CN105885439A - Protective wax based on surface modification graphene and preparation method thereof - Google Patents
Protective wax based on surface modification graphene and preparation method thereof Download PDFInfo
- Publication number
- CN105885439A CN105885439A CN201410422976.8A CN201410422976A CN105885439A CN 105885439 A CN105885439 A CN 105885439A CN 201410422976 A CN201410422976 A CN 201410422976A CN 105885439 A CN105885439 A CN 105885439A
- Authority
- CN
- China
- Prior art keywords
- graphene
- protection wax
- graphite alkene
- surface modified
- modified graphite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Protective wax based on surface modification graphene is disclosed. According to the invention, performance of protective wax is improved and boosted. Bile salt or its derivative surface modification treated graphene, which accounts for 0.001-6% of mass of the protective wax, is directly added into protective wax. The treated graphene has good stability and dispersity in the protective wax. In comparison with traditional protective wax, corrosion resistance, mechanical damage resistance and storage stability of the protective wax of the invention are enhanced.
Description
Technical field
The present invention relates to a kind of protection wax, a kind of protection wax based on surface modified graphite alkene and preparation method thereof.
Background technology
Protection wax is to dissolve wax in (emulsifying) is dispersed in suitable solvent to make mastic or liquid; after being coated onto the surfaces such as leather shoes, floor, furniture, automobile; solvent volatilization loss; stay surface a thin layer cere; the surface of article is played a protective role, prevents daylight, rainwater, the damage of acid mist and machinery scuffing, collision etc..Traditional protection wax product corrosion protection ability, adhesion property is poor, and appearance is unsightly.For topper, owing to often by high salt fog damp and hot, high, strong ultraviolet radiation, requiring higher to corrosion resisting property, traditional protection wax can not meet requirement at all, therefore in the urgent need to the highest novel protected wax of exploitation performance and appearance requirement.
Graphene perfect two dimensional surface honeycomb crystal lattice structure creates the performance that Graphene is unique, such as mechanical property, electric conductivity and heat conductivility.Compared with the protection wax being not added with Graphene, the mechanical property of the protection wax that with the addition of Graphene is obviously improved, and heat conductivility is the most also significantly improved.Graphene is mainly based upon it disperses uniformly with the form of monolithic layer in the base the raising of protection wax substrate performance, but owing to the concentration of graphene suspension can not be the lowest, and Graphene price is high, easily reunite, and seriously limits its application.How by Graphene and protection wax perfect adaptation, give full play of the Graphene improvement to mechanical property, be the novel protection wax series products based on Graphene of exploitation must faced by a difficult problem.
Summary of the invention
For above-mentioned technical problem, it is an object of the invention to provide a kind of protection wax based on surface modified graphite alkene and preparation method thereof, to improve etch resistant properties and the performance of resistant to mechanical damage of protection wax.
As one aspect of the present invention; the invention provides a kind of protection wax based on surface modified graphite alkene; wherein being added to by the Graphene that bile salt or derivatives thereof processed in protection wax, it is 0.001-6% that the Graphene that described bile salt or derivatives thereof processed accounts for the mass fraction of protection wax.
Preferably, it is 0.01-0.1% that the Graphene that wherein said bile salt or derivatives thereof processed accounts for the mass fraction of protection wax.
Wherein, described bile salt includes but not limited to selected from cholic acid, deoxycholic acid, chenodeoxy cholic acid, lithocholic acid, glycocholic acid, glycochenodeoxycholate, taurocholic acid, the sodium salt of cattle sulphur chenodeoxy cholic acid or potassium salt.
Wherein, described bile salt is preferably NaTDC or sodium cholate.
Wherein, described Graphene is to be by mechanically pulling off Graphene prepared by method, chemical oxidization method, crystal epitaxy method, chemical vapour deposition technique, organic synthesis method or CNT stripping method.
Wherein, described Graphene preferred thickness is 0.17-1.4nm, and sheet footpath size is 1～20 μm.
As another aspect of the present invention, present invention also offers the preparation method of a kind of protection wax based on surface modified graphite alkene, comprise the following steps:
Being dissolved in water by Graphene, dispersion processes the weak solution obtaining Graphene；
Adding in water by bile salt or derivatives thereof, stirring obtains its aqueous solution；
By weak solution and the aqueous solution stirring mixing of described bile salt or derivatives thereof of described Graphene, under conditions of stirring, dropwise drip reducing agent, react 24 hours；
Washed product, is centrifugally separating to obtain surface-functionalized Graphene；
The described Graphene obtained is added in protection wax by certain mass fraction, uniformly mixes.
Wherein, described Graphene is to be by mechanically pulling off Graphene prepared by method, chemical oxidization method, crystal epitaxy method, chemical vapour deposition technique, organic synthesis method or CNT stripping method.
Wherein, described Graphene thickness is 0.17-1.4nm, and sheet footpath size is 1～20 μm.
Wherein, described bile salt includes but not limited to selected from cholic acid, deoxycholic acid, chenodeoxy cholic acid, lithocholic acid, glycocholic acid, glycochenodeoxycholate, taurocholic acid, the sodium salt of cattle sulphur chenodeoxy cholic acid or potassium salt.
Wherein, described bile salt or derivatives thereof is preferably NaTDC or sodium cholate.
Wherein, described reducing agent is hydrazine hydrate or sodium borohydride.
Wherein, it is 0.001-6% that the Graphene that described bile salt or derivatives thereof processed accounts for the mass fraction of protection wax.
Wherein, the Graphene that described bile salt or derivatives thereof processed accounts for the mass fraction of protection wax and is preferably 0.01-0.1%.
By technique scheme; the present invention uses bile salt or derivatives thereof to process Graphene; obtain the Graphene that can be dispersed in water steadily in the long term; it is mixed and adds in protection wax; can more preferable dispersed graphite alkene so that the protection etch resistant properties of wax, bruise resistance and stable storing performance are all greatly improved.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, the present invention is described in further detail.
Protection wax, is to dissolve wax in (emulsifying) is dispersed in suitable solvent to make mastic or liquid, may be used for the protective action on the surfaces such as leather shoes, floor, furniture, automobile, prevent daylight, rainwater, the damage of acid mist and machinery scuffing, collision etc..That protects wax is mainly composed of wax, and macromolecule synthesising wax or natural resin can be used to purify wax, such as Brazil wax, microwax, paraffin etc..
The general name of the acids of secretion in bile acid, i.e. bile.Bile acid (bile acid) in normal person's bile can be divided into two big classes by structure: a class is sequestered bile acid, including cholic acid (cholic acid), deoxycholic acid (deoxycholic acid), chenodeoxy cholic acid (chenodeoxy cholic acid) and a small amount of lithocholic acid (litho chalic acid)；Another kind of be above-mentioned free bile acid be combined with glycine or taurine product, claim conjugated bile acids, mainly include glycocholic acid, glycochenodeoxycholate, taurocholic acid and cattle sulphur chenodeoxy cholic acid etc..Bile salt, then be the salt of bile acid, such as sodium salt, potassium salt etc..The derivant of bile salt, then be that the hydrogen atom in bile salt or atomic group are replaced and derivative product by other atoms or atomic group, such as UDCA, Na-gallbladder acyl-(3-O-nitro-D-Ser) etc..
The protection wax based on Graphene of the present invention uses bile salt or derivatives thereof that graphenic surface is carried out functionalization, to improve the water-soluble dispersion problem of Graphene, improves the protection etch resistant properties of wax, bruise resistance and stable storing performance.
Bile salt used in the present invention; include but not limited to bile acid; as selected from the sodium salt of cholic acid, deoxycholic acid, chenodeoxy cholic acid, lithocholic acid, glycocholic acid, glycochenodeoxycholate, taurocholic acid, cattle sulphur chenodeoxy cholic acid etc. or potassium salt, the most preferably NaTDC, sodium cholate.
Graphene used in the present invention, can be various known Graphenes, such as it is by mechanically pulling off Graphene prepared by the methods such as method, chemical oxidization method, crystal epitaxy method, chemical vapour deposition technique, organic synthesis method and CNT stripping method, can also be through being processed further the Graphene processed, such as single-layer graphene, graphene oxide, reduced graphene, functionalization graphene etc..The thickness of described Graphene and sheet footpath are neglected greatly and are actually needed selection, and preferred thickness is 0.17-1.4nm, and sheet footpath size is 1～20 μm.
In the protection wax based on surface modified graphite alkene of the present invention, it is 0.001-6%, preferably 0.01-0.1% that the Graphene processed through bile salt or derivatives thereof accounts for the mass fraction of protection wax.
Specifically comprising the following steps that of the preparation method of the protection wax based on surface modified graphite alkene of the present invention
Graphene is dissolved in ultra-pure water, such as, disperses with microwave irradiation, obtain the weak solution of Graphene；
Adding in ultra-pure water by bile salt or derivatives thereof, stirring obtains its aqueous solution；
By weak solution and the aqueous solution stirring mixing of bile salt or derivatives thereof of Graphene, dropwise drip reducing agent, react 24 hours；
Wash with the mixed solvent of first alcohol and water, be centrifugally separating to obtain the Graphene of surface-functionalized process；
Graphene is added in protection wax by certain mass percent, uniformly mixes, obtain the protection wax based on Graphene of the present invention.
The reducing agent wherein used such as can use hydrazine hydrate, sodium borohydride.
Present invention also offers a kind of protection wax based on surface modified graphite alkene; the Graphene that bile salt or derivatives thereof processes is added in protection wax; the Graphene that bile salt or derivatives thereof processes accounts for protection wax 0.001-6wt%, preferably 0.01-0.1wt%.
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
The preparation of graphite oxide: utilize known modified Hummer method to prepare, specifically comprise the following steps that addition 230mL 98% concentrated sulphuric acid in dry conical flask, sub-cooled is to 0-4 DEG C, 10g natural flake graphite and the fixing mixture of 5g sodium nitrate is added under strong stirring, until completely dissolved, 30g KMnO is added several times4, controlling temperature between 10-15 DEG C, stir reaction 2.5 hours, solution is blackish green.Then conical flask is placed in the water bath with thermostatic control of 35 DEG C, continues stirring reaction 30 minutes.After reaction terminates, under stirring, it is continuously added to a certain amount of deionized water, controls temperature between 80-100 DEG C, continues stirring 30 minutes, with the deionized water dilute reaction solution warmed, then the H adding 5%2O2, stirring, filtered while hot, product after filtering fully is washed to pH value close to 7 with 5% hydrochloric acid and deionized water, and exists without SO42-with the detection of BaCl2 solution, then filtration product (i.e. precipitate) is dried 48 hours in 60 DEG C of baking ovens, grind into powder and sieve, obtain graphite oxide powder.
NaTDC processes the preparation of Graphene: the graphite oxide powder obtained 1～1.5g is dissolved in deionized water that (concentration can adjust with visual response degree, such as can add 250-500g deionized water with 1g graphite oxide powder), microwave irradiation disperses, add the aqueous solution of the NaTDC that 5.3g concentration is 0.25～0.5mol/L, it is warming up to 80 DEG C, dropping 2-10ml hydrazine hydrate, and reaction was filtered after 24 hours with this understanding, being rinsed repeatedly with first alcohol and water successively by the product obtained, vacuum drying obtains the Graphene of NaTDC surface modification.
The Graphene of the NaTDC surface modification of 0.001wt% is joined in protection wax, be uniformly mixed.
Embodiment 2
The preparation of the Graphene that sodium cholate processes: preparing of graphite oxide powder body is same as in Example 1.1～1.5g graphite oxide powder is dissolved in deionized water that (concentration can adjust with visual response degree, such as can add 250～500g deionized water with 1g graphite oxide powder), microwave irradiation disperses, add the aqueous solution of the sodium cholate that 5.4g concentration is 0.25～0.5mol/L, it is warming up to 80 DEG C, the sodium borohydride of dropping 2-10ml, and reaction was filtered after 24 hours with this understanding, being rinsed repeatedly with first alcohol and water successively by the product obtained, vacuum drying obtains the Graphene of sodium cholate surface modification.
The Graphene of the sodium cholate surface modification of 0.001wt% is joined in protection wax, stir 1 hour.
Embodiment 3-5
NaTDC is same as in Example 1 to the method for graphite oxide surface modification, differ only in modified Graphene join protection wax in mass percent be respectively 0.01%, 0.4% and 6%.
Embodiment 6-8
Sodium cholate is same as in Example 2 to the method for graphite oxide surface modification, differ only in modified Graphene join protection wax in mass percent be respectively 0.02%, 0.8% and 6%.
Comparative example 1,2
The method preparing graphite oxide powder is same as in Example 1, differs only in and is added without bile salt, but according to improve hummer method directly with hydrazine hydrate or sodium borohydride to graphite oxide powder reduction, obtain black graphene powder.
Respectively unmodified for 0.001wt% and 6wt% graphene powder is joined in protection wax, be uniformly mixed.
Corrosion resisting property is evaluated:
Use traditional salt spray test, after being exposed 72 hours in 5% salt fog by detection film test piece, whether have corrosion to judge to protect the decay resistance of wax.
Mechanical damage performance evaluation:
The ISO 12137-1:1997 Test Method for Mar Resistance of Coatings Film of employing standard, on the protection wax uniform thickness paint test paint film will prepared by the embodiment of the present invention and comparative example, 45 ° of scriber tests.
Detecting embodiment various aspects of performance, result is as shown in table 1 below:
The each embodiment of table 1 and comparative example's test result list
| Embodiment | Corrosion resisting property | Mechanical damage performance |
| Embodiment 1 | Excellent | Good |
| Embodiment 2 | Excellent | Good |
| Embodiment 3 | Excellent | Excellent |
| Embodiment 4 | Excellent | Excellent |
| Embodiment 5 | Excellent | Excellent |
| Embodiment 6 | Excellent | Excellent |
| Embodiment 7 | Excellent | Excellent |
| Embodiment 8 | Excellent | Excellent |
| Comparative example 1 | Difference | Difference |
| Comparative example 2 | Medium | Excellent |
By experiment above; after the Graphene through the process of bile salt or derivatives thereof of the present invention adds in protection wax; can more preferable dispersed graphite alkene so that the protection etch resistant properties of wax, bruise resistance and stable storing performance are all greatly improved.And the Graphene processed without bile salt or derivatives thereof, although mechanical damage performance can be improved in the case of big addition, but owing to dispersion inequality also causes the deterioration of other performances.
Although embodiment illustrate only the bile salt or derivatives thereof surface modification to graphene oxide, but this area is it is appreciated that by the inspiration of above-described embodiment, such scheme is equally applicable to the modification of other type graphite alkene.
Particular embodiments described above; the purpose of the present invention, technical scheme and beneficial effect are further described; it it should be understood that; the foregoing is only the specific embodiment of the present invention; it is not limited to the present invention; all within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. done, should be included within the scope of the present invention.
Claims (14)
1. a protection wax based on surface modified graphite alkene, wherein adds in protection wax by the Graphene that bile salt or derivatives thereof processed, and it is 0.001-6% that the Graphene that described bile salt or derivatives thereof processed accounts for the mass fraction of protection wax.
Protection wax based on surface modified graphite alkene the most according to claim 1, it is 0.01-0.1% that the Graphene that wherein said bile salt or derivatives thereof processed accounts for the mass fraction of protection wax.
Protection wax based on surface modified graphite alkene the most according to claim 1, wherein said bile salt includes but not limited to selected from cholic acid, deoxycholic acid, chenodeoxy cholic acid, lithocholic acid, glycocholic acid, glycochenodeoxycholate, taurocholic acid, the sodium salt of cattle sulphur chenodeoxy cholic acid or potassium salt.
Protection wax based on surface modified graphite alkene the most according to claim 3, wherein said bile salt is NaTDC or sodium cholate.
Protection wax based on surface modified graphite alkene the most according to claim 1, wherein said Graphene is to be by mechanically pulling off Graphene prepared by method, chemical oxidization method, crystal epitaxy method, chemical vapour deposition technique, organic synthesis method or CNT stripping method.
Protection wax based on surface modified graphite alkene the most according to claim 1, wherein said Graphene thickness is 0.17-1.4nm, and sheet footpath size is 1～20 μm.
7. a preparation method for protection wax based on surface modified graphite alkene, comprises the following steps:
Being dissolved in water by Graphene, dispersion processes the weak solution obtaining Graphene；
Adding in water by bile salt or derivatives thereof, stirring obtains its aqueous solution；
By weak solution and the aqueous solution stirring mixing of described bile salt or derivatives thereof of described Graphene, under conditions of stirring, dropwise drip reducing agent, react 24 hours；
Washed product, is centrifugally separating to obtain surface-functionalized Graphene；
The described Graphene obtained is added in protection wax by certain mass fraction, uniformly mixes.
The preparation method of protection wax based on surface modified graphite alkene the most according to claim 7, wherein said Graphene is to be by mechanically pulling off Graphene prepared by method, chemical oxidization method, crystal epitaxy method, chemical vapour deposition technique, organic synthesis method or CNT stripping method.
The preparation method of protection wax based on surface modified graphite alkene the most according to claim 7, wherein said Graphene thickness is 0.17-1.4nm, and sheet footpath size is 1～20 μm.
The preparation method of protection wax based on surface modified graphite alkene the most according to claim 7, wherein said bile salt includes but not limited to selected from cholic acid, deoxycholic acid, chenodeoxy cholic acid, lithocholic acid, glycocholic acid, glycochenodeoxycholate, taurocholic acid, the sodium salt of cattle sulphur chenodeoxy cholic acid or potassium salt.
The preparation method of 11. protection waxes based on surface modified graphite alkene according to claim 7, wherein said bile salt or derivatives thereof is NaTDC or sodium cholate.
The preparation method of 12. protection waxes based on surface modified graphite alkene according to claim 7, wherein said reducing agent is hydrazine hydrate or sodium borohydride.
The preparation method of 13. protection waxes based on surface modified graphite alkene according to claim 7, it is 0.001-6% that the Graphene that wherein said bile salt or derivatives thereof processed accounts for the mass fraction of protection wax.
The preparation method of 14. protection waxes based on surface modified graphite alkene according to claim 13, it is 0.01-0.1% that the Graphene that wherein said bile salt or derivatives thereof processed accounts for the mass fraction of protection wax.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410422976.8A CN105885439A (en) | 2014-08-26 | 2014-08-26 | Protective wax based on surface modification graphene and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410422976.8A CN105885439A (en) | 2014-08-26 | 2014-08-26 | Protective wax based on surface modification graphene and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105885439A true CN105885439A (en) | 2016-08-24 |
Family
ID=57000757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410422976.8A Pending CN105885439A (en) | 2014-08-26 | 2014-08-26 | Protective wax based on surface modification graphene and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105885439A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113292864A (en) * | 2021-06-16 | 2021-08-24 | 辽宁东科新材料有限公司 | Graphene rubber protective wax |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102796454A (en) * | 2012-08-15 | 2012-11-28 | 深圳市彩虹精细化工股份有限公司 | Nanoparticle-containing automobile polishing protective wax and its preparation method |
| CN103011135A (en) * | 2011-09-20 | 2013-04-03 | 安炬科技股份有限公司 | Graphene preparation method |
| CN103468004A (en) * | 2013-09-25 | 2013-12-25 | 南京天诗新材料科技有限公司 | Nano-graphene loaded wax liquor, and preparation method and use thereof |
-
2014
- 2014-08-26 CN CN201410422976.8A patent/CN105885439A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011135A (en) * | 2011-09-20 | 2013-04-03 | 安炬科技股份有限公司 | Graphene preparation method |
| CN102796454A (en) * | 2012-08-15 | 2012-11-28 | 深圳市彩虹精细化工股份有限公司 | Nanoparticle-containing automobile polishing protective wax and its preparation method |
| CN103468004A (en) * | 2013-09-25 | 2013-12-25 | 南京天诗新材料科技有限公司 | Nano-graphene loaded wax liquor, and preparation method and use thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113292864A (en) * | 2021-06-16 | 2021-08-24 | 辽宁东科新材料有限公司 | Graphene rubber protective wax |
| CN113292864B (en) * | 2021-06-16 | 2022-03-29 | 辽宁东科新材料有限公司 | Graphene rubber protective wax |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104772156A (en) | Preparation method for graphene loaded cobalt nickel phosphide composite material | |
| JPH02294414A (en) | Production of fine copper powder | |
| CN107558175A (en) | A kind of preparation method of glass/zinc oxide | |
| CN110304662A (en) | Silicone hydroxyl magnetic bead and its preparation method and application | |
| CN105885439A (en) | Protective wax based on surface modification graphene and preparation method thereof | |
| TW201307208A (en) | Micro-scaled flake silver particles and method for producing the same | |
| CN104877404A (en) | Organic-inorganic composite corrosion resistant coating and preparation method thereof | |
| KR20150121426A (en) | Coating Layer Structure For Prevention Of Corrosion And The Manufacturing Method Thereof | |
| TWI326232B (en) | ||
| CN113559828B (en) | Polyacrylic acid magnetic nanocomposite, preparation method and application | |
| CN111117369A (en) | Polyaniline functionalized graphene conductive ink and preparation method thereof | |
| EP3447027B1 (en) | Functionalized graphene preparing method | |
| CN104261394B (en) | The preparation method of Graphene | |
| CN106633820A (en) | Antistatic low-light photocatalyst type formaldehyde remover and preparation method thereof | |
| CN106430155A (en) | Method for preparing graphene based on ionic liquid | |
| CN113861700A (en) | Hybrid material flame retardant, flame-retardant epoxy resin and preparation methods of hybrid material flame retardant and flame-retardant epoxy resin | |
| CN113215576B (en) | Preparation method and application of rare earth doped silicon dioxide intelligent corrosion inhibition system | |
| Liu et al. | Ternary SO 4 2−–ZrO 2–TiO 2 Solid Super Acid Catalyst for One-Step Synthesis of Adipicdihydrazide | |
| CN106241820A (en) | A kind of aeroge raw material and preparation method thereof | |
| CN104710652A (en) | Dendritic modified montmorillonite flame retardant and preparation method thereof | |
| CN107216058A (en) | A kind of graphene cement grinding aid and preparation method thereof | |
| KR910016880A (en) | Anti-glare and antistatic transparent coating composition, method for manufacturing the same, and image display coating the coating composition | |
| CN105448527B (en) | A kind of electrode material for ultracapacitor and preparation method thereof | |
| CN113845880A (en) | Silver nanowire @ polypyrrole-ferroferric oxide composite wave-absorbing material and preparation method thereof | |
| CN108795415A (en) | A kind of preparation method of Si modification europium complex fluorescent powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| DD01 | Delivery of document by public notice | ||
| DD01 | Delivery of document by public notice |
Addressee: Yan Liqun Document name: Notification that Application Deemed to be Withdrawn |
|
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160824 |