CN103214609A - Preparation method of monodisperse rosinyl polymer microsphere - Google Patents
Preparation method of monodisperse rosinyl polymer microsphere Download PDFInfo
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- CN103214609A CN103214609A CN2013101597462A CN201310159746A CN103214609A CN 103214609 A CN103214609 A CN 103214609A CN 2013101597462 A CN2013101597462 A CN 2013101597462A CN 201310159746 A CN201310159746 A CN 201310159746A CN 103214609 A CN103214609 A CN 103214609A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920000642 polymer Polymers 0.000 title abstract description 15
- 239000004005 microsphere Substances 0.000 title abstract description 10
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 22
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 14
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 4
- 239000002270 dispersing agent Substances 0.000 claims abstract description 3
- 239000011347 resin Substances 0.000 claims description 28
- 229920005989 resin Polymers 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 12
- -1 2-acryloxy ethyl Chemical group 0.000 claims description 10
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 claims description 8
- 241000237502 Ostreidae Species 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 235000020636 oyster Nutrition 0.000 claims description 8
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 150000003254 radicals Chemical class 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- 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 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- ZRIHAIZYIMGOAB-UHFFFAOYSA-N butabarbital Chemical compound CCC(C)C1(CC)C(=O)NC(=O)NC1=O ZRIHAIZYIMGOAB-UHFFFAOYSA-N 0.000 claims description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003814 drug Substances 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 5
- 229920006397 acrylic thermoplastic Polymers 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 239000003112 inhibitor Substances 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 abstract 1
- 238000013268 sustained release Methods 0.000 abstract 1
- 239000012730 sustained-release form Substances 0.000 abstract 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 abstract 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 6
- 238000006392 deoxygenation reaction Methods 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000001900 immune effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of monodisperse rosinyl polymer microspheres. The monodisperse rosinyl polymer microspheres are obtained by taking rosin acrylics as monomers and adopting a conventional radical inhibitor and a dispersing agent in a mixed solution of alcohol and water through dispersion copolymerization. The preparation method is simple in process and easy to operate; and the prepared monodisperse rosinyl polymer microspheres are uniform in particle size and are controllable in the range from 0.8 microns to 3.0 microns. Due to adoption of the preparation method, rosins are endowed with wide applications, and the obtained polymer microspheres have good application prospect in the aspect of drug sustained release.
Description
Technical field
The invention belongs to the polymer materials preparation field, relate in particular to a kind of preparation method of single dispersed common resin based high molecular microballoon.
Background technology
Rosin is a kind of renewable natural resource, and its main component is a resinous acid.Have two two the chemical reaction centers of key of carboxyl and C=C in the rosin acid, esterification, Diels-Alder reaction, hydrogenation or oxidizing reaction etc. by these two positions can obtain the rosin deep processed product, also can introduce the monomer of acrylate group by the carboxyl of resinous acid as radical polymerization, further obtain the rosinyl polymkeric substance, be applied to many fields such as coating, medicament slow release material, tackiness agent.
Polymer microsphere be meant diameter at nano level to micron order, be shaped as the macromolecular material or the polymer composite of sphere or other solid.In recent decades, the micron order mono-disperse polymer microspheres has been widely used in various technical fields such as biomedicine, immunological technique, solid phase carrier and high performance liquid chromatography as functional high molecule material.Rosin has biocompatibility and biodegradability, and the polymer microballoon that obtains has a good application prospect at field of medicaments such as medicament slow releases.
Aspect the polymer microballoon technology of preparing, traditional emulsion polymerization can only prepare the polymer microballoon of particle diameter less than 1.0 μ m, and the particle diameter of the polymer microballoon of suspension polymerization preparation is between 100～1000 μ m, and size distribution is wide; Seed emulsion polymerization can prepare the monodisperse polymer micro-sphere of particle diameter at 1.0～100 μ m, but preparation process is loaded down with trivial details, and control is difficult, and the cycle is long.
Summary of the invention
The technical problem to be solved in the present invention provides that a kind of technology is simple, the preparation method of single dispersed common resin based high molecular microballoon of processing ease, product cut size homogeneous and narrowly distributing.
For solving the problems of the technologies described above, the present invention is by the following technical solutions: the preparation method of single dispersed common resin based high molecular microballoon is a monomer with rosin and crylic acid ester class, adopts conventional free radical initiator and dispersion agent, in the mixed solvent of alcohol and water, utilize dispersion copolymerization method to obtain.
Above-mentioned single each raw material of dispersed common resin based high molecular microballoon is pressed following proportioning: rosin and crylic acid esters monomer 0.2～0.8g, initiator amount is 0.20～2.0wt% of monomer consumption, dispersant dosage is 10～60wt% of monomer consumption, mixed solvent 15～35mL of volume ratio of alcohol to water 24:1～15:10.
The preparation method of above-mentioned single dispersed common resin based high molecular microballoon, may further comprise the steps: after material system is mixed, logical nitrogen 20 minutes stirs down at 40 ℃～80 ℃, and reaction obtains the oyster white suspension liquid, centrifugal settling in ultracentrifuge, inclining supernatant liquid, and through ultrasonic cleaning, repeatable operation for several times, microballoon after cleaning is dried to constant weight, promptly.
Rosin and crylic acid ester class is dehydrogenation abietic acid 2-acryloxy ethyl ester, nilox resin 2-acryloxy ethyl ester or rosin 2-acryloxy ethyl ester.
Radical initiator is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or benzoyl peroxide.
Dispersion agent is Polyvinylpyrolidone (PVP), hydroxypropylcellulose or polyvinyl alcohol.
Alcohol is the mixed solvent of methanol, propanol/water or isopropanol with the mixed solvent of water.
Single dispersed common resin based high molecular microspherulite diameter is 0.8～3.0 μ m.
At the problem that present polymer microballoon preparation exists, invention is a starting raw material with rosin, introduces acrylate group through the reaction of carboxyl, prepares single dispersed common resin based high molecular microballoon by dispersion copolymerization method.Technology of the present invention is simple, processing ease, makes single dispersed common resin based high molecular microspheres product uniform particle diameter, and is controlled in 0.8～3.0 mu m range.Use the present invention and can give rosin purposes widely, the gained polymer microsphere has a good application prospect at aspects such as medicament slow releases.
Embodiment
Embodiment 1
In round-bottomed flask, add 0.5g dehydrogenation abietic acid (2-acryloxy ethyl) ester, 25mL isopropanol (20:5), 0.2g Polyvinylpyrolidone (PVP), 0.001g Diisopropyl azodicarboxylate successively, after stirring and dissolving mixes, logical nitrogen 20min deoxygenation.60 ℃ of following mechanical stirring, reaction obtains the oyster white suspension liquid.Centrifugal settling in ultracentrifuge, inclining supernatant liquid, and through ultrasonic cleaning, repeatable operation four times is dried to constant weight with the microballoon after cleaning, and promptly obtains the single dispersed common resin based high molecular of white powder microballoon.
Embodiment 2
In round-bottomed flask, add 0.8g dehydrogenation abietic acid (2-acryloxy ethyl) ester, 25mL isopropanol (20:5), 0.2g Polyvinylpyrolidone (PVP), 0.003g Diisopropyl azodicarboxylate successively, after stirring and dissolving mixes, logical nitrogen 20min deoxygenation.60 ℃ of following mechanical stirring, react about 1.5h system and begin to occur white opacity, become the oyster white suspension liquid at last.Centrifugal settling in ultracentrifuge, inclining supernatant liquid, and through ultrasonic cleaning, repeatable operation four times is dried to constant weight with the microballoon after cleaning, and promptly obtains the single dispersed common resin based high molecular of white powder microballoon.
Embodiment 3
In round-bottomed flask, add 0.5g dehydrogenation abietic acid (2-acryloxy ethyl) ester, 25mL isopropanol (20:5), 0.2g Polyvinylpyrolidone (PVP), 0.003g Diisopropyl azodicarboxylate successively, after stirring and dissolving mixes, logical nitrogen 20min deoxygenation.50 ℃ of following mechanical stirring, react about 1.5h system and begin to occur white opacity, become the oyster white suspension liquid at last.Centrifugal settling in ultracentrifuge, inclining supernatant liquid, and through ultrasonic cleaning, repeatable operation four times is dried to constant weight with the microballoon after cleaning, and promptly obtains the single dispersed common resin based high molecular of white powder microballoon.
Embodiment 4
In round-bottomed flask, add 0.5g dehydrogenation abietic acid (2-acryloxy ethyl) ester, 25mL isopropanol (24:1), 0.2g Polyvinylpyrolidone (PVP), 0.003g Diisopropyl azodicarboxylate successively, after stirring and dissolving mixes, logical nitrogen 20min deoxygenation.60 ℃ of following mechanical stirring, react about 1.5h system and begin to occur white opacity, become the oyster white suspension liquid at last.Centrifugal settling in ultracentrifuge, inclining supernatant liquid, and through ultrasonic cleaning, repeatable operation four times is dried to constant weight with the microballoon after cleaning, and promptly obtains the single dispersed common resin based high molecular of white powder microballoon.
Embodiment 5
In round-bottomed flask, add 0.5g dehydrogenation abietic acid (2-acryloxy ethyl) ester, 25mL isopropanol (20:5), 0.05g Polyvinylpyrolidone (PVP), 0.003g Diisopropyl azodicarboxylate successively, after stirring and dissolving mixes, logical nitrogen 20min deoxygenation.60 ℃ of following mechanical stirring, react about 1.5h system and begin to occur white opacity, become the oyster white suspension liquid at last.Centrifugal settling in ultracentrifuge, inclining supernatant liquid, and through ultrasonic cleaning, repeatable operation four times is dried to constant weight with the microballoon after cleaning, and promptly obtains the single dispersed common resin based high molecular of white powder microballoon.
Embodiment 6
In round-bottomed flask, add 0.5g dehydrogenation abietic acid (2-acryloxy ethyl) ester, 25mL isopropanol (20:5), 0.2g Polyvinylpyrolidone (PVP), 0.005g Diisopropyl azodicarboxylate successively, after stirring and dissolving mixes, logical nitrogen 20min deoxygenation.60 ℃ of following mechanical stirring, react about 1.5h system and begin to occur white opacity, become the oyster white suspension liquid at last.Centrifugal settling in ultracentrifuge, inclining supernatant liquid, and through ultrasonic cleaning, repeatable operation four times is dried to constant weight with the microballoon after cleaning, and promptly obtains the single dispersed common resin based high molecular of white powder microballoon.
Adopt SEM to detect result such as table 1 single dispersed common resin based high molecular microballoon of embodiment 1 to 6.
The single dispersed common resin based high molecular of table 1 microballoon SEM detected result
Claims (8)
1. the preparation method of a single dispersed common resin based high molecular microballoon is characterized in that with rosin and crylic acid ester class be monomer, adopts conventional free radical initiator and dispersion agent, in the mixed solvent of alcohol and water, utilizes dispersion copolymerization method to obtain.
2. the preparation method of single dispersed common resin based high molecular microballoon according to claim 1, it is characterized in that each raw material is by following proportioning: rosin and crylic acid esters monomer 0.2～0.8g, initiator amount is 0.20～2.0wt% of monomer consumption, dispersant dosage is 10～60wt% of monomer consumption, mixed solvent 15～35mL of volume ratio of alcohol to water 24:1～15:10.
3. the preparation method of single dispersed common resin based high molecular microballoon according to claim 2, it is characterized in that may further comprise the steps: after material system is mixed, logical nitrogen 20 minutes stirs down at 40 ℃～80 ℃, and reaction obtains the oyster white suspension liquid, centrifugal settling in ultracentrifuge, inclining supernatant liquid, and through ultrasonic cleaning, repeatable operation for several times, microballoon after cleaning is dried to constant weight, promptly.
4. the preparation method of single dispersed common resin based high molecular microballoon according to claim 1 is characterized in that: described rosin and crylic acid ester class is dehydrogenation abietic acid 2-acryloxy ethyl ester, nilox resin 2-acryloxy ethyl ester or rosin 2-acryloxy ethyl ester.
5. the preparation method of single dispersed common resin based high molecular microballoon according to claim 1 is characterized in that: described radical initiator is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or benzoyl peroxide.
6. the preparation method of single dispersed common resin based high molecular microballoon according to claim 1 is characterized in that: described dispersion agent is Polyvinylpyrolidone (PVP), hydroxypropylcellulose or polyvinyl alcohol.
7. the preparation method of single dispersed common resin based high molecular microballoon according to claim 1 is characterized in that: the mixed solvent of described alcohol and water is the mixed solvent of methanol, propanol/water or isopropanol.
8. the preparation method of single dispersed common resin based high molecular microballoon according to claim 1 is characterized in that: described single dispersed common resin based high molecular microspherulite diameter is 0.8～3.0 μ m.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348422A (en) * | 2015-12-14 | 2016-02-24 | 南京林业大学 | Preparation method of rosinyl acrylamide polymer |
| CN106995681A (en) * | 2017-04-05 | 2017-08-01 | 东莞市佳乾新材料科技有限公司 | A kind of modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer and preparation method thereof |
| CN110668539A (en) * | 2019-09-23 | 2020-01-10 | 麻城市众创科技有限公司 | Stone cutting wastewater settling agent and preparation method and use method thereof |
| CN112280186A (en) * | 2020-11-11 | 2021-01-29 | 广西北海精一电力器材有限责任公司 | Protective layer cushion block for concrete pole and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731698A (en) * | 2012-07-10 | 2012-10-17 | 武汉工程大学 | Method for preparing monodisperse polymer microspheres |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731698A (en) * | 2012-07-10 | 2012-10-17 | 武汉工程大学 | Method for preparing monodisperse polymer microspheres |
Non-Patent Citations (1)
| Title |
|---|
| 曹同玉，刘庆普，胡金生: "《聚合物乳液合成原理性能及应用》", 30 April 1997, article "分散聚合", pages: 402-405 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348422A (en) * | 2015-12-14 | 2016-02-24 | 南京林业大学 | Preparation method of rosinyl acrylamide polymer |
| CN105348422B (en) * | 2015-12-14 | 2017-07-21 | 南京林业大学 | A kind of preparation method of abietyl acrylamide polymer |
| CN106995681A (en) * | 2017-04-05 | 2017-08-01 | 东莞市佳乾新材料科技有限公司 | A kind of modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer and preparation method thereof |
| CN106995681B (en) * | 2017-04-05 | 2018-09-18 | 东莞市佳乾新材料科技有限公司 | A kind of modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer and preparation method thereof |
| CN110668539A (en) * | 2019-09-23 | 2020-01-10 | 麻城市众创科技有限公司 | Stone cutting wastewater settling agent and preparation method and use method thereof |
| CN112280186A (en) * | 2020-11-11 | 2021-01-29 | 广西北海精一电力器材有限责任公司 | Protective layer cushion block for concrete pole and preparation method thereof |
| CN112280186B (en) * | 2020-11-11 | 2024-05-24 | 广西北海精一电力器材有限责任公司 | Protective layer cushion block for concrete pole and preparation method thereof |
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