CN105906854A - Graphene-modified natural latex polymer and modification method thereof - Google Patents
Graphene-modified natural latex polymer and modification method thereof Download PDFInfo
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Abstract
The invention discloses a graphene-modified natural latex polymer and a modification method thereof. The modification method comprises modifying graphene through a coupling agent, uniformly dispersing the modified functionalized graphene in natural rubber to obtain the graphene-modified natural latex polymer and the modification method solves the problem of nonuniform dispersion of graphene in natural rubber. The graphene-modified natural latex polymer improves mechanical properties by 20-200%, improves barrier properties and blocks various viruses. The modification method of the graphene-modified natural latex polymer utilizes easily available raw materials and easily realizes large scale production. The invention also discloses the graphene-modified natural latex polymer prepared through the modification method.
Description
Technical field
The invention belongs to the technical field of compositions of natural rubber, concrete for a kind of Graphene modified natural emulsion polymer and method of modifying thereof.
Background technology
Natural rubber has the combination property of excellence, and resulting product has the performances such as excellent elasticity, higher intensity, bigger percentage elongation and less creep, is widely used in chemical industry.But natural rubber can not meet a lot of actual needs in terms of the physical and mechanical properties such as pure glue hardness, hot strength, it would be highly desirable to by modification, to improve the performance such as its intensity, wear-resisting, aging resistance, widens its application.
Nano material has special skin effect, small-size effect, quantum size effect and quantum tunneling effect, it material list being composited reveals the performances such as mechanics, calorifics, optics and the electromagnetism of uniqueness.In rubber industry, the compound research strengthening particle about Conventional nano such as carbon black, White Carbon black, clays is the most extensively carried out, and have developed the natural rubber nano composite material of excellent performance.Along with the new applications to nanostructures of development, nano zine oxide, nano-calcium carbonate, CNT and the nanofiber etc. of technology, natural rubber nano composite material various aspects of performance is made also to obtain the lifting of certain depth, but current result of study is being seen, due to disperse water adjustment, cause effect in composite physical property raising degree limited, and complex process, less stable.
Graphene is the Two-dimensional Carbon nano material of a kind of monoatomic thickness, has optical, electrical, the hot and mechanical property of excellence, and huge specific surface area.Can be combined by covalently or non-covalently effect (hydrogen bond, π-π effect, electrostatic interaction etc.) between Graphene and macromolecule. these interactions had both added Graphene dissolubility in macromolecule or dispersibility, it is also possible to improve the performance of composite or expand its function.
Summary 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 method of modifying thereof, in natural rubber, disperse uneven problem solving Graphene.
For reaching above-mentioned purpose, the present invention provides following technical scheme:
Present invention firstly provides a kind of Graphene modified natural emulsion polymer modification process, comprised the steps:
Present invention firstly provides a kind of Graphene modified natural emulsion polymer modification process, comprised the steps:
1) first the coupling agent that graphene oxide and mass percentage content are 2%-100% is dissolved in the dehydrated alcohol under continuously stirred state, add graphene oxide, form uniform dispersion, it is heated to 60-80 DEG C, and continue to react 10-24h, the paste product obtained is first with absolute ethanol washing, remove unnecessary unreacted coupling agent, again with distilled water wash, the paste product do not dried after washing is scattered in distilled water, add hydrazine hydrate, and at 80-100 DEG C reduction reaction 4-6h, the addition quality of described hydrazine hydrate is 0.5-5 times that described graphene oxide adds quality；Again with excess dehydrated alcohol and distilled water wash products therefrom, the functionalization graphene that dried acquisition is modified；
2) it is configured to, by soluble in water for described modified functionalization graphene, the graphene solution that mass concentration is 0.1%-1%, adds the dispersant that quality is Graphene quality 2-10 times, it is thus achieved that uniform and stable functionalization graphene nano dispersion fluid A；
3), after the natural emulsion solution under continuously stirred state adding stabilizer and surfactant, stirring 0.5-5 hour is continued；It is slow added into described graphene nano dispersion liquid A, continues stirring 5-10min；Add accelerator, age resistor, vulcanizing agent and vulcanizing activator, it is thus achieved that latex mixed liquid B；
4) described latex mixed liquid B is carried out presulfurization process: described latex mixed liquid B water-bath limit heating edge low rate mixing will be used to process, heating-up temperature 40-80 DEG C, 2-5 hour heat time heating time, make semi-cure latex C；
5) after described semi-cure latex C being parked 12-24h, it is carried out high speed centrifugation, it is thus achieved that refinement semi-cure latex D；
6) described refinement semi-cure latex D mould dip forming post-heating is dried, obtains Graphene modified natural emulsion polymer.
Further, in described step 1), described coupling agent is the mixture of at least one in silane coupler, titanate coupling agent and aluminate coupling agent.
Further, described step 2) in, described dispersant is the mixed liquor of at least one in ammonia, KOH, casein, paregal O, sodium hexameta phosphate, dispersant NF, cetyl benzenesulfonic acid, cetyl benzenesulfonic acid sodium, stabilizer LW, isopropyl naphthalene sulfonate and sodium isobutyl naphthalene sulfonate.
Further, described step 2) in, in described graphene nano dispersion liquid A, the concentration of Graphene is 0.5-50mg/ml.
Further, in described step 3), the mass concentration of described natural emulsion solution is 10-50%.
Further, in described Graphene modified natural emulsion polymer, the mass content of Graphene is 0.1-10%.
Further, in described step 3), the number proportioning added is: with 60% natural emulsion as 100phr；Described stabilizing agent dosage is 0.5-5phr, and described stabilizer is ammonia, KOH, stabilizer LW or casein；Described dosage of surfactant is 0.5-2phr, and described surfactant is paregal O, sodium hexameta phosphate, dispersant NF, cetyl benzenesulfonic acid, cetyl benzenesulfonic acid sodium, isopropyl naphthalene sulfonate or sodium isobutyl naphthalene sulfonate；Described accelerator dosage is 0.2-2phr, and described accelerator is (DDC)2Zn, tetrabenzyl thiuram-disulfide or zinc dibenzyl dithiocarbamate；Described aging inhibitor dosage is 0.5-3phr, and described age resistor is 2,6-di-tert-butyl-4-methy phenol；Described vulcanizing agent consumption is 1-2phr, and described vulcanizing agent is sulfur；Described vulcanizing activator consumption is 0.5-5phr, and described vulcanizing activator is zinc oxide.
Further, the size dimension of described functionalization graphene is 200-800nm, and thickness is 1-3nm.
Further, also include step 7), described Graphene modified natural emulsion polymer is carried out solidified forming process, and the temperature that solidified forming processes is 100-150 DEG C.
The invention allows for a kind of Graphene modified natural emulsion polymer, it uses Graphene modified natural emulsion polymer modification process as above to prepare.
The beneficial effects of the present invention is:
The Graphene modified natural emulsion polymer modification process of the present invention, application coupling agent is modified by Graphene, the most modified functionalization graphene is dispersed in natural rubber, solves Graphene and disperses uneven problem in natural rubber, it is thus achieved that modified natural rubber；The Graphene modified natural emulsion polymer that the present invention obtains; mechanical property obtains and improves 20 ~ 200%, and barrier property improves, and can intercept various virus; and the raw material that Graphene modified natural emulsion polymer modification process of the present invention uses is easy to get, easy large-scale production.
Accompanying drawing explanation
In order to make the purpose of the present invention, technical scheme and beneficial effect clearer, the present invention provides drawings described below to illustrate:
Fig. 1 is the preparation flow figure of Graphene modified natural emulsion polymer modification process of the present invention.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described, so that those skilled in the art can be better understood from 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 steps:
1) first the coupling agent that graphene oxide and mass percentage content are 2%-100% is dissolved in the dehydrated alcohol under continuously stirred state, add graphene oxide, form uniform dispersion, it is heated to 60-80 DEG C, and continue to react 10-24h, the paste product obtained is first with absolute ethanol washing, remove unnecessary unreacted coupling agent, again with distilled water wash, the paste product do not dried after washing is scattered in distilled water, add hydrazine hydrate, and at 80-100 DEG C reduction reaction 4-6h, the addition quality of described hydrazine hydrate is 0.5-5 times that described graphene oxide adds quality；Again with excess dehydrated alcohol and distilled water wash products therefrom, the functionalization graphene that dried acquisition is modified；The size dimension of functionalization graphene is 200-800nm, and thickness is 1-3nm.Described coupling agent is the mixture of at least one in silane coupler, titanate coupling agent and aluminate coupling agent.
2) it is configured to, by soluble in water for described modified functionalization graphene, the graphene solution that mass concentration is 0.1%-1%, adds the dispersant that quality is Graphene quality 2-10 times, it is thus achieved that uniform and stable functionalization graphene nano dispersion fluid A；Described dispersant is the mixed liquor of at least one in ammonia, KOH, casein, paregal O, sodium hexameta phosphate, dispersant NF, cetyl benzenesulfonic acid, cetyl benzenesulfonic acid sodium, stabilizer LW, isopropyl naphthalene sulfonate and sodium isobutyl naphthalene sulfonate.In described graphene nano dispersion liquid A, the concentration of Graphene is 0.5-50mg/ml.
3), after the natural emulsion solution under continuously stirred state adding stabilizer and surfactant, stirring 0.5-5 hour is continued；It is slow added into described graphene nano dispersion liquid A, continues stirring 5-10min；Add accelerator, age resistor, vulcanizing agent and vulcanizing activator, it is thus achieved that latex mixed liquid B.The mass concentration of described natural emulsion solution is 10-50%.
And the number proportioning added is: with 60% natural emulsion as 100phr；Described stabilizing agent dosage is 0.5-5phr, and described stabilizer is ammonia, KOH, stabilizer LW or casein；
Described dosage of surfactant is 0.5-2phr, and described surfactant is paregal O, sodium hexameta phosphate, dispersant NF, cetyl benzenesulfonic acid, cetyl benzenesulfonic acid sodium, isopropyl naphthalene sulfonate or sodium isobutyl naphthalene sulfonate；Described accelerator dosage is 0.2-2phr；
Described accelerator is (DDC)2Zn, tetrabenzyl thiuram-disulfide or zinc dibenzyl dithiocarbamate；
Described aging inhibitor dosage is 0.5-3phr, and described age resistor is 2,6-di-tert-butyl-4-methy phenol；
Described vulcanizing agent consumption is 1-2phr, and described vulcanizing agent is sulfur；
Described vulcanizing activator consumption is 0.5-5phr, and described vulcanizing activator is zinc oxide.
4) described latex mixed liquid B is carried out presulfurization process: described latex mixed liquid B water-bath limit heating edge low rate mixing will be used to process, heating-up temperature 40-80 DEG C, 2-5 hour heat time heating time, make semi-cure latex C；
5) after described semi-cure latex C being parked 12-24h, it is carried out high speed centrifugation, it is thus achieved that refinement semi-cure latex D；
6) described refinement semi-cure latex D mould dip forming post-heating is dried, obtains Graphene modified natural emulsion polymer.And in Graphene modified natural emulsion polymer, the mass content of Graphene is 0.1-10%.
7) described Graphene modified natural emulsion polymer is carried out solidified forming process, and the temperature that solidified forming processes is 100-150 DEG C.
The invention allows for a kind of Graphene modified natural emulsion polymer, it uses Graphene modified natural emulsion polymer modification process as above to prepare.
The Graphene modified natural emulsion polymer modification process of the present invention, application coupling agent is modified by Graphene, the most modified functionalization graphene is dispersed in natural rubber, solves Graphene and disperses uneven problem in natural rubber, it is thus achieved that modified natural rubber；The Graphene modified natural emulsion polymer that the present invention obtains; mechanical property obtains and improves 20 ~ 200%, and barrier property improves, and can intercept various virus; and the raw material that Graphene modified natural emulsion polymer modification process of the present invention uses is easy to get, easy large-scale production.
Embodiment
1
The Graphene modified natural emulsion polymer modification process of the present invention, comprises the steps:
1) first the coupling agent that graphene oxide and mass percentage content are 50% is dissolved in the dehydrated alcohol under continuously stirred state, add graphene oxide, form uniform dispersion, it is heated to 80 DEG C, and continue to react 15h, the paste product obtained is first with absolute ethanol washing, remove unnecessary unreacted coupling agent, again with distilled water wash, the paste product do not dried after washing is scattered in distilled water, adding hydrazine hydrate, and reduction reaction 6h at 100 DEG C, the addition quality of described hydrazine hydrate is 3 times that described graphene oxide adds quality；Again with excess dehydrated alcohol and distilled water wash products therefrom, the functionalization graphene that dried acquisition is modified；The size dimension of functionalization graphene is 200-800nm, and thickness is 1-3nm.Described coupling agent is the mixture of at least one in silane coupler, titanate coupling agent and aluminate coupling agent, and the coupling agent of the present embodiment is silane coupler.
2) it is configured to, by soluble in water for described modified functionalization graphene, the graphene solution that mass concentration is 1%, adds the dispersant that quality is Graphene quality 6 times, it is thus achieved that uniform and stable functionalization graphene nano dispersion fluid A.Described dispersant is the mixed liquor of at least one in ammonia, KOH, casein, paregal O, sodium hexameta phosphate, dispersant NF, cetyl benzenesulfonic acid, cetyl benzenesulfonic acid sodium, stabilizer LW, isopropyl naphthalene sulfonate and sodium isobutyl naphthalene sulfonate.The mixed liquor that described dispersant is ammonia, KOH, casein, paregal O and sodium hexameta phosphate of the present embodiment.And the concentration of Graphene is 25mg/ml in the graphene nano dispersion liquid A of the present embodiment.
3), after the natural emulsion solution under continuously stirred state adding stabilizer and surfactant, stirring 5 hours is continued；It is slow added into described graphene nano dispersion liquid A, continues stirring 10min；Add accelerator, age resistor, vulcanizing agent and vulcanizing activator, it is thus achieved that latex mixed liquid B.The mass concentration of described natural emulsion solution is 30%.
And the number proportioning added is: with 60% natural emulsion as 100phr；Described stabilizing agent dosage is 5phr, and described stabilizer is ammonia, KOH, stabilizer LW or casein, and the stabilizer of the present embodiment is ammonia.
Described dosage of surfactant is 1phr, described surfactant is paregal O, sodium hexameta phosphate, dispersant NF, cetyl benzenesulfonic acid, cetyl benzenesulfonic acid sodium, isopropyl naphthalene sulfonate or sodium isobutyl naphthalene sulfonate, and the surfactant of the present embodiment is isopropyl naphthalene sulfonate.
Described accelerator dosage is 0.2phr, and described accelerator is (DDC)2Zn, tetrabenzyl thiuram-disulfide or zinc dibenzyl dithiocarbamate, and the accelerator of the present embodiment is (DDC)2Zn.
Described aging inhibitor dosage is 2phr, and described age resistor is 2,6-di-tert-butyl-4-methy phenol.
Described vulcanizing agent consumption is 1phr, and described vulcanizing agent is sulfur.
Described vulcanizing activator consumption is 5phr, and described vulcanizing activator is zinc oxide.
4) described latex mixed liquid B is carried out presulfurization process: described latex mixed liquid B water-bath limit heating edge low rate mixing will be used to process, heating-up temperature 60 DEG C, 3 hours heat time heating times, make semi-cure latex C；
5) after described semi-cure latex C being parked 24h, it is carried out high speed centrifugation, it is thus achieved that refinement semi-cure latex D；
6) described refinement semi-cure latex D mould dip forming post-heating is dried, obtains Graphene modified natural emulsion polymer.And in Graphene modified natural emulsion polymer, the mass content of Graphene is 5%.
7) described Graphene modified natural emulsion polymer is carried out solidified forming process, and the temperature that solidified forming processes is 150 DEG C.
The invention allows for a kind of Graphene modified natural emulsion polymer, it uses Graphene modified natural emulsion polymer modification process as above to prepare.
The Graphene modified natural emulsion polymer modification process of the present invention, application coupling agent is modified by Graphene, the most modified functionalization graphene is dispersed in natural rubber, solves Graphene and disperses uneven problem in natural rubber, it is thus achieved that modified natural rubber；The Graphene modified natural emulsion polymer that the present invention obtains; mechanical property obtains and improves 20 ~ 200%, and barrier property improves, and can intercept various virus; and the raw material that Graphene modified natural emulsion polymer modification process of the present invention uses is easy to get, easy large-scale production.
Embodiment
2
The Graphene modified natural emulsion polymer modification process of the present invention, comprises the steps:
1) first the coupling agent that graphene oxide and mass percentage content are 2% is dissolved in the dehydrated alcohol under continuously stirred state, add graphene oxide, form uniform dispersion, it is heated to 60 DEG C, and continue to react 24h, the paste product obtained is first with absolute ethanol washing, remove unnecessary unreacted coupling agent, again with distilled water wash, the paste product do not dried after washing is scattered in distilled water, adding hydrazine hydrate, and reduction reaction 4h at 80 DEG C, the addition quality of described hydrazine hydrate is 0.5 times that described graphene oxide adds quality；Again with excess dehydrated alcohol and distilled water wash products therefrom, the functionalization graphene that dried acquisition is modified；The size dimension of functionalization graphene is 200-800nm, and thickness is 1-3nm.Described coupling agent is the mixture of at least one in silane coupler, titanate coupling agent and aluminate coupling agent, and the coupling agent of the present embodiment is silane coupler.
2) it is configured to, by soluble in water for described modified functionalization graphene, the graphene solution that mass concentration is 0.1%, adds the dispersant that quality is Graphene quality 2 times, it is thus achieved that uniform and stable functionalization graphene nano dispersion fluid A.Described dispersant is the mixed liquor of at least one in ammonia, KOH, casein, paregal O, sodium hexameta phosphate, dispersant NF, cetyl benzenesulfonic acid, cetyl benzenesulfonic acid sodium, stabilizer LW, isopropyl naphthalene sulfonate and sodium isobutyl naphthalene sulfonate.The mixed liquor that described dispersant is isopropyl naphthalene sulfonate and sodium isobutyl naphthalene sulfonate of the present embodiment.And the concentration of Graphene is 0.5mg/ml in the graphene nano dispersion liquid A of the present embodiment.
3), after the natural emulsion solution under continuously stirred state adding stabilizer and surfactant, stirring 0.5 hour is continued；It is slow added into described graphene nano dispersion liquid A, continues stirring 5min；Add accelerator, age resistor, vulcanizing agent and vulcanizing activator, it is thus achieved that latex mixed liquid B.The mass concentration of described natural emulsion solution is 10%.
And the number proportioning added is: with 60% natural emulsion as 100phr；Described stabilizing agent dosage is 0.5phr, and described stabilizer is ammonia, KOH, stabilizer LW or casein, and the stabilizer of the present embodiment is stabilizer LW.
Described dosage of surfactant is 2phr, described surfactant is paregal O, sodium hexameta phosphate, dispersant NF, cetyl benzenesulfonic acid, cetyl benzenesulfonic acid sodium, isopropyl naphthalene sulfonate or sodium isobutyl naphthalene sulfonate, and the surfactant of the present embodiment is cetyl benzenesulfonic acid sodium.
Described accelerator dosage is 2phr, and described accelerator is (DDC)2Zn, tetrabenzyl thiuram-disulfide or zinc dibenzyl dithiocarbamate, and the accelerator of the present embodiment is tetrabenzyl thiuram-disulfide.
Described aging inhibitor dosage is 3phr, and described age resistor is 2,6-di-tert-butyl-4-methy phenol.
Described vulcanizing agent consumption is 2phr, and described vulcanizing agent is sulfur.
Described vulcanizing activator consumption is 3phr, and described vulcanizing activator is zinc oxide.
4) described latex mixed liquid B is carried out presulfurization process: described latex mixed liquid B water-bath limit heating edge low rate mixing will be used to process, heating-up temperature 40 DEG C, 5 hours heat time heating times, make semi-cure latex C；
5) after described semi-cure latex C being parked 12h, it is carried out high speed centrifugation, it is thus achieved that refinement semi-cure latex D；
6) described refinement semi-cure latex D mould dip forming post-heating is dried, obtains Graphene modified natural emulsion polymer.And in Graphene modified natural emulsion polymer, the mass content of Graphene is 0.1%.
7) described Graphene modified natural emulsion polymer is carried out solidified forming process, and the temperature that solidified forming processes is 100 DEG C.
The invention allows for a kind of Graphene modified natural emulsion polymer, it uses Graphene modified natural emulsion polymer modification process as above to prepare.
The Graphene modified natural emulsion polymer modification process of the present invention, application coupling agent is modified by Graphene, the most modified functionalization graphene is dispersed in natural rubber, solves Graphene and disperses uneven problem in natural rubber, it is thus achieved that modified natural rubber；The Graphene modified natural emulsion polymer that the present invention obtains; mechanical property obtains and improves 20 ~ 200%, and barrier property improves, and can intercept various virus; and the raw material that Graphene modified natural emulsion polymer modification process of the present invention uses is easy to get, easy large-scale production.
Embodiment
3
The Graphene modified natural emulsion polymer modification process of the present invention, comprises the steps:
1) first the coupling agent that graphene oxide and mass percentage content are 100% is dissolved in the dehydrated alcohol under continuously stirred state, add graphene oxide, form uniform dispersion, it is heated to 70 DEG C, and continue to react 10h, the paste product obtained is first with absolute ethanol washing, remove unnecessary unreacted coupling agent, again with distilled water wash, the paste product do not dried after washing is scattered in distilled water, adding hydrazine hydrate, and reduction reaction 5h at 85 DEG C, the addition quality of described hydrazine hydrate is 5 times that described graphene oxide adds quality；Again with excess dehydrated alcohol and distilled water wash products therefrom, the functionalization graphene that dried acquisition is modified；The size dimension of functionalization graphene is 200-800nm, and thickness is 1-3nm.Described coupling agent is the mixture of at least one in silane coupler, titanate coupling agent and aluminate coupling agent, and the coupling agent of the present embodiment is silane coupler.
2) it is configured to, by soluble in water for described modified functionalization graphene, the graphene solution that mass concentration is 0.5%, adds the dispersant that quality is Graphene quality 10 times, it is thus achieved that uniform and stable functionalization graphene nano dispersion fluid A.Described dispersant is the mixed liquor of at least one in ammonia, KOH, casein, paregal O, sodium hexameta phosphate, dispersant NF, cetyl benzenesulfonic acid, cetyl benzenesulfonic acid sodium, stabilizer LW, isopropyl naphthalene sulfonate and sodium isobutyl naphthalene sulfonate.The described dispersant of the present embodiment is cetyl benzenesulfonic acid sodium.And the concentration of Graphene is 50 in the graphene nano dispersion liquid A of the present embodiment
mg/ml。
3), after the natural emulsion solution under continuously stirred state adding stabilizer and surfactant, stirring 2 hours is continued；It is slow added into described graphene nano dispersion liquid A, continues stirring 8min；Add accelerator, age resistor, vulcanizing agent and vulcanizing activator, it is thus achieved that latex mixed liquid B.The mass concentration of described natural emulsion solution is 50%.
And the number proportioning added is: with 60% natural emulsion as 100phr；Described stabilizing agent dosage is 2phr, and described stabilizer is ammonia, KOH, stabilizer LW or casein, and the stabilizer of the present embodiment is casein.
Described dosage of surfactant is 0.5phr, described surfactant is paregal O, sodium hexameta phosphate, dispersant NF, cetyl benzenesulfonic acid, cetyl benzenesulfonic acid sodium, isopropyl naphthalene sulfonate or sodium isobutyl naphthalene sulfonate, and the surfactant of the present embodiment is paregal O.
Described accelerator dosage is 1phr, and described accelerator is (DDC)2Zn, tetrabenzyl thiuram-disulfide or zinc dibenzyl dithiocarbamate, and the accelerator of the present embodiment is zinc dibenzyl dithiocarbamate.
Described aging inhibitor dosage is 0.5phr, and described age resistor is 2,6-di-tert-butyl-4-methy phenol.
Described vulcanizing agent consumption is 1.5phr, and described vulcanizing agent is sulfur.
Described vulcanizing activator consumption is 0.5phr, and described vulcanizing activator is zinc oxide.
4) described latex mixed liquid B is carried out presulfurization process: described latex mixed liquid B water-bath limit heating edge low rate mixing will be used to process, heating-up temperature 80 DEG C, 2 hours heat time heating times, make semi-cure latex C；
5) after described semi-cure latex C being parked 16h, it is carried out high speed centrifugation, it is thus achieved that refinement semi-cure latex D；
6) described refinement semi-cure latex D mould dip forming post-heating is dried, obtains Graphene modified natural emulsion polymer.And in Graphene modified natural emulsion polymer, the mass content of Graphene is 10%.
7) described Graphene modified natural emulsion polymer is carried out solidified forming process, and the temperature that solidified forming processes is 125 DEG C.
The invention allows for a kind of Graphene modified natural emulsion polymer, it uses Graphene modified natural emulsion polymer modification process as above to prepare.
The Graphene modified natural emulsion polymer modification process of the present invention, application coupling agent is modified by Graphene, the most modified functionalization graphene is dispersed in natural rubber, solves Graphene and disperses uneven problem in natural rubber, it is thus achieved that modified natural rubber；The Graphene modified natural emulsion polymer that the present invention obtains; mechanical property obtains and improves 20 ~ 200%, and barrier property improves, and can intercept various virus; and the raw material that Graphene modified natural emulsion polymer modification process of the present invention uses is easy to get, easy large-scale production.
Embodiment described above is only the preferred embodiment lifted by absolutely proving the present invention, and protection scope of the present invention is not limited to this.The equivalent that those skilled in the art are made on the basis of the present invention substitutes or conversion, all within protection scope of the present invention.Protection scope of the present invention is as the criterion with claims.
Claims (10)
1. a Graphene modified natural emulsion polymer modification process, it is characterised in that: comprise the steps:
1) first the coupling agent that graphene oxide and mass percentage content are 2%-100% is dissolved in the dehydrated alcohol under continuously stirred state, add graphene oxide, form uniform dispersion, it is heated to 60-80 DEG C, and continue to react 10-24h, the paste product obtained is first with absolute ethanol washing, remove unnecessary unreacted coupling agent, again with distilled water wash, the paste product do not dried after washing is scattered in distilled water, add hydrazine hydrate, and at 80-100 DEG C reduction reaction 4-6h, the addition quality of described hydrazine hydrate is 0.5-5 times that described graphene oxide adds quality；Again with excess dehydrated alcohol and distilled water wash products therefrom, the functionalization graphene that dried acquisition is modified；
2) it is configured to, by soluble in water for described modified functionalization graphene, the graphene solution that mass concentration is 0.1%-1%, adds the dispersant that quality is Graphene quality 2-10 times, it is thus achieved that uniform and stable functionalization graphene nano dispersion fluid A；
3), after the natural emulsion solution under continuously stirred state adding stabilizer and surfactant, stirring 0.5-5 hour is continued；It is slow added into described graphene nano dispersion liquid A, continues stirring 5-10min；Add accelerator, age resistor, vulcanizing agent and vulcanizing activator, it is thus achieved that latex mixed liquid B；
4) described latex mixed liquid B is carried out presulfurization process: described latex mixed liquid B water-bath limit heating edge low rate mixing will be used to process, heating-up temperature 40-80 DEG C, 2-5 hour heat time heating time, make semi-cure latex C；
5) after described semi-cure latex C being parked 12-24h, it is carried out high speed centrifugation, it is thus achieved that refinement semi-cure latex D；
6) described refinement semi-cure latex D mould dip forming post-heating is dried, obtains Graphene modified natural emulsion polymer.
Graphene modified natural emulsion polymer modification process the most according to claim 1, it is characterised in that: in described step 1), described coupling agent is the mixture of at least one in silane coupler, titanate coupling agent and aluminate coupling agent.
Graphene modified natural emulsion polymer modification process the most according to claim 1, it is characterized in that: described step 2) in, described dispersant is the mixed liquor of at least one in ammonia, KOH, casein, paregal O, sodium hexameta phosphate, dispersant NF, cetyl benzenesulfonic acid, cetyl benzenesulfonic acid sodium, stabilizer LW, isopropyl naphthalene sulfonate and sodium isobutyl naphthalene sulfonate.
Graphene modified natural emulsion polymer modification process the most according to claim 1, it is characterised in that: described step 2) in, in described graphene nano dispersion liquid A, the concentration of Graphene is 0.5-50mg/ml.
Graphene modified natural emulsion polymer modification process the most according to claim 4, it is characterised in that: in described step 3), the mass concentration of described natural emulsion solution is 10-50%.
Graphene modified natural emulsion polymer modification process the most according to claim 5, it is characterised in that: in described Graphene modified natural emulsion polymer, the mass content of Graphene is 0.1-10%.
Graphene modified natural emulsion polymer modification process the most according to claim 1, it is characterised in that: in described step 3), the number proportioning added is: with 60% natural emulsion as 100phr；Described stabilizing agent dosage is 0.5-5phr, and described stabilizer is ammonia, KOH, stabilizer LW or casein；Described dosage of surfactant is 0.5-2phr, and described surfactant is paregal O, sodium hexameta phosphate, dispersant NF, cetyl benzenesulfonic acid, cetyl benzenesulfonic acid sodium, isopropyl naphthalene sulfonate or sodium isobutyl naphthalene sulfonate；Described accelerator dosage is 0.2-2phr, and described accelerator is (DDC)2Zn, tetrabenzyl thiuram-disulfide or zinc dibenzyl dithiocarbamate；Described aging inhibitor dosage is 0.5-3phr, and described age resistor is 2,6-di-tert-butyl-4-methy phenol；Described vulcanizing agent consumption is 1-2phr, and described vulcanizing agent is sulfur；Described vulcanizing activator consumption is 0.5-5phr, and described vulcanizing activator is zinc oxide.
Graphene modified natural emulsion polymer modification process the most according to claim 1, it is characterised in that: the size dimension of described functionalization graphene is 200-800nm, and thickness is 1-3nm.
Graphene modified natural emulsion polymer modification process the most according to claim 1, it is characterised in that: also include step 7), described Graphene modified natural emulsion polymer is carried out solidified forming process, and the temperature that solidified forming processes is 100-150 DEG C.
10. a Graphene modified natural emulsion polymer, it is characterised in that: it uses the Graphene modified natural emulsion polymer modification process as described in any one of claim 1-9 to prepare.
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