CN1320012C - Combination containing acrylamide - Google Patents
Combination containing acrylamide Download PDFInfo
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- CN1320012C CN1320012C CNB2005100245866A CN200510024586A CN1320012C CN 1320012 C CN1320012 C CN 1320012C CN B2005100245866 A CNB2005100245866 A CN B2005100245866A CN 200510024586 A CN200510024586 A CN 200510024586A CN 1320012 C CN1320012 C CN 1320012C
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- acrylamide
- cooh
- methyl
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Abstract
The present invention relates to a composition containing acrylamide which comprises (A), acrylamide monomers; (B), acrylic ester or acrylamide monomers; (C), a photoinitiator occupying 0.1% to 15% of the mass of the composition. The proportion of the monomers A to the monomers B can be arbitrarily regulated. Polymer thin films prepared from the composition can be used as controlled release films of a transdermal drug delivery system TDDs. The reification performance of the thin films can be fine regulated by regulating the species and the content of the monomers A and the monomers B in the composition so as to quickly prepare the controlled release films of the transdermal drug delivery systems suitable for different kinds of medicine.
Description
Technical field
The present invention relates to a kind of photocurable monomer composition, be specifically related to a kind of composition that comprises acrylamide, can be used as the release-controlled film in the preparation transdermal delivery system.
Background technology
Transdermal delivery system is meant that medicine discharges from the device of particular design, by complete skin absorption, enters the controlled release drug administration formulation of systemic blood system.Transdermal delivery system can be divided into two big class, i.e. membrane controlled release type and skeleton dispersion patterns basically.The membrane controlled release type transdermal delivery system is that medicine or transdermal absorption accelerator are rolled into the storage storehouse by release-controlled film or other controlled-release materials, by the character control release rate of drugs of release-controlled film or controlled-release material.Scopolamine (trade(brand)name Transderm-Scop), clonidine (trade(brand)name Catapres TTS) are film controlling types in the at present commercially available patch, and controlling diaphragm is a microporous polypropylene membrane; Pannonit (trade(brand)name Transderm-Nitro), fentanyl (trade(brand)name Duragesic), estradiol (trade(brand)name Estraderm), testosterone (trade(brand)name Androderm) are film controlling types, and release-controlled film is a polyethylene vinyl acetate; Nicotine (trade(brand)name trade(brand)name NicoDerm CQ) is a film controlling type, and controlling diaphragm is a polyethylene film.
At European patent No.46069, U.S. Patent No. 3,797 is described in 494 and utilizes microporous membrane control rate of releasing drug.The hole of film from 0.1 to 0.85, the curvature of film from 1 to 10, from 10 to 100 microns of film thicknesses, the film of usefulness has polypropylene, tetrafluoroethylene, polycarbonate, polyvinyl chloride, cellulose acetate, nitrocellulose, polyacrylonitrile etc. for example.Their shortcoming is that the kind of the microporous membrane that can Gong select for use is few, does not satisfy the formulation that more medicine is made percutaneous dosing.
In U.S. Patent No. 6,537, the Scopolamine Patch that is described among the 571B1, U.S. Patent No. 4,681, the Deponit TTS that is described in 584, used release-controlled film all is the multipolymer of ethene-vinyl acetate.Shortcoming is an organic solvent residue problem in the ethylene-vinyl acetate copolymer, and needs constantly to regulate the content of vinyl acetate between to for plastic to regulate the permeability of medicine.
At European patent No.1103260A2, in the clonidine patch that is described among the U.S. Patent No. 2004/0028726A1, utilize vinylformic acid-(2-ethyl) own ester, methyl methacrylate, vinylformic acid and vinyl acetate, Raolical polymerizable takes place, and the multipolymer that obtains can be controlled the release of medicine simultaneously as pressure-sensitive adhesive layer and bin-storing layer in the patch.Shortcoming is that Raolical polymerizable is influenced by several factors, factors such as the time that responds, temperature of reaction, raw material initial concentration, solvent, and also there is the residue problem of organic solvent in patch.
The film of in transdermal delivery system, using, generally speaking the release-controlled film kind lacks, and alternative little, this brings very big obstruction for the exploitation of percutaneous drug administration preparation.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of excellent curing performance that has is provided, can produce the monomer composition of the polymkeric substance that can be used for the release-controlled film in the transdermal delivery system.
For the shortcoming that the kind that solves release-controlled film in the existing transdermal delivery system lacks, the present invention finds that on extensive and deep research basis it is abundant to adopt a kind of special photo curable monomer composition just can obtain kind, the release-controlled film of excellent performance.Said composition comprises: (A) a kind of acrylamide monomer; (B) a kind of acrylate or acrylamide monomer; (C) a kind of light trigger accounts for 0.1%～15% of composition quality; The ratio of monomer A, B can be regulated arbitrarily in the composition.
The acrylamide monomers of using among the present invention can be used general formula CR
2R
1=CR
3CONR
4Expression, wherein R
1, R
2, R
3, R
4Can be any substituting group, comprise N-(1,1-dimethyl-3-oxo butyl)-acrylamide, N-(methylol) acrylamide, N-[three (methylol) methyl] acrylamide, N-[3-(dimethylamino) propyl group] Methacrylamide.Using acrylamide monomer among the present invention is N-(1,1-dimethyl-3-oxo butyl)-acrylamide, but is not limited only to this monomer, and the derivative of all acrylamides can be as this monomer potential alternative.The acrylic amide example can be listed below: (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, N-(butoxymethyl) (methyl) acrylamide, N-(methylol) (methyl) acrylamide, N-[(trishydroxymethyl) methyl] (methyl) acrylamide, N-[3-(dimethylamino) propyl group] (methyl) acrylamide or the like, but be not limited to above listed substituting group.
The acrylic ester monomer of using among the present invention can be used general formula CR
2R
1=CR
3COOR
4Expression, wherein R
1, R
2, R
3Can be any substituting group, such as-H ,-CH
3,-C
6H
5,-CH=CH
2,-OH ,-COOH ,-OCH
3,-SO
3H ,-NH
2,-N (CH
3)
3Cl or the like, but be not limited to above listed substituting group.
R in the described acrylic ester monomer general formula
4Substituting group can be an alkyl, the R that uses among the present invention
4Substituting group is that the monomer of alkyl is a vinylformic acid n-dodecane ester, but is not limited only to this monomer, all R
4Substituting group is that the acrylate of alkyl can be exemplified below :-CH as this monomer potential alternative
3,-C
2H
5,-C
3H
7,-(CH
2)
3CH
3,-(CH
2)
4CH
3,-(CH
2)
5CH
3,-(CH
2)
7CH
3,-(CH
2)
11CH
3Or the like, but be not limited to above listed substituting group.
R in the described acrylic ester monomer general formula
4Substituting group can be the group that hydroxyl replaces, and the example of using among the present invention is 2-hydroxyl-3-phenoxy group propyl acrylate, but is not limited only to this monomer, all R
4Substituting group is that the acrylate of the group of hydroxyl replacement can be as this monomer potential alternative.Be exemplified below :-CH
2OH ,-(CH
2)
2OH ,-(CH
2)
3OH ,-(CH
2)
4OH ,-(CH
2)
5OH ,-CH
2CH (OH) CH
3,-CH
2CH (OH) C
2H
5,-CH
2CH (OH) C
3H
7,-CH
2CH (OH) CH
2OC
6H
5,-C
2H
5CH (OH) CH
3,-C
2H
5CH (OH) C
2H
5,-C
3H
6CH (OH) CH
3,-C
3H
6CH (OH) C
2H
5,-C
3H
6(OH) CH
2OC
6H
5Or the like, but be not limited to above listed substituting group.
R in the described acrylic ester monomer general formula
4Substituting group can be the group that ester group replaces, the example of using among the present invention is 1, the 6-hexanediol dimethacrylate, but be not limited only to this monomer, and all R4 substituting groups are that the acrylate of the group of ester group replacement can be as this monomer potential alternative.Be exemplified below :-CH
2OOCCH=CH
2,-(CH
2)
2OOCCH=CH
2,-(CH
2)
3OOCCH=CH
2,-(CH
2)
4OOCCH=CH
2,-(CH
2)
5OOCCH=CH
2,-(CH
2)
6OOCCH=CH
2,-(CH
2)
8OOCCH=CH
2,-(CH
2)
2OOCC (CH
3)=CH
2,-(CH
2)
3OOCC (CH
3)=CH
2,-(CH
2)
4OOCC (CH
3)=CH
2,-(CH
2)
5OOCC (CH
3)=CH
2,-(CH
2)
6OOCC (CH
3)=CH
2,-(CH
2)
8OOCC (CH
3)=CH
2Or the like, but be not limited to above listed substituting group.
R in the described acrylic ester monomer general formula
4Substituting group can be the group of carboxyl substituted, and the example of using among the present invention is the 2-carboxy ethyl acrylate, but is not limited only to this monomer, all R
4Substituting group is that the acrylate of the group of carboxyl substituted can be as this monomer potential alternative.Be exemplified below :-CH
2COOH ,-(CH
2)
2COOH ,-(CH
2)
3COOH ,-(CH
2)
4COOH ,-(CH
2)
5COOH ,-(CH
2)
6COOH ,-(CH
2)
8COOH ,-(CH
2)
12COOH or the like, but be not limited to above listed substituting group.
R in the described acrylic ester monomer general formula
4Substituting group can also be the group that alkoxyl group replaces, and the example of using among the present invention is a 2-butoxy ethyl propenoate, but is not limited only to this monomer, all R
4Substituting group is that the acrylate of alkoxyl group can be as this monomer potential alternative.Be exemplified below :-CH
2OCH
2CH
3,-CH
2O (CH
2)
2CH
3,-CH
2O (CH
2)
3CH
3,-CH
2O (CH
2)
4CH
3,-CH
2O (CH
2)
6CH
3,-CH
2O (CH
2)
8CH
3,-(CH
2)
2OCH
2,-(CH
2)
2OCH
2CH
3,-(CH
2)
2O (CH
2)
2CH
3,-(CH
2)
3O (CH
2)
2CH
3,-(CH
2)
2O (CH
2)
4CH
3Or the like, but be not limited to above listed substituting group.
Among the present invention can with light trigger comprise the initiator of the ultraviolet light polymerization that is useful on, as diphenyl peroxide ketone, 1-hydroxycyclohexylphenylketone, bitter almond oil camphor propyl ether, but not only be confined to these light triggers, all are for the UV-light sensitivity, and the light trigger that can trigger monomer be cured reaction is all unrestricted.
The polymeric film that preparation of compositions among the present invention obtains can be used as the release-controlled film in the transdermal delivery system (TDDs), by regulating kind and the content of monomer A, B in the composition, can finely tune the film physical and chemical performance, prepare the release-controlled film in the transdermal delivery system that is applicable to different pharmaceutical fast.Can in mixing solutions, add softening agent when adopting preparation of compositions release-controlled film of the present invention, comprise Citrate trianion, phthalate, sebacate etc., can further improve the physicals of release-controlled film.The present invention has widened the material category of the release-controlled film in the preparation transdermal delivery system, has enlarged the material range of choice.
Description of drawings
Fig. 1, Fig. 2 are that N-(1,1-dimethyl-3-oxo butyl)-acrylamide is got 30ul with vinylformic acid-(4-hydroxyl) butyl ester after mixing at 5: 5 by mass ratio, the permeability experiment of the cured film that ultraviolet light polymerization obtains and the comparison of zoodermic transdermal test in vitro experiment.
Fig. 3, Fig. 4 are that N-(1,1-dimethyl-3-oxo butyl)-acrylamide is got 30ul with vinylformic acid-(4-hydroxyl) butyl ester after mixing at 2: 8 by mass ratio, the permeability experiment of the cured film that ultraviolet light polymerization obtains.
Embodiment
The following example of the present invention proposes for illustration purpose, and is not construed as limiting the invention.
Embodiment 1
N-(1,1-dimethyl-3-oxo butyl)-acrylamide is mixed by mass ratio with vinylformic acid-(4-hydroxyl) butyl ester at 5: 5, add the diphenyl peroxide ketone of 5% (w/w) again, get mixing solutions 30ul, be placed on the carrier substrates, coating is paved, and places ultraviolet light polymerization instrument completion of cure.
The cured film that obtains places the Franz diffusion cell of improvement, is the wintergreen oil solution of the Naproxen Base of 1mg/ml in the supply pool, and accepting in the pond is the phosphate buffered saline buffer of pH7.4.Utilize the rate of release of efficient liquid phase chromatographic analysis wintergreen oil and Naproxen Base.
Animal skin is relatively got fresh Kunming kind small white mouse skin of abdomen and is placed the Franz diffusion cell of improvement, is the wintergreen oil solution of the Naproxen Base of 1mg/ml in the supply pool, and accepting the pond is the phosphate buffered saline buffer of pH7.4.Utilize the rate of release of efficient liquid phase chromatographic analysis wintergreen oil and Naproxen Base.See Fig. 1: curve 1 is that wintergreen oil is tested zoodermic transdermal test in vitro, and curve 2 is wintergreen oil permeability experiments (correlation coefficient r=0.9933) to cured film; Fig. 2: curve 1 is the permeability experiment (correlation coefficient r=0.9973) of Naproxen Base to cured film, and curve 2 is that Naproxen Base is tested zoodermic transdermal test in vitro, and cured film has linear controlled-release function to medicine as can be seen from Figure.
Embodiment 2
N-(1,1-dimethyl-3-oxo butyl)-acrylamide is mixed by mass ratio with vinylformic acid-(4-hydroxyl) butyl ester at 2: 8, add the diphenyl peroxide ketone of 5% (w/w) again, get mixing solutions 30ul, be placed on the carrier substrates, coating is paved, and places ultraviolet light polymerization instrument completion of cure.
The cured film that obtains places the Franz diffusion cell of improvement, is the wintergreen oil solution of the Naproxen Base of 1mg/ml in the supply pool, and accepting in the pond is the phosphate buffered saline buffer of pH7.4.Utilize the rate of release of efficient liquid phase chromatographic analysis wintergreen oil and Naproxen Base.See Fig. 3: wintergreen oil is to the permeability experiment (correlation coefficient r=0.9828) of cured film; Fig. 4: Naproxen Base is to the permeability experiment (correlation coefficient r=0.9877) of cured film.
Embodiment 3
With N-(1,1-dimethyl-3-oxo butyl)-acrylamide and 1, the 6-hexanediol dimethacrylate is pressed mass ratio and is mixed at 5: 5, the diphenyl peroxide ketone that adds 15% (w/w) again, get mixing solutions 30ul, be placed on the carrier substrates, coating is paved, and places ultraviolet light polymerization instrument completion of cure.
Embodiment 4
With N-(1,1-dimethyl-3-oxo butyl)-acrylamide mixes by mass ratio with vinylformic acid n-dodecane ester at 7: 3, the 1-hydroxycyclohexylphenylketone that adds 8% (w/w) again, dissolving, filter, get mixing solutions 30ul, be placed on the carrier substrates, coating is paved, and places ultraviolet light polymerization instrument completion of cure.
N-(1,1-dimethyl-3-oxo butyl)-acrylamide is mixed by mass ratio with the 2-carboxy ethyl acrylate at 6: 4, add the diphenyl peroxide ketone of 5% (w/w) again, get mixing solutions 30ul, be placed on the carrier substrates, coating is paved, and places ultraviolet light polymerization instrument completion of cure.
Embodiment 6
N-(1,1-dimethyl-3-oxo butyl)-acrylamide is mixed by mass ratio with 2-butoxy ethyl propenoate at 8: 2, add the bitter almond oil camphor propyl ether of 0.1% (w/w) again, get mixing solutions 30ul, be placed on the carrier substrates, coating is paved, and places ultraviolet light polymerization instrument completion of cure.
Claims (3)
1, a kind of composition that comprises acrylamide is characterized in that said composition comprises: (A) a kind of acrylamide monomer; (B) a kind of acrylate or acrylamide monomer; (C) a kind of light trigger that is used for ultraviolet light polymerization accounts for 0.1%～15% of composition quality; The ratio of monomer A, B can be regulated arbitrarily in the composition;
Described acrylamide monomer general formula CR
2R
1=CR
3CONR
4Expression, wherein R
1, R
2, R
3, R
4It is any substituting group; Described acrylate monomer general formula CR
2' R
1'=CR
3' COOR
4' expression, wherein R
1', R
2', R
3' be selected from-H ,-CH
3,-C
6H
5,-CH=CH
2,-OH ,-COOH ,-OCH
3,-SO
3H ,-NH
2Or-N (CH
3)
3Cl, R
4' be selected from alkyl, hydroxyl, ester group, carboxyl or alkoxyl group.
2,, it is characterized in that the R in the described acrylate monomer general formula according to the composition of claim 1
4' be selected from-CH
3,-C
2H
5,-C
3H
7,-(CH
2)
3CH
3,-(CH
2)
4CH
3,-(CH
2)
5CH
3,-(CH
2)
7CH
3,-(CH
2)
11CH
3,-CH
2OH ,-(CH
2)
2OH ,-(CH
2)
3OH ,-(CH
2)
4OH ,-(CH
2)
5OH ,-CH
2CH (OH) CH
3,-CH
2CH (OH) C
2H
5,-CH
2CH (OH) C
3H
7,-CH
2CH (OH) CH
2OC
6H
5,-C
2H
5CH (OH) CH
3,-C
2H
5CH (OH) C
2H
5,-C
3H
6CH (OH) CH
3,-C
3H
6CH (OH) C
2H
5,-C
3H
6(OH) CH
2OC
6H
5,-CH
2OOCCH=CH
2,-(CH
2)
2OOCCH=CH
2,-(CH
2)
3OOCCH=CH
2,-(CH
2)
4OOCCH=CH
2,-(CH
2)
5OOCCH=CH
2,-(CH
2)
6OOCCH=CH
2,-(CH
2)
8OOCCH=CH
2,-(CH
2)
2OOCC (CH
3)=CH
2,-(CH
2)
3OOCC (CH
3)=CH
2,-(CH
2)
4OOCC (CH
3)=CH
2,-(CH
2)
5OOCC (CH
3)=CH
2,-(CH
2)
6OOCC (CH
3)=CH
2,-(CH
2)
8OOCC (CH
3)=CH
2,-CH
2COOH ,-(CH
2)
2COOH ,-(CH
2)
3COOH ,-(CH
2)
4COOH ,-(CH
2)
5COOH ,-(CH
2)
6COOH ,-(CH
2)
8COOH ,-(CH
2)
12COOH ,-CH
2OCH
2CH
3,-CH
2O (CH
2)
2CH
3,-CH
2O (CH
2)
3CH
3,-CH
2O (CH
2)
4CH
3,-CH
2O (CH
2)
6CH
3,-CH
2O (CH
2)
8CH
3,-(CH
2)
2OCH
2,-(CH
2)
2OCH
2CH
3,-(CH
2)
2O (CH
2)
2CH
3,-(CH
2)
3O (CH
2)
2CH
3Or-(CH
2)
2O (CH
2)
4CH
3
3, composition according to claim 1, it is characterized in that described acrylamide monomer is selected from N-(1,1-dimethyl-3-oxo butyl)-acrylamide, N-(methylol) acrylamide, N-[three (methylol) methyl] acrylamide, N-[3-(dimethylamino) propyl group] Methacrylamide, (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, N-(butoxymethyl) (methyl) acrylamide, N-(methylol) (methyl) acrylamide, the N-[(trishydroxymethyl) methyl] (methyl) acrylamide or N-[3-(dimethylamino) propyl group] (methyl) acrylamide; Described acrylate monomer is selected from vinylformic acid n-dodecane ester, 2-hydroxyl-3-phenoxy group propyl acrylate, 1,6-hexanediol dimethacrylate, 2-carboxy ethyl acrylate or 2-butoxy ethyl propenoate.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100245866A CN1320012C (en) | 2005-03-24 | 2005-03-24 | Combination containing acrylamide |
| PCT/CN2006/000509 WO2006099818A1 (en) | 2005-03-24 | 2006-03-24 | Light curable monomer compostion and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100245866A CN1320012C (en) | 2005-03-24 | 2005-03-24 | Combination containing acrylamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1687161A CN1687161A (en) | 2005-10-26 |
| CN1320012C true CN1320012C (en) | 2007-06-06 |
Family
ID=35305203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100245866A Expired - Fee Related CN1320012C (en) | 2005-03-24 | 2005-03-24 | Combination containing acrylamide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1320012C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016127020A1 (en) * | 2015-02-06 | 2016-08-11 | Noven Pharmaceuticals, Inc. | Pressure-sensitive adhesives for transdermal drug delivery |
| EP3210945B1 (en) * | 2016-02-29 | 2019-04-10 | Agfa-Gevaert | Method of manufacturing an etched glass article |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0913445A1 (en) * | 1997-10-28 | 1999-05-06 | National Starch and Chemical Investment Holding Corporation | Enhancer tolerant pressure sensitive adhesives for transdermal drug delivery |
| CN1332188A (en) * | 2001-08-01 | 2002-01-23 | 华中科技大学 | Polymer gel for orally taken and colon released medicine and its prepn |
| US20040131826A1 (en) * | 2003-01-06 | 2004-07-08 | General Electric Company | Radiation curable microstructure-bearing articles |
-
2005
- 2005-03-24 CN CNB2005100245866A patent/CN1320012C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0913445A1 (en) * | 1997-10-28 | 1999-05-06 | National Starch and Chemical Investment Holding Corporation | Enhancer tolerant pressure sensitive adhesives for transdermal drug delivery |
| CN1332188A (en) * | 2001-08-01 | 2002-01-23 | 华中科技大学 | Polymer gel for orally taken and colon released medicine and its prepn |
| US20040131826A1 (en) * | 2003-01-06 | 2004-07-08 | General Electric Company | Radiation curable microstructure-bearing articles |
Non-Patent Citations (1)
| Title |
|---|
| 丙烯酰胺/丙烯酸水凝胶的pH敏感性研究 李剑 陈捷，化学工程师，第2003年第5期 2003 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1687161A (en) | 2005-10-26 |
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Granted publication date: 20070606 Termination date: 20140324 |