CN106750545B - A kind of zinc stearate/graphene oxide composite material and preparation method thereof - Google Patents
A kind of zinc stearate/graphene oxide composite material and preparation method thereof Download PDFInfo
- Publication number
- CN106750545B CN106750545B CN201710020152.1A CN201710020152A CN106750545B CN 106750545 B CN106750545 B CN 106750545B CN 201710020152 A CN201710020152 A CN 201710020152A CN 106750545 B CN106750545 B CN 106750545B
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- zinc stearate
- zinc
- composite material
- present
- 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.)
- Active
Links
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 title claims abstract description 149
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 143
- 239000002131 composite material Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims description 43
- 239000011701 zinc Substances 0.000 claims abstract description 42
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 19
- 235000021355 Stearic acid Nutrition 0.000 claims description 18
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 18
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 18
- 239000008117 stearic acid Substances 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000004246 zinc acetate Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 6
- 229960001763 zinc sulfate Drugs 0.000 claims description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 6
- 239000005060 rubber Substances 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 4
- 238000005253 cladding Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- XIVNZHXRIPJOIZ-UHFFFAOYSA-N octadecanoic acid;zinc Chemical compound [Zn].CCCCCCCCCCCCCCCCCC(O)=O XIVNZHXRIPJOIZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 55
- 239000000047 product Substances 0.000 description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 29
- 238000000034 method Methods 0.000 description 26
- 235000019441 ethanol Nutrition 0.000 description 21
- 239000004800 polyvinyl chloride Substances 0.000 description 14
- 229920000915 polyvinyl chloride Polymers 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- MVLVMROFTAUDAG-UHFFFAOYSA-N ethyl octadecanoate Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 description 6
- 239000012760 heat stabilizer Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000007500 overflow downdraw method Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- KYIDJMYDIPHNJS-UHFFFAOYSA-N ethanol;octadecanoic acid Chemical compound CCO.CCCCCCCCCCCCCCCCCC(O)=O KYIDJMYDIPHNJS-UHFFFAOYSA-N 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- 238000003483 aging Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 239000001293 FEMA 3089 Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000000346 nonvolatile oil Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229940095696 soap product Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The present invention provides a kind of zinc stearate/graphene oxide composite materials, including zinc stearate and the graphene oxide for being compounded in zinc stearate surface.The present invention carries out zinc stearate with graphene oxide compound, the sheet zinc stearate composite material of micron level is obtained, size is uniform, regular appearance, graphene oxide is coated on zinc stearate surface by chemical bond, the clad structure of graphene oxide cladding stearic acid zinc metal sheet, or the stratiform overlaying structure of " zinc stearate-graphene-zinc stearate " are formed, zinc stearate/graphene oxide composite material provided by the invention has better thermal stability and lubricity.
Description
Technical field
The invention belongs to zinc stearate technical field of composite materials more particularly to a kind of zinc stearate/graphene oxide are multiple
Condensation material and preparation method thereof.
Background technique
Zinc stearate (Zinc stearate) also known as zinc octadecanate or Stearic Acid zinc, molecular formula C36H70O4Zn, molecule
Amount is 632.33, and white powder is not soluble in water, is dissolved in the organic solvents such as ethyl alcohol, benzene, toluene or the turpentine oil of heat；Encounter acid point
Solution is at stearic acid and corresponding salt；Have under the dry condition fire danger, there is hygroscopicity under humidified condition.It is commonly divided into
Solidity zinc stearate and water-based zinc stearate.
There are two types of the production methods of zinc stearate: water law and fusion method.Usually, the aobvious acid of the zinc stearate of water law production
Property, melting Faxian alkalinity.Water law is also known as wet process under conditions of water is medium, and catalyst is added, and controls certain temperature, pressure
Then metal hydroxides is added in power, replace onto catalyst metal ion by catalyst, then pass through catalyst itself
It replaces on stearic acid again, to achieve the purpose that generate metal salt.Fusion method is also known as dry method, refers to the item existing for catalyst
Under part, it is directly added into metal oxide (zinc oxide) in the stearic acid of melting, controls certain temperature, pressure and mixing speed,
Stearate is obtained by reaction.
Zinc stearate is used in the additive that one kind in many polymer has multiple functions, unique and various based on it
The physicochemical property of change, many key areas such as plastics, coating, lubricating grease, weaving, building, papermaking, pigment obtain extensively and
Important application, and constantly there is new application approach to be developed, main application field is coating, plastics and rubber
Industry；Such as it can be used as heat stabilizer, lubricant, lubricating grease, promotor or thickener in resin art, usually as PVC tree
Rouge heat stabilizer.PVC (polyvinyl chloride) is to be only second to most wide one of the plastics of polyethylene dosage maximum, purposes in the world at present,
And the performances such as, insulation fire-retardant with its, wear-resistant have won wide market.Polyvinyl chloride resin and its product are lacked due to the structure of itself
It falls into, the shortcomings that there is easy thermal degradation and agings, it is 160 DEG C of processing temperature or more also higher than 120 DEG C of decomposition temperature；Therefore,
PVC will be become into product, just must add heat stabilizer during machine-shaping, to delay or prevent the heat of polyvinyl chloride resin
Degradation, and be exactly that small molecule is sloughed by thermal decomposition the main reason for polyvinyl chloride heat ageing, on the one hand zinc stearate can capture
The hydrogen chloride split away off, on the other hand can also replace present in chlorine atom in allyl chloride, generate more stable ester,
To eliminate the initiation source of dehydrochlorination in polymeric material.Therefore, zinc stearate is generally selected in field as PVC plastic
Heat stabilizer and lubricant.
In view of the important use of zinc stearate, zinc stearate is further modified always in industry, to improve
Its performance expands its application field, and the preparation process of zinc stearate is also to limit its bottleneck for continuing development, stearic acid
The production technology of zinc is broadly divided into double decomposition and two kinds of fusion method, generallys use double decomposition work in manufacturer at home
Skill.Raw material used in this method has the raw materials such as stearic acid, zinc sulfate, caustic soda, after metathesis reaction, washes, drying,
The technique of some column such as drying finally obtains finished product.Although its reaction condition is mild, by control reaction temperature, etc. techniques item
Part, can obtain that color is good, the higher metallic soap product of purity, but its own has inevitable defect -- and production capacity is low and energy
Consumption is high, and if reaction mass is liquid-solid than high, production efficiency is low；It needs to consume a large amount of water to be washed, amplification quantity saliferous and press from both sides side by side
Waste water with organic matter；Energy consumption for drying is big, and product apparent density is small, and dust from flying is serious；More importantly double decomposition is raw
The zinc stearate of production shows very poor transparency in coating, is unable to get extensive use.
Therefore, a kind of modification zinc stearate material with more preferable performance how is obtained, tradition can also be especially solved
Defect in preparation method, it has also become many line R&D and production personnel and urgently to be resolved important of manufacturer is asked in the industry in industry
Topic.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of zinc stearate/graphene oxide composite wood
Material and preparation method thereof, zinc stearate/graphene oxide composite material provided by the invention have preferable thermal stability, and
Preparation method simple process, mild condition, safety and environmental protection are suitble to large-scale industrial production.
The present invention provides a kind of zinc stearate/graphene oxide composite material, including zinc stearate and it is compounded in tristearin
The graphene oxide of sour zinc surface.
Preferably, the zinc stearate is sheet zinc stearate；
The graphene oxide with a thickness of 0.1~0.5nm；
The mass ratio of the zinc stearate and the graphene oxide is 1000:(1~50).
Preferably, the piece diameter of the zinc stearate/graphene oxide composite material is 4~12 μm；
Zinc stearate/the graphene oxide composite material with a thickness of 30~70nm.
The present invention provides a kind of preparation methods of zinc stearate/graphene oxide composite material, comprising the following steps:
A) by graphene oxide, organic solvent miscible with water and water after dispersion, graphene oxide dispersion is obtained
Liquid；
B after the graphene oxide dispersion for) obtaining above-mentioned steps and the mixing of zinc source, precursor solution is obtained；
C) precursor solution for obtaining above-mentioned steps obtains zinc stearate/graphene oxide after being reacted with stearic acid
Composite material.
Preferably, in the graphene oxide dispersion, the mass fraction of graphene oxide is 0.5 ‰~5 ‰；
The organic solvent miscible with water includes that alcohols solvent, amine solvent, ketones solvent and high molecular polymer are molten
One of agent is a variety of；
The mass ratio of the organic solvent and water miscible with water is (0.01~1): 1.
Preferably, the zinc source is zinc source solution；
The concentration of zinc source solution is 0.01~0.5mol/L；
The zinc source includes one of zinc acetate, zinc chloride, zinc nitrate, zinc sulfate and zinc perchlorate or a variety of；
The mass ratio of zinc ion is 1:(1~10 in the graphene oxide and the zinc source).
Preferably, described to be mixed into ultrasonic disperse；
The mixed temperature is 20~60 DEG C；The mixed time is 10~60min.
Preferably, the step C) specifically:
It is slowly added to stearic acid organic solution into the precursor solution that above-mentioned steps obtain, obtains tristearin after being reacted
Sour zinc/graphene oxide composite material；
The molar ratio of zinc ion is (1.5~2.5) in the stearic acid and the zinc source: 1；
The temperature of the reaction is 60~100 DEG C；The time of the reaction is 90~150min.
Preferably, the concentration of the stearic acid organic solution is 0.1~0.3mol/L；
Solvent in the tristearin acid organic solution includes that alcohols solvent, benzene kind solvent, polynary alkanes solvent and ethers are molten
One of agent is a variety of；
The rate being slowly added to is 0.3~0.7mL/s.
The present invention also provides zinc stearate/graphene oxide composite material described in above-mentioned technical proposal any one or
Zinc stearate/graphene oxide composite material prepared by above-mentioned technical proposal any one is led in rubber product or resin additive
Application in domain.
The present invention provides a kind of zinc stearate/graphene oxide composite material, including zinc stearate and it is compounded in tristearin
The graphene oxide of sour zinc surface.Compared with prior art, the present invention needs further for the performance of existing zinc stearate
The status of promotion, zinc stearate and graphene oxide progress is compound, obtain the sheet zinc stearate composite wood of micron level
Material, size is uniform, regular appearance, and graphene oxide is coated on zinc stearate surface by chemical bond, forms graphite oxide
Alkene coats the clad structure of stearic acid zinc metal sheet, or the stratiform overlaying structure of " zinc stearate-graphene-zinc stearate ", this hair
Zinc stearate/graphene oxide composite material of bright offer has better thermal stability and lubricity.The experimental results showed that this
Zinc stearate/graphene oxide composite material of invention preparation compares common zinc stearate, and thermal stability raising reaches
116%.
Detailed description of the invention
Fig. 1 is that the embodiment of the present invention 1 prepares zinc stearate/graphene oxide composite material process flow diagram；
Fig. 2 is zinc stearate/graphene oxide composite material XRD x ray diffraction map of preparation of the embodiment of the present invention；
Fig. 3 is that zinc stearate/graphene oxide composite material scanning electron microscope prepared by the embodiment of the present invention 1 is shone
Piece；
Fig. 4 is that zinc stearate/graphene oxide composite material scanning electron microscope prepared by the embodiment of the present invention 2 is shone
Piece；
Fig. 5 is the electron scanning micrograph of conventional zinc stearate；
Fig. 6 is that zinc stearate/graphene oxide composite material scanning electron microscope prepared by the embodiment of the present invention 3 is shone
Piece.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are intended merely to further illustrate the features and advantages of the present invention, rather than to invention claim
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art
The preparation of conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, present invention preferably employs analyze pure or zinc stearate and
The conventional purity used in graphene oxide field.
The present invention provides a kind of zinc stearate/graphene oxide composite material, including zinc stearate and it is compounded in tristearin
The graphene oxide of sour zinc surface.
The zinc stearate is not particularly limited in the present invention, is with zinc stearate material well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical condition, combining case and properties of product
The bright zinc stearate material is preferably sheet zinc stearate material.The graphene oxide is not particularly limited in the present invention,
With graphene oxide composite material well known to those skilled in the art, those skilled in the art can according to practical condition,
Combining case and properties of product are selected and are adjusted material.
The size dimension of the zinc stearate/graphene oxide composite material is not particularly limited in the present invention, with ability
The size dimension of zinc stearate composite material known to field technique personnel, those skilled in the art can be according to actual productions
Situation, combining case and properties of product are selected and are adjusted, zinc stearate/graphene oxide composite material of the present invention
Piece diameter be preferably 4~12 μm, more preferably 6~10 μm, most preferably 7~9 μm；Zinc stearate of the present invention/oxidation stone
The thickness of black alkene composite material is preferably 30~70nm, more preferably 40~60nm, most preferably 45~55nm.
The present invention is to the actual conditions of the graphene oxide layer of the zinc stearate/graphene oxide composite material without spy
It not limiting, those skilled in the art can select and adjust according to practical condition, combining case and properties of product,
The thickness of graphene oxide of the present invention is preferably 0.1~0.5nm, more preferably 0.2~0.4nm, most preferably 0.25~
0.35nm。
The mass ratio of the zinc stearate/graphene oxide composite material is not particularly limited in the present invention, this field skill
Art personnel can select and adjust according to practical condition, combining case and properties of product, tristearin of the present invention
The mass ratio of sour zinc and the graphene oxide is preferably 1000:(1~50), more preferably 1000:(5~40), most preferably
1000:(15~30).
The present invention to it is described it is compound be not particularly limited, with composite definitions well known to those skilled in the art, this hair
It is bright preferably to coat, partly coat, being laminated, deposition, adulterating or grow, it more preferably coats, partly coat or be laminated, most preferably wrap
It covers or is laminated.The cladding and stacking is not particularly limited in the present invention, with cladding well known to those skilled in the art and stacking
Definition, those skilled in the art can select and adjust according to practical condition, combining case and properties of product
It is whole.
The present invention provides a kind of preparation methods of zinc stearate/graphene oxide composite material, comprising the following steps:
A) by graphene oxide, organic solvent miscible with water and water after dispersion, graphene oxide dispersion is obtained
Liquid；
B after the graphene oxide dispersion for) obtaining above-mentioned steps and the mixing of zinc source, precursor solution is obtained；
C) precursor solution for obtaining above-mentioned steps obtains zinc stearate/graphene oxide after being reacted with stearic acid
Composite material.
The present invention obtains oxidation stone first by graphene oxide, organic solvent miscible with water and water after dispersion
Black alkene dispersion liquid.
The graphene oxide is not particularly limited in the present invention, is with graphene oxide well known to those skilled in the art
Can, those skilled in the art can select and adjust according to practical condition, combining case and properties of product；This hair
The bright source to the graphene oxide is not particularly limited, and is prepared with preparation method well known to those skilled in the art or commercially available
Purchase, those skilled in the art can select and adjust according to practical condition, combining case and properties of product
It is whole.
The organic solvent miscible with water is not particularly limited in the present invention, with well known to those skilled in the art and water
The organic solvent to dissolve each other, those skilled in the art can according to practical condition, combining case and properties of product into
Row selection and adjustment, organic solvent miscible with water of the present invention preferably include alcohols solvent, amine solvent, ketones solvent and
One of high molecular polymer solvent is a variety of, more preferably ethyl alcohol, acetone, toluene or ether, most preferably ethyl alcohol.
The additional amount of the organic solvent miscible with water is not particularly limited in the present invention, ripe with those skilled in the art
The conventional proportions known, those skilled in the art can carry out according to practical condition, combining case and properties of product
Selection and adjustment, the mass ratio of organic solvent and water miscible with water of the present invention are preferably (0.01~1): 1, more preferably
(0.1~0.9): 1, more preferably (0.3~0.7): 1, most preferably (0.4~0.6): 1.The present invention is to the graphene oxide
Additional amount be not particularly limited, those skilled in the art can be according to practical condition, combining case and properties of product
It being selected and is adjusted, in graphene oxide dispersion of the present invention, the mass fraction of graphene oxide is preferably 0.5 ‰~
5 ‰, more preferably 1 ‰~4 ‰, most preferably 2 ‰~3 ‰.
The mode of the dispersion is not particularly limited in the present invention, is with dispersing method well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical condition, combining case and properties of product
The bright dispersion is preferably ultrasonic disperse.The time of the dispersion is not particularly limited in the present invention, with those skilled in the art
Well known jitter time, those skilled in the art can according to practical condition, combining case and properties of product into
Row selection and adjustment, the time of dispersion of the present invention is preferably 10~40min, more preferably 15~35min, most preferably 20
~30min.The frequency of the dispersion is not particularly limited in the present invention, is with dispersion frequency well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical condition, combining case and properties of product
The frequency of the bright dispersion is preferably 20~80KHz, more preferably 30~60KHz, most preferably 40~50KHz.
Above-mentioned steps of the present invention have obtained graphene oxide two phase dispersant liquids in water and organic solvent, then by the oxidation
After graphene dispersing solution and the mixing of zinc source, precursor solution is obtained.
The zinc source is not particularly limited in the present invention, with zinc source well known to those skilled in the art, this field skill
Art personnel can select and adjust according to practical condition, product requirement and quality requirement, and zinc source of the present invention is excellent
Choosing includes one of zinc acetate, zinc chloride, zinc nitrate, zinc sulfate and zinc perchlorate or a variety of, more preferably zinc acetate, chlorination
Zinc, zinc nitrate, zinc sulfate or zinc perchlorate, most preferably zinc acetate.The present invention is not special to the additional proportion in the zinc source
Limitation, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The mass ratio of zinc ion is preferably 1:(1~10 in the bright graphene oxide and the zinc source), more preferably 1:(3~8), most
Preferably 1:(4~7).The present invention is the reaction effect for further increasing mixed effect and later period, and the zinc source is preferably zinc
Source solution.The concentration of zinc source solution is not particularly limited in the present invention, with normal concentration well known to those skilled in the art
, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, this
The concentration for inventing zinc source solution is preferably 0.01~0.5mol/L, more preferably 0.05~0.4mol/L, most preferably 0.1
~0.3mol/L.
The present invention is to be further ensured that the effect and the reaction effect in later period of mixing dispersion, the step B) it is preferably upward
It states after the mixing of zinc source is added dropwise in the graphene oxide dispersion that step obtains, obtains precursor solution.The present invention is to the dropwise addition
Speed be not particularly limited, with rate of addition well known to those skilled in the art, those skilled in the art can basis
Practical condition, product requirement and quality requirement are selected and are adjusted, and the rate of dropwise addition of the present invention is preferably 0.3~
0.7mL/s, more preferably 0.4~0.6mL/s, most preferably 0.45~0.55mL/s.
The mixed temperature is not particularly limited in the present invention, is with mixed temperature well known to those skilled in the art
Can, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, the present invention
The mixed temperature is preferably 20~60 DEG C, more preferably 30~50 DEG C, most preferably 35~45 DEG C.The present invention is to described mixed
The time of conjunction is not particularly limited, and with incorporation time well known to those skilled in the art, those skilled in the art can root
It is selected and is adjusted according to practical condition, product requirement and quality requirement, the mixed time of the present invention is preferably 10
~60min, more preferably 20~50min, most preferably 30~40min.The present invention does not limit the mixed mode especially
System, with mixed method well known to those skilled in the art, those skilled in the art can be according to practical condition, product
It is required that and quality requirement selected and adjusted, it is of the present invention mixing be preferably ultrasonic disperse.The present invention is to the ultrasound point
Scattered frequency is not particularly limited, and with dispersion frequency well known to those skilled in the art, those skilled in the art can root
It is selected and is adjusted according to practical condition, product requirement and quality requirement, the frequency of dispersion of the present invention is preferably 20
~80KHz, more preferably 30~60KHz, most preferably 40~50KHz.
The precursor solution that the present invention finally obtains above-mentioned steps obtains zinc stearate/oxygen after reacting with stearic acid
Graphite alkene composite material.
The present invention is to be further ensured that the effect and the reaction effect in later period of mixing dispersion, above-mentioned steps, i.e., the described step
C it preferably) is slowly added to stearic acid organic solution into the precursor solution that above-mentioned steps obtain, obtains tristearin after being reacted
Sour zinc/graphene oxide composite material.
The solvent in the stearic acid organic solution is not particularly limited in the present invention, with well known to those skilled in the art
Conventional organic solvent, those skilled in the art can select according to practical condition, product requirement and quality requirement
It selects and adjusts, it is molten that the solvent in tristearin acid organic solution of the present invention preferably includes alcohols solvent, benzene kind solvent, polynary alkanes
One of agent and ether solvent are a variety of, more preferably ethyl alcohol, acetone, toluene or ether, most preferably ethyl alcohol；It specifically can be with
It is consistent with aforementioned organic solvent miscible with water.The stearic additional amount is not particularly limited in the present invention, this field
Technical staff can select and adjust according to practical condition, product requirement and quality requirement, tristearin of the present invention
The sour molar ratio with zinc ion in the zinc source is (1.5~2.5): 1, more preferably (1.7~2.3): 1, most preferably (1.9
~2.1): 1.The concentration of the stearic acid organic solution is not particularly limited in the present invention, with well known to those skilled in the art
The concentration of conventional soln, those skilled in the art can carry out according to practical condition, product requirement and quality requirement
The concentration of selection and adjustment, tristearin acid organic solution of the present invention is preferably 0.1~0.3mol/L, more preferably 0.15~
0.25mol/L, most preferably 0.17~0.23mol/L.
The speed being slowly added to is not particularly limited in the present invention, with rate of addition well known to those skilled in the art
, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
It is slowly added to preferably instill described in bright, the rate of the instillation is preferably 0.3~0.7mL/s, more preferably 0.4~0.6mL/
S, most preferably 0.45~0.55mL/s.The condition of the reaction is not particularly limited in the present invention, and those skilled in the art can
To be selected and be adjusted according to practical condition, product requirement and quality requirement, the temperature of reaction of the present invention is preferred
It is 60~100 DEG C, more preferably 70~90 DEG C, most preferably 75~85 DEG C；The time of the reaction is preferably 90~150min,
More preferably 100~140min, most preferably 110~130min.
The present invention is to further increase the performance of product and the integrality of integrated artistic and operability, after the reaction also
Including postprocessing working procedures.The postprocessing working procedures are not particularly limited in the present invention, with rear place well known to those skilled in the art
Science and engineering sequence, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement
Whole, postprocessing working procedures of the present invention preferably include separation, washing and one of dry or a variety of, are more preferably followed successively by point
From, washing and dry.
The isolated mode is not particularly limited in the present invention, is with separate mode well known to those skilled in the art
Can, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, the present invention
The isolated mode preferably filters；The mode of the washing is not particularly limited in the present invention, with those skilled in the art
Well known mode of washing, those skilled in the art can carry out according to practical condition, product requirement and quality requirement
Selection and adjustment, the mode of washing of the present invention is preferably washed and alcohol washes alternately multiple washing；Time of the washing
Number preferably 2~5 times, more preferably 3~4 times.The mode of the drying is not particularly limited in the present invention, with art technology
Drying mode known to personnel, those skilled in the art can be according to practical condition, product requirement and quality requirements
It is selected and is adjusted, the mode of drying of the present invention is preferably dried in vacuo；The temperature of the drying is preferably 40~70
DEG C, more preferably 45~65 DEG C, most preferably 50~60 DEG C.
The present invention is double decomposition i.e. fixed oil and caustic soda after saponification for the zinc stearate largely used now
It is standby with zinc sulfate metathetical, it is granulated progress zinc stearate synthesis after also having partial high pressure frit reaction, or use wet-chemical
Method realizes the chemical synthesis of zinc stearate, and there are complicated for operation, steps flow chart is cumbersome or the higher problem of production cost.The present invention
Zinc stearate/graphene composite material is prepared using one-step synthesis chemical method, the double decomposition and fusion method of abandoning tradition use
Zinc stearate/graphene oxide composite material, method letter has been prepared in improved wet chemistry method under normal pressure, cryogenic conditions
It is single easy to operate, it is easy to scale, repeatability preparation, obtained composite material size is uniform, and pattern is easily controllable, has good
Application prospect, and the controllable continuous preparation of zinc stearate is realized, and by the graphene coated of high-intensity and high-tenacity on surface
Or stacking is compound, improves the dispersibility and workability of composite material, facilitates thermal stability after PVC is added as auxiliary agent
It improves.
Technical solution of the present invention may further also be preferably more common reaction raw materials, such as zinc acetate both reduced
Reaction step, and synthesis cost is reduced, meanwhile, also realization low-temperature atmosphere-pressure environment preparation substantially reduces the requirement to reaction environment,
It is easy to scale, preparation of industrialization, does not use that hydrazine hydrate is contour to endanger reducing agent during simultaneous reactions, avoids environmental pollution.
The present invention also provides zinc stearate/graphene oxide composite material described in above-mentioned technical proposal any one or
Zinc stearate/graphene oxide composite material prepared by above-mentioned technical proposal any one is led in rubber product or resin additive
Application in domain.
The resin is not particularly limited in the present invention, with resin well known to those skilled in the art, this field skill
Art personnel can select and adjust according to practical condition, product requirement and quality requirement, and resin of the present invention is excellent
It is selected as polyvinyl chloride resin.The resin additive is not particularly limited in the present invention, is with resin additive well known to those skilled in the art
Can, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, the present invention
The resin additive is preferably heat stabilizer and/or lubricant, more preferably heat stabilizer or lubricant.
Above-mentioned steps of the present invention provide a kind of zinc stearate/graphene oxide composite material and preparation method thereof, innovation
Property use one step chemistry method of formation prepare zinc stearate/graphene composite material, which is uniformly dispersed, and size is equal
One, wherein in the form of sheets, composite gauge is 5~10 μm to zinc stearate, and with a thickness of 20~50nm, which has special packet
It covers and stepped construction, in the fields such as rubber and PVC plastic applications well prospect；And the present invention prepares the side of zinc stearate material
Method avoids realizing low-temperature atmosphere-pressure preparation using autoclave.The present invention further preferably uses zinc acetate as raw material, takes
The generation crude zinc oxide materials of routine are made under normal pressure, cryogenic conditions in final reaction step preferably by the way of oil bath heating
Standby zinc stearate/graphene composite material, is effectively reduced energy consumption needed for reaction system, reduces step needed for reacting, and improves product
Purity improves the repeatability of composite material, does not use catalyst, improves reaction conversion ratio, while reducing operation and reaction
Step reduces production cost, while extensive industrialization preparation may be implemented, and repeatability is high；The present invention is in technical side simultaneously
The raw material that hydrazine hydrate etc. has environmental hazard is not used during case, it is green and pollution-free.The experimental results showed that the present invention
Zinc stearate/graphene oxide composite material of preparation compares common zinc stearate, and thermal stability raising has reached 116%.
In order to further illustrate the present invention, with reference to embodiments to zinc stearate/graphene oxide provided by the invention
Composite material and preparation method is described in detail, but it is to be understood that these embodiments are with the technology of the present invention side
Implemented under premised on case, the detailed implementation method and specific operation process are given, only to further illustrate this hair
Bright feature and advantage, rather than limiting to the claimed invention, protection scope of the present invention are also not necessarily limited to following realities
Apply example.
Embodiment 1
The present embodiment prepares zinc stearate/graphene composite material by following steps:
One, graphene solution prepared by Hummers method is dissolved in (graphene matter in the mixed liquor of deionized water and ethyl alcohol
Amount score be 0.5 ‰) (ethyl alcohol and water volume ratio be 1:1), it is ultrasonic under room temperature and stir 20min and obtain graphene dispersion solution；
Two, the aqueous zinc acetate solution of 0.1mol/L is prepared, magnetic agitation obtains acetic acid zinc solution to state is clarified under room temperature；
Three, the stearic acid ethanol solution of 0.2mol/L is prepared, magnetic agitation obtains stearic acid ethyl alcohol to state is clarified under room temperature
Solution；
Four, the acetic acid zinc solution of (0.5mL/s) step 2 is slowly added dropwise into the dispersion solution of GO obtained in step 1, after
Continual ultrasonic and 30min is stirred at 40 DEG C, obtains precursor solution；
Five, the stearic acid ethyl alcohol that (0.3mL/s) step 3 is slowly added dropwise into precursor solution obtained in step 4 is molten
Liquid, after be transferred to oil bath, reaction 120min is condensed back under the conditions of being kept for 80 DEG C, obtains gray precipitate；
Six, gray precipitate will be obtained in step 5 filters separation, after ultrapure water and ethyl alcohol wash 3 times respectively, 50 DEG C of vacuum
It is dry, obtain zinc stearate/graphene oxide composite material.
Referring to Fig. 1, Fig. 1 is that the embodiment of the present invention 1 prepares the process flow letter of zinc stearate/graphene oxide composite material
Figure.
Material structure analysis is carried out to zinc stearate/graphene oxide composite material of above-mentioned steps of the present invention preparation.
Referring to fig. 2, Fig. 2 is that zinc stearate/graphene oxide composite material XRD ray of preparation of the embodiment of the present invention spreads out
Penetrate map.As shown in Figure 2, zinc stearate/graphene oxide composite material has successfully been prepared in the present invention.
It is zinc stearate/graphene oxide composite material scanning electron prepared by the embodiment of the present invention 1 referring to Fig. 3, Fig. 3
Microscope photo.
From the figure 3, it may be seen that zinc stearate slabbing, size is at 10 μm or so, and the thickness of nanometer sheet is in 50nm or so, in sheet
The surface of zinc stearate is coated with one layer of graphene oxide, forms zinc stearate/graphene oxide composite material, composite material point
It dissipates uniformly, size uniformity.
Material property analysis is carried out to zinc stearate/graphene oxide composite material of above-mentioned steps of the present invention preparation, it will
Pure zinc stearate and zinc stearate/graphene oxide composite material be separately added into injection molding in PVC plastic (zinc stearate and its
2%) composite material additional amount is.
Referring to table 1, table 1 is the zinc stearate/graphene oxide composite material and common tristearin of preparation of the embodiment of the present invention
The performance table of comparisons of sour zinc.
Embodiment 2
The present embodiment prepares zinc stearate/graphene composite material by following steps:
One, graphene solution prepared by Hummers method is dissolved in (graphene matter in the mixed liquor of deionized water and ethyl alcohol
Amount score be 1 ‰) (ethyl alcohol and water volume ratio be 1:1), it is ultrasonic under room temperature and stir 20min and obtain graphene dispersion solution；
Two, the aqueous zinc acetate solution of 0.15mol/L is prepared, magnetic agitation obtains acetic acid zinc solution to state is clarified under room temperature；
Three, the stearic acid ethanol solution of 0.3mol/L is prepared, magnetic agitation obtains stearic acid ethyl alcohol to state is clarified under room temperature
Solution；
Four, the acetic acid zinc solution of (0.5mL/s) step 2 is slowly added dropwise into the dispersion solution of GO obtained in step 1, after
Continual ultrasonic and 30min is stirred at 40 DEG C, obtains precursor solution；
Five, the stearic acid ethyl alcohol that (0.3mL/s) step 3 is slowly added dropwise into precursor solution obtained in step 4 is molten
Liquid, after be transferred to oil bath, reaction 120min is condensed back under the conditions of being kept for 70 DEG C, obtains gray precipitate；
Six, gray precipitate will be obtained in step 5 filters separation, after ultrapure water and ethyl alcohol wash 3 times respectively, 50 DEG C of vacuum
It is dry, obtain zinc stearate/graphene composite material.
Material structure analysis is carried out to zinc stearate/graphene oxide composite material of above-mentioned steps of the present invention preparation.
Referring to fig. 2, Fig. 2 is that zinc stearate/graphene oxide composite material XRD ray of preparation of the embodiment of the present invention spreads out
Penetrate map.As shown in Figure 2, zinc stearate/graphene oxide composite material has successfully been prepared in the present invention.
Referring to fig. 4, Fig. 4 is zinc stearate/graphene oxide composite material scanning electron prepared by the embodiment of the present invention 2
Microscope photo.It is the electron scanning micrograph of conventional zinc stearate referring to Fig. 5, Fig. 5.It can by Fig. 4 and Fig. 5 comparison
Know, zinc stearate slabbing, size is at 10 μm or so, and the thickness of nanometer sheet is in 20nm or so, on the surface of sheet zinc stearate
It is coated with one layer of graphene oxide, forms zinc stearate/graphene composite material, composite material is uniformly dispersed, size uniformity, phase
Than conventional sheet zinc stearate, it is thicker that surface layer is compounded with accordion graphene oxide layer, and piece diameter is smaller, it may be possible to be based on oxygen
Core after the addition of graphite alkene as growth in situ, two sides grows zinc stearate, therefore the lamella of composite material thickens.
Material property analysis is carried out to zinc stearate/graphene oxide composite material of above-mentioned steps of the present invention preparation, it will
Pure zinc stearate and zinc stearate/graphene oxide composite material be separately added into injection molding in PVC plastic (zinc stearate and its
2%) composite material additional amount is.
Referring to table 1, table 1 is the zinc stearate/graphene oxide composite material and common tristearin of preparation of the embodiment of the present invention
The performance table of comparisons of sour zinc.
Embodiment 3
The present embodiment prepares zinc stearate/graphene composite material by following steps:
One, graphene solution prepared by Hummers method is dissolved in deionized water to (graphene mass fraction is
0.5 ‰), ultrasound and stirs 20min under room temperature and obtains graphene dispersion solution；
Two, the aqueous zinc acetate solution of 0.2mol/L is prepared, magnetic agitation obtains acetic acid zinc solution to state is clarified under room temperature；
Three, the stearic acid ethanol solution of 0.4mol/L is prepared, magnetic agitation obtains stearic acid ethyl alcohol to state is clarified under room temperature
Solution；
Four, the acetic acid zinc solution of (0.5mL/s) step 2 is slowly added dropwise into the dispersion solution of GO obtained in step 1, after
Continual ultrasonic and 30min is stirred at 40 DEG C, obtains precursor solution；
Five, the stearic acid ethyl alcohol that (0.3mL/s) step 3 is slowly added dropwise into precursor solution obtained in step 4 is molten
Liquid, after be transferred to oil bath, reaction 90min is condensed back under the conditions of being kept for 80 DEG C, obtains gray precipitate；
Six, gray precipitate will be obtained in step 5 filters separation, after ultrapure water and ethyl alcohol wash 3 times respectively, 50 DEG C of vacuum
It is dry, obtain zinc stearate/graphene composite material.
Material structure analysis is carried out to zinc stearate/graphene oxide composite material of above-mentioned steps of the present invention preparation.
Referring to fig. 2, Fig. 2 is that zinc stearate/graphene oxide composite material XRD ray of preparation of the embodiment of the present invention spreads out
Penetrate map.As shown in Figure 2, zinc stearate/graphene oxide composite material has successfully been prepared in the present invention.
It is zinc stearate/graphene oxide composite material scanning electron prepared by the embodiment of the present invention 3 referring to Fig. 6, Fig. 6
Microscope photo.It will be appreciated from fig. 6 that zinc stearate slabbing, size at 10 μm or so, the thickness of nanometer sheet in 20nm or so,
The surface of sheet zinc stearate is coated with one layer of graphene oxide, forms zinc stearate/graphene oxide composite material, composite wood
Material is uniformly dispersed, size uniformity.
Material property analysis is carried out to zinc stearate/graphene oxide composite material of above-mentioned steps of the present invention preparation, it will
Pure zinc stearate and zinc stearate/graphene oxide composite material be separately added into injection molding in PVC plastic (zinc stearate and its
2%) composite material additional amount is.
Referring to table 1, table 1 is the zinc stearate/graphene oxide composite material and common tristearin of preparation of the embodiment of the present invention
The performance table of comparisons of sour zinc.
Zinc stearate/graphene oxide composite material of 1 embodiment of the present invention of table preparation and the performance of common zinc stearate
The table of comparisons
| Sample name | Heat-stable time (min) is pure | Heat-stable time (min) graphene is compound |
| No. 1 | 25 | 54 |
| No. 2 | 25 | 46 |
| No. 3 | 25 | 42 |
A kind of zinc stearate/graphene oxide composite material provided by the invention and preparation method thereof has been carried out in detail above
Thin introduction, used herein a specific example illustrates the principle and implementation of the invention, above embodiments
Illustrate to be merely used to help understand method and its core concept of the invention, including best mode, and but also this field
Any technical staff can practice the present invention, including any device or system of manufacture and use, and implement the side of any combination
Method.It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, may be used also
With several improvements and modifications are made to the present invention, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
The range of the invention patent protection is defined by the claims, and may include those skilled in the art it is conceivable that other realities
Apply example.If these other embodiments, which have, is not different from the structural element of claim character express, or if they
Equivalent structural elements including the character express with claim without essence difference, then these other embodiments should also be included in
In the scope of the claims.
Claims (10)
1. a kind of zinc stearate/graphene oxide composite material, which is characterized in that including zinc stearate and be compounded in zinc stearate
The graphene oxide on surface.
2. zinc stearate/graphene oxide composite material according to claim 1, which is characterized in that the zinc stearate
For sheet zinc stearate；
The graphene oxide with a thickness of 0.1~0.5nm；
The mass ratio of the zinc stearate and the graphene oxide is 1000:(1~50).
3. zinc stearate/graphene oxide composite material according to claim 2, which is characterized in that the zinc stearate/
The piece diameter of graphene oxide composite material is 4~12 μm；
Zinc stearate/the graphene oxide composite material with a thickness of 30~70nm.
4. a kind of preparation method of zinc stearate/graphene oxide composite material, which comprises the following steps:
A graphene oxide, organic solvent miscible with water and water) are obtained into graphene oxide dispersion after dispersion；
B after the graphene oxide dispersion for) obtaining above-mentioned steps and the mixing of zinc source, precursor solution is obtained；
C) it is compound to obtain zinc stearate/graphene oxide for the precursor solution for obtaining above-mentioned steps after being reacted with stearic acid
Material.
5. the preparation method according to claim 4, which is characterized in that in the graphene oxide dispersion, graphite oxide
The mass fraction of alkene is 0.5 ‰~5 ‰；
The organic solvent miscible with water includes in alcohols solvent, amine solvent, ketones solvent and high molecular polymer solvent
It is one or more；
The mass ratio of the organic solvent and water miscible with water is (0.01~1): 1.
6. the preparation method according to claim 4, which is characterized in that the zinc source is zinc source solution；
The concentration of zinc source solution is 0.01~0.5mol/L；
The zinc source includes one of zinc acetate, zinc chloride, zinc nitrate, zinc sulfate and zinc perchlorate or a variety of；
The mass ratio of zinc ion is 1:(1~10 in the graphene oxide and the zinc source).
7. the preparation method according to claim 4, which is characterized in that described to be mixed into ultrasonic disperse；
The mixed temperature is 20~60 DEG C；The mixed time is 10~60min.
8. according to preparation method described in claim 4~7 any one, which is characterized in that the step C) specifically:
It is slowly added to stearic acid organic solution into the precursor solution that above-mentioned steps obtain, obtains stearic acid after being reacted
Zinc/graphene oxide composite material；
The molar ratio of zinc ion is (1.5~2.5) in the stearic acid and the zinc source: 1；
The temperature of the reaction is 60~100 DEG C；The time of the reaction is 90~150min.
9. preparation method according to claim 8, which is characterized in that it is described tristearin acid organic solution concentration be 0.1~
0.3mol/L；
Solvent in the tristearin acid organic solution includes in alcohols solvent, benzene kind solvent, polynary alkanes solvent and ether solvent
It is one or more；
The rate being slowly added to is 0.3~0.7mL/s.
10. zinc stearate/graphene oxide composite material or claim 5~9 times described in Claims 1 to 4 any one
Zinc stearate/graphene oxide composite material prepared by preparation method described in meaning one is led in rubber product or resin additive
Application in domain.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710020152.1A CN106750545B (en) | 2017-01-11 | 2017-01-11 | A kind of zinc stearate/graphene oxide composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710020152.1A CN106750545B (en) | 2017-01-11 | 2017-01-11 | A kind of zinc stearate/graphene oxide composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106750545A CN106750545A (en) | 2017-05-31 |
| CN106750545B true CN106750545B (en) | 2019-02-19 |
Family
ID=58947872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710020152.1A Active CN106750545B (en) | 2017-01-11 | 2017-01-11 | A kind of zinc stearate/graphene oxide composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106750545B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109666198B (en) * | 2017-10-16 | 2021-09-14 | 山东欧铂新材料有限公司 | Graphene oxide reinforced rubber composite material and preparation method thereof |
| CN108148485A (en) * | 2018-01-13 | 2018-06-12 | 常州大学 | A kind of heatproof shock resistance graphene epoxy anticorrosion composite coating |
| CN108854592B (en) * | 2018-06-14 | 2020-09-25 | 江苏大学 | Graphene oxide/isostearic acid composite separation membrane and preparation method and application thereof |
| CN110964231A (en) * | 2018-09-30 | 2020-04-07 | 山东欧铂新材料有限公司 | Unsaturated carboxylic acid metal salt/graphene oxide composite material, preparation method thereof and functionalized graphene reinforced nitrile rubber |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580716B (en) * | 2012-01-18 | 2014-02-26 | 黑龙江大学 | Method for synthesizing zinc oxide/graphene composite by solvothermal method |
| CN103599769B (en) * | 2013-11-21 | 2015-04-15 | 福州大学 | ZnSn (OH)6 nanometer cubic particle/graphene sandwich structure compound light catalyst |
| CN104098088B (en) * | 2014-06-17 | 2016-04-13 | 华南理工大学 | The preparation method of the grapheme modified hybrid material of a kind of nano zine oxide |
-
2017
- 2017-01-11 CN CN201710020152.1A patent/CN106750545B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106750545A (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106750545B (en) | A kind of zinc stearate/graphene oxide composite material and preparation method thereof | |
| CN104961131B (en) | A kind of preparation method of sulfonation two dimension titanium carbide nanometer sheet | |
| CN102653628B (en) | Preparation method and application of nano sol modified waterborne polyurethane emulsion | |
| CN101134586B (en) | Method for preparing nano alumina hollow ball | |
| WO2017128929A1 (en) | Method for preparing graphene dispersion and article thereof | |
| CN103332726B (en) | The hydrothermal synthesis method of tin dioxide nanometer material | |
| JP2010229586A (en) | Composite composition | |
| CN104876638B (en) | A kind of nanometer porous pottery pore creating material and its preparation method and application | |
| CN107500303B (en) | A kind of mesoporous magnesium silicate microballoon and its hydro-thermal-thermal transition preparation method | |
| CN106592258A (en) | High-gloss ink-jet printing canvas and preparation method thereof | |
| CN106492779B (en) | Core-shell structure rare earth titanate-dioxide composite nanofiber catalysis material preparation method | |
| CN104852069B (en) | A kind of preparation method and applications of self-supporting sulfonic acid funtionalized surface graphene oxide paper with holes | |
| CN102926198A (en) | Spinning sizing agent | |
| CN113522064B (en) | Preparation method of novel MOF-based hydrogel gas separation membrane | |
| CN108554407A (en) | Nano-copper base catalyst and preparation method thereof | |
| CN109207066A (en) | A kind of aquosity heat insulating heat preserving paint and preparation method thereof | |
| WO2023197682A1 (en) | Method for efficiently preparing boron nitride nanosheet | |
| CN109135107A (en) | A kind of Environment-friendlywear-resistant wear-resistant resistance to compression PVC pipe and preparation method thereof | |
| CN105462297A (en) | Self-cleaning aqueous aluminum paste and preparation method thereof | |
| CN107641977A (en) | A kind of graphene glass wall base cloth and preparation method thereof | |
| CN106279733A (en) | Coating, hydrophobicity siliceous film and the preparation method of hydrophobicity siliceous film | |
| CN106854389A (en) | A kind of micaceous iron oxide/graphene oxide composite material and preparation method thereof | |
| CN110563036A (en) | bismuth oxide nano material rich in oxygen vacancy and preparation method thereof | |
| CN113979471B (en) | Synthetic method of rutile type titanium dioxide nano-composite | |
| CN101407337A (en) | Method of preparing perovskite type zirconate hollow nano material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190505 Address after: 257000 West of HaoChun Road, Dongying District, Dongying City, Shandong Province Patentee after: SHANDONG HI-TECH CHEMICAL GROUP Co.,Ltd. Address before: 257088 Dongying Port Economic Development Zone, Dongying City, Shandong Province, west of Donggang Road and north of Gangbei Road Patentee before: SHANDONG OBO NEW MATERIAL Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191122 Address after: Floor 15, building 38, ecological Valley, University Science Park, 38 Huanghe Road, Dongying District, Dongying City, Shandong Province, 257000 Patentee after: Shandong Haike Innovation Research Institute Co.,Ltd. Address before: 257000 West of HaoChun Road, Dongying District, Dongying City, Shandong Province Patentee before: SHANDONG HI-TECH CHEMICAL GROUP Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201228 Address after: 257000 to the west of Donggang road and north of Gangbei 1st Road, Dongying Port Economic Development Zone, Dongying City, Shandong Province Patentee after: SHANDONG OBO NEW MATERIAL Co.,Ltd. Address before: 257000 15 / F, building 38, ecological Valley, University Science and Technology Park, 38 Huanghe Road, Dongying District, Dongying City, Shandong Province Patentee before: Shandong Haike Innovation Research Institute Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210623 Address after: 257000 15 / F, building 38, ecological Valley, University Science and Technology Park, 38 Huanghe Road, Dongying District, Dongying City, Shandong Province Patentee after: Shandong Haike Innovation Research Institute Co.,Ltd. Address before: 257000 to the west of Donggang road and north of Gangbei 1st Road, Dongying Port Economic Development Zone, Dongying City, Shandong Province Patentee before: SHANDONG OBO NEW MATERIAL Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230718 Address after: No.22, 501, No.200 Xingpu Road, Suzhou Industrial Park, Suzhou Area, China (Jiangsu) Pilot Free Trade Zone, 215000, Jiangsu Province Patentee after: Haike Technology Innovation Service (Jiangsu) Co.,Ltd. Address before: 257000 15 / F, building 38, ecological Valley, University Science and Technology Park, 38 Huanghe Road, Dongying District, Dongying City, Shandong Province Patentee before: Shandong Haike Innovation Research Institute Co.,Ltd. |