CN116751411B - Application of modified sepiolite in rubber - Google Patents
Application of modified sepiolite in rubber Download PDFInfo
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- CN116751411B CN116751411B CN202310838218.3A CN202310838218A CN116751411B CN 116751411 B CN116751411 B CN 116751411B CN 202310838218 A CN202310838218 A CN 202310838218A CN 116751411 B CN116751411 B CN 116751411B
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- 239000004113 Sepiolite Substances 0.000 title claims abstract description 67
- 229910052624 sepiolite Inorganic materials 0.000 title claims abstract description 67
- 235000019355 sepiolite Nutrition 0.000 title claims abstract description 67
- 229920001971 elastomer Polymers 0.000 title claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000006229 carbon black Substances 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000004513 sizing Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 229920000126 latex Polymers 0.000 claims abstract description 10
- 239000002002 slurry Substances 0.000 claims abstract description 10
- 239000004816 latex Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229960000892 attapulgite Drugs 0.000 claims abstract description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 230000003311 flocculating effect Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 23
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 10
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229920006150 hyperbranched polyester Polymers 0.000 claims description 10
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 10
- 239000003377 acid catalyst Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- JGOICJFFICGNEJ-UHFFFAOYSA-M disodium;3-[dihydroxy(oxido)silyl]propanoate Chemical compound [Na+].[Na+].O[Si](O)([O-])CCC([O-])=O JGOICJFFICGNEJ-UHFFFAOYSA-M 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 4
- 229960002447 thiram Drugs 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- FEPCMSPFPMPWJK-OLPJDRRASA-N maleopimaric acid Chemical compound C([C@]12C=C([C@H](C[C@@H]11)[C@H]3C(OC(=O)[C@@H]23)=O)C(C)C)C[C@@H]2[C@]1(C)CCC[C@@]2(C)C(O)=O FEPCMSPFPMPWJK-OLPJDRRASA-N 0.000 claims description 3
- 229920000136 polysorbate Polymers 0.000 claims description 3
- 229950008882 polysorbate Drugs 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- XTRDKALNCIHHNI-UHFFFAOYSA-N 2,6-dinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=CC=C1[N+]([O-])=O XTRDKALNCIHHNI-UHFFFAOYSA-N 0.000 claims description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 2
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 2
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 claims description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000000010 aprotic solvent Substances 0.000 claims description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 2
- -1 polyoxyethylene nonylphenol Polymers 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000256103 Simuliidae Species 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000010057 rubber processing Methods 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- GJOWSEBTWQNKPC-UHFFFAOYSA-N 3-methyloxiran-2-ol Chemical compound CC1OC1O GJOWSEBTWQNKPC-UHFFFAOYSA-N 0.000 description 1
- 206010003591 Ataxia Diseases 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000010092 rubber production Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application provides an application of modified sepiolite in rubber, and a preparation method of the rubber comprises the following steps: a) Preparing a mixed system, water and a surfactant into slurry, wherein the mixed system comprises modified sepiolite, white carbon black, attapulgite and aluminum oxide; b) Adding the slurry obtained in the step a) into natural latex, uniformly stirring to obtain a latex mixed solution, and then flocculating, washing and dehydrating to obtain a sizing material; c) Placing the sizing material prepared in the step b) into an internal mixer for first-stage mixing, and standing for 10-20h after mixing is finished until the sizing material is subjected to piece-down; d) And c), placing the substances, the vulcanizing agent and the accelerator obtained in the step c) into an internal mixer for secondary mixing to obtain the finished rubber, wherein the temperature of a roller in the secondary mixing is 30-40 ℃. The modified sepiolite disclosed by the application is applied to rubber, can improve the tensile strength and tearing strength of the rubber, and ensures that the rolling resistance of the rubber is lower and the wet land gripping performance is better.
Description
Technical Field
The application belongs to the technical field of rubber processing and production, and particularly relates to application of modified sepiolite in rubber.
Background
Rubber refers to a high elastic polymer material with reversible deformation, and is elastic at room temperature. Rubber is widely used as a basic raw material in the rubber industry for manufacturing tires, hoses, tapes, cables, and other various rubber products. The existing rubber is added with a large amount of reinforcing materials during processing to improve the mechanical strength and wear resistance of the rubber, wherein the white carbon black can not only reduce the rolling resistance and heat generation of the rubber, but also improve the tensile strength and tear strength of the rubber, has good ageing resistance and other characteristics, and is widely used as the reinforcing materials, but due to the characteristics of large specific surface area, high free energy of the surface and easiness in combining with other atoms of the white carbon black particles, the white carbon black is difficult to uniformly disperse into the rubber materials, so that the performance of the rubber is not obviously improved, and due to the fact that the specific gravity of the white carbon black is small, the white carbon black flies around in the feeding and mixing processes, and serious pollution of production environment is caused.
In order to improve the dispersibility of the white carbon black in rubber and avoid the problem that the white carbon black flies everywhere, a wet mixing technology is used for preparing water dispersion from the pre-processed white carbon black and other fillers, the water dispersion is fully mixed with rubber latex in a liquid state, and then the rubber compound is produced through the processes of coagulation, desolventizing, drying and the like.
Sepiolite is a fibrous hydrous magnesium silicate mineral. Hydroxyl groups contained on the surface of the sepiolite can be quickly swelled and dispersed when meeting water or polar solution, so that monomer fibers or smaller fiber bundles are randomly dispersed into a mutually restricted network, the specific surface area of the sepiolite after dispersion is increased, based on the characteristics, the sepiolite can be added into rubber to reduce the aggregation phenomenon of white carbon black, so that the tensile strength and tearing strength of the rubber are improved, the rolling resistance is reduced, the wet grip performance is improved, but the tensile strength, the tearing strength and the rolling resistance are improved, and the wet grip performance is still improved.
Aiming at the problem that the prior sepiolite is still added to meet the requirement on the rubber performance, how to modify the sepiolite, when the modified sepiolite is used for rubber processing, the white carbon black agglomeration phenomenon is further weakened, the tensile strength and the tearing strength of the rubber are obviously improved, the rolling resistance is reduced, and the wet land gripping performance is obviously improved, so the application is a problem to be solved urgently.
Disclosure of Invention
The application aims to provide an application of modified sepiolite in rubber, so as to solve the problems in the background art.
In order to achieve the above purpose, the present application provides the following technical solutions: the application of the modified sepiolite in rubber is characterized in that the preparation method of the rubber comprises the following steps:
a) Preparing a mixed system, water and a surfactant into slurry, wherein the mixed system comprises modified sepiolite, white carbon black, attapulgite and aluminum oxide;
b) Adding the slurry obtained in the step a) into natural latex, uniformly stirring to obtain a latex mixed solution, and then flocculating, washing and dehydrating to obtain a sizing material;
c) Placing the sizing material prepared in the step b) into an internal mixer for first-stage mixing, and standing for 10-20h after mixing is finished until the sizing material is subjected to piece-down;
d) And c), placing the substances, the vulcanizing agent and the accelerator obtained in the step c) into an internal mixer for secondary mixing to obtain the finished rubber, wherein the temperature of a roller in the secondary mixing is 30-40 ℃.
As a further improvement, the mass ratio of the mixing system, water and surfactant is (80-100): (500-1500): (0.1-1).
As a further improvement, the mass ratio of the modified sepiolite, the white carbon black, the attapulgite and the aluminum oxide is (2-10): (10-25): (1-3): (2-4).
As a further improvement, the mass ratio of the natural latex to the slurry is 100: (10-45).
As a further improvement, the preparation method of the modified sepiolite comprises the following steps:
1.1 Mixing the pretreated sepiolite and the acidic aqueous solution, and then carrying out water bath heating at the water bath heating temperature of 30-80 ℃ for 1-3 hours to obtain the acid-activated sepiolite;
1.2 Adding carboxyethyl silane triol sodium salt and an organic solvent I into the step 1.1) for reaction, wherein the reaction temperature is 80-120 ℃, the reaction time is 5-10 hours, and filtering, washing and drying are carried out after the reaction is finished to obtain silane modified sepiolite;
1.3 Adding the silane modified sepiolite and the rosin-based hyperbranched polyester prepared in the step 1.2) into a mixed solution of an organic solvent II and water, then adding an acid catalyst I and a polymerization inhibitor for reaction, wherein the reaction temperature is 110-125 ℃, removing impurities, washing and drying in vacuum to obtain the modified sepiolite.
As a further improvement, the preparation method of the rosin-based hyperbranched polyester comprises the following steps:
and (3) adding the maleopimaric acid, the glycidol and the acid catalyst II into an aprotic solvent for reaction in an inert atmosphere, continuously reacting for 0.5h-5h under the vacuum degree of 0.1-100kPa after the reaction temperature is 100-150 ℃ and the acid value is lower than 10mg/g, and obtaining the rosin-based hyperbranched polyester after precipitation, filtration, separation and drying.
As a further improvement, the preparation method of the pretreated sepiolite comprises the following steps:
fully mixing the ground sepiolite with water, standing for 10-20h, taking an upper sepiolite suspension, carrying out suction filtration, washing and drying to obtain the pretreated sepiolite, wherein the weight ratio of the ground sepiolite to the water is 1:50-70.
As a further improvement, the polymerization inhibitor is at least one of hydroquinone, p-hydroxyanisole, p-tert-butylcatechol and 2, 6-dinitrotoluene; the acid catalyst I and the acid catalyst II are at least one of sulfuric acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid.
As a further improvement, the surfactant is at least one of sodium dodecyl benzene sulfonate, polyoxyethylene nonylphenol ether and polysorbate.
As a further improvement, the vulcanizing agent is at least one of vulcanized resin and sulfur; the accelerator is at least one of thiuram accelerator and thiazole accelerator.
As a further improvement, the thiuram accelerator is at least one of tetramethyl thiuram disulfide and tetraethyl thiuram disulfide.
As a further improvement, the thiazole accelerator is at least one of accelerator M and accelerator DM.
Compared with the prior art, the application has the beneficial effects that: the modified sepiolite provided by the application enhances the reinforcing capability of the white carbon black, reduces the agglomeration phenomenon of the white carbon black, can improve the tensile strength and the tearing strength of rubber when applied to the rubber, and has lower rolling resistance and better wet land gripping performance.
Detailed Description
The application will be described below in connection with specific embodiments. The following examples are illustrative of the present application and are not intended to limit the present application. Other combinations and various modifications within the spirit of the application may be made without departing from the spirit or scope of the application.
In the following examples, except for rosin-based hyperbranched polyesters, modified sepiolite, commercially available from Hebei Jiegui mineral products Co., ltd, under the product number 0077-41, were used as the compound monomers and the related reagents; carboxyethyl silanetriol sodium salt was purchased from Jin Jinle chemical company, inc; sodium dodecyl benzene sulfonate was purchased from ataxia source baolai chemical technology limited; polysorbate was purchased from shandong homoblue chemical company, model t60; natural latex was purchased from Shenzhen Jitian chemical Co.
The preparation method of the rosin-based hyperbranched polyester comprises the following steps:
under inert atmosphere, adding 10g of maleopimaric acid, 3.7g of epoxy propanol and 0.1g of p-toluenesulfonic acid into 50g of N, N-dimethylacetamide for reaction, wherein the reaction temperature is 120 ℃, the acid value is lower than 10mg/g, continuing to react for 2 hours under the vacuum degree of 100kPa, cooling, precipitating with a large amount of deionized water, filtering, washing and vacuum drying (the drying temperature is 60 ℃), thus obtaining the rosin-based hyperbranched polyester.
The preparation of the pretreated sepiolite comprises the following steps:
fully mixing the ground sepiolite (the particle size of the sepiolite is 1mm after grinding by a ball mill) with water (wherein the weight of the sepiolite after grinding is 20g, the volume ratio of the water is 1000mL, the stirring speed is 80r/min when fully mixing, the stirring time is 1 h), standing for 18h, taking the upper sepiolite suspension, carrying out suction filtration, washing by distilled water, and carrying out vacuum drying for 20h to obtain pretreated sepiolite;
the preparation of the modified sepiolite comprises the following steps:
1.1 Mixing the prepared 15g of pretreated sepiolite with 300g of hydrochloric acid aqueous solution (the concentration of the hydrochloric acid aqueous solution is 2 mol/L), and then carrying out water bath heating, wherein the water bath heating temperature is 60 ℃, the water bath heating time is 2 hours, and the heating is completed to prepare the acid-activated sepiolite;
1.2 Adding 50g of carboxyethyl silane triol sodium salt and 300mL of absolute ethyl alcohol into the step 1.1) for reaction, wherein the reaction temperature is 80 ℃, the reaction time is 10 hours, and after the reaction is finished, filtering, washing with chloroform, washing with ethanol in sequence and vacuum drying at 60 ℃ for 24 hours to prepare silane modified sepiolite;
1.3 10g of silane-modified sepiolite and 15g of rosin-based hyperbranched polyester obtained in the step 1.2) are added into a mixed solution of 50g of toluene and water (wherein the weight ratio of toluene to water is 1:0.2), then 0.15g of concentrated sulfuric acid with the mass fraction of 98% and 0.3g of hydroquinone are added for reaction, the reaction temperature is 115 ℃, after the reaction is carried out for 8 hours, toluene is removed by reduced pressure distillation, and 15% of Na is used by mass fraction 2 CO 3 Neutralizing sulfuric acid with water solution, washing with water until pH is neutral, and drying the product in a vacuum oven at 70 ℃ to obtain the modified sepiolite.
The preparation of the mixed systems 1-7 comprises the following steps:
the components and the contents required by the mixed system are respectively weighed and evenly mixed, the evenly mixed stirring speed is 60r/min, and the stirring time is 10min.
In the mixed systems 1-7, the required components and the content of each component are shown in tables 1-2:
TABLE 1
TABLE 2
| Component (g) | Mixed system 5 | Mixed system 6 | Mixed system 7 |
| Modified sepiolite | 3 | / | / |
| Sepiolite | / | 3 | / |
| White carbon black | 20 | 20 | 20 |
| Attapulgite | 4 | 2 | 2 |
| Aluminum oxide | 3 | 3 | 3 |
The rubber of examples 1-6 and comparative examples 1-2 was prepared as follows:
a) Preparing a slurry from the mixed system, water and a surfactant, wherein the stirring speed is 60r/min and the stirring time is 20min;
b) Adding the slurry obtained in the step a) into natural latex, stirring uniformly to obtain a latex mixed solution (stirring speed is 60r/min, stirring time is 30 min), then adding acetic acid into the latex mixed solution to enable the pH value of the mixed solution to be 4, uniformly flocculating the latex, rolling the coagulated latex for three times by a latex washer, and washing and dehydrating the latex by tap water;
c) Placing the sizing material prepared in the step b) into an internal mixer for first-stage mixing, wherein the rotating speed during mixing is 50r/min, so that the components in the sizing material are uniformly mixed, and standing for 15h after mixing is finished until the sizing material is subjected to piece-down;
d) And c), placing the substances, the vulcanizing agent and the accelerator obtained in the step c) into an internal mixer for secondary mixing to obtain the finished rubber, wherein the temperature of a roller during secondary mixing is 40 ℃.
The required components and the contents of the components in examples 1 to 6 and comparative examples 1 to 2 are shown in tables 3 to 4:
TABLE 3 Table 3
TABLE 4 Table 4
Tensile strength, tear strength test: according to GB/T528 2009;
dynamic performance test: dynamic Mechanical Analyzer (DMA) was a VR-7120 dynamic thermo-mechanical analyzer (manufactured by UESHIMA corporation, japan) for measuring dynamic properties of vulcanized rubber under the following conditions: a stretch mode; frequency, 12Hz; static strain 7%, dynamic strain 0.25%; temperature rise, 2 ℃/min, tan delta value of 0 ℃ represents the wet grip performance of the vulcanized rubber, the higher the tan delta value is, the better the wet grip performance is, tan delta value of 60 ℃ represents the rolling resistance of the vulcanized rubber, and the lower the tan delta value is, the lower the rolling resistance is;
hardness testing: the hardness at room temperature was measured according to GB/T531.1-2008.
The results are shown in tables 5-6:
TABLE 5
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Tensile Strength (MPa) | 37.5 | 38.1 | 36.9 | 37.3 |
| Tear strength (kN) | 116 | 112 | 120 | 115 |
| Hardness (shore A) | 58 | 57 | 59 | 58 |
| 0℃tanδ | 0.478 | 0.481 | 0.476 | 0.482 |
| 60℃tanδ | 0.058 | 0.059 | 0.061 | 0.058 |
TABLE 6
| Example 5 | Example 6 | Comparative example 1 | Comparative example 2 | |
| Tensile Strength (MPa) | 29.3 | 28.9 | 27.9 | 21.4 |
| Tear strength (Kg/m) | 110 | 108 | 100 | 85 |
| Hardness (23 ℃ C.) | 65 | 64 | 68 | 72 |
| 0℃tanδ | 0.421 | 0.418 | 0.384 | 0.351 |
| 60℃tanδ | 0.120 | 0.124 | 0.153 | 0.231 |
As can be seen from the comparison of the example 1 and the comparative examples 1-2, the rubber prepared by using the modified sepiolite has better tensile strength, tearing strength and hardness, lower rolling resistance and better wet grip performance;
as can be seen from comparison of examples 1 and examples 5-6, the mass ratio of the modified sepiolite, the white carbon black, the attapulgite and the aluminum oxide of the mixed system is in a proper range, so that the tensile strength, the tearing strength and the hardness of the rubber are further improved, the rolling resistance is lower, and the wet land gripping performance is better;
as can be seen from comparison of examples 1-4, the rubber prepared by the preparation method provided by the application has good tensile strength, tear strength and hardness, lower rolling resistance and better wet grip performance;
in conclusion, the modified sepiolite provided by the application enhances the reinforcing capability of the white carbon black, weakens the aggregation phenomenon of the white carbon black, can improve the tensile strength and the tearing strength of rubber when applied to the rubber, and ensures that the rolling resistance of the rubber is lower and the wet land gripping performance is better.
The above embodiments are only for illustrating the technical concept and features of the present application, and are intended to enable those skilled in the art to understand the present application and to implement it, but not limit the scope of the present application, and all equivalent changes or modifications made according to the spirit of the present application should be included in the scope of the present application.
Claims (7)
1. The application of the modified sepiolite in rubber is characterized in that: the preparation method of the rubber comprises the following steps:
a) Preparing a mixed system, water and a surfactant into slurry, wherein the mixed system comprises modified sepiolite, white carbon black, attapulgite and aluminum oxide;
b) Adding the slurry obtained in the step a) into natural latex, uniformly stirring to obtain a latex mixed solution, and then flocculating, washing and dehydrating to obtain a sizing material;
c) Placing the sizing material prepared in the step b) into an internal mixer for first-stage mixing, and standing for 10-20h after mixing is finished until the sizing material is subjected to piece-down;
d) Placing the substances, the vulcanizing agent and the accelerator obtained in the step c) into an internal mixer for second-stage mixing to obtain finished rubber, wherein the temperature of a roller in the second-stage mixing is 30-40 ℃;
the preparation method of the modified sepiolite comprises the following steps:
1.1 Mixing the pretreated sepiolite and the acidic aqueous solution, and then carrying out water bath heating at the water bath heating temperature of 30-80 ℃ for 1-3 hours to obtain the acid-activated sepiolite;
1.2 Adding carboxyethyl silane triol sodium salt and an organic solvent I into the step 1.1) for reaction, wherein the reaction temperature is 80-120 ℃, the reaction time is 5-10 hours, and filtering, washing and drying are carried out after the reaction is finished to obtain silane modified sepiolite;
1.3 Adding the silane modified sepiolite and the rosin-based hyperbranched polyester prepared in the step 1.2) into a mixed solution of an organic solvent II and water, then adding an acid catalyst I and a polymerization inhibitor for reaction, wherein the reaction temperature is 110-125 ℃, removing impurities, washing and vacuum drying to obtain the modified sepiolite;
the preparation method of the rosin-based hyperbranched polyester comprises the following steps:
adding maleopimaric acid, glycidol and an acid catalyst II into an aprotic solvent for reaction in an inert atmosphere, after the reaction temperature is 100-150 ℃ and the acid value is lower than 10mg/g, continuing to react for 0.5-5 h under the vacuum degree of 0.1-100kPa, and after the reaction is finished, precipitating, filtering, separating and drying to obtain rosin-based hyperbranched polyester;
the preparation method of the pretreated sepiolite comprises the following steps:
fully mixing the ground sepiolite with water, standing for 10-20h, taking an upper sepiolite suspension, carrying out suction filtration, washing and drying to obtain the pretreated sepiolite, wherein the weight ratio of the ground sepiolite to the water is 1:50-70.
2. The use of a modified sepiolite in rubber according to claim 1, characterized in that: the mass ratio of the mixed system to the water to the surfactant is (80-100): (500-1500): (0.1-1).
3. The use of a modified sepiolite in rubber according to claim 1, characterized in that: the mass ratio of the modified sepiolite to the white carbon black to the attapulgite to the aluminum oxide is (2-10): (10-25): (1-3): (2-4).
4. The use of a modified sepiolite in rubber according to claim 1, characterized in that: the mass ratio of the natural latex to the slurry is 100: (10-45).
5. The use of a modified sepiolite in rubber according to claim 1, characterized in that: the polymerization inhibitor is at least one of hydroquinone, p-hydroxyanisole, p-tert-butyl catechol and 2, 6-dinitrotoluene; the acid catalyst I and the acid catalyst II are at least one of sulfuric acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid.
6. The use of a modified sepiolite in rubber according to claim 1, characterized in that: the surfactant is at least one of sodium dodecyl benzene sulfonate, polyoxyethylene nonylphenol ether and polysorbate.
7. Use of a modified sepiolite according to claim 1 or 6 in rubber, characterized in that: the vulcanizing agent is at least one of vulcanized resin and sulfur; the accelerator is at least one of thiuram accelerator and thiazole accelerator.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11246707A (en) * | 1998-03-04 | 1999-09-14 | Yokohama Rubber Co Ltd:The | Tread rubber composition for studless tire |
| JP2001072802A (en) * | 1999-09-08 | 2001-03-21 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
| JP5092058B1 (en) * | 2011-06-21 | 2012-12-05 | 住友ゴム工業株式会社 | Rubber composition for tire installation and tire using the same |
| CN108192155A (en) * | 2016-12-08 | 2018-06-22 | 北京橡胶工业研究设计院有限公司 | For the graphene native rubber composite material and preparation method of conveyer belt coating rubber |
| CN113429806A (en) * | 2021-07-03 | 2021-09-24 | 江苏爱特恩高分子材料有限公司 | Preparation method of high-dispersion modified white carbon black for rubber filler |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES482033A1 (en) * | 1979-06-28 | 1980-04-01 | Tolsa Sa | Process for obtaining silane derivatives of sepiolite by reaction with alkoxy-silanes to improve their reinforcing capacity in polymers |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11246707A (en) * | 1998-03-04 | 1999-09-14 | Yokohama Rubber Co Ltd:The | Tread rubber composition for studless tire |
| JP2001072802A (en) * | 1999-09-08 | 2001-03-21 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
| JP5092058B1 (en) * | 2011-06-21 | 2012-12-05 | 住友ゴム工業株式会社 | Rubber composition for tire installation and tire using the same |
| CN108192155A (en) * | 2016-12-08 | 2018-06-22 | 北京橡胶工业研究设计院有限公司 | For the graphene native rubber composite material and preparation method of conveyer belt coating rubber |
| CN113429806A (en) * | 2021-07-03 | 2021-09-24 | 江苏爱特恩高分子材料有限公司 | Preparation method of high-dispersion modified white carbon black for rubber filler |
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