CN112321957A - High-cleanness rubber plug - Google Patents

High-cleanness rubber plug Download PDF

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Publication number
CN112321957A
CN112321957A CN202011198355.8A CN202011198355A CN112321957A CN 112321957 A CN112321957 A CN 112321957A CN 202011198355 A CN202011198355 A CN 202011198355A CN 112321957 A CN112321957 A CN 112321957A
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China
Prior art keywords
rubber plug
exxpro3433
plug according
high cleanliness
rubber
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Pending
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CN202011198355.8A
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Chinese (zh)
Inventor
扈永刚
杜彬
王元浩
逯纪伟
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Shandong Pharmaceutical Glass Co Ltd
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Shandong Pharmaceutical Glass Co Ltd
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Priority to CN202011198355.8A priority Critical patent/CN112321957A/en
Publication of CN112321957A publication Critical patent/CN112321957A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C08L23/283Halogenated homo- or copolymers of iso-olefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2296Oxides; Hydroxides of metals of zinc

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a matched product of a medicinal glass product, in particular to a high-cleanness rubber plug which is prepared by taking an EXXPRO3433 special elastomer as a matrix rubber and alkyl phenyl-phenol disulfide resin J-PV7 as a vulcanizing agent through mixing, vulcanizing and forming. The invention has the following advantages: (1) the use of an alkyl-phenyl-phenol disulfide resin J-PV7 as a vulcanizing agent for EXXPRO3433 specialty elastomers; (2) the proper vulcanization speed is achieved by adjusting the dosage of the alkyl phenyl-phenol disulfide resin J-PV7 and zinc oxide, and simultaneously, the leaching of lower free sulfur and zinc ions in the formula is ensured. (3) Compared with the butyl rubber plug existing in the current market, the formula product has lower extracts and extractives.

Description

High-cleanness rubber plug
Technical Field
The invention relates to a matched product of a medicinal glass product, in particular to a high-cleanness rubber plug.
Background
The medicine is a special commodity directly related to human health and safety, and besides the inherent performance of the medicine, the packaging of the medicine, particularly the packaging material directly contacting the medicine, plays a decisive role in the medicine. The butyl rubber plug is used as a packaging material which is in direct contact with the medicine, and the inherent cleanliness of the butyl rubber plug has great influence on the medicine. The butyl rubber plug has a complex formula, uses more raw materials, is absorbed, adsorbed, leached and permeated by medicines after being packaged with the medicines with stronger molecular activity, generates the compatibility problem of the rubber plug and the medicines, and is more prominent to part of cephalosporins, part of large infusion solutions, more traditional Chinese medicine injection preparations and the like.
Therefore, the proper material is selected to manufacture the butyl rubber bottle stopper with higher internal cleanliness, so that the possibility of absorption, adsorption, leaching and permeation of the medicine is reduced, and the method becomes a development trend of the butyl rubber bottle stopper.
The commonly used butyl rubber bottle stopper at present is easy to interact when contacting with medicines, so that the risk of polluting the medicines exists; when the rubber plug is in long-term contact with the medicine, small molecular substances in the rubber plug migrate into the medicine, so that the medicine quality and potential safety hazards are caused; and has poor compatibility with medicines, thus easily causing the failure and the deterioration of the medicines.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the high-cleanness rubber plug which has good compatibility with medicines, can ensure the stability of the medicines, can greatly reduce extracts and extractables and does not pollute the medicines in long-term storage.
The high-cleanness rubber plug is prepared by taking an EXXPRO3433 special elastomer as a matrix rubber and taking alkyl phenyl-phenol disulfide resin J-PV7 as a vulcanizing agent through mixing, vulcanizing and forming.
Wherein the EXXPRO3433 special elastomer is a special elastomer with the mark of 3433 produced by Exxon Mobil chemical company in the United states, and belongs to the field of butyl rubber. The Exxpro specialty elastomer is a brominated polymer made from isobutylene and para-methylstyrene (PMS) copolymer. The copolymer has wide monomer ratio and molecular weight selection range, and products with different bromination degrees can be obtained by brominating the copolymer, so that Exxpro special elastomers with different brands can be obtained. Wherein Exxpro3433 is brominated-p-methylstyrene. Bromination selectively occurs on the methyl group of PMS, providing active benzyl bromide functionality, which is also critical for vulcanization and various modifications of Exxpro specialty elastomers. The unique performance comes from a fully saturated polyisobutene framework and a high-activity benzyl bromide functional group.
The alkylphenyl disulfide resin J-PV7 was manufactured by Nippon Kabushiki Kaisha.
Furthermore, the mass of the alkyl phenyl-phenol disulfide resin J-PV7 is 1-3% of that of the EXXPRO3433 special elastomer.
Furthermore, the zinc oxide powder also comprises an active agent, wherein the active agent is zinc oxide. The mass of the zinc oxide is 3-5% of that of the EXXPRO3433 special elastomer.
Still further, the composite material also comprises a filler, wherein the filler is calcined kaolin. The mass of the calcined kaolin is 60-80% of that of the EXXPRO3433 special elastomer.
Furthermore, the paint also comprises a pigment, wherein the pigment is one or two of titanium dioxide or carbon black. The mass of the pigment is 2.1-3.3% of that of the EXXPRO3433 special elastomer.
The high-cleanness rubber plug is prepared by the conventional mixing and vulcanization molding process without special limitation. The method specifically comprises the following steps:
(1) mixing: after the raw materials are qualified, the raw materials are mixed according to the formula, and then banburying and open milling are carried out to mix various raw materials.
(2) Preforming: the rubber compound is extruded, rolled, cooled and cut into pieces for storage.
(3) And (3) vulcanization molding: according to the specified process, chemical crosslinking and vulcanization molding are carried out in vulcanization equipment.
(4) Removing edges: and punching the vulcanized rubber sheet to form a single product.
(5) Cleaning: the product is cleaned, and the product cleanliness is improved.
In summary, the invention has the following advantages:
(1) the use of an alkyl-phenyl-phenol disulfide resin J-PV7 as a vulcanizing agent for EXXPRO3433 specialty elastomers;
(2) variable verification is carried out by adjusting the dosage of the alkyl phenyl-phenol disulfide resin J-PV7 and zinc oxide, the optimal proportion of the two is determined according to the inspection data of the actual extraction of free sulfur and zinc ions, so that the proper vulcanization speed is achieved, the two can fully react, less unreacted substances in the product are ensured, and the leaching of lower free sulfur and zinc ions in the formula is ensured.
(3) Compared with the butyl rubber plug existing in the current market, the formula product has lower extracts and extractives.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
Figure BDA0002754641980000031
the preparation process is not particularly limited, and the conventional mixing and vulcanization molding processes are adopted. The method specifically comprises the following steps:
(1) mixing: after the raw materials are qualified, the raw materials are mixed according to the formula, and then banburying and open milling are carried out to mix various raw materials.
(2) Preforming: the rubber compound is extruded, rolled, cooled and cut into pieces for storage.
(3) And (3) vulcanization molding: according to the specified process, chemical crosslinking and vulcanization molding are carried out in vulcanization equipment.
(4) Removing edges: and punching the vulcanized rubber sheet to form a single product.
(5) Cleaning: the product is cleaned, and the product cleanliness is improved.
Example 2:
Figure BDA0002754641980000032
the preparation process is the same as in example 1.
Example 3:
Figure BDA0002754641980000041
the preparation process is the same as in example 1.
Example 4:
Figure BDA0002754641980000042
the preparation process is the same as in example 1.
Comparative example 1:
Figure BDA0002754641980000043
the preparation process is the same as in example 1.
Test example:
the quick test was performed for examples 1 to 4.
Vulcanization conditions are as follows: 193 ℃ for 6 min.
Figure BDA0002754641980000051
Through comparison of quick test data of examples 1 to 4, the highest torque values of examples 2, 3 and 4 accord with an expected adjustment direction, the vulcanization speed and the vulcanization degree of the examples meet production requirements, but the content of extractable free sulfur and zinc ions is verified according to an extract experiment in actual selection, and the optimal proportion is determined.
Extract data:
Figure BDA0002754641980000052
through analysis of extract detection data, the data of examples 2 and 3 are expected, but the content of zinc ions in example 3 is higher than that in example 2, so that the best choice is selected from example 2, and the fact that the alkyl phenyl phenol disulfide resin J-PV7 and zinc oxide can achieve a proper vulcanization speed and simultaneously ensure low leaching of free sulfur and zinc ions in the formula can be proved.
A partial extractables test was performed for example 2 and comparative example 1, and the data are shown in the following table:
Figure BDA0002754641980000061
note: ND means not detected
Through the partial extract detection data of comparative example 2 and comparative example 1, the cleanliness of example 2 is obviously better than that of comparative example 1, so that the fact that the extract and the extract are low can be proved.

Claims (8)

1. A high clean plug is characterized in that: the rubber is prepared by taking EXXPRO3433 special elastomer as matrix rubber and alkyl phenyl-phenol disulfide resin J-PV7 as a vulcanizing agent through mixing, vulcanizing and molding.
2. The high cleanliness rubber plug according to claim 1, wherein: the mass of the alkyl phenyl-phenol disulfide resin J-PV7 is 1-3% of that of the EXXPRO3433 special elastomer.
3. The high cleanliness rubber plug according to claim 1, wherein: the zinc oxide powder also comprises an active agent, wherein the active agent is zinc oxide.
4. The high cleanliness rubber plug according to claim 3, wherein: the mass of the zinc oxide is 3-5% of that of the EXXPRO3433 special elastomer.
5. The high cleanliness rubber plug according to claim 1, wherein: the composite material also comprises a filler, wherein the filler is calcined kaolin.
6. The high cleanliness rubber plug according to claim 5, wherein: the mass of the calcined kaolin is 60-80% of that of the EXXPRO3433 special elastomer.
7. The high cleanliness rubber plug according to claim 1, wherein: the paint also comprises a pigment, wherein the pigment is one or two of titanium dioxide or carbon black.
8. The high cleanliness rubber plug according to claim 7, wherein: the mass of the pigment is 2.1-3.3% of that of the EXXPRO3433 special elastomer.
CN202011198355.8A 2020-10-31 2020-10-31 High-cleanness rubber plug Pending CN112321957A (en)

Priority Applications (1)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116003924A (en) * 2022-12-21 2023-04-25 山东省药用玻璃股份有限公司 Preparation formula and preparation process of pre-filled and sealed piston

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2589214A1 (en) * 2004-12-29 2006-07-06 Exxonmobil Chemical Patents Inc. Processable filled, curable halogenated isoolefin elastomers
CN101909882A (en) * 2007-11-14 2010-12-08 陶氏环球技术公司 Articles and methods of making the same
CN101991501A (en) * 2009-08-27 2011-03-30 郑州市翱翔医药包装有限公司 Ultraclean medicinal bottle plug and manufacturing method thereof
CN110776699A (en) * 2019-10-28 2020-02-11 郑州大学 Radiation-resistant sterilizing medicinal thermoplastic elastomer and preparation method thereof
CN111019254A (en) * 2019-12-23 2020-04-17 山东省药用玻璃股份有限公司 Brominated butyl rubber plug for alkali-resistant medicine and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2589214A1 (en) * 2004-12-29 2006-07-06 Exxonmobil Chemical Patents Inc. Processable filled, curable halogenated isoolefin elastomers
CN101909882A (en) * 2007-11-14 2010-12-08 陶氏环球技术公司 Articles and methods of making the same
CN101991501A (en) * 2009-08-27 2011-03-30 郑州市翱翔医药包装有限公司 Ultraclean medicinal bottle plug and manufacturing method thereof
CN110776699A (en) * 2019-10-28 2020-02-11 郑州大学 Radiation-resistant sterilizing medicinal thermoplastic elastomer and preparation method thereof
CN111019254A (en) * 2019-12-23 2020-04-17 山东省药用玻璃股份有限公司 Brominated butyl rubber plug for alkali-resistant medicine and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116003924A (en) * 2022-12-21 2023-04-25 山东省药用玻璃股份有限公司 Preparation formula and preparation process of pre-filled and sealed piston

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Application publication date: 20210205