CN104558708B - Multifunctional rubber vulcanizate containing polyvinyl pyrrolidone modified graphene oxide and preparation method thereof - Google Patents
Multifunctional rubber vulcanizate containing polyvinyl pyrrolidone modified graphene oxide and preparation method thereof Download PDFInfo
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- CN104558708B CN104558708B CN201510025703.4A CN201510025703A CN104558708B CN 104558708 B CN104558708 B CN 104558708B CN 201510025703 A CN201510025703 A CN 201510025703A CN 104558708 B CN104558708 B CN 104558708B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229920000036 polyvinylpyrrolidone Polymers 0.000 title claims abstract description 69
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 title claims abstract description 69
- 229920001971 elastomer Polymers 0.000 title claims abstract description 66
- 239000005060 rubber Substances 0.000 title claims abstract description 66
- 239000001267 polyvinylpyrrolidone Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000004073 vulcanization Methods 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008117 stearic acid Substances 0.000 claims abstract description 8
- 239000011787 zinc oxide Substances 0.000 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims abstract description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 244000043261 Hevea brasiliensis Species 0.000 claims description 11
- 229920003052 natural elastomer Polymers 0.000 claims description 11
- 229920001194 natural rubber Polymers 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 239000003599 detergent Substances 0.000 claims description 5
- 229920000126 latex Polymers 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229940069744 2,2'-dithiobisbenzothiazole Drugs 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical group C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims 1
- -1 polyethylene Polymers 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 10
- 239000003292 glue Substances 0.000 description 16
- 239000000470 constituent Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 8
- 235000001508 sulfur Nutrition 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 239000004636 vulcanized rubber Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 206010054949 Metaplasia Diseases 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a kind of Multifunctional rubber vulcanizate containing polyvinyl pyrrolidone modified graphene oxide and preparation method thereof.Including following mass parts: rubber matrix 100 parts, polyvinyl pyrrolidone modified graphene oxide 14 parts, 25 parts of age resistor, zinc oxide 3 10 parts, stearic acid 13 parts, vulcanization accelerator 0.5 1 parts and vulcanizing agent 13 parts.The Multifunctional rubber vulcanizate that the present invention prepares has the several functions such as excellent mechanical, heat conduction and solvent resistant concurrently.
Description
Technical field
The invention belongs to rubber polymer composite and preparation method thereof, particularly a kind of containing polyvinylpyrrolidone
Modified graphene oxide, have Multifunctional rubber vulcanizates of performance such as excellent mechanical, heat conduction and solvent resistant and preparation method thereof concurrently.
Background technology
Multifunctional rubber vulcanizate, i.e. has the vulcanization of rubber glue of the performances such as excellent mechanical, heat conduction and solvent resistant concurrently, is rubber
One of study hotspot in industry.Graphene oxide, is a kind of two-dimensional material, have mechanical strength high (63GPa), modulus high,
Specific surface area is big and the feature of good barrier property, and prepares simple, and low cost receives as New Type of Carbon sill and extensively closes
Note.But, owing to surface of graphene oxide contains a large amount of oxygen-containing functional group, therefore, graphene oxide is in polarity specific rubber
Application effective, such as carboxy terminated nitrile rubber (Journal of Materials Science, 2013,48,1571-1577),
Brombutyl (Polymer Degradation and Stability, 2013,98,2208-2214) etc..And in non-pole
In property rubber, such as natural rubber, butadiene-styrene rubber etc., the application poor effect of graphene oxide.Such as, document " Journal of
Applied Polymer Science, 2013,129,2342-2351 " report emulsion method and prepare graphene oxide/natural rubber
Glue composite.But owing to graphene oxide and natural rubber interface compatibility are poor, graphene oxide in natural rubber only
(≤1wt%) can be added on a small quantity；Thus lifting to mechanical property is limited.Therefore, surface of graphene oxide is modified, changes
It is apt to the interface compatibility of itself and non-polar rubber, is the important channel preparing Multifunctional rubber vulcanizate.Document " Polymer,
2013,54,1930-1937 " report coupling agent graft modification graphene oxide, and be prepared for modified oxidized stone by solwution method
Ink alkene/native rubber composite material.But, the method for modified graphene oxide of document report is loaded down with trivial details, and (ultrasonic, backflow 24 is little
Time), and prepare composite material needs substantial amounts of organic solvent, it is difficult to realize large-scale popularization.Patent
201310035966.4 disclose a kind of ion liquid modified graphene oxide/natural rubber vulcanized rubber and preparation method thereof,
Method of modifying therein needs to use a large amount of acetone, is difficult to equally promote on a large scale.
Inventors noted that polyvinylpyrrolidone is a kind of nonionic, nontoxic, amphiphilic macromolecule, there is excellence
Water solublity, its water-wet side can modified graphene oxide easily and effectively, its hydrophobic end and non-polar rubber have good simultaneously
The compatibility.Therefore, use polyvinylpyrrolidone can form bridge between graphene oxide and non-polar rubber, improve oxygen
Functionalized graphene degree of scatter in rubber, in order to prepare Multifunctional rubber vulcanizate.It addition, polyvinylpyrrolidone is excellent
Water solublity make modified graphene oxide can as an aqueous solution with rubber latex be blended, it is simple to large-scale industry metaplasia
Produce.But, so far, have no containing polyvinyl pyrrolidone modified graphene oxide, have excellent mechanical, heat conduction and resistance to molten concurrently
The report of the functionalized rubber vulcanizate of the performances such as agent.
Summary of the invention
Object of the present invention is to provide one to contain modified graphene oxide, have excellent mechanical, heat conduction and solvent resistant concurrently
Multifunctional rubber vulcanizate etc. performance and preparation method thereof.
Realize the technical solution of the present invention:
A kind of Multifunctional rubber vulcanizate containing polyvinyl pyrrolidone modified graphene oxide, in parts by weight, comprises
Rubber matrix 100 parts, polyvinyl pyrrolidone modified graphene oxide 1-4 part, age resistor 2-5 part, zinc oxide 3-10 part, tristearin
Acid 1-3 part, vulcanization accelerator 0.5-1 part and vulcanizing agent 1-3 part.
Wherein, in described polyvinyl pyrrolidone modified graphene oxide, graphene oxide and polyvinylpyrrolidone
Mass ratio is 1:1～1:5.
The average length of described polyvinyl pyrrolidone modified graphene oxide is 610nm, average thickness is 3nm.
Described rubber matrix is selected from any one or a few in natural rubber, butadiene-styrene rubber and butadiene rubber.
Described age resistor is N-isopropyl-N'-diphenyl-para-phenylene diamine (4010NA) and 2,2,4-trimethyl-1,2-dihydro
Change any one or two kinds in quinoline polymer (RD).
Described vulcanization accelerator is 2,2'-dithio-bis-benzothiazole (DM) and N-cyclohexyl-2-[4-morpholinodithio time sulphur
Any one or two kinds in amide (CZ).
Described vulcanizing agent is sulfur.
A kind of preparation method of the Multifunctional rubber vulcanizate containing polyvinyl pyrrolidone modified graphene oxide, including with
Lower step:
Step one: the preparation of polyvinyl pyrrolidone modified graphene oxide: joined by graphite oxide in aqueous solution is super
Sound disperses, and adds polyvinylpyrrolidone, continues ultrasonic agitation, obtains polyvinyl pyrrolidone modified graphene oxide water-soluble
Liquid；
Step 2: the polyvinyl pyrrolidone modified graphene oxide water solution that step one prepares is mixed with rubber latex
Stirring, and add gel, gel detergent is dried, and obtains the rubber mix containing polyvinyl pyrrolidone modified graphene oxide
Thing；
Step 3: the rubber composition containing polyvinyl pyrrolidone modified graphene oxide that step 2 is prepared and oxidation
Zinc, stearic acid, age resistor, vulcanization accelerator and vulcanizing agent carry out on a mill until mixing after, park, measure sulfuric with vulcameter
The change time, then obtain the Multifunctional rubber sulfuration containing polyvinyl pyrrolidone modified graphene oxide with vulcanizing press compacting
Glue.
In step one, the ultrasonic time of graphite oxide is 0.5-1h, and power is 100-300W；Add polyvinylpyrrolidone
After ultrasonic time be 0.5-1h, power 100-300W.
Compared with prior art, its remarkable advantage is the present invention:
(1) preparation process is simple and convenient, is suitable for large-scale application；The vulcanization of rubber glue prepared have concurrently excellent mechanical,
The performance such as heat conduction and solvent resistant.
(2) when filling 4 parts of polyvinyl pyrrolidone modified graphene oxides, the hot strength of natural rubber vulcanized rubber reaches
26.67MPa, tearing strength reaches 47.89kN/m, heat conductivity 0.143W/mK, and the adsorption exponent to toluene is 2.78mol%, inhales
Attached speed 0.204mol%/min.Compared with the natural rubber vulcanized rubber being not filled by filler, hot strength, tearing strength and heat conduction
Coefficient improves 56%, 140% and 28%, and adsorption exponent and the rate of adsorption to toluene reduce 46% and 55%.With do not change
Property graphene oxide fill natural rubber vulcanized rubber compare, hot strength, tearing strength and heat conductivity are respectively increased
90%, 68% and 20%, adsorption exponent and the rate of adsorption reduce 20% and 22%.
Below in conjunction with the accompanying drawings the present invention is described in further detail.
Accompanying drawing explanation
The XRD diffraction pattern of Fig. 1 vulcanization of rubber glue, the vulcanization of rubber glue of (a) comparative example 1；The vulcanization of rubber of (b) comparative example 2
Glue；The vulcanization of rubber glue of (c) embodiment 4.
The AFM figure of Fig. 2 polyvinyl pyrrolidone modified graphene oxide, (a) AFM schematic surface；(b) AFM height map.
Detailed description of the invention
A kind of Multifunctional rubber vulcanizate containing polyvinyl pyrrolidone modified graphene oxide of the present invention, including following
Component: rubber 100 parts, polyvinyl pyrrolidone modified graphene oxide 1-4 part, age resistor 2-5 part, zinc oxide 3-10 part, firmly
Fat acid 1-3 part, vulcanization accelerator 0.5-1 part, vulcanizing agent 1-3 part.
The preparation method of a kind of Multifunctional rubber vulcanizate containing modified graphene oxide of the present invention, including following step
Rapid:
Step one: the preparation of polyvinyl pyrrolidone modified graphene oxide: joined by graphite oxide in aqueous solution is super
Sound disperses, ultrasonic time 0.5-1h, and power is 100-300W, adds polyvinylpyrrolidone, continues ultrasonic agitation, ultrasonic time
For 0.5-1h, power 100-300W, obtain polyvinyl pyrrolidone modified graphene oxide water solution；
Step 2: the polyvinyl pyrrolidone modified graphene oxide water solution that step one prepares is mixed with rubber latex
Stirring, and add gel, gel detergent is dried, and obtains the rubber mix containing polyvinyl pyrrolidone modified graphene oxide
Thing；
Step 3: the rubber composition containing polyvinyl pyrrolidone modified graphene oxide that step 2 is prepared and oxidation
Zinc, stearic acid, age resistor, accelerator and vulcanizing agent carry out on a mill until mixing after, park, with vulcameter measure optimum cure time
Between, then obtain the Multifunctional rubber vulcanizate containing polyvinyl pyrrolidone modified graphene oxide with vulcanizing press compacting.
Prepared Multifunctional rubber vulcanizate is carried out following performance test.
(1) tensile property:
Think carefully in Shenzhen according to GB/T528-2009 standard and test on CMT4254 electronic universal puller system, stretching speed
Degree 500mm/min.Record rubber determine stretch 100% modulus (M100), surely stretch 300% modulus (M300), hot strength, extension at break
Rate.The sample with the biggest hot strength is the best.
(2) tear resistance:
Tear resistance test is thought carefully in Shenzhen according to GB/T529-2008 standard and is carried out on CMT4254 electronic universal puller system
Test, speed is 500mm/min, the tearing strength of record rubber.The sample with the biggest tearing strength is the best.
(3) heat conductivility:
The LFA 447 laser heat conduction that heat conductivility test produces in NETZSCH company of Germany according to ASTM E1461 standard
Test on instrument.The sample with the biggest heat conductivity is the best.
(4) solvent resistance:
Solvent resistance test is tested in toluene solvant according to GB/T 1690-2006 standard.There is the least solvent adsorption
Index Q (quality of Q=100* (molal weight of the quality/solvent of adsorption solvent)/rubber) and the least rate of adsorption dQ/dt
Sample is the best.
Below by embodiment and comparative example, the invention will be further described.
Embodiment 1
1 part of graphite oxide is disperseed in aqueous, the ultrasonic 1h of 100W, add 1 part of polyvinylpyrrolidone, power 100W
Ultrasonic agitation 1h, obtains polyvinyl pyrrolidone modified graphene oxide water solution, wherein polyvinyl pyrrolidone modified oxidation
The size of Graphene such as Fig. 2；Being added dropwise to natural rubber latex Ruzhong, mix and blend, and add gel, gel detergent dries
Dry, obtain the rubber composition containing 1 part of modified graphene oxide；By its further with 3 parts of zinc oxide, 1 part of stearic acid, 2 parts of RD,
0.5 part of DM and 3 parts of sulfurs carry out on a mill until mixing after, park, measure sulfurizing time with vulcameter, then use compression molding
Machine-processed vulcanization of rubber glue.Wherein, the XRD diffraction of vulcanizate is as shown in Figure 1.Vulcanizate detailed performance such as table 1.
Embodiment 2
The method repeating embodiment 1 by each constituent content specified, but use containing 2 parts of polyvinylpyrrolidones in formula
Modified graphene oxide.Vulcanizate detailed performance such as table 1.
Embodiment 3
The method repeating embodiment 1 by each constituent content specified, but use containing 3 parts of polyvinylpyrrolidones in formula
Modified graphene oxide.Vulcanizate detailed performance such as table 1.
Embodiment 4
The method repeating embodiment 1 by each constituent content specified, but use containing 4 parts of polyvinylpyrrolidones in formula
Modified graphene oxide.Vulcanizate detailed performance such as table 1.
Embodiment 5
2 parts of graphite oxides are disperseed in aqueous, the ultrasonic 0.5h of 300W, add 5 parts of polyvinylpyrrolidones, power
300W ultrasonic agitation 0.5h, obtains polyvinyl pyrrolidone modified graphene oxide water solution, and wherein polyvinylpyrrolidone changes
Size such as Fig. 2 of property graphene oxide；Being added dropwise in styrene butadiene rubber latex, mix and blend, and add gel, gel is washed
Wash drying, obtain the rubber composition containing 2 parts of modified graphene oxides；By its further with 5 parts of zinc oxide, 2 parts of stearic acid, 2
Part 4010NA, 1 part of CZ and 2.5 parts of sulfurs carry out on a mill until mixing after, park, measure sulfurizing time with vulcameter, then
Vulcanization of rubber glue is prepared with vulcanizing press.Vulcanizate detailed performance such as table 1.
Embodiment 6
The method repeating embodiment 3 by each constituent content specified, but use containing 3 parts of polyvinylpyrrolidones in formula
Modified graphene oxide.Vulcanizate detailed performance such as table 1.
Embodiment 7
2 parts of part graphite oxides are disperseed in aqueous, the ultrasonic 0.5h of 200W, add 3 parts of polyvinylpyrrolidones, power
200W ultrasonic agitation 0.5h, obtains polyvinyl pyrrolidone modified graphene oxide water solution, and wherein polyvinylpyrrolidone changes
Size such as Fig. 2 of property graphene oxide；It is added dropwise to natural rubber and cis-butadiene cement Ruzhong, wherein Heveatex and cis-butadiene cement breast
Dry glue ratio is 9:1, mix and blend, and adds gel, and gel detergent is dried, and obtains the rubber containing 1 part of modified graphene oxide
Glue mixture；By its further with 10 parts of zinc oxide, 3 parts of stearic acid, 2 parts of 4010NA, 3 parts of RD, 0.5 part of DM, 0.5 part of CZ and 1
Part sulfur carry out on a mill until mixing after, park, measure sulfurizing time with vulcameter, then prepare rubber with vulcanizing press
Vulcanizate.Vulcanizate detailed performance such as table 1.
Embodiment 8
The method repeating embodiment 7 by each constituent content specified, but use containing 3 parts of polyvinylpyrrolidones in formula
Modified graphene oxide.Vulcanizate detailed performance such as table 1.
Comparative example 1
The method repeating embodiment 1 by each constituent content specified, but without modified graphene oxide in formula.Its
In, the XRD diffraction of vulcanizate is as shown in Figure 1.Vulcanizate detailed performance such as table 1.
Comparative example 2
The method repeating embodiment 4 by each constituent content specified, but in formula, use unmodified graphene oxide.Its
In, the XRD diffraction of vulcanizate is as shown in Figure 1.Vulcanizate detailed performance such as table 1.
Comparative example 3
The method repeating embodiment 4 by each constituent content specified, but in formula, use polyvinyl pyrrolidone modified
The size of graphene oxide is, average length 80nm, and thickness is 4nm.Vulcanizate detailed performance such as table 1.
Comparative example 4
The method repeating embodiment 5 by each constituent content specified, but without modified graphene oxide in formula.Sulfuration
Glue detailed performance such as table 1.
Comparative example 5
The method repeating embodiment 5 by each constituent content specified, but in formula, use unmodified graphene oxide.Sulfur
Change glue detailed performance such as table 1.
Comparative example 6
The method repeating embodiment 7 by each constituent content specified, but without modified graphene oxide in formula.Sulfuration
Glue detailed performance such as table 1.
Comparative example 7
The method repeating embodiment 7 by each constituent content specified, but in formula, use unmodified graphene oxide.Sulfur
Change glue detailed performance such as table 1.
Table 1
Claims (9)
1. the Multifunctional rubber vulcanizate containing polyvinyl pyrrolidone modified graphene oxide, it is characterised in that include with
Lower mass parts: rubber matrix 100 parts, polyvinyl pyrrolidone modified graphene oxide 1-4 part, age resistor 2-5 part, zinc oxide 3-
10 parts, stearic acid 1-3 part, vulcanization accelerator 0.5-1 part and vulcanizing agent 1-3 part.
Multifunctional rubber vulcanizate containing polyvinyl pyrrolidone modified graphene oxide the most according to claim 1, its
Being characterised by, in polyvinyl pyrrolidone modified graphene oxide, graphene oxide and polyvinylpyrrolidone mass ratio are 1:1
～1:5.
Multifunctional rubber vulcanizate containing polyvinyl pyrrolidone modified graphene oxide the most according to claim 1, its
Being characterised by, the average length of described polyvinyl pyrrolidone modified graphene oxide is 610nm, average thickness is 3nm.
Multifunctional rubber vulcanizate containing polyvinyl pyrrolidone modified graphene oxide the most according to claim 1, its
Being characterised by, described rubber matrix is selected from any one or a few in natural rubber, butadiene-styrene rubber and butadiene rubber.
Multifunctional rubber vulcanizate containing polyvinyl pyrrolidone modified graphene oxide the most according to claim 1, its
Being characterised by, described age resistor is N-isopropyl-N'-diphenyl-para-phenylene diamine and 2,2,4-trimethyl-1,2-dihyaroquinoline
Any one or two kinds in polymer.
Multifunctional rubber vulcanizate containing polyvinyl pyrrolidone modified graphene oxide the most according to claim 1, its
Being characterised by, described vulcanization accelerator is 2,2'-dithio-bis-benzothiazole and N cyclohexyl 2 benzothiazole sulfenamide
In any one or two kinds.
Multifunctional rubber vulcanizate containing polyvinyl pyrrolidone modified graphene oxide the most according to claim 1, its
Being characterised by, described vulcanizing agent is sulfur.
8. the Multifunctional rubber vulcanizate containing polyvinyl pyrrolidone modified graphene oxide as described in claim 1-7 is arbitrary
Preparation method, it is characterised in that comprise the following steps:
Step one: the preparation of polyvinyl pyrrolidone modified graphene oxide: graphite oxide is joined in aqueous solution, ultrasonic point
Dissipate, add polyvinylpyrrolidone, continue ultrasonic agitation, obtain polyvinyl pyrrolidone modified graphene oxide water solution；
Step 2: polyvinyl pyrrolidone modified graphene oxide water solution step one prepared mixes with rubber latex stirs
Mixing, and add gel, gel detergent is dried, and obtains the rubber composition containing polyvinyl pyrrolidone modified graphene oxide；
Step 3: the rubber composition containing polyvinyl pyrrolidone modified graphene oxide and zinc oxide that step 2 is prepared,
Stearic acid, age resistor, vulcanization accelerator and vulcanizing agent carry out on a mill until mixing after, park, measure optimum cure with vulcameter
Time, then obtain the Multifunctional rubber vulcanizate containing polyvinyl pyrrolidone modified graphene oxide with vulcanizing press compacting.
9. the preparation of the Multifunctional rubber vulcanizate containing polyvinyl pyrrolidone modified graphene oxide as claimed in claim 8
Method, it is characterised in that in step one, the ultrasonic time of graphite oxide is 0.5-1h, and power is 100-300W；Add polyethylene
Ultrasonic time after ketopyrrolidine is 0.5-1h, power 100-300W.
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| CN102604175B (en) * | 2012-02-23 | 2014-04-16 | 北京化工大学 | Method for preparing graphene oxide/white carbon black/rubber nanocomposite |
| CN103102514B (en) * | 2013-01-30 | 2015-01-21 | 南京理工大学 | Ionic liquid modified graphene oxide/natural rubber vulcanized rubber and preparation method thereof |
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