CN107353448B - A kind of natural rubber/modified white carbon black composite material and preparation method - Google Patents
A kind of natural rubber/modified white carbon black composite material and preparation method Download PDFInfo
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- CN107353448B CN107353448B CN201710596539.1A CN201710596539A CN107353448B CN 107353448 B CN107353448 B CN 107353448B CN 201710596539 A CN201710596539 A CN 201710596539A CN 107353448 B CN107353448 B CN 107353448B
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- natural rubber
- white carbon
- carbon black
- modified
- thioacetic acid
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- 244000043261 Hevea brasiliensis Species 0.000 title claims abstract description 158
- 229920003052 natural elastomer Polymers 0.000 title claims abstract description 158
- 229920001194 natural rubber Polymers 0.000 title claims abstract description 158
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000006229 carbon black Substances 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims description 20
- -1 rare-earth thioglycolate salt Chemical class 0.000 claims abstract description 90
- 239000004593 Epoxy Substances 0.000 claims abstract description 58
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 39
- 229920001732 Lignosulfonate Polymers 0.000 claims abstract description 23
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 18
- 239000003292 glue Substances 0.000 claims abstract description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 34
- 238000004073 vulcanization Methods 0.000 claims description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 21
- 239000005864 Sulphur Substances 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 238000006735 epoxidation reaction Methods 0.000 claims description 17
- 239000011787 zinc oxide Substances 0.000 claims description 17
- 238000002604 ultrasonography Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 14
- 235000021355 Stearic acid Nutrition 0.000 claims description 13
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 13
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 13
- 239000008117 stearic acid Substances 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 12
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims description 11
- 238000007711 solidification Methods 0.000 claims description 11
- 230000008023 solidification Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 10
- CWERGRDVMFNCDR-UHFFFAOYSA-N alpha-mercaptoacetic acid Natural products OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 claims description 7
- IOJUPLGTWVMSFF-UHFFFAOYSA-N cyclobenzothiazole Natural products C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- XRNHYQRYOYKIJE-UHFFFAOYSA-N [La].C(C)(=S)O Chemical compound [La].C(C)(=S)O XRNHYQRYOYKIJE-UHFFFAOYSA-N 0.000 claims description 5
- 229920005551 calcium lignosulfonate Polymers 0.000 claims description 5
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims description 5
- 229910052773 Promethium Inorganic materials 0.000 claims description 3
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims description 3
- 229940071127 thioglycolate Drugs 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 description 15
- 125000003700 epoxy group Chemical group 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 229920001971 elastomer Polymers 0.000 description 11
- 239000005060 rubber Substances 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000007605 air drying Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000035924 thermogenesis Effects 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000002242 deionisation method Methods 0.000 description 5
- 239000004816 latex Substances 0.000 description 5
- 229920000126 latex Polymers 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 150000000921 Gadolinium Chemical class 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 150000001216 Samarium Chemical class 0.000 description 1
- TZTIBQDIWZSCPU-UHFFFAOYSA-N [Ce].C(C)(=O)O.NC(=N)N Chemical compound [Ce].C(C)(=O)O.NC(=N)N TZTIBQDIWZSCPU-UHFFFAOYSA-N 0.000 description 1
- HGYBXYCVIRVHIZ-UHFFFAOYSA-N [Gd].C(C)(=O)O.NC(=N)N Chemical compound [Gd].C(C)(=O)O.NC(=N)N HGYBXYCVIRVHIZ-UHFFFAOYSA-N 0.000 description 1
- PMKUBWKBGUXOFP-UHFFFAOYSA-N [La].C(C)(=O)O.NC(=N)N Chemical compound [La].C(C)(=O)O.NC(=N)N PMKUBWKBGUXOFP-UHFFFAOYSA-N 0.000 description 1
- APJQBAMMDHKMQG-UHFFFAOYSA-N [Nd].C(C)(=O)O.NC(=N)N Chemical compound [Nd].C(C)(=O)O.NC(=N)N APJQBAMMDHKMQG-UHFFFAOYSA-N 0.000 description 1
- YGIDPRFMQSWWDR-UHFFFAOYSA-N [Sm].C(C)(=O)O.NC(=N)N Chemical compound [Sm].C(C)(=O)O.NC(=N)N YGIDPRFMQSWWDR-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation 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
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 210000004885 white matter Anatomy 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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)
- Processes Of Treating Macromolecular Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention provides a kind of natural rubber/modified white carbon black composite materials, include the component of following parts by weight：100 parts of natural rubber, 0.1~10 part of rare-earth thioglycolate salt, 0.05~0.2 part of lignosulfonates, 0.2~20 part of dry glue meter emulsus epoxy natural rubber, 10~100 parts of white carbon vulcanize 0.2~12 part of processing aid.Natural rubber provided by the invention/modified white carbon black composite materials property is good, heat is low, has excellent fatigue performance.
Description
Technical field
The present invention relates to the technical field of rubber, more particularly to a kind of natural rubber/modified white carbon black composite material and its
Preparation method.
Background technology
There are a large amount of hydroxyl group and unsaturated bond, it is in hydrophily to make its surface on white carbon surface, and polarity is strong, hygroscopic
The very strong space network of intermolecular force is interconnected to be not easy so being also easy to produce agglomeration between hard charcoal black track producing particle
In the dispersion in rubber matrix, often white carbon is modified.
Epoxy group in epoxy natural rubber strand has reactivity, can be generated with white carbon surface stronger
Dipole, hydrogen bond even covalent bond effect, can improve dispersion of the white carbon in rubber matrix.But due to the natural rubber of epoxidation
Epoxy group in glue and unstable, easy open loop, so as to cause white carbon, dispersibility is still poor in rubber matrix, and meeting
The mechanical property of composite material is caused to reduce, especially tearing strength reduces, and thermogenesis performance improves.
Invention content
In view of this, present invention aims at a kind of natural rubber/modified white carbon black composite material of offer and its preparation sides
Method.Natural rubber provided by the invention/modified white carbon black composite materials property is good, heat is low and fatigue performance is good.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme：
The present invention provides a kind of natural rubber/modified white carbon black composite materials, include the component of following parts by weight：Naturally
100 parts of rubber, 0.1~10 part of rare-earth thioglycolate salt, 0.05~0.2 part of lignosulfonates, dry glue meter emulsus epoxidation day
0.2~20 part of T PNR, 10~100 parts of white carbon vulcanize 0.2~12 part of processing aid.
Preferably, the rare-earth thioglycolate salt includes thioacetic acid lanthanum, thioacetic acid cerium, thioacetic acid praseodymium, sulfydryl second
Sour neodymium, thioacetic acid promethium, thioacetic acid samarium, thioacetic acid europium, thioacetic acid gadolinium, thioacetic acid terbium, thioacetic acid dysprosium, sulfydryl second
One in sour holmium, thioacetic acid erbium, thioacetic acid thulium, thioacetic acid ytterbium, thioacetic acid lutetium, thioacetic acid scandium and thioacetic acid yttrium
Kind or several mixtures.
Preferably, the lignosulfonates include sodium lignin sulfonate and/or calcium lignosulfonate.
Preferably, the epoxidation level of the emulsus epoxy natural rubber is 5~50.
Preferably, the vulcanization processing aid is sulphur, N tert butyl benzothiazole 2 sulfenamide, zinc oxide and hard
The mixture of resin acid.
Preferably, the solid content of the emulsus epoxy natural rubber is 10~20%.
The present invention provides the preparation methods of natural rubber described in said program/modified white carbon black composite material, including with
Lower step：
Thioglycolic acid rare-earth salts and lignosulfonates are subjected to ultrasonic disperse in water, obtain modified rare-earth thioglycolate
Salt dispersion；
The modified rare-earth thioglycolate salt dispersion and emulsus epoxy natural rubber are mixed and are heat-treated, is obtained
Modified emulsus epoxy natural rubber；
Solidification processing is carried out after the modified emulsus epoxy natural rubber and white carbon aqueous solution are mixed successively and is done
It is dry, obtain modified white carbon black；
Will the modified white carbon black, natural rubber and vulcanization processing aid be kneaded after vulcanize, obtain natural rubber/change
Property white carbon black composite material.
Preferably, the temperature of the ultrasound is 40~60 DEG C；The time of the ultrasound is 4~6h；The power of the ultrasound
For 700~800W.
Preferably, the temperature of the heat treatment is 50~80 DEG C；The time of the heat treatment is 0.1~2h.
Preferably, the temperature of the drying is 50~80 DEG C；The time of the drying is 2~48h.
The present invention provides a kind of natural rubber/modified white carbon black composite materials, include the component of following parts by weight：Naturally
100 parts of rubber, 0.1~10 part of rare-earth thioglycolate salt, 0.05~0.2 part of lignosulfonates, dry glue meter emulsus epoxidation day
0.2~20 part of T PNR, 10~100 parts of white carbon vulcanize 0.2~12 part of processing aid.The present invention utilizes lignosulfonates
Hydrogenbond effect occurs for the epoxy group in the hydroxyl and epoxy natural rubber in molecular structure, improves the natural rubber of epoxidation
The stability of epoxy group in glue；With the hydroxyl group in white carbon hydrogen can occur for the hydroxyl in lignosulfonates simultaneously
Key combination improves the dispersibility of white carbon；The present invention utilizes mercapto groups and epoxidation day in rare-earth thioglycolate salt
Complexing, coordination occur for the epoxy group of T PNR, improve the stability of epoxy natural rubber epoxide epoxy group group；Profit simultaneously
The ageing-resistant performance that natural rubber is improved with rare earth ion, finally obtains that mechanical property is good, tearing strength is high, heat is low, resistance to tired
The good natural rubber of labor performance/modified white carbon black composite material.Embodiment the result shows that, natural rubber provided by the invention/
The tensile strength of modified white carbon black composite material can reach 27.21MPa, and elongation rate of tensile failure can reach 621%；Tearing strength
40.6MPa can be reached, compression fatigue Wen Sheng is down to 19 DEG C.
It is provided by the invention the present invention also provides a kind of preparation method of natural rubber/modified white carbon black composite material
Preparation method is modified Thioglycolic acid rare-earth salts using lignosulfonates, improves the dispersibility of Thioglycolic acid rare-earth salts,
It recycles modified Thioglycolic acid rare-earth salts dispersion to be modified emulsus epoxy natural rubber, stablizes the natural rubber of epoxidation
Then epoxy group in glue is modified white carbon using modified epoxy natural rubber, improve white carbon in rubber-based
Modified white carbon black and natural rubber are finally kneaded and are vulcanized by the dispersibility in body, obtain natural rubber/modified white carbon black
Composite material.Preparation method step provided by the invention is simple, of low cost, is easy to large-scale production.
Specific implementation mode
The present invention provides a kind of natural rubber/modified white carbon black composite materials, include the component of following parts by weight：Naturally
100 parts of rubber, 0.1~10 part of rare-earth thioglycolate salt, 0.05~0.2 part of lignosulfonates, dry glue meter emulsus epoxidation day
0.2~20 part of T PNR, 10~100 parts of white carbon vulcanize 0.2~12 part of processing aid.
Natural rubber provided by the invention/modified white carbon black composite material is using natural rubber as matrix, in the present invention, institute
The parts by weight for stating natural rubber are 100 parts by weight；The natural rubber be it is a kind of with cis- 1,4- polyisoprene be mainly at
The natural polymer divided, rubber hydrocarbon (cis- Isosorbide-5-Nitrae-polyisoprene) content also contain a small amount of egg 90% or more
White matter, aliphatic acid, sugar and ash grade；The present invention does not have particular/special requirement to the source of the natural rubber, uses this field skill
The natural rubber in the known source of art personnel, specific such as commercially available natural rubber, in an embodiment of the present invention, preferably
Commercially available 10# standards natural rubber.
On the basis of 100 parts by weight of natural rubber, natural rubber provided by the invention/modified white carbon black composite material includes
0.1~10 parts by weight of rare-earth thioglycolate salt, preferably 1~6 parts by weight, more preferably 2~4 parts by weight.In the present invention, institute
It states rare-earth thioglycolate salt and preferably includes thioacetic acid lanthanum, thioacetic acid cerium, thioacetic acid praseodymium, thioacetic acid neodymium, thioacetic acid
Promethium, thioacetic acid samarium, thioacetic acid europium, thioacetic acid gadolinium, thioacetic acid terbium, thioacetic acid dysprosium, thioacetic acid holmium, thioacetic acid
One or more of erbium, thioacetic acid thulium, thioacetic acid ytterbium, thioacetic acid lutetium, thioacetic acid scandium and thioacetic acid yttrium mix
Close object；The present invention does not require the type and mass ratio of rare-earth thioglycolate salt in the rare-earth thioglycolate salt mixture,
The rare-earth thioglycolate salt of any kind may be used, mixed with arbitrary mass ratio.The present invention utilizes rare-earth thioglycolate
Thin base group in salt is reacted with the epoxy group in epoxy natural rubber, improves epoxy natural rubber epoxide epoxy group group
Stability, while utilizing the ageing-resistant performance of rare earth ion raising natural rubber.
On the basis of 100 parts by weight of natural rubber, natural rubber provided by the invention/modified white carbon black composite material includes
0.05~0.2 parts by weight of lignosulfonates, preferably 0.1~0.15 parts by weight.In the present invention, the lignosulfonates
Preferably include sodium lignin sulfonate and/or calcium lignosulfonate.The present invention utilizes the hydroxyl in lignosulfonate molecules structure
Hydrogenbond effect occurs with the epoxy group in epoxy natural rubber, improves the epoxy group in epoxy natural rubber
Stability, while Hydrogenbond effect can occur with the hydroxyl group in white carbon for the hydroxyl in lignosulfonates, to
Further increase the dispersibility of white carbon.
On the basis of 100 parts by weight of natural rubber, natural rubber provided by the invention/modified white carbon black composite material includes
0.2~20 parts by weight of dry glue meter emulsus epoxy natural rubber, preferably 1~15 parts by weight, more preferably 5~10 parts by weight.
In the present invention, the epoxidation level of the emulsus epoxy natural rubber is preferably 5~50, and more preferably 10~45, it is optimal
It is selected as 20~30；The solid content of the emulsus epoxy natural rubber is preferably 10~20%, and more preferably 15~18%.
On the basis of 100 parts by weight of natural rubber, natural rubber provided by the invention/modified white carbon black composite material includes
10~100 parts by weight of white carbon, preferably 20~80 parts by weight, more preferably 30~70 parts by weight.In the present invention, described white
The grain size of carbon black is preferably 10~100nm, more preferably 20~60nm, most preferably 30~50nm.
On the basis of 100 parts by weight of natural rubber, natural rubber provided by the invention/modified white carbon black composite material includes
Vulcanize 0.2~12 parts by weight of processing aid, preferably 1~10 parts by weight, more preferably 5~7 parts by weight.In the present invention, institute
State vulcanization processing aid be preferably one kind in sulphur, N tert butyl benzothiazole 2 sulfenamide, zinc oxide and stearic acid or
Several mixtures, more preferably sulphur, N tert butyl benzothiazole 2 sulfenamide (accelerator NS), zinc oxide and tristearin
The mixture of acid；Sulphur in the sulphur, N tert butyl benzothiazole 2 sulfenamide, zinc oxide and stearic mixture,
N tert butyl benzothiazole 2 sulfenamide, zinc oxide and stearic mass ratio are preferably 1~3:0.5~2：3~5:1~
3, more preferably 1.5~2.5:0.7~1.5:4~4.5:1.5~2.
The present invention is to the rare-earth thioglycolate salt, lignosulfonates, dry glue meter emulsus epoxy natural rubber, hard charcoal
Black and vulcanization processing aid source does not have particular/special requirement, using the above-mentioned substance in source known to those skilled in the art,
Specific such as commercially available above-mentioned substance.
The present invention provides the preparation methods of natural rubber described in said program/modified white carbon black composite material, including with
Lower step：
Thioglycolic acid rare-earth salts and lignosulfonates are subjected to ultrasonic disperse in water, obtain modified rare-earth thioglycolate
Salt dispersion；
The modified rare-earth thioglycolate salt dispersion and emulsus epoxy natural rubber are mixed and are heat-treated, is obtained
Modified emulsus epoxy natural rubber；
Solidification processing is carried out after the modified emulsus epoxy natural rubber and white carbon aqueous solution are mixed successively and is done
It is dry, obtain modified white carbon black；
Will the modified white carbon black, natural rubber and vulcanization processing aid be kneaded after vulcanize, obtain natural rubber/change
Property white carbon black composite material.
Thioglycolic acid rare-earth salts and lignosulfonates are carried out ultrasonic disperse by the present invention in water, obtain modified sulfydryl second
Acid rare earth salt dispersion.In the present invention, the power of the ultrasound is preferably 700~1000W, more preferably 800~950W；Institute
The temperature for stating ultrasound is preferably 30~80 DEG C, more preferably 40~60 DEG C；The time of the ultrasound is preferably 0.2~5h, more excellent
It is selected as 1~4h；The present invention preferably carries out ultrasound under stirring conditions, and the rotating speed of the stirring is preferably 200~400r/min,
More preferably 250~350r/min.In the present invention, the water is preferably deionized water；The water and Thioglycolic acid rare-earth salts
Mass ratio be preferably 20~30：0.1~10:, more preferably 25:0.1~10；In the present invention, the Thioglycolic acid rare earth
Consistent described in the dosage of salt and lignosulfonates and type and above-mentioned technical proposal, details are not described herein.
In the present invention, lignosulfonates have the function of that surfactant, the present invention utilize lignosulfonates pair
Thioglycolic acid rare-earth salts is modified, and increases the dispersibility of Thioglycolic acid rare-earth salts, obtains modified rare-earth thioglycolate salt dispersion
Body.
After obtaining modified rare-earth thioglycolate salt dispersion, the present invention by the modified rare-earth thioglycolate salt dispersion and
The mixing of emulsus epoxy natural rubber is heat-treated, and modified emulsus epoxy natural rubber is obtained.In the present invention, the heat
The temperature of processing is preferably 50~80 DEG C, more preferably 60~70 DEG C；The time of the heat treatment is preferably 0.1~2h, more excellent
It is selected as 0.5~1.5h；It is consistent described in the dosage and above-mentioned technical proposal of the emulsus epoxy natural rubber, it is no longer superfluous herein
It states.In the heat treatment process of the present invention, the ring in hydroxyl and epoxy natural rubber in lignosulfonate molecules structure
Hydrogenbond effect occurs for oxygen groups, and the epoxy group of mercapto groups and epoxy natural rubber in rare-earth thioglycolate occurs
Complex coordination acts on, and to improve the stability of epoxy natural rubber epoxide epoxy group group, it is natural that gained is modified emulsus epoxidation
Epoxy group in rubber is stablized, and open loop is not easy.
After obtaining modified emulsus epoxy natural rubber, the present invention is by the modified emulsus epoxy natural rubber and hard charcoal
Solidification processing and drying are carried out successively after the solution mixing of Heisui River, obtain modified white carbon black.In the present invention, the white carbon is water-soluble
The solid content of liquid is preferably 10~20%, and more preferably 15%；Ultrasound after the present invention preferably mixes white carbon and water, obtains white
Carbon black aqueous solution；The present invention does not have particular/special requirement to the power of the ultrasound and time, can obtain finely dispersed white carbon
Aqueous solution.
The present invention mixes the modified emulsus epoxy natural rubber and white carbon aqueous solution preferably under ultrasound condition,
In the present invention, the time of the ultrasound is preferably 5~60min, more preferably 20~40min；The temperature of the ultrasound is room
Temperature, without carrying out additional heating or cooling；The power of the ultrasound is preferably 700~1000W, more preferably 800~900W；
The present invention preferably carries out ultrasound under stirring conditions, and the rotating speed of the stirring is preferably 200~500r/min, more preferably
350~450r/min.
After the modified emulsus epoxy natural rubber and white carbon aqueous solution are mixed, the present invention will be modified emulsus epoxy
The mixture for changing natural rubber and white carbon aqueous solution carries out solidification processing and drying successively, obtains modified white carbon black.In this hair
In bright, the solidification processing is particularly preferred as acetic acid solidification, formic acid solidification, steam coagulation or calcium chloride solidification, more preferably steams
Vapour solidifies；The present invention does not have particular/special requirement to the concrete operations condition of the solidification processing, using known to those skilled in the art
Solidification treatment conditions.
In the present invention, the temperature of the drying is preferably 50~80 DEG C, more preferably 60~70 DEG C；The drying when
Between preferably 2~48h, more preferably 5~40h, most preferably 10~30h；The drying is preferably heated-air drying；After drying
The modified white carbon black arrived is flour, is easy to disperse in natural rubber matrix.
In the present invention, there is stable epoxy group in modified epoxy natural rubber strand, it can be with white carbon
Surface generates stronger dipole, hydrogen bond and covalent bond effect, improves the dispersibility of white carbon, and the hydroxyl in lignin xanthate
Hydrogenbond effect can occur with the hydroxyl in white carbon, further increase the dispersibility of white carbon.
After obtaining modified white carbon black, after the modified white carbon black, natural rubber and vulcanization processing aid are kneaded by the present invention
Vulcanized, obtains natural rubber/modified white carbon black composite material.In the present invention, the natural rubber and sulphur auxiliary chemicals
Dosage and type with it is consistent described in above-mentioned technical proposal, details are not described herein；The present invention does not have particular/special requirement to mixing method,
It is kneaded using method well known to those skilled in the art, it is specific as being kneaded on the double roll mill.
After the completion of mixing, the present invention vulcanizes obtained mixing product, and it is compound to obtain natural rubber/modified white carbon black
Material.In the present invention, the temperature of the vulcanization is preferably 140~150 DEG C, more preferably 145 DEG C；The present invention will be preferably kneaded
Product samples place 12h, then detect and determine its optimum sulfurating time, and sulphur is carried out to being kneaded product according to determining vulcanization time
Change；The present invention does not have particular/special requirement to the detection method of the optimum sulfurating time, uses side well known to those skilled in the art
Method is specifically such as measured using vulcameter.The present invention makes the chain molecule in mixing product be cross-linked by vulcanization
Network molecule further enhances the mechanical property and ageing-resistant performance of natural rubber/modified white carbon black composite material.
With reference to embodiment to natural rubber provided by the invention/modified white carbon black composite material and preparation method into
Row detailed description, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
A kind of natural rubber/modified white carbon black composite material, includes the component of following parts by weight：100 parts of natural rubber, mercapto
0.1 part of guanidine-acetic acid lanthanum, 0.05 part of sodium lignin sulfonate, 20 parts of dry glue meter emulsus epoxy natural rubber, 10 parts of white carbon, sulphur
1.5 parts, 1.5 parts of accelerator NS, 4 parts of zinc oxide, 1 part of stearic acid.
The preparation method of above-mentioned natural rubber/modified white carbon black composite material is：0.1 part is added in 20 parts of deionization
Thioacetic acid lanthanum, control ultrasonic power be 750W, in the state of ultrasonic disperse, be added 0.05 part of sodium lignin sulfonate, set
5h is continuously stirred in 50 DEG C of water-bath, control stir speed (S.S.) is 400r/min, and modified thioacetic acid lanthanum is made, spare；
By the sulfydryl of 20 parts of emulsus epoxy natural rubber (epoxidation level 40) and modification that latex solid content is 10%
Lanthanum acetate is heat-treated 2h at 80 DEG C, obtains modified emulsus epoxy natural rubber；
10 parts of white carbons are prepared into the white carbon aqueous solution that solid content is 10%, by modified emulsus epoxy natural rubber
Ultrasonic agitation 10min (ultrasonic power 700W, stir speed (S.S.) 450r/min) after being mixed with white carbon aqueous solution, it is solidifying through formic acid
Gu process, 50 DEG C of heated-air drying 48h, obtain powdered modified white carbon；
By modified white carbon black and 100 parts of 10# standards natural rubbers, vulcanization processing aid (1.5 parts of sulphur, 1.5 parts of accelerating agents
NS, 4 parts of zinc oxide, 1 part of stearic acid) it is kneaded, it will be kneaded after product parks 12h and survey optimum sulfurating time T90, in tablet sulphur
Vulcanized (145 DEG C × T90 of conditions of vulcanization) on change machine, obtains natural rubber/modified white carbon black composite material.
According to GB/T528-2009 (measurement of vulcanized rubber or thermoplastic elastomer tensile stress-strain performance), GB/
T1687-1993 (vulcanized rubber is risen in angular test medium temperature and the measurement part 2 of fatigue performance compresses angular test) is to institute
Natural rubber/mechanical property of modified white carbon black composite material, thermogenesis performance are measured, test result is shown in Table 1.
Embodiment 2
A kind of natural rubber/modified white carbon black composite material, includes the component of following parts by weight：100 parts of natural rubber, mercapto
5 parts of guanidine-acetic acid cerium, 0.1 part of calcium lignosulfonate, 5 parts of dry glue meter emulsus epoxy natural rubber, 30 parts of white carbon, sulphur 2.25
Part, 0.7 part of accelerator NS, 5 parts of zinc oxide, 1 part of stearic acid.
The preparation method of above-mentioned natural rubber/modified white carbon black composite material is：5 parts are added in 25 parts of deionization
Thioacetic acid cerium, control ultrasonic power is 1000W, in the state of ultrasonic disperse, 0.1 part of calcium lignosulfonate is added, is placed in
0.2h is continuously stirred in 80 DEG C of water-bath, control stir speed (S.S.) is 400r/min, and modified thioacetic acid cerium is made, spare；
By the emulsus epoxy natural rubber (epoxidation level 25) that latex solid content is 10% and the thioacetic acid being modified
Cerium is heat-treated 2h at 80 DEG C, obtains modified emulsus epoxy natural rubber；
30 parts of white carbons are prepared into the white carbon aqueous solution that solid content is 15%, by modified emulsus epoxy natural rubber
It is mixed with white carbon aqueous solution, ultrasonic agitation 60min (ultrasonic power 750W, stir speed (S.S.) 400r/min) is solidifying through acetic acid
Gu process, 60 DEG C of heated-air drying 36h, obtain the white carbon of the modification of powdery；
By modified white carbon black and 100 parts of 10# standards natural rubbers, vulcanization processing aid (2.25 parts of sulphur, 0.7 part of promotion
Agent NS, 5 parts of zinc oxide, 1 part of stearic acid) it is kneaded on the double roll mill, it will be kneaded after product parks 12h and survey optimum cure
Time T90 is vulcanized (145 DEG C × T90 of conditions of vulcanization) on vulcanizing press, it is multiple to obtain natural rubber/modified white carbon black
Condensation material.
According to GB/T528-2009, GB/T1687-1993 to the mechanics of gained natural rubber/modified white carbon black composite material
Performance, thermogenesis performance are measured, and test result is shown in Table 1.
Embodiment 3
A kind of natural rubber/modified white carbon black composite material, includes the component of following parts by weight：100 parts of natural rubber, mercapto
10 parts of guanidine-acetic acid neodymium, 0.2 part of sodium lignin sulfonate, 10 parts of dry glue meter emulsus epoxy natural rubber, 50 parts of white carbon, sulphur
1.5 parts, 1.0 parts of accelerator NS, 5 parts of zinc oxide, 2 parts of stearic acid.
The preparation method of above-mentioned natural rubber/modified white carbon black composite material is：10 parts are added in 30 parts of deionization
Thioacetic acid neodymium, control ultrasonic power be 800W, in the state of ultrasonic disperse, be added 0.2 part of sodium lignin sulfonate, be placed in
2h is continuously stirred in 60 DEG C of water-bath, control stir speed (S.S.) is 350r/min, and modified thioacetic acid neodymium is made, spare；
By the emulsus epoxy natural rubber (epoxidation level 5) that latex solid content is 20% and the thioacetic acid neodymium being modified
It is heat-treated 1h at 60 DEG C, obtains modified emulsus epoxy natural rubber；
50 parts of white carbons are prepared into the white carbon aqueous solution that solid content is 15%, by modified emulsus epoxy natural rubber
It is mixed with white carbon aqueous solution, ultrasonic agitation 60min (ultrasonic power 800W, stir speed (S.S.) 500r/min) is solidifying through steam
Gu process, 80 DEG C of heated-air drying for 24 hours, obtains the white carbon of the modification of powdery；
By modified white carbon black and 100 parts of 10# standards natural rubbers, vulcanization processing aid (1.5 parts of sulphur, 1.0 parts of accelerating agents
NS, 5 parts of zinc oxide, 2 parts of stearic acid) it is kneaded on the double roll mill, product will be kneaded and parked when surveying optimum cure after 12h
Between T90, vulcanized (145 DEG C × T90 of conditions of vulcanization) on vulcanizing press, it is compound to obtain natural rubber/modified white carbon black
Material.
According to GB/T528-2009, GB/T1687-1993 to the mechanics of gained natural rubber/modified white carbon black composite material
Performance, thermogenesis performance are measured, and test result is shown in Table 1.
Embodiment 4
A kind of natural rubber/modified white carbon black composite material, includes the component of following parts by weight：100 parts of natural rubber, mercapto
10 parts of guanidine-acetic acid samarium, 0.15 part of sodium lignin sulfonate, 15 parts of dry glue meter emulsus epoxy natural rubber, 100 parts of white carbon, sulphur
1.5 parts, 1.5 parts of accelerator NS, 5 parts of zinc oxide, 2 parts of stearic acid.
The preparation method of above-mentioned natural rubber/modified white carbon black composite material is：10 parts are added in 30 parts of deionization
Thioacetic acid samarium, control ultrasonic power be 900W, in the state of ultrasonic disperse, be added 0.15 part of sodium lignin sulfonate, set
3h is continuously stirred in 70 DEG C of water-bath, control stir speed (S.S.) is 250r/min, and modified thioacetic acid samarium is made, spare；
By the emulsus epoxy natural rubber (epoxidation level 50) that latex solid content is 20% and the thioacetic acid being modified
Samarium is heat-treated 2h at 65 DEG C, obtains modified emulsus epoxy natural rubber；
100 parts of white carbons are prepared into the white carbon aqueous solution that solid content is 15%, by the modified natural rubber of emulsus epoxidation
Glue and the mixing of white carbon aqueous solution, ultrasonic agitation 50min (ultrasonic power 850W, stir speed (S.S.) 450r/min), through steam
Solidifying process processing, 60 DEG C of heated-air drying 36h obtain the white carbon of the modification of powdery；
By modified white carbon black and 100 parts of 10# standards natural rubbers, vulcanization processing aid (1.5 parts of sulphur, 1.5 parts of accelerating agents
NS, 5 parts of zinc oxide, 2 parts of stearic acid) it is kneaded on the double roll mill, product will be kneaded and parked when surveying optimum cure after 12h
Between T90, vulcanized (145 DEG C × T90 of conditions of vulcanization) on vulcanizing press, it is compound to obtain natural rubber/modified white carbon black
Material.
According to GB/T528-2009, GB/T1687-1993 to the mechanics of gained natural rubber/modified white carbon black composite material
Performance, thermogenesis performance are measured, and test result is shown in Table 1.
Embodiment 5
A kind of natural rubber/modified white carbon black composite material, includes the component of following parts by weight：100 parts of natural rubber, mercapto
3 parts of guanidine-acetic acid gadolinium, 0.1 part of sodium lignin sulfonate, 10 parts of dry glue meter emulsus epoxy natural rubber, 70 parts of white carbon, sulphur 2
Part, 1.75 parts of accelerator NS, 4 parts of zinc oxide, 1 part of stearic acid.
The preparation method of above-mentioned natural rubber/modified white carbon black composite material is：3 parts are added in 25 parts of deionization
Thioacetic acid gadolinium, control ultrasonic power is 850W, in the state of ultrasonic disperse, 0.1 part of sodium lignin sulfonate is added, is placed in 75
DEG C water-bath in continuously stir 2.5h, control stir speed (S.S.) is 350r/min, and modified thioacetic acid gadolinium is made, spare；
By the emulsus epoxy natural rubber (epoxidation level 35) that latex solid content is 15% and the thioacetic acid being modified
Gadolinium is heat-treated 1.5h at 75 DEG C, obtains modified emulsus epoxy natural rubber；
70 parts of white carbons are prepared into the white carbon aqueous solution that solid content is 10%, by modified emulsus epoxy natural rubber
It is mixed with white carbon aqueous solution, ultrasonic agitation 50min (ultrasonic power 950W, stir speed (S.S.) 350r/min) is solidifying through steam
Gu process, 70 DEG C of heated-air drying 10h, obtain the white carbon of the modification of powdery；
By modified white carbon black and 100 parts of 10# standards natural rubbers, vulcanization processing aid (2 parts of sulphur, 1.75 parts of accelerating agents
NS, 4 parts of zinc oxide, 1 part of stearic acid) it is kneaded on the double roll mill, product will be kneaded and parked when surveying optimum cure after 12h
Between T90, vulcanized (140 DEG C × T90 of conditions of vulcanization) on vulcanizing press, it is compound to obtain natural rubber/modified white carbon black
Material.
According to GB/T528-2009, GB/T1687-1993 to the mechanics of gained natural rubber/modified white carbon black composite material
Performance, thermogenesis performance are measured, and test result is shown in Table 1.
Comparative example 1
It selects 10# standard natural rubbers to carry out mixed refining process, is formulated as 100 parts of 10# standard rubbers, 5 parts of zinc oxide, stearic acid
2 parts, 0.7 part of accelerator NS, 2.25 parts of sulphur, 40 parts of white carbon.Optimum sulfurating time T90 is surveyed after parking 12h, in tablet sulphur
Vulcanized on change machine (145 DEG C × T90 of conditions of vulcanization).The performance of sizing material, test knot are tested according to method described in embodiment 1
Fruit is shown in Table 1.
The performance test knot of natural rubber/modified white carbon black composite material prepared by 1 Examples 1 to 5 of table and comparative example 1
Fruit
Natural rubber provided by the invention/modified white carbon black composite material is can be seen that according to the data in table 1 to stretch by force
Degree, elongation rate of tensile failure and tearing strength significantly improve, and compression fatigue temperature, which rises, to be significantly reduced, and illustrates natural rubber provided by the invention
Glue/modified white carbon black composite material has excellent mechanical property and fatigue performance.
As seen from the above embodiment, natural rubber provided by the invention/modified white carbon black composite materials property is good, raw
Heat is low, and fatigue performance is good, and the preparation method of natural rubber provided by the invention/modified white carbon black composite material is simple, at
This is low, is easy to industrialized production.
As seen from the above embodiment, the present invention is the above is only a preferred embodiment of the present invention, it is noted that for
For those skilled in the art, without departing from the principle of the present invention, can also make it is several improvement and
Retouching, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of natural rubber/modified white carbon black composite material, includes the component of following parts by weight：100 parts of natural rubber, sulfydryl
0.1~10 part of acetic acid rare-earth salts, 0.05~0.2 part of lignosulfonates, dry glue meter emulsus epoxy natural rubber 0.2~20
Part, 10~100 parts of white carbon vulcanizes 0.2~12 part of processing aid.
2. natural rubber according to claim 1/modified white carbon black composite material, which is characterized in that the thioacetic acid
Rare-earth salts include thioacetic acid lanthanum, thioacetic acid cerium, thioacetic acid praseodymium, thioacetic acid neodymium, thioacetic acid promethium, thioacetic acid samarium,
Thioacetic acid europium, thioacetic acid gadolinium, thioacetic acid terbium, thioacetic acid dysprosium, thioacetic acid holmium, thioacetic acid erbium, thioacetic acid thulium,
The mixture of one or more of thioacetic acid ytterbium, thioacetic acid lutetium, thioacetic acid scandium and thioacetic acid yttrium.
3. natural rubber according to claim 1/modified white carbon black composite material, which is characterized in that the lignin
Sulfonate includes sodium lignin sulfonate and/or calcium lignosulfonate.
4. natural rubber according to claim 1/modified white carbon black composite material, which is characterized in that the emulsus epoxy
The epoxidation level for changing natural rubber is 5~50.
5. natural rubber according to claim 1/modified white carbon black composite material, which is characterized in that the vulcanization processing
Auxiliary agent is the mixture of one or more of sulphur, N tert butyl benzothiazole 2 sulfenamide, zinc oxide and stearic acid.
6. natural rubber according to claim 1 or 4/modified white carbon black composite material, which is characterized in that the emulsus ring
The solid content for aoxidizing natural rubber is 10~20%.
7. the preparation method of natural rubber described in claim 1~6 any one/modified white carbon black composite material, including it is following
Step：
Thioglycolic acid rare-earth salts and lignosulfonates are subjected to ultrasonic disperse in water, obtain modified rare-earth thioglycolate salinity
Granular media；
The modified rare-earth thioglycolate salt dispersion and emulsus epoxy natural rubber are mixed and are heat-treated, is modified
Emulsus epoxy natural rubber；
Solidification processing and drying are carried out successively after the modified emulsus epoxy natural rubber and white carbon aqueous solution are mixed, and are obtained
To modified white carbon black；
Vulcanize after the modified white carbon black, natural rubber and vulcanization processing aid are kneaded, it is white to obtain natural rubber/modification
Carbon black composite material.
8. preparation method according to claim 7, which is characterized in that the temperature of the ultrasound is 40~60 DEG C；It is described super
The time of sound is 4~6h；The power of the ultrasound is 700~800W.
9. preparation method according to claim 7, which is characterized in that the temperature of the heat treatment is 50~80 DEG C；It is described
The time of heat treatment is 0.1~2h.
10. preparation method according to claim 7, which is characterized in that the temperature of the drying is 50~80 DEG C；It is described dry
The dry time is 2~48h.
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