CN111423534B - Preparation method of enteric-coated drug packaging material polyacrylic resin II - Google Patents
Preparation method of enteric-coated drug packaging material polyacrylic resin II Download PDFInfo
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- CN111423534B CN111423534B CN202010415817.0A CN202010415817A CN111423534B CN 111423534 B CN111423534 B CN 111423534B CN 202010415817 A CN202010415817 A CN 202010415817A CN 111423534 B CN111423534 B CN 111423534B
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- emulsifier
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- methacrylic acid
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- methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
Abstract
The invention provides a preparation method of an enteric-coated drug packaging material polyacrylic resin II, which takes a natural emulsifier and an anionic emulsifier as composite emulsifiers and adopts a normal-temperature semi-continuous emulsion polymerization method under the action of a catalyst. The polyacrylic resin II product obtained by the preparation method has stable indexes, moderate acid value, small fluctuation range and basically constant viscosity, and all indexes meet the requirements of national pharmacopoeia standards.
Description
Technical Field
The invention belongs to the technical field of medicine packaging materials, and particularly relates to a preparation method of an enteric-coated medicine packaging material polyacrylic resin II.
Background
The polyacrylic resin II is prepared from methacrylic acid and methyl methacrylate according to the weight ratio of 1: 1 at a pH of 6.0 or more, and is insoluble in water or ether, soluble in a polar organic solvent, and swellable in acetone. The polyacrylic resin II is insoluble in gastric juice and only soluble in intestinal juice, and is one of enteric coating materials recorded in Chinese pharmacopoeia.
The industrial exploration of the synthetic process of film coating materials of polyacrylate drugs began in the 30 s of the 20 th century and in 1972 for tablet coating. At present, some acrylic resin coating materials produced at home and abroad are produced by bulk polymerization or solution polymerization with an organic solvent as a medium, and then are dispersed by water and the organic solvent is extracted to obtain the acrylic resin coating material. The organic solvent is flammable and explosive when being volatilized, so that not only can serious environmental pollution be caused, but also the prepared organic solution has large viscosity, low concentration and large operation volume, so that the production flow is long, the production cost is high, although the performance is excellent, the comprehensive cost is higher, and the popularization and the application of the organic solvent in the market are restricted.
The preparation of the novel aqueous enteric acrylic resin emulsion, published by "Fine and specialty Chemicals" at volume 15 of 2007, volume 14, of "Sunjiko et al introduces the synthesis of the novel aqueous enteric acrylic resin emulsion with internal plasticization effect by using Methyl Methacrylate (MMA), methacrylic acid (MAA) and Butyl Acrylate (BA) monomers as raw materials, ammonium persulfate as an initiator, a nonionic surfactant OP and an anionic surfactant sodium dodecyl sulfate which are compounded as an emulsifier, and sodium bicarbonate as a pH value buffer, and adopting an emulsion polymerization method. Where a non-food additive surfactant OP is used, the safety of the final product as a pharmaceutical coating is not described for evaluation.
CN101003599(2007-7-25) discloses a polymethacrylic resin emulsion and a preparation method thereof, which are used for drug coating materials. The liquid-state polymethacrylic resin emulsion is prepared from methyl methacrylate, butyl acrylate, sodium dodecyl sulfate, potassium persulfate and purified water as raw materials, but the product cannot be used for enteric coating, and has poor quality, complex preparation method and low production efficiency.
CN103059214 (published by disclaimer 2015-12-23) discloses an enteric pharmaceutical adjuvant polymethacrylate emulsion and a preparation method thereof, wherein an APEO-free double-bond-containing allyl anionic reactive emulsifier and a non-ionic emulsifier are used as a composite emulsification system, methacrylic acid and ethyl acrylate are used as reaction monomers, potassium persulfate or ammonium persulfate is used as an initiator, and a pre-emulsification polymerization process is adopted to prepare the enteric pharmaceutical adjuvant polymethacrylate emulsion. The anionic emulsifier adopted in the preparation process comprises a reactive emulsifier and sodium dodecyl sulfate, and the addition of the reactive emulsifier in the reaction process can cause the emulsion to generate a large amount of foam, which is not beneficial to continuous production and material addition.
Disclosure of Invention
In order to solve the problems existing in the prior art of the preparation process of the existing polyacrylate medicament film coating material, the invention provides a preparation method of an enteric medicament coating material polyacrylic resin II. The technical scheme of the invention is as follows:
a preparation method of an enteric-coated drug packaging material polyacrylic resin II comprises the following raw materials in parts by weight:
monomer (b): 12-15% of methacrylic acid; 12-15% of methyl methacrylate;
initiator: 0.05-0.1% of persulfate;
emulsifier: 0.15-0.25% of anionic emulsifier; 0.5-0.8% of natural emulsifier;
catalyst: 0.1-0.25%;
and the balance: deionized water;
the method mainly comprises the following steps:
(1) putting raw materials of deionized water, an initiator and an emulsifier into a reaction kettle according to the weight ratio, and uniformly stirring;
(2) taking part of methacrylic acid and methacrylic acid methyl, mixing uniformly, adding into a reaction kettle, adding a catalyst while stirring until the mixture is uniformly stirred;
(3) slowly adding the rest methacrylic acid and methacrylic acid methyl into the reaction kettle dropwise, demulsifying after complete reaction at normal temperature, and purifying to obtain the polymethyl methacrylate II.
Further, the initiator is persulfate, and is selected from one or more of ammonium persulfate, potassium persulfate and sodium persulfate; further, the initiator is ammonium persulfate.
Further, the emulsifier is composed of an anionic emulsifier and a natural emulsifier; wherein the anionic emulsifier is sodium dodecyl sulfate, and the natural emulsifier is soybean lecithin.
Further, the catalyst is ethylene glycol titanium.
Further, in the step (1), the stirring speed is 50-100rpm, and the stirring is carried out for 15-20 minutes.
Further, in the step (2), one third of the total amount of methacrylic acid and methyl methacrylate are taken, uniformly mixed and added into a reaction kettle, the catalyst is added while stirring, and after the catalyst is completely added, the stirring is continued for 20 to 30 minutes;
further, in the step (3), the residual methacrylic acid and the residual methyl methacrylate are uniformly mixed and then added into a dropping funnel, the uniform dropping is completed within 2-3 hours, then the reaction is continued for 1 hour at normal temperature, and demulsification and purification are carried out.
Further, in the step (3), the demulsification can be carried out by a conventional manner, such as methanol demulsification; the purification can be carried out by conventional methods, such as precipitation, suction filtration and drying; further, the drying is spray drying or reduced pressure drying.
Compared with the prior art, the invention has the beneficial effects that:
(1) in the invention, a natural emulsifier and an anionic emulsifier are used as a composite emulsifier, a normal-temperature semi-continuous emulsion polymerization method is adopted under the action of a catalyst, no monomer accumulation is generated in the preparation process, the copolymerization composition of the generated polymer is uniform, and the physical and chemical properties of the obtained final product, namely the polyacrylic resin II, meet the requirements of pharmacopoeia standards.
(2) In the invention, the anionic emulsifier sodium dodecyl sulfate and the natural emulsifier soybean lecithin are used as the composite emulsifier, the composite emulsifier does not contain APEO, and the natural emulsifier has high safety and low irritation. Under the action of the catalyst ethylene glycol titanium, the reaction activity of monomer methacrylic acid and methacrylic acid methyl is greatly improved, so that the polymerization reaction can be carried out at normal temperature.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The reagents used in this example are commercially available, in which:
methacrylic acid, available from winning creative degussa specialty chemistry (shanghai) limited, specifications: chemical purity
Methyl methacrylate, available from winning creative degussa specialty chemicals (shanghai) ltd, specifications: chemically pure sodium dodecyl sulfate, available from ninx-system pharmaceutical products, inc, of Hunan, specifications: chemical purity
Ammonium persulfate, purchased from superbard initiator fertilizer combination ltd, specifications: chemical purity
Potassium persulfate, available from superbard initiator fertilizer company, specification: chemical purity
Sodium persulfate, available from Younaide initiator Hefei GmbH, Specification: chemical purity
Soybean lecithin, purchased from Shanxi Xintiandoman Biotechnology Co., Ltd,
titanium glycolate, available from Ziboxiao photoproductive materials Co., Ltd, with the specification: 7 to 10.5 percent.
Example 1
(1) Raw materials: 120g of methacrylic acid; methyl methacrylate 120;
initiator: 0.5g of ammonium persulfate;
emulsifier: 1.5g of sodium dodecyl sulfate; 8g of soybean lecithin;
catalyst: 1g of ethylene glycol titanium;
and the balance: 750g of deionized water;
750g of deionized water, 0.5g of ammonium persulfate and 1.5g of sodium dodecyl sulfate; adding 8g of soybean lecithin into a reaction kettle, stirring for 15 minutes, adding 30g of methacrylic acid and 30g of methyl methacrylate, adding 1g of ethylene glycol titanium while stirring, and continuing to stir for 20 minutes after all the catalyst is added; and uniformly mixing the remaining 90g of methacrylic acid and 90g of methyl methacrylate, transferring the mixture into a dropping funnel, dropwise adding the mixture into a reaction kettle at the speed of 1.5ml/min, continuously reacting at normal temperature for 1 hour after the dropwise adding is finished, adding methanol to demulsify the emulsion, and performing precipitation, suction filtration and vacuum drying to obtain the polyacrylic resin II.
Example 2
(1) Raw materials: 150g of methacrylic acid; methyl methacrylate 150;
initiator: 1.0g of potassium persulfate;
emulsifier: 2.5g of sodium dodecyl sulfate; 5g of soybean lecithin;
catalyst: 1.5g of titanium glycol;
and the balance: 690g of deionized water;
690g of deionized water, 1.0g of potassium persulfate and 2.5g of sodium dodecyl sulfate; adding 5g of soybean lecithin into a reaction kettle, stirring for 20 minutes, adding 50g of methacrylic acid and 50g of methyl methacrylate, adding 1.5g of ethylene glycol titanium while stirring, and continuing to stir for 20 minutes after all the catalyst is added; and uniformly mixing the residual 100g of methacrylic acid and 100g of methyl methacrylate, transferring the mixture into a dropping funnel, dropwise adding the mixture into a reaction kettle at the speed of 1.5ml/min, continuously reacting at normal temperature for 1 hour after the dropwise adding is finished, adding methanol to demulsify the emulsion, and performing precipitation, suction filtration and vacuum drying to obtain the polyacrylic resin II.
Example 3
(1) Raw materials: 135g of methacrylic acid; methyl methacrylate 135;
initiator: 0.8g of sodium persulfate;
emulsifier: 2g of sodium dodecyl sulfate; 6g of soybean lecithin;
catalyst: 2.5g of titanium glycol;
and the balance: 720g of deionized water;
720g of deionized water, 0.8g of sodium persulfate and 2g of sodium dodecyl sulfate; adding 6g of soybean lecithin into a reaction kettle, stirring for 20 minutes, adding 45g of methacrylic acid and 45g of methyl methacrylate, adding 2.5g of ethylene glycol titanium while stirring, and continuing to stir for 20 minutes after all the catalyst is added; and uniformly mixing the remaining 90g of methacrylic acid and 90g of methyl methacrylate, transferring the mixture into a dropping funnel, dropwise adding the mixture into a reaction kettle at the speed of 1.2ml/min, continuously reacting at normal temperature for 1 hour after the dropwise adding is finished, adding methanol to demulsify the emulsion, and performing precipitation, suction filtration and vacuum drying to obtain the polyacrylic resin II.
The polyacrylic acid resin II obtained in the above examples was identified according to the pharmaceutical standards of polyacrylic acid resin II on page 626 of the fourth section of the Chinese pharmacopoeia II 2015 edition. The identification results are shown below:
from the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
1) the product prepared by the preparation method provided by the invention has stable key index indexes, moderate acid value, small fluctuation range and basically constant viscosity, and all indexes meet the requirements of national pharmacopoeia standards.
2) The normal-temperature semi-continuous emulsion polymerization method is adopted under the action of a catalyst, no monomer accumulation is generated in the preparation process, and the generated polymer has uniform copolymerization composition.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A preparation method of an enteric-coated drug packaging material polyacrylic resin II is characterized by comprising the following raw materials in parts by weight:
monomer (b): 12-15% of methacrylic acid; 12-15% of methyl methacrylate;
initiator: 0.05-0.1% of persulfate;
emulsifier: 0.15-0.25% of anionic emulsifier; 0.5-0.8% of natural emulsifier;
catalyst: 0.1-0.25%;
and the balance: deionized water;
the preparation method mainly comprises the following steps:
(1) putting raw materials of deionized water, an initiator and an emulsifier into a reaction kettle according to the weight ratio, and uniformly stirring;
(2) taking part of methacrylic acid and methyl methacrylate, uniformly mixing, adding into a reaction kettle, and adding a catalyst while stirring until the mixture is uniformly stirred;
(3) slowly dropwise adding the rest methacrylic acid and the rest methyl methacrylate into a reaction kettle, performing complete reaction at normal temperature, demulsifying, and purifying to obtain polymethyl methacrylate II;
the anionic emulsifier is sodium dodecyl sulfate, and the natural emulsifier is soybean lecithin;
the catalyst is ethylene glycol titanium;
and (3) uniformly mixing the residual methacrylic acid and methyl methacrylate, adding the mixture into a dropping funnel, finishing dropping at a constant speed within 2-3 hours, continuously reacting at normal temperature for 1 hour, demulsifying and purifying.
2. The preparation method according to claim 1, wherein the initiator is a persulfate selected from one or more of ammonium persulfate, potassium persulfate and sodium persulfate.
3. The production method according to claim 1, wherein in the step (1), the stirring is carried out at a rate of 50 to 100rpm for 15 to 20 minutes.
4. The preparation method according to claim 1, wherein in the step (2), one third of the total amount of the methacrylic acid and the methyl methacrylate are uniformly mixed and added into the reaction kettle, the catalyst is added while stirring, and after the catalyst is completely added, the stirring is continued for 20 to 30 minutes.
5. The method of claim 1, wherein the demulsification in step (3) is performed by adding methanol.
6. The method according to claim 1, wherein in the step (3), the purification comprises precipitation, suction filtration and drying.
7. The method of claim 6, wherein the drying is spray drying.
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| CN202010415817.0A CN111423534B (en) | 2020-05-16 | 2020-05-16 | Preparation method of enteric-coated drug packaging material polyacrylic resin II |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5416157A (en) * | 1993-09-09 | 1995-05-16 | Eastman Chemical Company | Process for improving mechanical shear stability of acrylic enteric polymers |
| CN102432737A (en) * | 2011-09-07 | 2012-05-02 | 张绍国 | Controlled-release enteric acrylic resin latex and preparation method thereof |
| CN102504081A (en) * | 2011-10-21 | 2012-06-20 | 湖州展望药业有限公司 | Preparation method of medicinal methacrylate resin polymer |
| CN109608597A (en) * | 2018-11-22 | 2019-04-12 | 山东同创精细化工股份有限公司 | A kind of high water resistant AKD lotion and preparation method thereof |
-
2020
- 2020-05-16 CN CN202010415817.0A patent/CN111423534B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5416157A (en) * | 1993-09-09 | 1995-05-16 | Eastman Chemical Company | Process for improving mechanical shear stability of acrylic enteric polymers |
| CN102432737A (en) * | 2011-09-07 | 2012-05-02 | 张绍国 | Controlled-release enteric acrylic resin latex and preparation method thereof |
| CN102504081A (en) * | 2011-10-21 | 2012-06-20 | 湖州展望药业有限公司 | Preparation method of medicinal methacrylate resin polymer |
| CN109608597A (en) * | 2018-11-22 | 2019-04-12 | 山东同创精细化工股份有限公司 | A kind of high water resistant AKD lotion and preparation method thereof |
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