CN104788755A - Preparation method of oil-extended oxygenated graphene solution co-coagulation rubber - Google Patents
Preparation method of oil-extended oxygenated graphene solution co-coagulation rubber Download PDFInfo
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- CN104788755A CN104788755A CN201510112111.6A CN201510112111A CN104788755A CN 104788755 A CN104788755 A CN 104788755A CN 201510112111 A CN201510112111 A CN 201510112111A CN 104788755 A CN104788755 A CN 104788755A
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- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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Abstract
The invention discloses a reparation method of oil-extended oxygenated graphene solution co-coagulation rubber. The oil-extended oxygenated graphene solution co-coagulation rubber mainly comprises, by weight, 100 parts of rubber, 1-80 parts of oil, 1-80 parts of graphene oxide, 0.1-5 parts of an antioxidant and 0.1-5 parts of a coupling agent. The preparation method comprises the following steps: adding graphene oxide, oil, the coupling agent and the antioxidant into a rubber solution, and stirring at a maintained temperature of 30-60DEG C for 1-30h; blending water steam in the above obtained mixture, and evaporating out and recovering solvent oil by using a distillation and separation device; and drying to prepare the oil-extended oxygenated graphene solution co-coagulation rubber. The method overcomes the disadvantages of non-uniform dispersion of a nano-filler, high energy consumption and poor physical performances of traditional mechanical blending methods, and has the advantages of simple preparation process, low cost and easy popularization. In a nanometer composite material prepared in the invention, graphene oxycarbide is uniformly dispersed in the rubber substrate, and has effective reinforcing and antistatic effects. The solution co-coagulation rubber prepared through the method has excellent performances, and has greatly improved mechanical performances, wear resistance and antistatic property.
Description
Technical field
The present invention relates to polymer based nanocomposites technical field, particularly relate to a kind of oil-filled preparation method filling the common beta-rubber of graphene oxide solution.
Background technology
Rubber is important strategic materials, and because of the snappiness that it is special, its application is throughout the every field of national economy.But the maximum shortcoming of rubber is that intensity is low, must add strengthening agent and just have use value.For a long time, carbon black and white carbon black as the strengthening agent of rubber in occupation of dominant position.But carbon black is except seriously polluted, its source also depends on petroleum-based energy goods and materials, expensive.And white carbon black not only reinforcing effect is not ideal enough, and expensive.Therefore, find a kind of cheap, environment friendly and pollution-free and that reinforcing effect is excellent reinforcing rubber material is the emphasis that scientific worker studies always.
Graphene oxide is a kind of important derivative of Graphene, and its structure is substantially identical with Graphene.Polar functional group on graphene oxide two-dimensional basal plane, as carbonyl and the carboxyl of hydroxyl and epoxy group(ing) and edge, makes graphene oxide have good wetting ability, and easily and some polar organic molecule and polymer formation nano composite material.The hydrophilic radical of graphene oxide enhances the interfacial interaction between graphene oxide and body material, improves the mechanical property of matrix material, has widened its development space, is expected to the high quality filler becoming polymer nanocomposites.
At present more active about the research of graphene oxide in polymer composite, the mechanical property improving polymeric matrix makes some progress, but it not yet gives play to desirable effect improving in the mechanical property of rubber matrix.Trace it to its cause and be mainly graphene oxide there is higher surface-area and surface energy, and the viscosity of conventional rubber is larger, directly graphene oxide is added in solid rubber by traditional mechanical mixing method, graphene oxide can be reunited at rubber matrix, be difficult to peel off into laminated structure in rubber matrix, limit the performance of graphene oxide strengthening action.
The nano composite material that Chinese patent " mechanical mixing method prepares the method for graphene oxide/white carbon black/rubber nanocomposite " (patent No.: ZL201310157282.1) adopts mechanical mixing method that graphene oxide and white carbon black compound are obtained high dispersing, highly peel off.Graphene oxide mixes with natural rubber latex by Chinese patent " a kind of graphene oxide/black rubber nano composite material and preparation method thereof " (patent No.: ZL201310146476.1), and after ultrasonic disperse, natural rubber/graphene oxide rubber master batch has been prepared in flocculation.Chinese patent " preparation method of the graphene oxide/rubber nano composite material peeled off completely " (patent No.: ZL201110454000.5) adopts emulsion compound to combine with flocculation process, or emulsion compound combines with drying process with atomizing, prepare graphene oxide/rubber nano composite material.There will be when graphene oxide loading level is large when adopting emulsion flocculation or drying process with atomizing to prepare rubber/stannic oxide/graphene nano matrix material, partial oxidation Graphene remains in flocculation clear liquid, the phenomenon of the poor-performing of the matrix material of preparation.And when adopting mechanical mixing method, there will be dust from flying, energy consumption increases, disperses the phenomenons such as uneven, be difficult to be applied to suitability for industrialized production.Aforesaid method does not all relate to solution method and prepares rubber/graphene oxide composite material.
Oil is an integral part indispensable in rubber item, and adding of oil can reduce mixing time, reduce energy consumption, improves the processing characteristics of rubber.And oil-extended rubber to have heat-dissipating little, hysteresis loss is few, and low temperature deflects the advantages such as the life-span is long.If produce the solution flocculated stage of rubber at solution polymerization process, add oil simultaneously and prepare nano composite material together with graphene oxide, low molecular oil effectively can infiltrate graphene oxide, make graphene oxide more easily and rubber macromolecule chain infiltrate and combine, a large amount of graphene oxides can be made easily to be scattered in uniformly in rubber, to make graphene oxide play effective reinforcement, wear-resisting, antistatic property.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, propose a kind of oil-filled preparation method filling the common beta-rubber of graphene oxide solution.It, after being mixed with graphene oxide, oil, coupling agent, anti-aging agent by rubber solutions, is distilled and is sloughed solvent oil, and namely drying has been prepared oil-filled graphene oxide solution of filling and be total to beta-rubber.
The technical scheme that the present invention takes is:
The oil-filled common beta-rubber of graphene oxide solution that fills of the present invention is made up of the raw material of following weight part: rubber solutions 100, oily 1-80, graphene oxide 1-80, coupling agent 0.1-5, anti-aging agent 0.1-5.
Described rubber solutions is the rubber solutions utilizing solution polymerization process to produce, and comprising: the one in cis-1,4-polybutadiene rubber solution, solution polymerized butadiene styrene rubber solution, polyisoprene rubber solution, polyisobutylene rubber solution, ethylene-propylene rubber(EPR) solution, silicone rubber solution.
Described oil refers to conventional non-volatile oils, comprises aromatic hydrocarbon oil, process oil, naphthenic oil, machine oil, white oil; The rubber prepared through chemosynthesis commonly uses tenderizer, ester class tenderizer; Peanut oil, Oleum Gossypii semen, rapeseed oil, plam oil, animal grease and modification derivant thereof.
The preparation method of described oxidation is as follows: graphite being joined concentration is in the sulfuric acid of 70-98 wt%, stir after 10-30 minute, add potassium permanganate wherein, controlling temperature of reaction is 0-10 DEG C of stirring reaction 1-3 hour, the hydrogen peroxide of 10-30 wt% is added in reaction system, ultrasonic stripping is after 10-30 minute, centrifugal, washing, dry, namely obtained graphene oxide.
Described anti-aging agent is conventional anti-aging agent, and coupling agent is conventional coupling agents.
Prepare oil-filled method of filling the common beta-rubber of graphene oxide solution of the present invention, it is characterized in that: the concrete steps of described method are as follows: join in rubber solutions by graphene oxide, oil, coupling agent, anti-aging agent, temperature keeps 30-60 DEG C to stir 1-30 minute; In said mixture, pass into water vapour, utilize fractionation by distillation device, solvent oil is steamed and is separated; Namely drying has been prepared oil-filled graphene oxide solution of filling and has been total to beta-rubber.
Positively effect of the present invention is as follows:
(1) of the present inventionly oil-filledly fill graphene oxide solution reinforcing rubber, wear-resisting, antistatic property is excellent.Low molecular oil effectively can infiltrate graphene oxide, makes graphene oxide peel off into laminated structure on a large scale and is scattered in uniformly in rubber, serve effective strengthening action.
(2) method of the present invention can be produced oil-filled graphene oxide solution of filling and is total to beta-rubber under the prerequisite substantially not changing the existing production technique of solution polymerization rubber plant, and technique is simple, workable, is easy to industrialization.
Embodiment
The following examples describe in further detail of the present invention.
Embodiment 1-3: fill graphene oxide solution solidifying cis-1,4-polybutadiene rubber altogether to fill aromatic hydrocarbon oil, illustrate that the present invention is oil-filled and fill preparation method and the performance that graphene oxide solution is total to beta-rubber.
(1) preparation of graphene oxide: graphite being joined concentration is in the sulfuric acid of 98%, stirs after 20 minutes, adds potassium permanganate wherein, and control temperature of reaction is less than 10 DEG C of stirring in water bath and reacts 3 hours.In reaction system, add certain deionized water dilution, continue stirring in water bath.The hydrogen peroxide of 20% is added in system, through ultrasonic stripping after 15 minutes, centrifugal, washing, dry, namely obtain graphene oxide.
(2) oil-filled preparation of filling the common beta-rubber of graphene oxide solution: by graphene oxide, oil, coupling agent, anti-aging agent according to necessarily joining in cis-1,4-polybutadiene rubber solution than row, stir 20 minutes at 60 DEG C; In said mixture, pass into water vapour, distill solvent oil and reclaim; Namely drying has been prepared oil-filled graphene oxide solution of filling and has been coagulated cis-1,4-polybutadiene rubber altogether.
Comparative example 1-3: cis-1,4-polybutadiene rubber, graphene oxide, oil, coupling agent, anti-aging agent employing mechanical mixing method are prepared oil-filled graphene oxide solution of filling and coagulated cis-1,4-polybutadiene rubber altogether, contrast with embodiment 1-3, illustrate that the present invention is oil-filled and fill the performance that graphene oxide solution coagulates cis-1,4-polybutadiene rubber altogether.
Sulfurizing formula and cure conditions:
(1) oil-filled oxygenation functionalized graphene cis-1,4-polybutadiene rubber
Sulfurizing formula: nano composite material (containing pure cis-1,4-polybutadiene rubber 100) variable, ZnO 5, SA 1, CZ 0.7, S 1.5; Cure conditions: 143 DEG C × 30min
Performance test: carry out according to national standard.
The performance of the oil-filled oxygenation functionalized graphene cis-1,4-polybutadiene rubber prepared according to above-mentioned formula and technique is in table 3.
As shown in Table 3, what the mechanical property of the oil-filled oxygenation functionalized graphene cis-1,4-polybutadiene rubber adopting solution coagulation method to prepare all was better than adopting mechanical mixing method to prepare oil-filledly rushes graphene oxide cis-1,4-polybutadiene rubber.The oil-filled oxygenation functionalized graphene cis-1,4-polybutadiene rubber that the antistatic property of the oil-filled oxygenation functionalized graphene cis-1,4-polybutadiene rubber adopting solution coagulation method to prepare and wear resisting property comparatively adopt mechanical mixing method to prepare has raising by a larger margin.Illustrate that adopt the present invention to prepare oil-filled fills the cogelled over-all properties with excellence of graphene oxide solution.
Although illustrate and describe embodiments of the invention, for the ordinary skill in the art, be appreciated that and can carry out multiple change, amendment, replacement and modification to these embodiments without departing from the principles and spirit of the present invention, scope of the present invention is by claims and equivalents thereof.
Claims (7)
1. oil-filled graphene oxide solution of filling is total to a beta-rubber, it is characterized in that: the described oil-filled common beta-rubber of graphene oxide solution that fills is made up of the raw material of following weight part: rubber solutions 100, oily 1-80, graphene oxide 1-80, coupling agent 0.1-5, anti-aging agent 0.1-5.
2. oil-filled graphene oxide solution of filling is total to beta-rubber as claimed in claim 1, it is characterized in that: described rubber solutions is the rubber solutions utilizing solution polymerization process to produce.
3. oil-filled graphene oxide solution of filling is total to beta-rubber as claimed in claim 1, it is characterized in that: described rubber solutions is the one in cis-1,4-polybutadiene rubber solution, solution polymerized butadiene styrene rubber solution, polyisoprene rubber solution, polyisobutylene rubber solution, ethylene-propylene rubber(EPR) solution, silicone rubber solution.
4. oil-filled graphene oxide solution of filling is total to beta-rubber as claimed in claim 1, it is characterized in that: described oil comprises aromatic hydrocarbon oil, process oil, naphthenic oil, machine oil, white oil; The rubber prepared through chemosynthesis commonly uses tenderizer, ester class tenderizer; Peanut oil, Oleum Gossypii semen, rapeseed oil, plam oil, animal grease and modification derivant thereof.
5. oil-filled graphene oxide solution of filling is total to beta-rubber as claimed in claim 1, it is characterized in that: described tenderizer is ester class tenderizer.
6. oil-filled graphene oxide solution of filling is total to beta-rubber as claimed in claim 1, it is characterized in that: the preparation method of described graphene oxide is as follows: graphite being joined concentration is in the sulfuric acid of 70-98 wt%, stir after 10-30 minute, add potassium permanganate wherein, controlling temperature of reaction is 0-10 DEG C of stirring reaction 1-3 hour, adds the hydrogen peroxide of 10-30 wt%, after ultrasonic stripping 10-30 minute in reaction system, centrifugal, washing, dry, namely obtain graphene oxide.
7. the oil-filled preparation method filling graphene oxide solution altogether beta-rubber as claimed in claim 1, it is characterized in that: the concrete steps of described method are as follows: join in rubber solutions by graphene oxide, oil, coupling agent, anti-aging agent, temperature keeps 30-60 DEG C to stir 1-30 minute; In said mixture, pass into water vapour, utilize fractionation by distillation device, solvent oil is steamed and is separated; Namely drying has been prepared oil-filled graphene oxide solution of filling and has been total to beta-rubber.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105482155A (en) * | 2016-01-22 | 2016-04-13 | 杨超 | Processing method for modifying rubber with graphene |
| CN106977924A (en) * | 2017-03-24 | 2017-07-25 | 合肥羿振电力设备有限公司 | It is a kind of for composite insulating material of cable and preparation method thereof |
| CN108129718A (en) * | 2018-01-16 | 2018-06-08 | 青岛双星轮胎工业有限公司 | A kind of preparation method of the oil-filled solution polymerized butadiene styrene rubber composite material of graphene-containing |
| CN109796646A (en) * | 2018-12-12 | 2019-05-24 | 青岛大学 | A kind of oil-filled type complex solution of carbon nano-tube modification phyllosilicate collaboration enhancing is total to gel rubber and preparation method thereof |
| CN111218068A (en) * | 2019-04-23 | 2020-06-02 | 烟台桑尼橡胶有限公司 | Formula and preparation process of graphene-containing high-wear-resistance rubber dam and gas shield dam |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104072834A (en) * | 2014-06-27 | 2014-10-01 | 青岛大学 | Oil-filled and carbon nano tube filled emulsion coprecipitated rubber and preparation method thereof |
| CN104072832A (en) * | 2014-06-27 | 2014-10-01 | 青岛大学 | Oil-filled and graphene oxide emulsion-filled co-coagulated rubber and preparation method thereof |
| CN104072827A (en) * | 2014-06-27 | 2014-10-01 | 青岛大学 | Oil and carbon nano tube filled solution conglutination rubber and preparation method thereof |
-
2015
- 2015-03-15 CN CN201510112111.6A patent/CN104788755A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104072834A (en) * | 2014-06-27 | 2014-10-01 | 青岛大学 | Oil-filled and carbon nano tube filled emulsion coprecipitated rubber and preparation method thereof |
| CN104072832A (en) * | 2014-06-27 | 2014-10-01 | 青岛大学 | Oil-filled and graphene oxide emulsion-filled co-coagulated rubber and preparation method thereof |
| CN104072827A (en) * | 2014-06-27 | 2014-10-01 | 青岛大学 | Oil and carbon nano tube filled solution conglutination rubber and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105482155A (en) * | 2016-01-22 | 2016-04-13 | 杨超 | Processing method for modifying rubber with graphene |
| CN106977924A (en) * | 2017-03-24 | 2017-07-25 | 合肥羿振电力设备有限公司 | It is a kind of for composite insulating material of cable and preparation method thereof |
| CN108129718A (en) * | 2018-01-16 | 2018-06-08 | 青岛双星轮胎工业有限公司 | A kind of preparation method of the oil-filled solution polymerized butadiene styrene rubber composite material of graphene-containing |
| CN109796646A (en) * | 2018-12-12 | 2019-05-24 | 青岛大学 | A kind of oil-filled type complex solution of carbon nano-tube modification phyllosilicate collaboration enhancing is total to gel rubber and preparation method thereof |
| CN111218068A (en) * | 2019-04-23 | 2020-06-02 | 烟台桑尼橡胶有限公司 | Formula and preparation process of graphene-containing high-wear-resistance rubber dam and gas shield dam |
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Application publication date: 20150722 |