CN102140208A - Modified-surface halogenated butyl rubber stopper and preparation method thereof - Google Patents
Modified-surface halogenated butyl rubber stopper and preparation method thereof Download PDFInfo
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- CN102140208A CN102140208A CN 201110054663 CN201110054663A CN102140208A CN 102140208 A CN102140208 A CN 102140208A CN 201110054663 CN201110054663 CN 201110054663 CN 201110054663 A CN201110054663 A CN 201110054663A CN 102140208 A CN102140208 A CN 102140208A
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- butyl rubber
- halogenated butyl
- rubber plug
- bromide
- finishing
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Abstract
The invention relates to a modified-surface halogenated butyl rubber stopper and a preparation method thereof. The modified-surface halogenated butyl rubber stopper comprises a halogenated butyl rubber stopper and a modified layer arranged on the surface of the halogenated butyl rubber stopper, wherein the modified layer is formed by modification by solution containing low polyaryletherketone. The preparation method of the modified-surface halogenated butyl rubber stopper comprises the following steps: 1, providing the halogenated butyl rubber stopper; 2, cleaning and drying the halogenated butyl rubber stopper; 3, placing the cleaned and dried halogenated butyl rubber stopper in solution containing low polyaryletherketone, and stirring at a constant temperature of 60 to 100 DEG C in the presence of nitrogen for 12 to 36 hours; and 4, taking the halogenated butyl rubber stopper out from the solution, cleaning and drying with water, ethanol and chloroform in turn to obtain the modified-surface halogenated butyl rubber stopper. In the invention, a polymer material surface modification technique is used to perform low-cost and high-efficiency chemical modification of the surface of the halogenated butyl rubber stopper to prevent the halogenated butyl rubber stopper from contacting medicine, so the compatibility between the halogenated butyl rubber stopper and the medicine is improved, and the medicine administration safety is improved.
Description
Technical field
The present invention relates to the medical rubber plug technical field, particularly halogenated butyl rubber plug of a kind of finishing and preparation method thereof.
Background technology
Medicine is the special commodity of a class, and its drug effect and quality are directly connected to the health and safety of the person, and pharmaceutical packing material and packaged form, especially immediate packaging materials play a part very important to the stability that guarantees medicine.Unfavorable wrapping material can cause the absorption of active constituents of medicine on wrapping material, perhaps adsorb the composition in the wrapping material, even chemical reaction takes place with it, and cause the inefficacy of medicine, also can produce serious toxic side effect sometimes.Therefore, estimating the whether suitable of drug packing material selection, is the important indicator that drug quality is estimated.
Halogenated butyl rubber plug is compared with natural plug, and it is low to have a rate of moisture absorption, and chemical is good, and resistance to air loss is good, and distinguishing features such as no physiology toxic side effect replace natural plug, gradually in the widespread use of drug packaging industry.
Fast development along with pharmaceutical industries, pharmacy corporation is also progressively improving the specification of quality of butyl rubber plug, conventional physics, chemistry and biological property have become minimum requirements, the particle contamination that bottle stopper brought and day by day become the focus of concern with the compatibility problem of medicine, the compatibility problems of medicine and butyl rubber plug is just seriously perplexing drug manufacturing enterprise and butyl rubber plug manufacturing enterprise.
Based on a large amount of problems that present medicinal butyl rubber stopper exists in pharmaceutical industries, State Food and Drug Administration issued " using the notice of the cephalosporin injection supervision and management of butyl rubber plug about further reinforcement " (state's food medicine prison is done [2008] No. 765) on December 26th, 2008.Notice request each province (district, city) food and medicine supervisory and management department will strengthen drug manufacturing enterprise is used the supervision of butyl rubber plug.The butyl rubber plug that consistency experiment when drug manufacturing enterprise should be according to equipment registration is determined is produced medicine, if the manufacturer of change butyl rubber plug, the butyl rubber plug consistency of reply medicine and change is carried out verification experimental verification, meets the requirements and reports location province (distinguish, city) food and medicine supervisory and management department can use after putting on record.
Consider that from the storage aspect of medicine plug should have good chemical stability, resistance to air loss, ageing resistance and the low property separated out.In the actual use, butyl rubber plug directly contacts with medicine, although isoprene-isobutylene rubber itself is relatively cleaner, but in the course of processing of plug owing to need to add the number of chemical auxiliary agent, and to just can produce the medicinal butyl rubber stopper that has use value through sulfidation, thereby inevitably can be in rubber plug body more remaining not by the reaction residual of chemical bonding, do not participate in the material, pyrolysated product and the sulfuration resultant that react.These materials might react to each other by mode such as absorption, absorption, infiltration and extracting and medicine, thus influence and pollute medicine.
Summary of the invention
The object of the present invention is to provide a kind of halogenated butyl rubber plug of finishing, can improve the consistency of medicinal halogenated butyl rubber plug and medicine (particularly cephalosporin medicine) greatly, improve drug safety.
Another object of the present invention is to provide a kind of preparation method of halogenated butyl rubber plug of finishing, utilize the polymer surface modification technique, low cost and chemically modified are efficiently carried out in the halogenated butyl rubber plug surface, the blocking-up halogenated butyl rubber plug contacts with medicine, this method technology is simple, and cost is low, and is easy to implement, pollution-free, effect is obvious.
For achieving the above object, the invention provides a kind of halogenated butyl rubber plug of finishing, it comprises halogenated butyl rubber plug and is located at its surperficial decorative layer that described decorative layer is modified by the solution that contains oligomeric polyaryletherketone and formed.
Described oligomeric polyaryletherketone molecular-weight average is 2000-5000, and the concentration in solution is counted 1-10mol/L according to its repeating unit.
Described solution also comprises component: zinc powder, salt of wormwood or yellow soda ash, nickeliferous material, bromide, N, N '-dimethyl formamide or N, N '-N,N-DIMETHYLACETAMIDE.
Described nickeliferous material is nickelous chloride or nickelous bromide, and bromide is Sodium Bromide or Potassium Bromide.
The present invention also provides a kind of preparation method of halogenated butyl rubber plug of above-mentioned finishing, may further comprise the steps:
Step 1 provides halogenated butyl rubber plug;
Step 2, cleaning, dry halogenated butyl rubber plug;
Step 3 is put into the solution that contains oligomeric polyaryletherketone with the halogenated butyl rubber plug behind the cleaning-drying, and constant temperature 60-100 ℃ was stirred 12-36 hour under condition of nitrogen gas;
Step 4 is taken out halogenated butyl rubber plug in solution, water, ethanol, chloroform clean and be dry successively, promptly obtains the halogenated butyl rubber plug of finishing.
Described solution also comprises component: zinc powder, salt of wormwood or yellow soda ash, nickeliferous material, bromide, N, N '-dimethyl formamide or N, N '-N,N-DIMETHYLACETAMIDE.
Described nickeliferous material is nickelous chloride or nickelous bromide, and bromide is Sodium Bromide or Potassium Bromide.
Described oligomeric polyaryletherketone molecular-weight average is 2000-5000, and the concentration in solution is counted 1-10mol/L according to its repeating unit.
Nickeliferous material and bromide equivalent in the described solution, N, N '-dimethyl formamide or N, N '-N,N-DIMETHYLACETAMIDE is the proportioning interpolation of 1-10mol/L according to making nickel content ultimate density.
Beneficial effect of the present invention: preparation method's technology of the present invention is simple, easily implement, utilize the polymer surface modification technique, low cost and chemically modified are efficiently carried out in the halogenated butyl rubber plug surface, and the blocking-up halogenated butyl rubber plug contacts with medicine, thereby improves the consistency of halogenated butyl rubber plug and medicine, the special consistency that improves halogenated butyl rubber plug to cephalosporins medicine, improve drug safety, and also reduce halogenated butyl rubber plug import dependency, reduce the packing cost of enterprise.
Embodiment
The invention provides a kind of halogenated butyl rubber plug of finishing, comprise halogenated butyl rubber plug and be located at its surperficial decorative layer, described decorative layer is modified by the solution that contains oligomeric polyaryletherketone and is formed, and halogenated butyl rubber plug can be that be shaped or commercially available medicinal halogenated butyl rubber plug.
Described oligomeric polyaryletherketone molecular-weight average is 2000-5000, and the concentration in solution is counted 1-10mol/L according to its repeating unit.Described solution also comprises component: zinc powder, salt of wormwood or yellow soda ash, nickeliferous material, bromide, N, N '-dimethyl formamide or N, N '-N,N-DIMETHYLACETAMIDE.Wherein nickeliferous material is nickelous chloride or nickelous bromide, and bromide is Sodium Bromide or Potassium Bromide.
The present invention utilizes the physical and chemical stability of oligomeric polyaryletherketone excellence, reach the purpose that contacts between blocking-up halogenated butyl rubber plug and the medicine, avoid in the rubber plug body more remaining not by the reaction residual of chemical bonding, the material, pyrolysated product and the sulfuration resultant that do not participate in reacting react to each other by modes such as absorption, absorption, infiltration and extracting and medicine, thereby influence and the pollution medicine.
The preparation method of the halogenated butyl rubber plug of above-mentioned finishing of the present invention may further comprise the steps:
Step 1 provides halogenated butyl rubber plug; Can adopt that be shaped or commercially available medicinal halogenated butyl rubber plug.
Step 2, cleaning, dry halogenated butyl rubber plug; Stain by clean removing the halogenated butyl rubber plug surface, lubricating oil, residual impurity etc.
Step 3 is put into the solution that contains oligomeric polyaryletherketone with the halogenated butyl rubber plug behind the cleaning-drying, and constant temperature 60-100 ℃ was stirred 12-36 hour under condition of nitrogen gas; Wherein oligomeric polyaryletherketone molecular-weight average is 2000-5000, and the concentration in solution is counted 1-10mol/L according to its repeating unit.Described solution also comprises component: zinc powder, salt of wormwood or yellow soda ash, nickeliferous material, bromide, N, N '-dimethyl formamide or N, N '-N,N-DIMETHYLACETAMIDE, wherein nickeliferous material is nickelous chloride or nickelous bromide, bromide is Sodium Bromide or Potassium Bromide, each amounts of components: with the zinc powder consumption is X mol (X is any institute expense numerical value), then salt of wormwood or yellow soda ash are 2-10X mol, nickelous chloride or nickelous bromide are 0.2-1X mol, Sodium Bromide or Potassium Bromide are 0.2-1X mol (with nickelous chloride or nickelous bromide equivalent), N, N '-dimethyl formamide or N, N '-N,N-DIMETHYLACETAMIDE is the proportioning interpolation of 1-10mol/L according to making nickel content ultimate density.
Step 4 is taken out halogenated butyl rubber plug in solution, water, ethanol, chloroform clean and be dry successively, promptly obtains the halogenated butyl rubber plug of finishing.
Now the embodiment of the invention is described in detail as follows, but the present invention is confined to scope of embodiments.
Embodiment 1:
Contain oligomeric polyaryletherketone, zinc powder, salt of wormwood, nickelous chloride, Sodium Bromide and N with putting into after commercially available halogenated butyl rubber plug cleaning and the drying, carry out finishing in the solution of N '-dimethyl formamide, constant temperature stirred 24 hours for 80 ℃ under condition of nitrogen gas, take out then, water, ethanol, chloroform clean and are dry successively.
Embodiment 2:
Contain oligomeric polyaryletherketone, zinc powder, salt of wormwood, nickelous bromide with putting into after commercially available halogenated butyl rubber plug cleaning and the drying, reach N, carry out finishing in the solution of N '-dimethyl formamide, constant temperature stirred 24 hours for 80 ℃ under condition of nitrogen gas, take out then, water, ethanol, chloroform clean and are dry successively.
Embodiment 3:
Contain oligomeric polyaryletherketone, zinc powder, yellow soda ash, nickelous chloride, Sodium Bromide and N with putting into after commercially available halogenated butyl rubber plug cleaning and the drying, carry out finishing in the solution of N '-dimethyl formamide, constant temperature stirred 24 hours for 80 ℃ under condition of nitrogen gas, take out then, water, ethanol, chloroform clean and are dry successively.
Embodiment 4:
Contain oligomeric polyaryletherketone, zinc powder, salt of wormwood, nickelous chloride, Potassium Bromide and N with putting into after commercially available halogenated butyl rubber plug cleaning and the drying, carry out finishing in the solution of N '-dimethyl formamide, constant temperature stirred 24 hours for 80 ℃ under condition of nitrogen gas, take out then, water, ethanol, chloroform clean and are dry successively.
Embodiment 5:
Contain oligomeric polyaryletherketone, zinc powder, salt of wormwood, nickelous chloride, Sodium Bromide and N with putting into after commercially available halogenated butyl rubber plug cleaning and the drying, carry out finishing in the solution of N '-N,N-DIMETHYLACETAMIDE, constant temperature stirred 24 hours for 80 ℃ under condition of nitrogen gas, take out then, water, ethanol, chloroform clean and are dry successively.
Embodiment 6:
Contain oligomeric polyaryletherketone, zinc powder, salt of wormwood, nickelous chloride, Sodium Bromide and N with putting into after commercially available halogenated butyl rubber plug cleaning and the drying, carry out finishing in the solution of N '-dimethyl formamide, constant temperature stirred 24 hours for 60 ℃ under condition of nitrogen gas, take out then, water, ethanol, chloroform clean and are dry successively.
Embodiment 7:
Contain oligomeric polyaryletherketone, zinc powder, salt of wormwood, nickelous chloride, Sodium Bromide and N with putting into after commercially available halogenated butyl rubber plug cleaning and the drying, carry out finishing in the solution of N '-dimethyl formamide, constant temperature stirred 12 hours for 80 ℃ under condition of nitrogen gas, take out then, water, ethanol, chloroform clean and are dry successively.
The halogenated butyl rubber plug of the resulting finishing of the various embodiments described above all meets country to the consistency requirement (state food medicine prison do [2008] No. 765) of cephalosporin drug packages with butyl rubber plug.
In sum, preparation method's technology of the present invention is simple, easily implement, utilize the polymer surface modification technique, low cost and chemically modified are efficiently carried out in the halogenated butyl rubber plug surface, the blocking-up halogenated butyl rubber plug contacts with medicine, thereby improve the consistency of halogenated butyl rubber plug and medicine, improve the consistency of halogenated butyl rubber plug especially, improve drug safety cephalosporins medicine, and also reduce halogenated butyl rubber plug import dependency, reduce the packing cost of enterprise.
The above for the person of ordinary skill of the art, can make other various corresponding changes and distortion according to technical scheme of the present invention and technical conceive, and all these changes and distortion all should belong to the protection domain of claim of the present invention.
Claims (9)
1. the halogenated butyl rubber plug of a finishing is characterized in that, comprises halogenated butyl rubber plug and is located at its surperficial decorative layer, and described decorative layer is modified by the solution that contains oligomeric polyaryletherketone and formed.
2. the halogenated butyl rubber plug of finishing as claimed in claim 1 is characterized in that, described oligomeric polyaryletherketone molecular-weight average is 2000-5000, and the concentration in solution is counted 1-10mol/L according to its repeating unit.
3. the halogenated butyl rubber plug of finishing as claimed in claim 1 is characterized in that, described solution also comprises component: zinc powder, salt of wormwood or yellow soda ash, nickeliferous material, bromide, N, N '-dimethyl formamide or N, N '-N,N-DIMETHYLACETAMIDE.
4. the halogenated butyl rubber plug of finishing as claimed in claim 3 is characterized in that, described nickeliferous material is nickelous chloride or nickelous bromide, and bromide is Sodium Bromide or Potassium Bromide.
5. the preparation method of the halogenated butyl rubber plug of a finishing as claimed in claim 1 is characterized in that, may further comprise the steps:
Step 1 provides halogenated butyl rubber plug;
Step 2, cleaning, dry halogenated butyl rubber plug;
Step 3 is put into the solution that contains oligomeric polyaryletherketone with the halogenated butyl rubber plug behind the cleaning-drying, and constant temperature 60-100 ℃ was stirred 12-36 hour under condition of nitrogen gas;
Step 4 is taken out halogenated butyl rubber plug in solution, water, ethanol, chloroform clean and be dry successively, promptly obtains the halogenated butyl rubber plug of finishing.
6. the preparation method of the halogenated butyl rubber plug of finishing as claimed in claim 5, it is characterized in that, described solution also comprises component: zinc powder, salt of wormwood or yellow soda ash, nickeliferous material, bromide, N, N '-dimethyl formamide or N, N '-N,N-DIMETHYLACETAMIDE.
7. the preparation method of the halogenated butyl rubber plug of finishing as claimed in claim 6 is characterized in that, described nickeliferous material is nickelous chloride or nickelous bromide, and bromide is Sodium Bromide or Potassium Bromide.
8. the preparation method of the halogenated butyl rubber plug of finishing as claimed in claim 5 is characterized in that, described oligomeric polyaryletherketone molecular-weight average is 2000-5000, and the concentration in solution is counted 1-10mol/L according to its repeating unit.
9. the preparation method of the halogenated butyl rubber plug of finishing as claimed in claim 6, it is characterized in that nickeliferous material and bromide equivalent in the described solution, N, N '-dimethyl formamide or N, N '-N,N-DIMETHYLACETAMIDE is the proportioning interpolation of 1-10mol/L according to making nickel content ultimate density.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110054663 CN102140208B (en) | 2011-03-08 | 2011-03-08 | Modified-surface halogenated butyl rubber stopper and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110054663 CN102140208B (en) | 2011-03-08 | 2011-03-08 | Modified-surface halogenated butyl rubber stopper and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102140208A true CN102140208A (en) | 2011-08-03 |
| CN102140208B CN102140208B (en) | 2013-06-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110054663 Expired - Fee Related CN102140208B (en) | 2011-03-08 | 2011-03-08 | Modified-surface halogenated butyl rubber stopper and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59200649A (en) * | 1983-04-26 | 1984-11-14 | ダイキン工業株式会社 | Rubber stopper for medicine |
| CN1552301A (en) * | 2003-06-04 | 2004-12-08 | 上海天汇化学有限公司 | Preparation of medicinal film coated rubber plug |
| CN101147719A (en) * | 2007-09-19 | 2008-03-26 | 湖北华强科技有限责任公司 | Medical local film capsule and producing method thereof |
| CN101756788A (en) * | 2009-12-31 | 2010-06-30 | 山东省药用玻璃股份有限公司 | Polyethylene terephthalate (PET) filming rubber plug |
| EP2250992A1 (en) * | 2009-05-13 | 2010-11-17 | Hubei Huaqiang High-Tech Co., Ltd. | Rubber plug partially coated with PET film and preparation method thereof |
-
2011
- 2011-03-08 CN CN 201110054663 patent/CN102140208B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59200649A (en) * | 1983-04-26 | 1984-11-14 | ダイキン工業株式会社 | Rubber stopper for medicine |
| CN1552301A (en) * | 2003-06-04 | 2004-12-08 | 上海天汇化学有限公司 | Preparation of medicinal film coated rubber plug |
| CN101147719A (en) * | 2007-09-19 | 2008-03-26 | 湖北华强科技有限责任公司 | Medical local film capsule and producing method thereof |
| EP2250992A1 (en) * | 2009-05-13 | 2010-11-17 | Hubei Huaqiang High-Tech Co., Ltd. | Rubber plug partially coated with PET film and preparation method thereof |
| CN101756788A (en) * | 2009-12-31 | 2010-06-30 | 山东省药用玻璃股份有限公司 | Polyethylene terephthalate (PET) filming rubber plug |
Non-Patent Citations (1)
| Title |
|---|
| 《中国橡胶》 20070820 刘海洪 丁基胶塞的膜技术现状与发展趋势 , 第16期 * |
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| CN102140208B (en) | 2013-06-19 |
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Granted publication date: 20130619 Termination date: 20160308 |