CN112961263B - Chitosan-based multifunctional macromolecular rubber anti-aging agent and preparation method and application thereof - Google Patents
Chitosan-based multifunctional macromolecular rubber anti-aging agent and preparation method and application thereof Download PDFInfo
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- C08L9/06—Copolymers with styrene
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Abstract
The invention discloses a shellA polysaccharide-based multifunctional macromolecular rubber anti-aging agent, a preparation method and application thereof. The chitosan-based multifunctional macromolecular rubber antioxidant is prepared by carrying out chemical reaction on active amino on chitosan and a phenol antioxidant containing carboxyl in the presence of a solvent, a dehydrating agent and a catalyst. The chitosan-based multifunctional macromolecular rubber antioxidant provided by the invention is environment-friendly and not easy to migrate, not only can obviously improve the thermal oxidation aging resistance of a rubber material, but also has excellent extraction resistance, can exert a lasting thermal oxidation aging resistance on the rubber material, can promote rubber vulcanization, and obviously reduce the normal vulcanization time TC90And the dosage of the vulcanization accelerator is reduced.
Description
Technical Field
The invention belongs to the technical field of rubber additives, and particularly relates to a chitosan-based multifunctional macromolecular rubber antioxidant and a preparation method and application thereof.
Background
The rubber auxiliaries are various and comprise vulcanizing agents, vulcanization accelerators, anti-aging agents, reinforcing agents and the like, wherein the rubber anti-aging agents are indispensable rubber auxiliaries in a rubber material formula system, but the traditional rubber anti-aging agents are generally single in function and low in molecular weight, have the defects of easy volatilization, poor thermal stability, poor compatibility, solvent extraction resistance and the like, are easy to volatilize under heat in the using process, migrate to the surface of a rubber material along with the increase of the using time, are lost due to the contact with the solvent extraction and the like, and the performance and the service life of the rubber material are obviously reduced; meanwhile, the rubber antioxidant is diffused to the surrounding environment due to the migration to the surface, the extraction by a solvent and the like, so that the surrounding environment is polluted, and even the health and safety of people are harmed. Therefore, the development of the efficient and environment-friendly multifunctional rubber antioxidant can not only make up for the obvious defects of the traditional rubber antioxidant, is beneficial to improving the performance of rubber products, but also can meet the requirement of 'green chemistry'.
The macromolecular rubber antioxidant has the advantages of higher relative molecular mass, better migration resistance, solvent extraction resistance, difficult volatilization in the processing process and the like, is a rubber antioxidant with durable thermal-oxidative aging resistance effect, and has become an important development direction of the rubber antioxidant. At present, the methods for preparing the macromolecular rubber antioxidant at home and abroad mainly comprise the following two methods: firstly, a small molecular compound with an anti-aging functional group is taken as a polymerization monomer, and the monomer polymerization type macromolecular rubber anti-aging agent is prepared through polymerization reaction. For example, Kim et al have synthesized phenolic hydroxyl group-containing macromolecular antioxidants by copolymerizing phenolic hydroxyl group-containing and maleimide compounds as monomers for preparing the macromolecular antioxidants with Methyl Methacrylate (MMA) in various proportions (Synthesis and properties of new polymer halogenated synthesized phenolic antioxidants, bulletin of the Korea Chemical Society,2003,24(12): 1853-; stephan et al, using a polymerizable compound containing a hindered phenol and a terminal diene group as a monomer for preparing a macromolecular antioxidant, polymerize under the action of a Hoveyda-Grubbs secondary catalyst to obtain a macromolecular antioxidant having a number average molecular weight of 3000-5600 g/mol (Immobilization of inorganic long-term stabilization of polymeric. European Polymer Journal,2013, 49(12): 4257-4264.). The macromolecular anti-aging agent generally has good migration resistance, extraction resistance and high thermal stability, but the preparation conditions are harsh, the process is relatively complex, the yield is low, and most of the prepared macromolecular anti-aging agents have low content of effective functional groups. Secondly, the chemical reaction of the existing micromolecule anti-aging agent and the macromolecular compound is utilized to introduce the micromolecule anti-aging agent into the structure of the macromolecular compound to prepare the macromolecular anti-aging agent. For example, Xie lake, etc. grafts 2, 6-di-tert-butyl-4-hydroxymethyl phenol (DBHMP) as small molecule antioxidant onto natural large molecule beta-cyclodextrin (beta-CD) to synthesize beta-CD-DBHMP (synthetic and antioxidant properties of a steady-shaped macromolecular antioxidant base on beta-cyclodextrin. materials Letters,2015,151: 72-74.). The solvent extraction resistance of the macromolecular anti-aging agent is superior to that of the corresponding traditional micromolecular anti-aging agent, but the anti-aging performance is not obviously improved, and the required addition amount is larger. Wangyonghong and the like take isophorone diisocyanate as a bridging agent to connect a micromolecule bisphenol anti-aging agent to hydroxyl-terminated polybutadiene to prepare a polymer type anti-aging agent, and although the thermal oxidation aging resistance of the polymer type anti-aging agent is superior to that of the corresponding micromolecule bisphenol anti-aging agent, the addition amount is more (CN 102516488A).
Chitosan is a natural organic high molecular compound widely present in crustaceans such as shrimps, crabs and the like, and the yield thereof is inferior to cellulose in biomass. As a recyclable renewable resource, the chitosan has huge yield, and the substance taking the chitosan as a carrier can be designed and synthesized to be applied to rubber materials by utilizing two active groups, namely hydroxyl and amino, contained in the molecular structure of the chitosan to carry out controllable chemical modification or control the aggregation state structure of the chitosan.
Disclosure of Invention
In order to overcome the obvious defects of the existing rubber antioxidant, the invention mainly aims to provide a preparation method of the chitosan-based multifunctional macromolecular rubber antioxidant. The chitosan-based multifunctional macromolecular rubber antioxidant (COS-AO) provided by the invention is prepared by the chemical reaction of active hydroxyl and amino on Chitosan (COS) and a phenol Antioxidant (AO) containing carboxyl in the presence of a solvent, a dehydrating agent and a catalyst. The chitosan-based multifunctional macromolecular rubber antioxidant provided by the invention is environment-friendly and not easy to migrate, not only can obviously improve the thermal oxidation aging resistance of a rubber material, but also can exert a lasting thermal oxidation aging resistance on the rubber material, and simultaneously can promote rubber vulcanization, and obviously reduce the positive vulcanization time TC90And the dosage of the vulcanization accelerator is reduced.
The invention also aims to provide the chitosan-based multifunctional macromolecular rubber anti-aging agent prepared by the method.
The invention further aims to provide the application of the chitosan-based multifunctional macromolecular rubber antioxidant in rubber.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a chitosan-based multifunctional macromolecular rubber antioxidant comprises the following steps:
using a solvent as a reaction medium, reacting Chitosan (COS) and a phenol Antioxidant (AO) containing carboxyl at 20-60 ℃ for 24-96 h under the action of a dehydrating agent and a catalyst, purifying, and drying to obtain the chitosan-based multifunctional macromolecular rubber antioxidant (COS-AO).
Preferably, the chain unit molar ratio of the carboxyl-containing phenolic Antioxidant (AO) to the Chitosan (COS) is 0.5-3: 1.
preferably, the structural general formula of the phenolic Antioxidant (AO) containing carboxyl is as follows:
in the formula R1、R2Selected from, but not limited to: at least one of methyl, ethyl, propyl, methoxy, ethoxy, propoxy, hydroxy, and tert-butyl;
in the formula n1Is any number of 0, 1, 2, 3 and 4.
Preferably, the molar ratio of the dehydrating agent to the carboxyl group-containing phenolic Antioxidant (AO) is 1-2.5: 1; the dehydrating agent is selected from, but not limited to: at least one of 1-hydroxybenzotriazole, dicyclohexylcarbodiimide, N' -diisopropylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride.
Preferably, the molar ratio of the catalyst to the carboxyl group-containing phenolic Antioxidant (AO) is 0.1 to 0.5: 1; the catalyst is selected from, but not limited to: at least one of 4-dimethylaminopyridine, pyridine and triethylamine.
Preferably, the solvent is selected from, but not limited to: at least one of N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and dichloromethane.
Preferably, the dosage of the solvent is 5 to 10 times of the total mass of the Chitosan (COS) and the phenol Antioxidant (AO).
Preferably, the purification method is: filtering and washing the reaction product mixed solution; the drying temperature is between room temperature (or 25 ℃) and 60 ℃, and the drying is carried out to constant weight.
Preferably, the Chitosan (COS) and the carboxyl-containing phenolic Antioxidant (AO) are fully stirred in a solvent, and then the dehydrating agent and the catalyst are added.
Preferably, the preparation method of the chitosan-based multifunctional macromolecular rubber antioxidant comprises the following steps:
(1) fully stirring Chitosan (COS) and a phenol anti-aging Agent (AO) containing carboxyl in a solvent for 24 hours, adding a dehydrating agent and a catalyst, and reacting at 20-60 ℃ for 24-96 hours;
(2) and (2) filtering, washing and other post-treatment purification of the reaction product prepared in the step (1), and drying in vacuum to constant weight to obtain the chitosan-based multifunctional macromolecular rubber antioxidant (COS-AO).
The chemical reaction equation of the step (1) is as follows:
a chitosan-based multifunctional macromolecular rubber anti-aging agent is prepared by the method.
Preferably, the structural general formula of the chitosan-based multifunctional macromolecular rubber antioxidant is as follows:
in the formula R1、R2Selected from, but not limited to: methyl, ethyl, propyl, methoxy, ethoxy, propoxy, hydroxy, tert-butyl;
in the formula n1Is any number of 0, 1, 2, 3 and 4.
The application of the chitosan-based multifunctional macromolecular rubber antioxidant in the rubber field.
Preferably, the application is: the chitosan-based multifunctional macromolecular rubber antioxidant is used for preparing rubber products or rubber compounds, wherein the mass ratio of the chitosan-based multifunctional macromolecular rubber antioxidant to rubber is (2-15): 100.
a rubber product comprises the following components in parts by weight: 100 parts of rubber, 2 parts of stearic acid, 5 parts of zinc oxide, 30 parts of carbon black and/or white carbon black, 2-15 parts of the chitosan-based multifunctional macromolecular rubber antioxidant, 0.8-2 parts of accelerator NS, 0.2-0.5 part of accelerator DM and 2 parts of sulfur.
Preferably, the rubbers include, but are not limited to: one or more of natural rubber, styrene butadiene rubber, nitrile butadiene rubber, chloroprene rubber, ethylene propylene rubber and isoprene rubber.
The preparation method of the rubber product comprises the following steps:
(1) uniformly mixing rubber, stearic acid, zinc oxide, carbon black and/or white carbon black and a chitosan-based multifunctional macromolecular rubber antioxidant, adding sulfur, an accelerator NS and an accelerator DM, and uniformly mixing to obtain a rubber compound;
(2) standing the mixed rubber obtained in the step (1) for a certain time, and then tabletting and vulcanizing to obtain the rubber product.
Preferably, the parking time in the step (2) is 12-24 h, the vulcanization temperature is 150-180 ℃, and the vulcanization time is the positive vulcanization time T at the corresponding vulcanization temperatureC90。
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the molecular structure of the chitosan-based multifunctional macromolecular rubber antioxidant provided by the invention contains a phenol antioxidant group with thermal oxidation aging resistance, and the molecular structure has excellent thermal oxidation aging resistance on rubber materials.
(2) The chitosan structure in the chitosan-based multifunctional macromolecular rubber antioxidant and the micromolecular phenol antioxidant structure have synergistic effect, and the normal vulcanization time T can be obviously reducedC90The rubber vulcanization is promoted, and the amount of the vulcanization accelerator can be reduced.
(3) The chitosan-based multifunctional macromolecular rubber anti-aging agent provided by the invention has the advantages of large molecular weight, good compatibility with polymers, difficult volatilization, good migration resistance, solvent extraction resistance and the like, and can exert a lasting thermal oxidation aging resistance effect on rubber materials.
(4) The carrier of the chitosan-based multifunctional macromolecular rubber antioxidant provided by the invention is natural macromolecular chitosan, the chitosan-based multifunctional macromolecular rubber antioxidant is abundant in reserves in nature, easy to obtain and relatively environment-friendly, the hydroxyl and amino in the structure of the chitosan-based multifunctional macromolecular rubber antioxidant have high reaction activity, and the chitosan-based multifunctional macromolecular rubber antioxidant is easier to chemically modify, and is used as a synthetic raw material of the rubber antioxidant, so that the chitosan-based multifunctional macromolecular rubber antioxidant is beneficial to comprehensive utilization of biomass resources and meets the development requirement of green chemistry.
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.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
Example 1: synthesis of chitosan-based multifunctional macromolecular rubber antioxidant COS-AO-1
(1) Adding 3.0g (chain mole number is 18.0mmol) of Chitosan (COS) (the number average molecular weight is 3000), 2.5g (9.0mmol) of carboxyl-containing phenolic antioxidant 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid (AO-1) and 100mL of dimethyl sulfoxide into a 250mL three-neck flask with mechanical stirring and nitrogen protection, stirring for 24h, adding 1.9g (9.0mmol) of dehydrating agent dicyclohexylcarbodiimide and 0.11g (0.9mmol) of catalyst 4-dimethylaminopyridine, reacting for 96h at 20 ℃, and finishing the reaction;
(2) and (2) filtering, washing and other post-treatment purification of the reaction product prepared in the step (1), and drying in vacuum at 40 ℃ to constant weight to obtain the chitosan-based multifunctional macromolecular rubber auxiliary agent COS-AO-1.
And carrying out infrared spectrum and nuclear magnetic resonance hydrogen spectrum characterization on the COS-AO-1. Compared with chitosan, COS-AO-1 has 3 new characteristic peaks in the infrared spectrogram of 1740cm-1Characteristic peak of carbonyl group at 1660 cm-1Characteristic peak sum of amide I band at position 1561cm-1Characteristic peak of amide II band, and absorption peak of amino and hydroxyl from COS at 3345cm-1The wide peak of (A) is shifted to 3433cm-1And the peak width becomes narrow; in a nuclear magnetic resonance hydrogen spectrogram, 2 groups of new characteristic peaks appear, namely an absorption peak of hydrogen in tertiary butyl with chemical shift of 0.8-1.8 ppm and an absorption peak of hydrogen in benzene ring with chemical shift of 6.8-7.0 ppm. Both analytical results demonstrate that: the structure of the chitosan-based multifunctional macromolecular rubber antioxidant COS-AO-1 is consistent with the structure.
Example 2: synthesis of chitosan-based multifunctional macromolecular rubber antioxidant COS-AO-2
(1) After 3.0g (18.0 mmol in moles per unit) of Chitosan (COS) (3000 in number average molecular weight), 4.5g (27.0mmol) of a carboxyl group-containing phenolic antioxidant 3- (3, 5-dimethyl-4-hydroxyphenyl) formic acid (AO-2) and 150mL of N-methylpyrrolidone were added to a 250mL three-necked flask equipped with mechanical stirring and nitrogen protection, and stirred for 12 hours, 3.4g (40.5mmol) of dehydrating agent N, N' -diisopropylcarbodiimide and 0.64g (8.1mmol) of catalytic pyridine were added, and the reaction was terminated after 48 hours at 40 ℃;
(2) and (2) filtering, washing and other post-treatment purification of the reaction product prepared in the step (1), and drying in vacuum at 40 ℃ to constant weight to obtain the chitosan-based multifunctional macromolecular rubber auxiliary agent COS-AO-2.
And carrying out infrared spectrum and nuclear magnetic resonance hydrogen spectrum characterization on the COS-AO-2. Compared with chitosan, COS-AO-2 has 3 new characteristic peaks in the infrared spectrogram, each of which is 1760cm-1Characteristic peak of carbonyl group at, 1650 cm-1Characteristic peak of amide I band and 1576cm-1Characteristic peak of amide II band, and absorption peak of amino and hydroxyl from COS at 3345cm-1The wide peak of (A) is shifted to 3433cm-1And the peak width becomes narrow; in a nuclear magnetic resonance hydrogen spectrogram, 2 groups of new characteristic peaks appear, namely an absorption peak of hydrogen in methyl with chemical shift of 2.0-2.2 ppm and an absorption peak of hydrogen in benzene ring with chemical shift of 6.8-7.0 ppm. Both analytical results demonstrate that: the structure of the chitosan-based multifunctional macromolecular rubber antioxidant COS-AO-2 is consistent with the structure.
Example 3: synthesis of chitosan-based multifunctional macromolecular rubber antioxidant COS-AO-3
(1) Adding 3.0g (the mole number of chain units is 18.0mmol) of Chitosan (COS) (the number average molecular weight is 3000) and 15.1g (54.0mmol) of a phenolic antioxidant containing carboxyl, namely 3- (3-methoxy-5-tert-butyl-4-hydroxyphenyl) pentanoic acid (AO-3) and a mixed solvent of 100mL of N, N-dimethylformamide and 100mL of dimethyl sulfoxide into a 250mL three-neck flask with mechanical stirring and nitrogen protection, stirring for 12h, adding 18.2g (135.0mmol) of dehydrating agent, namely 1-hydroxybenzotriazole and 2.73g (27.0mmol) of catalyst triethylamine, reacting for 24h at 60 ℃, and finishing the reaction;
(2) and (2) filtering, washing and other post-treatment purification of the reaction product prepared in the step (1), and drying in vacuum at 40 ℃ to constant weight to obtain the chitosan-based multifunctional macromolecular rubber auxiliary agent COS-AO-3.
And carrying out infrared spectrum and nuclear magnetic resonance hydrogen spectrum characterization on the COS-AO-3. Compared with chitosan, COS-AO-3 has 3 new characteristic peaks in the infrared spectrogram, wherein the characteristic peaks are 1750cm respectively-1Characteristic peak of carbonyl group at 1670 cm-1Characteristic peak of amide I band and 1546cm-1Characteristic peak of amide II band, and absorption peak of amino and hydroxyl from COS at 3345cm-1The wide peak of (A) is shifted to 3433cm-1And the peak width becomes narrow; in a nuclear magnetic resonance hydrogen spectrogram, 3 groups of new characteristic peaks appear, namely an absorption peak of hydrogen in tertiary butyl with chemical shift of 0.8-1.8 ppm, an absorption peak of hydrogen in methoxyl with chemical shift of 3.5-3.8 ppm and an absorption peak of hydrogen in benzene ring with chemical shift of 6.8-7.0 ppm. Both analytical results demonstrate that: the structure of the chitosan-based multifunctional macromolecular rubber antioxidant COS-AO-3 is consistent with the structure.
Example 4: application of chitosan-based multifunctional macromolecular rubber antioxidant COS-AO-3 in styrene butadiene rubber
(1) According to the mass parts, 100 parts of styrene butadiene rubber is thinly passed through an open mill for 8 times, then 2 parts of stearic acid, 5 parts of zinc oxide, 30 parts of white carbon black and 6 parts of chitosan-based multifunctional macromolecular rubber antioxidant COS-AO-3 are added and uniformly mixed, then 1.2 parts of accelerator NS, 0.3 part of accelerator DM and 2 parts of sulfur are added and uniformly mixed, and then the mixture is taken out to obtain the mixed rubber containing the chitosan-based multifunctional macromolecular rubber antioxidant.
(2) The mixed rubber is pressed into sheets on a flat vulcanizing machine after being parked for 24 hours according to the positive vulcanization time TC90And (4) vulcanizing, wherein the vulcanizing temperature is 160 ℃. And standing the vulcanized sample at room temperature for 24 hours, and then carrying out a thermal oxidation aging resistance test and an extraction resistance test.
The vulcanization characteristics of the styrene-butadiene rubber compound of this example are shown in Table 1, and the thermal oxidative aging resistance and the extraction resistance are shown in Table 2.
As can be seen from Table 1, the positive vulcanization time T of the styrene-butadiene rubber composition of this exampleC909.53min, a vulcanization rate index CRI of 14.58, while the positive vulcanization time T of the styrene-butadiene rubber mixture of comparative example 1C90Is 17.45min and a vulcanization rate index CRI of 8.18, a positive vulcanization time T of 60% of comparative example 1 being the only amount of accelerator NS and accelerator DM added to the styrene-butadiene rubber composition of this exampleC90But obviously shortens the vulcanization rate index CRI and obviously increases the vulcanization rate index CRI, which shows that the addition of COS-AO-3 has obvious promotion effect on the vulcanization of the styrene butadiene rubber; ② minimum Torque (M) of the styrene-butadiene rubber composition of the exampleL) Maximum torque (M)H) And DeltaM are both larger than those of the styrene-butadiene rubber compound in the comparative example 1, which shows that the addition of COS-AO-3 improves the crosslinking degree of the styrene-butadiene rubber compound.
As can be seen from Table 2, the styrene-butadiene vulcanizate of the present example has a greater tensile product aging coefficient (k) than comparative example 1, comparative example 2 and comparative example 3, which shows that the styrene-butadiene vulcanizate added with COS-AO-3 has better thermal oxidation aging resistance. ② after extraction for 72h by methanol, after 100 ℃ thermal oxidation accelerated aging for 48h, the tensile product aging coefficient (k) of the embodiment is reduced from 0.68 to 0.51, the retention rate of the k value is 75.0 percent, which shows that COS-AO-3 has excellent extraction resistance and can exert lasting thermal oxidation resistance on the butadiene-styrene vulcanized rubber.
Example 5: application of chitosan-based multifunctional macromolecular rubber antioxidant COS-AO-2 in styrene butadiene rubber
(1) According to the mass parts, 100 parts of styrene butadiene rubber is thinly passed through an open mill for 8 times, then 2 parts of stearic acid, 5 parts of zinc oxide, 30 parts of white carbon black and 15 parts of chitosan-based multifunctional macromolecular rubber antioxidant COS-AO-2 are added and uniformly mixed, then 0.8 part of accelerator NS, 0.2 part of accelerator DM and 2 parts of sulfur are added and uniformly mixed, and then the mixture is taken out to obtain the mixed rubber containing the chitosan-based multifunctional macromolecular rubber antioxidant.
(2) The mixed rubber is pressed into sheets on a flat vulcanizing machine after being parked for 24 hours according to the positive vulcanization time TC90And (4) vulcanizing, wherein the vulcanizing temperature is 160 ℃. And standing the vulcanized sample at room temperature for 24 hours, and then carrying out a thermal oxidation aging resistance test and an extraction resistance test.
The vulcanization characteristics of the styrene-butadiene rubber compound of this example are shown in Table 1, and the thermal oxidative aging resistance and the extraction resistance are shown in Table 2.
As can be seen from Table 1, the positive vulcanization time T of the styrene-butadiene rubber composition of this exampleC907.57min and a vulcanization rate index CRI of 18.25, and a positive vulcanization time T of 40% as compared with comparative example 1 was observed although the amounts of the accelerator NS and the accelerator DM added to the styrene-butadiene rubber composition of this example were only 40% as compared with comparative example 1C90The curing rate index CRI is obviously increased, which shows that the addition of COS-AO-2 has obvious promotion effect on the curing of the styrene butadiene rubber; ② minimum Torque (M) of the styrene-butadiene rubber composition of the exampleL) Maximum torque (M)H) And DeltaM are both larger than those of the styrene-butadiene rubber compound in the comparative example 1, which shows that the addition of COS-AO-2 improves the crosslinking degree of the styrene-butadiene rubber compound.
As can be seen from Table 2, the styrene-butadiene vulcanizate of the present example has a greater tensile product aging coefficient (k) than comparative example 1, comparative example 2 and comparative example 3, which shows that the styrene-butadiene vulcanizate added with COS-AO-2 has better thermal oxidation aging resistance. ② after extraction for 72h by methanol, after 100 ℃ thermal oxidation accelerated aging for 48h, the tensile product aging coefficient (k) of the embodiment is reduced from 0.62 to 0.42, the k value retention rate is 67.7 percent, which shows that COS-AO-2 has good extraction resistance and can exert durable thermal oxidation resistance on the butadiene-styrene vulcanized rubber.
Example 6: application of chitosan-based multifunctional macromolecular rubber antioxidant COS-AO-1 in styrene butadiene rubber
(1) According to the mass parts, 100 parts of styrene butadiene rubber is thinly passed through an open mill for 8 times, then 2 parts of stearic acid, 5 parts of zinc oxide, 30 parts of white carbon black and 2 parts of chitosan-based multifunctional macromolecular rubber antioxidant COS-AO-1 are added and uniformly mixed, then 2 parts of accelerator NS, 0.5 part of accelerator DM and 2 parts of sulfur are added and uniformly mixed, and then the mixture is taken out of a sheet, so that the mixed rubber containing the chitosan-based multifunctional macromolecular rubber antioxidant is obtained.
(2) The mixed rubber is pressed into sheets on a flat vulcanizing machine after being parked for 24 hours according to the positive vulcanization time TC90And (4) vulcanizing, wherein the vulcanizing temperature is 160 ℃. And standing the vulcanized sample at room temperature for 24 hours, and then carrying out a thermal oxidation aging resistance test and an extraction resistance test.
The vulcanization characteristics of the styrene-butadiene rubber compound of this example are shown in Table 1, and the thermal oxidative aging resistance and the extraction resistance are shown in Table 2.
As can be seen from Table 1, the styrene-butadiene kneading of the present examplePositive vulcanization time T of the rubberC9012.66min, a cure rate index CRI of 10.82, a positive cure time T compared to comparative example 1C90The curing rate index CRI is obviously increased, which shows that the addition of COS-AO-1 has obvious promotion effect on the curing of the styrene butadiene rubber; ② minimum Torque (M) of the styrene-butadiene rubber composition of the exampleL) Maximum torque (M)H) And DeltaM are both larger than those of the styrene-butadiene rubber compound in the comparative example 1, which shows that the addition of COS-AO-1 improves the crosslinking degree of the styrene-butadiene rubber compound.
As can be seen from Table 2, the styrene-butadiene vulcanizate of the present example has a greater tensile product aging coefficient (k) than comparative example 1, comparative example 2 and comparative example 3, which shows that the styrene-butadiene vulcanizate added with COS-AO-1 has better thermal oxidation aging resistance. ② after extraction for 72h by methanol, after aging for 48h by thermal oxidation at 100 ℃, the tensile product aging coefficient (k) of the embodiment is reduced from 0.65 to 0.46, the k value retention rate is 70.8 percent, which is obviously higher than the retention rate of the tensile product aging coefficient (k) of comparative example 1 and comparative example 3, which shows that the extraction resistance of COS-AO-1 is good, and the extraction resistance of COS-AO-1 is better than that of corresponding micromolecular phenolic antioxidant 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid (AO-1), and the antioxidant can exert lasting thermal oxidation resistance on the butadiene-styrene vulcanized rubber.
Comparative example 1: styrene butadiene rubber without rubber antioxidant
In order to illustrate the thermo-oxidative aging resistant effect and the vulcanization acceleration effect of the chitosan-based multifunctional macromolecular rubber antioxidant, styrene butadiene rubber without the rubber antioxidant is used as a comparative example.
(1) According to the mass parts, 100 parts of styrene butadiene rubber is thinly passed through an open mill for 8 times, then 2 parts of stearic acid, 5 parts of zinc oxide and 30 parts of white carbon black are added and uniformly mixed, then 2 parts of accelerator NS, 0.5 part of accelerator DM and 2 parts of sulfur are added and uniformly mixed, and then the mixture is produced into sheets, so that the rubber compound without the rubber antioxidant is obtained.
(2) The mixed rubber is pressed into sheets on a flat vulcanizing machine after being parked for 24 hours according to the positive vulcanization time TC90And (4) vulcanizing, wherein the vulcanizing temperature is 160 ℃. And standing the vulcanized sample at room temperature for 24 hours, and then carrying out a thermal oxidation aging resistance test and an extraction resistance test.
The vulcanization characteristic parameters of the styrene-butadiene rubber compound of the comparative example are shown in Table 1, and the thermal oxidative aging resistance and the extraction resistance are shown in Table 2.
As can be seen from Table 1, the positive vulcanization time T of the styrene-butadiene rubber composition of this comparative exampleC9017.45min, a cure rate index CRI of 8.18, a positive cure time T compared to examples 4, 5 and 6C90The significantly longer cure rate index, CRI, is significantly less, indicating that the cure rate of the comparative styrene-butadiene compound is significantly slower than that of examples 4, 5 and 6.② minimum Torque (M) of styrene-butadiene rubber composition of this comparative exampleL) Maximum torque (M)H) And Δ M are all less than the styrene-butadiene mixes of examples 4, 5 and 6, indicating that the styrene-butadiene mix of this comparative example is less crosslinked than the styrene-butadiene mixes of examples 4, 5 and 6.
As can be seen from Table 2, the tensile product aging coefficient (k) of the vulcanized styrene-butadiene rubber of the present comparative example was only 0.37, indicating that the vulcanized styrene-butadiene rubber without the addition of the rubber antioxidant had poor thermal oxidative aging resistance. After extraction with methanol for 72h and then accelerated aging with 100 ℃ hot oxygen for 48h, the tensile product aging coefficient (k) of the vulcanized styrene-butadiene rubber of the comparative example is reduced to 0.17, which shows that the thermal oxidation aging resistance of the vulcanized styrene-butadiene rubber is further reduced.
Comparative example 2: styrene butadiene rubber added with rubber antioxidant MB
In order to illustrate the advantages of the chitosan-based multifunctional macromolecular rubber antioxidant, styrene butadiene rubber added with an industrially common rubber antioxidant MB is taken as a comparative example.
(1) According to the mass parts, 100 parts of styrene butadiene rubber is thinly passed through an open mill for 8 times, then 2 parts of stearic acid, 5 parts of zinc oxide, 30 parts of white carbon black and 2 parts of rubber antioxidant MB are added and uniformly mixed, then 2 parts of accelerator NS, 0.5 part of accelerator DM and 2 parts of sulfur are added and uniformly mixed, and finally the mixture is produced into sheets, so that the rubber compound containing the rubber antioxidant MB is obtained.
(2) The mixed rubber is pressed into sheets on a flat vulcanizing machine after being parked for 24 hours according to the positive vulcanization time TC90And (4) vulcanizing, wherein the vulcanizing temperature is 160 ℃. And standing the vulcanized sample at room temperature for 24 hours, and then carrying out a thermal oxidation aging resistance test and an extraction resistance test.
The thermal oxidative aging resistance of the vulcanized styrene-butadiene rubber of the comparative example is shown in Table 2.
As can be seen from Table 2, the vulcanized styrene-butadiene rubber of the present comparative example has a tensile product aging coefficient (k) of 0.54, which is significantly increased as compared with comparative example 1, indicating that the vulcanized styrene-butadiene rubber to which the rubber antioxidant MB is added exhibits superior thermo-oxidative aging resistance, which is substantially the same as that of comparative example 3. However, the tensile volume aging coefficient (k) of the vulcanized styrene-butadiene rubber of the present comparative example is significantly smaller than that of examples 4, 5 and 6, indicating that the vulcanized styrene-butadiene rubber of the present comparative example is not as good as that of examples 4, 5 and 6 in terms of heat and oxygen aging resistance.
Comparative example 3: styrene butadiene rubber added with phenolic antioxidant 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid (AO-1)
In order to illustrate the thermo-oxidative aging resistance and extraction resistance of the prepared chitosan-based multifunctional macromolecular rubber antioxidant, a phenol antioxidant 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid (AO-1) was used as a comparative example.
(1) According to the mass parts, 100 parts of styrene butadiene rubber is thinly passed through an open mill for 8 times, then 2 parts of stearic acid, 5 parts of zinc oxide, 30 parts of white carbon black and 2 parts of phenol antioxidant 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid (AO-1) are added and uniformly mixed, then 2 parts of accelerator NS, 0.5 part of accelerator DM and 2 parts of sulfur are added and uniformly mixed, and finally the mixture is taken out of a sheet to obtain the rubber compound containing the rubber antioxidant AO-1.
(2) The mixed rubber is pressed into sheets on a flat vulcanizing machine after being parked for 24 hours according to the positive vulcanization time TC90And (4) vulcanizing, wherein the vulcanizing temperature is 160 ℃. And standing the vulcanized sample at room temperature for 24 hours, and then carrying out a thermal oxidation aging resistance test and an extraction resistance test.
The thermal oxidative aging resistance and extraction resistance of the vulcanized styrene-butadiene rubber of the comparative example are shown in Table 2.
As seen from Table 2, the styrene-butadiene vulcanizate of the present comparative example has a tensile product aging coefficient (k) of 0.56, which is substantially the same as that of comparative example 2, indicating that both have substantially the same resistance to thermal oxidative aging, but has a lower tensile product aging coefficient (k) than the styrene-butadiene vulcanizates of examples 4, 5 and 6, indicating that the styrene-butadiene vulcanizate of the present comparative example has poor resistance to thermal oxidative aging. After being extracted by methanol for 72h and then being subjected to thermal oxidation accelerated aging at 100 ℃ for 48h, the tensile product aging coefficient (k) of the vulcanized styrene-butadiene rubber of the comparative example is reduced from 0.56 to 0.31, the retention rate of the k value is 55.4 percent and is obviously smaller than that of the tensile product aging coefficient (k) of the examples 4, 5 and 6, and the extraction resistance of the small molecular phenol antioxidant 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid (AO-1) is lower than that of the chitosan-based multifunctional macromolecular rubber antioxidant COS-AO.
Performance characterization method
1. Testing the tensile strength and the elongation at break of the styrene butadiene rubber: according to GB/T528-2009.
2. Testing the thermo-oxidative aging resistance of styrene butadiene rubber: the aging is carried out according to GB/T3512-2001, the aging temperature is 100 ℃, and the aging time is 48 hours.
The tensile product aging coefficient (k) is used as an evaluation index of the aging resistance, the tensile product f is tensile strength multiplied by elongation at break, the tensile product retention rate is used as the aging coefficient, and the tensile product aging coefficient is calculated by adopting a formula (1).
The greater the tensile product aging coefficient, the greater the aging resistance.
In the formula: k-tensile product aging coefficient; f. ofaTensile product after aging of the test specimen; f. ofuTensile product before aging of the test specimens.
3. Testing the solvent extraction resistance of the anti-aging agent: extracting and soaking in methanol for 72h, and then carrying out thermal oxidation accelerated aging (100 ℃ for 48 h). The tensile product aging coefficient retention ratio k before and after extractionrCharacterization of extraction resistance, krThe larger the size, the better the extraction resistance. k is a radical ofrCalculating according to the formula (2):
in the formula: k is a radical ofr-retention of tensile product aging coefficient;
k-aging coefficient after extracting for 72h by methanol and then accelerating aging for 48h by thermal oxidation at 100 ℃;
k0-the aging coefficient after direct 100 ℃ thermal oxygen accelerated aging for 48h without extraction treatment;
TABLE 1 vulcanization characteristic parameters of styrene-butadiene rubber mixes
TABLE 2 thermal oxidative aging resistance and extraction resistance of vulcanized styrene-butadiene rubber
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a chitosan-based multifunctional macromolecular rubber antioxidant is characterized by comprising the following steps:
reacting chitosan and a phenol anti-aging agent containing carboxyl for 24-96 h at 20-60 ℃ under the action of a dehydrating agent and a catalyst by taking a solvent as a reaction medium, purifying, and drying to obtain the chitosan-based multifunctional macromolecular rubber anti-aging agent;
the dehydrating agent is at least one of 1-hydroxybenzotriazole, dicyclohexylcarbodiimide, N' -diisopropylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride;
the catalyst is at least one of 4-dimethylamino pyridine, pyridine and triethylamine;
the structural general formula of the phenolic antioxidant containing carboxyl is as follows:
in the formula R1、R2Is at least one of methyl, ethyl, propyl, methoxy, ethoxy, propoxy, hydroxyl and tert-butyl; n is1Is an integer of 0 to 4.
2. The method for preparing the chitosan-based multifunctional macromolecular rubber antioxidant according to claim 1, wherein the chain link molar ratio of the carboxyl-containing phenolic antioxidant to the chitosan is 0.5-3: 1.
3. the method for preparing the chitosan-based multifunctional macromolecular rubber antioxidant according to claim 1, wherein the molar ratio of the dehydrating agent to the carboxyl-containing phenolic antioxidant is 1-2.5: 1.
4. the method for preparing the chitosan-based multifunctional macromolecular rubber antioxidant according to claim 1, wherein the molar ratio of the catalyst to the carboxyl group-containing phenol antioxidant is 0.1-0.5: 1.
5. the method for preparing a chitosan-based multifunctional macromolecular rubber antioxidant according to claim 1, wherein the solvent is at least one of N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and dichloromethane; the dosage of the solvent is 5-10 times of the total mass of the chitosan and the phenol anti-aging agent;
the purification method comprises the following steps: filtering and washing the reaction product mixed solution; the drying temperature is room temperature to 60 ℃, and the drying is carried out to constant weight; and fully stirring the chitosan and the phenol anti-aging agent containing carboxyl in a solvent, and then adding a dehydrating agent and a catalyst.
6. A chitosan-based multifunctional macromolecular rubber antioxidant prepared by the method of any one of claims 1 to 5.
7. The use of the chitosan-based multi-functional macromolecular rubber antioxidant according to claim 6 in the rubber field.
8. The application of the chitosan-based multifunctional macromolecular rubber antioxidant in the rubber field according to claim 7, wherein the chitosan-based multifunctional macromolecular rubber antioxidant is used for preparing rubber products or rubber composites, wherein the mass ratio of the chitosan-based multifunctional macromolecular rubber antioxidant to rubber is 2-15: 100.
9. a rubber product is characterized by comprising the following components in parts by weight: 100 parts of rubber, 2 parts of stearic acid, 5 parts of zinc oxide, 30 parts of carbon black and/or white carbon black, 2 to 15 parts of the chitosan-based multifunctional macromolecular rubber antioxidant according to claim 6, 0.8 to 2 parts of accelerator NS, 0.2 to 0.5 part of accelerator DM and 2 parts of sulfur;
the rubber is at least one of natural rubber, styrene-butadiene rubber, nitrile rubber, chloroprene rubber, ethylene propylene rubber and isoprene rubber.
10. A method of making a rubber article as defined in claim 9, comprising the steps of:
(1) uniformly mixing rubber, stearic acid, zinc oxide, carbon black and/or white carbon black and a chitosan-based multifunctional macromolecular rubber antioxidant, adding sulfur, an accelerator NS and an accelerator DM, and uniformly mixing to obtain a rubber compound;
(2) standing the mixed rubber obtained in the step (1) for a certain time, and then tabletting and vulcanizing to obtain the rubber product.
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