CN116640370A - Grafting modified natural rubber, preparation method and rubber composition containing grafting modified natural rubber - Google Patents
Grafting modified natural rubber, preparation method and rubber composition containing grafting modified natural rubber Download PDFInfo
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- CN116640370A CN116640370A CN202310412530.6A CN202310412530A CN116640370A CN 116640370 A CN116640370 A CN 116640370A CN 202310412530 A CN202310412530 A CN 202310412530A CN 116640370 A CN116640370 A CN 116640370A
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- 244000043261 Hevea brasiliensis Species 0.000 title claims abstract description 124
- 229920003052 natural elastomer Polymers 0.000 title claims abstract description 123
- 229920001194 natural rubber Polymers 0.000 title claims abstract description 123
- 229920001971 elastomer Polymers 0.000 title claims abstract description 93
- 239000005060 rubber Substances 0.000 title claims abstract description 91
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000006229 carbon black Substances 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 14
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 14
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 7
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 238000004073 vulcanization Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 18
- 229920006173 natural rubber latex Polymers 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- FLVLHHSRQUTOJM-UHFFFAOYSA-M sodium;2-methylpropoxymethanedithioate Chemical compound [Na+].CC(C)COC([S-])=S FLVLHHSRQUTOJM-UHFFFAOYSA-M 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- MKIJJIMOAABWGF-UHFFFAOYSA-N methyl 2-sulfanylacetate Chemical compound COC(=O)CS MKIJJIMOAABWGF-UHFFFAOYSA-N 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 6
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 claims description 4
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 claims description 4
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 claims description 2
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012190 activator Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 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 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims 1
- 230000003078 antioxidant effect Effects 0.000 claims 1
- 239000004636 vulcanized rubber Substances 0.000 abstract description 15
- 239000000243 solution Substances 0.000 description 25
- 239000003921 oil Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 12
- 238000005299 abrasion Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 230000008961 swelling Effects 0.000 description 8
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229920000126 latex Polymers 0.000 description 5
- 239000004816 latex Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 241000221020 Hevea Species 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 230000020169 heat generation Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- PVBRSNZAOAJRKO-UHFFFAOYSA-N ethyl 2-sulfanylacetate Chemical compound CCOC(=O)CS PVBRSNZAOAJRKO-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 238000012784 weak cation exchange Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- 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
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
-
- 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)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a grafting modified natural rubber, a preparation method and a rubber composition containing the grafting modified natural rubber, wherein the composition contains 40-60 parts of grafting modified natural rubber, 2-3 parts of vulcanizing agent, 1-3 parts of nano kaolin, 0.1-2 parts of vulcanizing auxiliary agent, 2-4 parts of activating agent, 0.5-2 parts of anti-aging agent and 2-3 parts of surface modified white carbon black, and vulcanized rubber prepared from the composition has good air tightness, wear resistance and oil resistance.
Description
Technical Field
The invention relates to the technical field of rubber, in particular to a grafted modified natural rubber, a preparation method thereof and a rubber composition containing the grafted modified natural rubber.
Background
The rubber is a high-elasticity polymer material with reversible deformation, and is divided into natural rubber and synthetic rubber.
The natural rubber is mainly derived from Hevea rubber, when the skin of the Hevea rubber is cut, milky juice is discharged, the milky juice is called latex, and the latex is coagulated, washed, molded and dried to obtain the natural rubber. The synthetic rubber is prepared by an artificial synthesis method, and different types of rubber such as styrene-butadiene rubber, nitrile rubber, butadiene rubber, isoprene rubber, chloroprene rubber and the like can be synthesized by adopting different monomer raw materials.
The natural rubber can be classified into standard rubber, smoke film, concentrated rubber, light-colored film, clear rubber, air-dried film and the like, is a renewable natural green raw material, is prepared from rubber tree collected latex, is a polymer of isoprene, and has good wear resistance, high elasticity, breaking strength and elongation.
The excellent performance of the natural rubber can lead the natural rubber to be widely applied to petroleum exploitation, mine drilling, medical treatment, sanitation, aerospace, national defense, military industry and precise instruments, and even high-precision products such as large computers, large ion pair impact and the like.
The slurry conveying equipment of the rubber material and metal auxiliary is widely applied to oil exploitation and mine drilling. Rubber materials are extremely easy to cause the phenomena of degumming, tearing, blending and the like due to the friction and swelling effects in the application process. The service life of the auxiliary is directly influenced by the failure of the rubber, and the abrasion mechanism of the rubber and the swelling of the rubber under the crude oil medium are in close relation.
The oil resistance of rubber generally refers to the ability to resist the action of nonpolar oils, which generally attack elastomers in two ways, on the one hand, the oils can be immersed in the structure of the polymer chains of the elastomer, causing swelling phenomena thereof, so that the overall properties are reduced; on the other hand, part of soluble compounding agent in the vulcanized rubber sample can be extracted by oil, so that the uniformity of the dispersion of the filler in the original vulcanized rubber is influenced, the cross-linked structure of the filler is destroyed, and the performance of rubber is further influenced.
However, since a great number of irregular reactive double bonds exist on the main chain of the natural rubber, the thermal oxygen stability is seriously affected, and meanwhile, the oil resistance has inherent defects due to the influence of the nonpolar structure, so that the application of the natural rubber is limited.
The existing chemical modification method of natural rubber comprises cyclization modification, epoxidation modification, hydrogenation modification, chlorination modification, graft copolymerization and the like. The method for chemically modifying the oil resistance of the natural rubber mainly comprises epoxidation modification and graft copolymerization modification, but the epoxidation modified natural rubber still faces the technical problems of easy ring opening and more byproducts, and the traditional graft copolymerization can be accompanied with side reactions such as macromolecular degradation and crosslinking of the natural rubber.
CN 104854136A discloses a method for producing a modified natural rubber, which is a highly purified, modified natural rubber having a pH adjusted to 2 to 7, by removing impurities other than natural polyisoprenoid components, such as phospholipids and proteins, in which the isoprenoid component is covered with the above impurity components, and if the impurity components are removed, the structure of the isoprenoid component is changed so that its interaction with a compounding agent is changed to reduce energy loss or improve durability. However, the step of washing the coagulated rubber, which is an acidic compound used in the process, is troublesome, and it is necessary to repeatedly wash it about 10 times to adjust the pH to a desired level.
CN 110938174A discloses a graft modified natural rubber, which is obtained by graft polymerizing natural rubber with acrylate monomers, and is applied to pneumatic tires, abrasion and heat generation are improved, the side wall can inhibit flex crack, the apex and the supporting rubber can improve hardness and stretching stress, the physical properties and processability are kept unchanged, the consumption of inorganic filler is reduced, the heat generation of the prepared tire is low, but the inventor only researches the abrasion heat generation problem, and does not do related oil resistance study.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention aims to solve the problem of poor oil resistance of natural rubber.
In order to achieve the above purpose, the invention provides a grafted modified natural rubber, a preparation method thereof and a rubber composition containing the grafted modified natural rubber, and vulcanized rubber prepared from the rubber composition has good air tightness, wear resistance and oil resistance.
The preparation method of the graft modified natural rubber comprises the following steps:
(1) Pre-emulsified natural rubber: diluting natural rubber latex with water, adding sodium dodecyl sulfate, stirring at normal temperature, and then opening a nitrogen valve to introduce nitrogen to obtain pre-emulsified natural rubber;
(2) Preparation of graft modified natural rubber: dissolving methyl thioglycolate in ammonia water to obtain a solution L1; dissolving 2, 2-dimethylolpropionic acid with N-methylpyrrolidone to obtain a solution L2; adding the L1 and L2 solutions into the pre-emulsified natural rubber in sequence, and then placing the pre-emulsified natural rubber in a photochemical reactor, wherein N is 2 Stirring at normal temperature under atmosphere, and irradiating with ultraviolet lamp; washing the precipitated gel with ethanol, and washing the precipitated gel with CHCl 3 Recrystallizing to obtain a rubber sample, and drying the rubber sample to obtain the grafted modified natural rubber.
Further, the mass ratio of the water to the natural rubber latex is 5-10:1.
further, the sodium dodecyl sulfate accounts for 3-10% of the mass of the natural rubber latex.
Further, the mass volume ratio of the natural rubber latex to the ammonia water is 2-4: 1g/mL; the concentration of the ammonia water is 26-30wt% of the commercial ammonia water.
Further, the addition amount of the ethyl thioglycolate is 10-90% of the mass of the natural rubber latex.
Further, the addition amount of the 2, 2-dimethylolpropionic acid is 0.5 to 2 percent of the mass of the natural rubber latex.
Further, the mass ratio of the N-methyl pyrrolidone to the 2, 2-dimethylolpropionic acid is 10-15:1.
further, the ultraviolet lamp irradiates for 10-35min under the ultraviolet lamp with the wavelength of 300-400 nm, and the irradiation distance is 30-50 cm.
The grafting rate of the grafted modified natural rubber obtained by the invention is 10-70%, and the grafting efficiency is 45-95%.
The invention also provides a rubber composition containing the grafted modified natural rubber, which comprises the following components in parts by mass: 40-60 parts of the grafted modified natural rubber, 2-3 parts of vulcanizing agent, 3-6 parts of nano kaolin, 0.1-2 parts of vulcanizing auxiliary agent, 2-4 parts of activating agent, 0.5-2 parts of anti-aging agent and 2-3 parts of white carbon black.
The vulcanizing agent is one or two or more of dicumyl peroxide, sulfur and sodium isobutyl xanthate; the preferred vulcanizing agent is sodium isobutyl xanthate.
The vulcanization aid is zinc dimethyl dithiocarbamate, tetraethylthiuram disulfide, zinc dibutyl dithiocarbamate and N-tertiary butyl-2-benzothiazole sulfenamide; the preferred vulcanization aid is zinc dibutyl dithiocarbamate.
The activator is zinc oxide.
The anti-aging agent is one or two or more of N-phenyl-alpha-naphthylamine, N-phenyl-beta-naphthylamine, 2, 6-di-tert-butyl-p-cresol, styrenated phenol, 4-methyl-6-tert-butylphenol, 2, 5-di-tert-butylhydroquinone and p-phenylenediamine; the preferred anti-aging agent is p-phenylenediamine.
The preparation method of the white carbon black is characterized in that the white carbon black is surface modified white carbon black, and the preparation method comprises the following steps: placing silicon dioxide in a drying oven at 70-100 ℃ for drying for 1-3 hours; weighing 20-40 g of dry silicon dioxide and 3-8 g of ammonium cerium nitrate; 700-900 mL of N, N-dimethylformamide is added; heating the solution to 50-80 ℃ and reacting for 1-2 hours; adding 30-40 g of solid NaOH; cooling the solution to 30-40 ℃, stirring for 0.5-1 hour, and then dripping 60-80 g CS into the solution 2 The method comprises the steps of carrying out a first treatment on the surface of the And (3) preserving heat for 3-4 hours after the dripping is finished, filtering, and placing the filter cake in a vacuum drying oven at 40-50 ℃ for drying for 20-24 hours to obtain the modified white carbon black.
The invention also provides a preparation method of the rubber composition containing the grafted modified natural rubber, which comprises the following steps of:
s1, weighing 40-60 parts of grafted modified natural rubber, 3-6 parts of nano kaolin and 2-3 parts of surface modified carbon black, and mixing to obtain a mixed rubber sample;
s2, placing the rubber compound sample for 12-18 hours, and using a vulcanizing instrument to make a torque-time curve of the rubber compound, and determining vulcanizing time and corresponding vulcanizing temperature by using the curve;
s3, placing the mixed rubber sample obtained in the step S1 into a mould, adding 2-3 parts of vulcanizing agent, 0.1-2 parts of vulcanizing auxiliary agent, 2-4 parts of activating agent and 0.5-2 parts of anti-aging agent, and carrying out vulcanization reaction by using a vulcanizing machine to obtain the rubber composition of the grafted modified natural rubber after vulcanization is finished.
Further, the vulcanization temperature in the step S3 is 140-160 ℃, and the vulcanization time is t 90 +3min; the preferred curing time is 150℃and 15 minutes.
The following are some of the raw materials used in the present invention:
natural rubber: mainly from Hevea rubber, when the skin of the Hevea rubber is cut, milky juice is discharged, namely latex, and the latex is coagulated, washed, molded and dried to obtain the natural rubber. More than 90% of the natural rubber consists of cis-1, 4-polyisoprene, and the content of other non-rubber substances is less than 10%. The natural rubber has the relative density of 0.94, the refractive index of 1.522, the elastic modulus of 2-4 MPa, the softening at 130-140 ℃, the degradation at 200 ℃, and after sulfur vulcanization, the natural rubber has better elasticity, slightly plasticity, small hysteresis loss and low dynamic heat generation at normal temperature.
Nano kaolin: the white flake crystalline powder is slightly soluble in hydrochloric acid and cool acid at normal temperature, is easy to disperse in water or other liquid, and has good covering performance and high whiteness. Has good plasticity and high cohesiveness, excellent electrical insulation, strong ion adsorption and weak cation exchange.
White carbon black: namely amorphous silicon dioxide, also called hydrated silicon dioxide, the molecular structure is SiO 2 ·nH 2 O is white, nontoxic and amorphous powder, has excellent performances of porosity, light weight, good chemical stability, high temperature resistance, no combustion, good insulativity and the like, and white carbon black is divided into two types of white carbon black by a gas phase method and precipitated white carbon black by different preparation methods. The particle diameter of the weather white carbon black is small, about 15-25 nm, and the specific surface area is as high as 50-400 m 2 And/g, less impurity. Precipitated white carbon black particlesThe diameter is relatively large, about 20-40 nm, the impurities are more, and the white carbon black forms primary aggregates and secondary aggregates due to the large surface cohesive energy.
The invention has the beneficial effects that:
(1) The invention provides a preparation method of graft modified natural rubber latex, which introduces polar ester groups on double bonds of a main chain of natural rubber, and successfully improves the oil resistance of the natural rubber.
(2) The invention adopts surface grafting to carry out surface modification treatment on the white carbon black, reduces the surface polarity of the white carbon black, and improves the dispersion of the white carbon black in the rubber matrix and the compatibility of the white carbon black with the rubber matrix.
(3) The vulcanized rubber of the rubber composition prepared by the invention has good air tightness, wear resistance and oil resistance.
Detailed Description
The invention will be described in further detail with reference to specific examples. The procedures, conditions, experimental methods, etc. for carrying out the present invention are common general knowledge and knowledge in the art, except for the following specific references, and the present invention is not particularly limited.
The sources of some of the raw materials in the examples of the present invention are as follows, and the raw materials used in the examples are all available from conventional commercial sources or can be prepared by conventional methods unless specifically indicated otherwise:
the natural rubber was purchased from Hainan natural rubber industry group Co., ltd., and was used at a concentration of 60%.
The nano kaolin is calcined kaolin, and is purchased from construction materials processing Co., ltd. In Lingshou county, the whiteness is 98%, and the specification is 6000 meshes.
Sodium isobutyl orthoxanthate, purchased from Hubei Jiujingsu Feng Longhua, inc., purity 99%, product number 00084.
Silica, commercially available from Zhengzhou Yuand food additives Inc., 99.9% content, model number food grade.
Zinc oxide, purchased from wuhanji chemical industry limited, has an active substance content of 99% and a pH of 7-9.
P-phenylenediamine, purchased from Jinan Yuno chemical Co., ltd, has a content of 98% and is of industrial grade.
The grafting rate and the grafting efficiency of the grafting modified natural rubber are measured as follows: the graft copolymer (M1) with a certain mass is weighed and put in a rope extractor, and is extracted for 24 hours by petroleum ether and acetone respectively, and is dried to constant weight in vacuum. The calculation formulas of the grafting ratio (G) and the Grafting Efficiency (GE) are respectively grafting ratio (G) = (M1-W)/W multiplied by 100%; grafting Efficiency (GE) = (M1-W)/mx100%; m1: the weight g of the residue after final extraction; w is the dry basis weight g of the natural rubber; m: and g, charging the mass g of methyl thioglycolate monomer.
Example 1:
a natural rubber composition is prepared by the following steps:
s1, weighing 100g of natural rubber, 10g of kaolin and 5g of white carbon black, and mixing in a double-roll open mill to obtain a rubber compound sample;
s2, placing the mixed rubber sample obtained in the step S1 for 15 hours, placing the mixed rubber sample in a mold with the thickness of 1mm, adding 4g of sodium isobutyl xanthate, 1g of zinc dibutyl dithiocarbamate, 5g of zinc oxide and 1g of p-phenylenediamine, and carrying out vulcanization reaction by using a flat vulcanizing machine, wherein the vulcanization temperature is 150 ℃, the vulcanization time is 15 minutes, and obtaining the rubber composition of the natural rubber after the vulcanization is finished.
Example 2
A composition comprising a graft modified natural rubber, which is prepared by the process comprising:
s1, weighing 100g of graft modified natural rubber, 10g of kaolin and 5g of white carbon black, and mixing in a double-roll open mill to obtain a rubber compound sample;
s2, placing the mixed rubber sample obtained in the step S1 for 15 hours, placing the mixed rubber sample in a mold with the thickness of 1mm, adding 4g of sodium isobutyl xanthate, 1g of zinc dibutyl dithiocarbamate, 5g of zinc oxide and 1g of p-phenylenediamine, and carrying out vulcanization reaction by using a flat vulcanizing machine at the vulcanization temperature of 150 ℃ for 15 minutes to obtain the rubber composition containing the grafted modified natural rubber after the vulcanization is finished.
The preparation method of the grafted modified natural rubber comprises the following steps:
(1) Pre-emulsified natural rubber: placing 100g of natural rubber latex in a container, adding 600g of deionized water for dilution, then adding 10g of sodium dodecyl sulfate into the container, stirring for 10min at normal temperature, opening a nitrogen valve, and introducing for 10min to obtain pre-emulsified natural rubber;
(2) Preparation of graft modified natural rubber: 50g of methyl thioglycolate was dissolved in a beaker with 30mL of commercially available 27wt% ammonia water under stirring to give a solution L1, 2g of 2, 2-dimethylolpropionic acid was dissolved in a centrifuge tube with 20-g N-methylpyrrolidone to give a solution L2, the L1 and L2 solutions were sequentially added to a pre-emulsified natural rubber, the vessel was placed in a photochemical reactor, and N 2 Stirring at 30 ℃ under the atmosphere, and finishing the reaction after irradiating for 30min by an ultraviolet lamp; the irradiation wavelength of the ultraviolet lamp is 365nm; washing the precipitated gel with 300mL of ethanol, and washing the precipitated gel with 500mL of CHCl 3 Recrystallizing to obtain a rubber sample, and drying the rubber sample in a vacuum drying oven at 50 ℃ for 24 hours to obtain grafted modified natural rubber; the grafting rate of the grafting modified natural rubber is 55%, and the grafting efficiency is 75%.
Example 3:
a composition comprising a graft modified natural rubber, which is prepared by the process comprising:
s1, weighing 100g of grafted modified natural rubber, 10g of nano kaolin and 5g of white carbon black, and mixing in a double-roll open mill to obtain a rubber compound sample;
s2, placing the mixed rubber sample obtained in the step S1 for 15 hours, placing the mixed rubber sample in a mold with the thickness of 1mm, adding 4g of sodium isobutyl xanthate, 1g of zinc dibutyl dithiocarbamate, 5g of zinc oxide and 1g of p-phenylenediamine, and carrying out vulcanization reaction by using a flat vulcanizing machine at the vulcanization temperature of 150 ℃ for 15 minutes to obtain the rubber composition containing the grafted modified natural rubber after the vulcanization is finished.
The preparation method of the grafted modified natural rubber comprises the following steps:
(1) Pre-emulsified natural rubber: placing 100g of natural rubber latex in a container, adding 600g of deionized water for dilution, then adding 10g of sodium dodecyl sulfate into the container, stirring for 10min at normal temperature, opening a nitrogen valve, and introducing for 10min to obtain pre-emulsified natural rubber;
(2) Preparation of graft modified natural rubber: 50g of methyl thioglycolate was dissolved in a beaker with 30mL of commercially available 27wt% ammonia water under stirring to give a solution L1, 2g of 2, 2-dimethylolpropionic acid was dissolved in a centrifuge tube with 20-g N-methylpyrrolidone to give a solution L2, the L1 and L2 solutions were sequentially added to a pre-emulsified natural rubber, the vessel was placed in a photochemical reactor, and N 2 Stirring at 30 ℃ under the atmosphere, and finishing the reaction after irradiating for 30min by an ultraviolet lamp; the irradiation wavelength of the ultraviolet lamp is 365nm; washing the precipitated gel with 300mL of ethanol, and washing the precipitated gel with 500mL of CHCl 3 Recrystallizing to obtain a rubber sample, and drying the rubber sample in a vacuum drying oven at 50 ℃ for 24 hours to obtain grafted modified natural rubber; the grafting rate of the grafting modified natural rubber is 55%, and the grafting efficiency is 75%.
Example 4
A composition comprising a graft modified natural rubber, which is prepared by the process comprising:
s1, weighing 100g of graft modified natural rubber, 10g of kaolin and 5g of surface modified white carbon black, and mixing in a double-roll open mill to obtain a rubber compound sample;
s2, placing the mixed rubber sample obtained in the step S1 for 15 hours, placing the mixed rubber sample in a mold with the thickness of 1mm, adding 4g of sodium isobutyl xanthate, 1g of zinc dibutyl dithiocarbamate, 5g of zinc oxide and 1g of p-phenylenediamine, and carrying out vulcanization reaction by using a flat vulcanizing machine at the vulcanization temperature of 150 ℃ for 15 minutes to obtain the rubber composition containing the grafted modified natural rubber after the vulcanization is finished.
The preparation method of the grafted modified natural rubber comprises the following steps:
(1) Pre-emulsified natural rubber: placing 100g of natural rubber latex in a container, adding 600g of deionized water for dilution, then adding 10g of sodium dodecyl sulfate into the container, stirring for 10min at normal temperature, opening a nitrogen valve, and introducing for 10min to obtain pre-emulsified natural rubber;
(2) Preparation of graft modified natural rubber: 50g of methyl thioglycolate was dissolved in a beaker with 30mL of commercially available 27wt% aqueous ammonia to give solution L1, and the solution was dissolved with stirringDissolving 2g of 2, 2-dimethylolpropionic acid with 20-g N-methylpyrrolidone in a centrifuge tube to obtain a solution L2, sequentially adding the L1 and L2 solutions into pre-emulsified natural rubber, placing the container in a photochemical reactor, and adding N 2 Stirring at 30 ℃ under the atmosphere, and finishing the reaction after irradiating for 30min by an ultraviolet lamp; the irradiation wavelength of the ultraviolet lamp is 365nm; washing the precipitated gel with 300mL of ethanol, and washing the precipitated gel with 500mL of CHCl 3 Recrystallizing to obtain a rubber sample, and drying the rubber sample in a vacuum drying oven at 50 ℃ for 24 hours to obtain grafted modified natural rubber; the grafting rate of the grafting modified natural rubber is 55%, and the grafting efficiency is 75%.
The preparation method of the surface modified white carbon black comprises the following steps: drying the silicon dioxide in a drying oven at 80 ℃ for 2 hours; 30g of dry silica and 5g of ammonium cerium nitrate are weighed; 750mL of N, N-dimethylformamide was added; heating the solution to 60 ℃ and reacting for 1 hour; 40g of solid NaOH was added; the solution was cooled to 35℃and stirred for 0.5 hour, after which 7g of CS was added dropwise to the solution 2 The method comprises the steps of carrying out a first treatment on the surface of the And (3) preserving the heat for 4 hours after the dripping is finished, filtering, and placing the filter cake in a vacuum drying oven at 40 ℃ for drying for 24 hours to obtain the modified white carbon black.
Example 5
A composition comprising a graft modified natural rubber, which is prepared by the process comprising:
s1, weighing 100g of grafted modified natural rubber, 10g of nano kaolin and 5g of surface modified white carbon black, and mixing in a double-roll open mill to obtain a rubber compound sample;
s2, placing the mixed rubber sample obtained in the step S1 for 15 hours, placing the mixed rubber sample in a mold with the thickness of 1mm, adding 4g of sodium isobutyl xanthate, 1g of zinc dibutyl dithiocarbamate, 5g of zinc oxide and 1g of p-phenylenediamine, and carrying out vulcanization reaction by using a flat vulcanizing machine at the vulcanization temperature of 150 ℃ for 15 minutes to obtain the rubber composition containing the grafted modified natural rubber after the vulcanization is finished.
The preparation method of the grafted modified natural rubber comprises the following steps:
(1) Pre-emulsified natural rubber: placing 100g of natural rubber latex in a container, adding 600g of deionized water for dilution, then adding 10g of sodium dodecyl sulfate into the container, stirring for 10min at normal temperature, opening a nitrogen valve, and introducing for 10min to obtain pre-emulsified natural rubber;
(2) Preparation of graft modified natural rubber: 50g of methyl thioglycolate was dissolved in a beaker with 30mL of commercially available 27wt% ammonia water under stirring to give a solution L1, 2g of 2, 2-dimethylolpropionic acid was dissolved in a centrifuge tube with 20-g N-methylpyrrolidone to give a solution L2, the L1 and L2 solutions were sequentially added to a pre-emulsified natural rubber, the vessel was placed in a photochemical reactor, and N 2 Stirring at 30 ℃ under the atmosphere, and finishing the reaction after irradiating for 30min by an ultraviolet lamp; the irradiation wavelength of the ultraviolet lamp is 365nm; washing the precipitated gel with 300mL of ethanol, and washing the precipitated gel with 500mL of CHCl 3 Recrystallizing to obtain a rubber sample, and drying the rubber sample in a vacuum drying oven at 50 ℃ for 24 hours to obtain grafted modified natural rubber; the grafting rate of the grafting modified natural rubber is 55%, and the grafting efficiency is 75%.
The preparation method of the surface modified white carbon black comprises the following steps: drying the silicon dioxide in a drying oven at 80 ℃ for 2 hours; 30g of dry silica and 5g of ammonium cerium nitrate are weighed; 750mL of N, N-dimethylformamide was added; heating the solution to 60 ℃ and reacting for 1 hour; 40g of solid NaOH was added; the solution was cooled to 35℃and stirred for 0.5 hour, after which 7g of CS was added dropwise to the solution 2 The method comprises the steps of carrying out a first treatment on the surface of the And (3) preserving the heat for 4 hours after the dripping is finished, filtering, and placing the filter cake in a vacuum drying oven at 40 ℃ for drying for 24 hours to obtain the modified white carbon black.
Test case
And (3) air tightness test: the air tightness of the vulcanizates of examples 1-5 was tested according to GB/T7755-2003 determination of air permeability of vulcanizates or thermoplastic rubbers using a labthink VAC-V2 air tightness tester. The specific test results are shown in Table 1
Table 1: vulcanized rubber air tightness test data
| Permeability coefficient (cm) 2 ·s·Pa) | |
| Example 1 | 5.3×10 -14 |
| Example 2 | 4.7×10 -14 |
| Example 3 | 4.2×10 -14 |
| Example 4 | 3.7×10 -14 |
| Example 5 | 3.2×10 -14 |
The lower the permeability coefficient is, the better the air tightness of the material is, the nano kaolin with a lamellar structure and the grafted modified white carbon black are uniformly dispersed in the grafted modified natural rubber matrix, and the diffusion of gas molecules in the rubber is effectively prevented.
Abrasion resistance test: the vulcanized rubber samples obtained in examples 1 to 5 were subjected to abrasion resistance test by using an MZ-4062 reciprocating friction tester according to GB/T1689-2014 "determination of abrasion resistance of vulcanized rubber", the number of times of friction was fixed, and the weight of the rubbed sample was weighed in grams. The larger the number, the worse the abrasion resistance. The specific test method is as follows:
(1) Fixing the well-adhered sample on a foot wheel shaft, and starting a motor to enable the sample to rotate clockwise; (2) Taking down the sample after pre-grinding for 15-20 min, brushing off the rubber scraps, and weighing the mass m of the rubber scraps 1 Accurate to 0.001g; (3) experiments were performed using pre-ground samples. After the sample runs for 1.61km, the motor is turned off, the sample is taken down, and the brush is usedRemoving the rubber scraps, and weighing m within 1h 2 Accurate to 0.001g. The mass calculation formula of the friction loss of the sample is as follows:
m 0 ＝m 1 -m 2
m 0 the unit is gram of the mass of the friction loss of the sample; m is m 1 The mass of the sample after pre-grinding is given in grams; m is m 2 The mass of the sample after test is expressed in grams.
The specific test results are shown in Table 2.
Table 2: vulcanized rubber sample wear resistance test data
| Examples numbering | Wear resistance (friction loss quality g) |
| Example 1 | 2.38 |
| Example 2 | 2.05 |
| Example 3 | 1.56 |
| Example 4 | 1.34 |
| Example 5 | 1.18 |
The smaller the friction loss mass, the better the wear resistance of the material. The essence of abrasion is that when the composite material slides and rubs on a rough surface, local overlarge stress tears rubber particles in a small area and pulls away from a body to form individual small particles, the strength of filler particles (white carbon black) is high, cracking is difficult to occur, and the filler is difficult to separate from a matrix after good modification, so that the wear resistance of the material is improved.
Oil resistance test: the vulcanized gums obtained in examples 1 to 5 were subjected to a swelling degree test (mass change rate after soaking for 24 hours at 100 ℃) according to the GB/T1690-2010 standard, and the specific test method is as follows: and respectively cutting vulcanized rubber with certain mass, putting the vulcanized rubber into IRM901 and IRM903 standard oil, soaking for 24 hours at 100 ℃, and taking out a rubber sample. The standard oil on the surface of the gel sample is cleaned by ethanol, and the mass is weighed. The swelling degree of the gum sample is calculated as follows:
Swelling ratios(％)＝(Ws-Wo)/(Wo)×100
where Ws and W. The weights of the vulcanized rubber samples before and after swelling, respectively.
The swelling degree of the graft modified natural rubber and the graft modified natural rubber composition in the standard oil IRM901 and the standard oil IRM9031 is shown in table 3:
table 3: oil resistance test data of vulcanized rubber sample
| Sample of | IRM901 | IRM903 |
| Example 1 | 65％ | 125％ |
| Example 2 | 40％ | 120％ |
| Example 3 | 60％ | 105％ |
| Example 4 | 38％ | 100％ |
| Example 5 | 35％ | 95％ |
Because IRM903 standard oil has higher polarity and aromatic hydrocarbon structure and lower aniline point, the general rubber product is more resistant to corrosion of IRM901 standard oil under high temperature condition.
As can be seen from the comparison of the data in Table 3, the vulcanized rubber prepared from the grafted and modified natural rubber has lower swelling degree than the vulcanized rubber prepared from the natural rubber, probably because the grafted natural rubber is connected with ester base groups on the molecular chains of the rubber compared with the natural rubber, and the modified natural rubber with better oil resistance is obtained.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (10)
1. A rubber composition comprising a graft-modified natural rubber, characterized by comprising the following components in parts by mass: 40-60 parts of grafting modified natural rubber, 2-3 parts of vulcanizing agent, 3-6 parts of nano kaolin, 0.1-2 parts of vulcanizing auxiliary agent, 2-4 parts of activating agent, 0.5-2 parts of anti-aging agent and 2-3 parts of white carbon black.
2. A rubber composition comprising a graft modified natural rubber as claimed in claim 1, wherein: the vulcanizing agent is one or two or more of dicumyl peroxide, sulfur and sodium isobutyl xanthate.
3. A rubber composition comprising a graft modified natural rubber as claimed in claim 1, wherein: the vulcanization aid is any one of zinc dimethyl dithiocarbamate, tetraethylthiuram disulfide, zinc dibutyl dithiocarbamate and N-tertiary butyl-2-benzothiazole sulfenamide; the activator is zinc oxide.
4. A rubber composition comprising a graft modified natural rubber as claimed in claim 1, wherein: the antioxidant is one or two or more of N-phenyl-alpha-naphthylamine, N-phenyl-beta-naphthylamine, 2, 6-di-tert-butyl-p-cresol, styrenated phenol, 4-methyl-6-tert-butylphenol, 2, 5-di-tert-butylhydroquinone and p-phenylenediamine.
5. The rubber composition comprising a graft-modified natural rubber as claimed in claim 1, wherein said white carbon black is a surface-modified white carbon black.
6. A rubber composition comprising a graft modified natural rubber as claimed in claim 1, wherein said graft modified natural rubber is prepared by a process comprising:
(1) Pre-emulsified natural rubber: diluting natural rubber latex with water, adding sodium dodecyl sulfate, stirring at normal temperature, and then opening a nitrogen valve to introduce nitrogen to obtain pre-emulsified natural rubber;
(2) Preparation of graft modified natural rubber: dissolving methyl thioglycolate in ammonia water to obtain a solution L1; dissolving 2, 2-dimethylolpropionic acid with N-methylpyrrolidone to obtain a solution L2; adding the L1 and L2 solutions into the pre-emulsified natural rubber in sequence, and then placing the pre-emulsified natural rubber in a photochemical reactor, wherein N is 2 Stirring at normal temperature under atmosphere, and irradiating with ultraviolet lamp; washing the precipitated gel with ethanol, and washing the precipitated gel with CHCl 3 Recrystallizing to obtain a rubber sample, and drying the rubber sample to obtain the grafted modified natural rubber.
7. A rubber composition comprising a graft-modified natural rubber as described in claim 6, wherein: the mass ratio of water to natural rubber latex in the step (1) is 5-10:1, a step of; the sodium dodecyl sulfate accounts for 3-10% of the mass of the natural rubber latex.
8. The rubber composition comprising a graft-modified natural rubber according to claim 6, wherein the mass to volume ratio of the natural rubber latex to the aqueous ammonia in the step (2) is 2 to 4:1g/mL; the concentration of the ammonia water is 26-30wt% of the commercial ammonia water; the addition amount of the thioglycollic acid ethyl ester is 10-90% of the mass of the natural rubber latex; the addition amount of the 2, 2-dimethylolpropionic acid is 0.5-2% of the mass of the natural rubber latex; the addition amount of the 2, 2-dimethylolpropionic acid is 0.5-2% of the mass of the natural rubber latex; the irradiation of the ultraviolet lamp is carried out for 10-35min under the ultraviolet lamp with the wavelength of 300-400 nm, and the irradiation distance is 30-50 cm.
9. A rubber composition comprising a graft modified natural rubber as described in claim 5The preparation method of the surface modified white carbon black is characterized by comprising the following steps: placing silicon dioxide in a drying oven at 70-100 ℃ for drying for 1-3 hours; weighing 20-40 g of dry silicon dioxide and 3-8 g of ammonium cerium nitrate; 700-900 mL of N, N-dimethylformamide is added; heating the solution to 50-80 ℃ and reacting for 1-2 hours; adding 30-40 g of solid NaOH; cooling the solution to 30-40 ℃, stirring for 0.5-1 hour, and then dripping 60-80 g CS into the solution 2 The method comprises the steps of carrying out a first treatment on the surface of the And (3) preserving heat for 3-4 hours after the dripping is finished, filtering, and placing the filter cake in a vacuum drying oven at 40-50 ℃ for drying for 20-24 hours to obtain the modified white carbon black.
10. A rubber composition comprising a graft-modified natural rubber as claimed in claim 1, characterized in that it is prepared by a process comprising the steps of:
s1, weighing 40-60 parts of grafted modified natural rubber, 3-6 parts of nano kaolin and 2-3 parts of white carbon black, and mixing to obtain a mixed rubber sample;
s2, placing the rubber compound sample for 12-18 hours, and using a vulcanizing instrument to make a torque-time curve of the rubber compound, and determining vulcanizing time and corresponding vulcanizing temperature by using the curve;
s3, placing the mixed rubber sample obtained in the step S1 into a mould, adding 2-3 parts of vulcanizing agent, 0.1-2 parts of vulcanizing auxiliary agent, 2-4 parts of activating agent and 0.5-2 parts of anti-aging agent, and carrying out vulcanization reaction by using a vulcanizing machine to obtain the rubber composition of the grafted modified natural rubber after vulcanization is finished.
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