CN104558708A - Multifunctional vulcanized rubber containing polyvinylpyrrolidone-modified graphene oxide and preparation method of multifunctional vulcanized rubber - Google Patents
Multifunctional vulcanized rubber containing polyvinylpyrrolidone-modified graphene oxide and preparation method of multifunctional vulcanized rubber Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Polymers [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000004636 vulcanized rubber Substances 0.000 title abstract description 10
- 229920001971 elastomer Polymers 0.000 claims abstract description 105
- 239000005060 rubber Substances 0.000 claims abstract description 104
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 10
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 10
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008117 stearic acid Substances 0.000 claims abstract description 10
- 239000011787 zinc oxide Substances 0.000 claims abstract description 10
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 67
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 67
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 65
- 238000004073 vulcanization Methods 0.000 claims description 16
- 229910021389 graphene Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 244000043261 Hevea brasiliensis Species 0.000 claims description 10
- 229920003052 natural elastomer Polymers 0.000 claims description 10
- 229920001194 natural rubber Polymers 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 6
- 239000003599 detergent Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 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
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims description 3
- 229940069744 2,2'-dithiobisbenzothiazole Drugs 0.000 claims description 2
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 claims description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 16
- 239000002904 solvent Substances 0.000 abstract description 11
- 230000005226 mechanical processes and functions Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003292 glue Substances 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 9
- 239000002131 composite material Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920006173 natural rubber latex Polymers 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 229920005557 bromobutyl Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000000806 elastomer Substances 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
- 125000000524 functional group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 238000010992 reflux Methods 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
Abstract
The invention discloses multifunctional vulcanized rubber containing polyvinylpyrrolidone-modified graphene oxide and a preparation method of the multifunctional vulcanized rubber. The multifunctional vulcanized rubber comprises the following components in parts by mass: 100 parts of rubber matrix, 1-4 parts of polyvinylpyrrolidone-modified graphene oxide, 2-5 parts of an anti-aging agent, 3-10 parts of zinc oxide, 1-3 parts of stearic acid, 0.5-1 part of a vulcanizing accelerator and 1-3 parts of a vulcanizing agent. The multifunctional vulcanized rubber prepared by the method has a plurality of functions, such as a mechanical function, a heat-conducting function and a solvent-resistant function.
Description
Technical field
The invention belongs to rubber polymer matrix material and preparation method thereof, particularly a kind of containing polyvinyl pyrrolidone modified graphene oxide, the Multifunctional rubber cross-linked rubber having the performances such as excellent mechanical, heat conduction and solvent resistant concurrently and preparation method thereof.
Background technology
Multifunctional rubber cross-linked rubber, namely having the vulcanization of rubber glue of the performances such as excellent mechanical, heat conduction and solvent resistant concurrently, is one of study hotspot in rubber industry.Graphene oxide is a kind of two-dimensional material, has physical strength high (63GPa), modulus is high, specific surface area is large and the feature of good barrier property, and preparation is simple, and cost is low, receives extensive concern as New Type of Carbon sill.But, because surface of graphene oxide contains a large amount of oxygen-containing functional group, therefore, the effect of graphene oxide in polarity specialty elastomer is good, as carboxy nitrile rubber (Journal of Materials Science, 2013,48,1571-1577), brominated butyl rubber (Polymer Degradation and Stability, 2013,98,2208-2214) etc.And in non-polar rubber, as natural rubber, styrene-butadiene rubber(SBR) etc., the effect of graphene oxide is not good.Such as, document " Journal of Applied Polymer Science, 2013,129,2342-2351 " reports emulsion method and prepares graphene oxide/native rubber composite material.But due to graphene oxide and natural rubber interface compatibility poor, graphene oxide only can add on a small quantity (≤1wt%) in natural rubber; Thus limited to the lifting of mechanical property.Therefore, carry out modification to surface of graphene oxide, improving the interface compatibility of itself and non-polar rubber, is the important channel of preparing Multifunctional rubber cross-linked rubber.Document " Polymer, 2013,54,1930-1937 " reports coupling agent graft modification graphene oxide, and has prepared modified graphene oxide/native rubber composite material by solution method.But the method for the modified graphene oxide of bibliographical information is loaded down with trivial details (ultrasonic, to reflux 24 hours), and prepares in composite material and need a large amount of organic solvents, be difficult to realize large-scale popularization.Patent 201310035966.4 discloses a kind of ion liquid modified graphene oxide/natural rubber vulcanized rubber and preparation method thereof, and method of modifying wherein needs to use a large amount of acetone, is difficult to equally realize large-scale popularization.
Contriver notices, polyvinylpyrrolidone is a kind of non-ionic type, nontoxic, amphiphilic macromolecule, has excellent water-soluble, and its water-wet side can modified graphene oxide easily and effectively, and its hydrophobic end and non-polar rubber have good consistency simultaneously.Therefore, adopt polyvinylpyrrolidone can form bridge between graphene oxide and non-polar rubber, improve the degree of scatter of graphene oxide in rubber, so that prepare Multifunctional rubber cross-linked rubber.In addition, polyvinylpyrrolidone excellence water-soluble makes modified graphene oxide can be blended with rubber latex as an aqueous solution, is convenient to large-scale industrial production.But, so far, have no containing polyvinyl pyrrolidone modified graphene oxide, the report having the functionalized rubber cross-linked rubber of the performances such as excellent mechanical, heat conduction and solvent resistant concurrently.
Summary of the invention
The object of the present invention is to provide a kind of containing modified graphene oxide, the Multifunctional rubber cross-linked rubber that has the performances such as excellent mechanical, heat conduction and solvent resistant concurrently and preparation method thereof.
Realize technical solution of the present invention:
A kind of Multifunctional rubber cross-linked rubber containing polyvinyl pyrrolidone modified graphene oxide, with parts by weight, comprise rubber matrix 100 parts, polyvinyl pyrrolidone modified graphene oxide 1-4 part, anti-aging agent 2-5 part, zinc oxide 3-10 part, stearic 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 are 1:1 ~ 1:5.
The mean length of described polyvinyl pyrrolidone modified graphene oxide is 610nm, mean thickness is 3nm.
Described rubber matrix be selected from natural rubber, styrene-butadiene rubber(SBR) and cis-1,4-polybutadiene rubber any one or a few.
Described anti-aging agent is any one or two kinds in N-sec.-propyl-N'-diphenyl-para-phenylene diamine (4010NA) and 2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer (RD).
Described vulcanization accelerator is any one or two kinds in 2,2'-dithio-bis-benzothiazole (DM) and N cyclohexyl 2 benzothiazole sulfenamide (CZ).
Described vulcanizing agent is Sulfur.
Containing a preparation method for the Multifunctional rubber cross-linked rubber of polyvinyl pyrrolidone modified graphene oxide, comprise the following steps:
Step one: the preparation of polyvinyl pyrrolidone modified graphene oxide: joined by graphite oxide in the aqueous solution, ultrasonic disperse, add polyvinylpyrrolidone, continues ultrasonic agitation, obtains polyvinyl pyrrolidone modified graphene oxide water solution;
Step 2: the polyvinyl pyrrolidone modified graphene oxide water solution obtained by step one and rubber latex mix and blend, and add gelifying agent, gel detergent is dried, and obtains the rubber stock containing polyvinyl pyrrolidone modified graphene oxide;
Step 3: step 2 is obtained containing the rubber stock of polyvinyl pyrrolidone modified graphene oxide and zinc oxide, stearic acid, anti-aging agent, vulcanization accelerator and vulcanizing agent carry out on a mill until mixing after, park, measure sulfurizing time with vulkameter, then obtain the Multifunctional rubber cross-linked rubber containing polyvinyl pyrrolidone modified graphene oxide with vulcanizing press compacting.
In step one, the ultrasonic time of graphite oxide is 0.5-1h, and power is 100-300W; Adding the ultrasonic time after polyvinylpyrrolidone is 0.5-1h, power 100-300W.
Compared with prior art, its remarkable advantage is in the present invention:
(1) preparation process is simple and convenient, is applicable to large-scale application; The vulcanization of rubber glue prepared has the performances such as excellent mechanical, heat conduction and solvent resistant concurrently.
(2) when filling 4 parts of polyvinyl pyrrolidone modified graphene oxides, the tensile strength of natural rubber vulcanized rubber reaches 26.67MPa, and tear strength reaches 47.89kN/m, thermal conductivity 0.143W/mK, be 2.78mol%, adsorption rate 0.204mol%/min to the adsorption exponent of toluene.Compared with the natural rubber vulcanized rubber of not filling filler, tensile strength, tear strength and thermal conductivity improve 56%, 140% and 28%, reduce 46% and 55% to the adsorption exponent of toluene and adsorption rate.Compared with the natural rubber vulcanized rubber of filling with unmodified graphene oxide, tensile strength, tear strength and thermal conductivity improve 90%, 68% and 20% respectively, and adsorption exponent and adsorption rate reduce 20% and 22%.
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Accompanying drawing explanation
The XRD diffractogram of Fig. 1 vulcanization of rubber glue, the vulcanization of rubber glue of (a) comparative example 1; The vulcanization of rubber glue of (b) comparative example 2; 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.
Embodiment
A kind of Multifunctional rubber cross-linked rubber containing polyvinyl pyrrolidone modified graphene oxide of the present invention, comprise following component: rubber 100 parts, polyvinyl pyrrolidone modified graphene oxide 1-4 part, anti-aging agent 2-5 part, zinc oxide 3-10 part, stearic acid 1-3 part, vulcanization accelerator 0.5-1 part, vulcanizing agent 1-3 part.
The preparation method of a kind of Multifunctional rubber cross-linked rubber containing modified graphene oxide of the present invention, comprises the following steps:
Step one: the preparation of polyvinyl pyrrolidone modified graphene oxide: graphite oxide is joined in the aqueous solution, ultrasonic disperse, ultrasonic time 0.5-1h, power is 100-300W, add polyvinylpyrrolidone, continue ultrasonic agitation, ultrasonic time is 0.5-1h, power 100-300W, obtains polyvinyl pyrrolidone modified graphene oxide water solution;
Step 2: the polyvinyl pyrrolidone modified graphene oxide water solution obtained by step one and rubber latex mix and blend, and add gelifying agent, gel detergent is dried, and obtains the rubber stock containing polyvinyl pyrrolidone modified graphene oxide;
Step 3: step 2 is obtained containing the rubber stock of polyvinyl pyrrolidone modified graphene oxide and zinc oxide, stearic acid, anti-aging agent, promotor and vulcanizing agent carry out on a mill until mixing after, park, measure sulfurizing time with vulkameter, then obtain the Multifunctional rubber cross-linked rubber containing polyvinyl pyrrolidone modified graphene oxide with vulcanizing press compacting.
Obtained Multifunctional rubber cross-linked rubber is carried out following performance test.
(1) tensile property:
To think carefully in Shenzhen according to GB/T528-2009 standard and CMT4254 electronic universal puller system is tested, draw speed 500mm/min.Record rubber determine stretch 100% modulus (M
100), surely stretch 300% modulus (M
300), tensile strength, elongation at break.The sample with larger tensile strength is better.
(2) tear resistance:
Tear resistance test to be thought carefully in Shenzhen according to GB/T529-2008 standard CMT4254 electronic universal puller system is tested, and speed is 500mm/min, the tear strength of record rubber.The sample with larger tear strength is better.
(3) heat conductivility:
LFA 447 laser heat conducting instrument that heat conductivility test is produced in German NETZSCH company according to ASTM E1461 standard is tested.The sample with larger thermal conductivity is better.
(4) solvent resistance:
Solvent resistance test is tested in toluene solvant according to GB/T 1690-2006 standard.There is less solvent adsorption index Q (quality of Q=100* (molar mass of the quality/solvent of adsorption solvent)/rubber) and the sample of less adsorption rate dQ/dt better.
Below by embodiment and comparative example, the invention will be further described.
Embodiment 1
By 1 part of graphite oxide dispersion in aqueous, the ultrasonic 1h of 100W, adds 1 part of polyvinylpyrrolidone, power 100W ultrasonic agitation 1h, obtain polyvinyl pyrrolidone modified graphene oxide water solution, wherein the size of polyvinyl pyrrolidone modified graphene oxide is as Fig. 2; Be added dropwise to natural rubber latex Ruzhong, mix and blend, and add gelifying agent, gel detergent is dried, and obtains the rubber stock containing 1 part of modified graphene oxide; It is carried out on a mill until with 3 parts of zinc oxide, 1 part of stearic acid, 2 parts of RD, 0.5 part of DM and 3 part Sulfur further mixing after, park, measure sulfurizing time with vulkameter, then obtain vulcanization of rubber glue with vulcanizing press.Wherein, the XRD diffraction of cross-linked rubber as shown in Figure 1.Cross-linked rubber detailed performance is as table 1.
Embodiment 2
Repeat the method for embodiment 1 by each component concentration of specifying, but adopt containing 2 parts of polyvinyl pyrrolidone modified graphene oxides in formula.Cross-linked rubber detailed performance is as table 1.
Embodiment 3
Repeat the method for embodiment 1 by each component concentration of specifying, but adopt containing 3 parts of polyvinyl pyrrolidone modified graphene oxides in formula.Cross-linked rubber detailed performance is as table 1.
Embodiment 4
Repeat the method for embodiment 1 by each component concentration of specifying, but adopt containing 4 parts of polyvinyl pyrrolidone modified graphene oxides in formula.Cross-linked rubber detailed performance is as table 1.
Embodiment 5
By 2 parts of graphite oxide dispersions in aqueous, the ultrasonic 0.5h of 300W, adds 5 parts of polyvinylpyrrolidones, power 300W ultrasonic agitation 0.5h, obtain polyvinyl pyrrolidone modified graphene oxide water solution, wherein the size of polyvinyl pyrrolidone modified graphene oxide is as Fig. 2; Be added dropwise in styrene butadiene rubber latex, mix and blend, and add gelifying agent, gel detergent is dried, and obtains the rubber stock containing 2 parts of modified graphene oxides; It is carried out on a mill until with 5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of 4010NA, 1 part of CZ and 2.5 part Sulfur further mixing after, park, measure sulfurizing time with vulkameter, then obtain vulcanization of rubber glue with vulcanizing press.Cross-linked rubber detailed performance is as table 1.
Embodiment 6
Repeat the method for embodiment 3 by each component concentration of specifying, but adopt containing 3 parts of polyvinyl pyrrolidone modified graphene oxides in formula.Cross-linked rubber detailed performance is as table 1.
Embodiment 7
By 2 parts of part graphite oxide dispersions in aqueous, the ultrasonic 0.5h of 200W, adds 3 parts of polyvinylpyrrolidones, power 200W ultrasonic agitation 0.5h, obtain polyvinyl pyrrolidone modified graphene oxide water solution, wherein the size of polyvinyl pyrrolidone modified graphene oxide is as Fig. 2; Be added dropwise to natural rubber and cis-butadiene cement Ruzhong, wherein natural rubber latex and the dry glue ratio of cis-butadiene cement breast are 9:1, mix and blend, and add gelifying agent, and gel detergent is dried, and obtains the rubber stock containing 1 part of modified graphene oxide; It is carried out on a mill until 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 further mixing after, park, measure sulfurizing time with vulkameter, then obtain vulcanization of rubber glue with vulcanizing press.Cross-linked rubber detailed performance is as table 1.
Embodiment 8
Repeat the method for embodiment 7 by each component concentration of specifying, but adopt containing 3 parts of polyvinyl pyrrolidone modified graphene oxides in formula.Cross-linked rubber detailed performance is as table 1.
Comparative example 1
The method of embodiment 1 is repeated by each component concentration of specifying, but not containing modified graphene oxide in formula.Wherein, the XRD diffraction of cross-linked rubber as shown in Figure 1.Cross-linked rubber detailed performance is as table 1.
Comparative example 2
Repeat the method for embodiment 4 by each component concentration of specifying, but in formula, adopt unmodified graphene oxide.Wherein, the XRD diffraction of cross-linked rubber as shown in Figure 1.Cross-linked rubber detailed performance is as table 1.
Comparative example 3
Repeat the method for embodiment 4 by each component concentration of specifying, but in formula, adopt polyvinyl pyrrolidone modified graphene oxide to be of a size of, mean length 80nm, thickness is 4nm.Cross-linked rubber detailed performance is as table 1.
Comparative example 4
The method of embodiment 5 is repeated by each component concentration of specifying, but not containing modified graphene oxide in formula.Cross-linked rubber detailed performance is as table 1.
Comparative example 5
Repeat the method for embodiment 5 by each component concentration of specifying, but in formula, adopt unmodified graphene oxide.Cross-linked rubber detailed performance is as table 1.
Comparative example 6
The method of embodiment 7 is repeated by each component concentration of specifying, but not containing modified graphene oxide in formula.Cross-linked rubber detailed performance is as table 1.
Comparative example 7
Repeat the method for embodiment 7 by each component concentration of specifying, but in formula, adopt unmodified graphene oxide.Cross-linked rubber detailed performance is as table 1.
Table 1
Claims (9)
1. the Multifunctional rubber cross-linked rubber containing polyvinyl pyrrolidone modified graphene oxide, it is characterized in that, comprise following mass parts: rubber matrix 100 parts, polyvinyl pyrrolidone modified graphene oxide 1-4 part, anti-aging agent 2-5 part, zinc oxide 3-10 part, stearic acid 1-3 part, vulcanization accelerator 0.5-1 part and vulcanizing agent 1-3 part.
2. the Multifunctional rubber cross-linked rubber containing polyvinyl pyrrolidone modified graphene oxide according to claim 1, it is characterized in that, in polyvinyl pyrrolidone modified graphene oxide, graphene oxide and polyvinylpyrrolidone mass ratio are 1:1 ~ 1:5.
3. the Multifunctional rubber cross-linked rubber containing polyvinyl pyrrolidone modified graphene oxide according to claim 1, is characterized in that, the mean length of described polyvinyl pyrrolidone modified graphene oxide is 610nm, mean thickness is 3nm.
4. the Multifunctional rubber cross-linked rubber containing polyvinyl pyrrolidone modified graphene oxide according to claim 1, is characterized in that, described rubber matrix be selected from natural rubber, styrene-butadiene rubber(SBR) and cis-1,4-polybutadiene rubber any one or a few.
5. the Multifunctional rubber cross-linked rubber containing polyvinyl pyrrolidone modified graphene oxide according to claim 1, it is characterized in that, described anti-aging agent is N-sec.-propyl-N'-diphenyl-para-phenylene diamine and 2,2, any one or two kinds in 4-trimethylammonium-1,2-dihyaroquinoline polymer.
6. the Multifunctional rubber cross-linked rubber containing polyvinyl pyrrolidone modified graphene oxide according to claim 1, it is characterized in that, described vulcanization accelerator is any one or two kinds in 2,2'-dithio-bis-benzothiazole and N cyclohexyl 2 benzothiazole sulfenamide.
7. the Multifunctional rubber cross-linked rubber containing polyvinyl pyrrolidone modified graphene oxide according to claim 1, it is characterized in that, described vulcanizing agent is Sulfur.
8. the preparation method of the Multifunctional rubber cross-linked rubber containing polyvinyl pyrrolidone modified graphene oxide as described in as arbitrary in claim 1-7, is characterized in that, comprise the following steps:
Step one: the preparation of polyvinyl pyrrolidone modified graphene oxide: joined by graphite oxide in the aqueous solution, ultrasonic disperse, add polyvinylpyrrolidone, continues ultrasonic agitation, obtains polyvinyl pyrrolidone modified graphene oxide water solution;
Step 2: the polyvinyl pyrrolidone modified graphene oxide water solution obtained by step one and rubber latex mix and blend, and add gelifying agent, gel detergent is dried, and obtains the rubber stock containing polyvinyl pyrrolidone modified graphene oxide;
Step 3: step 2 is obtained containing the rubber stock of polyvinyl pyrrolidone modified graphene oxide and zinc oxide, stearic acid, anti-aging agent, vulcanization accelerator and vulcanizing agent carry out on a mill until mixing after, park, measure sulfurizing time with vulkameter, then obtain the Multifunctional rubber cross-linked rubber containing polyvinyl pyrrolidone modified graphene oxide with vulcanizing press compacting.
9. the preparation method of the Multifunctional rubber cross-linked rubber containing polyvinyl pyrrolidone modified graphene oxide as claimed in claim 8, it is characterized in that, in step one, the ultrasonic time of graphite oxide is 0.5-1h, and power is 100-300W; Adding the ultrasonic time after polyvinylpyrrolidone is 0.5-1h, power 100-300W.
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| CN104893042A (en) * | 2015-05-26 | 2015-09-09 | 南京理工大学 | Rubber vulcanized rubber containing ionic liquid modified graphene oxide and preparation method of vulcanized rubber |
| CN106589460A (en) * | 2016-12-13 | 2017-04-26 | 华南理工大学 | Rubber chemical reduced and modified graphene oxide as well as preparation method and application thereof |
| CN106854387A (en) * | 2017-01-04 | 2017-06-16 | 华南理工大学 | A kind of rubber antioxidant reduction and modified graphene oxide and preparation method and application |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532629A (en) * | 2011-12-30 | 2012-07-04 | 北京化工大学 | Preparation method of completely peeled oxidation graphene/ rubber nanometer composite material |
| CN102604175A (en) * | 2012-02-23 | 2012-07-25 | 北京化工大学 | Method for preparing graphene oxide/white carbon black/rubber nanocomposite |
| CN103102514A (en) * | 2013-01-30 | 2013-05-15 | 南京理工大学 | Ionic liquid modified graphene oxide/natural rubber vulcanized rubber and preparation method thereof |
| CN103224656A (en) * | 2013-04-24 | 2013-07-31 | 北京化工大学 | Oxidized grapheme/carbon black rubber nanocomposite and preparation method thereof |
| CN104211053A (en) * | 2014-09-04 | 2014-12-17 | 济宁利特纳米技术有限责任公司 | Preparation method of modified graphene aqueous dispersion |
-
2015
- 2015-01-19 CN CN201510025703.4A patent/CN104558708B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532629A (en) * | 2011-12-30 | 2012-07-04 | 北京化工大学 | Preparation method of completely peeled oxidation graphene/ rubber nanometer composite material |
| CN102604175A (en) * | 2012-02-23 | 2012-07-25 | 北京化工大学 | Method for preparing graphene oxide/white carbon black/rubber nanocomposite |
| CN103102514A (en) * | 2013-01-30 | 2013-05-15 | 南京理工大学 | Ionic liquid modified graphene oxide/natural rubber vulcanized rubber and preparation method thereof |
| CN103224656A (en) * | 2013-04-24 | 2013-07-31 | 北京化工大学 | Oxidized grapheme/carbon black rubber nanocomposite and preparation method thereof |
| CN104211053A (en) * | 2014-09-04 | 2014-12-17 | 济宁利特纳米技术有限责任公司 | Preparation method of modified graphene aqueous dispersion |
Cited By (18)
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| CN108503905A (en) * | 2018-05-03 | 2018-09-07 | 江苏通用科技股份有限公司 | Graphite oxide alkenyl rubber composite material and preparation method thereof |
| CN109021293A (en) * | 2018-06-12 | 2018-12-18 | 华南理工大学 | A kind of functional graphene oxide support type rubber antioxidant and the preparation method and application thereof |
| CN109233011A (en) * | 2018-07-24 | 2019-01-18 | 黄山市尚义橡塑制品有限公司 | Modified graphene rubber and preparation method thereof |
| CN109957155A (en) * | 2019-03-20 | 2019-07-02 | 中红普林（北京）医疗用品高新技术研究院有限公司 | A kind of preparation method of the modified polyisoprene surgical operation gloves of graphene oxide |
| CN112300580A (en) * | 2020-11-07 | 2021-02-02 | 芜湖市航创祥路汽车部件有限公司 | Composite rubber with wear resistance for automobile sealing element |
| CN115340713A (en) * | 2021-05-13 | 2022-11-15 | 北京石墨烯研究院有限公司 | Graphene modified rubber composite material and preparation method thereof |
| CN115386146A (en) * | 2021-05-25 | 2022-11-25 | 北京石墨烯研究院有限公司 | Graphene-modified rubber composition and graphene tread rubber |
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