CN109021293A - A kind of functional graphene oxide support type rubber antioxidant and the preparation method and application thereof - Google Patents
A kind of functional graphene oxide support type rubber antioxidant and the preparation method and application thereof Download PDFInfo
- Publication number
- CN109021293A CN109021293A CN201810598387.3A CN201810598387A CN109021293A CN 109021293 A CN109021293 A CN 109021293A CN 201810598387 A CN201810598387 A CN 201810598387A CN 109021293 A CN109021293 A CN 109021293A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- rubber
- preparation
- support type
- type rubber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- 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
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- C08K5/13—Phenols; Phenolates
-
- 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
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The invention discloses a kind of functional graphene oxide support type rubber antioxidants and the preparation method and application thereof, belong to rubber chemicals and anti-aging field.The present invention by silane coupling agent, graphene oxide and water mixing, is stirred to react 4-8h under the conditions of 100-140 DEG C first；Phenol antiager is added, is stirred to react 6-10h under conditions of 50-70 DEG C；It is finally that product centrifugal vacuum is dry, functional graphene oxide support type rubber antioxidant is obtained, this support type rubber antioxidant can significantly improve anti-aging agent to the aging protection effect of rubber, and have the function of reinforcing agent concurrently.The present invention saves raw material, the volatilization migration of small molecule anti-aging agent can also be reduced simultaneously, improve the combination of matrix and interface, and its preparation process environmental protection, efficiently, energy saving, product recovery rate is high, it is a kind of real environmental-friendly new type rubber auxiliary agent, is with a wide range of applications in rubber industry.
Description
Technical field
The invention belongs to rubber chemicals synthesis and prevent old field, and in particular to a kind of functional graphene oxide support type rubber
Glue anti-aging agent and the preparation method and application thereof.
Background technique
Anti-aging agent, a kind of factors such as oxygen, heat, light, ozone, mechanical stress, heavy metal ion that can prevent or inhibit are broken
Bad product properties, the compounding agent for extending product storage and service life, are one of principal item of rubber chemicals.Industry at present is often
Rubber antioxidant, which exists, prevents that old effect is not high, has the problems such as pollution, synthesis technology is complicated to environment.Liquid phase method type support type
Rubber antioxidant successfully prepares and applies (ZL201310292284.1 such as Jia Zhixin), then graphene oxide-loaded type rubber
Glue auxiliary agent is applied less.Functional graphene oxide support type rubber antioxidant compared with white carbon black support type rubber chemicals,
The anti-old efficiency for improving anti-aging agent to a greater extent, is really achieved requirement environmentally protective, energy-efficient, at low cost, also for
The industrialized production of support type rubber chemicals provides a possibility that very big.
Phenol antiager has the advantages that its uniqueness: nontoxic, harmless, no color stain, and small pollution of the environment can be extensively
It applies in plastics and rubber industry.Phenolic hydroxyl group contained in its structure also can directly with the silicone hydroxyl of silane coupling agent or oxidation
Hydroxyl reaction on graphene surface, to prepare high performance support type phenol antiager.Functional graphene oxide is negative
Load type rubber antioxidant saves raw material, while also having the dispersion and interface cohesion promoted filler in rubber matrix, reducing and prevent
Old agent migration etc. also has many advantages, such as to reduce environmental pollution, is easy to operate, energy saving, meeting environmentally protective, sustainable development reason
It reads.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of functional graphene oxide support type rubber
The preparation method of anti-aging agent prepares phenols support type rubber antioxidant using liquid phase method.Synthesis technology of the invention is simple, former
Material price is cheap, while being also conducive to industrialized production and energy conservation and environmental protection, meets the requirement of rubber industry metaplasia production, has well
Application prospect.
A kind of functional graphene oxide being prepared another object of the present invention is to provide above-mentioned preparation method is negative
Load type rubber antioxidant, the support type rubber antioxidant have efficient, multi-functional, environmental-friendly, low migration, low cost etc. excellent
Point.
Third object of the present invention is to provide a kind of application of functional graphene oxide support type rubber antioxidant.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of functional graphene oxide support type rubber antioxidant, comprising the following steps:
(1) silane coupling agent, graphene oxide and water are mixed, is then stirred to react under conditions of 100-140 DEG C；
(2) intermediate product obtained in step (1) is cooled to 50-70 DEG C, then sequentially adds phenol antiager and had
Machine tin catalyst is stirred to react under the conditions of 50-70 DEG C；
(3) reaction product centrifugal vacuum obtained in step (2) is dry, obtain functional graphene oxide support type rubber
Glue anti-aging agent.
Preferably, silane coupling agent described in step (1) is coupling agent KH560, coupling agent KH550 and coupling agent
One or more of KH570, further preferably coupling agent KH560.
Preferably, the time being stirred to react described in step (1) is 4-8h.
Preferably, step (1) stirring is the speed high-speed stirred with 200-400rpm.
Preferably, the silane coupling agent, graphene oxide and water (1-2) in mass ratio: (1-3): (70-90), into one
Step is preferably (1-2): (1-3): 80.
Preferably, the mass ratio of the silane coupling agent, graphene oxide, phenol antiager and water is (1-2): (1-
3): (0.5-1.5): (70-90).
Preferably, phenol antiager described in step (2) is 2,6-di-tert-butyl p-cresol, 2,2 '-methylene-bis- (4-
- 6 tert-butyl phenol of methyl), 2,2 '-thiobis (4) one of methyl-6-tert-butylphenols and 2-mercaptobenzimidazole or several
Kind, further preferably 2,6-di-tert-butyl p-cresol (antioxidant 264).
Preferably, step (2) organotin catalysts are dibutyltin dilaurate catalyst or two acetic acid dibutyl
Tin catalyst, further preferably dibutyltin dilaurate catalyst.The organotin catalysts are preferably diluted with ethyl alcohol
It is added in reaction system by way of dropwise addition again afterwards.
Preferably, the dosage of the organotin catalysts is the 4~6% of graphene oxide quality, further preferably
5%.
Preferably, step (2) stirring is the speed high-speed stirred with 200-400rpm.
Preferably, the time being stirred to react described in step (2) is 6-10h.
Preferably, step (3) vacuum drying is dried in vacuo 8-12h under the conditions of being 50-70 DEG C.
A kind of functional graphene oxide support type rubber antioxidant as made from above-described preparation method.
A kind of above-described functional graphene oxide support type rubber antioxidant is in vulcanized rubber preparation field
Using.
Preferably, the support type rubber antioxidant is as rubber chemicals.
Preferably, the rubber is butadiene-styrene rubber, natural rubber or other synthetic rubber.
Compared with prior art, the invention has the following advantages that
(1) efficiently: silane coupling agent and graphene oxide pair in functional graphene oxide support type rubber antioxidant
Anti-aging agent has activation, while having biggish specific surface area, for anti-aging agent participate in chemical reaction prevent ageing of rubber into
Journey provides biggish reacting environment, is a kind of efficient anti-aging agent so that ageing of rubber protective performance can be improved.
(2) multi-functional: functional graphene oxide support type rubber antioxidant selects graphene oxide as carrier, due to
Organic coupling agent is introduced in filler surface, the hydroxyl reaction of surface of graphene oxide hydroxyl and coupling agent can be effectively improved
Hydrogen bond action between filler mitigates the agglomeration between filler grain, improves the compatibility of filler and rubber matrix, promotes
Dispersion of the filler in rubber matrix, the interface cohesion of reinforcement filler and rubber, the reinforcing effect so as to improve filler to rubber.
Therefore, it is more to have anti-aging agent, reinforcing agent, interface modifier etc. concurrently with functional graphene oxide support type rubber antioxidant of the invention
Weight effect.
(3) it saves raw material: being compared with white carbon black, graphene oxide dosage is few and effect is good, reduces preparation cost.
(4) energy conservation and environmental protection: the reaction temperature of preparation method of the present invention is relatively low, and the reaction time is short, is an energy-efficient table
Existing, furthermore functional graphene oxide support type rubber antioxidant is selected nontoxic, free of contamination phenol antiager with it is nontoxic
Graphene oxide be made, by the combination of covalent bond, the volatilization and migration of small molecule can be effectively reduced, improve the work of anti-aging agent
Use efficiency.
Detailed description of the invention
Fig. 1 is the thermal weight loss of graphite oxide (GO), functional graphene oxide support type rubber antioxidant (f-GO-264)
Curve graph.
Fig. 2 is the tensile property curve graph of styrene-butadiene rubber composite material.
Fig. 3 is the draftability of the styrene-butadiene rubber composite material of different number support type rubber antioxidant (f-GO-264) preparations
It can curve graph.
Fig. 4 is styrene-butadiene rubber composite material under 100 DEG C of aging conditions, the corresponding tensile strength of different thermo-oxidative ageing number of days
Conservation rate analysis chart.
Fig. 5 is styrene-butadiene rubber composite material under 100 DEG C of aging conditions, the corresponding extension at break of different thermo-oxidative ageing number of days
Rate conservation rate analysis chart.
Specific embodiment
Specific implementation of the invention is further described below in conjunction with example and attached drawing, but embodiments of the present invention
It is without being limited thereto.
The tensile strength of following resulting materials is tested using 528-2009 national standard of GB/T.
Embodiment 1
(1) by silane coupling agent KH560, graphene oxide and water in mass ratio 1.5 (1.5g): 2:80 is mixed in 500ml
In three-necked flask, 6h is stirred to react under conditions of 120 DEG C；
(2) intermediate product obtained in step (1) is cooled to 60 DEG C, 1g phenol antiager 264 and oxidation is then added
The dibutyl tin dilaurate of graphene dosage 5% is stirred to react 8h under the conditions of 60 DEG C.
(3) reaction product obtained in step (2) is centrifuged 60 DEG C of vacuum drying 10h, obtains functional graphene oxide
Support type rubber antioxidant (f-GO-264).
The thermogravimetric curve of functional graphene oxide support type rubber antioxidant (f-GO-264) manufactured in the present embodiment
Figure is as shown in Figure 1.As shown in Figure 1, the weight-loss ratio of the graphene oxide-loaded type rubber antioxidant after coupling agent modified is larger,
It is caused by being decomposed because of small molecule anti-aging agent as the temperature rises and coupling agent.
It is multiple that functional graphene oxide support type rubber antioxidant (f-GO-264) produced above is prepared into butadiene-styrene rubber
Condensation material (SBR/f-GO-264), basic recipe are shown in Table 1, and the unit of dosage of each component is phr.According to rubber basic recipe,
According to the charging sequence of activator (ZnO+St), filler (f-GO-264), promotor (CZ+DM), sulphur (S), in open mill
It is kneaded, respectively obtains SBR rubber composite material, SBR/f-GO-264 rubber composite material.
Table 1
Fig. 2 be kneaded after rubber composite material 160 DEG C at a temperature of, compression molding instrument vulcanization after butadiene-styrene rubber
The tensile property curve graph of vulcanizate, as can be seen from the figure: the butadiene-styrene rubber of rubber antioxidant containing support type (f-GO-264)
The tensile strength of vulcanizate is apparently higher than the tensile strength of the butadiene-styrene rubber vulcanizate of unmodified antioxidant 264 small molecule.This
Illustrate that antioxidant 264 anti-aging efficiency after load is significantly improved.
Fig. 3 is the draftability of the styrene-butadiene rubber composite material of different number support type rubber antioxidant (f-GO-264) preparations
Energy curve graph, as can be seen from the figure with the increase of silane coupling agent KH560 and graphene oxide dosage, butadiene-styrene rubber is compound
The tensile strength of material is gradually increased, this illustrates that silane coupling agent KH560 promotes point of the graphene oxide in rubber matrix
It dissipates, improves the mechanical property of butadiene-styrene rubber composite material.
Fig. 4 be kneaded after rubber composite material 160 DEG C at a temperature of, compression molding instrument vulcanization after butadiene-styrene rubber
Vulcanizate the stretching strength retentivity of 100 DEG C of thermo-oxidative ageing different number of days variation, as can be seen from the figure: containing support type
The tensile strength of the butadiene-styrene rubber vulcanizate of rubber antioxidant (f-GO-264) is highest, hence it is evident that is higher than unmodified anti-aging agent
The conservation rate of the butadiene-styrene rubber vulcanizate of 264 small molecules.This illustrates that antioxidant 264 anti-aging efficiency after load has significantly
It improves.
Fig. 5 be kneaded after rubber composite material 160 DEG C at a temperature of, compression molding instrument vulcanization after butadiene-styrene rubber
Vulcanizate the elongation at break conservation rate of 100 DEG C of thermo-oxidative ageing different number of days variation, as can be seen from the figure: containing load
The butadiene-styrene rubber vulcanizate of type rubber antioxidant (f-GO-264) is that elongation at break conservation rate is highest, hence it is evident that higher than not changing
The conservation rate of the butadiene-styrene rubber vulcanizate of the antioxidant 264 small molecule of property.This illustrates that antioxidant 264 anti-aging after load is imitated
Rate is significantly improved.
Embodiment 2
(1) by silane coupling agent KH560, graphene oxide and water in mass ratio 1.5 (1.5g): 2:80 is mixed in 500ml
In three-necked flask, 6h is stirred to react under conditions of 120 DEG C；
(2) reaction product obtained in step (1) is centrifuged 60 DEG C of vacuum drying 10h.
Functional graphene oxide made from the present embodiment (f-GO) is prepared into styrene-butadiene rubber composite material (SBR/f-GO/
264), basic recipe is shown in Table 2, and the unit of dosage of each component is phr.According to rubber basic recipe, according to activator (ZnO+
St), the charging sequence of filler (f-GO), anti-aging agent (264), promotor (CZ+DM), sulphur (S), is kneaded in open mill, point
SBR rubber composite material, SBR/f-GO/264 rubber composite material are not obtained.
Table 2
Fig. 4 be kneaded after rubber composite material 160 DEG C at a temperature of, compression molding instrument vulcanization after butadiene-styrene rubber
Vulcanizate the stretching strength retentivity of 100 DEG C of thermo-oxidative ageing different number of days variation, as can be seen from the figure: butadiene-styrene rubber sulphur
The stretching strength retentivity for changing glue (SBR/f-GO/264) is higher than the butadiene-styrene rubber vulcanizate of unmodified antioxidant 264 small molecule
Conservation rate.This illustrates that dispersion of the graphene oxide after coupling agent modified in rubber matrix improves, and improves anti-old effect
Rate.
Fig. 5 be kneaded after rubber composite material 160 DEG C at a temperature of, compression molding instrument vulcanization after butadiene-styrene rubber
Vulcanizate the elongation at break conservation rate of 100 DEG C of thermo-oxidative ageing different number of days variation, as can be seen from the figure: can from figure
To find out: it is small that the elongation at break conservation rate of butadiene-styrene rubber vulcanizate (SBR/f-GO/264) is higher than unmodified antioxidant 264
The conservation rate of the butadiene-styrene rubber vulcanizate of molecule.This illustrates point of the graphene oxide after coupling agent modified in rubber matrix
Dissipating improves, and improves and prevents old efficiency.
Embodiment 3
(1) it prepares styrene-butadiene rubber composite material (SBR/GO/264), basic recipe is shown in Table 3, the unit of dosage of each component
For phr.According to rubber basic recipe, according to activator (ZnO+St), filler (GO), anti-aging agent (264), promotor (CZ+DM),
The charging sequence of sulphur (S), is kneaded in open mill, respectively obtains SBR rubber composite material, SBR/GO/264 rubber composite wood
Material.
Table 3
Embodiment 4
(1) silane coupling agent KH560, graphene oxide and in mass ratio 1 (1g): 1:80 of water are mixed in tri- mouthfuls of 500ml
In flask, 6h is stirred to react under conditions of 120 DEG C；
(2) intermediate product obtained in step (1) is cooled to 60 DEG C, 1g phenol antiager 264 and oxidation is then added
The dibutyl tin dilaurate of graphene dosage 5wt% is stirred to react 8h under the conditions of 60 DEG C.
(3) reaction product obtained in step (2) is centrifuged 60 DEG C of vacuum drying 10h, obtains functional graphene oxide
Support type rubber antioxidant (f-GO-264).
It is bent by the thermal weight loss of functional graphene oxide support type rubber antioxidant (f-GO-264) manufactured in the present embodiment
Line chart is because with temperature it is found that the weight-loss ratio of the graphene oxide-loaded type rubber antioxidant after coupling agent modified is larger
Caused by the raising small molecule anti-aging agent and coupling agent of degree decompose.
It is multiple that functional graphene oxide support type rubber antioxidant (f-GO-264) produced above is prepared into butadiene-styrene rubber
Condensation material (SBR/f-GO-264), basic recipe are shown in Table 4, and the unit of dosage of each component is phr.According to rubber basic recipe,
According to the charging sequence of activator (ZnO+St), filler (f-GO-264), promotor (CZ+DM), sulphur (S), in open mill
It is kneaded, respectively obtains SBR rubber composite material, SBR/f-GO-264 rubber composite material.
Table 4
Fig. 3 is the draftability of the styrene-butadiene rubber composite material of different number support type rubber antioxidant (f-GO-264) preparations
Energy curve graph can work as silane coupling agent KH560 from figure, and graphene oxide mass ratio is 1 (1g): when 1, butadiene-styrene rubber is compound
The stretching of material is minimum, it is known that with the increase of silane coupling agent KH560 and the graphene oxide amount of having, styrene-butadiene rubber composite material
Tensile strength be gradually increased, this illustrates that silane coupling agent KH560 promotes dispersion of the graphene oxide in rubber matrix, mentions
The high mechanical property of butadiene-styrene rubber composite material.
Embodiment 5
(1) silane coupling agent KH560, graphene oxide and in mass ratio 2 (2g): 3:80 of water are mixed in tri- mouthfuls of 500ml
In flask, 6h is stirred to react under conditions of 120 DEG C；
(2) intermediate product obtained in step (1) is cooled to 60 DEG C, 1g phenol antiager 264 and oxidation is then added
The dibutyl tin dilaurate of graphene dosage 5wt% is stirred to react 8h under the conditions of 60 DEG C.
(3) reaction product obtained in step (2) is centrifuged 60 DEG C of vacuum drying 10h, obtains functional graphene oxide
Support type rubber antioxidant (f-GO-264).
It is bent by the thermal weight loss of functional graphene oxide support type rubber antioxidant (f-GO-264) manufactured in the present embodiment
Line chart is because with temperature it is found that the weight-loss ratio of the graphene oxide-loaded type rubber antioxidant after coupling agent modified is larger
Caused by the raising small molecule anti-aging agent and coupling agent of degree decompose.
It is multiple that functional graphene oxide support type rubber antioxidant (f-GO-264) produced above is prepared into butadiene-styrene rubber
Condensation material (SBR/f-GO-264), basic recipe are shown in Table 5, and the unit of dosage of each component is phr.According to rubber basic recipe,
According to the charging sequence of activator (ZnO+St), filler (f-GO-264), promotor (CZ+DM), sulphur (S), in open mill
It is kneaded, respectively obtains SBR rubber composite material, SBR/f-GO-264 rubber composite material.
Table 5
Fig. 3 is the draftability of the styrene-butadiene rubber composite material of different number support type rubber antioxidant (f-GO-264) preparations
Energy curve graph, as can be seen from the figure with the increase of silane coupling agent KH560 and the graphene oxide amount of having, butadiene-styrene rubber is compound
The tensile strength of material is gradually increased, this illustrates that silane coupling agent KH560 promotes point of the graphene oxide in rubber matrix
It dissipates, improves the mechanical property of butadiene-styrene rubber composite material.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of functional graphene oxide support type rubber antioxidant, which comprises the following steps:
(1) silane coupling agent, graphene oxide and water are mixed, is then stirred to react under conditions of 100-140 DEG C；
(2) intermediate product obtained in step (1) is cooled to 50-70 DEG C, then sequentially adds phenol antiager and organotin
Catalyst is stirred to react under the conditions of 50-70 DEG C；
(3) reaction product centrifugal vacuum obtained in step (2) is dry, it is anti-to obtain functional graphene oxide support type rubber
Old agent.
2. preparation method according to claim 1, which is characterized in that silane coupling agent described in step (1) is coupling
Agent KH560, one or more of coupling agent KH550 and coupling agent KH570.
3. preparation method according to claim 1, which is characterized in that the time being stirred to react described in step (1) is 4-
8h。
4. preparation method according to claim 1, which is characterized in that the silane coupling agent, graphene oxide, phenols are anti-
The mass ratio of old agent and water is (1-2): (1-3): (0.5-1.5): (70-90).
5. preparation method according to claim 1, which is characterized in that phenol antiager described in step (2) is 2,6- bis-
Butylated Hydroxytoluene, 2,2 '-methylene-bis- (- 6 tert-butyl phenol of 4- methyl), 2,2 '-thiobis (4) methyl-6-tert butyl benzene
One or more of phenol and 2-mercaptobenzimidazole.
6. preparation method according to claim 1, which is characterized in that step (2) organotin catalysts are two laurels
Sour dibutyl tin catalyst or dibutyltin diacetate catalyst.
7. preparation method according to claim 1, it is characterised in that: the dosage of the organotin catalysts is graphite oxide
The 4~6% of alkene quality.
8. preparation method according to claim 1, which is characterized in that the time being stirred to react described in step (2) is 6-
10h。
9. a kind of functional graphene oxide support type rubber as made from the described in any item preparation methods of claim 1-8 is prevented
Old agent.
10. a kind of functional graphene oxide support type rubber antioxidant as claimed in claim 9 is applied to preparation vulcanized rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810598387.3A CN109021293A (en) | 2018-06-12 | 2018-06-12 | A kind of functional graphene oxide support type rubber antioxidant and the preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810598387.3A CN109021293A (en) | 2018-06-12 | 2018-06-12 | A kind of functional graphene oxide support type rubber antioxidant and the preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109021293A true CN109021293A (en) | 2018-12-18 |
Family
ID=64612599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810598387.3A Pending CN109021293A (en) | 2018-06-12 | 2018-06-12 | A kind of functional graphene oxide support type rubber antioxidant and the preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109021293A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110117390A (en) * | 2019-05-23 | 2019-08-13 | 河北科技大学 | A kind of graphene oxide modified anti-aging agent, thermo oxidative aging rubber and preparation method comprising it |
| CN111303489A (en) * | 2020-03-30 | 2020-06-19 | 华南理工大学 | Environment-friendly rubber accelerator modified filler and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558708A (en) * | 2015-01-19 | 2015-04-29 | 南京理工大学 | Multifunctional vulcanized rubber containing polyvinylpyrrolidone-modified graphene oxide and preparation method of multifunctional vulcanized rubber |
| CN105670040A (en) * | 2016-02-25 | 2016-06-15 | 华南理工大学 | Loaded rubber anti-aging agent and preparation method and application thereof |
| 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 |
| CN106928646A (en) * | 2017-03-09 | 2017-07-07 | 南通山剑石墨设备有限公司 | A kind of Graphene phenol-formaldehyde resin modified and preparation method thereof |
| CN107857897A (en) * | 2017-10-30 | 2018-03-30 | 华南理工大学 | A kind of hindered phenol functionalization graphene and its preparation method and application |
-
2018
- 2018-06-12 CN CN201810598387.3A patent/CN109021293A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558708A (en) * | 2015-01-19 | 2015-04-29 | 南京理工大学 | Multifunctional vulcanized rubber containing polyvinylpyrrolidone-modified graphene oxide and preparation method of multifunctional vulcanized rubber |
| CN105670040A (en) * | 2016-02-25 | 2016-06-15 | 华南理工大学 | Loaded rubber anti-aging agent and preparation method and application thereof |
| 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 |
| CN106928646A (en) * | 2017-03-09 | 2017-07-07 | 南通山剑石墨设备有限公司 | A kind of Graphene phenol-formaldehyde resin modified and preparation method thereof |
| CN107857897A (en) * | 2017-10-30 | 2018-03-30 | 华南理工大学 | A kind of hindered phenol functionalization graphene and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 黄国家等: ""石墨烯和氧化石墨烯的表面功能化改性"", 《化学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110117390A (en) * | 2019-05-23 | 2019-08-13 | 河北科技大学 | A kind of graphene oxide modified anti-aging agent, thermo oxidative aging rubber and preparation method comprising it |
| CN110117390B (en) * | 2019-05-23 | 2021-08-10 | 河北科技大学 | Graphene oxide modified anti-aging agent, thermal-oxidative-aging-resistant rubber containing graphene oxide modified anti-aging agent and preparation method of thermal-oxidative-aging-resistant rubber |
| CN111303489A (en) * | 2020-03-30 | 2020-06-19 | 华南理工大学 | Environment-friendly rubber accelerator modified filler and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104725729B (en) | A kind of EPT rubber composite material and its preparation | |
| CN105670040A (en) | Loaded rubber anti-aging agent and preparation method and application thereof | |
| CN104610587A (en) | Vulcanized rubber with self-repairing and recyclability characteristics as well as preparation method and application thereof | |
| CN108610511A (en) | A kind of functionalization two-dimensional layer transition metal carbide material f-MXene and preparation method thereof and the application in rubber | |
| CN103396592A (en) | Supported rubber anti-aging agent, as well as preparation method and application thereof | |
| CN107383475B (en) | Lignin/nitrile rubber composite material and preparation method thereof | |
| CN109467770B (en) | Rubber composite material using cardanol glycidyl ether modified white carbon black and preparation method thereof | |
| CN107266753B (en) | High tensile, high-wearing feature graphene/rubber composite wiper item and preparation method | |
| CN108641150B (en) | Rubber material capable of being repeatedly processed and preparation method thereof | |
| CN109021293A (en) | A kind of functional graphene oxide support type rubber antioxidant and the preparation method and application thereof | |
| CN109251375A (en) | Radial-ply tyre tread rubber composition containing isopthalic dihydrazide and preparation method thereof | |
| CN110117390B (en) | Graphene oxide modified anti-aging agent, thermal-oxidative-aging-resistant rubber containing graphene oxide modified anti-aging agent and preparation method of thermal-oxidative-aging-resistant rubber | |
| CN113462040A (en) | Preparation method of graphene-silicon dioxide modified natural rubber composite material with high thermal conductivity and excellent low-thermophysical property for tire | |
| CN106700160A (en) | Preparation method of supported rubber vulcanizing agent and application thereof | |
| CN115322462B (en) | Neoprene compound for automobile wiper blade and preparation method and application thereof | |
| CN110240746A (en) | A kind of anti-skidding heat-proof aging EVA, NR composite foam material and preparation method thereof | |
| CN109694505B (en) | Rubber composition containing organic acid zinc phenolic resin compound and preparation method and application thereof | |
| CN111748133B (en) | Application of lignin in preparation of radial tires | |
| CN113321855A (en) | Low-heat-generation high-wear-resistance white carbon black/rubber composite material and preparation method and application thereof | |
| JP2011052146A (en) | Rubber composition for tire and pneumatic tire | |
| CN107163412A (en) | A kind of ethylene propylene diene rubber and preparation method thereof | |
| CN111171271B (en) | Preparation method of heat-resistant polyurethane elastomer | |
| CN109666448A (en) | A kind of photovoltaic module dealcoholized type sealant and preparation method thereof | |
| CN110204787A (en) | A method of zinc oxide is loaded in surface of graphene oxide | |
| CN106496825B (en) | A kind of rubber plastic blend damping rubber and preparation method thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181218 |