CN105906854B - Graphene modified natural emulsion polymer and its method of modifying - Google Patents
Graphene modified natural emulsion polymer and its method of modifying Download PDFInfo
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Abstract
The invention discloses a kind of method of modifying of graphene modified natural emulsion polymer, graphene is modified using coupling agent, then modified functionalization graphene is dispersed in natural rubber, solves the problem of graphene disperses uneven in natural rubber, obtain modified natural rubber；The graphene modified natural emulsion polymer that the present invention is obtained; mechanical property, which is obtained, improves 20 ~ 200%, and barrier property is improved, and can obstruct various viruses; and the raw material that graphene modified natural emulsion polymer modification process of the present invention is used is easy to get, easy large-scale production.The invention also discloses a kind of graphene modified natural emulsion polymer prepared using above-mentioned graphene modified natural emulsion polymer process.
Description
Technical field
The invention belongs to the technical field of compositions of natural rubber, specifically it polymerize for a kind of graphene modified natural emulsion
Thing and its method of modifying.
Background technology
Natural rubber has excellent combination property, and resulting product has excellent elasticity, and higher intensity, larger stretches
The performance such as long rate and less creep, is widely used in chemical industry.But natural rubber is in pure glue hardness, stretching
The need for many reality can not be met in terms of the physical and mechanical properties such as intensity, it would be highly desirable to by modification, with improve its intensity, it is wear-resisting,
The performance such as anti-aging, widens its application field.
Nano material has special skin effect, small-size effect, quantum size effect and quantum tunneling effect, by it
The material being composited shows the performances such as mechanics, calorifics, optics and the electromagnetism of uniqueness.In rubber industry, relevant carbon black,
The compound research of the Conventional nanos such as White Carbon black, clay enhancing particle is carried out extensively, have developed the natural rubber of excellent performance
Glue nano composite material.As the development of technology, nano zine oxide, nano-calcium carbonate, CNT and nanofiber etc. are newly received
The application of rice material, makes natural rubber nano composite material various aspects of performance also obtain the lifting of certain depth, but with regard to mesh
Preceding result of study is seen, due to disperse water adjustment, causes effect in composite physical property raising degree limited, and technique
Complexity, less stable.
Graphene is a kind of two-dimentional carbon nanomaterial of monoatomic thickness, with excellent light, electricity, heat and mechanical property,
And huge specific surface area.Can be (hydrogen bond, π-π effects, quiet by covalently or non-covalently acting between graphene and macromolecule
Electro ultrafiltration etc.) carry out compound these interactions of and both add dissolubility or dispersiveness of the graphene in macromolecule, can also
Improve the performance of composite or expand its function.
The content of the invention
In view of this, it is an object of the invention to provide a kind of graphene modified natural emulsion polymer and its modification side
Method, to solve the problem of graphene disperses uneven in natural rubber.
To reach above-mentioned purpose, the present invention provides following technical scheme：
Present invention firstly provides a kind of graphene modified natural emulsion polymer modification process, comprise the following steps：
Present invention firstly provides a kind of graphene modified natural emulsion polymer modification process, comprise the following steps：
1）Graphene oxide and mass percentage content are dissolved under lasting stirring for 2%-100% coupling agent first
Absolute ethyl alcohol in, add graphene oxide, form uniform dispersion, be heated to 60-80 DEG C, and continue to react 10-24h,
Obtained paste product is first washed with absolute ethyl alcohol, removes unnecessary unreacted coupling agent, then with distillation water washing, after washing
The paste product do not dried is scattered in distilled water, adds hydrazine hydrate, and in reduction reaction 4-6h at 80-100 DEG C, the hydration
The addition quality of hydrazine is 0.5-5 times that the graphene oxide adds quality；Again with excessive absolute ethyl alcohol and distillation water washing institute
Product is obtained, modified functionalization graphene is obtained after drying；
2）By the modified functionalization graphene it is soluble in water be configured to mass concentration be 0.1%-1% graphene it is molten
Liquid, adds the dispersant that quality is 2-10 times of graphene quality, obtains uniform and stable functionalization graphene nano dispersion fluid A；
3）Added into the natural emulsion solution under lasting stirring after stabilizer and surfactant, continue to stir
0.5-5 hours；The graphene nano dispersion liquid A is slow added into, continues to stir 5-10min；Add accelerator, prevent old
Agent, vulcanizing agent and vulcanizing activator, obtain latex mixed liquid B；
4）Presulfurization processing is carried out to the latex mixed liquid B：Will the latex mixed liquid B using water-bath while heating while
Processing is mixed slowly, heat time 2-5 hour, semi-cure latex C is made in 40-80 DEG C of heating-up temperature；
5）The semi-cure latex C is parked after 12-24h, high speed centrifugation is carried out to it, refinement semi-cure glue is obtained
Newborn D；
6）By refinement semi-cure latex D heat dryings after mould dip forming, graphene modified natural breast is obtained
Xanthan polymer.
Further, the step 1）In, the coupling agent is silane coupler, titanate coupling agent and aluminate coupling agent
At least one of mixture.
Further, the step 2）In, the dispersant is ammoniacal liquor, KOH, casein, paregal O, calgon, scattered
Agent NF, cetyl benzenesulfonic acid, cetyl benzenesulfonic acid sodium, stabilizer LW, isopropyl naphthalene sulfonate and sodium isobutyl naphthalene sulfonate
At least one of mixed liquor.
Further, the step 2）In, the concentration of graphene is 0.5-50mg/ml in the graphene nano dispersion liquid A.
Further, the step 3）In, the mass concentration of the natural emulsion solution is 10-50%.
Further, in the graphene modified natural emulsion polymer, the mass content of graphene is 0.1-10%.
Further, the step 3）In, the number proportioning added is：Using 60% natural emulsion as 100phr；The stabilization
Agent consumption is 0.5-5phr, and the stabilizer is ammoniacal liquor, KOH, stabilizer LW or casein；The dosage of surfactant is 0.5-
2phr, the surfactant is paregal O, calgon, dispersant NF, cetyl benzenesulfonic acid, cetyl benzene sulphur
Sour sodium, isopropyl naphthalene sulfonate or sodium isobutyl naphthalene sulfonate；The accelerator dosage is 0.2-2phr, and the accelerator is diethyl
Base zinc dithiocarbamate, tetrabenzyl thiuram-disulfide or zinc dibenzyl dithiocarbamate；The aging inhibitor dosage
For 0.5-3phr, the age resistor is 2,6- di-tert-butyl-4-methy phenols；The vulcanizing agent consumption is 1-2phr, the sulphur
Agent is sulphur；The vulcanizing activator consumption is 0.5-5phr, and the vulcanizing activator is zinc oxide.
Further, the size dimension of the functionalization graphene is 200-800nm, and thickness is 1-3nm.
Further, in addition to step 7）, solidified forming processing is carried out to the graphene modified natural emulsion polymer, and
The temperature of solidified forming processing is 100-150 DEG C.
The invention also provides a kind of graphene modified natural emulsion polymer, it uses graphene as described above to be modified
Natural emulsion polymer modification process is prepared.
The beneficial effects of the present invention are：
Graphene, is modified, then by the graphene modified natural emulsion polymer modification process of the present invention using coupling agent
Modified functionalization graphene is dispersed in natural rubber, is solved graphene and is disperseed uneven in natural rubber
Problem, obtains modified natural rubber；The graphene modified natural emulsion polymer that the present invention is obtained, mechanical property is improved
20 ~ 200%, barrier property is improved, and can obstruct various viruses, and graphene modified natural emulsion polymer modification of the present invention
The raw material that method is used is easy to get, easy large-scale production.
Brief description of the drawings
In order that the purpose of the present invention, technical scheme and beneficial effect are clearer, the present invention provides drawings described below and carried out
Explanation：
Fig. 1 is the preparation flow figure of graphene modified natural emulsion polymer modification process of the present invention.
Embodiment
With reference to specific embodiment, the invention will be further described, so that those skilled in the art can be more preferable
Understand the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
The graphene modified natural emulsion polymer modification process of the present invention, comprises the following steps：
1）Graphene oxide and mass percentage content are dissolved under lasting stirring for 2%-100% coupling agent first
Absolute ethyl alcohol in, add graphene oxide, form uniform dispersion, be heated to 60-80 DEG C, and continue to react 10-24h,
Obtained paste product is first washed with absolute ethyl alcohol, removes unnecessary unreacted coupling agent, then with distillation water washing, after washing
The paste product do not dried is scattered in distilled water, adds hydrazine hydrate, and in reduction reaction 4-6h at 80-100 DEG C, the hydration
The addition quality of hydrazine is 0.5-5 times that the graphene oxide adds quality；Again with excessive absolute ethyl alcohol and distillation water washing institute
Product is obtained, modified functionalization graphene is obtained after drying；The size dimension of functionalization graphene is 200-800nm, thickness
For 1-3nm.The coupling agent is the mixture of at least one of silane coupler, titanate coupling agent and aluminate coupling agent.
2）By the modified functionalization graphene it is soluble in water be configured to mass concentration be 0.1%-1% graphene it is molten
Liquid, adds the dispersant that quality is 2-10 times of graphene quality, obtains uniform and stable functionalization graphene nano dispersion fluid A；
The dispersant is ammoniacal liquor, KOH, casein, paregal O, calgon, dispersant NF, cetyl benzenesulfonic acid, cetyl
The mixed liquor of at least one of benzene sulfonic acid sodium salt, stabilizer LW, isopropyl naphthalene sulfonate and sodium isobutyl naphthalene sulfonate.The graphene
The concentration of graphene is 0.5-50mg/ml in nano dispersion fluid A.
3）Added into the natural emulsion solution under lasting stirring after stabilizer and surfactant, continue to stir
0.5-5 hours；The graphene nano dispersion liquid A is slow added into, continues to stir 5-10min；Add accelerator, prevent old
Agent, vulcanizing agent and vulcanizing activator, obtain latex mixed liquid B.The mass concentration of the natural emulsion solution is 10-50%.
And the number proportioning added is：Using 60% natural emulsion as 100phr；The stabilizing agent dosage is 0.5-5phr,
The stabilizer is ammoniacal liquor, KOH, stabilizer LW or casein；
The dosage of surfactant is 0.5-2phr, and the surfactant is paregal O, calgon, disperseed
Agent NF, cetyl benzenesulfonic acid, cetyl benzenesulfonic acid sodium, isopropyl naphthalene sulfonate or sodium isobutyl naphthalene sulfonate；It is described to promote
Agent consumption is 0.2-2phr；
The accelerator is zinc diethyl dithiocarbamate, tetrabenzyl thiuram-disulfide or dibenzyl dithio ammonia
Base zinc formate；
The aging inhibitor dosage is 0.5-3phr, and the age resistor is 2,6- di-tert-butyl-4-methy phenols；
The vulcanizing agent consumption is 1-2phr, and the vulcanizing agent is sulphur；
The vulcanizing activator consumption is 0.5-5phr, and the vulcanizing activator is zinc oxide.
4）Presulfurization processing is carried out to the latex mixed liquid B：Will the latex mixed liquid B using water-bath while heating while
Processing is mixed slowly, heat time 2-5 hour, semi-cure latex C is made in 40-80 DEG C of heating-up temperature；
5）The semi-cure latex C is parked after 12-24h, high speed centrifugation is carried out to it, refinement semi-cure glue is obtained
Newborn D；
6）By refinement semi-cure latex D heat dryings after mould dip forming, graphene modified natural breast is obtained
Xanthan polymer.And in graphene modified natural emulsion polymer, the mass content of graphene is 0.1-10%.
7）Solidified forming processing, and the temperature of solidified forming processing are carried out to the graphene modified natural emulsion polymer
For 100-150 DEG C.
The invention also provides a kind of graphene modified natural emulsion polymer, it uses graphene as described above to be modified
Natural emulsion polymer modification process is prepared.
Graphene, is modified, then by the graphene modified natural emulsion polymer modification process of the present invention using coupling agent
Modified functionalization graphene is dispersed in natural rubber, is solved graphene and is disperseed uneven in natural rubber
Problem, obtains modified natural rubber；The graphene modified natural emulsion polymer that the present invention is obtained, mechanical property is improved
20 ~ 200%, barrier property is improved, and can obstruct various viruses, and graphene modified natural emulsion polymer modification of the present invention
The raw material that method is used is easy to get, easy large-scale production.
Embodiment 1
The graphene modified natural emulsion polymer modification process of the present invention, comprises the following steps：
1）Graphene oxide and mass percentage content are dissolved in nothing under lasting stirring for 50% coupling agent first
In water-ethanol, graphene oxide is added, uniform dispersion is formed, 80 DEG C are heated to, and continues to react 15h, obtained pasty state
Product is first washed with absolute ethyl alcohol, removes unnecessary unreacted coupling agent, then with distillation water washing, the paste that will not dried after washing
Shape product is scattered in distilled water, adds hydrazine hydrate, and in reduction reaction 6h at 100 DEG C, the addition quality of the hydrazine hydrate is
The graphene oxide adds 3 times of quality；Again with excessive absolute ethyl alcohol and distillation water washing products therefrom, changed after drying
Functionalization graphene after property；The size dimension of functionalization graphene is 200-800nm, and thickness is 1-3nm.The coupling agent is
The mixture of at least one of silane coupler, titanate coupling agent and aluminate coupling agent, the coupling agent of the present embodiment is silicon
Alkane coupling agent.
2）It is 1% graphene solution by the modified functionalization graphene mass concentration soluble in water that is configured to, plus
Enter the dispersant that quality is 6 times of graphene quality, obtain uniform and stable functionalization graphene nano dispersion fluid A.It is described scattered
Agent is ammoniacal liquor, KOH, casein, paregal O, calgon, dispersant NF, cetyl benzenesulfonic acid, cetyl benzenesulfonic acid
The mixed liquor of at least one of sodium, stabilizer LW, isopropyl naphthalene sulfonate and sodium isobutyl naphthalene sulfonate.Described point of the present embodiment
Powder is the mixed liquor of ammoniacal liquor, KOH, casein, paregal O and calgon.And the graphene nano dispersion liquid A of the present embodiment
The concentration of middle graphene is 25mg/ml.
3）Added into the natural emulsion solution under lasting stirring after stabilizer and surfactant, continue to stir 5
Hour；The graphene nano dispersion liquid A is slow added into, continues to stir 10min；Add accelerator, age resistor, vulcanizing agent
And vulcanizing activator, obtain latex mixed liquid B.The mass concentration of the natural emulsion solution is 30%.
And the number proportioning added is：Using 60% natural emulsion as 100phr；The stabilizing agent dosage is 5phr, described
Stabilizer is ammoniacal liquor, KOH, stabilizer LW or casein, and the stabilizer of the present embodiment is ammoniacal liquor.
The dosage of surfactant be 1phr, the surfactant be paregal O, calgon, dispersant NF,
Cetyl benzenesulfonic acid, cetyl benzenesulfonic acid sodium, isopropyl naphthalene sulfonate or sodium isobutyl naphthalene sulfonate, the surface of the present embodiment
Activating agent is isopropyl naphthalene sulfonate.
The accelerator dosage is 0.2phr, and the accelerator is zinc diethyl dithiocarbamate, the sulphur of tetrabenzyl two
Change thiuram or zinc dibenzyl dithiocarbamate, the accelerator of the present embodiment is zinc diethyl dithiocarbamate.
The aging inhibitor dosage is 2phr, and the age resistor is 2,6- di-tert-butyl-4-methy phenols.
The vulcanizing agent consumption is 1phr, and the vulcanizing agent is sulphur.
The vulcanizing activator consumption is 5phr, and the vulcanizing activator is zinc oxide.
4）Presulfurization processing is carried out to the latex mixed liquid B：Will the latex mixed liquid B using water-bath while heating while
Processing is mixed slowly, 3 hours heat times, semi-cure latex C is made in 60 DEG C of heating-up temperature；
5）The semi-cure latex C is parked after 24h, high speed centrifugation is carried out to it, refinement semi-cure latex is obtained
D；
6）By refinement semi-cure latex D heat dryings after mould dip forming, graphene modified natural breast is obtained
Xanthan polymer.And in graphene modified natural emulsion polymer, the mass content of graphene is 5%.
7）Solidified forming processing, and the temperature of solidified forming processing are carried out to the graphene modified natural emulsion polymer
For 150 DEG C.
The invention also provides a kind of graphene modified natural emulsion polymer, it uses graphene as described above to be modified
Natural emulsion polymer modification process is prepared.
Graphene, is modified, then by the graphene modified natural emulsion polymer modification process of the present invention using coupling agent
Modified functionalization graphene is dispersed in natural rubber, is solved graphene and is disperseed uneven in natural rubber
Problem, obtains modified natural rubber；The graphene modified natural emulsion polymer that the present invention is obtained, mechanical property is improved
20 ~ 200%, barrier property is improved, and can obstruct various viruses, and graphene modified natural emulsion polymer modification of the present invention
The raw material that method is used is easy to get, easy large-scale production.
Embodiment 2
The graphene modified natural emulsion polymer modification process of the present invention, comprises the following steps：
1）Graphene oxide and mass percentage content are dissolved in nothing under lasting stirring for 2% coupling agent first
In water-ethanol, graphene oxide is added, uniform dispersion is formed, 60 DEG C are heated to, and continues to react 24h, obtained pasty state
Product is first washed with absolute ethyl alcohol, removes unnecessary unreacted coupling agent, then with distillation water washing, the paste that will not dried after washing
Shape product is scattered in distilled water, adds hydrazine hydrate, and in reduction reaction 4h at 80 DEG C, the addition quality of the hydrazine hydrate is institute
State 0.5 times that graphene oxide adds quality；Again with excessive absolute ethyl alcohol and distillation water washing products therefrom, changed after drying
Functionalization graphene after property；The size dimension of functionalization graphene is 200-800nm, and thickness is 1-3nm.The coupling agent is
The mixture of at least one of silane coupler, titanate coupling agent and aluminate coupling agent, the coupling agent of the present embodiment is silicon
Alkane coupling agent.
2）It is 0.1% graphene solution by the modified functionalization graphene mass concentration soluble in water that is configured to,
The dispersant that quality is 2 times of graphene quality is added, uniform and stable functionalization graphene nano dispersion fluid A is obtained.Described point
Powder is ammoniacal liquor, KOH, casein, paregal O, calgon, dispersant NF, cetyl benzenesulfonic acid, cetyl benzenesulfonic acid
The mixed liquor of at least one of sodium, stabilizer LW, isopropyl naphthalene sulfonate and sodium isobutyl naphthalene sulfonate.Described point of the present embodiment
Powder is the mixed liquor of isopropyl naphthalene sulfonate and sodium isobutyl naphthalene sulfonate.And in the graphene nano dispersion liquid A of the present embodiment
The concentration of graphene is 0.5mg/ml.
3）Added into the natural emulsion solution under lasting stirring after stabilizer and surfactant, continue to stir
0.5 hour；The graphene nano dispersion liquid A is slow added into, continues to stir 5min；Add accelerator, age resistor, vulcanization
Agent and vulcanizing activator, obtain latex mixed liquid B.The mass concentration of the natural emulsion solution is 10%.
And the number proportioning added is：Using 60% natural emulsion as 100phr；The stabilizing agent dosage is 0.5phr, institute
Stabilizer is stated for ammoniacal liquor, KOH, stabilizer LW or casein, the stabilizer of the present embodiment is stabilizer LW.
The dosage of surfactant be 2phr, the surfactant be paregal O, calgon, dispersant NF,
Cetyl benzenesulfonic acid, cetyl benzenesulfonic acid sodium, isopropyl naphthalene sulfonate or sodium isobutyl naphthalene sulfonate, the surface of the present embodiment
Activating agent is cetyl benzenesulfonic acid sodium.
The accelerator dosage is 2phr, and the accelerator is zinc diethyl dithiocarbamate, tetrabenzyl curing
Thiuram or zinc dibenzyl dithiocarbamate, the accelerator of the present embodiment is tetrabenzyl thiuram-disulfide.
The aging inhibitor dosage is 3phr, and the age resistor is 2,6- di-tert-butyl-4-methy phenols.
The vulcanizing agent consumption is 2phr, and the vulcanizing agent is sulphur.
The vulcanizing activator consumption is 3phr, and the vulcanizing activator is zinc oxide.
4）Presulfurization processing is carried out to the latex mixed liquid B：Will the latex mixed liquid B using water-bath while heating while
Processing is mixed slowly, 5 hours heat times, semi-cure latex C is made in 40 DEG C of heating-up temperature；
5）The semi-cure latex C is parked after 12h, high speed centrifugation is carried out to it, refinement semi-cure latex is obtained
D；
6）By refinement semi-cure latex D heat dryings after mould dip forming, graphene modified natural breast is obtained
Xanthan polymer.And in graphene modified natural emulsion polymer, the mass content of graphene is 0.1%.
7）Solidified forming processing, and the temperature of solidified forming processing are carried out to the graphene modified natural emulsion polymer
For 100 DEG C.
The invention also provides a kind of graphene modified natural emulsion polymer, it uses graphene as described above to be modified
Natural emulsion polymer modification process is prepared.
Graphene, is modified, then by the graphene modified natural emulsion polymer modification process of the present invention using coupling agent
Modified functionalization graphene is dispersed in natural rubber, is solved graphene and is disperseed uneven in natural rubber
Problem, obtains modified natural rubber；The graphene modified natural emulsion polymer that the present invention is obtained, mechanical property is improved
20 ~ 200%, barrier property is improved, and can obstruct various viruses, and graphene modified natural emulsion polymer modification of the present invention
The raw material that method is used is easy to get, easy large-scale production.
Embodiment 3
The graphene modified natural emulsion polymer modification process of the present invention, comprises the following steps：
1）Graphene oxide and mass percentage content are dissolved under lasting stirring for 100% coupling agent first
In absolute ethyl alcohol, graphene oxide is added, uniform dispersion is formed, 70 DEG C are heated to, and continues to react 10h, obtained paste
Shape product is first washed with absolute ethyl alcohol, removes unnecessary unreacted coupling agent, then with distillation water washing, by what is do not dried after washing
Paste product is scattered in distilled water, adds hydrazine hydrate, and in reduction reaction 5h at 85 DEG C, the addition quality of the hydrazine hydrate is
The graphene oxide adds 5 times of quality；Again with excessive absolute ethyl alcohol and distillation water washing products therefrom, changed after drying
Functionalization graphene after property；The size dimension of functionalization graphene is 200-800nm, and thickness is 1-3nm.The coupling agent is
The mixture of at least one of silane coupler, titanate coupling agent and aluminate coupling agent, the coupling agent of the present embodiment is silicon
Alkane coupling agent.
2）It is 0.5% graphene solution by the modified functionalization graphene mass concentration soluble in water that is configured to,
The dispersant that quality is 10 times of graphene quality is added, uniform and stable functionalization graphene nano dispersion fluid A is obtained.Described point
Powder is ammoniacal liquor, KOH, casein, paregal O, calgon, dispersant NF, cetyl benzenesulfonic acid, cetyl benzenesulfonic acid
The mixed liquor of at least one of sodium, stabilizer LW, isopropyl naphthalene sulfonate and sodium isobutyl naphthalene sulfonate.Described point of the present embodiment
Powder is cetyl benzenesulfonic acid sodium.And the concentration of graphene is 50 mg/ml in the graphene nano dispersion liquid A of the present embodiment.
3）Added into the natural emulsion solution under lasting stirring after stabilizer and surfactant, continue to stir 2
Hour；The graphene nano dispersion liquid A is slow added into, continues to stir 8min；Add accelerator, age resistor, vulcanizing agent
And vulcanizing activator, obtain latex mixed liquid B.The mass concentration of the natural emulsion solution is 50%.
And the number proportioning added is：Using 60% natural emulsion as 100phr；The stabilizing agent dosage is 2phr, described
Stabilizer is ammoniacal liquor, KOH, stabilizer LW or casein, and the stabilizer of the present embodiment is casein.
The dosage of surfactant is 0.5phr, and the surfactant is paregal O, calgon, dispersant
NF, cetyl benzenesulfonic acid, cetyl benzenesulfonic acid sodium, isopropyl naphthalene sulfonate or sodium isobutyl naphthalene sulfonate, the present embodiment
Surfactant is paregal O.
The accelerator dosage is 1phr, and the accelerator is zinc diethyl dithiocarbamate, tetrabenzyl curing
Thiuram or zinc dibenzyl dithiocarbamate, the accelerator of the present embodiment is zinc dibenzyl dithiocarbamate.
The aging inhibitor dosage is 0.5phr, and the age resistor is 2,6- di-tert-butyl-4-methy phenols.
The vulcanizing agent consumption is 1.5phr, and the vulcanizing agent is sulphur.
The vulcanizing activator consumption is 0.5phr, and the vulcanizing activator is zinc oxide.
4）Presulfurization processing is carried out to the latex mixed liquid B：Will the latex mixed liquid B using water-bath while heating while
Processing is mixed slowly, 2 hours heat times, semi-cure latex C is made in 80 DEG C of heating-up temperature；
5）The semi-cure latex C is parked after 16h, high speed centrifugation is carried out to it, refinement semi-cure latex is obtained
D；
6）By refinement semi-cure latex D heat dryings after mould dip forming, graphene modified natural breast is obtained
Xanthan polymer.And in graphene modified natural emulsion polymer, the mass content of graphene is 10%.
7）Solidified forming processing, and the temperature of solidified forming processing are carried out to the graphene modified natural emulsion polymer
For 125 DEG C.
The invention also provides a kind of graphene modified natural emulsion polymer, it uses graphene as described above to be modified
Natural emulsion polymer modification process is prepared.
Graphene, is modified, then by the graphene modified natural emulsion polymer modification process of the present invention using coupling agent
Modified functionalization graphene is dispersed in natural rubber, is solved graphene and is disperseed uneven in natural rubber
Problem, obtains modified natural rubber；The graphene modified natural emulsion polymer that the present invention is obtained, mechanical property is improved
20 ~ 200%, barrier property is improved, and can obstruct various viruses, and graphene modified natural emulsion polymer modification of the present invention
The raw material that method is used is easy to get, easy large-scale production.
Embodiment described above is only the preferred embodiment to absolutely prove the present invention and being lifted, protection model of the invention
Enclose not limited to this.Equivalent substitute or conversion that those skilled in the art are made on the basis of the present invention, in the present invention
Protection domain within.Protection scope of the present invention is defined by claims.
Claims (10)
1. a kind of graphene modified natural emulsion polymer modification process, it is characterised in that：Comprise the following steps：
1）Graphene oxide and mass percentage content are dissolved in the nothing under lasting stirring for 2%-100% coupling agent first
In water-ethanol, graphene oxide is added, uniform dispersion is formed, 60-80 DEG C is heated to, and continues to react 10-24h, is obtained
Paste product first washed with absolute ethyl alcohol, remove unnecessary unreacted coupling agent, then with water washing is distilled, will not dried after washing
Dry paste product is scattered in distilled water, adds hydrazine hydrate, and in reduction reaction 4-6h at 80-100 DEG C, the hydrazine hydrate
It is 0.5-5 times that the graphene oxide adds quality to add quality；Produced again with obtained by excessive absolute ethyl alcohol and distillation water washing
Thing, modified functionalization graphene is obtained after drying；
2）By the modified functionalization graphene graphene solution soluble in water for being configured to mass concentration for 0.1%-1%,
The dispersant that quality is 2-10 times of graphene quality is added, uniform and stable functionalization graphene nano dispersion fluid A is obtained；
3）Added into the natural emulsion solution under lasting stirring after stabilizer and surfactant, continue to stir 0.5-5
Hour；The graphene nano dispersion liquid A is slow added into, continues to stir 5-10min；Add accelerator, age resistor, vulcanization
Agent and vulcanizing activator, obtain latex mixed liquid B；
4）Presulfurization processing is carried out to the latex mixed liquid B：Will the latex mixed liquid B using water-bath while heating while at a slow speed
Heat time 2-5 hour, semi-cure latex C is made in stir process, 40-80 DEG C of heating-up temperature；
5）The semi-cure latex C is parked after 12-24h, high speed centrifugation is carried out to it, refinement semi-cure latex D is obtained；
6）By refinement semi-cure latex D heat dryings after mould dip forming, obtain graphene modified natural emulsion and gather
Compound.
2. graphene modified natural emulsion polymer modification process according to claim 1, it is characterised in that：The step
1）In, the coupling agent is the mixture of at least one of silane coupler, titanate coupling agent and aluminate coupling agent.
3. graphene modified natural emulsion polymer modification process according to claim 1, it is characterised in that：The step
2）In, the dispersant is ammoniacal liquor, KOH, casein, paregal O, calgon, dispersant NF, cetyl benzenesulfonic acid, ten
The mixed liquor of at least one of six sodium alkyl benzene sulfonates, stabilizer LW, isopropyl naphthalene sulfonate and sodium isobutyl naphthalene sulfonate.
4. graphene modified natural emulsion polymer modification process according to claim 1, it is characterised in that：The step
2）In, the concentration of graphene is 0.5-50mg/ml in the graphene nano dispersion liquid A.
5. graphene modified natural emulsion polymer modification process according to claim 4, it is characterised in that：The step
3）In, the mass concentration of the natural emulsion solution is 10-50%.
6. graphene modified natural emulsion polymer modification process according to claim 5, it is characterised in that：The graphite
In alkene modified natural emulsion polymer, the mass content of graphene is 0.1-10%.
7. graphene modified natural emulsion polymer modification process according to claim 1, it is characterised in that：The step
3）In, the number proportioning added is：Using 60% natural emulsion as 100phr；The stabilizing agent dosage is 0.5-5phr, described steady
Agent is determined for ammoniacal liquor, KOH, stabilizer LW or casein；The dosage of surfactant is 0.5-2phr, and the surfactant is flat
Flat plus O, calgon, dispersant NF, cetyl benzenesulfonic acid, cetyl benzenesulfonic acid sodium, isopropyl naphthalene sulfonate or different
Sodium butylnaphthalenesulfonate；The accelerator dosage is 0.2-2phr, and the accelerator is zinc diethyl dithiocarbamate, four benzyls
Base thiuram-disulfide or zinc dibenzyl dithiocarbamate；The aging inhibitor dosage is 0.5-3phr, and the age resistor is
2,6- di-tert-butyl-4-methy phenols；The vulcanizing agent consumption is 1-2phr, and the vulcanizing agent is sulphur；The sulfurate activity
Agent consumption is 0.5-5phr, and the vulcanizing activator is zinc oxide.
8. graphene modified natural emulsion polymer modification process according to claim 1, it is characterised in that：The function
The size dimension of graphite alkene is 200-800nm, and thickness is 1-3nm.
9. graphene modified natural emulsion polymer modification process according to claim 1, it is characterised in that：Also include step
Rapid 7）, solidified forming processing is carried out to the graphene modified natural emulsion polymer, and the temperature of solidified forming processing is
100-150℃。
10. a kind of graphene modified natural emulsion polymer, it is characterised in that：It is used as described in claim any one of 1-9
Graphene modified natural emulsion polymer modification process prepare.
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| MY194301A (en) * | 2016-11-03 | 2022-11-27 | Karex Holdings Sdn Bhd | Polyisoprene latex graphene composites and method of making them |
| CN108192155A (en) * | 2016-12-08 | 2018-06-22 | 北京橡胶工业研究设计院有限公司 | For the graphene native rubber composite material and preparation method of conveyer belt coating rubber |
| CN106832453B (en) * | 2017-02-24 | 2018-12-11 | 山东圣泉新材料股份有限公司 | A kind of graphene modified natural emulsion material and its preparation method and application |
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| CN108748836A (en) * | 2018-06-20 | 2018-11-06 | 温州超泰乳胶制品有限公司 | Graphene latex pillow production technology |
| CN108748837A (en) * | 2018-06-20 | 2018-11-06 | 温州超泰乳胶制品有限公司 | Add the latex pillow production technology of graphene |
| CN109280237A (en) * | 2018-09-12 | 2019-01-29 | 陈贝妮 | A kind of modified latex pillow and preparation method thereof |
| CN109438748B (en) * | 2018-10-12 | 2021-05-07 | 苏州鼎烯聚材纳米科技有限公司 | Continuous production method of high-thermal-conductivity graphene latex sponge for mattress |
| CN109679173A (en) * | 2019-01-10 | 2019-04-26 | 安徽理工大学 | A kind of solution polymerized butadiene styrene rubber composite material and preparation method |
| CN111171399B (en) * | 2020-02-05 | 2022-01-14 | 中国热带农业科学院农产品加工研究所 | Natural rubber composite material and preparation method thereof |
| CN111995860B (en) * | 2020-04-15 | 2022-04-19 | 重庆门朵新材料科技有限公司 | Graphene-reinforced waterborne polyurethane high-barrier material and condom |
| CN111978570A (en) * | 2020-09-01 | 2020-11-24 | 重庆中科烯维科技有限公司 | Method for vulcanizing and packaging graphene modified natural latex |
| CN112951617B (en) * | 2021-02-05 | 2022-10-11 | 广州金立电子有限公司 | Electrochemical capacitor and preparation method thereof |
| CN114889175B (en) * | 2022-05-25 | 2023-07-18 | 福州大学 | Preparation and application of modified graphene oxide/hydroxyapatite nanowire composite paper |
| CN115819839A (en) * | 2022-11-17 | 2023-03-21 | 山东玲珑轮胎股份有限公司 | Preparation method of modified graphene master batch |
| CN117430874A (en) * | 2023-12-20 | 2024-01-23 | 亚都医疗科技(河南)有限公司 | High-barrier rubber slurry, rubber glove and preparation method thereof |
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| CN104403130B (en) * | 2014-11-12 | 2017-02-15 | 青岛科技大学 | Preparation method of functionalized graphene and application thereof |
| CN105037835A (en) * | 2015-05-13 | 2015-11-11 | 范志明 | Novel condom based on graphene modification technology and production method thereof |
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