CN115058087A - Medical rubber composition and rubber part - Google Patents
Medical rubber composition and rubber part Download PDFInfo
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- CN115058087A CN115058087A CN202210925811.7A CN202210925811A CN115058087A CN 115058087 A CN115058087 A CN 115058087A CN 202210925811 A CN202210925811 A CN 202210925811A CN 115058087 A CN115058087 A CN 115058087A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions 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
- C08L23/28—Compositions 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
- C08L23/283—Halogenated homo- or copolymers of iso-olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- 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)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a medical rubber composition and a rubber part, and relates to the technical field of medical rubber.
Description
Technical Field
The invention relates to the technical field of medical rubber, in particular to a medical rubber composition and a rubber part.
Background
The rubber product for medical use is used in hospital to treat diseases and is used to replace some organs and tissues in human body. It can be divided into two categories, external use and internal use. The rubber used is NR, IIR, PU, silicon rubber and the like. The continuous vulcanization can be produced by molding, injection molding or extrusion molding according to the product structure. The product is widely used in medical health institutions and the pharmaceutical industry. At present, the medical rubber products mainly comprise: medical silicone rubber catheters, medical rubber tubes, pure rubber tubes, medical rubber plugs, medical transfusion rubber plugs, antibiotic bottle plugs; vaccine bottle stoppers, butyl albumin bottle stoppers, butyl rubber bottle stoppers, medical air cushions, sterilized rubber medical gloves, disposable rubber examination gloves, artificial silica gel organs and the like. As a medical rubber product, besides physical properties, the rubber product must be ensured to be nontoxic and chemically inert, and particularly, the rubber product in vivo has the characteristics of no pathogenicity, no damage to adjacent tissues, no allergy, good aging performance and the like.
Under the current technical development level, manufacturers can basically achieve no toxic or side effect of medical rubber products, in order to increase the use scenes of the products, technicians often improve the various performances of rubber parts by utilizing a mode of performance complementation among components in the composition, but through research, three important parameters of the medical rubber composition are found: in general, the conventional rubber composition for medical use cannot achieve the combination of high air permeability, high elasticity and high strength at the same time, because it is very difficult to achieve the combination of air permeability, elasticity (elongation at break, permanent set ratio after compression/tension), and strength, and often the combination of air permeability, elasticity and strength are reduced after the air permeability of a material is increased or the combination of air permeability and strength is reduced after the elasticity of a material is increased by adjusting the components and processes of the composition.
Disclosure of Invention
In order to solve the problems, the invention provides a medical rubber composition and a rubber part which can enable the rubber part to have high air permeability, high elasticity and high strength, and the specific scheme is as follows:
the invention provides a medical rubber composition, which comprises halogenated butyl rubber, polyimide resin, polyolefin resin, organic acid metal salt, a cross-linking agent and an antioxidant.
Preferably, the organic acid metal salt comprises one or more of hydroxyl benzene sulfonic acid, salicylic acid and acetic acid; the metal is selected from one or more of calcium, magnesium and zinc.
Preferably, the organic acid metal salt comprises one or more of zinc acetate, calcium dobesilate, ammonium benzoate calcium salicylate and magnesium salicylate.
Preferably, the metal salt of an organic acid comprises zinc acetate and calcium benzonate amine salicylate in a mass ratio of 1: 2.
Preferably, the polyimide resin is selected from one or more of polyetherimide, polyamide-imide and bismaleimide.
Preferably, the polyimide resin is 1.38 to 1.41g/cm 3 。
Preferably, the polyolefin resin is selected from one or more of polyethylene and polypropylene; further, the polymerization degree of the polyethylene is 180-220, and the polymerization degree of the polypropylene is 110-170.
Preferably, the halogenated butyl rubber is selected from chlorinated butyl rubber or brominated butyl rubber.
Preferably, the chlorinated butyl rubber has a bound chlorine content of from 1.0 to 1.2% by weight and a double bond content of from 1.2 to 1.4 mol%.
Preferably, the brominated butyl rubber has a bromine-bound mass fraction of 1.8 to 2.0 wt% and a double bond content of 1.2 to 1.4 mol%.
Preferably, the cross-linking agent is selected from one or more of magnesium oxide, calcium oxide, zinc oxide and copper oxide.
Preferably, the antioxidant comprises one or more than two of antioxidant 168 and antioxidant 1010.
Preferably, the medical rubber composition comprises the following components in parts by weight: 70-90 parts of halogenated butyl rubber, 2-10 parts of polyimide resin, 1-5 parts of polyolefin resin, 1-3 parts of organic acid metal salt, 2-6 parts of cross-linking agent and 2-3 parts of antioxidant.
The present invention also provides a rubber member containing the medical rubber composition.
Preferably, the preparation method of the rubber component comprises the following steps:
adding halogenated butyl rubber, polyimide resin and polyolefin resin into an internal mixer, and mixing for 30-50min at the temperature of 220-; adding organic acid metal salt, cross-linking agent and antioxidant, and mixing at 210 ℃ and 180rpm at 140 ℃ for 3-7 min; molding for 5-25min at the temperature of 140 ℃ and 160 ℃ and under the pressure of 0.5-1.0 MPa.
Advantageous effects
The invention has the beneficial effects that:
in the prior art, chinese patent CN201811600037.2 discloses an organic acid metal salt phenolic resin complex and a preparation method thereof, wherein an organic acid metal salt and phenolic hydroxyl of phenolic resin form a complex, a central ion of the complex is a metal ion with coordination ability, and a coordination ion surrounding the metal ion is a carboxylate ion, a hydroxide ion, and a phenoxy ion. The advantage of this structure is that the phenolic resin is further cross-linked by complexation of phenolic hydroxyl groups with metal ions, which is directly reflected by an increase in the glass transition temperature of the composite and an increase in the softening point of the resin. The coordination bond formed by the complex structure belongs to a dynamic cross-linking bond, and can be formed again after the coordination bond is broken, so that the function of reinforcing the resin matrix is achieved. In addition, the formation of such coordinate bonds is related to the phenolic hydroxyl groups of the phenolic resin, which generally do not participate in chemical reactions during the resin production process and the curing and crosslinking process of the resin. Chinese patent CN202011336788.5 discloses a rubber composition containing organic acid metal salt phenolic resin compound, a preparation method and an application thereof, wherein organic acid long chains of organic acid metal salts in the organic acid metal salt phenolic resin compound can also increase the compatibility of resin and rubber, and simultaneously, metal ions of the organic acid metal salts in the organic acid metal salt phenolic resin compound and an oxide layer on the surface of a steel wire have interaction, so that the acting force on the interface of the rubber and a steel wire is increased, and the dynamic cross-linking bond formed by complexing the organic acid metal salts and resorcinol-formaldehyde resin is beneficial to improving the aging resistance of an adhesive. It can be seen that in the prior art, the composition of organic acid metal salt and resin and rubber is based on the action mechanism of organic acid metal salt and phenolic resin, if the composition is separated from phenolic resin, the action of organic acid metal salt in the composite can not be established, and the effect is to promote the single performance of resin or promote the acting force between the composition and metal (foreign matter), and the balance improvement of the multi-aspect parameter performance of rubber material is not involved.
The present invention achieves the effect of simultaneously satisfying the air permeability, elasticity and strength of a rubber member by adding a specific resin and a specific metal salt of an organic acid to a rubber composition.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The following examples and comparative examples are parallel runs, with the same processing steps and parameters, unless otherwise indicated.
Reagents used in the examples of the present invention: chlorinated butyl rubber: CHLOROBUTYL1066 (stabilizer: NS, halogen content: 1.26%, Mooney viscosity: 38ML1+8(125 ℃ C.), specific gravity: 0.92) manufactured by JAN butyl; at least one of LANXESS X _ butylcb 1240 manufactured by LANXESS corporation. Brominated butyl rubber: BROMOBUTYL 2255 (stabilizer: NS, halogen content: 2.0%, Mooney viscosity: 46ML1+8(125 ℃ C.), specific gravity: 0.93) manufactured by JEOL corporation; at least one of LANXESS X _ BUTYL BBX2 manufactured by LANXESS corporation.
Comparative example 0A rubber composition for medical use
The medical rubber composition comprises halogenated butyl rubber, a cross-linking agent and an antioxidant.
The halogenated butyl rubber is selected from chlorinated butyl rubber CHLOROBUTYL 1066.
The cross-linking agent is selected from magnesium oxide.
The antioxidant comprises a mixture of an antioxidant 168 and an antioxidant 1010 in a mass ratio of 1: 1.
The medical rubber composition comprises the following components in parts by weight: 70 parts of halogenated butyl rubber, 4 parts of a crosslinking agent and 3 parts of an antioxidant.
The preparation method of the rubber part comprises the following steps:
adding halogenated butyl rubber into an internal mixer, and mixing for 30min at 230 ℃ and 120 rpm; adding cross-linking agent and antioxidant, and mixing at 190 deg.C and 150rpm for 5 min; molding at 150 deg.C under 1.0MPa for 20 min.
Example 1A rubber composition for medical use
The medical rubber composition comprises halogenated butyl rubber, polyimide resin, polyolefin resin, organic acid metal salt, cross-linking agent and antioxidant.
The organic acid metal salt includes zinc acetate.
The polyimide resin is selected from polyetherimides.
The polyimide resin is 1.38g/cm 3 。
The polyolefin resin is selected from polyethylene, and the polymerization degree of the polyethylene is 180-190.
The halogenated butyl rubber is selected from chlorinated butyl rubber CHLOROBUTYL 1066.
The cross-linking agent is selected from magnesium oxide.
The antioxidant comprises a mixture of an antioxidant 168 and an antioxidant 1010 in a mass ratio of 1: 1.
The medical rubber composition comprises the following components in parts by weight: 70 parts of halogenated butyl rubber, 8 parts of polyimide resin, 5 parts of polyolefin resin, 3 parts of organic acid metal salt, 4 parts of cross-linking agent and 3 parts of antioxidant.
The preparation method of the rubber part comprises the following steps:
adding halogenated butyl rubber, polyimide resin and polyolefin resin into an internal mixer, and mixing at 230 ℃ and 120rpm for 30 min; adding organic acid metal salt, cross-linking agent and antioxidant, and mixing at 190 deg.C and 150rpm for 5 min; molding at 150 deg.C under 1.0MPa for 20 min.
Example 2A rubber composition for medical use
The medical rubber composition comprises halogenated butyl rubber, polyimide resin, polyolefin resin, organic acid metal salt, cross-linking agent and antioxidant.
The metal salt of an organic acid includes calcium dobesilate.
The polyimide resin is selected from polyamide-imide.
The polyimide resin is 1.38g/cm 3 。
The polyolefin resin is selected from polyethylene, and the polymerization degree of the polyethylene is 210-220.
The halogenated butyl rubber is selected from chlorinated butyl rubber CHLOROBUTYL 1066.
The cross-linking agent is selected from calcium oxide.
The antioxidant comprises a mixture of an antioxidant 168 and an antioxidant 1010 in a mass ratio of 1: 1.
The medical rubber composition comprises the following components in parts by weight: 80 parts of halogenated butyl rubber, 6 parts of polyimide resin, 4 parts of polyolefin resin, 3 parts of organic acid metal salt, 4 parts of cross-linking agent and 3 parts of antioxidant.
The preparation method of the rubber part comprises the following steps:
adding halogenated butyl rubber, polyimide resin and polyolefin resin into an internal mixer, and mixing at 230 ℃ and 120rpm for 30 min; adding organic acid metal salt, cross-linking agent and antioxidant, and mixing at 190 deg.C and 150rpm for 5 min; molding at 150 deg.C under 1.0MPa for 20 min.
Example 3A rubber composition for medical use
The medical rubber composition comprises halogenated butyl rubber, polyimide resin, polyolefin resin, organic acid metal salt, cross-linking agent and antioxidant.
The metal salt of an organic acid comprises magnesium salicylate.
The polyimide resin is selected from bismaleimide.
The polyimide resin is 1.41g/cm 3 。
The polyolefin resin is selected from polypropylene, and the polymerization degree of the polypropylene is 150-170.
The halogenated butyl rubber is selected from brominated butyl rubber Bromobutyl 2255.
The cross-linking agent is selected from zinc oxide.
The antioxidant comprises a mixture of an antioxidant 168 and an antioxidant 1010 in a mass ratio of 1: 1.
The medical rubber composition comprises the following components in parts by weight: 90 parts of halogenated butyl rubber, 2 parts of polyimide resin, 2 parts of polyolefin resin, 3 parts of organic acid metal salt, 4 parts of cross-linking agent and 3 parts of antioxidant.
The preparation method of the rubber part comprises the following steps:
adding halogenated butyl rubber, polyimide resin and polyolefin resin into an internal mixer, and mixing at 230 ℃ and 120rpm for 30 min; adding organic acid metal salt, cross-linking agent and antioxidant, and mixing at 190 deg.C and 150rpm for 5 min; molding at 150 deg.C under 1.0MPa for 20 min.
Example 4A rubber composition for medical use
The medical rubber composition comprises halogenated butyl rubber, polyimide resin, polyolefin resin, organic acid metal salt, cross-linking agent and antioxidant.
The metal salt of an organic acid comprises ammonium benzoate calcium salicylate.
The polyimide resin is selected from polyetherimides.
The polyimide resin is 1.38g/cm 3 。
The polyolefin resin is selected from polyethylene, and the polymerization degree of the polyethylene is 180-190.
The halogenated butyl rubber is selected from chlorinated butyl rubber CHLOROBUTYL 1066.
The cross-linking agent is selected from magnesium oxide.
The antioxidant comprises a mixture of an antioxidant 168 and an antioxidant 1010 in a mass ratio of 1: 1.
The medical rubber composition comprises the following components in parts by weight: 70 parts of halogenated butyl rubber, 8 parts of polyimide resin, 5 parts of polyolefin resin, 3 parts of organic acid metal salt, 4 parts of cross-linking agent and 3 parts of antioxidant.
The preparation method of the rubber part comprises the following steps:
adding halogenated butyl rubber, polyimide resin and polyolefin resin into an internal mixer, and mixing at 230 ℃ and 120rpm for 30 min; adding organic acid metal salt, cross-linking agent and antioxidant, and mixing at 190 deg.C and 150rpm for 5 min; molding at 150 deg.C under 1.0MPa for 20 min.
Example 5A rubber composition for medical use
The medical rubber composition comprises halogenated butyl rubber, polyimide resin, polyolefin resin, organic acid metal salt, cross-linking agent and antioxidant.
The organic acid metal salt comprises zinc acetate and ammonium benzoate calcium salicylate with the mass ratio of 1: 2.
The polyimide resin is selected from polyetherimides.
The polyimide resin is 1.38g/cm 3 。
The polyolefin resin is selected from polyethylene, and the polymerization degree of the polyethylene is 180-190.
The halogenated butyl rubber is selected from chlorinated butyl rubber CHLOROBUTYL 1066.
The cross-linking agent is selected from magnesium oxide.
The antioxidant comprises a mixture of an antioxidant 168 and an antioxidant 1010 in a mass ratio of 1: 1.
The medical rubber composition comprises the following components in parts by weight: 70 parts of halogenated butyl rubber, 8 parts of polyimide resin, 5 parts of polyolefin resin, 3 parts of organic acid metal salt, 4 parts of cross-linking agent and 3 parts of antioxidant.
The preparation method of the rubber part comprises the following steps:
adding halogenated butyl rubber, polyimide resin and polyolefin resin into an internal mixer, and mixing at 230 ℃ and 120rpm for 30 min; adding organic acid metal salt, cross-linking agent and antioxidant, and mixing at 190 deg.C and 150rpm for 5 min; molding at 150 deg.C under 1.0MPa for 20 min.
Comparative examples 1 to 4: corresponding to examples 1 to 4, respectively, and differing from examples 1 to 4 in that: no organic acid metal salt is added.
Comparative example 5: the difference from example 5 is that: the organic acid metal salt comprises zinc acetate and ammonium benzoate calcium salicylate with the mass ratio of 2: 1.
Comparative example 6: the differences from example 5 are: the organic acid metal salt comprises zinc acetate and ammonium benzoate calcium salicylate with the mass ratio of 1: 1.
Comparative example 7: the difference from example 5 is that: the organic acid metal salt comprises zinc acetate and ammonium benzoate calcium salicylate with the mass ratio of 1: 3.
Comparative example 8: the difference from example 5 is that: the organic acid metal salt comprises zinc acetate and calcium dobesilate in a mass ratio of 1: 2.
Comparative example 9: the difference from example 5 is that: the organic acid metal salt comprises zinc acetate and magnesium salicylate in a mass ratio of 1: 2.
Comparative example 10: the difference from example 5 is that: the organic acid metal salt comprises calcium dobesilate and calcium benzonate salicylate in a mass ratio of 1: 2.
Comparative example 11: the difference from example 5 is that: the organic acid metal salt comprises magnesium salicylate and ammonium benzoate calcium salicylate with the mass ratio of 1: 2.
The properties of the rubber parts prepared in the above examples were examined and the results are shown in Table 1.
TABLE 1 Property parameters of the products of the examples and comparative examples
As can be seen from the above table, the medical rubber composition provided by the present invention can combine high air permeability, high elasticity and high strength.
While the preferred embodiments and examples of the present invention have been described in detail, the present invention is not limited to the embodiments and examples, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. A medical rubber composition characterized by: comprises halogenated butyl rubber, polyimide resin, polyolefin resin, organic acid metal salt, cross-linking agent and antioxidant.
2. The medical rubber composition according to claim 1, wherein: the organic acid metal salt, wherein the organic acid comprises one or more of hydroxyl benzene sulfonic acid, salicylic acid and acetic acid; the metal is one or more selected from calcium, magnesium and zinc.
3. The medical rubber composition according to claim 1, wherein: the organic acid metal salt comprises one or more of zinc acetate, calcium dobesilate, ammonium benzoate calcium salicylate and magnesium salicylate.
4. The medical rubber composition according to claim 1, wherein: the polyimide resin is selected from one or more of polyetherimide, polyamide-imide and bismaleimide.
5. The medical rubber composition according to claim 1, wherein: the polyolefin resin is selected from one or more of polyethylene and polypropylene; the polymerization degree of the polyethylene is 180-220, and the polymerization degree of the polypropylene is 110-170.
6. The medical rubber composition according to claim 1, wherein: the halogenated butyl rubber is selected from chlorinated butyl rubber or brominated butyl rubber.
7. The medical rubber composition according to claim 6, wherein: the content of the combined chlorine of the chlorinated butyl rubber is 1.0 to 1.2 weight percent, and the content of double bonds is 1.2 to 1.4mol percent; the brominated butyl rubber has the mass fraction of bromine combined with 1.8-2.0 wt% and the double bond content of 1.2-1.4 mol%.
8. The medical rubber composition according to claim 1, wherein: the medical rubber composition comprises the following components in parts by weight: 70-90 parts of halogenated butyl rubber, 2-10 parts of polyimide resin, 1-5 parts of polyolefin resin, 1-3 parts of organic acid metal salt, 2-6 parts of cross-linking agent and 2-3 parts of antioxidant.
9. A rubber member comprising the medical rubber composition according to claims 1 to 8.
10. The rubber component of claim 9, wherein: the preparation method of the rubber part comprises the following steps: adding halogenated butyl rubber, polyimide resin and polyolefin resin into an internal mixer, and mixing for 30-50min at the temperature of 220-; adding organic acid metal salt, cross-linking agent and antioxidant, and mixing at 210 ℃ and 180rpm at 140 ℃ for 3-7 min; molding at 160 deg.C and 0.5-1.0MPa for 5-25min at 140 deg.C.
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| JPH06245977A (en) * | 1993-02-25 | 1994-09-06 | Nissho Corp | Rubber plug for medical treatment container |
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| CN112898693A (en) * | 2019-11-19 | 2021-06-04 | 住友橡胶工业株式会社 | Medical rubber composition and medical rubber member |
-
2022
- 2022-08-03 CN CN202210925811.7A patent/CN115058087A/en active Pending
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| JPH06245977A (en) * | 1993-02-25 | 1994-09-06 | Nissho Corp | Rubber plug for medical treatment container |
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