CN114874499B - Graphene oxide loaded rare earth vulcanization accelerator and preparation method thereof - Google Patents
Graphene oxide loaded rare earth vulcanization accelerator and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a graphene oxide loaded rare earth vulcanization accelerator and a preparation method thereof. The structural general formula of the accelerator is as follows: re (Re) x (TC) y /GO z Wherein Re is one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium; TC is a ligand and has a structure shown as a formula (I):
r is methyl, ethyl, butyl, isopropyl, octyl and phenyl, R' is methyl, ethyl, butyl, isopropyl, octyl and phenyl; x, Y, Z are mass fractions of Re, TC and GO, x=15 to 30%, y=60 to 75%, and z=9 to 15%, respectively. The novel supported accelerator can effectively improve the dispersion of the rubber accelerator in rubber, enhance the interaction between graphene oxide and a rubber molecular chain, increase the crosslinking density of the rubber composite material and improve the comprehensive performance of the composite material.
Description
Technical Field
The invention relates to the technical field of rubber accelerators, in particular to a graphene oxide loaded rare earth vulcanization accelerator, a preparation method thereof and a rubber composite material. The novel supported accelerator can effectively improve the dispersion of the rubber accelerator in rubber, enhance the interaction between graphene oxide and rubber molecular chains, improve the internal crosslinking network structure of the rubber, increase the crosslinking density of the rubber composite material and improve the comprehensive performance of the composite material.
Background
In the microstructure of rubber, the cross-linked network structure is of great importance, and not only has a certain effect on the enhancement of the static mechanical property of the rubber, but also has remarkable influence on the improvement of the wear resistance of the rubber, the reduction of fatigue heat generation and the improvement of the dynamic mechanical property. The vulcanization accelerator plays an important role in a sulfur vulcanization system, not only can increase the vulcanization speed, but also can adjust the type of sulfur in a sulfur crosslinking network and the overall crosslinking density. Therefore, how to disperse the vulcanization accelerator in the rubber and make it fully participate in the crosslinking reaction has important application significance. The rare earth vulcanization accelerator can obviously enhance the activity of the rubber accelerator and improve the vulcanization efficiency of rubber due to the strong coordination effect of rare earth elements. The crosslinking reaction is effectively promoted even in the absence of zinc oxide activator or in the presence of small amounts of zinc oxide.
Graphene oxide is one of the materials with the highest known strength, and can obviously increase the tensile strength, the tearing strength, the fatigue resistance and the like of the rubber composite material after being compounded with rubber. Meanwhile, the graphene oxide of the single-layer can generate free radicals in the high-temperature vulcanization process, participate in the vulcanization process of rubber, and improve the crosslinking density. The edge of the graphene oxide contains rich oxygen-containing functional groups, and the existence of the functional groups is favorable for reacting with other organic matters or metal ions, so that the loading of other inorganic particles or organic particles is realized.
Therefore, the invention provides a graphene oxide loaded rare earth accelerator and a preparation method thereof, which can effectively improve the dispersion of the accelerator in rubber, improve the interaction between graphene oxide and a rubber molecular chain, improve the internal cross-linked network structure of the rubber, increase the cross-linked density of a rubber composite material and improve the comprehensive performance of the composite material.
Disclosure of Invention
The invention aims to provide a rare earth vulcanization accelerator loaded by graphene oxide, a preparation method thereof and a rubber composite material. The rubber composite material prepared by the supported rare earth vulcanization accelerator has good static mechanical property and dynamic mechanical property.
The invention aims to provide a rare earth vulcanization accelerator loaded by graphene oxide, which comprises rare earth ions, ligands and graphene oxide.
The structural general formula is as follows:
Re x (TC) y /GO z wherein:
wherein Re represents one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
TC is a ligand and has a structure shown as a formula (I):
r may be methyl, ethyl, butyl, isopropyl, octyl, phenyl, etc., and R' may be methyl, ethyl, butyl, isopropyl, octyl, phenyl, etc. R and R' may be the same or different.
TC is a dialkyl dithiocarbamate ion, preferably one of a dimethyl dithiocarbamate ion, a diethyl dithiocarbamate ion, a dibutyl dithiocarbamate ion, a methylphenyl dithiocarbamate ion, a diisopropyl dithiocarbamate ion, and a diphenyl dithiocarbamate ion.
GO is graphene oxide.
X, Y, Z are mass fractions of Re, TC, GO, x=15-30%, y=60-75%, z=9-15%, preferably x=20-25%, y=65-70%, z=10-12%, respectively.
The rare earth vulcanization accelerator is prepared by utilizing a coordination reaction of rare earth ions and dialkyl dithiocarbamate in a solvent, and then the prepared rare earth vulcanization accelerator is reacted with graphene oxide solution to obtain the graphene oxide-loaded rare earth vulcanization accelerator.
The second purpose of the invention is to provide a preparation method of the graphene oxide loaded rare earth vulcanization accelerator, which comprises the following steps:
(1) Reacting rare earth metal salt with an organic ligand to obtain a rare earth vulcanization accelerator;
(2) And reacting the rare earth vulcanization accelerator with graphene oxide to obtain the graphene oxide-loaded rare earth vulcanization accelerator.
The graphene oxide loaded rare earth vulcanization accelerator is prepared from components including graphene oxide, rare earth metal salt and organic ligand.
Wherein the rare earth metal element (RE) may be one or a combination of two of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium.
The rare earth metal salt is preferably a rare earth metal halide salt.
The organic ligand is preferably dialkyl dithiocarbamate, more preferably at least one of dimethyl dithiocarbamate, diethyl dithiocarbamate, dibutyl dithiocarbamate, methylphenyl dithiocarbamate, diisopropyl dithiocarbamate, diphenyl dithiocarbamate.
In the step (1), the molar ratio of the rare earth metal salt to the organic ligand is 1: (1 to 4), preferably 1: (2-4), e.g., 1:1, 1:2, 1:3, 1:4, etc.
In the step (1), the reaction temperature is 30-90 ℃, preferably 60-80 ℃; the reaction time is 1 to 12 hours, preferably 6 to 10 hours.
In the step (2), the mass ratio of the rare earth vulcanization accelerator to the graphene oxide is (9-5): 1, preferably (7 to 5): 1, for example 9:1, 8:1, 7:1, 6:1, 5:1, etc.
In the step (2), the reaction temperature is 30-90 ℃, preferably 60-80 ℃; the reaction time is 1 to 12 hours, preferably 6 to 10 hours.
According to a preferred embodiment of the invention, the preparation method comprises the following steps:
step one: dispersing rare earth metal salt, dialkyl dithiocarbamate and graphene oxide in a solvent respectively, and further performing ultrasonic dispersion to prepare three uniformly dispersed solutions or suspensions;
step two: heating to 40-80 ℃, slowly adding rare earth metal salt solution into ethylene glycol solution of dialkyl dithiocarbamate, stirring for 1-12 h at the constant temperature of 30-90 ℃, and filtering and washing precipitate to prepare the rare earth vulcanization accelerator;
step three: preparing the prepared rare earth vulcanization accelerator into a dispersion liquid, slowly dripping the dispersion liquid into graphene oxide suspension liquid, reacting the mixed liquid for 1-12 hours at the constant temperature of 30-90 ℃, filtering and washing the precipitate, and drying the precipitate to constant weight to prepare the graphene oxide loaded rare earth vulcanization accelerator.
In the first step, the solvent comprises one or a combination of more of ethanol, glycol, isopropanol, N-dimethylformamide, dimethyl sulfoxide and tetrahydrofuran.
The invention further provides a rubber composite material, which comprises rubber and the graphene oxide loaded rare earth vulcanization accelerator.
The amount of the graphene oxide-loaded rare earth vulcanization accelerator is 0.1 to 30 parts, preferably 1 to 10 parts, based on 100 parts by weight of the rubber.
The rubber can be at least one of natural rubber, styrene-butadiene rubber, butyl rubber, nitrile rubber, ethylene propylene diene monomer rubber, chloroprene rubber and polyacrylate rubber.
The graphene oxide loaded rare earth vulcanization accelerator can be applied to the preparation of rubber composite materials and products thereof.
The graphene oxide loaded rare earth vulcanization accelerator prepared by coordination self-assembly is a novel low-temperature efficient vulcanization accelerator, and the prepared rubber composite material has good static and dynamic mechanical properties, improves the dispersibility and uniformity of graphene oxide in the rubber composite material, and lays a foundation for preparing the high-performance rubber composite material.
Drawings
Fig. 1 is a sample of the rare earth vulcanization accelerator of example 5 and graphene oxide-supported rare earth vulcanization accelerator.
Fig. 2 is an SEM image of the rare earth vulcanization accelerator of example 5.
FIG. 3 is an SEM image of a rare earth-supported graphene oxide vulcanization accelerator of example 5
Fig. 4 shows the vulcanization curves of example 5, comparative example 1 and blank example 1.
FIG. 5 is a vulcanization performance curve of each styrene-butadiene rubber in the application example.
FIG. 6 shows the crosslink density of styrene-butadiene rubber (GO-REC and ZDC) in the application example.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The raw materials used in the specific embodiment of the present invention are commercially available.
The prepared rubber compound is vulcanized and pressed into tablets at 160 ℃.
Example 1
The preparation method of the graphene oxide loaded rare earth vulcanization accelerator comprises the following steps:
0.3mol of SmCl 3 In a glycol solution at 70 ℃, 0.3mol of sodium diphenyldithiocarbamate was dissolved in a glycol solution at 70 ℃, and graphene oxide was dissolved in a glycol solution at 45 ℃. SmCl is added 3 Slowly dripping the glycol solution into the glycol solution of the sodium diphenyl dithiocarbamate, carrying out water bath reaction for 5 hours at the temperature of 70 ℃ and the rotating speed of 230 r, filtering, and washing with glycol for 3 times. And (3) dissolving the reaction product in glycol solution to obtain rare earth vulcanization accelerator dispersion liquid. Slowly dripping the rare earth vulcanization accelerator dispersion liquid into a glycol solution of graphene oxide, wherein the mass ratio of the rare earth vulcanization accelerator to the graphene oxide is 6:1, water bath reaction is carried out under the condition that the temperature is 70 ℃ and the rotating speed is 230 revolutionsFiltering after 5 hours, washing with glycol for 3 times, and drying with anhydrous calcium sulfate to constant weight to obtain black powder, namely the target product.
Example 2
The preparation method of the graphene oxide loaded rare earth vulcanization accelerator comprises the following steps:
0.3mol of CeCl 3 In an ethylene glycol solution at 80 ℃, 0.6mol of sodium dimethyldithiocarbamate was dissolved in an ethylene glycol solution at 80 ℃, and graphene oxide was dissolved in an ethylene glycol solution at 45 ℃. CeCl is added 3 Slowly dripping the ethylene glycol solution into the ethylene glycol solution of the sodium dimethyldithiocarbamate, carrying out water bath reaction for 4 hours at the temperature of 80 ℃ and the rotating speed of 230 r, filtering, and washing with the ethylene glycol for 3 times. And (3) dissolving the reaction product in glycol solution to obtain rare earth vulcanization accelerator dispersion liquid. Slowly dripping the rare earth vulcanization accelerator dispersion liquid into a glycol solution of graphene oxide, wherein the mass ratio of the rare earth vulcanization accelerator to the graphene oxide is 6:1, carrying out water bath reaction for 4 hours at the temperature of 80 ℃ and the rotating speed of 230 r, filtering, washing with glycol for 3 times, and drying with anhydrous calcium sulfate to constant weight to obtain black powder, namely a target product.
Example 3
The preparation method of the graphene oxide loaded rare earth vulcanization accelerator comprises the following steps:
0.3mol of PrCl 3 In a 60℃ethylene glycol solution, 0.9mol of sodium dibutyldithiocarbamate was dissolved in a 60℃ethylene glycol solution, and graphene oxide was dissolved in a 45℃ethylene glycol solution. PrCl is added to 3 Slowly dripping the ethylene glycol solution into the ethylene glycol solution of the sodium dibutyl dithiocarbamate, carrying out water bath reaction for 6 hours at the temperature of 60 ℃ and the rotating speed of 230 r, filtering, and washing with the ethylene glycol for 3 times. And (3) dissolving the reaction product in glycol solution to obtain rare earth vulcanization accelerator dispersion liquid. Slowly dripping the rare earth vulcanization accelerator dispersion liquid into a glycol solution of graphene oxide, wherein the mass ratio of the rare earth vulcanization accelerator to the graphene oxide is 6:1, carrying out water bath reaction for 6 hours at the temperature of 60 ℃ and the rotating speed of 230 r, filtering, washing with glycol for 3 times, and drying with anhydrous calcium sulfateDrying to constant weight to obtain black powder, namely the target product.
Example 4
The preparation method of the graphene oxide loaded rare earth vulcanization accelerator comprises the following steps:
0.3mol of NdCl 3 In a glycol solution at 50℃0.75mol of sodium methylphenyl dithiocarbamate was dissolved in a glycol solution at 70℃and graphene oxide was dissolved in a glycol solution at 45 ℃. NdCl 3 Slowly dripping the ethylene glycol solution of methyl phenyl dithiocarbamic acid into the ethylene glycol solution of methyl phenyl dithiocarbamic acid, carrying out water bath reaction for 7 hours at the temperature of 50 ℃ and the rotating speed of 230 r, filtering, and washing 3 times by using the ethylene glycol. And (3) dissolving the reaction product in glycol solution to obtain rare earth vulcanization accelerator dispersion liquid. Slowly dripping the rare earth vulcanization accelerator dispersion liquid into a glycol solution of graphene oxide, wherein the mass ratio of the rare earth vulcanization accelerator to the graphene oxide is 6:1, carrying out water bath reaction for 7 hours at 50 ℃ and the rotating speed of 230 r, filtering, washing with glycol for 3 times, and drying with anhydrous calcium sulfate to constant weight to obtain black powder, namely the target product.
Example 5
The preparation method of the graphene oxide loaded rare earth vulcanization accelerator comprises the following steps:
0.3mol of LaCl 3 In a 60℃ethylene glycol solution, 0.12mol of sodium diethyldithiocarbamate was dissolved in a 60℃ethylene glycol solution, and graphene oxide was dissolved in a 45℃ethylene glycol solution. LaCl is added 3 Slowly dripping the ethylene glycol solution into the ethylene glycol solution of the sodium diethyl dithiocarbamate, carrying out water bath reaction for 6 hours at the temperature of 60 ℃ and the rotating speed of 230 r, filtering, washing for 3 times by using the ethylene glycol, and drying to obtain a reaction product rare earth vulcanization accelerator. Dissolving rare earth vulcanization accelerator in glycol solution to obtain rare earth vulcanization accelerator dispersion liquid. Slowly dripping rare earth vulcanization accelerator dispersion into ethylene glycol solution of graphene oxide, carrying out water bath reaction for 6 hours at the temperature of 60 ℃ and the rotating speed of 230 r, filtering, washing the ethylene glycol for 3 times, and drying the ethylene glycol solution with anhydrous calcium sulfate to constant weight to obtain black powder, namely a target product, and preparing a sampleThe product is shown in FIG. 1.
Comparative example 1
The preparation method of the rare earth vulcanization accelerator comprises the following steps:
0.3mol of LaCl 3 In a 60℃ethylene glycol solution, 0.12mol of sodium diethyldithiocarbamate was dissolved in a 60℃ethylene glycol solution, and graphene oxide was dissolved in a 45℃ethylene glycol solution. LaCl is added 3 Slowly dripping the ethylene glycol solution into the ethylene glycol solution of the sodium diethyl dithiocarbamate, carrying out water bath reaction for 6 hours at the temperature of 60 ℃ and the rotating speed of 230 r, filtering, washing for 3 times by using the ethylene glycol, and drying by using anhydrous calcium sulfate until the weight is constant, thus obtaining the yellowish white powder, namely the target product.
SEM characterization was performed on the rare earth vulcanization accelerator prepared in example 5 and the graphene oxide-supported rare earth vulcanization accelerator, and the results are shown in fig. 2 and 3. As can be seen from fig. 2, the microstructure of the prepared rare earth vulcanization accelerator shows a lump shape and is poor in dispersibility. As can be seen from FIG. 3, the prepared graphene oxide loaded rare earth vulcanization accelerator has small granularity and good dispersibility.
The graphene oxide-supported rare earth vulcanization accelerator and rare earth vulcanization accelerator DM (a commonly used accelerator) prepared in example 5 and comparative example 1 were prepared into styrene-butadiene rubber composites. The formulation of the compounds is shown in Table 1, and the compounds are prepared by an internal mixer according to a conventional method, and the sample numbers are abbreviated as example 5, comparative example 1 and blank example 1.
The vulcanization properties and static mechanical properties of the rubber composites of example 5, comparative example 1, and blank example 5 prepared by using the formulations in table 1 are shown in fig. 4 and table 2.
TABLE 1
TABLE 2
Application example
The graphene oxide-supported rare earth vulcanization accelerator (GO-REC) and rare earth vulcanization accelerator (REC) prepared in the above example 5, and commercial accelerators ZDC (without zinc oxide stearic acid) and ZDC-ZS (with zinc oxide stearic acid) were used to prepare styrene-butadiene rubber composite materials, and the difference between the above accelerators and the formulations in Table 1 was that the amounts of the accelerators were 2 parts.
The preferred embodiments of the present invention have been specifically described above, but are not limited to the embodiments of the present invention. It is believed that further modifications and improvements to the technical solutions of the present invention can be made by the expert in the rubber field without departing from the spirit of the invention, all falling within the scope of protection defined by the claims of the present invention.
Claims (13)
1. A rare earth vulcanization accelerator loaded by graphene oxide has the following structural general formula:
Re x (TC) y /GO z ，
wherein Re is one or more than two of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium;
TC is a ligand and has a structure shown as a formula (I):
r is methyl, ethyl, butyl, isopropyl, octyl and phenyl, R' is methyl, ethyl, butyl, isopropyl, octyl and phenyl;
x, y and z are mass fractions of Re, TC and GO respectively, x=15-30%, y=60-75%, and z=9-15%;
the rare earth vulcanization accelerator loaded by graphene oxide is prepared by the following steps:
(1) Reacting rare earth metal salt with an organic ligand to obtain a rare earth vulcanization accelerator;
(2) And reacting the rare earth vulcanization accelerator with graphene oxide to obtain the graphene oxide-loaded rare earth vulcanization accelerator.
2. The graphene oxide-supported rare earth vulcanization accelerator according to claim 1, wherein:
x＝20～25％，y＝65～70％，z＝10～12％。
3. a method for preparing the graphene oxide-supported vulcanization accelerator according to claim 1 or 2, comprising the steps of:
(1) Reacting rare earth metal salt with an organic ligand to obtain a rare earth vulcanization accelerator;
(2) And reacting the rare earth vulcanization accelerator with graphene oxide to obtain the graphene oxide-loaded rare earth vulcanization accelerator.
4. A method of preparation according to claim 3, characterized in that: in the step (1), the step of (a),
the rare earth metal salt is rare earth metal halide salt; and/or the number of the groups of groups,
the organic ligand is dialkyl dithiocarbamate.
5. The method of manufacturing according to claim 4, wherein:
the organic ligand is at least one of dimethyl dithiocarbamate, diethyl dithiocarbamate, dibutyl dithiocarbamate, methylphenyl dithiocarbamate, diisopropyl dithiocarbamate and diphenyl dithiocarbamate.
6. A method of preparation according to claim 3, characterized in that:
in the step (1), the molar ratio of the rare earth metal salt to the organic ligand is 1: (1-4).
7. The method of manufacturing according to claim 6, wherein:
the molar ratio of the rare earth metal salt to the organic ligand is 1: (2-4).
8. A method of preparation according to claim 3, characterized in that:
in the step (1), the reaction temperature is 30-90 ℃ and the reaction time is 1-12 h.
9. A method of preparation according to claim 3, characterized in that: in the step (2), the step of (C),
the mass ratio of the rare earth vulcanization accelerator to the graphene oxide is (9-5): 1, a step of;
the reaction temperature is 30-90 ℃ and the reaction time is 1-12 h.
10. The method of manufacturing according to claim 9, wherein:
the mass ratio of the rare earth vulcanization accelerator to the graphene oxide is (7-5): 1.
11. a rubber composite comprising rubber and the graphene oxide-supported rare earth vulcanization accelerator of claim 1 or 2.
12. The rubber composite according to claim 11, wherein:
the rubber is at least one of natural rubber, styrene-butadiene rubber, butyl rubber, nitrile rubber, ethylene propylene diene monomer rubber, chloroprene rubber and polyacrylate rubber.
13. The rubber composite according to claim 11, wherein:
and the dosage of the rare earth vulcanization accelerator loaded by the graphene oxide is 0.1-30 parts by weight based on 100 parts by weight of the rubber.
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| GB722107A (en) * | 1951-11-27 | 1955-01-19 | Dunlop Rubber Co | Manufacture of rubber products |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB722107A (en) * | 1951-11-27 | 1955-01-19 | Dunlop Rubber Co | Manufacture of rubber products |
| CN106243140A (en) * | 2016-09-07 | 2016-12-21 | 北京化工大学 | A kind of aminodithioformic acid tert-butylhydroquinone closes rare earth compounding rubber chemicals |
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