CN1323840A - Aqueous high molecular film material for medicine coating - Google Patents
Aqueous high molecular film material for medicine coating Download PDFInfo
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- CN1323840A CN1323840A CN 01115057 CN01115057A CN1323840A CN 1323840 A CN1323840 A CN 1323840A CN 01115057 CN01115057 CN 01115057 CN 01115057 A CN01115057 A CN 01115057A CN 1323840 A CN1323840 A CN 1323840A
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- Prior art keywords
- methyl methacrylate
- dimethylaminoethyl methacrylate
- high molecular
- film material
- molecular film
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000576 coating method Methods 0.000 title claims abstract description 17
- 239000011248 coating agent Substances 0.000 title claims abstract description 15
- 239000003814 drug Substances 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 title claims abstract description 12
- 239000002120 nanofilm Substances 0.000 title claims 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000839 emulsion Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract 2
- 239000002904 solvent Substances 0.000 claims abstract 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 238000009413 insulation Methods 0.000 claims 2
- 230000001804 emulsifying effect Effects 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 abstract 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 abstract 2
- 239000002897 polymer film coating Substances 0.000 abstract 1
- 210000002784 stomach Anatomy 0.000 abstract 1
- 229940079593 drug Drugs 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007888 film coating Substances 0.000 description 3
- 238000009501 film coating Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000009495 sugar coating Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 206010013911 Dysgeusia Diseases 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本发明涉及一类甲基丙烯酸甲酯、甲基丙烯酸二甲胺基乙酯共聚物的乳液聚合方法，该共聚物乳液可直接用于胃溶型药物的薄膜包衣。The invention relates to a method for emulsion polymerization of a copolymer of methyl methacrylate and dimethylaminoethyl methacrylate. The copolymer emulsion can be directly used for film coating of stomach-soluble drugs.
药物包衣是目前防止药物受光、热、潮等的影响而变质或掩盖药物不良味道，防止药物有效成分挥发的最主要方法。由于高分子包衣材料可以在药物片剂或胶囊表面形成坚韧的极薄的弹性膜，又能在口服一定时间或一定部位，尤其是在一定pH值下溶解或崩解，已逐渐代替了易吸潮、易破裂而且需较厚的包衣膜的糖衣材料。一般高分子包衣膜的厚度仅为传统包衣膜的1～2％，因此达到所需厚度的衣膜所需时间可大幅度下降，由8～9小时下降至1～2小时。其中，丙烯酸类聚合物是最常用的薄膜包衣材料。Drug coating is currently the most important method to prevent the drug from deteriorating due to the influence of light, heat, tide, etc. or to cover up the bad taste of the drug, and to prevent the active ingredients of the drug from volatilizing. Since polymer coating materials can form a tough and extremely thin elastic film on the surface of pharmaceutical tablets or capsules, and can be dissolved or disintegrated after oral administration for a certain period of time or at a certain part, especially at a certain pH value, it has gradually replaced the easy Sugar-coating material that absorbs moisture, is easy to break and requires a thick coating film. Generally, the thickness of the polymer coating film is only 1-2% of the traditional coating film, so the time required to achieve the required thickness of the coating film can be greatly reduced, from 8-9 hours to 1-2 hours. Among them, acrylic polymers are the most commonly used film coating materials.
目前，市场上有两类胃溶型丙烯酸酯类药物薄膜包衣材料：一是以有机溶剂如乙醇、异丙醇、丙酮等为分散介质的固体聚合物材料，由本体聚合或溶液聚合方法得到，呈粒状或条状。由于在包衣过程中大量采用有机溶剂，聚合过程也采用有机溶剂，环境污染程度很大，已逐渐被淘汰。二是德国Rohm公司生产的水性粉体。其生产工艺为：采用本体聚合法制备出聚合物包衣材料，以一种有机溶剂溶解，然后喷雾干燥得到。该类材料的优点是可以水为分散介质，包衣过程中的环境污染程度小，但也存在生产流程长，生产成本高的缺点，而且其在水中的溶解速度非常慢，需要至少4小时以上，因此包衣成本远远高于传统的糖衣材料，推广应用受到限制。At present, there are two types of gastric-soluble acrylate drug film coating materials on the market: one is a solid polymer material that uses organic solvents such as ethanol, isopropanol, acetone, etc. as a dispersion medium, and is obtained by bulk polymerization or solution polymerization. , in the form of granules or strips. Due to the use of organic solvents in large quantities in the coating process and the use of organic solvents in the polymerization process, the degree of environmental pollution is very large and has been gradually eliminated. The second is the water-based powder produced by the German Rohm company. Its production process is as follows: the polymer coating material is prepared by bulk polymerization, dissolved in an organic solvent, and then spray-dried to obtain. The advantage of this type of material is that water can be used as the dispersion medium, and the degree of environmental pollution during the coating process is small, but it also has the disadvantages of long production process and high production cost, and its dissolution rate in water is very slow, requiring at least 4 hours , so the cost of coating is much higher than that of traditional sugar-coating materials, and its popularization and application are limited.
本发明的技术关键在于聚合工艺，由于共聚单体中水溶性单体甲基丙烯酸二甲氨基乙酯含量高达50％以上，反应初期水溶液中甲基丙烯酸二甲氨基乙酯优先聚合，控制水溶液聚合进行的程度和时间，也就是水溶液中水溶性齐聚物的分子量和浓度决定着乳液聚合的成败，控制合适，该齐聚物将成为后续乳液聚合的辅助乳化剂，便可以制得稳定的乳液。The technical key of the present invention lies in the polymerization process. Since the content of the water-soluble monomer dimethylaminoethyl methacrylate in the comonomer is as high as more than 50%, the dimethylaminoethyl methacrylate in the aqueous solution at the initial stage of the reaction is preferentially polymerized, and the aqueous solution polymerization is controlled. The degree and time of the process, that is, the molecular weight and concentration of the water-soluble oligomer in the aqueous solution determine the success or failure of the emulsion polymerization. If the control is appropriate, the oligomer will become an auxiliary emulsifier for the subsequent emulsion polymerization, and a stable emulsion can be obtained. .
本发明以乳液聚合方法制备水性药物包衣材料-甲基丙烯酸甲酯/甲基丙烯酸二甲胺基乙酯共聚物乳液，该乳液可采用传统的包衣配方直接用于药物包衣。也可用喷雾干燥法制成粉剂，用于水性或油性包衣。本发明甲基丙烯酸甲酯/甲基丙烯酸二甲胺基乙酯共聚物乳液的组份及配比：The invention prepares the water-based drug coating material-methyl methacrylate/dimethylaminoethyl methacrylate copolymer emulsion by the emulsion polymerization method, and the emulsion can be directly used for drug coating by adopting a traditional coating formula. It can also be made into powder by spray drying method for water-based or oil-based coating. Components and proportioning of methyl methacrylate/dimethylaminoethyl methacrylate copolymer emulsion of the present invention:
组份 质量百分比(％)Component Mass % (%)
甲基丙烯酸甲酯 10～15Methyl methacrylate 10～15
甲基丙烯酸二甲胺基乙酯 15～20Dimethylaminoethyl methacrylate 15～20
OP乳化剂 0.1～0.2OP emulsifier 0.1～0.2
十六烷基三甲基溴化铵 0.4～0.6Hexadecyltrimethylammonium bromide 0.4～0.6
过硫酸铵 0.1～0.2Ammonium persulfate 0.1～0.2
碳酸氢钠 0.05～0.1Sodium bicarbonate 0.05～0.1
去离子水 余量Deionized water balance
本发明甲基丙烯酸甲酯/甲基丙烯酸二甲胺基乙酯共聚物乳液的生产工艺：The production technology of methyl methacrylate/dimethylaminoethyl methacrylate copolymer emulsion of the present invention:
将乳化剂OP、十六烷基三甲基溴化铵、碳酸氢钠、甲基丙烯酸甲酯、甲基丙烯酸二甲胺基乙酯与去离子水混合于反应瓶中，升温至80℃，快速搅拌乳化。一次性加入2/3的引发剂过硫酸铵，保温反应1.5～2h，再加入余下的1/3引发剂，保温反应3h以上，冷却出料得到稳定的聚合物乳液。Mix emulsifier OP, cetyltrimethylammonium bromide, sodium bicarbonate, methyl methacrylate, dimethylaminoethyl methacrylate and deionized water in a reaction flask, heat up to 80°C, Stir quickly to emulsify. Add 2/3 of the initiator ammonium persulfate at one time, keep it warm for 1.5-2 hours, then add the remaining 1/3 of the initiator, keep it warm for more than 3 hours, cool and discharge to obtain a stable polymer emulsion.
本发明较传统的生产工艺大大缩短了步骤，一步聚合即可得到；而且不用任何有机溶剂，环境污染程度大大下降。Compared with the traditional production process, the invention greatly shortens the steps, and can be obtained by one-step polymerization; moreover, no organic solvent is used, and the degree of environmental pollution is greatly reduced.
实施例1：Example 1:
将1升反应瓶中加入414.2g去离子水、甲基丙烯酸甲酯90g、甲基丙烯酸二甲胺基乙酯90g、OP乳化剂0.7g、十六烷基三甲基溴化铵2.8g、碳酸氢钠0.7g混合均匀，快速搅拌乳化，升温至80℃，加入0.6g过硫酸铵，反应2h后，加入剩余的0.3g引发剂，保温反应3h，降温出料。所得乳液固含量30％，甲基丙烯酸甲酯/甲基丙烯酸二甲胺基乙酯质量比为1∶1。Add 414.2g of deionized water, 90g of methyl methacrylate, 90g of dimethylaminoethyl methacrylate, 0.7g of OP emulsifier, 2.8g of cetyltrimethylammonium bromide, Mix 0.7g of sodium bicarbonate evenly, quickly stir and emulsify, raise the temperature to 80°C, add 0.6g of ammonium persulfate, react for 2 hours, add the remaining 0.3g of initiator, keep the reaction for 3 hours, cool down and discharge. The solid content of the obtained emulsion was 30%, and the mass ratio of methyl methacrylate/dimethylaminoethyl methacrylate was 1:1.
实施例2：Example 2:
将1升反应瓶中加入414.5g去离子水、甲基丙烯酸甲酯70g、甲基丙烯酸二甲胺基乙酯110g、OP乳化剂0.7g、十六烷基三甲基溴化铵2.8g、碳酸氢钠0.4g混合均匀，快速搅拌乳化，升温至80℃，加入0.6g过硫酸铵，反应2h后，加入剩余的0.3g引发剂，保温反应3h，降温出料。所得乳液固含量30％，甲基丙烯酸甲酯/甲基丙烯酸二甲胺基乙酯质量比为1∶1.57。Add 414.5g of deionized water, 70g of methyl methacrylate, 110g of dimethylaminoethyl methacrylate, 0.7g of OP emulsifier, 2.8g of cetyltrimethylammonium bromide, Mix 0.4g of sodium bicarbonate evenly, quickly stir and emulsify, raise the temperature to 80°C, add 0.6g of ammonium persulfate, react for 2 hours, add the remaining 0.3g of initiator, keep the reaction for 3 hours, cool down and discharge. The solid content of the obtained emulsion was 30%, and the mass ratio of methyl methacrylate/dimethylaminoethyl methacrylate was 1:1.57.
实施例3：Example 3:
将1升反应瓶中加入354.2g去离子水、甲基丙烯酸甲酯93.4g、甲基丙烯酸二甲胺基乙酯146.6g、OP乳化剂0.7g、十六烷基三甲基溴化铵2.8g、碳酸氢钠0.4g混合均匀，快速搅拌乳化，升温至80℃，加入0.8g过硫酸铵，反应2h后，加入剩余的0.4g引发剂，保温反应3h，降温出料。所得乳液固含量40％，甲基丙烯酸甲酯/甲基丙烯酸二甲胺基乙酯质量比为1∶1.57。Add 354.2 g of deionized water, 93.4 g of methyl methacrylate, 146.6 g of dimethylaminoethyl methacrylate, 0.7 g of OP emulsifier, and 2.8 g of cetyltrimethylammonium bromide into a 1-liter reaction flask. g. Mix 0.4g of sodium bicarbonate evenly, quickly stir and emulsify, heat up to 80°C, add 0.8g of ammonium persulfate, react for 2 hours, add the remaining 0.4g of initiator, keep warm for 3 hours, cool down and discharge. The solid content of the obtained emulsion was 40%, and the mass ratio of methyl methacrylate/dimethylaminoethyl methacrylate was 1:1.57.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011150572A CN1152067C (en) | 2001-06-20 | 2001-06-20 | Preparation process of water-based polymer film material for drug coating |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011150572A CN1152067C (en) | 2001-06-20 | 2001-06-20 | Preparation process of water-based polymer film material for drug coating |
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| Publication Number | Publication Date |
|---|---|
| CN1323840A true CN1323840A (en) | 2001-11-28 |
| CN1152067C CN1152067C (en) | 2004-06-02 |
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| CNB011150572A Expired - Fee Related CN1152067C (en) | 2001-06-20 | 2001-06-20 | Preparation process of water-based polymer film material for drug coating |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104650283A (en) * | 2015-02-13 | 2015-05-27 | 温州小伦包衣技术有限公司 | Preparation method and application of medicinal aqueous acrylic resin aqueous dispersion and product produced from medicinal aqueous acrylic resin aqueous dispersion |
| CN106578469A (en) * | 2016-12-16 | 2017-04-26 | 山东阜力康动物营养有限公司 | Rumen by-pass coating product and preparation method thereof |
| CN111410714A (en) * | 2020-05-16 | 2020-07-14 | 连云港万泰医药辅料技术有限公司 | Preparation method of gastric-soluble coating material polyacrylic resin IV |
| US12031128B2 (en) | 2021-04-07 | 2024-07-09 | Battelle Memorial Institute | Rapid design, build, test, and learn technologies for identifying and using non-viral carriers |
| US12109223B2 (en) | 2020-12-03 | 2024-10-08 | Battelle Memorial Institute | Polymer nanoparticle and DNA nanostructure compositions and methods for non-viral delivery |
| US12441996B2 (en) | 2023-12-08 | 2025-10-14 | Battelle Memorial Institute | Use of DNA origami nanostructures for molecular information based data storage systems |
| US12458606B2 (en) | 2023-09-29 | 2025-11-04 | Battelle Memorial Institute | Polymer nanoparticle compositions for in vivo expression of polypeptides |
-
2001
- 2001-06-20 CN CNB011150572A patent/CN1152067C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104650283A (en) * | 2015-02-13 | 2015-05-27 | 温州小伦包衣技术有限公司 | Preparation method and application of medicinal aqueous acrylic resin aqueous dispersion and product produced from medicinal aqueous acrylic resin aqueous dispersion |
| CN106578469A (en) * | 2016-12-16 | 2017-04-26 | 山东阜力康动物营养有限公司 | Rumen by-pass coating product and preparation method thereof |
| CN111410714A (en) * | 2020-05-16 | 2020-07-14 | 连云港万泰医药辅料技术有限公司 | Preparation method of gastric-soluble coating material polyacrylic resin IV |
| US12109223B2 (en) | 2020-12-03 | 2024-10-08 | Battelle Memorial Institute | Polymer nanoparticle and DNA nanostructure compositions and methods for non-viral delivery |
| US12433910B2 (en) | 2020-12-03 | 2025-10-07 | Battelle Memorial Institute | Polymer nanoparticle and DNA nanostructure compositions and methods for non-viral delivery |
| US12031128B2 (en) | 2021-04-07 | 2024-07-09 | Battelle Memorial Institute | Rapid design, build, test, and learn technologies for identifying and using non-viral carriers |
| US12458606B2 (en) | 2023-09-29 | 2025-11-04 | Battelle Memorial Institute | Polymer nanoparticle compositions for in vivo expression of polypeptides |
| US12441996B2 (en) | 2023-12-08 | 2025-10-14 | Battelle Memorial Institute | Use of DNA origami nanostructures for molecular information based data storage systems |
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| CN1152067C (en) | 2004-06-02 |
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