CN114426714A - Lignin/styrene butadiene rubber composite solid particle and synthetic method thereof - Google Patents
Lignin/styrene butadiene rubber composite solid particle and synthetic method thereof Download PDFInfo
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- CN114426714A CN114426714A CN202011076114.6A CN202011076114A CN114426714A CN 114426714 A CN114426714 A CN 114426714A CN 202011076114 A CN202011076114 A CN 202011076114A CN 114426714 A CN114426714 A CN 114426714A
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- lignin
- butadiene rubber
- reaction
- styrene butadiene
- styrene
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- 229920005610 lignin Polymers 0.000 title claims abstract description 123
- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 84
- 239000002245 particle Substances 0.000 title claims abstract description 51
- 239000007787 solid Substances 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000010189 synthetic method Methods 0.000 title claims description 3
- 239000011246 composite particle Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 22
- 239000003513 alkali Substances 0.000 claims abstract description 21
- 229920000126 latex Polymers 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 14
- 239000008098 formaldehyde solution Substances 0.000 claims abstract description 13
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 13
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 34
- 239000004816 latex Substances 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 235000002639 sodium chloride Nutrition 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- KZTCAXCBXSIQSS-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-4-n-phenylbenzene-1,4-diamine Chemical compound C=1C=C(N)C=CC=1N(C(C)CC(C)C)C1=CC=CC=C1 KZTCAXCBXSIQSS-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
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- UEZWYKZHXASYJN-UHFFFAOYSA-N cyclohexylthiophthalimide Chemical compound O=C1C2=CC=CC=C2C(=O)N1SC1CCCCC1 UEZWYKZHXASYJN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- PKDCQJMRWCHQOH-UHFFFAOYSA-N triethoxysilicon Chemical compound CCO[Si](OCC)OCC PKDCQJMRWCHQOH-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 230000007071 enzymatic hydrolysis Effects 0.000 claims description 2
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 238000004537 pulping Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 229920001971 elastomer Polymers 0.000 description 23
- 239000005060 rubber Substances 0.000 description 23
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 21
- 229920001568 phenolic resin Polymers 0.000 description 21
- 239000005011 phenolic resin Substances 0.000 description 21
- 230000014759 maintenance of location Effects 0.000 description 14
- 239000003292 glue Substances 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 238000010074 rubber mixing Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- -1 and the like Chemical compound 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007031 hydroxymethylation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 238000010092 rubber production Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/005—Processes for mixing polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2309/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2497/00—Characterised by the use of lignin-containing materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Compounds Of Unknown Constitution (AREA)
Abstract
The invention relates to a lignin/butadiene styrene rubber composite solid particle and a synthesis method thereof, wherein lignin is dissolved in alkali liquor, phenol and formaldehyde solution are added for reaction, and butadiene styrene rubber latex is added for continuous reaction after the reaction is finished to obtain mixed liquor; adding the mixed solution and the inorganic acid solution into the electrolyte solution for reaction, separating out solid composite particles, filtering, washing and drying to obtain the product. The composite solid particles prepared by the invention have the grain diameter of more than 10 meshes accounting for more than 95wt%, and have good comprehensive use performance after being mixed to prepare the lignin-based styrene-butadiene rubber.
Description
Technical Field
The invention belongs to the field of rubber composite materials, and particularly relates to lignin/styrene butadiene rubber composite solid particles and a synthesis method thereof.
Background
Styrene Butadiene Rubber (SBR) is a random copolymer of butadiene and styrene. It is the backbone product of the first large variety of synthetic rubber and rubber industry, and is one of the rubbers which realize industrial production at the earliest. However, since the styrene butadiene rubber is a non-self-reinforcing rubber, the styrene butadiene rubber must be used in combination with a reinforcing agent, and the commonly used reinforcing agent includes carbon black, white carbon black, organic resin, lignin and the like, wherein the lignin is a natural organic polymer with an aromatic ring structure and is second to cellulose in nature, but no way for resource utilization of industrial lignin is found by people so far, and more than 95% of lignin is directly discharged into rivers or is burnt after concentration, so that environmental pollution and resource waste are caused. At present, researchers add lignin into styrene butadiene rubber to improve the mechanical properties of the rubber, such as tensile strength, stress at definite elongation, wear resistance and the like, improve the ultraviolet resistance and aging resistance of the rubber, and prolong the service life of rubber products.
In the traditional lignin/styrene butadiene rubber compounding process, lignin powder and styrene butadiene rubber are compounded in a mixing mode, but the method has the defects of uneven dispersion, easy agglomeration and the like of lignin particles in a rubber material, and the method preferably uses ultrafine lignin powder for improving the dispersibility, so that the ultrafine lignin powder is easy to float, pollution is brought to the operating environment, and potential safety hazards exist.
In order to solve the above problems in the process of compounding lignin and styrene butadiene rubber, research on co-precipitation of lignin and styrene butadiene rubber in liquid phase has become a hot spot in recent years. For example, patent CN102718995A discloses an industrial lignin reinforced rubber and a preparation method thereof, which is characterized in that: (1) comprises lignin dispersion, latex and a small amount of plasticizer and processing oil, or comprises multicomponent lignin dispersion, latex and a small amount of plasticizer and processing oil; (2) the lignin dispersion is taken as a lignin suspension in water, the mass part of the lignin is 5-30%, the multi-component lignin dispersion is a lignin and inorganic filler suspension in water, and the mass ratio of the lignin to the water is 5-30: 95-70; (3) in lignin dispersions and multicomponent lignin dispersions, hydroxymethylation of lignin modifies lignin. The preparation method comprises the following steps: (1) preparing lignin, (2) preparing lignin dispersion, (3) preparing latex, (4) coprecipitating and coagulating, and (5) preparing industrial lignin reinforced rubber. The invention combines the lignin and the drying process of the rubber production process without reducing the physical and mechanical properties of the rubber compound, thereby reducing the power consumption of rubber mixing.
However, when liquid phase coprecipitation of the lignin/styrene butadiene rubber composite material is performed, due to the introduction of lignin molecules, on one hand, rubber particles are coated, and on the other hand, the lignin does not have a crosslinking characteristic, so that crosslinking between normal rubber particles is reduced, the particle size of the obtained lignin/styrene butadiene rubber composite material is too small, and the phenomena of glue leakage (the rubber particles fall from a chain belt gap) and glue flying (the rubber particles are blown up by drying air flow) can occur in the subsequent drying process of the belt type drying oven, so that equipment failure and rubber loss are caused. Therefore, no relevant report is provided on how to solve the problem that the colloidal particles are too small in the liquid phase coprecipitation process of the lignin/styrene butadiene rubber composite material.
Disclosure of Invention
The inventor of the application discovers that the particle size of the composite particles prepared by the method is too small when the lignin-based styrene-butadiene rubber composite particles are prepared by adopting a liquid-phase coprecipitation method, and after analysis, the particle size is found to be caused by the influence of the introduction of lignin molecules on normal crosslinking among rubber particles. Aiming at the problem, the invention provides lignin/styrene butadiene rubber composite solid particles and a synthesis method thereof, and the proportion of the particle size of the prepared composite solid particles larger than 10 meshes is more than 95 wt%.
The invention provides a method for synthesizing lignin/styrene butadiene rubber composite solid particles, which comprises the following steps:
(1) dissolving lignin in alkali liquor, adding phenol and formaldehyde solution for reaction, adding butadiene styrene rubber latex after the reaction is finished, and continuing the reaction to obtain mixed liquor;
(2) and (2) adding the mixed solution obtained in the step (1) and an inorganic acid solution into an electrolyte solution for reaction, separating out solid composite particles, filtering, washing and drying to obtain the product.
In the present invention, the lignin in the step (1) is at least one of alkali lignin obtained by alkali pulping in paper industry, enzymatic lignin obtained in cellulosic ethanol industry, lignin extracted from lignocellulose by using an organic solvent, and the like. These lignins can be made by oneself or can be obtained commercially.
In the present invention, the alkali in step (1) is an inorganic alkali, and may be at least one of sodium hydroxide, potassium hydroxide, and the like.
In the invention, the mass ratio of the alkali to the lignin in the step (1) is 0.05-0.2: 1.
In the invention, the mass concentration of the alkali liquor in the step (1) is 1% to the saturated concentration, and preferably 10% -20%.
In the invention, the mass ratio of the phenol to the lignin in the step (1) is 0.125-0.32: 1.
In the invention, the concentration of the formaldehyde solution in the step (1) is 35wt% -37wt%, and the mass ratio of formaldehyde to phenol is 0.4-0.7: 1.
In the invention, the reaction temperature of the step (1) is 60-90 ℃, preferably 70-80 ℃; the stirring speed of the reaction is 100-1000r/min, and the reaction time is 2-3 h.
In the present invention, the styrene-butadiene rubber latex of step (1) has a solid content of less than 40wt%, preferably 20wt% to 25 wt%.
In the invention, the lignin in the step (1) accounts for 4-45% of the mass of the styrene butadiene rubber, and preferably 5-30%.
In the invention, after the styrene butadiene rubber latex is added in the step (1), the reaction is continued for 5min to 10min at the stirring speed of 100 r/min to 1000 r/min.
In the present invention, the inorganic acid in the step (2) is at least one of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and the like, and sulfuric acid is preferable.
In the invention, the mass concentration of the inorganic acid solution in the step (2) is 1-20%, preferably 5-10%.
In the invention, the dosage of the inorganic acid solution in the step (2) is determined according to the pH value of the system, and the pH value is 3-5 after mixing.
In the present invention, the electrolyte in step (2) is at least one of a sodium salt and/or a potassium salt, preferably at least one of sodium chloride, sodium sulfate, sodium phosphate, potassium chloride, potassium sulfate, potassium nitrate, and the like, and more preferably sodium chloride.
In the invention, the mass concentration of the electrolyte solution in the step (2) is 0.1-1.0%, preferably 0.2-0.5%.
In the present invention, the mass ratio of the electrolyte solution in the step (2) to the mixed solution in the step (1) is 1-5:1, preferably 2-3: 1.
In the present invention, the rate of adding the mixed solution to the electrolyte solution in the step (2) is 5 to 50mL/s, preferably 10 to 30 mL/s.
In the invention, the reaction temperature in the step (2) is 30-80 ℃, preferably 50-60 ℃; the stirring speed of the reaction is 50-300r/min, preferably 150-200 r/min.
In the invention, solid composite particles are separated by filtering in the step (2), washed to be neutral, and dried for 2-5h in a belt type drying oven at the temperature of 100-130 ℃.
The lignin/styrene butadiene rubber composite solid particles are prepared by the method, wherein the proportion of the particle size of more than 10 meshes is more than 95 wt%. In the prepared composite solid particles, the styrene butadiene rubber content is 69wt% -94.3wt%, the lignin content is 4.7wt% -22.0wt%, and the phenolic resin content is 1wt% -10.3wt% based on the total mass.
The invention also provides lignin-based styrene-butadiene rubber which is prepared by mixing and vulcanizing the lignin/styrene-butadiene rubber composite solid particles prepared by the method according to a certain rubber compound formula. The prepared lignin-based styrene butadiene rubber has good physical and mechanical properties and thermal-oxidative aging resistance.
The formula of the styrene-butadiene rubber compound mainly comprises lignin/styrene-butadiene rubber composite solid particles prepared by the invention, white carbon black, stearic acid, zinc oxide, N- (1, 3-dimethylbutyl) -N-phenyl-p-phenylenediamine, N- (1, 1-dimethylethyl) -2-benzothiazole sulfenamide, bis- [ gamma- (triethoxy silicon) propyl ] tetrasulfide, N' -diphenyl guanidine, sulfur and N-cyclohexyl thiophthalimide.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the lignin is modified by the phenolic resin through condensation crosslinking between aldehyde groups and phenolic hydroxyl groups of lignin, and then the lignin/styrene butadiene rubber composite solid particles are precipitated through coprecipitation with styrene butadiene rubber latex, so that the particle size of the composite solid particles is effectively improved, wherein the mass ratio of the particles larger than 10 meshes is more than 95%, and the problem of over-small particle size of colloidal particles during liquid phase coprecipitation of the lignin/styrene butadiene rubber latex is solved.
(2) The lignin/butadiene styrene rubber composite solid particles with large particle sizes are prepared by the method, so that the phenomena of glue leakage (colloidal particles fall from the gaps of the chain belts) and glue flying (colloidal particles are blown up by drying air flow) in the drying process are effectively avoided, and equipment faults and rubber loss are reduced.
(3) After the lignin/styrene butadiene rubber composite solid particles prepared by the method are mixed to prepare the lignin-based styrene butadiene rubber, the good physical and mechanical properties and the thermal-oxidative aging resistance are maintained, and particularly the thermal-oxidative aging resistance of the rubber can be effectively improved.
Detailed Description
The method and effects of the present invention will be described in further detail with reference to examples. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments. In the present invention, wt% is a mass fraction.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The experimental materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.
In the present invention, the styrene-butadiene rubber mass = styrene-butadiene rubber latex mass × solid content. The particle size of the lignin/styrene butadiene rubber composite particles is judged according to the retention rate of a 10-mesh stainless steel screen to the composite particles: rejection = mass of composite particles (dry basis) filtered through a 10 mesh stainless steel screen)/(mass of composite particles (dry basis) filtered through a 10 mesh stainless steel screen) + mass of composite particles (dry basis) filtered through a 200 mesh stainless steel screen).
The styrene butadiene rubber compound formula provided by the invention comprises the following components: the phenolic resin modified lignin/styrene-butadiene rubber composite material comprises, by mass, 100 parts of styrene-butadiene rubber, 10-60 parts of white carbon black, 1-3 parts of stearic acid, 1-7 parts of zinc oxide, 1-5 parts of an anti-aging agent N- (1, 3-dimethylbutyl) -N-phenyl-p-phenylenediamine, 0.5-1.5 parts of an accelerator N- (1, 1-dimethylethyl) -2-benzothiazole sulfenamide, 2-6 parts of a coupling agent bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide, 1-3 parts of an accelerator N, N' -diphenylguanidine, 0.5-2 parts of sulfur and 0.1-0.5 part of an anti-scorching agent N-cyclohexyl thiophthalimide.
Example 1
(1) Dissolving 10g of alkali lignin in 100g of 2wt% sodium hydroxide solution, adding 1.9g of phenol and 3g of 37wt% formaldehyde solution, and stirring and reacting for 2 hours at 80 ℃ and 500 rpm; then adding 24wt% of styrene butadiene rubber latex with lignin accounting for 10% of the mass of the styrene butadiene rubber, and continuously stirring for reaction for 5min to obtain a mixed solution.
(2) Preparing a sodium chloride solution with the concentration of 0.2wt%, adding the mixed solution into the sodium chloride solution at the speed of 10mL/s and adding a sulfuric acid solution with the concentration of 10wt% at the same time according to the mass ratio of the electrolyte solution to the mixed solution in the step (1) of 2:1 at the conditions of 60 ℃ and 150r/min, and keeping the pH value of the whole system between 3 and 5. After the reaction is finished, filtering and separating the lignin/styrene butadiene rubber composite solid particles by using 10-mesh and 200-mesh stainless steel screens in an up-and-down overlapping mode respectively, washing the solid particles to be neutral by using water, wherein the composite particles with large particle sizes recovered from the 10-mesh screen are dried for 3 hours at the temperature of 110 ℃ in a belt type drying box, and the phenomena of glue leakage and glue flying are not generated in the continuous drying; the composite particles with small particle size obtained from the 200-mesh screen are dried for 3 hours in a common oven at 110 ℃, and the retention rate of the 10-mesh screen is calculated to be 99.1wt% according to the mass of the composite particles with two different sizes. Wherein, the styrene butadiene rubber content in the composite particles is 88.5wt%, the lignin content is 8.8wt%, and the phenolic resin content is 2.7 wt%.
Example 2
(1) Dissolving 10g of alkali lignin in 100g of 1wt% potassium hydroxide solution, then adding 1.3g of phenol and 2.1g of 37wt% formaldehyde solution, and stirring and reacting for 2 hours at 60 ℃ and 100 rpm; then adding butadiene styrene rubber latex with the solid content of 20wt% according to the condition that the lignin accounts for 5% of the mass of the butadiene styrene rubber, and continuously stirring for reaction for 5min to obtain a mixed solution.
(2) Preparing a 0.1wt% potassium chloride solution, adding the mixed solution into the potassium chloride solution at a speed of 5mL/s at a temperature of 30 ℃ and a speed of 50r/min according to a mass ratio of the electrolyte solution to the mixed solution of 1:1, and simultaneously adding a 1wt% sulfuric acid solution to keep the pH value of the whole system between 3 and 5. After the reaction is finished, filtering and separating the lignin/styrene butadiene rubber composite solid particles by using 10-mesh and 200-mesh stainless steel screens in an up-down overlapping mode respectively, washing the solid particles to be neutral by using water, wherein the composite particles with large particle sizes recovered from the 10-mesh screen are dried for 2 hours at the temperature of 100 ℃ in a belt type drying oven, and the phenomena of glue leakage and glue flying are not generated in continuous drying; the small-particle size composite particles obtained in the 200-mesh screen are dried for 2 hours in a common oven at 100 ℃, and the retention rate of the 10-mesh screen is calculated to be 98.2wt% according to the mass of the composite particles with two different sizes. Wherein, the styrene butadiene rubber content in the composite particles is 93.9wt%, the lignin content is 4.7wt%, and the phenolic resin content is 1.4 wt%.
Example 3
(1) Dissolving 10g of alkali lignin in 20g of 10wt% sodium hydroxide solution, adding 3.2g of phenol and 4.7g of 37wt% formaldehyde solution, and stirring and reacting at 90 ℃ and 1000rpm for 3 h; then adding 30wt% of styrene butadiene rubber latex with solid content of 30wt% of lignin based on the mass of styrene butadiene rubber, and continuously stirring and reacting for 10min to obtain a mixed solution.
(2) Preparing a sodium sulfate solution with the concentration of 1.0wt%, adding the mixed solution into the sodium sulfate solution at the speed of 30mL/s and adding a sulfuric acid solution with the concentration of 20wt% according to the mass ratio of the electrolyte solution to the mixed solution in the step (1) of 3:1 at the conditions of 80 ℃ and 300r/min, always keeping the pH value of the whole system between 3 and 5, after the reaction is finished, filtering and separating the phenolic resin modified lignin/styrene butadiene rubber composite solid particles in a manner of vertically overlapping by using 10-mesh and 200-mesh stainless steel screens respectively, washing the solid particles with water to be neutral, wherein the lignin/styrene butadiene rubber with large particle size recovered from the 10-mesh screen is dried for 5 hours at the temperature of 120 ℃ in a belt drying box, and the phenomena of glue leakage and glue flying are not generated in the continuous drying; the small-particle size composite particles obtained from the 200-mesh screen are dried for 5 hours in a common oven at 120 ℃, and the retention rate of the 10-mesh screen is calculated to be 97.4wt% according to the mass of the composite particles with two different sizes. Wherein, the styrene butadiene rubber content in the composite particles is 71.9wt%, the lignin content is 21.6wt%, and the phenolic resin content is 6.5 wt%.
Example 4
The difference from example 1 is that: in step (1), 1.3g of phenol and 2.2g of a 37wt% formaldehyde solution were added to the lignin solution. The phenolic resin modified lignin/styrene butadiene rubber composite particles are respectively sieved by screens of 10 meshes and 200 meshes, and the retention rate of the 10 meshes of screens is calculated to be 97.7 percent after drying. Wherein, the styrene butadiene rubber content in the composite particles is 89.3wt%, the lignin content is 8.9wt%, and the phenolic resin content is 1.8 wt%.
Example 5
The difference from example 1 is that: in step (1), 3.1g of phenol and 5.1g of a 37wt% formaldehyde solution were added to the lignin solution. The phenolic resin modified lignin/butadiene styrene rubber composite particles are respectively sieved by screens of 10 meshes and 200 meshes, and the retention rate of the 10 meshes of screens is calculated to be 98.0 percent after drying. Wherein, the styrene butadiene rubber content in the composite particles is 87wt%, the lignin content is 8.7wt%, and the phenolic resin content is 4.3 wt%.
Example 6
The difference from example 1 is that: in the step (2), hydrochloric acid is used as the inorganic acid, and potassium chloride is used as the electrolyte. The phenolic resin modified lignin/butadiene styrene rubber composite particles are respectively sieved by screens of 10 meshes and 200 meshes, and the retention rate of the 10 meshes of screens is calculated to be 98.7 percent after drying. Wherein, the styrene butadiene rubber content in the composite particles is 88.2wt%, the lignin content is 9.0wt%, and the phenolic resin content is 2.8 wt%.
Example 7
The difference from example 1 is that: in the step (2), nitric acid is used as the inorganic acid, and sodium sulfate is used as the electrolyte. The phenolic resin modified lignin/styrene butadiene rubber composite particles are respectively sieved by screens of 10 meshes and 200 meshes, and the retention rate of the 10 meshes of screens is calculated to be 99.0 percent after drying. Wherein, the styrene butadiene rubber content in the composite particles is 88.0wt%, the lignin content is 8.9wt%, and the phenolic resin content is 3.1 wt%.
Example 8
The difference from example 1 is that: the lignin is enzymatic hydrolysis lignin obtained in cellulosic ethanol industry. The lignin/styrene butadiene rubber composite particles are respectively screened by screens of 10 meshes and 200 meshes, and the rejection rate of the screen of 10 meshes is calculated to be 97.1 percent after drying. Wherein, the styrene butadiene rubber content in the composite particles is 89.0wt%, the lignin content is 8.5wt%, and the phenolic resin content is 2.5 wt%.
Example 9
The difference from example 1 is that: lignin is lignin extracted from lignocellulose with an organic solvent. The lignin/styrene butadiene rubber composite particles are respectively screened by screens of 10 meshes and 200 meshes, and the retention rate of the screen of 10 meshes is calculated to be 97.6 percent after drying. Wherein, the styrene butadiene rubber content in the composite particles is 88.6wt%, the lignin content is 8.7wt%, and the phenolic resin content is 2.7 wt%.
Comparative example 1
The difference from example 1 is that: dissolving lignin in alkali liquor, and directly adding styrene butadiene rubber latex for reaction without adding phenol and formaldehyde solution for reaction. The retention rate of a 10-mesh screen after drying is calculated to be only 16.0wt%, and composite particles with large particle sizes account for less.
Comparative example 2
The difference from example 1 is that: dissolving lignin in alkali liquor, adding phenol and formaldehyde solution for reaction, and then adding styrene butadiene rubber latex to obtain a mixed solution; and (3) adding the mixed solution, the styrene butadiene rubber latex and the inorganic acid solution into the electrolyte solution for reaction in the step (2). The retention rate of the lignin/styrene butadiene rubber composite particles with a 10-mesh screen reaches 66.4%, but the situation that the styrene butadiene rubber and the modified lignin are co-precipitated unevenly in a liquid phase and part of the modified lignin is lost occurs in the experimental process.
Comparative example 3
The difference from example 1 is that: dissolving lignin in alkali liquor, adding phenol and formaldehyde solution for reaction, and then adding styrene butadiene rubber latex to obtain a mixed solution; and (3) adding the mixed solution and the inorganic acid solution into the electrolyte solution for reaction in the step (2) to obtain a product. The product and the styrene butadiene rubber are added into a rubber compound formula according to the same proportion for mixing.
Comparative example 4
The difference from example 1 is that: without the preparation method, lignin and styrene butadiene rubber which are equal to those in example 1 are added for mixing in the subsequent rubber mixing.
Test example
The phenolic resin modified lignin/styrene butadiene rubber composite particles prepared in the examples and the comparative examples are mixed according to the following formula: the phenolic resin modified lignin/styrene-butadiene rubber composite particle comprises, by mass, 100 parts of styrene-butadiene rubber, 50 parts of white carbon black, 2 parts of stearic acid, 3.5 parts of zinc oxide, 3 parts of N- (1, 3-dimethylbutyl) -N-phenyl-p-phenylenediamine, 1 part of N- (1, 1-dimethylethyl) -2-benzothiazole sulfenamide, 4 parts of bis- [ gamma- (triethoxy silicon) propyl ] tetrasulfide, 2 parts of N, N' -diphenyl guanidine, 1.2 parts of sulfur and 0.3 part of N-cyclohexyl thiophthalimide. After mixing and vulcanization, testing physical and mechanical properties; and then carrying out thermo-oxidative aging treatment on the mixed vulcanized rubber for 72h at 70 ℃ in an air atmosphere, and testing the relevant physical and mechanical properties of the mixed vulcanized rubber. In addition, the same amount of styrene-butadiene rubber as the phenolic resin modified lignin/styrene-butadiene rubber composite particles in the mixing formula was used for mixing, vulcanization and testing as a reference, and the test results are shown in table 1.
TABLE 1 Properties of the compounded vulcanizates
As shown in Table 1, the phenolic resin modified lignin/styrene butadiene rubber composite particles prepared by the method can effectively improve the retention rate of a 10-mesh screen of the composite particles. Meanwhile, due to the introduction of a large number of phenol structures in the composite particles, the tensile strength retention rate and the elongation at break retention rate of the rubber after aging treatment can be effectively improved, and the thermal oxidation resistance of the rubber is improved.
Claims (19)
1. A synthetic method of lignin/styrene butadiene rubber composite solid particles is characterized by comprising the following steps:
(1) dissolving lignin in alkali liquor, adding phenol and formaldehyde solution for reaction, adding butadiene styrene rubber latex after the reaction is finished, and continuing the reaction to obtain mixed liquor;
(2) and (2) adding the mixed solution obtained in the step (1) and an inorganic acid solution into an electrolyte solution for reaction, separating out solid composite particles, filtering, washing and drying to obtain the product.
2. The method of claim 1, wherein: the lignin in the step (1) is at least one of alkali lignin obtained by alkali pulping in the paper making industry, enzymatic hydrolysis lignin obtained in the cellulosic ethanol industry or lignin extracted from lignocellulose by adopting an organic solvent.
3. The method of claim 1, wherein: the mass ratio of the alkali to the lignin in the step (1) is 0.05-0.2: 1.
4. A method according to claim 1 or 3, characterized in that: the alkali in the step (1) is inorganic alkali, preferably at least one of sodium hydroxide and potassium hydroxide; the mass concentration of the alkali liquor is 1% to the saturated concentration, and preferably 10% -20%.
5. The method of claim 1, wherein: the mass ratio of the phenol to the lignin in the step (1) is 0.125-0.32: 1.
6. The method of claim 1, wherein: the concentration of the formaldehyde solution in the step (1) is 35wt% -37wt%, and the mass ratio of formaldehyde to phenol is 0.4-0.7: 1.
7. The method of claim 1, wherein: the reaction temperature of the step (1) is 60-90 ℃, and the optimal temperature is 70-80 ℃; the stirring speed of the reaction is 100-1000r/min, and the reaction time is 2-3 h.
8. The method of claim 1, wherein: the solid content of the styrene-butadiene rubber latex in the step (1) is less than 40wt%, and preferably 20wt% to 25 wt%.
9. The method according to claim 1 or 8, characterized in that: in the step (1), the lignin accounts for 4-45% of the mass of the styrene butadiene rubber, and preferably 5-30%.
10. The method of claim 1, wherein: after the styrene butadiene rubber latex is added in the step (1), continuously reacting for 5min-10min at the stirring speed of 100-1000 r/min.
11. The method of claim 1, wherein: the inorganic acid in the step (2) is at least one of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, preferably sulfuric acid; the mass concentration of the inorganic acid solution is 1-20%, preferably 5-10%.
12. The method according to claim 1 or 11, characterized in that: the dosage of the inorganic acid solution in the step (2) is determined according to the pH value of the system, and the pH value is 3-5 after mixing.
13. The method of claim 1, wherein: the electrolyte in the step (2) is at least one of sodium salt and/or potassium salt, preferably at least one of sodium chloride, sodium sulfate, sodium phosphate, potassium chloride, potassium sulfate, potassium nitrate and the like, and more preferably sodium chloride.
14. The method according to claim 1 or 13, characterized in that: the mass concentration of the electrolyte solution in the step (2) is 0.1-1.0%, and preferably 0.2-0.5%.
15. The method according to claim 1 or 13, characterized in that: the mass ratio of the electrolyte solution in the step (2) to the mixed solution in the step (1) is 1-5:1, preferably 2-3: 1.
16. The method of claim 1, wherein: the rate of adding the mixed solution to the electrolyte solution in the step (2) is 5 to 50mL/s, preferably 10 to 30 mL/s.
17. The method of claim 1, wherein: the reaction temperature of the step (2) is 30-80 ℃, preferably 50-60 ℃; the stirring speed of the reaction is 50-300r/min, preferably 150-200 r/min.
18. A lignin/styrene butadiene rubber composite particle characterized by being prepared by the method of any one of claims 1 to 17.
19. The use of the lignin/styrene butadiene rubber composite particle as claimed in claim 18, wherein: mixing and vulcanizing according to a styrene butadiene rubber compound formula to obtain lignin-based styrene butadiene rubber; the formula of the styrene-butadiene rubber compound mainly comprises lignin/styrene-butadiene rubber composite solid particles, white carbon black, stearic acid, zinc oxide, N- (1, 3-dimethyl butyl) -N-phenyl p-phenylenediamine, N- (1, 1-dimethyl ethyl) -2-benzothiazole sulfenamide, bis- [ gamma- (triethoxy silicon) propyl ] tetrasulfide, N' -diphenyl guanidine, sulfur and N-cyclohexyl thiophthalimide.
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| CN103756060A (en) * | 2013-12-16 | 2014-04-30 | 华南理工大学 | Rubber composite material filled by cardanol modified lignin and preparation method thereof |
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| US3247135A (en) * | 1961-02-10 | 1966-04-19 | West Virginia Pulp & Paper Co | Lignin reinforced rubber and method of preparation thereof |
| DE1299861B (en) * | 1961-02-10 | 1969-07-24 | West Virginia Pulp & Paper Co | Reinforcing agent for natural or synthetic rubber |
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| US4306999A (en) * | 1979-11-23 | 1981-12-22 | American Can Company | High solids, low viscosity lignin solutions |
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