CN107400299A - The method of modifying and rubber stopper of graphene medical grade rubber, rubber - Google Patents
The method of modifying and rubber stopper of graphene medical grade rubber, rubber Download PDFInfo
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- CN107400299A CN107400299A CN201710589258.3A CN201710589258A CN107400299A CN 107400299 A CN107400299 A CN 107400299A CN 201710589258 A CN201710589258 A CN 201710589258A CN 107400299 A CN107400299 A CN 107400299A
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- rubber
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- auxiliary agent
- carbon black
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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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
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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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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- 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)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention provides a kind of method of modifying of rubber:Including according to rubber:Graphene:Carbon black:Auxiliary agent is 100:0.1‑2:30:0.5 5 mass ratio is fed;The rubber, graphene, carbon black and auxiliary agent are kneaded, wherein the graphene is the graphene with high BET specific surface area.The present invention also provides a kind of rubber master batch being modified using this method and the rubber stopper prepared with the rubber master batch.
Description
Technical field
The invention belongs to polymer composite, medical grade rubber field, is related to a kind of graphene Medical rubber plug master batch
Preparation method.
Background technology
Medical grade rubber bottle stopper is the heat-resistant powder filler product for having definite shape, size, medicinal for glass, plastics etc.
The sealing of flask mouth.It is general to use the sizing materials such as NR, IIR and SBR to make, wherein IIR is main production application rubber stopper now
Raw material.Because IIR has good chemical stability and heat endurance, most prominent is air-tightness and watertightness.But
It is in the sealing of some medicines, the medicine turbidity of IIR rubber stoppers is unable to reach gratifying effect.Turbidity generally refers to water
The obstruction degree that middle suspension is occurred when being passed through to light, in Medical rubber plug field, this concept just refers to butyl rubber
The degree of the Substances Pollution medicines such as small molecule, free sizing material in plug, general turbidity are lower, then it represents that phase of the rubber stopper to medicine
Capacitive is preferable, and performance is more excellent.IIR rubber stoppers can add a variety of fillers when preparing, and filer content is higher, so free
Small molecule, sizing material, filler etc. are higher, and then the turbidity of some medicines is very high, does not reach using standard.In general method of modifying is simultaneously
This phenomenon can not be improved, some can only improve drug compatibility by aluminum coated steel, but the method can make complex process
Degree increase, cost increase, and also easily tilting comes off barrier film in use, influences using effect.In addition, pass
System method also needs to add substantial amounts of carbon black in preparation process, so mechanical strength cannot ensure that fragmentation is serious.
The technology contents listed in the prior art only represent the technology that inventor is grasped, and are not considered as naturally
It is the novelty and creativeness that prior art and being used for evaluates the present invention.
The content of the invention
For one or more defects existing for prior art, the present invention provides a kind of graphene medical grade rubber, including:
Rubber, graphene, carbon black, and auxiliary agent,
The rubber, graphene, the mass ratio of carbon black and auxiliary agent are 100:(0.1-2):30:(0.5-5).
According to an aspect of the present invention, the graphene is the graphene with high BET specific surface area;Preferably, institute
The BET specific surface area of graphene is stated in 300m2/ more than g;It is further preferred that the BET specific surface area of the graphene exists
450m2/ more than g.
According to an aspect of the present invention, the rubber is butyl rubber.
According to an aspect of the present invention, the auxiliary agent is graphite oxide.
According to an aspect of the present invention, the mass ratio of the rubber, graphene, carbon black and auxiliary agent is 100:0.5:30:
1。
Present invention also offers a kind of method of modifying of rubber:Including:According to rubber:Graphene:Carbon black:Auxiliary agent is
100:0.1-2:30:0.5-5 mass ratio is fed;It is kneaded with to the rubber, graphene, carbon black and auxiliary agent.
According to an aspect of the present invention, the rubber is butyl rubber.
According to an aspect of the present invention, the auxiliary agent is graphite oxide.
According to an aspect of the present invention, the graphene is the graphene with high BET specific surface area;Preferably, institute
The BET specific surface area of graphene is stated in 300m2/ more than g;It is further preferred that the BET specific surface area of the graphene exists
450m2/ more than g.
According to an aspect of the present invention, the rubber, graphene, carbon black and auxiliary agent are entered using banbury or mill
Row is kneaded.
According to an aspect of the present invention, the banbury or mill are heated to 90-120 DEG C, preferably 110 DEG C, protected
Temperature constant is held, rubber, graphene, carbon black, auxiliary agent is added and starts to be kneaded.
According to an aspect of the present invention, 10min-30min is kneaded to the rubber, graphene, carbon black and auxiliary agent, preferably
15min。
The present invention also provides a kind of rubber master batch being modified according to the above method.
The present invention also provides a kind of rubber stopper prepared using the rubber master batch.
The present invention can reduce the medicine turbidity of Medical rubber plug, improve drug compatibility.Utilize the high BET (BE of graphene
> 300m2/g), the features such as shielding action is strong, adsorption capacity is strong, realize this purpose.In addition, the addition of graphene is also
It can be the mechanical property enhancing of rubber, reduce fragmentation.
Embodiment
Hereinafter, some exemplary embodiments are simply just described.As one skilled in the art will recognize that
Like that, without departing from the spirit or scope of the present invention, described implementation can be changed by various different modes
Example.Therefore, description is considered essentially illustrative rather than restrictive.
The preferred embodiments of the present invention are illustrated below, it will be appreciated that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
One embodiment of the present of invention is related to a kind of graphene medical grade rubber, including:Rubber, graphene, carbon black, and help
Agent, the rubber, graphene, the mass ratio of carbon black and auxiliary agent are 100:(0.1-2):30:(0.5-5).Such as:Rubber, graphite
The mass ratio of alkene, carbon black and auxiliary agent is 100:0.1:30:5 or 100:0.2:30:0.5 or 100:1:30:3 or 100:1.2:
30:1.5, etc..The BET specific surface area of the graphene is in 300m2/ more than g;Preferably, the BET specific surface area of the graphene
In 450m2/ more than g.The rubber is butyl rubber.The auxiliary agent is graphite oxide.
As the preferred embodiment of such scheme, the rubber, graphene, the mass ratio of carbon black and auxiliary agent are 100:
0.5:30:1。
An alternative embodiment of the invention is related to a kind of preparation method of graphene medical grade rubber master batch or changing for rubber
Property method, this method include:According to butyl rubber:Graphene:Carbon black:The mass ratio of auxiliary agent is 100:0.1-2:30:0.5-5 enters
Row charging, is preferably in a proportion of about 100:0.5:30:1, then start to be kneaded, be kneaded 10min-30min, preferably 15min, obtain
Graphene butyl rubber master batch.Graphene used is the graphene with high BET specific surface area prepared by oxidation-reduction method,
Its BET > 300m2/ g, preferably in 450m2/ more than g.Method after being improved using the present invention, gained elastomeric material structure are more caused
It is close, reduce the compatibility with other materials, improve the resistance to corrosion of elastomeric material, there is screen disadvantage effect well.
Illustrated above by taking butyl rubber as an example.It will appreciated by the skilled person that the present invention can be with profit
Implemented with other rubber raw materials, such as the rubber such as medical silica-gel, medical SEBS.
According to one embodiment of present invention, above-mentioned raw materials are kneaded using banbury or mill.Such as will be close
Mill or mill are heated to 90-120 DEG C, preferably 110 DEG C, keeping temperature constant, add butyl rubber, graphene, charcoal
Black, auxiliary agent, then start to be kneaded.
Graphene used is, for example, the high BET specific surface area graphene prepared by oxidation-reduction method.High BET specific surface area
Graphene have the characteristics that shielding action is strong, adsorption capacity is strong, therefore the medicine turbidity of rubber can be reduced.Meanwhile this hair
Bright the features such as also using small graphene density, light weight, big stiffness, just reached using powder amount during few additive
The effect of powder amount during the high addition of other fillers, so often graphene only needs addition little by little can just reach very
Good performance, it is more beneficial for improving the intensity of rubber stopper, reduces fragmentation, reduce medicine turbidity, improve medicine phase
Capacitive.
Auxiliary agent can for example include graphite oxide, and addition graphite oxide is dispersant, improve graphene in butyl rubber
Dispersion effect, the general addition of graphite oxide be graphene quality 10%-50%.
Illustrate the method for modifying of the present invention below by specific example.
Example one
Banbury is warming up to 110 DEG C, temperature is constant.Weigh butyl rubber 1000g, graphene 5g, carbon black 300g, auxiliary agent
10g, it is put into the constant banbury of temperature, is kneaded 15min, finally obtains graphene butyl rubber master batch.
Example two
Mill is warming up to 110 DEG C, temperature is constant.Weigh butyl rubber 1000g, graphene 5g, carbon black 300g, auxiliary agent
10g, it is put into the constant banbury of temperature, is kneaded 15min, finally obtains graphene butyl rubber master batch.
Example three
Banbury is warming up to 90 DEG C, temperature is constant.Weigh butyl rubber 1000g, graphene 5g, carbon black 300g, auxiliary agent
10g, it is put into the constant banbury of temperature, is kneaded 15min, finally obtains graphene butyl rubber master batch.
Example four
Banbury is warming up to 120 DEG C, temperature is constant.Weigh butyl rubber 1000g, graphene 5g, carbon black 300g, auxiliary agent
10g, it is put into the constant banbury of temperature, is kneaded 15min, finally obtains graphene butyl rubber master batch.
Example five
Banbury is warming up to 110 DEG C, temperature is constant.Weigh butyl rubber 1000g, graphene 1g, carbon black 300g, auxiliary agent
10g, it is put into the constant banbury of temperature, is kneaded 15min, finally obtains graphene butyl rubber master batch.
Example six
Banbury is warming up to 110 DEG C, temperature is constant.Butyl rubber 1000g is weighed, graphene 20g, carbon black 300g, is helped
Agent 10g, it is put into the constant banbury of temperature, is kneaded 15min, finally obtains graphene butyl rubber master batch.
Example seven
Banbury is warming up to 110 DEG C, temperature is constant.Weigh butyl rubber 1000g, graphene 5g, carbon black 300g, auxiliary agent
50g, it is put into the constant banbury of temperature, is kneaded 15min, finally obtains graphene butyl rubber master batch.
Following Table I, Table II and Table III respectively illustrates the physics and chemical property of raw material and modified materials (embodiment 1)
Contrast.
From Table I, by the modified rubber master batch of the method for the present invention, hardness softens, darkened.Therefore adopt
The Medical bottle stopper elasticity prepared with the rubber master batch is more preferable, and translucency is weaker, helps to maintain the stabilization of medicine.
From Table II, by the modified rubber master batch of the method for the present invention, its chemical characteristic complies fully with requirement.
Especially turbidity has obvious reduction.Turbidity refers to the obstruction degree occurred when suspension passes through to light in water, and medicine is turbid
Degree is exactly on this basis, to refer to fine organic matter and inorganic matter, planktonic organism, microorganism and colloidal substance in medicine
Deng.
From Table III, according to medicine intermiscibility contrast test, the medicine of the modified rubber master batch of the method through the present invention
Thing intermiscibility substantially reduces, and reduction degree may be up to 75.1%.Absolutely prove it is modified by this invention after rubber master batch substantially have
Help improve medicine stability.
Table I
According to another embodiment of the invention, a kind of rubber master batch prepared according to the above method is also provided.
According to another embodiment of the invention, further relate to a kind of rubber master batch, including rubber, graphene, carbon black,
And auxiliary agent.Wherein described graphene is the graphene with high BET specific surface area, and its BET specific surface area is more than 300, preferably
More than 450.The rubber, graphene, the mass ratio of carbon black and auxiliary agent are 100:0.1-2:30:0.5-5, it is preferably in a proportion of
About 100:0.5:30:1.
Finally it should be noted that:The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention,
Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still may be used
To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic.
Within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., it should be included in the present invention's
Within protection domain.
Claims (10)
1. a kind of graphene medical grade rubber, including:
Rubber, graphene, carbon black, and auxiliary agent,
The rubber, graphene, the mass ratio of carbon black and auxiliary agent are 100:(0.1-2):30:(0.5-5).
2. graphene medical grade rubber as claimed in claim 1, it is characterised in that:The graphene is to compare surface with high BET
Long-pending graphene;Preferably, the BET specific surface area of the graphene is in 300m2/ more than g;It is further preferred that the graphite
The BET specific surface area of alkene is in 450m2/ more than g.
3. graphene medical grade rubber as claimed in claim 1, it is characterised in that:The rubber is butyl rubber;And/or institute
It is graphite oxide to state auxiliary agent.
4. according to the graphene medical grade rubber described in claim any one of 1-3, it is characterised in that:The rubber, graphene, charcoal
Black and auxiliary agent mass ratio is 100:0.5:30:1.
5. a kind of method of modifying of rubber, including:
Fed according to the component and each component mass ratio of any one of Claims 1-4 graphene medical grade rubber;With
The rubber, graphene, carbon black and auxiliary agent are kneaded.
6. the method for modifying of rubber according to claim 5, it is characterised in that:Using banbury or mill to the rubber
Glue, graphene, carbon black and auxiliary agent are kneaded.
7. the method for modifying of rubber according to claim 6, it is characterised in that:The banbury or mill are heated to
90-120 DEG C, preferably 110 DEG C, keeping temperature constant, add rubber, graphene, carbon black, auxiliary agent and start to be kneaded.
8. the method for modifying of the rubber according to any one of claim 5-7, it is characterised in that:To the rubber, graphite
Alkene, carbon black and auxiliary agent are kneaded 10min-30min, preferably 15min.
A kind of 9. rubber master batch being modified according to any one of claim 5-7 method.
A kind of 10. rubber stopper prepared using rubber master batch as claimed in claim 9.
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102850671A (en) * | 2012-09-27 | 2013-01-02 | 应城市恒天药业包装有限公司 | Oral liquid rubber plug material and preparation method thereof |
WO2013083999A2 (en) * | 2011-12-08 | 2013-06-13 | Nanoridge Materials, Incorporated | Nano-enhanced elastomers |
CN105175954A (en) * | 2015-09-29 | 2015-12-23 | 中国航空工业集团公司北京航空材料研究院 | Graphene-containing fluororubber nanocomposite with low gas permeability and preparation method |
CN105419129A (en) * | 2015-12-11 | 2016-03-23 | 江苏润德医用材料有限公司 | Preparation method and application of graphene-halogenated butyl rubber composite |
CN105837963A (en) * | 2016-04-22 | 2016-08-10 | 岳阳瑞森达橡塑工业有限公司 | Butyl rubber composite material applicable to curing bladders |
CN106046632A (en) * | 2016-08-19 | 2016-10-26 | 青岛海力威新材料科技股份有限公司 | Graphene-modified fluororubber and preparation method thereof |
CN106117681A (en) * | 2016-07-13 | 2016-11-16 | 成都创威新材料有限公司 | A kind of neoprene/graphene composite material and preparation method thereof |
CN106279804A (en) * | 2016-08-16 | 2017-01-04 | 青岛蓝湾烯碳材料科技有限责任公司 | The preparation method of graphene microchip/white carbon black compounded rubber |
-
2017
- 2017-07-19 CN CN201710589258.3A patent/CN107400299A/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013083999A2 (en) * | 2011-12-08 | 2013-06-13 | Nanoridge Materials, Incorporated | Nano-enhanced elastomers |
CN102850671A (en) * | 2012-09-27 | 2013-01-02 | 应城市恒天药业包装有限公司 | Oral liquid rubber plug material and preparation method thereof |
CN105175954A (en) * | 2015-09-29 | 2015-12-23 | 中国航空工业集团公司北京航空材料研究院 | Graphene-containing fluororubber nanocomposite with low gas permeability and preparation method |
CN105419129A (en) * | 2015-12-11 | 2016-03-23 | 江苏润德医用材料有限公司 | Preparation method and application of graphene-halogenated butyl rubber composite |
CN105837963A (en) * | 2016-04-22 | 2016-08-10 | 岳阳瑞森达橡塑工业有限公司 | Butyl rubber composite material applicable to curing bladders |
CN106117681A (en) * | 2016-07-13 | 2016-11-16 | 成都创威新材料有限公司 | A kind of neoprene/graphene composite material and preparation method thereof |
CN106279804A (en) * | 2016-08-16 | 2017-01-04 | 青岛蓝湾烯碳材料科技有限责任公司 | The preparation method of graphene microchip/white carbon black compounded rubber |
CN106046632A (en) * | 2016-08-19 | 2016-10-26 | 青岛海力威新材料科技股份有限公司 | Graphene-modified fluororubber and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
梁滔: "石墨烯填充橡胶复合材料研究进展", 《"科迈杯"第1 2 届全国橡胶助剂生产和应用技术研讨会论文集》 * |
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