CN107722168A - A kind of preparation method of the medicinal EUDRAGIT aqueous copolymer dispersion of middle osmotic sustained release of low monomer residue - Google Patents
A kind of preparation method of the medicinal EUDRAGIT aqueous copolymer dispersion of middle osmotic sustained release of low monomer residue Download PDFInfo
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- CN107722168A CN107722168A CN201710977195.9A CN201710977195A CN107722168A CN 107722168 A CN107722168 A CN 107722168A CN 201710977195 A CN201710977195 A CN 201710977195A CN 107722168 A CN107722168 A CN 107722168A
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- monomer residue
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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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- 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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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/10—Dispersions; Emulsions
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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
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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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
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- Chemical & Material Sciences (AREA)
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- Polymers & Plastics (AREA)
- Pharmacology & Pharmacy (AREA)
- Animal Behavior & Ethology (AREA)
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Abstract
The invention discloses a kind of preparation method of the medicinal EUDRAGIT aqueous copolymer dispersion of the middle osmotic sustained release of low monomer residue, and it is made up of the raw material of following weight parts：Ethyl acrylate 90 110, methyl methacrylate 45 65, potassium peroxydisulfate or ammonium persulfate 0.2 1.2, neopelex or lauryl sodium sulfate 15, N oleoyls amino acid sodium 0.1 0.5, APES（OP‑10）0.25 1.5, purified water 320 410.Its process of preparing is the emulsion polymerization technique for raising temperature activated implode in the later stage, and process is simple；Monomer residue≤0.01% of gained aqueous dispersion（w/w）, plasticity is good, need not add plasticizer and easy film forming.
Description
Technical field
The invention mainly relates to a kind of medicinal ethyl acrylate-methyl methacrylate of the middle osmotic sustained release of low monomer residue
The preparation method of aqueous copolymer dispersion, belong to pharmaceutical polymerses field.
Background technology
At present, many medicines need that the sustained release preparation that rate of releasing drug is not influenceed by pipe intestinal digesting liquid is made, and the country uses
Thermosensitive Material Used for Controlled Releasing of Medicine be to use high viscosity（15×104cp）Hydroxypropyl methylcellulose be added to tabletting in medicine as framework material,
Reach the purpose slowly discharged using its gelation；Or answered with acrylic acid resinⅡ or No. III and hydroxypropyl methylcellulose
Match somebody with somebody, add part other materials, be coated after being configured to ethanol dissolving.It is molten with acrylic acid resinⅡ or No. III ethanol prepared
Liquid is coated.Its shortcoming is：Unstable product quality, cost is high, inflammable, explosive.This technique is in western developed countries such as America and Europes
Eliminated substantially in last century end then using polyacrylic resin aqueous dispersion as coating auxiliary material.
EUDRAGIT NE 30 D aqueous dispersion be novel polypropylene acid resin aqueous dispersion it
One, key property be the particle diameter of dispersion particle between 10-1000nm, aqueous dispersion outward appearance is in emulsus, also known as latax.This
A little particles are stablized due to thermal convection current and Brownian movement, and storage process will not precipitate；Another characteristic is solids content height [28 ~ 30%
（w/w）], evaporation power consumption is low, and viscosity is low, is easy to spray coating process, and coating efficiency is higher.In film forming procedure, latex particle shape
Into accumulation horizon, with moisture evaporation, surface tension increase, make micelle tight clusters, formed in MFT environment above
Film.The water resistant permeability of this film is better than the film formed with organic solvent coating solution, and avoids very big using organic solvent
Ground reduces the danger of fire alarm and blast.The performance of this kind of aqueous dispersion, safety and cost advantage are obvious.
Used as pharmaceutic adjuvant, in addition to molecular size range and chemical constitution, it is desirable to which acrylate monomer residual does not surpass
0.01% is crossed, Typical Representative is that the moisture of the EUDRAGIT NE 30 D of German Ying Chuan companies production dissipates especially
Special strange NE30D, the synthesis technique that pertinent literature provides are：Using the water added with proper amount of surfactant APES as
Decentralized medium, trigger ethyl acrylate and methyl methacrylate monomer with potassium peroxydisulfate（Mass ratio 2:1）Free radical is carried out to be total to
The aqueous dispersion of solid content about 30% is made in poly- reaction synthesis.Jain Mukul etc. [Eur. Polym. J., 2002,38:
735] it is decentralized medium with the water added with appropriate anionic, propylene is triggered to free radical
Acetoacetic ester and methyl methacrylate emulsion polymerization have carried out system research, and the copolymerization that maximum weight average molecular weight is 54.8 ten thousand is made
Thing, and point out that the increase of amount of initiator is advantageous to conversion ratio raising, the increase for emulsifying dosage is advantageous to the increasing of latax stability
Greatly.Guan Jie [synthesis of methyl methacrylate ethyl acrylate copolymer and sign, Zhejiang University's master thesis,
2006.5] APES is used（OP-10）The water dispersion medium of structure, with potassium peroxydisulfate trigger ethyl acrylate and
Methyl methacrylate monomer carries out free radicals copolymerization reaction acrylic acid synthesizing ethyl ester-methylmethacrylate copolymer moisture and dissipated
Body, conversion ratio are difficult to close to 100%.But how to solve level of residual monomers is that pertinent literature is NM.
Because the boiling point of water is lower than ethyl acrylate and methyl methacrylate, it is difficult to pass through（Decompression）The method of distillation
Residual monomer is removed from aqueous dispersion.
The content of the invention
The object of the invention is exactly in order to solve the defects of prior art, using polymerization later stage rise reaction temperature（90-100
℃）The emulsion polymerization technique technology of implode is excited, monomer residue is reduced to 0.01% and less, quality meets medicinal requirements.This
Invention is achieved through the following technical solutions：
A kind of system of the medicinal EUDRAGIT NE 30 D aqueous dispersion of middle osmotic sustained release of low monomer residue
Preparation Method, it is made up of the raw material of following weight parts：
Ethyl acrylate 90-110, methyl methacrylate 45-65, potassium peroxydisulfate or ammonium persulfate 0.2-1.2, detergent alkylate
Sodium sulfonate or lauryl sodium sulfate 1-5, N- oleoyl amino acid sodium 0.1-1, APES（OP-10）0.25-
1.5th, purified water 320-410.
Heated up using the later stage（90-100℃）Implode is excited to prepare EUDRAGIT NE 30 D
The emulsion polymerization technique operating procedure of aqueous dispersion is as follows：
（1）By described weight proportion by raw material propylene acetoacetic ester, methyl methacrylate, APES（OP-
10）, neopelex or lauryl sodium sulfate, N- oleoyl amino acid sodiums put into retort, agitating and heating
It is warming up to 70-80 DEG C of emulsification；
（2）Under agitation, the initiator potassium persulfate or ammonium persulfate solution that are dissolved with purified water are added drop-wise in retort, dripped
Add 1-3h, retort temperature is maintained at 70-80 DEG C；
（3）After completion of dropwise addition, it is rapidly heated and excites implode to react to 90-100 DEG C, continues after reacting 1-2h, naturally cool to room
Temperature, produce the finished product that monomer residue is less than 0.01%.
Wherein, emulsifying agent used is APES（OP-10）, neopelex or dodecyl sulphur
The ternary complex of sour sodium and N- oleoyl amino acid sodium.
It is that ethyl acrylate and methyl methacrylate mix total monomer conversion that later stage heating, which excites the starting point of implode,
Rate reaches 60-90% and is defined, preferably 70-80%.
It is an advantage of the invention that：
Using ethyl acrylate, methyl methacrylate as raw material, using potassium peroxydisulfate or ammonium persulfate as initiator, gathered with alkyl phenol
Oxygen vinethene（OP-10）, neopelex or the tri compound of lauryl sodium sulfate and N- oleoyl amino acid sodiums
Thing is emulsifying agent, by first stirring and emulsifying, initiation reaction, then is rapidly heated and excites implode to react, and is made the third of low monomer residue
Olefin(e) acid ethyl ester-methylmethacrylate copolymer aqueous dispersion；It is the emulsion polymerization that solvent is carried out with water, entirely produced
Cheng Buyong organic solvents；Later stage uses the emulsion polymerization technique of rise temperature activated implode, the polymerization process being consequently formed
Flow is simple, production efficiency is high, production process safety, almost three-waste free discharge；The monomer residue of gained aqueous dispersion is low≤
0.01%（w/w）, without the lock out operation of removing residual monomer, plasticity is good, need not add plasticizer and easy film forming.
Embodiment
Embodiment 1
A kind of system of the medicinal EUDRAGIT NE 30 D aqueous dispersion of middle osmotic sustained release of low monomer residue
Preparation Method, it is to be prepared from the following raw materials in parts by weight：Ethyl acrylate 105, methyl methacrylate 55, purified water 390,
Potassium peroxydisulfate or ammonium persulfate 0.9, neopelex 2, N- oleoyls amino acid sodium 0.75, APES
（OP-10）0.25.
Its recipe step is as follows：
（1）By described weight proportion by raw material propylene acetoacetic ester, methyl methacrylate, purified water, alkylphenol-polyethenoxy
Ether（OP-10）, neopelex and N- oleoyl amino acid sodiums put into retort；
（2）Under agitation, the potassium peroxydisulfate or ammonium persulfate solution that are dissolved with purified water are added drop-wise in retort, 2h is dripped
Finish, retort temperature is maintained at 70-80 DEG C during dropwise addition；
（3）After dripping off, conversion ratio 84.5%；Then it is rapidly heated in 15min and excites implode to 89-91 DEG C, reacts 2h, it is naturally cold
But to room temperature, the milky aqueous dispersion of monomer residue total amount 0.009% is obtained.
Embodiment 2
A kind of system of the medicinal EUDRAGIT NE 30 D aqueous dispersion of middle osmotic sustained release of low monomer residue
Preparation Method, it is to be prepared from the following raw materials in parts by weight：Ethyl acrylate 95, methyl methacrylate 55, purified water 350,
Potassium peroxydisulfate or ammonium persulfate 0.9, lauryl sodium sulfate 1.5, N- oleoyls amino acid sodium 1.0, APES
（OP-10）0.5.
Its recipe step is as follows：
（1）By described weight proportion by raw material propylene acetoacetic ester, methyl methacrylate, purified water, alkylphenol-polyethenoxy
Ether（OP-10）, lauryl sodium sulfate and N- oleoyl amino acid sodiums put into retort, be heated with stirring to 79-81 DEG C of breast
Change；
（2）Under agitation, the potassium peroxydisulfate or ammonium persulfate solution that are dissolved with purified water are added drop-wise in retort, 2h is dripped
Finish, retort temperature is maintained at 70-80 DEG C during dropwise addition；
（3）Rear monomer conversion 76% is dripped off, in being rapidly heated in 15min to 96-98 DEG C, is continued after reacting 1.5h, natural cooling
To room temperature, the milky aqueous dispersion of monomer residue total amount 0.0081% is obtained.
Using reference example 1
It will be equivalent to the talcum powder and proper quantity of defoaming agent of polymer 75%（Methyl-silicone oil）It is added in a small amount of water, with high speed point
Scattered homogenizer homogenizes 5min, the EUDRAGIT NE 30 D that this suspension is slowly prepared with embodiment 1
Aqueous dispersion mixes and is diluted with water into solid content 15% (w/w) coating solution.Piece is taken to weigh about 250g chloride containing potassium 0.5mg piece
Core is placed in ordinary coating pot, and rotation is preheated to 30 DEG C or so hydrojet coatings, coating weight gain to about 16%（w/w）, pot rotation
Coated tablet is taken out after 15min, is placed in 38-40 DEG C of baking oven and dries 24h.Coating membrane is uniform, glossy, sustained release tablets it is external
Release releases the drug by zero mode, and is hardly influenceed by film exosmosis pressure.
Claims (5)
1. a kind of medicinal EUDRAGIT NE 30 D aqueous dispersion of the middle osmotic sustained release of low monomer residue
Preparation method：By raw material propylene acetoacetic ester, methyl methacrylate, APES, neopelex or
Lauryl sodium sulfate, N- oleoyl amino acid sodiums are put into retort, stirring heating, it is anti-that initiator solution insulation are added dropwise
Should, after completion of dropwise addition, it is rapidly heated and excites implode to react, naturally cool to room temperature, produces the small finished product of monomer residue rate.
A kind of 2. medicinal ethyl acrylate-methyl methacrylate of the middle osmotic sustained release of low monomer residue according to claim 1
The preparation method of ester copolymer aqueous dispersion, it is characterised in that it is made up of the raw material of following weight parts：
It is made up of the raw material of following weight parts：Ethyl acrylate 90-110, methyl methacrylate 45-65, potassium peroxydisulfate
Or ammonium persulfate 0.2-1.2, neopelex or lauryl sodium sulfate 1-5, N- oleoyl amino acid sodium 0.1-
0.5th, APES（OP-10）0.25-1.5, purified water 320-410.
A kind of 3. medicinal ethyl acrylate-methyl methacrylate of the middle osmotic sustained release of low monomer residue according to claim 1
The preparation method of ester copolymer aqueous dispersion, heats up using the later stage（90-100℃）Excite the emulsion polymerization technique side of implode
Method, it is characterised in that comprise the following steps：
（1）By described weight proportion by raw material propylene acetoacetic ester, methyl methacrylate, APES, 12
Sodium alkyl benzene sulfonate or lauryl sodium sulfate, N- oleoyl amino acid sodiums are put into retort, and stirring is warming up to 70-80
℃；
（2）Under stirring, the initiator potassium persulfate or ammonium persulfate solution that are dissolved with purified water are added drop-wise in retort, are added dropwise
1-3h, insulation reaction；
（3）After completion of dropwise addition, it is rapidly heated and excites implode to react to 90-100 DEG C, continues after reacting 1-2h, naturally cool to room
Temperature, produce the finished product that monomer residue is less than 0.01%.
A kind of 4. medicinal ethyl acrylate-methyl methacrylate of the middle osmotic sustained release of low monomer residue according to claim 2
The preparation method of ester copolymer aqueous dispersion, N- oleoyl amino acid sodiums are anion surfactants, and it is with alkyl phenol polyoxy
Vinethene（OP-10）Tri compound emulsifying agent is formed with neopelex.
A kind of 5. medicinal ethyl acrylate-methyl methacrylate of the middle osmotic sustained release of low monomer residue according to claim 3
The preparation method of ester copolymer aqueous dispersion, later stage heating（90-95℃）The starting point for exciting implode is ethyl acrylate and first
The total monomer conversion of base methyl acrylate mixing reaches 60-90% and is defined, preferably 70-80%.
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| CN201710977195.9A CN107722168A (en) | 2017-10-19 | 2017-10-19 | A kind of preparation method of the medicinal EUDRAGIT aqueous copolymer dispersion of middle osmotic sustained release of low monomer residue |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110713520A (en) * | 2019-11-06 | 2020-01-21 | 中国石油天然气股份有限公司 | Oleoyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide and preparation and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041395A (en) * | 2012-12-27 | 2013-04-17 | 悦康药业集团安徽天然制药有限公司 | Osmotic slow-release material in ethyl acrylate-methyl methacrylate copolymer aqueous dispersion and preparation method thereof |
-
2017
- 2017-10-19 CN CN201710977195.9A patent/CN107722168A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041395A (en) * | 2012-12-27 | 2013-04-17 | 悦康药业集团安徽天然制药有限公司 | Osmotic slow-release material in ethyl acrylate-methyl methacrylate copolymer aqueous dispersion and preparation method thereof |
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| 张旭之等编: "《丙烯衍生物工学》", 31 May 1995, 化学工业出版社 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110713520A (en) * | 2019-11-06 | 2020-01-21 | 中国石油天然气股份有限公司 | Oleoyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide and preparation and application thereof |
| CN110713520B (en) * | 2019-11-06 | 2021-01-01 | 中国石油天然气股份有限公司 | Oleoyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide and preparation and application thereof |
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Application publication date: 20180223 |