CN111892716A - Lignin-based multifunctional rubber additive and preparation method and application thereof - Google Patents
Lignin-based multifunctional rubber additive and preparation method and application thereof Download PDFInfo
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- CN111892716A CN111892716A CN202010717754.4A CN202010717754A CN111892716A CN 111892716 A CN111892716 A CN 111892716A CN 202010717754 A CN202010717754 A CN 202010717754A CN 111892716 A CN111892716 A CN 111892716A
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- 229920005610 lignin Polymers 0.000 title claims abstract description 167
- 229920001971 elastomer Polymers 0.000 title claims abstract description 136
- 239000005060 rubber Substances 0.000 title claims abstract description 136
- 239000000654 additive Substances 0.000 title claims abstract description 40
- 230000000996 additive effect Effects 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 12
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 47
- 238000002156 mixing Methods 0.000 claims description 30
- 239000012752 auxiliary agent Substances 0.000 claims description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
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- 238000000034 method Methods 0.000 claims description 18
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
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- 238000007599 discharging Methods 0.000 claims description 8
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- 239000000203 mixture Substances 0.000 claims description 7
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
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- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
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- 238000005119 centrifugation Methods 0.000 claims description 4
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
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- 239000003513 alkali Substances 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
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- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
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- 238000009835 boiling Methods 0.000 claims description 2
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- 229920003049 isoprene rubber Polymers 0.000 claims description 2
- 229920005611 kraft lignin Polymers 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
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- 230000002708 enhancing effect Effects 0.000 claims 1
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- 230000004580 weight loss Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
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- 239000002174 Styrene-butadiene Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- 201000001424 dextro-looped transposition of the great arteries Diseases 0.000 description 3
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- 238000011160 research Methods 0.000 description 3
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
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- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
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- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L11/00—Compositions of homopolymers or copolymers of chloroprene
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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Abstract
The invention provides a lignin-based multifunctional rubber additive and a preparation method and application thereof, belonging to the technical field of rubber additives. According to the invention, aromatic diamine is grafted to the surface of lignin by a silane coupling agent KH560 for functional modification, so that the lignin-based multifunctional rubber additive is prepared. The lignin-based multifunctional rubber additive prepared by the invention can obviously improve the thermal-oxidative aging resistance of the material, can stably exert an anti-aging effect for a long time, improves the dispersibility of the filler, has low cost, is non-toxic and not easy to migrate, and improves the tensile strength and the tearing strength of the material.
Description
Technical Field
The invention belongs to the technical field of rubber additives, and particularly relates to a lignin-based multifunctional rubber additive and a preparation method and application thereof.
Background
The rubber auxiliaries are various in types, particularly the design of a protection system, but most of the used anti-aging agents have the defects of single function, toxicity, easy migration and environmental pollution, so that the anti-aging agents are subjected to scaling in the application of rubber products. The novel, efficient and environment-friendly multifunctional rubber additive with one dosage and multiple purposes is developed, so that the performance of rubber products is improved, and the requirement of green chemistry can be met.
Lignin is a natural organic high molecular compound that provides sufficient strength and stiffness to plant cells, in amounts that are second only to cellulose in biomass. As renewable aromatic natural polymers, lignin is always discarded as straw and waste from pulping and papermaking or used as fuel, which not only causes serious pollution to the environment, but also has high added value due to lack of effective utilization means. The lignin has huge yield, a molecular structure has various active groups, such as phenolic hydroxyl, methoxyl, alcoholic hydroxyl, carboxyl, double bonds and the like, the chemical reaction activity of the lignin is improved or the aggregation structure and the strength of interaction force of the lignin are controlled by controllable chemical modification of the lignin structure, the lignin can be used as a reinforcing agent, an anti-aging agent, a coupling agent, a flame retardant and the like in a rubber material, the lignin meets the sustainable development requirement of green environmental protection, the dependence on fossil energy can be reduced, the environmental pollution is reduced, and in addition, the lignin has the advantages of small dust pollution, environment-friendly production mode, low cost and the like when being used for rubber production, so the application research of the lignin is a subject with remarkable economic value and social significance.
Qiuchao et al (CN 103224661A) take enzymolysis lignin with wide raw material source and low cost as a raw material, and the prepared polyolefin/enzymolysis lignin composite material has good comprehensive mechanical properties such as tensile strength and elongation at break, and is low in density, antioxidant and degradable, and the dosage of the enzymolysis lignin, the polyolefin plastic, the plasticizer and the lubricant is 100 parts, 100-400 parts, 5-20 parts and 40-100 parts respectively by mass. Liu Gung and the like (application of enzymatic lignin in SBR rubber materials, 2010, 57(12): 734-.
Jiang Liang and the like (CN 107892752A) introduce arylamine to the ortho position of lignin phenol through a Mannich reaction to prepare a novel multifunctional lignin arylamine macromolecular antioxidant, so that not only is the phenol functional group of lignin converted into a hindered phenol structure with better antioxidant effect, but also the aromatic amine is introduced to further enhance the antioxidant effect of the lignin, and the synergistic antioxidant effect is achieved.
Research of Chenjianhao (the research of the anti-aging performance of the lignin on polyolefin plastics, university of southern China, 2016) finds that pine lignin with high purity, high phenolic hydroxyl content and low ultraviolet transmittance is more suitable for being used as an anti-aging agent of LDPE, and under the action of thermal oxidation, polyphenol in the lignin can capture free radicals, so that the automatic oxidation circulation of polyolefin is prevented, and the anti-oxidation and anti-aging effects are achieved; under the action of ultraviolet light, the conjugated structure of the lignin can absorb the ultraviolet light, thereby playing a role in ultraviolet shielding. However, although the lignin has a certain anti-aging effect in rubber and polyolefin plastics, the anti-aging effect of the lignin is still lower than that of a common small-molecular anti-aging agent, and the anti-aging effect of the lignin is not obvious when the aging time is too long.
Disclosure of Invention
The invention aims to provide a lignin-based multifunctional rubber auxiliary agent which can exert an efficient anti-aging effect.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a preparation method of a lignin-based multifunctional rubber auxiliary agent, which comprises the following steps:
(1) dissolving aromatic diamine in toluene, adding KH560 while stirring, and stirring at 70-90 deg.C for 2-6h to obtain solution A;
(2) dissolving industrial lignin in an alkaline solution, and adjusting the pH value to obtain a solution B;
(3) adding the solution A into the solution B, and reacting for 36-60h at 90-110 ℃ to obtain a solution C;
(4) adding 1 time of deionized water into the solution C for dilution, and then adding strong acid until a brown product A is separated out;
(5) centrifuging to remove aromatic diamine to obtain a product B;
(6) and (3) putting the product B into a vacuum oven, and drying for 12-36h at the temperature of 60-80 ℃ to obtain the lignin-based multifunctional rubber additive.
Preferably, in the step (1), the ratio of aromatic diamine: toluene: KH560 is 1:30-50: 1.
Preferably, in the step (1), the aromatic diamine is one or a mixture of p-aminodiphenylamine and p-phenylenediamine.
Preferably, in the step (2), the industrial lignin is one of kraft lignin, alkali lignin, steam explosion lignin, biochemical lignin, enzymatic lignin, acetic acid lignin, high-boiling alcohol lignin, acetone lignin, ammonia lignin, phenol lignin, ionic liquid lignin, explosion lignin, supercritical extraction lignin and solvent lignin; the alkaline solution is one of 0.1-1% of sodium hydroxide solution, potassium hydroxide solution, calcium hydroxide solution or magnesium hydroxide solution.
Preferably, in the step (4), the strong acid is one of 10% to 30% sulfuric acid, nitric acid, hydrochloric acid and phosphoric acid.
Preferably, the rotating speed of the centrifugation is 6000-10000 r/min; the centrifugation time is 6-10 min.
In addition, the invention provides a lignin-based multifunctional rubber additive, which has the following structural general formula:
in addition, the invention provides an application of the lignin-based multifunctional rubber auxiliary agent, and the lignin-based multifunctional rubber auxiliary agent is used for improving the anti-aging effect of rubber.
In addition, the invention provides application of the lignin-based multifunctional rubber auxiliary agent in a polymer, wherein the lignin-based multifunctional rubber auxiliary agent is prepared from the following components in percentage by weight of 1-30: the prepared lignin-based multifunctional rubber auxiliary agent is added into a polymer according to the mass ratio of 100 and uniformly mixed, wherein the polymer comprises one or more of natural rubber, styrene-butadiene rubber, nitrile rubber, butadiene rubber, chloroprene rubber, ethylene propylene rubber, isoprene rubber and acrylate rubber, and the multifunctional rubber auxiliary agent is added in a manner of directly mixing with the rubber and mixing with rubber latex.
In addition, the invention provides the application of the lignin-based multifunctional rubber auxiliary agent in the polymer,
the method for directly mixing the lignin-based multifunctional rubber additive with the rubber is specifically any one of three methods: adding rubber, stearic acid, zinc oxide, carbon black and lignin-based multifunctional rubber auxiliary agent into an internal mixer, uniformly mixing and discharging rubber, then adding the rubber material on an open mill, blending with sulfur, an accelerator NS, an accelerator DM and an anti-scorching agent CTP, uniformly mixing and discharging to obtain a mixed rubber containing the lignin-based multifunctional rubber auxiliary agent, and standing and vulcanizing; adding rubber, stearic acid, zinc oxide, carbon black and lignin-based multifunctional rubber auxiliary agent into an internal mixer, uniformly mixing, adding sulfur, an accelerator NS, an accelerator DM and an anti-scorching agent CTP, blending to ensure that the rubber discharge temperature is less than 90 ℃, uniformly mixing, tabletting on an open mill to obtain mixed rubber containing the lignin-based multifunctional rubber auxiliary agent, and vulcanizing after standing; performing thin-pass on rubber on an open mill, adding stearic acid, zinc oxide, carbon black and lignin-based multifunctional rubber additive, uniformly mixing, then adding sulfur, an accelerator NS, an accelerator DM and an anti-scorching agent CTP, uniformly mixing, discharging to obtain a mixed rubber containing the lignin-based multifunctional rubber additive, standing and vulcanizing;
the method for blending the lignin-based multifunctional rubber auxiliary agent and the rubber latex comprises the steps of adding the lignin-based multifunctional rubber auxiliary agent into 0.25mol/L sodium hydroxide solution to prepare lignin solution with solid content of 10%, adding the solution into the rubber latex with solid content of 20%, stirring and mixing uniformly, demulsifying with dilute sulfuric acid, washing with deionized water, drying to obtain raw rubber containing the lignin-based multifunctional rubber auxiliary agent, and finally mixing and vulcanizing according to the method.
The invention has the beneficial effects that: the novel auxiliary agent is subjected to thermogravimetric analysis (TGA) and micro-quotient thermogravimetric analysis (DTGA), the auxiliary agent is obviously higher in decomposition temperature and obviously reduced in weight loss rate, because Si-O-Si bonds are generated in the dehydration condensation process of silicon hydroxyl groups and hydroxyl groups on the surface of the lignin in KH560, the Si-O-Si bonds can form a protective layer in the thermal cracking process of the novel auxiliary agent, the internal thermal cracking process of the material is slowed down, and the final product of thermal decomposition of the Si-O-Si bonds is SiO2Can react with carbon in lignin at high temperature to obtain good chemical heat shielding effect through partial desorption heat. Moreover, the composite material added with the novel auxiliary agent not only has excellent thermal-oxidative aging performance, the tensile strength of the composite material can be basically kept unchanged after the thermal-oxidative aging treatment is carried out for 120h at 70 ℃, but also has higher elongation at break and tear strength compared with the composite material added with the common lignin, which is probably caused by that KH560 consumes other polar groups on the surface of the lignin while reacting with hydroxyl on the surface of the lignin, so that the dispersibility of the lignin in a material matrix is enhanced.
Drawings
FIG. 1 example 1 thermogravimetric analysis (TGA) and micro-commercial thermogravimetric analysis (DTGA) analysis spectra of lignin-based multifunctional rubber additive A and biochemical lignin in nitrogen
FIG. 2 example 1 Infrared Spectrum of Lignin-based multifunctional rubber auxiliary A and Biochemical Lignin
FIG. 3 example 1 RPA analysis chart of lignin-based multifunctional rubber additive A, added biochemical lignin and non-added lignin mixed rubber
FIG. 4 example 1 Effect of Lignin-based polyfunctional rubber auxiliary A, Biochemical Lignin and antioxidant 4020 on the tensile Strength Retention ratio of rubber vulcanizate
FIG. 5 example 1 Effect of Lignin-based polyfunctional rubber auxiliary A, Biochemical Lignin and antioxidant 4020 on the conservation Rate of breaking Strength of rubber vulcanizate
FIG. 6 example 1 the effect of lignin-based multifunctional rubber auxiliary A, biochemical lignin and anti-aging agent 4020 on the aging coefficient of rubber vulcanizate.
Detailed Description
Example 1
(1) 9g of p-aminodiphenylamine was dissolved in 390g of toluene, 9g of KH560 was added thereto with stirring, and the mixture was stirred at 80 ℃ for 4 hours to obtain a solution A.
(2) Dissolving 30g of biochemical lignin in 100g of 0.1% sodium hydroxide solution, and adjusting the pH value to 11 to obtain a solution B;
(3) adding the solution A into the solution B, and reacting for 48 hours at 100 ℃ to obtain a solution C;
(4) 1000ml of deionized water was added to the solution C for dilution, and a 20% sulfuric acid solution was added until a brown product A precipitated.
(5) Centrifuging at the rotating speed of 8000 r/min for 8 min to remove unreacted p-aminodiphenylamine to obtain a product B;
(6) and (3) putting the product B into a vacuum oven, and drying for 24 hours at 70 ℃ to obtain the lignin-based multifunctional rubber additive A.
Example 2
(1) 10g of p-phenylenediamine was dissolved in 300g of toluene, 10g of KH560 was added thereto with stirring, and the mixture was stirred at 70 ℃ for 6 hours to obtain a solution A.
(2) Dissolving 5g of alkali lignin in 100g of 0.1% potassium hydroxide solution, and adjusting the pH value to 10 to obtain a solution B;
(3) adding the solution A into the solution B, and reacting for 60 hours at 90 ℃ to obtain a solution C;
(4) and adding 500ml of deionized water into the solution C for dilution, and adding a 10% nitric acid solution until a brown product A is precipitated.
(5) Centrifuging at the rotating speed of 6000 r/min for 10min to remove unreacted p-aminodiphenylamine to obtain a product B;
(6) and (3) putting the product B into a vacuum oven, and drying for 36 hours at the temperature of 60 ℃ to obtain the lignin-based multifunctional rubber auxiliary agent B.
Example 3
(1) 10g of p-aminodiphenylamine and p-phenylenediamine are mixed according to the proportion of 1: 1 mixture was dissolved in 500g of toluene, 10gKH560 was added with stirring, and the mixture was stirred at 70 ℃ for 2 hours to obtain solution A.
(2) Dissolving 20g of enzymatic hydrolysis lignin in 100g of 1% calcium hydroxide solution, and adjusting the pH value to 10 to obtain a solution B;
(3) adding the solution A into the solution B, and reacting for 36 hours at 110 ℃ to obtain a solution C;
(4) 1500ml of deionized water is added into the solution C for dilution, and a 30% hydrochloric acid solution is added until a brown product A is separated out.
(5) Centrifuging at the rotating speed of 10000r/min for 6 min to remove unreacted p-aminodiphenylamine to obtain a product B;
(6) and (3) putting the product B into a vacuum oven, and drying for 12h at 80 ℃ to obtain the lignin-based multifunctional rubber auxiliary C.
Experimental example 1
The maximum weight loss peak temperature and the carbon residue at 700 ℃ of the lignin-based multifunctional rubber additive A and the biochemical lignin in example 1 were compared, and the experimental results are shown in Table 1.
TABLE 1 maximum weight loss peak temperature and carbon residue of lignin and lignin-based antioxidants
| Peak temperature of maximum weight loss | Amount of carbon residue | |
| Biochemical lignin | 352℃ | 37.68% |
| Lignin-based multifunctional rubber additive A | 401℃ | 45.87% |
As can be seen from the table, the temperature corresponding to the maximum weight loss rate of the lignin-based multifunctional rubber additive A prepared by the invention is obviously higher than that of lignin, and the residual carbon content is higher.
Experimental example 2
Detection example 1 thermogravimetric analysis (TGA) and microchanneric thermogravimetric analysis (DTGA) of Lignin-based multifunctional rubber auxiliary A and Biochemical Lignin
As shown in fig. 1, the maximum weight loss rate of the lignin-based multifunctional rubber additive a prepared by the invention is smaller than that of biochemical lignin, which indicates that the lignin-based multifunctional rubber additive prepared by the invention has higher thermal stability.
Experimental example 3
Infrared spectrum for detecting lignin-based multifunctional rubber additive A and biochemical lignin in example 1
As shown in figure 2, the lignin-based multifunctional rubber additive A prepared by the invention is 1030 cm-1The peak of antisymmetric stretching vibration of Si-O-C bond is higher than that of lignin and is 447 cm-1And 581 cm-1The new peaks respectively appearing at the parts respectively show that the lignin-based multifunctional rubber additive A contains Si-O-Si bonds and O = CN bonds.
Experimental example 4
In the strain scanning process of the composite material, the phenomenon that the storage modulus G' is sharply reduced along with the increase of strain is called Payne effect, the phenomenon is caused by the damage and reconstruction of a filler network in the material, the strength of the Payne effect reflects the dispersion degree of the filler, and generally, the weakening of the Payne effect means that the dispersibility of the filler is better.
The result of RPA analysis of the mixed rubber of lignin and the bio-based antioxidant is shown in figure 3, along with the increase of strain, the storage modulus of a sample added with the bio-based antioxidant is always lower than that of a lignin sample, and the Payne effect is weakened, which shows that the bio-based antioxidant is beneficial to promoting the dispersibility of the filler in the SBR matrix.
Experimental example 5
10 parts of the lignin-based multifunctional rubber additive A obtained in example 1 and 10 parts of biochemical lignin were used for preparing a styrene-butadiene rubber composite material, and the mechanical properties of the styrene-butadiene rubber composite material and the biochemical lignin were compared.
The preparation steps are as follows:
(1) dissolving 30g of lignin-based multifunctional rubber additive in 200mL of 0.1% NaOH solution, adding deionized water to adjust the pH value to 10.5-12, and stirring the solution to fully dissolve the lignin-based multifunctional rubber additive A.
(2) 1500ml of styrene-butadiene latex with the solid content of 21.4 percent is taken to be heated in water bath at 60 ℃, lignin-based multifunctional rubber additive solution which is fully dissolved is slowly poured into the latex while stirring, after uniform stirring, emulsion breaking is carried out on the styrene-butadiene latex/lignin-based multifunctional rubber additive coprecipitation liquid by using 500ml of 0.05 percent dilute sulfuric acid, and the styrene-butadiene rubber/lignin-based multifunctional rubber additive coprecipitation gel is obtained.
(3) Kneading and crushing the coprecipitated rubber, soaking the crushed coprecipitated rubber in deionized water, washing the soaked coprecipitated rubber until the pH value is 6-8, dewatering and drying the coprecipitated rubber by using an open mill and an air blast drying box, and sealing for later use. The styrene butadiene rubber co-precipitation glue and the styrene butadiene rubber/lignin co-precipitation glue are prepared by the same method.
(4) Setting the feeding temperature of an internal mixer to be 60 ℃, setting the rotating speed to be 60 r/min, adding 100 parts of styrene-butadiene rubber/lignin-based multifunctional rubber auxiliary agent to perform coprecipitation after the set parameters reach the specified values, then adding 3.5 parts of zinc oxide, 3.5 parts of stearic acid and 0.3 part of anti-scorching agent, finally adding 50 parts of carbon black twice, and discharging the rubber in 8 min.
(5) And (3) placing the rubber material into a double-roll open mill for continuously mixing, then adding 1.5 parts of sulfur, 1.5 parts of accelerator NS and 1 part of accelerator D, uniformly mixing, then carrying out thin passing on the rubber material by a left cutter and a right cutter to the position of a rubber sheet 3/4 for 3 times, and then carrying out thin passing on the rubber material for 5 times and then discharging the rubber sheet. The styrene butadiene rubber co-precipitation rubber and the styrene butadiene rubber/lignin mixed rubber are prepared by the same method.
(6) The mixes were left for 2-24 hours, then the tensile and tear specimens were cut out in the calendering direction, and the other specimens were prepared as standard, the vulcanization temperature of the mix was 160 ℃ and the vulcanization time was (tc90+2) min. The styrene butadiene rubber co-precipitation rubber and the styrene butadiene rubber/lignin vulcanized rubber are prepared by the same method.
(7) And carrying out corresponding mechanical property detection.
The results are shown in Table 2
TABLE 2 physical and mechanical properties of lignin-based multifunctional rubber additive A/styrene butadiene rubber composite material
The results show that the lignin-based multifunctional rubber additive prepared by the invention can effectively improve the tensile strength, the elongation at break and the abrasion resistance of rubber, and obviously improve the tearing strength of the rubber.
Example 6
The vulcanized rubber added with 10 parts of lignin, 10 parts of lignin-based multifunctional rubber auxiliary agent A and 2 parts of anti-aging agent 4020 is aged for 24 hours, 72 hours and 120 hours respectively at 70 ℃, and the results of physical and mechanical properties are shown in Table 3 and FIGS. 4-6.
TABLE 3 ageing Properties of the samples
As can be seen from Table 3 and FIGS. 4 to 6, the lignin-based multifunctional rubber additive A prepared by the invention can significantly improve the heat resistance, oxidation resistance and aging resistance of rubber, and can maintain the aging resistance effect relatively stably for a long time.
Claims (10)
1. A preparation method of a lignin-based multifunctional rubber additive is characterized by comprising the following steps:
(1) dissolving aromatic diamine in toluene, adding KH560 while stirring, and stirring at 70-90 deg.C for 2-6h to obtain solution A;
(2) dissolving industrial lignin in an alkaline solution, and adjusting the pH value to 10-13 to obtain a solution B;
(3) adding the solution A into the solution B, and reacting for 36-60h at 90-110 ℃ to obtain a solution C;
(4) adding 1 time of deionized water into the solution C for dilution, and then adding strong acid until a brown product A is separated out;
(5) centrifuging to remove aromatic diamine to obtain a product B;
(6) and (3) putting the product B into a vacuum oven, and drying for 12-36h at the temperature of 60-80 ℃ to obtain the lignin-based multifunctional rubber additive.
2. The production method according to claim 1, wherein in the step (1), the ratio by mass of the aromatic diamine: toluene: KH560 is 1:30-50: 1.
3. The method according to claim 1, wherein in the step (1), the aromatic diamine is one or a mixture of p-aminodiphenylamine and p-phenylenediamine.
4. The preparation method according to claim 1, wherein in the step (2), the industrial lignin is one or more of kraft lignin, alkali lignin, steam explosion lignin, biochemical lignin, enzymatic lignin, acetic lignin, high boiling alcohol lignin, acetone lignin, ammonia lignin, phenol lignin, ionic liquid lignin, explosion lignin, supercritical extraction lignin and solvent-based lignin; the alkaline solution is one of 0.1-1% of sodium hydroxide solution, potassium hydroxide solution, calcium hydroxide solution or magnesium hydroxide solution.
5. The method according to claim 1, wherein in the step (4), the strong acid is one of 10% to 30% sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid.
6. The method as claimed in claim 1, wherein the rotation speed of the centrifugation is 6000-10000 r/min; the centrifugation time is 6-10 min.
7. The lignin-based multifunctional rubber additive is characterized by having the following structural general formula:
8. the application of the lignin-based multifunctional rubber auxiliary is characterized in that the lignin-based multifunctional rubber auxiliary can be used for improving the anti-aging effect of rubber and enhancing the dispersibility of lignin in a rubber matrix.
9. Use of a lignin-based multifunctional rubber compound according to claim 1 in polymers, wherein the ratio of the lignin-based multifunctional rubber compound to the lignin-based multifunctional rubber compound is in the range of 1 to 30: the prepared lignin-based multifunctional rubber auxiliary agent is added into a polymer according to the mass ratio of 100 and uniformly mixed, wherein the polymer comprises one or more of natural rubber, styrene-butadiene rubber, nitrile rubber, butadiene rubber, chloroprene rubber, ethylene propylene rubber, isoprene rubber and acrylate rubber, and the multifunctional rubber auxiliary agent is added in a manner of directly mixing with the rubber and mixing with rubber latex.
10. Use of a lignin-based multifunctional rubber compound as claimed in claim 9 in polymers, wherein:
the method for directly mixing the lignin-based multifunctional rubber additive with the rubber is specifically any one of three methods: adding rubber, stearic acid, zinc oxide, carbon black and lignin-based multifunctional rubber auxiliary agent into an internal mixer, uniformly mixing and discharging rubber, then adding the rubber material on an open mill, blending with sulfur, an accelerator NS, an accelerator DM and an anti-scorching agent CTP, uniformly mixing and discharging to obtain a mixed rubber containing the lignin-based multifunctional rubber auxiliary agent, and standing and vulcanizing; adding rubber, stearic acid, zinc oxide, carbon black and lignin-based multifunctional rubber auxiliary agent into an internal mixer, uniformly mixing, adding sulfur, an accelerator NS, an accelerator DM and an anti-scorching agent CTP, blending to ensure that the rubber discharge temperature is less than 90 ℃, uniformly mixing, tabletting on an open mill to obtain mixed rubber containing the lignin-based multifunctional rubber auxiliary agent, and vulcanizing after standing; performing thin-pass on rubber on an open mill, adding stearic acid, zinc oxide, carbon black and lignin-based multifunctional rubber additive, uniformly mixing, then adding sulfur, an accelerator NS, an accelerator DM and an anti-scorching agent CTP, uniformly mixing, discharging to obtain a mixed rubber containing the lignin-based multifunctional rubber additive, standing and vulcanizing;
the method for blending the lignin-based multifunctional rubber auxiliary and the rubber latex comprises the steps of adding the lignin-based multifunctional rubber auxiliary into 0.25mol/L sodium hydroxide solution to prepare lignin solution with solid content of 10%, adding the solution into the rubber latex with solid content of 20%, stirring and mixing uniformly, demulsifying with dilute sulfuric acid, washing with deionized water, drying to obtain raw rubber containing the lignin-based multifunctional rubber auxiliary, and finally mixing and vulcanizing according to the method.
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