, adding in above-mentioned polymers soln is the deionized water of 5 times of its volumes.Finally obtain containing the solution of the macromolecular vesicles of the about 200nm of size.
Embodiment 8.
Get 11.1g N-vinyl pyrrolidone and 3.36g N-n-methylolacrylamide is dissolved in the 100g dioxane.In system, add BPO0.323g, and add mercaptoethylamine 1.03g.Logical nitrogen is after 20 minutes, and closed reaction vessel reacted 24 hours down in 80 ℃.After reaction finished, adding was that the sherwood oil of 9 times of volumes of above-mentioned reaction product comes out polymer precipitation, and obtaining after the vacuum-drying with the amido is poly-(N-vinyl pyrrolidone-co-N-n-methylolacrylamide) of end group.
The hydrophobic polymer that has carboxylic group on the main chain is with embodiment 1.
Taking by weighing 0.15g is poly-(N-vinyl pyrrolidone-co-N-n-methylolacrylamide) and the poly-4-vinyl benzoic acid of 0.15g of end group with the amido, adds 20ml DMSO, makes its dissolving.Dropwise add deionized water in above-mentioned DMSO solution, and vigorous stirring,, continue to stir after 3 hours 20% until the volume content of deionized water, adding in above-mentioned polymers soln is the deionized water of 5 times of its volumes.Finally obtain containing the solution of the macromolecular vesicles of the about 150nm of size.
Embodiment 9.
The hydrophilic polymer that with amino is end group is with embodiment 2.
Get the 14.8g4-vinyl benzoic acid and the 0.128g butyl acrylate is dissolved in the 100g dimethyl sulfoxide (DMSO).In system, add BPO0.323g.Logical nitrogen is after 20 minutes, and closed reaction vessel reacted 16 hours down in 80 ℃.After reaction finished, adding was that the water of 5 times of volumes of above-mentioned reaction product comes out polymer precipitation, is gathered (4-vinyl benzoic acid-co-butyl acrylate) after the vacuum-drying.
Take by weighing poly-N-vinyl pyrrolidone and 0.15g poly-(4-vinyl benzoic acid-co-butyl acrylate) that 0.15g is end group with the amido, add 30ml DMSO, make its dissolving.Dropwise add deionized water in above-mentioned DMSO solution, and vigorous stirring,, continue to stir after 3 hours 20% until the volume content of deionized water, adding in above-mentioned polymers soln is the deionized water of 6 times of its volumes.Finally obtain containing the solution of the macromolecular vesicles of the about 100nm of size.
Embodiment 10.
The hydrophilic polymer that with amino is end group is with embodiment 2.
Get the 14.8g4-vinyl benzoic acid and the 8.6g methyl acrylate is dissolved in the 100g dimethyl sulfoxide (DMSO).In system, add BPO0.323g.Logical nitrogen is after 20 minutes, and closed reaction vessel reacted 16 hours down in 80 ℃.After reaction finished, adding was that the water of 10 times of volumes of above-mentioned reaction product comes out polymer precipitation, is gathered (4-vinyl benzoic acid-co-methyl acrylate) after the vacuum-drying.
Take by weighing poly-N-vinyl pyrrolidone and 0.3g poly-(4-vinyl benzoic acid-co-methyl acrylate) that 0.15g is end group with the amido, add 45ml DMSO, make its dissolving.Dropwise add deionized water in above-mentioned DMSO solution, and vigorous stirring,, continue to stir after 3 hours 20% until the volume content of deionized water, adding in above-mentioned polymers soln is the deionized water of 8 times of its volumes.Finally obtain containing the solution of the macromolecular vesicles of the about 200nm of size.
Claims (4)
1. synthetic method that under alkaline condition, has the macromolecular vesicles of pH response performance, be that the hydrophobic polymer that has carboxylic group on the hydrophilic polymer of end group and the main chain is a presoma with the amido, obtain macromolecular vesicles with the self-assembly in solvent of above-mentioned presoma; It is characterized in that:
(1) be hydrophilic polymer synthetic of end group with the amido: get hydrophilic monomer and be dissolved in the dioxane, making the quality percentage composition of hydrophilic monomer in dioxane is between 5～25%; Adding then is the initiator benzoyl peroxide of hydrophilic monomer molar content 0.1～5%, and adding is the mercaptoethylamine of hydrophilic monomer molar content 5～15%; Logical rare gas element is got rid of the air in the reaction vessel, and closed reaction vessel reacted 10～24 hours down in 60～90 ℃; After reaction finished, adding was that the sherwood oil of 5～10 times of volumes of above-mentioned reaction product comes out polymer precipitation vacuum-drying;
Described hydrophilic monomer is selected from a kind of in N-N-isopropylacrylamide, N hydroxymethyl acrylamide, the N-vinyl pyrrolidone or greater than a kind of mixture;
(2) have hydrophobic polymer synthetic of carboxylic group on the main chain: get the 4-vinyl benzoic acid and be dissolved in the dimethyl sulfoxide (DMSO), adding then is the initiator benzoyl peroxide of 4-vinyl benzoic acid molar content 0.1～5%, wherein the quality percentage composition of 4-vinyl benzoic acid in dimethyl sulfoxide (DMSO) is between 5～25%, or
The mixture of getting 4-vinyl benzoic acid and other hydrophobic monomer is dissolved in the dimethyl sulfoxide (DMSO), add then is the initiator benzoyl peroxide of 4-vinyl benzoic acid and other hydrophobic monomer mixture molar content 0.1～5%, wherein 4-vinyl benzoic acid and other hydrophobic monomer quality percentage composition in dimethyl sulfoxide (DMSO) is between 5～25%, and the mol ratio of other hydrophobic monomer and 4-vinyl benzoic acid is between 1: 100～1: 1;
Logical rare gas element is got rid of the air in the reaction vessel, and closed reaction vessel reacted 10～24 hours down in 60～90 ℃; After reaction finished, adding was that the deionized water of 5～10 times of volumes of above-mentioned reaction product comes out polymer precipitation vacuum-drying;
Described other hydrophobic monomer is selected from a kind of in vinylbenzene, methyl methacrylate, methyl acrylate, the butyl acrylate;
What (3) step (1) is obtained is that the hydrophobic polymer that has carboxyl on the hydrophilic polymer of end group and the main chain that step (2) obtains mixes with the amido, obtaining mixture of polymers, wherein is that the mass ratio that has the hydrophobic polymer of carboxyl on the hydrophilic polymer of end group and the main chain is between 1: 5～3: 1 with the amido;
(4) in the mixture of polymers that step (3) obtains, add cosolvent, making with the amido is the hydrophobic polymer dissolving that has carboxyl on the hydrophilic polymer of end group and the main chain, and to make the mass concentration of mixture of polymers in cosolvent be between 0.05～6%;
(5) in the polymers soln of step (4) preparation, dropwise add deionized water, and vigorous stirring, between 20～90%, and continue to stir 3～8 hours until the volume content of deionized water; Adding in above-mentioned polymers soln then is the deionized water of 5～10 times of its volumes, finally obtains containing the solution of macromolecular vesicles.
2. method according to claim 1 is characterized in that: described macromolecular vesicles has the pH response performance under alkaline condition, and its pH responding range is 6～9.
3. method according to claim 1 is characterized in that: the mass concentration of mixture of polymers in cosolvent is 1%.
4. according to claim 1 or 3 described methods, it is characterized in that: described cosolvent is selected from N, dinethylformamide, tetrahydrofuran (THF), a kind of in the dimethyl sulfoxide (DMSO) or greater than a kind of mixture.
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| Bas G. G. Lohmeijer and Ulrich S. Schubert.Supramolecular Engineering with Macromolecules: An Alternative Concept for Block Copolymers.《Angew. Chem. Int. Ed.》.2002,第41卷(第20期),3825-3829. * |
| Jian Qian and Feipeng Wu.Synthesis of Thermosensitive Hollow Spheres via a One-Pot Process.《Chem. Mater.》.2007,第19卷(第24期),5839-5841. * |
| 郭美琼.pH响应型聚合物囊泡的自组装及功能化.《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》.2008,摘要. * |
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