CN112159556B - Preparation method of rubber composite material with thermal reversible repeated processing performance - Google Patents
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Abstract
The invention discloses a preparation method of a rubber composite material with thermal reversible repeated processing performance. The preparation method comprises the following steps: and mixing unsaturated rubber and a modified filler loaded with a plurality of nitrogen-oxygen stable free radicals and carrying out thermal crosslinking to obtain the repeatedly processable thermally reversible rubber composite material. The modified filler loaded with a plurality of stable free radicals of nitrogen and oxygen is introduced into the rubber matrix, the stable free radicals of nitrogen and oxygen react with the rubber molecular chain to form an alkoxyamine structure as a crosslinking point, the temperature is controlled to control the crosslinking and the decrosslinking of the rubber, and finally the thermoreversible repeated processing of the rubber is realized. The prepared rubber composite material has excellent mechanical property, the material property retention rate is high after repeated processing treatment, a new method is developed for rubber recycling, and the rubber composite material conforms to the current green development era background.
Description
Technical Field
The invention relates to the field of thermally reversible materials, in particular to a preparation method of a thermally reversible crosslinked rubber composite material based on an alkoxyamine structure and taking a modified filler as a crosslinking point.
Background
The problem of recycling of rubber is always concerned, most of the traditional crosslinked rubber can be only treated in a burning and burying way due to the formation of an irreversible three-dimensional covalent crosslinked network structure, so that the environment is damaged, and the sustainable development process is influenced. Therefore, the irreversible rubber material is modified into the reversible regenerated material, and the problem of recycling of the waste rubber can be well solved. In recent research, rubber can be repeatedly processed by introducing a structure having a reversible reaction under certain conditions into a rubber matrix as a cross-linking point of the material to achieve rubber reproducibility. The reversible crosslinking structure is introduced into the rubber to replace the traditional irreversible crosslinking structure, so that the rubber can be recycled, and the method is a hot spot of the research on recyclable rubber in recent years.
The commonly used thermoreversible structural systems include a Diels-Alder system, an imine bond system, a borate bond system, a beta-hydroxy ester bond, a disulfide bond exchange system and the like, which have been widely studied, and nitroxide radicals are often used in the fields of controlling styrene living polymerization, biomacromolecule recognition, polymerization inhibitors and the like due to the extremely strong free radical trapping capacity. Furthermore, in the literature [ Veregin R P N, Georges M K, Kazmaier P M, et al. free radial polymerizations for narrow poly-dispersion resins: electron spin reactions sites of the kinetics and mechanism [ J ]. Macromolecules,1993,26(20):5316-5320 ], it was found that the combination of the nitroxide radical and the carbon radical can form an alkoxyamine structure with characteristics of cracking at high temperature and re-bonding at low temperature, so that we can predict that the alkoxyamine system can be applied to the thermoreversible material, and the alkoxyamine system has great development potential without being reported in the research of the thermoreversible rubber material field.
The preparation principle of the alkoxy amine thermal reversible rubber composite material is that a filler loaded with a plurality of nitroxide stable free radicals reacts with rubber at high temperature, and the nitroxide stable free radicals react with rubber molecular chains to form an alkoxy amine structure, so that reversible crosslinking of the rubber molecular chains is realized.
The repeated processing mechanism of the alkoxyamine thermal reversible rubber composite material is mainly that an alkoxyamine structure formed after a nitroxide stable free radical reacts with a rubber molecular chain has a thermal reversible property, the structure is decomposed at a high temperature to form a nitroxide stable free radical and a carbon free radical, and the nitroxide stable free radical and the carbon free radical are rapidly combined again at a low temperature to form the alkoxyamine structure. The rubber composite material taking the structure as the crosslinking point can be repeatedly processed and used for many times by controlling the crosslinking and the decrosslinking of the material through the temperature under the mechanism, thereby realizing the green utilization of the rubber material.
The invention starts from a filler, and firstly loads a plurality of nitrogen-oxygen stable free radicals on the surface of the filler through modification. And then hot-pressing the mixed rubber obtained by mixing the modified filler and the rubber, and reacting the nitrogen-oxygen stable free radical loaded by the filler with the rubber at a certain temperature and pressure to form an alkoxyamine covalent structure, namely a chemical crosslinking structure. Meanwhile, due to the thermal reversible characteristic of the alkoxyamine structure, the cross-linked topological network of the rubber composite material is decomposed at high temperature and recombined at low temperature to form the alkoxyamine structure, so that the reversible cross-linking of a rubber molecular chain is realized, and the rubber composite material is endowed with the capacity of repeated processing. The rubber composite material with the thermal reversible repeated processing characteristic has important theoretical and practical significance for the sustainable development of rubber.
Disclosure of Invention
The invention aims to provide a preparation method of a rubber composite material with thermal reversible repeated processing performance. The traditional rubber is repeatedly processed by utilizing the alkoxy amine thermal reversible structure and taking the modified filler as a crosslinking point, and the preparation method has simple steps and strong operability. The prepared rubber composite material has high performance retention rate.
The technical scheme of the invention is as follows.
A preparation method of a rubber composite material with thermal reversible repeated processing performance comprises the following steps:
(1) the filler reacts with a compound containing stable free radicals of nitrogen and oxygen to obtain a modified filler loaded with a plurality of stable free radicals of nitrogen and oxygen;
(2) and (3) mixing and thermally crosslinking the rubber and the modified filler obtained in the step (1) to obtain the rubber composite material with the thermal reversible repeated processing performance.
In the above method, the nitrogen-oxygen containing stable free radical compound has a characteristic group that reacts with the filler.
In the method, in the step (1), the reaction of the compound containing the stable free radical containing nitrogen and oxygen with the filler comprises the reaction of hydroxyl and carboxyl, the reaction of siloxy and hydroxyl, the reaction of amino and carboxyl, the reaction of epoxy and hydroxyl, and the reaction of isothiocyanate and carboxyl.
In the above method, the nitroxide-containing stable free radical-containing compound is at least one of 4-hydroxy-2, 2,6, 6-tetramethylpiperidinyloxy, 4-carboxy-2, 2,6, 6-tetramethylpiperidinyloxy, 4-amino-2, 2,6, 6-tetramethylpiperidinyloxy, 4-isothiocyanato-2, 2,6, 6-tetramethylpiperidinyloxy, 4-glycidyloxy-2, 2,6, 6-tetramethylpiperidinyloxy, 1-oxoyloxy, and 4-methacryloyloxy-2, 2,6, 6-tetramethylpiperidinyloxy, 1-oxoyloxy.
In the method, in the step (1), the filler is one or more of carbon black, graphene oxide, carbon nanotubes, silica, silicate and metal oxide; the metal oxide is more than one of aluminum oxide, zinc oxide, magnesium oxide, ferric oxide and titanium dioxide.
In the above method, in the step (2), the rubber is a rubber containing an unsaturated carbon-carbon double bond.
In the above method, in the step (1), the compound containing the stable free radical containing nitrogen and oxygen may directly react with the surface group of the filler, or may first undergo chemical modification and then react with the surface of the filler, wherein the chemical modification reaction is one of a reaction of isocyanate with hydroxyl and a copolymerization reaction of olefin.
In the method, the mass ratio of the filler to the nitrogen-oxygen containing stable free radical compound is 100:1-50, and the mass ratio of the rubber to the filler is 100: 0.5-100.
In the method, in the step (2), the thermal crosslinking temperature is 120-.
In the method, in the step (2), the rubber is one or more of natural rubber, butadiene rubber, styrene-butadiene rubber, nitrile rubber, isoprene rubber, chloroprene rubber and ethylene propylene diene monomer rubber.
The principle of the invention is as follows: the alkoxy amine structure formed after the nitrogen-oxygen stable free radical reacts with the rubber molecular chain has thermal reversibility, the structure is decomposed at high temperature to form a nitrogen-oxygen stable free radical and a carbon free radical, and the nitrogen-oxygen stable free radical and the carbon free radical are rapidly combined again at low temperature to form the alkoxy amine structure. In a rubber matrix, an alkoxyamine structure with thermo-reversible property is formed between a modified filler loaded with a plurality of nitrogen-oxygen stable free radicals and a rubber molecular chain, and the rubber composite material prepared by taking the structure as a cross-linking structure can realize repeated processing under temperature control under the mechanism, thereby realizing the cyclic utilization of rubber.
The invention has the following excellent effects: the rubber composite material with the repeated processing performance can be prepared, the modified filler loaded with the nitrogen-oxygen stable free radical can play a role of reinforcing the filler while participating in rubber thermal reversible crosslinking, the prepared thermal reversible rubber has excellent performance, and the performance retention rate is high after repeated processing; the method has simple operation steps, does not need to carry out additional modification on rubber, and only needs to mix the modified filler containing a plurality of nitrogen-oxygen stable free radicals with the rubber for reaction at a certain temperature and pressure; in addition, the heat reversible rubber composite material and the equipment used in the repeated processing process are all universal rubber processing equipment, and the large-scale industrial production is easy to implement.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto, and the process parameters not particularly mentioned may be performed by referring to the conventional techniques.
Example 1
Synthesizing the nitrogen-oxygen-containing stable free radical modified tetrapod-like zinc oxide whisker: 4.0g of 4-epoxypropyloxy-2, 2,6, 6-tetramethylpiperidine 1-oxygen free radical is dissolved in toluene, 20.0g of tetrapod-like zinc oxide whisker is added as a filler, the mixture reacts for 11 hours in an oil bath at 150 ℃ and under the nitrogen atmosphere, the epoxy group of the 4-epoxypropyloxy-2, 2,6, 6-tetramethylpiperidine-1-oxygen free radical and the hydroxyl group of the tetrapod-like zinc oxide whisker are fully reacted, the reaction product is washed by ethanol, filtered and dried in vacuum to constant weight, and the modified filler loaded with a plurality of nitrogen-oxygen stable free radicals is obtained, wherein the mass ratio of the filler to the compound containing the nitrogen-oxygen stable free radicals is 100: 20.
Preparing a thermally reversible nitrile rubber composite material: and (3) fully mixing the nitrile rubber and the modified filler on a two-roll open mill according to the mass ratio of 100:28, and performing die pressing on the mixed rubber at 130 ℃ for 50min to obtain the thermally reversible nitrile rubber composite material.
Repeated processing of the thermally reversible nitrile rubber composite material: and (3) placing the nitrile rubber composite material on a 130 ℃ hot mill, uniformly mixing, and then carrying out hot pressing again for 15min at the temperature of 130 ℃ to obtain the repeatedly processed nitrile rubber composite material.
Tensile test experiments show that the thermally reversible nitrile rubber composite material has good repeated processability. (as shown in Table 1)
Example 2
Synthesizing nitrogen-oxygen-containing stable free radical modified graphene: adding 2.0g of graphene serving as a filler into carbon tetrachloride, continuously introducing oxygen containing 2 wt% of ozone to prepare graphene with carboxyl on the surface, adding 1.0g of 4-isothiocyanato-2, 2,6, 6-tetramethylpiperidine 1-oxygen free radical, reacting for 6 hours in water bath at 30 ℃ and in a nitrogen atmosphere to ensure that the isothiocyanato of the 4-isothiocyanato-2, 2,6, 6-tetramethylpiperidine-1-oxygen free radical and the carboxyl on the surface of the graphene are fully reacted, fully washing a reaction product with ethanol, filtering and drying in vacuum to constant weight to obtain the modified filler loaded with a plurality of nitrogen-oxygen stable free radicals, wherein the mass ratio of the filler to the compound containing the nitrogen-oxygen stable free radicals is 100: 50.
Preparation of the thermally reversible chloroprene rubber composite material: fully mixing the chloroprene rubber and the modified filler on a double-roll open mill according to the mass ratio of 100:0.5, and performing compression molding on the mixed rubber for 20min at 160 ℃ to obtain the thermally reversible chloroprene rubber composite material.
Repeated processing of the thermally reversible chloroprene rubber composite material: and (3) placing the chloroprene rubber composite material on a 160 ℃ hot mill, uniformly mixing, and then carrying out hot pressing again for 7min at the temperature of 160 ℃ to obtain the repeatedly processed chloroprene rubber composite material.
Tensile test experiments show that the thermally reversible chloroprene rubber composite material has good repeated processability. (as shown in Table 1)
Example 3
Synthesizing nitrogen-oxygen-containing stable free radical modified silicon dioxide and graphene oxide: dissolving 12.0g of 4-carboxyl-2, 2,6, 6-tetramethylpiperidine-1-oxygen free radical in toluene, adding 30.0g of silicon dioxide and 10.0g of graphene oxide as fillers, reacting for 12 hours in an oil bath at 110 ℃ and in a nitrogen atmosphere to ensure that carboxyl on the 4-carboxyl-2, 2,6, 6-tetramethylpiperidine-1-oxygen free radical fully reacts with hydroxyl on the surfaces of the silicon dioxide and the graphene oxide, washing the reaction product fully with ethanol, filtering and drying in vacuum to constant weight to obtain the modified filler loaded with a plurality of nitrogen-oxygen stable free radicals, wherein the mass ratio of the filler to the compound containing the nitrogen-oxygen stable free radicals is 100: 30.
Preparing a heat-reversible natural rubber composite material: and (3) fully mixing the natural rubber and the modified filler in a two-roll open mill according to the mass ratio of 100:52, and performing die pressing on the mixed rubber at 170 ℃ for 40min to obtain the thermally reversible natural rubber composite material.
Repeated processing of the thermally reversible natural rubber composite: and (3) placing the natural rubber composite material on a 170 ℃ hot mill, uniformly mixing, and then carrying out hot pressing again for 8min at the temperature of 170 ℃ to obtain the repeatedly processed natural rubber composite material.
Tensile test experiments show that the thermally reversible natural rubber composite material has good repeated processability. (as shown in Table 1)
Example 4
Synthesizing nitrogen-oxygen-containing stable free radical modified montmorillonite: 1.0g of 4-hydroxy-2, 2,6, 6-tetramethylpiperidinyloxy was dissolved in toluene, and then 2.0g of isopropyltriethoxysilane isocyanate was slowly dropped to make propyltriethoxysilane isocyanateIsocyanate of silane and hydroxyl of 4-hydroxy-2, 2,6, 6-tetramethyl piperidinyloxy are fully reacted to obtain the chemically modified toluene solution containing the nitroxide stable free radical compound. The montmorillonite is one of silicate, 30.0g of montmorillonite is used as a filler, the mixture is uniformly stirred in deionized water, the mixture is poured into the toluene solution and fully reacts for 12 hours in 70 ℃ water bath and nitrogen atmosphere, so that the silicon-oxygen bond of the nitrogen-oxygen stable free radical compound after chemical modification fully reacts with the hydroxyl on the surface of the montmorillonite, the mixture is fully washed by ethanol, filtered and dried in vacuum to constant weight, and the modified filler loaded with a plurality of nitrogen-oxygen stable free radicals is obtained, wherein the mass ratio of the filler to the nitrogen-oxygen stable free radical compound is 100: 10. The infrared spectrum of the modified montmorillonite shows that 2980cm is in the modified montmorillonite-1、1355cm-1And 960cm-1Methyl antisymmetric stretching, methyl antisymmetric bending and piperidine ring stretching vibration are respectively adopted, so that the nitrogen-oxygen stable free radical is successfully loaded on the montmorillonite, and the modified montmorillonite loaded with the nitrogen-oxygen stable free radical is prepared.
Preparing a thermally reversible butadiene rubber composite material: fully mixing the butadiene rubber and the modified filler on a double-roll open mill according to the mass ratio of 100:10, and performing compression molding on the mixed rubber at 120 ℃ for 60min to obtain the butadiene rubber composite material. As can be seen from the infrared spectra before and after crosslinking of the butadiene rubber composite material, the infrared spectrum of the crosslinked rubber is 1646cm-1The absorption peak of the stretching vibration at the carbon-carbon double bond disappears, which proves that the carbon-carbon double bond structure is destroyed after the heat crosslinking of the mixed rubber, and 1265cm-1A new absorption peak appears corresponding to the stretching vibration of the nitrogen-oxygen bond in the alkoxyamine, which indicates that the alkoxyamine structure is formed in the crosslinked rubber.
Repeatedly processing the thermally reversible butadiene rubber composite material: and (3) placing the thermally reversible butadiene rubber composite material on a hot mill at 120 ℃ for mixing uniformly, and then hot-pressing for 20min again at 120 ℃ to obtain the repeatedly processed butadiene rubber composite material.
Tensile test experiments show that the thermally reversible butadiene rubber composite material has good repeated processability. (as shown in Table 1)
Example 5
Synthesizing the nitrogen-oxygen-containing stable free radical modified carbon nano tube: 4.0g of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxyl and 4.0g of 4-amino-2, 2,6, 6-tetramethylpiperidine-1-oxyl are dissolved in toluene, 20.0g of carbon nanotubes are added as a filler, reacting for 12 hours in an oil bath at 110 ℃ and in a nitrogen atmosphere, fully reacting hydroxyl of 4-hydroxyl-2, 2,6, 6-tetramethylpiperidine-1-oxygen free radical, amino of 4-amino-2, 2,6, 6-tetramethylpiperidine-1-oxygen free radical and carboxyl on the surface of the carbon nano tube, fully washing a reaction product with ethanol, filtering and drying in vacuum to constant weight to obtain the modified filler loaded with a plurality of nitrogen-oxygen stable free radicals, wherein the mass ratio of the filler to the compound containing the nitrogen-oxygen stable free radicals is 100: 40.
Preparing the thermally reversible ethylene propylene diene monomer composite material: and fully mixing the ethylene propylene diene monomer and the modified filler on a double-roll open mill according to the mass ratio of 100:5, and performing compression molding on the mixed rubber for 3min at 180 ℃ to obtain the thermally reversible ethylene propylene diene monomer composite material.
Repeatedly processing the thermally reversible ethylene propylene diene monomer composite material: and (3) placing the ethylene propylene diene monomer composite material on a 180 ℃ heat mixer for mixing uniformly, and then hot-pressing for 3min again at the temperature of 180 ℃ to obtain the ethylene propylene diene monomer composite material for repeated processing.
Tensile test experiments show that the thermally reversible ethylene propylene diene monomer composite material has good repeated processability. (as shown in Table 1)
Example 6
Synthesis of nitrogen-oxygen-containing stable free radical modified carbon black: 0.6g of 4-methacryloyloxy-2, 2,6, 6-tetramethylpiperidine 1-oxyl and 0.4g of vinyltrimethoxysilane are fully mixed in toluene, then 0.1g of benzoyl peroxide is added, and the mixture is placed in a water bath at 80 ℃ and in a nitrogen atmosphere for reaction for 8 hours, so that the double bond of the 4-methacryloyloxy-2, 2,6, 6-tetramethylpiperidine 1-oxyl and the double bond of the vinyltrimethoxysilane react to obtain the chemically modified nitroxide-containing stable free radical compound. And (2) taking 100.0g of carbon black as a filler, uniformly stirring in deionized water, pouring the carbon black into the toluene solution, reacting for 10 hours at 80 ℃ in a water bath and under a nitrogen atmosphere, fully reacting a silicon-oxygen bond of a chemically modified compound containing a stable free radical with a hydroxyl on the surface of the carbon black, fully washing a reaction product with ethanol, filtering, and drying in vacuum to constant weight to obtain the modified filler loaded with a plurality of stable free radicals containing nitrogen and oxygen, wherein the mass ratio of the filler to the compound containing the stable free radical containing nitrogen and oxygen is 100: 1.
Preparing the thermally reversible isoprene-butadiene-styrene composite material: fully mixing isoprene rubber, styrene-butadiene rubber and modified filler on a double-roll open mill according to the mass ratio of 75:25:100, and performing compression molding on the mixed rubber for 30min at 150 ℃ to obtain the thermally reversible isoprene-butadiene rubber composite material.
Repeated processing of the thermally reversible isoprene-butadiene-styrene composite material: and (3) uniformly mixing the isoprene-styrene-butadiene blended rubber composite material on a hot mill at 150 ℃, and then carrying out hot pressing again for 10min at the temperature of 150 ℃ to obtain the isoprene-styrene-butadiene blended rubber composite material for repeated processing.
Tensile test experiments show that the thermally reversible isoprene-butadiene-styrene composite material also has good repeated processability. (as shown in Table 1)
The properties of all samples and reprocessed samples were tested in full according to the corresponding Chinese national standard (GB/T528-2009), which is listed in Table 1.
TABLE 1 mechanics data table of thermally reversible reworked rubber composites
Claims (1)
1. A preparation method of a rubber composite material with thermal reversible repeated processing performance is characterized by comprising the following steps:
(1) the filler reacts with a compound containing stable free radicals of nitrogen and oxygen to obtain a modified filler loaded with a plurality of stable free radicals of nitrogen and oxygen;
(2) mixing rubber and the modified filler obtained in the step (1) and performing thermal crosslinking to obtain a rubber composite material with thermal reversible repeated processing performance;
the compound containing the nitrogen-oxygen stable free radical has a characteristic group which reacts with the filler;
the compound containing stable free radical of nitrogen and oxygen is more than one of 4-hydroxy-2, 2,6, 6-tetramethylpiperidinoxyl, 4-carboxy-2, 2,6, 6-tetramethylpiperidinoxyl, 4-amino-2, 2,6, 6-tetramethylpiperidinoxyl, 4-isothiocyanato-2, 2,6, 6-tetramethylpiperidinoxyl, 4-glycidyloxy-2, 2,6, 6-tetramethylpiperidinoxyl and 4-methacryloyloxy-2, 2,6, 6-tetramethylpiperidinoxyl;
the rubber is rubber containing unsaturated carbon-carbon double bonds;
in the step (1), the reaction of the compound containing the stable free radicals of nitrogen and oxygen and the filler comprises more than one of the reaction of hydroxyl and carboxyl, the reaction of siloxy and hydroxyl, the reaction of amino and carboxyl, the reaction of epoxy and hydroxyl and the reaction of isothiocyanate and carboxyl; the filler is more than one of carbon black, graphene oxide, carbon nano tube, silicon dioxide, silicate and metal oxide; the metal oxide is more than one of aluminum oxide, zinc oxide, magnesium oxide, ferric oxide and titanium dioxide; the compound containing the nitrogen-oxygen stable free radical directly reacts with the surface group of the filler, or is firstly chemically modified and then reacts with the surface of the filler, wherein the chemical modification reaction is one of the reaction of isocyanate and hydroxyl and the copolymerization reaction of olefin;
the mass ratio of the filler to the nitrogen-oxygen containing stable free radical compound is 100:1-50, and the mass ratio of the rubber to the filler is 100: 0.5-100;
in the step (2), the thermal crosslinking temperature is 120-180 ℃, and the time is 3-60 min; the rubber is more than one of natural rubber, butadiene rubber, styrene butadiene rubber, nitrile rubber, isoprene rubber, chloroprene rubber and ethylene propylene diene monomer rubber.
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