CN107841009B - Easily-processed anti-aging styrene butadiene rubber and preparation method thereof - Google Patents
Easily-processed anti-aging styrene butadiene rubber and preparation method thereof Download PDFInfo
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Abstract
The invention provides an easily-processed anti-aging styrene butadiene rubber and a preparation method thereof. The anti-aging softener is obtained by adding an olefin metathesis catalyst and a scorch-proof rubber antioxidant into styrene-butadiene rubber to react, wherein the Mooney viscosity of the easy-processing anti-aging styrene-butadiene rubber product is reduced by 0.2-2.0 units/part based on the addition amount of the softener relative to base rubber, compared with the situation that the tensile strength is reduced by 40-60% without adding the antioxidant, the tensile strength is reduced by 10-30% after adding 1-100 parts of the anti-aging softener, and the scorch time is delayed by 1-15 s/part.
Description
Technical Field
The invention relates to styrene butadiene rubber and a preparation method thereof, in particular to easily processed styrene butadiene rubber with anti-aging performance and a preparation method thereof.
Background
The rubber aging process is often accompanied by remarkable phenomena such as softening, stickiness and specking of the natural rubber which can be found in appearance after long-term storage; rubber products have the characteristics of deformation, embrittlement, hardening, cracking, mildew, dullness, color change and the like. The rubber has the changes of swelling, rheological property and the like in physical properties. The mechanical properties of the steel sheet are degraded by tensile strength, elongation at break, impact strength, bending strength, compressibility, elasticity, and the like. The anti-aging agent is generally added in the process of rubber condensation and processing, the general anti-aging agent is easy to separate out, and various load type, reaction type and composite type anti-aging agents are gradually applied. CN 95110559.0A composite rubber anti-aging agent is a compound of N-phenyl-N-sec-octyl p-phenylenediamine (668) and 2, 2, 4-trimethyl-1, 2-dihydroquinoline (RD) monomer adsorbed on solid carrier light calcium carbonate. The product can be used as a universal anti-aging agent and is widely applied to the synthesis and processing processes of natural rubber and synthetic rubber. CN104403109A the invention discloses a preparation method of a reactive dendriform polyamidoamine rubber anti-aging agent. The preparation method comprises the following steps: fully dissolving polyamidoamine in an organic solvent to be in a uniform state, dripping a reactant dissolved in the organic solvent in advance under the stirring condition, reacting for 0.5-24 h at the temperature of 10-60 ℃, and removing the organic solvent by reduced pressure distillation to obtain a reactive polyamidoamine rubber anti-aging agent with unsaturated double bonds, namely a reactive dendric polyamidoamine rubber anti-aging agent; has the obvious advantages of good anti-aging effect, high relative molecular weight, good compatibility with a polymer matrix, extraction resistance, environmental protection and the like. The anti-aging agents described in the patents are not developed specifically for the corresponding gum species and have poor compatibility.
The mixing of the antioxidant and the rubber requires high energy, and generally requires repeated kneading and mixing on an open mill or an internal mixer for a long time. In the open milling or banburying process, a certain amount of softener is generally required to be added. Generally, the low molecular weight substances can provide a certain flexibility to the rubber compound, and can increase the plasticity, fluidity and adhesiveness of the rubber compound so as to facilitate the technological operations such as compression, molding and the like. And the dispersion of the compounding agent is facilitated, the mixing temperature is reduced, and the processability of the rubber is improved. The softener most used in rubber processing is a petroleum softener, and CN201410018005.7 provides a wet-skid resistant rubber softener and a preparation process, wherein the softener comprises the following raw materials in parts by weight: naphthenic oil: 70-90 parts of alkene mixed resin: 10-30 parts of aluminum trichloride: 0.1 to 1.0 portion. The anti-wet-skid rubber softener has the advantages of various performances of environment-friendly aromatic oil and environment-friendly naphthenic oil, and has good anti-wet-skid performance, lower rolling resistance and good wear resistance. CN201110345185.6 discloses a rubber softener and a preparation method thereof, which comprises the following raw materials in parts by weight: 10-30% of asphalt and 90-70% of naphthenic oil; the asphalt modified rubber softener is nontoxic and lower than European Union safety standards, fills up the blank of domestic production, and greatly saves the cost of domestic tire production enterprises. The softening agents reported in the patent are actually physical plasticizers, mainly comprising aromatic oil, paraffin oil, naphthenic oil, heavy oil, paraffin, vaseline, asphalt, petroleum resin and the like, and have only filling and softening effects on rubber, no anti-aging effect and easy precipitation during the use of the product.
The Mooney scorch time of the styrene butadiene rubber can be used for measuring the scorch difficulty of the rubber material, and the longer the scorch time is, the less prone to the occurrence of the phenomenon of early vulcanization in the processing process. Scorch time can generally be measured by Mooney viscometer, the time required for the Mooney torque to reach 10%, denoted by T10, and the T10 of styrene butadiene rubber under standard test formulation is 2-3 min.
Disclosure of Invention
The invention aims to provide an easily-processed anti-aging styrene butadiene rubber and a preparation method thereof.
The easily-processed anti-aging styrene butadiene rubber comprises the following components in parts by mass: 100 parts of styrene-butadiene rubber and 1-100 parts of anti-aging softener, preferably 5-60 parts of anti-aging softener; the anti-aging softener is prepared by the following method: styrene butadiene rubber is dissolved in a solvent to prepare a solution with the weight percentage of 1-50% w, preferably 5-15% w, based on 100 parts by weight of styrene butadiene rubber, 0.1-1.0 part, preferably 0.1-0.3 part of olefin double decomposition catalyst and 1-50 parts, preferably 5-20 parts of scorch-proof rubber anti-aging agent are added, air and water are isolated at the temperature of 15-50 ℃, preferably 20-25 ℃, the reaction is carried out for 0.5-5 hours, preferably 1-2 hours, and glue solution after the reaction is removed through the solvent, so as to obtain the anti-aging softener.
The scorch-proof rubber anti-aging agent is prepared from a scorch-proof agent and an anti-aging agent through olefin double decomposition reaction, wherein the scorch-proof agent is a nitroso compound containing an ethylenically unsaturated substituent group, an organic acid or a thioamide; the anti-aging agent contains an ethylenically unsaturated substituent group, and contains a phenolic hydroxyl group and/or an amide group.
The scorch-proof rubber antioxidant is prepared by mixing the scorch-proof agent and the antioxidant in a weight ratio of 1: and (3) 0.1-5.0 mol ratio, and carrying out olefin double decomposition reaction to obtain the assistant.
The specific preparation method of the scorch-proof rubber antioxidant comprises the following steps: the scorch retarder and the anti-aging agent are mixed in a proportion of 1: 0.1-5.0 mol ratio, preparing a solution with the mass concentration of 1-30% by using a solvent, adding an olefin double decomposition catalyst accounting for 0.01-0.1% of the total mass of the anti-scorching agent and the anti-aging agent into the solution, isolating air and water, reacting at normal temperature for 0.5-8 h, and then removing the solvent by using a vacuum solvent removal device to prepare the anti-scorching rubber anti-aging agent.
The scorch retarder is nitroso compound containing alkene unsaturated substituent or organic acid or thioamide, and can be N-nitrosodi (vinyl benzene) amine, N-nitroso-styryl-beta-naphthylamine, N-nitroso-2-propenyl-2, 4-dimethyl-1, 2-dihydroquinoline polymer, vinyl benzoic acid, vinyl salicylic acid, butenyl salicylic acid, vinyl phthalic acid, N-vinyl cyclohexyl thiophthalimide, N-propenyl cyclohexyl thiophthalimide, etc.;
the Mn of the anti-aging softener prepared by the invention is 3000-100000.
The solvent is preferably a solvent which does not contain alkene in the structure and can dissolve styrene butadiene rubber; selected from hexane, cyclohexane, toluene, ethylbenzene, etc.
The anti-aging agent is a reaction type anti-aging agent containing an alkene unsaturated substituent group, and the structural formula of the anti-aging agent is as follows: RX;
wherein: r-an unsaturated olefin aliphatic chain segment containing 2-18 carbon atoms, which can be vinyl, propenyl, isopropenyl, isopentenyl, 3-pentenyl, 6-octenyl, tetramethylvinyl, 1-heptenyl, methacryloxypropyl, methacryloxy, preferably propenyl;
x is an organic moiety containing a phenolic hydroxyl group and/or an amide group;
the anti-aging agent can be 4-propenyl-2-methylphenol, propenyl phenol, isopropenyl phenol, 2,4, 6-triallyl phenol, 2, 6-diallyl-p-cresol, methacrylamide and N- (4-phenylaminophenyl) methacrylamide, and preferably propenyl phenol.
The olefin metathesis catalyst of the invention is a ruthenium carbene complex catalyst, which can be (o-isopropoxybenzylidene) (tricyclohexylphosphine) ruthenium (II) dichloride
Dichloro [ o-isopropoxybenzylidene ] group][1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazoleOxazoline subunit]Ruthenium complex
Etc. of Grubbs series catalysts having similar functions or other metal carbene catalysts having olefin metathesis function, preferably
The invention also provides a preparation method of the easy-processing anti-aging styrene butadiene rubber, which mainly comprises the following steps: the anti-aging softening agent and the styrene butadiene rubber are mixed according to a proportion to prepare the easily processed anti-aging styrene butadiene rubber.
The mixing can be carried out on an open mill or an internal mixer, and an open mill is preferably used.
The mixing process of the invention adopts the conventional mixing technology of rubber. The kneading temperature, the kneading time of the kneading frequency and the like are not particularly limited.
The invention also provides a preferable preparation method of the easy-processing styrene butadiene rubber, which comprises the following steps: firstly, mixing the styrene butadiene rubber on an open mill for 3-5 times at 45-55 ℃, then adding the anti-aging softener and mixing for 3-5 times to prepare the easily processed anti-aging styrene butadiene rubber.
Compared with the base rubber, the easily-processed styrene-butadiene rubber prepared by the invention has the advantages that the Mooney viscosity is reduced by 0.2-2.0 unit/part by the amount of the added softening agent, compared with the situation that the tensile strength is reduced by 40-60% without adding an anti-aging agent, the tensile strength is reduced by 10-30% after adding 1-100 parts of the anti-aging softening agent, and the scorch time is delayed by 1-15 s/part.
The term "part" as used herein means a part by mass.
The invention is based on the technical principle that:
wherein n > m
The chemical reaction equation (1) takes vinyl benzoic acid as a scorch retarder and isopropenyl phenol as an anti-aging agent to carry out olefin double decomposition reaction to prepare the scorch-proof rubber anti-aging agent; the formula (2) is that the molecular weight of the styrene-butadiene rubber is reduced under the action of an olefin metathesis catalyst, and simultaneously the styrene-butadiene rubber reacts with the scorch-proof rubber antioxidant generated by the formula (1) to introduce an anti-aging group and a scorch-proof group on a side group.
The softener is a double decomposition reaction product of styrene-butadiene rubber and a scorch-proof rubber antioxidant, has a similar composition with styrene-butadiene rubber, and has a softening effect on rubber due to low molecular weight. In the general rubber processing formula, the process oil is used as a softening agent, and micromolecular auxiliaries such as an anti-aging agent, an anti-scorching agent and the like are added, so that the auxiliaries are easily adsorbed to the surface by carbon black to reduce the action effect of the auxiliaries. The scheme chemically bonds the scorch retarder, the anti-aging agent and the softening agent, and can effectively prevent scorching and aging of rubber.
Detailed Description
The raw material auxiliaries required for the specific implementation of the invention are as follows:
(1) styrene butadiene rubber SBR1500, SBR1712, technical grade, langzhou petrochemical division;
(2) 2-propenyl phenol, 2-isopropenyl phenol, 2,4, 6-triallyl phenol, 2, 6-diallyl-p-cresol reagent grade, carbofuran technologies ltd;
(3) olefin metathesis catalyst:
ruthenium carbene catalyst, 500 mg/bottle, purity more than or equal to 98% w, Bailingwei science and technology Limited;
(4) hexane, cyclohexane, toluene, ethylbenzene, technical grade, langzhou petrochemical division;
(5) 2-vinylbenzoic acid, 3-vinylphthalic acid, reagent grade, gansu gacheng auxiliaries;
blending a softener with styrene butadiene rubber on an open mill, and testing the mechanical properties of the rubber before and after aging; the Mooney viscosity and the scorching time of the rubber are tested according to GB/T1232.1-2000, the rubber is aged according to the hot air aging test method of GB/T3512-.
The parts are all parts by mass; the percentages are mass percentages.
Example 1:
2-vinyl benzoic acid serving as an anti-scorching agent and 2-propenyl phenol serving as an anti-aging agent are mixed according to the weight ratio of 1.0: 5.0 mol ratio, preparing into 30% solution by mass concentration with hexane solvent, adding 0.1% olefin metathesis catalyst of the total amount of the scorch retarder and the anti-aging agent into the solution
Isolating air and water, reacting at normal temperature for 8h, and removing the solvent by using a vacuum solvent removal device to obtain the scorch-proof rubber antioxidant 1-1.
100 parts of styrene butadiene rubber SBR1500 is dissolved in hexane solvent to prepare 1.1 percent concentration solution, and 0.15 part of olefin metathesis catalyst is added
And 1.3 parts of scorch-proof rubber antioxidant 1-1, isolating air and water at 15.5 ℃, reacting for 0.51 hour, removing the glue solution after reaction by using a solvent to obtain the anti-aging softener, and measuring the Mn of the softener to be 90000.
100 parts of styrene butadiene rubber SBR1500 is mixed for 4 times at 75 ℃ on an open mill, 10 parts of the prepared anti-aging softener is added and mixed for 4 times to prepare a styrene butadiene rubber product, the Mooney viscosity is reduced to 50 from 52, the tensile strength before aging is reduced by 45 percent, the tensile strength after aging is reduced by 30 percent, and the scorching time is increased to 189 seconds from 125 seconds.
Comparative example 1:
compared with the embodiment 1, the other conditions are the same, except that the scorch-proof rubber antioxidant is not added, specifically comprising the following steps: 100 parts of styrene butadiene rubber SBR1500 is dissolved in a hexane solvent to prepare a 1.1 percent solution, and 0.15 part of olefin metathesis catalyst is added
Air and water were cut off at 15.5 ℃ and reacted for 0.51 hour, and the reacted gum solution was removed by a solvent to obtain a softener, whose Mn was measured to be 96000.
100 parts of styrene butadiene rubber SBR1500 is mixed for 4 times at 75 ℃ on an open mill, 10 parts of the prepared anti-aging softener is added and mixed for 4 times to prepare a styrene butadiene rubber product, and the Mooney viscosity is reduced to 50 from 52, the tensile strength before aging is reduced by 45 percent, and the tensile strength after aging is reduced by 48 percent. The aging performance is not improved, and the scorch time is as short as 90 s.
Example 2:
the scorch retarder 3-vinyl phthalic acid and the anti-aging agent 2,4, 6-triallyl phenol are mixed in a weight ratio of 1.0: 0.1 mol ratio, preparing into 1% solution by mass concentration with hexane solvent, adding 0.01% olefin metathesis catalyst of the total amount of the scorch retarder and the anti-aging agent into the solution
Isolating air and water, reacting at normal temperature for 0.5h, and removing the solvent by using a vacuum solvent removal device to obtain the scorch-proof rubber antioxidant 2-1.
100 parts of styrene butadiene rubber SBR1500 is dissolved in toluene solvent to prepare 10 percent solution, and 0.9 part of olefin metathesis catalyst is added
And 48 parts of scorch-resistant rubber antioxidant 2-1, isolating air and water at 49 ℃, reacting for 4.6 hours, removing the reacted glue solution through a solvent to obtain an anti-aging softener product, and measuring the Mn of the anti-aging softener product to be 3100.
The styrene butadiene rubber product is prepared by uniformly mixing 100 parts of styrene butadiene rubber SBR1500 and 14 parts of the prepared anti-aging softener on an open mill, and tests show that the Mooney viscosity is reduced to 32 from 52, the tensile strength before aging is reduced by 45 percent, the tensile strength after aging is reduced by 15 percent, and the scorching time is increased to 143s from 125 s.
Comparative example 2:
compared with example 2, the other conditions are the same, except that no olefin metathesis catalyst is added, specifically:
the scorch retarder 3-vinyl phthalic acid and the anti-aging agent 2,4, 6-triallyl phenol are mixed in a weight ratio of 1.0: mixing the components in a molar ratio of 0.1, preparing a solution with the mass concentration of 1% by using a hexane solvent, isolating air and water, reacting at normal temperature for 0.5h, and removing the solvent by using a vacuum solvent removal device to prepare the scorch-proof rubber antioxidant 2-1.
100 parts of styrene butadiene rubber SBR1500 is dissolved in a toluene solvent to prepare a solution with the mass concentration of 10%, 48 parts of scorch-proof rubber antioxidant 2-1 is added, air and water are isolated at 49 ℃, the reaction is carried out for 4.6 hours, the glue solution after the reaction is removed through the solvent, an anti-aging softener product is obtained, and the Mn is measured to be 170000.
The 100 parts of SBR1500 and 14 parts of the prepared anti-aging softener are mixed uniformly in an open mill at 50 ℃ to prepare a styrene butadiene rubber product, the Mooney viscosity is 52 and is not reduced, the tensile strength before aging is reduced by 45 percent, the tensile strength after aging is reduced by 35 percent, and the scorching time is increased from 125s to 129 s.
Example 3:
3-vinyl phthalic acid serving as an anti-scorching agent and 2, 6-diallyl-p-cresol serving as an anti-aging agent are mixed in a ratio of 1.0: 4.0 mol ratio, preparing into 10% solution by mass concentration with hexane solvent, adding olefin metathesis catalyst accounting for 0.09% of the total amount of the scorch retarder and the anti-aging agent into the solution
Isolating air and water, reacting at normal temperature for 4.5h, and removing the solvent by using a vacuum solvent removal device to obtain the scorch-proof rubber antioxidant 3-1.
100 parts of styrene butadiene rubber SBR1712 base rubber is dissolved in cyclohexane solvent to prepare 25 percent solution, and 0.4 part of olefin metathesis catalyst is added
And 25 parts of scorch-resistant rubber antioxidant 3-1, isolating air and water at 25 ℃, reacting for 2.5 hours, removing glue solution after reaction through a solvent to obtain an anti-aging softener product, and measuring the Mn of the product to be 60000.
And (2) uniformly mixing 100 parts of styrene butadiene rubber SBR1712 and 30 parts of the prepared anti-aging softener in an internal mixer to prepare a styrene butadiene rubber product, wherein the Mooney viscosity is reduced to 90 from 120, the tensile strength before aging is reduced by 56%, the tensile strength after aging is reduced by 10%, and the scorching time is increased from 125s to 212 s.
Comparative example 3:
compared with the example 3, the other conditions are the same, except that the aromatic oil is adopted as the softening agent, specifically: and (2) adding 30 parts of high aromatic oil into 100 parts of styrene butadiene rubber SBR1712 in an internal mixer to prepare a styrene butadiene rubber product, wherein the Mooney viscosity is reduced to 80 from 120, the tensile strength is reduced by 56 percent before aging, the tensile strength is reduced by 70 percent after aging, and the scorching time is 130 s.
Example 4:
2-vinyl benzoic acid serving as an anti-scorching agent and 2-isopropenyl phenol serving as an anti-aging agent are mixed in a ratio of 1.0: 3.0 mol ratio, preparing into 15% solution by mass concentration with hexane solvent, adding 0.029% olefin metathesis catalyst in the total amount of the scorch retarder and the anti-aging agent into the solution
Air and water are isolated, the solvent is removed by a vacuum solvent removal device after the reaction is carried out for 4.8 hours at normal temperature, and the scorch-proof rubber antioxidant 4-1 is prepared.
100 parts of styrene butadiene rubber SBR1712 base rubber is dissolved in a toluene solvent to prepare a 40 percent solution, and 0.5 part of olefin metathesis catalyst is added
And 10 parts of scorch-resistant rubber anti-aging agent 4-1, isolating air and water at 15 ℃, reacting for 3 hours, removing the glue solution after the reaction through a solvent to obtain an anti-aging type softener product, and measuring that the Mn of the product is 40000.
100 parts of styrene butadiene rubber SBR1712 is mixed for 4 times at 60 ℃ on an open mill, 38 parts of the prepared anti-aging softener is added for mixing for 5 times to prepare the easily processed anti-aging styrene butadiene rubber, the Mooney viscosity is reduced to 60 from 120, the tensile strength before aging is reduced by 56 percent, the tensile strength after aging is reduced by 28 percent, and the scorching time is increased to 194 seconds from 125 seconds.
Comparative example 4:
compared with the example 4, the other conditions are the same, except that 2-isopropyl phenol is adopted as the anti-aging agent, no double bond is generated, and the following concrete conditions are adopted:
mixing a scorch retarder 2-vinylbenzoic acid and an anti-aging agent 2-isopropyl phenol in a ratio of 1.0: 3.0 mol ratio, preparing into 15% solution by mass concentration with hexane solvent, adding 0.029% olefin metathesis catalyst in the total amount of the scorch retarder and the anti-aging agent into the solution
Isolating air and water, reacting at normal temperature for 4.8h, and removing the solvent by using a vacuum solvent removal device to obtain the scorch-proof rubber antioxidant 4-2.
100 parts of styrene butadiene rubber SBR1712 base rubber is dissolved in a toluene solvent to prepare a 40 percent solution, and 0.5 part of olefin metathesis catalyst is added
And 10 parts of scorch-resistant rubber antioxidant 4-2, isolating air and water at 15 ℃, reacting for 3 hours, removing the reacted glue solution through a solvent to obtain an anti-aging softener product, and measuring the Mn of the product to be 59000.
100 parts of styrene butadiene rubber SBR1712 is mixed for 4 times at 60 ℃ on an open mill, 38 parts of the anti-aging softener is added and mixed for 5 times to prepare a styrene butadiene rubber product, the Mooney viscosity is reduced to 80 from 120, the tensile strength before aging is reduced by 56 percent, the tensile strength after aging is reduced by 40 percent, the anti-aging performance is poor, and the scorching time is increased to 196s from 125 s.
Example 5:
2-vinylbenzoic acid serving as an anti-scorching agent and 2, 6-diallyl-p-cresol serving as an anti-aging agent are mixed in a proportion of 1.0: 3.7 mol ratio, preparing a solution with the mass concentration of 19 percent by using a hexane solvent, and adding an olefin double decomposition catalyst accounting for 0.05 percent of the total mass of the anti-coking agent and the anti-aging agent into the solution
Isolating air and water, reacting at normal temperature for 7h, and removing the solvent by using a vacuum solvent removal device to obtain the scorch-proof rubber antioxidant 5-1.
100 parts of styrene butadiene rubber SBR1500 is dissolved in hexane solvent to prepare 30 percent solution, and 0.18 part of olefin metathesis catalyst is added
And 12 parts of scorch-resistant rubber antioxidant 5-1, isolating air and water at 35 ℃, reacting for 4 hours, removing glue solution after reaction through a solvent to obtain an anti-aging softener product, and measuring the Mn of the anti-aging softener product to be 98000.
The styrene butadiene rubber product is prepared by uniformly mixing 100 parts of styrene butadiene rubber SBR1500 and 95 parts of the prepared anti-aging softener on an open mill, and tests show that the Mooney viscosity is reduced to 32 from 52, the tensile strength before aging is reduced by 45 percent, the tensile strength after aging is reduced by 19 percent, and the scorching time is increased to 174s from 125 s.
Comparative example 5:
compared with the embodiment 5, the other conditions are the same, except that the anti-aging agent and the anti-scorching agent are added in the post-processing procedure, specifically: 100 parts of styrene butadiene rubber SBR1500 is dissolved in hexane solvent to prepare 30 percent solution, and 0.18 part of olefin metathesis catalyst is added
Air and water were cut off at 35 ℃ and reacted for 4 hours, and the reacted gum solution was removed with a solvent to obtain a softener product, whose Mn was measured to be 101000.
100 parts of SBR (styrene butadiene rubber) 1500 and 95 parts of the prepared softener, 12 parts of rubber anti-aging agent 2, 6-diallyl-p-cresol and 12 parts of anti-scorching agent 2-vinyl benzoic acid which are relative to the mass of the softener are uniformly mixed on an open mill to prepare a styrene butadiene rubber product, and through tests, the Mooney viscosity is reduced to 49 from 52, the tensile strength before aging is reduced by 45%, the tensile strength after aging is reduced by 33%, and the scorching time is increased to 134s from 125 s.
Example 6:
2-vinylbenzoic acid serving as an anti-scorching agent and 2,4, 6-triallyl phenol serving as an anti-aging agent are mixed in a ratio of 1.0: mixing at a molar ratio of 4.5, preparing into 25% solution with hexane solvent, adding the total substances of scorch retarder and anti-aging agent into the solution0.06% of the amount of olefin metathesis catalyst
Isolating air and water, reacting at normal temperature for 4h, and removing the solvent by using a vacuum solvent removal device to obtain the scorch-proof rubber antioxidant 6-1.
100 parts of styrene butadiene rubber SBR1500 is dissolved in cyclohexane solvent to prepare 20 percent solution, and 0.9 part of olefin double decomposition catalyst is added
And 38 parts of scorch-resistant rubber antioxidant 6-1, isolating air and water at 28 ℃, reacting for 3.2 hours, removing glue solution after reaction through a solvent to obtain an anti-aging softener product, and measuring the Mn of the anti-aging softener product to be 8000.
100 parts of styrene butadiene rubber SBR1500 is mixed for 3 times at 70 ℃ on an open mill, 1.1 part of the prepared anti-aging softener is added for mixing for 5 times to prepare a styrene butadiene rubber product, the Mooney viscosity is reduced to 50 from 52, the tensile strength before aging is reduced by 45 percent, the tensile strength after aging is reduced by 23 percent, and the scorching time is increased to 184s from 125 s.
Comparative example 6:
compared with the example 6, the other conditions are the same, except that the aromatic oil is adopted as the softening agent, and the anti-aging agent is added, specifically: 100 parts of styrene butadiene rubber SBR1500 is mixed for 3 times at 70 ℃ on an open mill, 1.1 parts of high aromatic oil and 38 parts of anti-aging agent 2,4, 6-triallyl phenol are added, and the mixture is mixed for 3 times at 70 ℃ on the open mill to prepare a styrene butadiene rubber product, through tests, the Mooney viscosity is reduced to 50 from 52, the tensile strength before aging is reduced by 45 percent, the tensile strength after aging is reduced by 41 percent, and the scorching time is increased to 274s from 125 s.
Example 7:
2-vinylbenzoic acid serving as an anti-scorching agent and 2, 6-diallyl-p-cresol serving as an anti-aging agent are mixed in a proportion of 1.0: 4.5 mol ratio, preparing a solution with the mass concentration of 25 percent by using a hexane solvent, and adding an olefin double decomposition catalyst accounting for 0.06 percent of the total mass of the anti-coking agent and the anti-aging agent into the solution
Isolating air and water, reacting at normal temperature for 4h, and removing the solvent by using a vacuum solvent removal device to obtain the scorch-proof rubber antioxidant 7-1.
100 parts of styrene butadiene rubber SBR1500 is dissolved in hexane solvent to prepare 18 percent solution, and 0.95 part of olefin metathesis catalyst is added
And 48 parts of scorch-resistant rubber antioxidant 7-1, isolating air and water at 48 ℃, reacting for 3.2 hours, removing glue solution after reaction through a solvent to obtain an anti-aging softener product, and measuring the Mn of the anti-aging softener product to be 7200.
The styrene butadiene rubber product is prepared by uniformly mixing 100 parts of styrene butadiene rubber SBR1500 and 70 parts of the prepared anti-aging softener in an internal mixer, and tests show that the Mooney viscosity is reduced from 52 to 39, the tensile strength before aging is reduced by 45 percent, the tensile strength after aging is reduced by 13 percent, and the scorching time is increased from 125s to 194 s.
Comparative example 7:
compared with the example 7, the other conditions are the same, except that the softening agent is added with the anti-aging agent for reaction for a period of time after the double decomposition catalyst is added for reaction in the preparation process of the softening agent, and then the anti-scorching agent is added for reaction for a period of time, specifically: 100 parts of styrene butadiene rubber SBR1500 is dissolved in hexane solvent to prepare 18 percent solution, and 0.95 part of olefin metathesis catalyst is added
And (2) isolating air and water at 48 ℃ for reaction for 2h, adding 48 parts of anti-aging agent 2, 6-diallyl-p-cresol, isolating air and water at 48 ℃ for reaction for 1.2 h, adding 10 parts of anti-scorching agent 2-vinylbenzoic acid, isolating air and water at 48 ℃ for reaction for 2h, and removing glue solution after reaction by using a solvent to obtain an anti-aging softener product, wherein the Mn of the anti-aging softener product is 120000.
The styrene butadiene rubber product is prepared by uniformly mixing 100 parts of styrene butadiene rubber SBR1500 and 70 parts of the prepared anti-aging softener in an internal mixer, and tests show that the Mooney viscosity is reduced from 52 to 49, the tensile strength before aging is reduced by 45 percent, the tensile strength after aging is reduced by 31 percent, and the scorching time is increased from 125s to 144 s.
Claims (15)
1. An easily-processed anti-aging styrene butadiene rubber comprises the following components in parts by mass: 100 parts of styrene-butadiene rubber and 1-100 parts of anti-aging softener; the anti-aging softening agent is characterized by being prepared by the following method: dissolving styrene-butadiene rubber in a solvent to prepare a 1-50 w% solution, adding 0.1-1.0 part of olefin double decomposition catalyst and 1-50 parts of anti-scorching rubber anti-aging agent into the solution based on 100 parts by mass of styrene-butadiene rubber, isolating air and water at 15-50 ℃, reacting for 0.5-5 hours, and removing the reacted glue solution through the solvent to obtain an anti-aging softener; the scorch-proof rubber anti-aging agent is prepared by olefin double decomposition reaction of the scorch-proof agent and the anti-aging agent; the scorch retarder is a nitroso compound containing ethylenically unsaturated substituent, organic acid or thioamide; the anti-aging agent contains an ethylenically unsaturated substituent group, and the anti-aging agent contains a phenolic hydroxyl group and/or an amide group; the preparation method of the scorch-proof rubber antioxidant comprises the following steps: mixing a scorch retarder and an anti-aging agent in a ratio of 1: 0.1-5.0 mol ratio, preparing a solution with the mass concentration of 1-30% by using a solvent, adding an olefin double decomposition catalyst accounting for 0.01-0.1% of the total mass of the anti-scorching agent and the anti-aging agent into the solution, isolating air and water, reacting at normal temperature for 0.5-8 h, and then removing the solvent by using a vacuum solvent removal device to prepare the anti-scorching rubber anti-aging agent.
2. The easy-to-process anti-aging styrene butadiene rubber as claimed in claim 1, wherein the anti-aging softener has Mn of 3000-100000.
3. The easy-to-process anti-aging styrene-butadiene rubber according to claim 1, wherein the solvent is a solvent capable of dissolving styrene-butadiene rubber without containing an olefin in the structure.
4. The easy-to-process anti-aging styrene-butadiene rubber according to claim 1, wherein the solvent is selected from hexane, cyclohexane, toluene or ethylbenzene.
5. The easy-to-process anti-aging styrene-butadiene rubber according to claim 1, wherein the scorch retarder is selected from the group consisting of N-nitrosodi (vinylbenzene) amine, N-nitroso-styryl- β -naphthylamine, N-nitroso-2-propenyl-2, 4-dimethyl-1, 2-dihydroquinoline polymer, vinylbenzoic acid, vinyl salicylic acid, butenyl salicylic acid, vinyl phthalic acid, N-vinylcyclohexyl thiophthalimide, and N-propenyl cyclohexylthiophthalimide.
6. The easy-to-process anti-aging styrene butadiene rubber as claimed in claim 1, wherein the anti-aging agent has the structural formula: RX; wherein: r contains an unsaturated olefin aliphatic chain segment with 2-18 carbon atoms; x is an organic moiety containing a phenolic hydroxyl group and/or an amide group.
7. The easy-to-process anti-aging styrene-butadiene rubber according to claim 6, wherein the anti-aging agent has a structural formula in which R is selected from the group consisting of vinyl, propenyl, isopropenyl, isopentenyl, 3-pentenyl, 6-octenyl, trimethylvinyl, 1-heptenyl, methacryloxypropyl, and methacryloxy.
8. The easy-to-process anti-aging styrene-butadiene rubber according to claim 6, wherein the anti-aging agent is selected from the group consisting of 4-propenyl-2-methylphenol, propenyl phenol, isopropenyl phenol, 2,4, 6-triallyl phenol, 2, 6-diallyl-p-cresol and methacrylamide.
9. The easy-to-process anti-aging styrene-butadiene rubber according to claim 1, wherein the olefin metathesis catalyst is a metal carbene catalyst having an olefin metathesis function.
10. The easy-to-process anti-aging styrene-butadiene rubber according to claim 1, wherein the olefin compound isThe decomposition catalyst is selected from (o-isopropoxybenzylidene) (tricyclohexylphosphine) ruthenium (II) dichloride
Dichloro [ o-isopropoxybenzylidene ] group][1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolinylidene]Ruthenium complex
11. The easy-to-process anti-aging styrene-butadiene rubber according to claim 1, wherein 0.1 to 0.3 part by mass of an olefin metathesis catalyst is added to 100 parts by mass of the styrene-butadiene rubber in the preparation of the anti-aging softener.
12. The easy-to-process anti-aging styrene-butadiene rubber according to claim 1, wherein 5 to 20 parts by mass of the scorch inhibiting rubber antioxidant is added to 100 parts by mass of the styrene-butadiene rubber in the preparation of the anti-aging softener.
13. The easy-to-process anti-aging styrene-butadiene rubber according to claim 1, wherein the anti-aging softener is contained in an amount of 5 to 60 parts per 100 parts of the easy-to-process anti-aging styrene-butadiene rubber.
14. The method for preparing easily processable anti-aging styrene butadiene rubber as claimed in claim 1, wherein the method mainly comprises mixing the anti-aging softener and styrene butadiene rubber in proportion.
15. The method of preparing a processable anti-aging styrene-butadiene rubber as claimed in claim 14, wherein the method comprises: firstly, mixing the styrene butadiene rubber on an open mill for 3-5 times at 45-55 ℃, then adding the anti-aging softener and mixing for 3-5 times to obtain the easily processed anti-aging styrene butadiene rubber.
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