CN110511452A - Graphene natural rubber macromolecule control bacterium mixed foaming material and preparation method thereof - Google Patents
Graphene natural rubber macromolecule control bacterium mixed foaming material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of graphene natural rubber macromolecule control bacterium mixed foaming material and preparation method thereof, the graphene natural rubber macromolecule control bacterium mixed foaming material is by including that the raw material of following parts by weight is made: 66~75 parts of natural rubber, 17.5~23 parts of polyolefin elastomer, 9~11 parts of nano active medium, 2.4~3 parts of graphene, mould proof 1.2~1.7 parts of control microbial inoculum, 1.7~2.1 parts of zinc oxide, 1.4~1.7 parts of zinc stearate, 1.6~1.9 parts of stearic acid, 2.3~2.8 parts of crosslinking agent, 1.5~1.8 parts of foaming agent.Graphene natural rubber macromolecule control bacterium mixed foaming material antibacterial and mouldproof effect of the invention is good；Tensile strength is high, and elongation at break is big, and mechanical property is good.
Description
Technical field
The present invention relates to rubber product technical fields, and in particular to a kind of graphene natural rubber macromolecule control bacterium mixing hair
Foam material and preparation method thereof.
Background technique
Natural rubber (NR) is a kind of with cis- Isosorbide-5-Nitrae-polyisoprene natural polymer as main component,
91%~94% is rubber hydrocarbon (cis- Isosorbide-5-Nitrae-polyisoprene) in ingredient, remaining is non-for protein, fatty acid, ash content, carbohydrate etc.
Rubber material.Generally chip solid, relative density 0.94, refractive index 1.522, elasticity modulus 2~4MPa, at 130~140 DEG C
Softening, 150~160 DEG C are glued soft, and 200 DEG C of whens start to degrade.There are higher elasticity, slightly plasticity, crystallization at low temperatures hardening under room temperature.
There is preferable alkali resistance, but intolerant to strong acid.Not soluble in water, lower ketones and alcohols, in nonpolar solvent such as chloroform, four chlorinations
It can be swollen in carbon etc..
The structure of natural rubber is mainly the chain structure of macromolecular, molecular weight and its distribution and aggregated structure, natural rubber
The macromolecular chain structure unit of glue is isoprene, and macromolecular chain is mainly to be made of poly- isoolefine, and content accounts for percentage in rubber
97 or more, have aldehyde radical on strand, averagely there is one on every macromolecular chain, exactly aldehyde radical occur condensation or with
Protein breakdown products react to form branching, crosslinking, so that rubber storage medium viscosity increases, on natural rubber macromolecular chain
There are also epoxy groups, relatively more active.The macromolecular end of natural gum, which is inferred, is generally dimethyl-allyl, and the other end is pyrophosphoric acid
Ester group, end group, the aldehyde radical of strand and the element of polymerization are all seldom, in terms of the molecular weight of natural rubber and its distribution,
Wider range of molecular weight, according to foreign countries, at 30,000 or so, natural raw rubber, rubber compound vulcanizes most molecular weight
The intensity of glue is relatively high, and general natural rubber intensity is up to three megapascal.The high mechanical strength of natural rubber main reason is that
It is arranged from reinforcement rubber series, and macromolecular chain can be made to be orientated to form crystallization along stress direction when stretched, and crystal grain point is amorphous big
Reinforcing effect is played in molecule, the same high reason of the intensity that do not expanded is the close of fine particle in its internal structure
It is aggregated and causes.
Natural rubber is usually used in all kinds of tire products, medical supplies, space material, sebific duct, hand as general material
Set, waterproof material etc..Although NR has good comprehensive performance, NR belongs to unsaturated, non-polar rubber.Chemical property
Vivaciously, it is resistance to it is old, heat resistance is poor, and easily have an effect with hydro carbons oil solvent.Therefore, usually right to improve its performance disadvantage
It is blended etc. and is modified, and improves properties, service life and the application range of NR.
But used Natural rubber foam material there is problems at present:
1, do not have antibacterial and mouldproof effect or antibacterial and mouldproof effect is poor, material surface is easy to grow bacterium, mould etc. micro-
Biology；
2, after foamed, tensile strength is substantially reduced, and elongation at break becomes smaller, poor mechanical property, and comprehensive service performance is poor.
Summary of the invention
Based on the above situation, the purpose of the present invention is to provide a kind of graphene natural rubber macromolecule control bacterium mixed foamings
Material and preparation method thereof can effectively solve problem above.
In order to solve the above technical problems, present invention provide the technical scheme that
A kind of graphene natural rubber macromolecule control bacterium mixed foaming material is made of the raw material for including following parts by weight:
66~75 parts of natural rubber, 9~11 parts of nano active medium, 2.4~3 parts of graphene, is prevented 17.5~23 parts of polyolefin elastomer
Mould 1.2~1.7 parts of control microbial inoculum, 1.7~2.1 parts of zinc oxide, 1.4~1.7 parts of zinc stearate, 1.6~1.9 parts of stearic acid, crosslinking
2.3~2.8 parts of agent, 1.5~1.8 parts of foaming agent；The mould proof control microbial inoculum is the B5000 antibacterial agent of BASF；The polyene
Olefin elastomer is that the POE8999 type polyolefin elastomer, POE8150 type polyolefin elastomer and POE7467 type of Dow are poly-
The mixture of olefin elastomer；The crosslinking agent is cumyl peroxide, 1,1- di-t-butyl peroxy -3,3,5- trimethyl
The mixture of hexamethylene and zinc dimethacrylate；The graphene is edge graphene oxide.
Preferably, the graphene natural rubber macromolecule control bacterium mixed foaming material is by the raw material including following parts by weight
It is made: 70 parts of natural rubber, 20 parts of polyolefin elastomer, 10 parts of nano active medium, 2.7 parts of graphene, mould proof control microbial inoculum
1.45 parts, 1.9 parts of zinc oxide, 1.55 parts of zinc stearate, 1.75 parts of stearic acid, 2.65 parts of crosslinking agent, 1.62 parts of foaming agent.
Preferably, the graphene natural rubber macromolecule control bacterium mixed foaming material is by the raw material including following parts by weight
It is made: 71 parts of natural rubber, 21.2 parts of polyolefin elastomer, 10.4 parts of nano active medium, 2.83 parts of graphene, mould proof control bacterium
1.5 parts of agent, 1.8 parts of zinc oxide, 1.6 parts of zinc stearate, 1.8 parts of stearic acid, 2.72 parts of crosslinking agent, 1.65 parts of foaming agent.
Preferably, the POE8999 type polyolefin elastomer, POE8150 type polyolefin elastomer and POE7467 type polyene
POE8999 type polyolefin elastomer, POE8150 type polyolefin elastomer and POE7467 type polyene in the mixture of olefin elastomer
The mass ratio of olefin elastomer is 12:(9~11): (13~16).
Preferably, the cumyl peroxide, 1,1- di-t-butyl peroxy -3,3,5- trimethyl-cyclohexane and diformazan
Sulphur, 1,1 di tert butylperoxy 3,3,5 trimethylcyclohexane and dimethacrylate in the mixture of base zinc acrylate resin
The mass ratio of zinc is 10:(13~16): (4~5).
Preferably, carboxyl relative amount is 22.5%~25.6% in the edge graphene oxide.
It is more preferable with the other components phase same sex in this way, it is easy to be uniformly dispersed, and graphene (integral multi-layered structure is not destroyed)
Performance obtained better holding.
Preferably, the nano active medium is nano-titanium dioxide.
Preferably, the zinc oxide is activated zinc oxide.
Preferably, the foaming agent is azodicarbonamide.
The present invention also provides the preparation method of the graphene natural rubber macromolecule control bacterium mixed foaming material described in one kind,
Include the following steps:
A, by weight respectively claim natural rubber, polyolefin elastomer, nano active medium, graphene, mould proof control microbial inoculum,
Zinc oxide, zinc stearate, stearic acid, crosslinking agent and foaming agent；
B, natural rubber is sent into mixer, 13~15min of mastication is carried out under conditions of temperature is 145~148 DEG C, out
Material；Natural rubber room temperature after mastication stores 48h or more, spare；
C, by the natural rubber handled well through step B mastication and polyolefin elastomer, nano active medium, graphene, anti-
Mould control microbial inoculum, zinc oxide, zinc stearate, stearic acid are sent into mixer together, the mixing 10 under conditions of temperature is 82~86 DEG C
~14min；Then 10~12min of mixing under conditions of temperature is 105~108 DEG C；Then crosslinking agent and foaming agent, In is added
Temperature is 9~12min of mixing under conditions of 118~122 DEG C, and discharging obtains mixing glue mixture；
D, the mixing glue mixture for obtaining step C is sent into open mill, thins on a mill 2~4 times, slice obtains
Mill glue mixture；
E, mill glue mixture is finally sent into hot-pressing and foaming in mold, and be cooled and shaped, then carry out sanction sample, obtained described
Graphene natural rubber macromolecule control bacterium mixed foaming material graphene natural rubber macromolecule control bacterium mixed foaming material.
Compared with prior art, the present invention have the following advantages that and the utility model has the advantages that
Graphene natural rubber macromolecule control bacterium mixed foaming material of the invention is made up of selected raw material, and is optimized each
Material content has selected natural rubber, polyolefin elastomer, nano active medium, the graphene, mould proof control bacterium of appropriate proportion
Agent, zinc oxide, zinc stearate, stearic acid, crosslinking agent and foaming agent had not only given full play to respective advantage, but also be complementary to one another, mutually
Promote, promotes the quality stability of product, graphene natural rubber macromolecule control bacterium mixed foaming material antibacterial and mouldproof obtained
Effect is good；Tensile strength is high, and elongation at break is big, and mechanical property is good.
The natural rubber of graphene natural rubber macromolecule control bacterium mixed foaming material addition proper proportion of the invention gathers
Olefin elastomer ensure that as the primary raw material of graphene natural rubber macromolecule control bacterium mixed foaming material of the invention
Graphene natural rubber macromolecule control bacterium mixed foaming material of the invention has tensile strength height, and elongation at break is big equal good
Mechanical property.
The nano active medium of proper proportion in graphene natural rubber macromolecule control bacterium mixed foaming material of the invention
It is (nano-titanium dioxide itself has certain antibacterial and mouldproof effect), graphene (having certain antibacterial and mouldproof effect in itself), mould proof
The addition for controlling microbial inoculum (anti-bacterium mildewproof additive) cooperates with other components, with the matrixes such as natural rubber, polyolefin elastomer
Material compatibility is good, and plays good synergistic effect, and graphene natural rubber macromolecule control bacterium of the invention is made to mix hair
Foam material has good antibacterial and mouldproof effect good；Nano active medium can also increase graphene natural rubber of the invention simultaneously
The mechanical properties such as the intensity of macromolecule control bacterium mixed foaming material.
Wherein, in graphene natural rubber macromolecule control bacterium mixed foaming material of the invention, the mould proof control microbial inoculum is
The B5000 antibacterial agent of BASF, with nano active medium (nano-titanium dioxide itself has certain antibacterial and mouldproof effect), stone
Black alkene (having certain antibacterial and mouldproof effect) in itself plays good synergistic effect, makes graphene natural rubber high score of the invention
Son control bacterium mixed foaming material has good antibacterial and mouldproof effect good；The polyolefin elastomer is Dow
The mixture of POE8999 type polyolefin elastomer, POE8150 type polyolefin elastomer and POE7467 type polyolefin elastomer, three
Kind polyolefin elastic volume property is similar and different, and three, which arranges in pairs or groups, to be used, it is ensured that while tensile strength, is increased
Add elongation at break, promotes mechanical property, rebound degree also can be improved；The crosslinking agent is cumyl peroxide, bis- uncle of 1,1-
Butyl peroxy -3,3, the mixture of 5- trimethyl-cyclohexane and zinc dimethacrylate, it is ensured that graphene day of the invention
Right rubber macromolecule control bacterium mixed foaming crosslink material is moderate, and cross-linked areas is evenly distributed, and can greatly promote tensile strength, fracture
The mechanical properties such as elongation, and odorlessness, more environmentally friendly, use is more comfortable；The graphene is edge graphene oxide, with other
The component phase same sex is good, is easy to be uniformly dispersed, and only selective oxidation, and the property retention of graphene is good.
Preparation method simple process of the invention, it is easy to operate, manpower and equipment cost are saved, ensure that of the invention
The superperformance of graphene natural rubber macromolecule control bacterium mixed foaming material.
Specific embodiment
It is right combined with specific embodiments below in order to make those skilled in the art more fully understand technical solution of the present invention
The preferred embodiments of the invention are described, but should not be understood as the limitation to this patent.
Test method described in following embodiments or test method are unless otherwise specified conventional method；The reagent
And material is obtained from routine business approach, or prepare in conventional manner unless otherwise specified.
Embodiment 1:
A kind of graphene natural rubber macromolecule control bacterium mixed foaming material is made of the raw material for including following parts by weight:
66~75 parts of natural rubber, 9~11 parts of nano active medium, 2.4~3 parts of graphene, is prevented 17.5~23 parts of polyolefin elastomer
Mould 1.2~1.7 parts of control microbial inoculum, 1.7~2.1 parts of zinc oxide, 1.4~1.7 parts of zinc stearate, 1.6~1.9 parts of stearic acid, crosslinking
2.3~2.8 parts of agent, 1.5~1.8 parts of foaming agent；The mould proof control microbial inoculum is the B5000 antibacterial agent of BASF；The polyene
Olefin elastomer is that the POE8999 type polyolefin elastomer, POE8150 type polyolefin elastomer and POE7467 type of Dow are poly-
The mixture of olefin elastomer；The crosslinking agent is cumyl peroxide, 1,1- di-t-butyl peroxy -3,3,5- trimethyl
The mixture of hexamethylene and zinc dimethacrylate；The graphene is edge graphene oxide.
Preferably, the graphene natural rubber macromolecule control bacterium mixed foaming material is by the raw material including following parts by weight
It is made: 70 parts of natural rubber, 20 parts of polyolefin elastomer, 10 parts of nano active medium, 2.7 parts of graphene, mould proof control microbial inoculum
1.45 parts, 1.9 parts of zinc oxide, 1.55 parts of zinc stearate, 1.75 parts of stearic acid, 2.65 parts of crosslinking agent, 1.62 parts of foaming agent.
Preferably, the graphene natural rubber macromolecule control bacterium mixed foaming material is by the raw material including following parts by weight
It is made: 71 parts of natural rubber, 21.2 parts of polyolefin elastomer, 10.4 parts of nano active medium, 2.83 parts of graphene, mould proof control bacterium
1.5 parts of agent, 1.8 parts of zinc oxide, 1.6 parts of zinc stearate, 1.8 parts of stearic acid, 2.72 parts of crosslinking agent, 1.65 parts of foaming agent.
Preferably, the POE8999 type polyolefin elastomer, POE8150 type polyolefin elastomer and POE7467 type polyene
POE8999 type polyolefin elastomer, POE8150 type polyolefin elastomer and POE7467 type polyene in the mixture of olefin elastomer
The mass ratio of olefin elastomer is 12:(9~11): (13~16).
Preferably, the cumyl peroxide, 1,1- di-t-butyl peroxy -3,3,5- trimethyl-cyclohexane and diformazan
Sulphur, 1,1 di tert butylperoxy 3,3,5 trimethylcyclohexane and dimethacrylate in the mixture of base zinc acrylate resin
The mass ratio of zinc is 10:(13~16): (4~5).
Preferably, carboxyl relative amount is 22.5%~25.6% in the edge graphene oxide.
Preferably, the nano active medium is nano-titanium dioxide.
Preferably, the zinc oxide is activated zinc oxide.
Preferably, the foaming agent is azodicarbonamide.
The present embodiment also provides the preparation side of graphene natural rubber macromolecule control bacterium mixed foaming material described in one kind
Method, including the following steps:
A, by weight respectively claim natural rubber, polyolefin elastomer, nano active medium, graphene, mould proof control microbial inoculum,
Zinc oxide, zinc stearate, stearic acid, crosslinking agent and foaming agent；
B, natural rubber is sent into mixer, 13~15min of mastication is carried out under conditions of temperature is 145~148 DEG C, out
Material；Natural rubber room temperature after mastication stores 48h or more, spare；
C, by the natural rubber handled well through step B mastication and polyolefin elastomer, nano active medium, graphene, anti-
Mould control microbial inoculum, zinc oxide, zinc stearate, stearic acid are sent into mixer together, the mixing 10 under conditions of temperature is 82~86 DEG C
~14min；Then 10~12min of mixing under conditions of temperature is 105~108 DEG C；Then crosslinking agent and foaming agent, In is added
Temperature is 9~12min of mixing under conditions of 118~122 DEG C, and discharging obtains mixing glue mixture；
D, the mixing glue mixture for obtaining step C is sent into open mill, thins on a mill 2~4 times, slice obtains
Mill glue mixture；
E, mill glue mixture is finally sent into hot-pressing and foaming in mold, and be cooled and shaped, then carry out sanction sample, obtained described
Graphene natural rubber macromolecule control bacterium mixed foaming material graphene natural rubber macromolecule control bacterium mixed foaming material.
Embodiment 2:
A kind of graphene natural rubber macromolecule control bacterium mixed foaming material is made of the raw material for including following parts by weight:
66 parts of natural rubber, 17.5 parts of polyolefin elastomer, 9 parts of nano active medium, 2.4 parts of graphene, mould proof 1.2 parts of control microbial inoculum,
1.7 parts of zinc oxide, 1.4 parts of zinc stearate, 1.6 parts of stearic acid, 2.3 parts of crosslinking agent, 1.5 parts of foaming agent；The mould proof control microbial inoculum
For the B5000 antibacterial agent of BASF；The polyolefin elastomer be Dow POE8999 type polyolefin elastomer,
The mixture of POE8150 type polyolefin elastomer and POE7467 type polyolefin elastomer；The crosslinking agent is peroxidating diisopropyl
The mixture of benzene, 1,1 di tert butylperoxy 3,3,5 trimethylcyclohexane and zinc dimethacrylate；The graphene is
Edge graphene oxide.
In the present embodiment, the POE8999 type polyolefin elastomer, POE8150 type polyolefin elastomer and POE7467
POE8999 type polyolefin elastomer, POE8150 type polyolefin elastomer and POE7467 in the mixture of type polyolefin elastomer
The mass ratio of type polyolefin elastomer is 12:9:13.
In the present embodiment, the cumyl peroxide, 1,1- di-t-butyl peroxy -3,3,5- trimethyl-cyclohexane
With sulphur, 1,1 di tert butylperoxy 3,3,5 trimethylcyclohexane and dimethyl in the mixture of zinc dimethacrylate
The mass ratio of zinc acrylate resin is 10:13:4.
In the present embodiment, carboxyl relative amount is 22.5% in the edge graphene oxide.
In the present embodiment, the nano active medium is nano-titanium dioxide.
In the present embodiment, the zinc oxide is activated zinc oxide.
In the present embodiment, the foaming agent is azodicarbonamide.
In the present embodiment, the preparation method of the graphene natural rubber macromolecule control bacterium mixed foaming material, packet
Include the following steps:
A, by weight respectively claim natural rubber, polyolefin elastomer, nano active medium, graphene, mould proof control microbial inoculum,
Zinc oxide, zinc stearate, stearic acid, crosslinking agent and foaming agent；
B, natural rubber is sent into mixer, mastication 15min, discharging is carried out under conditions of temperature is 145 DEG C；Mastication is complete
Natural rubber room temperature after finishing stores 48h or more, spare；
C, by the natural rubber handled well through step B mastication and polyolefin elastomer, nano active medium, graphene, anti-
Mould control microbial inoculum, zinc oxide, zinc stearate, stearic acid are sent into mixer together, mixing 14min under conditions of temperature is 82 DEG C；
Then mixing 12min under conditions of temperature is 105 DEG C；Then crosslinking agent and foaming agent is added, the condition for being 118 DEG C in temperature
Lower mixing 12min, discharging, obtains mixing glue mixture；
D, the mixing glue mixture for obtaining step C is sent into open mill, thins on a mill 2 times, slice obtains mill
Glue mixture；
E, mill glue mixture is finally sent into hot-pressing and foaming in mold, and be cooled and shaped, then carry out sanction sample, obtained described
Graphene natural rubber macromolecule control bacterium mixed foaming material graphene natural rubber macromolecule control bacterium mixed foaming material.
Embodiment 3:
A kind of graphene natural rubber macromolecule control bacterium mixed foaming material is made of the raw material for including following parts by weight:
75 parts of natural rubber, 23 parts of polyolefin elastomer, 11 parts of nano active medium, 3 parts of graphene, mould proof 1.7 parts of control microbial inoculum, oxidation
2.1 parts of zinc, 1.7 parts of zinc stearate, 1.9 parts of stearic acid, 2.8 parts of crosslinking agent, 1.8 parts of foaming agent；The mould proof control microbial inoculum is bar
The B5000 antibacterial agent of this husband；The polyolefin elastomer is POE8999 type polyolefin elastomer, the POE8150 of Dow
The mixture of type polyolefin elastomer and POE7467 type polyolefin elastomer；The crosslinking agent is cumyl peroxide, 1,1-
The mixture of di-t-butyl peroxy -3,3,5- trimethyl-cyclohexane and zinc dimethacrylate；The graphene is edge oxygen
Graphite alkene.
In the present embodiment, the POE8999 type polyolefin elastomer, POE8150 type polyolefin elastomer and POE7467
POE8999 type polyolefin elastomer, POE8150 type polyolefin elastomer and POE7467 in the mixture of type polyolefin elastomer
The mass ratio of type polyolefin elastomer is 12:11:16.
In the present embodiment, the cumyl peroxide, 1,1- di-t-butyl peroxy -3,3,5- trimethyl-cyclohexane
With sulphur, 1,1 di tert butylperoxy 3,3,5 trimethylcyclohexane and dimethyl in the mixture of zinc dimethacrylate
The mass ratio of zinc acrylate resin is 10:16:5.
In the present embodiment, carboxyl relative amount is 25.6% in the edge graphene oxide.
In the present embodiment, the nano active medium is nano-titanium dioxide.
In the present embodiment, the zinc oxide is activated zinc oxide.
In the present embodiment, the foaming agent is azodicarbonamide.
In the present embodiment, the preparation method of the graphene natural rubber macromolecule control bacterium mixed foaming material, packet
Include the following steps:
A, by weight respectively claim natural rubber, polyolefin elastomer, nano active medium, graphene, mould proof control microbial inoculum,
Zinc oxide, zinc stearate, stearic acid, crosslinking agent and foaming agent；
B, natural rubber is sent into mixer, mastication 13min, discharging is carried out under conditions of temperature is 148 DEG C；Mastication is complete
Natural rubber room temperature after finishing stores 48h or more, spare；
C, by the natural rubber handled well through step B mastication and polyolefin elastomer, nano active medium, graphene, anti-
Mould control microbial inoculum, zinc oxide, zinc stearate, stearic acid are sent into mixer together, mixing 10min under conditions of temperature is 86 DEG C；
Then mixing 10min under conditions of temperature is 108 DEG C；Then crosslinking agent and foaming agent is added, the condition for being 122 DEG C in temperature
Lower mixing 9min, discharging, obtains mixing glue mixture；
D, the mixing glue mixture for obtaining step C is sent into open mill, thins on a mill 4 times, slice obtains mill
Glue mixture；
E, mill glue mixture is finally sent into hot-pressing and foaming in mold, and be cooled and shaped, then carry out sanction sample, obtained described
Graphene natural rubber macromolecule control bacterium mixed foaming material graphene natural rubber macromolecule control bacterium mixed foaming material.
Embodiment 4:
A kind of graphene natural rubber macromolecule control bacterium mixed foaming material is made of the raw material for including following parts by weight:
70 parts of natural rubber, 20 parts of polyolefin elastomer, 10 parts of nano active medium, 2.7 parts of graphene, mould proof 1.45 parts of control microbial inoculum,
1.9 parts of zinc oxide, 1.55 parts of zinc stearate, 1.75 parts of stearic acid, 2.65 parts of crosslinking agent, 1.62 parts of foaming agent；The mould proof control
Microbial inoculum is the B5000 antibacterial agent of BASF；The polyolefin elastomer is the POE8999 type polyolefin elastic of Dow
The mixture of body, POE8150 type polyolefin elastomer and POE7467 type polyolefin elastomer；The crosslinking agent is peroxidating two
The mixture of isopropylbenzene, 1,1 di tert butylperoxy 3,3,5 trimethylcyclohexane and zinc dimethacrylate；The graphite
Alkene is edge graphene oxide.
In the present embodiment, the POE8999 type polyolefin elastomer, POE8150 type polyolefin elastomer and POE7467
POE8999 type polyolefin elastomer, POE8150 type polyolefin elastomer and POE7467 in the mixture of type polyolefin elastomer
The mass ratio of type polyolefin elastomer is 12:10:14.
In the present embodiment, the cumyl peroxide, 1,1- di-t-butyl peroxy -3,3,5- trimethyl-cyclohexane
With sulphur, 1,1 di tert butylperoxy 3,3,5 trimethylcyclohexane and dimethyl in the mixture of zinc dimethacrylate
The mass ratio of zinc acrylate resin is 10:14:4.3.
In the present embodiment, carboxyl relative amount is 23.8% in the edge graphene oxide.
In the present embodiment, the nano active medium is nano-titanium dioxide.
In the present embodiment, the zinc oxide is activated zinc oxide.
In the present embodiment, the foaming agent is azodicarbonamide.
In the present embodiment, the preparation method of the graphene natural rubber macromolecule control bacterium mixed foaming material, packet
Include the following steps:
A, by weight respectively claim natural rubber, polyolefin elastomer, nano active medium, graphene, mould proof control microbial inoculum,
Zinc oxide, zinc stearate, stearic acid, crosslinking agent and foaming agent；
B, natural rubber is sent into mixer, mastication 14min, discharging is carried out under conditions of temperature is 146 DEG C；Mastication is complete
Natural rubber room temperature after finishing stores 48h or more, spare；
C, by the natural rubber handled well through step B mastication and polyolefin elastomer, nano active medium, graphene, anti-
Mould control microbial inoculum, zinc oxide, zinc stearate, stearic acid are sent into mixer together, mixing 12min under conditions of temperature is 84 DEG C；
Then mixing 11min under conditions of temperature is 106 DEG C；Then crosslinking agent and foaming agent is added, the condition for being 120 DEG C in temperature
Lower mixing 10min, discharging, obtains mixing glue mixture；
D, the mixing glue mixture for obtaining step C is sent into open mill, thins on a mill 3 times, slice obtains mill
Glue mixture；
E, mill glue mixture is finally sent into hot-pressing and foaming in mold, and be cooled and shaped, then carry out sanction sample, obtained described
Graphene natural rubber macromolecule control bacterium mixed foaming material graphene natural rubber macromolecule control bacterium mixed foaming material.
Embodiment 5:
A kind of graphene natural rubber macromolecule control bacterium mixed foaming material is made of the raw material for including following parts by weight:
71 parts of natural rubber, 21.2 parts of polyolefin elastomer, 10.4 parts of nano active medium, 2.83 parts of graphene, mould proof control microbial inoculum 1.5
Part, 1.8 parts of zinc oxide, 1.6 parts of zinc stearate, 1.8 parts of stearic acid, 2.72 parts of crosslinking agent, 1.65 parts of foaming agent；The mould proof control
Microbial inoculum is the B5000 antibacterial agent of BASF；The polyolefin elastomer is the POE8999 type polyolefin elastic of Dow
The mixture of body, POE8150 type polyolefin elastomer and POE7467 type polyolefin elastomer；The crosslinking agent is peroxidating two
The mixture of isopropylbenzene, 1,1 di tert butylperoxy 3,3,5 trimethylcyclohexane and zinc dimethacrylate；The graphite
Alkene is edge graphene oxide.
In the present embodiment, the POE8999 type polyolefin elastomer, POE8150 type polyolefin elastomer and POE7467
POE8999 type polyolefin elastomer, POE8150 type polyolefin elastomer and POE7467 in the mixture of type polyolefin elastomer
The mass ratio of type polyolefin elastomer is 12:10.5:15.
In the present embodiment, the cumyl peroxide, 1,1- di-t-butyl peroxy -3,3,5- trimethyl-cyclohexane
With sulphur, 1,1 di tert butylperoxy 3,3,5 trimethylcyclohexane and dimethyl in the mixture of zinc dimethacrylate
The mass ratio of zinc acrylate resin is 10:15:4.7.
In the present embodiment, carboxyl relative amount is 24.3% in the edge graphene oxide.
In the present embodiment, the nano active medium is nano-titanium dioxide.
In the present embodiment, the zinc oxide is activated zinc oxide.
In the present embodiment, the foaming agent is azodicarbonamide.
In the present embodiment, the preparation method of the graphene natural rubber macromolecule control bacterium mixed foaming material, packet
Include the following steps:
A, by weight respectively claim natural rubber, polyolefin elastomer, nano active medium, graphene, mould proof control microbial inoculum,
Zinc oxide, zinc stearate, stearic acid, crosslinking agent and foaming agent；
B, natural rubber is sent into mixer, mastication 14min, discharging is carried out under conditions of temperature is 147 DEG C；Mastication is complete
Natural rubber room temperature after finishing stores 48h or more, spare；
C, by the natural rubber handled well through step B mastication and polyolefin elastomer, nano active medium, graphene, anti-
Mould control microbial inoculum, zinc oxide, zinc stearate, stearic acid are sent into mixer together, mixing 11min under conditions of temperature is 85 DEG C；
Then mixing 11min under conditions of temperature is 107 DEG C；Then crosslinking agent and foaming agent is added, the condition for being 121 DEG C in temperature
Lower mixing 11min, discharging, obtains mixing glue mixture；
D, the mixing glue mixture for obtaining step C is sent into open mill, thins on a mill 3 times, slice obtains mill
Glue mixture；
E, mill glue mixture is finally sent into hot-pressing and foaming in mold, and be cooled and shaped, then carry out sanction sample, obtained described
Graphene natural rubber macromolecule control bacterium mixed foaming material graphene natural rubber macromolecule control bacterium mixed foaming material.
The graphene natural rubber macromolecule control bacterium mixed foaming material that the embodiment of the present invention 2 to embodiment 5 is obtained below
Material and common Natural rubber foam material are tested for the property, and test result is as shown in table 1:
The effect of to fungi, is measured with ISO Method 486 for aspergillus niger ATCC6275.The mixture packet of fungi
ATCC6275 containing aspergillus niger, paecilomycerol ATCC18502, Trichoderma ATCC9645.Sample is placed on potato-agar glucose training
It supports on base, is cultivated in comprehensive nutrient culture medium with 10 drop (every drop 10ul, total 100ul) 10E5 fungal spore/ml, then
It is cultivated 15 days at 30 DEG C of temperature and the humidity of > 90%.Effect observes by the naked eye sample to measure.
Observe rating
Table 1
As can be seen from the above table, compared to common Natural rubber foam material, graphene natural rubber high score of the invention
Son control bacterium mixed foaming material has the advantage that antibacterial and mouldproof effect is good；Tensile strength is high, and elongation at break is big, mechanical property
It can be good.
The above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair
Limitation of the invention, protection scope of the present invention should be defined by the scope defined by the claims..For the art
For those of ordinary skill, without departing from the spirit and scope of the present invention, several improvements and modifications can also be made, these change
It also should be regarded as protection scope of the present invention into retouching.
Claims (10)
1. a kind of graphene natural rubber macromolecule control bacterium mixed foaming material, which is characterized in that by including following parts by weight
Raw material is made: 66~75 parts of natural rubber, 17.5~23 parts of polyolefin elastomer, 9~11 parts of nano active medium, graphene
2.4~3 parts, mould proof 1.2~1.7 parts of control microbial inoculum, 1.7~2.1 parts of zinc oxide, 1.4~1.7 parts of zinc stearate, stearic acid 1.6~
1.9 parts, 2.3~2.8 parts of crosslinking agent, 1.5~1.8 parts of foaming agent；The mould proof control microbial inoculum is the B5000 antibacterial of BASF
Agent；The polyolefin elastomer be the POE8999 type polyolefin elastomer of Dow, POE8150 type polyolefin elastomer and
The mixture of POE7467 type polyolefin elastomer；The crosslinking agent is cumyl peroxide, 1,1- di-t-butyl peroxy-
The mixture of 3,3,5- trimethyl-cyclohexane and zinc dimethacrylate；The graphene is edge graphene oxide.
2. graphene natural rubber macromolecule control bacterium mixed foaming material according to claim 1, which is characterized in that described
Graphene natural rubber macromolecule control bacterium mixed foaming material is by including that the raw material of following parts by weight is made: 70 parts of natural rubber,
It is 20 parts of polyolefin elastomer, 10 parts of nano active medium, 2.7 parts of graphene, mould proof 1.45 parts of control microbial inoculum, 1.9 parts of zinc oxide, hard
1.55 parts of resin acid zinc, 1.75 parts of stearic acid, 2.65 parts of crosslinking agent, 1.62 parts of foaming agent.
3. graphene natural rubber macromolecule control bacterium mixed foaming material according to claim 1, which is characterized in that described
Graphene natural rubber macromolecule control bacterium mixed foaming material is by including that the raw material of following parts by weight is made: 71 parts of natural rubber,
21.2 parts of polyolefin elastomer, 10.4 parts of nano active medium, 2.83 parts of graphene, mould proof 1.5 parts of control microbial inoculum, zinc oxide 1.8
Part, 1.6 parts of zinc stearate, 1.8 parts of stearic acid, 2.72 parts of crosslinking agent, 1.65 parts of foaming agent.
4. graphene natural rubber macromolecule control bacterium mixed foaming material according to any one of claims 1 to 3, feature
It is, the POE8999 type polyolefin elastomer, POE8150 type polyolefin elastomer and POE7467 type polyolefin elastomer
POE8999 type polyolefin elastomer in mixture, POE8150 type polyolefin elastomer and POE7467 type polyolefin elastomer
Mass ratio is 12:(9~11): (13~16).
5. graphene natural rubber macromolecule control bacterium mixed foaming material according to any one of claims 1 to 3, feature
It is, the cumyl peroxide, 1,1- di-t-butyl peroxy -3,3,5- trimethyl-cyclohexane and zinc dimethacrylate
Mixture in sulphur, 1,1 di tert butylperoxy 3,3,5 trimethylcyclohexane and zinc dimethacrylate quality it
Than for 10:(13~16): (4~5).
6. graphene natural rubber macromolecule control bacterium mixed foaming material according to any one of claims 1 to 3, feature
It is, carboxyl relative amount is 22.5%~25.6% in the edge graphene oxide.
7. graphene natural rubber macromolecule control bacterium mixed foaming material according to any one of claims 1 to 3, feature
It is, the nano active medium is nano-titanium dioxide.
8. graphene natural rubber macromolecule control bacterium mixed foaming material according to any one of claims 1 to 3, feature
It is, the zinc oxide is activated zinc oxide.
9. graphene natural rubber macromolecule control bacterium mixed foaming material according to any one of claims 1 to 3, feature
It is, the foaming agent is azodicarbonamide.
10. a kind of system of graphene natural rubber macromolecule control bacterium mixed foaming material as described in any one of claims 1 to 3
Preparation Method, characterized in that it comprises the following steps:
A, claim natural rubber, polyolefin elastomer, nano active medium, graphene, mould proof control microbial inoculum, oxidation respectively by weight
Zinc, zinc stearate, stearic acid, crosslinking agent and foaming agent；
B, natural rubber is sent into mixer, 13~15min of mastication, discharging is carried out under conditions of temperature is 145~148 DEG C；
Natural rubber room temperature after mastication stores 48h or more, spare；
C, by the natural rubber handled well through step B mastication and polyolefin elastomer, nano active medium, graphene, mould proof control
Microbial inoculum, zinc oxide, zinc stearate, stearic acid are sent into mixer together, temperature be 82~86 DEG C under conditions of mixing 10~
14min；Then 10~12min of mixing under conditions of temperature is 105~108 DEG C；Then crosslinking agent and foaming agent is added, in temperature
Degree is 9~12min of mixing under conditions of 118~122 DEG C, and discharging obtains mixing glue mixture；
D, the mixing glue mixture for obtaining step C is sent into open mill, thins on a mill 2~4 times, slice obtains mill
Glue mixture；
Mill glue mixture is finally sent into hot-pressing and foaming in mold, and is cooled and shaped, then carry out sanction sample, the graphene is obtained
Natural rubber macromolecule control bacterium mixed foaming material.
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