CN103214609B - The preparation method of monodisperse rosinyl polymer microsphere - Google Patents
The preparation method of monodisperse rosinyl polymer microsphere Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 37
- 239000004005 microsphere Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 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 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 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 15
- 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 15
- 150000002148 esters Chemical class 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000012046 mixed solvent Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 4
- 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
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 claims description 8
- 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
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000006356 dehydrogenation reaction Methods 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
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 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
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 239000012467 final product Substances 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
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000003814 drug Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 8
- -1 2-acryloyl-oxyethyl Chemical group 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 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000005698 Diels-Alder reaction Methods 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
- 229940079593 drug Drugs 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
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- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses a kind of preparation method of monodisperse rosinyl polymer microsphere, with rosin and crylic acid ester class for monomer, adopt conventional radical initiators and dispersion agent, in the mixed solvent of alcohol and water, utilize dispersion copolymerization method to obtain.Present invention process is simple, processing ease, and obtained monodisperse rosinyl polymer microsphere product cut size is homogeneous, controlled within the scope of 0.8 ~ 3.0 μm.Application the present invention can give rosin purposes widely, and gained polymer microsphere has a good application prospect in medicament slow release etc.
Description
Technical field
The invention belongs to polymer materials preparation field, particularly relate to a kind of preparation method of monodisperse rosinyl polymer microsphere.
Background technology
Rosin is a kind of renewable natural resource, and its main component is resinous acid.There are in rosin acid carboxyl and C=C double bond two chemical reaction centers, rosin deep processed product can be obtained by the esterification at these two positions, Diels-Alder reaction, hydrogenation or oxidizing reaction etc., carboxyl also by resinous acid introduces the monomer that acrylate group is used as radical polymerization, obtain rosinyl polymkeric substance further, be applied to many fields such as coating, Thermosensitive Material Used for Controlled Releasing of Medicine, tackiness agent.
Polymer microsphere refers to diameter at nano level to micron order, and shape is spherical or the macromolecular material of other solid or polymer composite.In recent decades, micron size polymer microsphere has been widely used in the 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 obtained has a good application prospect at field of medicaments such as medicament slow releases.
In polymer microballoon technology of preparing, traditional emulsion polymerization can only prepare the polymer microballoon that particle diameter is less than 1.0 μm, and the particle diameter of polymer microballoon prepared by suspension polymerization is between 100 ~ 1000 μm, and size distribution is wide; Seed emulsion polymerization can prepare particle diameter at the monodisperse polymer micro-sphere of 1.0 ~ 100 μm, but preparation process is loaded down with trivial details, and it is difficult to control, and the cycle is long.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of technique is simple, processing ease, product cut size are homogeneous and the preparation method of the monodisperse rosinyl polymer microsphere of narrowly distributing.
For solving the problems of the technologies described above, the present invention is by the following technical solutions: the preparation method of monodisperse rosinyl polymer microsphere, with rosin and crylic acid ester class for monomer, adopts conventional radical initiators and dispersion agent, in the mixed solvent of alcohol and water, dispersion copolymerization method is utilized to obtain.
The each raw material of above-mentioned monodisperse rosinyl polymer microsphere is according to the following ratio: 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, the mixed solvent 15 ~ 35mL of volume ratio of alcohol to water 24:1 ~ 15:10.
The preparation method of above-mentioned monodisperse rosinyl polymer microsphere, comprise the following steps: after material system is mixed, logical nitrogen 20 minutes, stirs, is obtained by reacting oyster white suspension liquid at 40 DEG C ~ 80 DEG C, centrifugal settling in ultracentrifuge, incline and supernatant liquid, through ultrasonic cleaning, repeatable operation for several times, microballoon after cleaning is dried to constant weight, obtains final product.
Rosin and crylic acid ester class is dehydrogenation abietic acid 2-acryloyloxyethyl isocyanate, nilox resin 2-acryloyloxyethyl isocyanate or rosin 2-acryloyloxyethyl isocyanate.
Radical initiator is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or benzoyl peroxide.
Dispersion agent is Polyvinylpyrolidone (PVP), hydroxypropylcellulose or polyvinyl alcohol.
The mixed solvent of alcohol and water is the mixed solvent of methanol/water, propanol/water or isopropanol/water.
Monodisperse rosinyl polymer microsphere particle diameter is 0.8 ~ 3.0 μm.
Prepare Problems existing for current polymer microballoon, inventing with rosin is starting raw material, and acrylate group is introduced in the reaction through carboxyl, prepares monodisperse rosinyl polymer microsphere by dispersion copolymerization method.Present invention process is simple, processing ease, and obtained monodisperse rosinyl polymer microsphere product cut size is homogeneous, controlled within the scope of 0.8 ~ 3.0 μm.Application the present invention can give rosin purposes widely, and gained polymer microsphere has a good application prospect in medicament slow release etc.
Embodiment
Embodiment 1
0.5g dehydrogenation abietic acid (2-acryloyl-oxyethyl) ester, 25mL isopropanol/water (20:5), 0.2g Polyvinylpyrolidone (PVP), 0.001g Diisopropyl azodicarboxylate is added successively in round-bottomed flask, after stirring and dissolving mixes, logical nitrogen 20min deoxygenation.Mechanical stirring at 60 DEG C, is obtained by reacting oyster white suspension liquid.Centrifugal settling in ultracentrifuge, inclines and supernatant liquid, and through ultrasonic cleaning, repeatable operation four times, is dried to constant weight by the microballoon after cleaning, namely obtains white powder monodisperse rosinyl polymer microsphere.
Embodiment 2
0.8g dehydrogenation abietic acid (2-acryloyl-oxyethyl) ester, 25mL isopropanol/water (20:5), 0.2g Polyvinylpyrolidone (PVP), 0.003g Diisopropyl azodicarboxylate is added successively in round-bottomed flask, after stirring and dissolving mixes, logical nitrogen 20min deoxygenation.Mechanical stirring at 60 DEG C, reaction is carried out about 1.5h system and is started to occur white opacity, finally becomes oyster white suspension liquid.Centrifugal settling in ultracentrifuge, inclines and supernatant liquid, and through ultrasonic cleaning, repeatable operation four times, is dried to constant weight by the microballoon after cleaning, namely obtains white powder monodisperse rosinyl polymer microsphere.
Embodiment 3
0.5g dehydrogenation abietic acid (2-acryloyl-oxyethyl) ester, 25mL isopropanol/water (20:5), 0.2g Polyvinylpyrolidone (PVP), 0.003g Diisopropyl azodicarboxylate is added successively in round-bottomed flask, after stirring and dissolving mixes, logical nitrogen 20min deoxygenation.Mechanical stirring at 50 DEG C, reaction is carried out about 1.5h system and is started to occur white opacity, finally becomes oyster white suspension liquid.Centrifugal settling in ultracentrifuge, inclines and supernatant liquid, and through ultrasonic cleaning, repeatable operation four times, is dried to constant weight by the microballoon after cleaning, namely obtains white powder monodisperse rosinyl polymer microsphere.
Embodiment 4
0.5g dehydrogenation abietic acid (2-acryloyl-oxyethyl) ester, 25mL isopropanol/water (24:1), 0.2g Polyvinylpyrolidone (PVP), 0.003g Diisopropyl azodicarboxylate is added successively in round-bottomed flask, after stirring and dissolving mixes, logical nitrogen 20min deoxygenation.Mechanical stirring at 60 DEG C, reaction is carried out about 1.5h system and is started to occur white opacity, finally becomes oyster white suspension liquid.Centrifugal settling in ultracentrifuge, inclines and supernatant liquid, and through ultrasonic cleaning, repeatable operation four times, is dried to constant weight by the microballoon after cleaning, namely obtains white powder monodisperse rosinyl polymer microsphere.
Embodiment 5
0.5g dehydrogenation abietic acid (2-acryloyl-oxyethyl) ester, 25mL isopropanol/water (20:5), 0.05g Polyvinylpyrolidone (PVP), 0.003g Diisopropyl azodicarboxylate is added successively in round-bottomed flask, after stirring and dissolving mixes, logical nitrogen 20min deoxygenation.Mechanical stirring at 60 DEG C, reaction is carried out about 1.5h system and is started to occur white opacity, finally becomes oyster white suspension liquid.Centrifugal settling in ultracentrifuge, inclines and supernatant liquid, and through ultrasonic cleaning, repeatable operation four times, is dried to constant weight by the microballoon after cleaning, namely obtains white powder monodisperse rosinyl polymer microsphere.
Embodiment 6
0.5g dehydrogenation abietic acid (2-acryloyl-oxyethyl) ester, 25mL isopropanol/water (20:5), 0.2g Polyvinylpyrolidone (PVP), 0.005g Diisopropyl azodicarboxylate is added successively in round-bottomed flask, after stirring and dissolving mixes, logical nitrogen 20min deoxygenation.Mechanical stirring at 60 DEG C, reaction is carried out about 1.5h system and is started to occur white opacity, finally becomes oyster white suspension liquid.Centrifugal settling in ultracentrifuge, inclines and supernatant liquid, and through ultrasonic cleaning, repeatable operation four times, is dried to constant weight by the microballoon after cleaning, namely obtains white powder monodisperse rosinyl polymer microsphere.
Adopt SEM to detect the monodisperse rosinyl polymer microsphere of embodiment 1 to 6, result is as table 1.
Table 1 monodisperse rosinyl polymer microsphere SEM detected result
Claims (5)
1. a preparation method for monodisperse rosinyl polymer microsphere, is characterized in that with rosin and crylic acid ester class for monomer, adopts conventional radical initiators and dispersion agent, in the mixed solvent of alcohol and water, utilizes dispersion copolymerization method to obtain; Each raw material is according to the following ratio: rosin and crylic acid esters monomer 0.2 ~ 0.8g, and initiator amount is 0.20 ~ 2.0wt% of monomer consumption, and dispersant dosage is 10 ~ 60wt% of monomer consumption, the mixed solvent 15 ~ 35mL of volume ratio of alcohol to water 24:1 ~ 15:10; This method comprises the following steps: after being mixed by material system, logical nitrogen 20 minutes, stir at 40 DEG C ~ 80 DEG C, be obtained by reacting oyster white suspension liquid, centrifugal settling in ultracentrifuge, inclines and supernatant liquid, through ultrasonic cleaning, microballoon after cleaning for several times, is dried to constant weight, obtains final product by repeatable operation; Described rosin and crylic acid ester class is dehydrogenation abietic acid 2-acryloyloxyethyl isocyanate, nilox resin 2-acryloyloxyethyl isocyanate or rosin 2-acryloyloxyethyl isocyanate.
2. the preparation method of monodisperse rosinyl polymer microsphere according to claim 1, is characterized in that: described radical initiator is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or benzoyl peroxide.
3. the preparation method of monodisperse rosinyl polymer microsphere according to claim 1, is characterized in that: described dispersion agent is Polyvinylpyrolidone (PVP), hydroxypropylcellulose or polyvinyl alcohol.
4. the preparation method of monodisperse rosinyl polymer microsphere according to claim 1, is characterized in that: the mixed solvent of described alcohol and water is the mixed solvent of methanol/water, propanol/water or isopropanol/water.
5. the preparation method of monodisperse rosinyl polymer microsphere according to claim 1, is characterized in that: described monodisperse rosinyl polymer microsphere particle diameter is 0.8 ~ 3.0 μm.
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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 |
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