CN107973950A - Environment-friendly type downhole well applications engineering tire tread rubber composition and preparation method thereof - Google Patents
Environment-friendly type downhole well applications engineering tire tread rubber composition and preparation method thereof Download PDFInfo
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- CN107973950A CN107973950A CN201711307077.3A CN201711307077A CN107973950A CN 107973950 A CN107973950 A CN 107973950A CN 201711307077 A CN201711307077 A CN 201711307077A CN 107973950 A CN107973950 A CN 107973950A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 67
- 239000005060 rubber Substances 0.000 title claims abstract description 67
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- 238000004513 sizing Methods 0.000 claims abstract description 35
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920006231 aramid fiber Polymers 0.000 claims abstract description 23
- 239000006229 carbon black Substances 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 238000011084 recovery Methods 0.000 claims abstract description 19
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 15
- 230000004048 modification Effects 0.000 claims abstract description 15
- 238000012986 modification Methods 0.000 claims abstract description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005864 Sulphur Substances 0.000 claims abstract description 9
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 239000011787 zinc oxide Substances 0.000 claims abstract description 7
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000008117 stearic acid Substances 0.000 claims abstract description 6
- 235000019241 carbon black Nutrition 0.000 claims description 21
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical class C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- WLLGXSLBOPFWQV-UHFFFAOYSA-N MGK 264 Chemical compound C1=CC2CC1C1C2C(=O)N(CC(CC)CCCC)C1=O WLLGXSLBOPFWQV-UHFFFAOYSA-N 0.000 claims 1
- 150000003851 azoles Chemical class 0.000 claims 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 17
- 230000032683 aging Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 239000003292 glue Substances 0.000 description 7
- 230000035882 stress Effects 0.000 description 7
- 238000004073 vulcanization Methods 0.000 description 6
- 229920001206 natural gum Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005336 cracking Methods 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001021 polysulfide Polymers 0.000 description 3
- 239000005077 polysulfide Substances 0.000 description 3
- 150000008117 polysulfides Polymers 0.000 description 3
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- YZRSLFIRGZJTAZ-UHFFFAOYSA-N 2-cyclohexyl-3-sulfanylideneisoindol-1-one Chemical group S=C1C2=CC=CC=C2C(=O)N1C1CCCCC1 YZRSLFIRGZJTAZ-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 241000270708 Testudinidae Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N cyclobenzothiazole Natural products C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 230000008821 health effect Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010363 phase shift Effects 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- 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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The present invention relates to environment-friendly type downhole well applications engineering tire tread rubber composition and preparation method thereof, belong to tire material technical field.It is made of following components by weight：100 parts of butadiene-styrene rubber, 30~70 parts of hard carbon black, 1~10 part of anti-tear crack resin, 1~5 part of modification of aramid fiber, 0.5~2 part of anti-recovery agent, 1~3 part of sulphur, 3~7 parts of antioxidant, 2~4 parts of accelerating agent, 1~4 part of crystallite protection wax, 1~10 part of zinc oxide, 1~5 part of stearic acid, 0.05~0.5 part of antiscorching agent.The present invention uses environment-friendly type butadiene-styrene rubber, and by introducing anti-tear crack resin, modification of aramid fiber, anti-recovery agent, overcome the prior art, tread rubber anti-cut, chunking resistance of the tire tread and wearability, fatigue durability, tearing-resistant performance and the belt cutting-resisting property of hysteresis heat and sizing material are improved, probability is blown out so as to reduce and greatly improved the service life of engineering tyre.
Description
Technical field
The present invention relates to environment-friendly type downhole well applications engineering tire tread rubber composition and preparation method thereof, belong to tire material
Expect technical field.
Background technology
The use environment of downhole well applications engineering tyre is quite severe, and Work places ratchel, sharp rubble can be found everywhere, and make
Harsh with condition, load is big and vehicle is worked continuously, and tire is often anti-with sharp stone and roadside stone in use
Multiple connection is touched, and this requires there is tire tread glue anti-cut, resistance to puncture, anti-collapse to use up that block, tear-proof and hardness are big, are unlikely to deform
Etc. performance.In addition, after if tyre surface cuts chip off-falling by stone, steel wire easily it is exposed in atmosphere, and underground tunnel has a large amount of ponding easy
Steel wire is set to blow out after getting rusty, so as to seriously affect the service life of tire and tire can be made hidden in the presence of safety in use
Suffer from.
Most tire plants using natural gum or natural gum and butadiene-styrene rubber and rubber system, the initial cracking of butadiene-styrene rubber
Energy, anti-cut, anti-puncture performance are better than natural gum, but butylbenzene tear strength of vulcanizate is poor, easily collapses and uses up block, and butadiene-styrene rubber is split
Mouth growth rate is fast, and tire middle and later periods belt cutting-resisting property is poor, influences the service life of tire.
In use, due to being subject to ectocine, cross-linked network can destroy tire in vulcanizate, cause to vulcanize
Glue physical property declines and causes tire to be scrapped.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of environment-friendly type downhole well applications engineering tire tread rubber composition
And preparation method thereof.
The present invention is realized using following technical solution：
A kind of environment-friendly type downhole well applications engineering tire tread rubber composition, is made of following components by weight：Fourth
100 parts of benzene glue, 30~70 parts of hard carbon black, 1~10 part of anti-tear crack resin, 1~5 part of modification of aramid fiber, anti-recovery agent
0.5~2 part, 1~3 part of sulphur, 3~7 parts of antioxidant, 2~4 parts of accelerating agent, 1~4 part of crystallite protection wax, 1~10 part of zinc oxide,
1~5 part of stearic acid, 0.05~0.5 part of antiscorching agent.
The butadiene-styrene rubber is environment-friendly type butadiene-styrene rubber 1502.
The anti-tear crack resin is SL6903.
The modification of aramid fiber is Sulfron3001.
The anti-recovery agent is SR-008.
The hard carbon black is N220 hard carbon blacks, N234 hard carbon blacks, one or both of N115 hard carbon blacks simultaneously
With.
The antioxidant is N- (1,3- dimethylbutyls)-N'- diphenyl-para-phenylene diamines, 2,2,4- trimethyl -1,2- dihydros
Change one or both of quinoline condensate to be used in combination.
The accelerating agent is N tert butyl benzothiazole 2 sulfenamide, one kind in 2,2'- dithio-bis-benzothiazoles
Or two kinds be used in combination.
The antiscorching agent is N- cyclohexylthiophthalimides.
A kind of preparation method of environment-friendly type downhole well applications engineering tire tread rubber composition, comprises the following steps：
(1) one section of mixing：By 100 parts of butadiene-styrene rubbers, 1~5 part of modification of aramid fiber, 1~10 part of anti-tear crack resin, 3~7 parts
Antioxidant, 1~10 part of zinc oxide, 1~5 part of stearic acid put into internal mixer mixing chamber and are kneaded 30~40s, rotor speed for 40~
50rmp, temperature carry bolt when reaching 90~100 DEG C, then add 50~70 parts of hard carbon blacks, and rotor speed is 30~40rmp,
Temperature carries bolt when reaching 120~130 DEG C and presses bolt again, be kneaded to sizing material temperature be 150~155 DEG C when dumping, one section of rubber master batch is put
It is cooled to room temperature in interior；
(2) two-stage mixing：By in one section of rubber master batch input mixer mixing room described in (1), 45~60s, rotor are kneaded
Rotating speed is 30~40rmp, carries bolt and presses bolt again, continues 45~60s of mixing under 30~40rmp rotating speeds, sizing material temperature reaches 150~
Dumping at 155 DEG C, is cooled to room temperature two sections of rubber master batch are disposed within；
(3) refining eventually：By two sections of rubber master batch described in (2) and 0.5~2 part of anti-recovery agent, 1~3 part of sulphur, 2~4 parts
Accelerating agent, 1~4 part of crystallite protection wax, 0.05~0.5 part of antiscorching agent are put into mixer mixing room, rotor speed for 20~
25rmp, carries bolt, pressure bolt, is respectively kneaded 30~40s, dumping when sizing material temperature reaches 100~110 DEG C, obtains environment-friendly type underground three times
Purposes engineering tire tread rubber composition.
The anti-cut of tread rubber, anti-puncture performance should be evaluated in terms of cracking resistance mouth produces and cracking resistance mouth increases by two.Tire
The breach of face glue is produced to be had compared with Important Relations with its hardness and tensile strength.In the gentle pressure of same load, the hardness of sizing material and drawing
It is bigger to stretch intensity, deformation is smaller caused by sharp objects, is more not likely to produce breach.The cracking resistance mouth of tread rubber increases to be stretched by force with it
Degree and elongation at break have compared with Important Relations.The tensile strength and elongation at break of sizing material are bigger, and absorbable deflection is bigger, resist
It is better that breach increases performance.
Using the initial crack resistance energy of the tire tread of butadiene-styrene rubber, anti-cut, anti-puncture performance better than natural gum or
The tyre surface for the rubber system that natural gum is combined with butadiene-styrene rubber, but the tensile strength of butadiene-styrene rubber, tearing strength are significantly lower than natural
Rubber, usual way are to increase the dosage of supporting material carbon black and carry out reinforcement to butadiene-styrene rubber using super abrasive carbon black,
But therewith producing, sizing material heat is excessive and cause tire accelerated ageing and shorten tyre life, so as to cause tyre life significantly to contract
It is short.
To overcome the shortcomings of to do environment-friendly type downhole well applications engineering tire tread using full butadiene-styrene rubber, the present invention adds at the same time
Aramid fiber, anti-tear crack resin and anti-recovery agent, experiment confirmation achieve good effect.
Anti-tear crack resin SL6903, is a kind of compound modified phenol-dicyclopentadiene (DCPD) tree of unsaturated olefin
Fat, is natural rosin and Petropols mixture.Often there is tyre surface breach, and breach in use in downhole well applications engineering tyre
The problems such as extending rapidly, causing tread chunking chip off-falling and bottom of trench to split, these problems are all related with the tear resistance of tread rubber.It is logical
Cross and add anti-tear crack resin, the tear resistance of sizing material can be improved, thus reduce downhole well applications tire in use on
State the generation of problem.
Modification of aramid fiber Sulfron3001, is a kind of high property using sulfur modified contraposition aromatic polyamides staple fiber
Energy rubber chemicals, are added in butadiene-styrene rubber, butadiene-styrene rubber sizing material can be improved without the use of a large amount of hard carbon blacks on a small quantity
Tensile strength, and the heat for reducing sizing material reaches the anti-degradability for improving the tire tread made of butadiene-styrene rubber, at the same time
The cross-bond network structure of vulcanizate is kept, further improves the anti-cut of tire tread, anti-puncture performance.
In the presence of vulcanizing system (sulphur, accelerating agent etc.), modification of aramid fiber Sulfron3001 and sulphur and accelerating agent
Reaction forms intermediate, forms associative key between rubber and aramid fiber, carbon black and aramid fiber, can strengthen rubber and charcoal
Interaction between black, thus the interaction between filler-filler can be reduced, the phase between reinforcer-polymer
Interaction, therefore achieve the purpose that to reduce sizing material heat by reducing carbon black loading in butadiene-styrene rubber, by adding a small amount of virtue
Synthetic fibre fiber, also can keep or improve the performances such as the tensile strength of sizing material.
In use, vulcanizate is due to being subject to heat, oxygen, ozone, moisture and external force effect to cause sulphur and rubber for tire
Irreversible scission of link and rearrangement occur for the polysulfide bond that glue is formed, and cause the reduction of polysulfide bond quantity, vulcanizating glue physical performance is as stretched
The decline of intensity, tearing strength, elongation at break.
By adding anti-recovery agent SR-008, chemical name：Two hydration hexa-methylene -1,6- bisthiosulfate disodiums
Salt.Its anti-recovery mechanism is directly to participate in vulcanization reaction by its molecule, by longer in its molecule with flexible
Sulphur atom cross-bond between hexa-methylene insertion rubber molecule, so as to compensate the reduction of polysulfide bond during tire used,
Make the physical property of vulcanizate be unlikely to decline it is too fast.
The present invention, as rubber system, improves downhole well applications engineering tire tread by using the full butadiene-styrene rubber of environment-friendly type
Anti-cut, anti-puncture performance, while in using rubber composition of the full butadiene-styrene rubber as downhole well applications engineering tire tread
The mode that anti-tear crack resin, modification of aramid fiber, anti-recovery agent carry out compounded combination is added, is keeping the initial tortoise of butadiene-styrene rubber
While fragility energy, anti-cut, anti-puncture performance, by adding modification of aramid fiber, the tensile strength of butadiene-styrene rubber is improved；It is logical
Cross and add anti-tear crack resin, improve the tearing strength of butadiene-styrene rubber；By adding anti-recovery agent, raising tire, which resists to collapse, to be used up
Block performance and middle and later periods anti-cut, resistance to puncture, chunking resistance of the tire tread, so as to reach using full butadiene-styrene rubber as rubber system
Downhole well applications engineering tire tread overall performances greatly improve.
Present invention has the advantages that：
(1) the full butadiene-styrene rubber 1502 of environment-friendly type is used, for downhole well applications engineering tire tread, its anti-cut, anti-thorn
Performance uses environment-friendly type former material better than the tyre surface that the rubber system that natural rubber or natural rubber are combined with butadiene-styrene rubber forms
Material, it is possible to reduce pollution of the tire to environment and the health effect to the producer, user；
(2) anti-tear crack resin is used, is had outside as the thickening property of resin, moreover it is possible to improve the tearing strength of sizing material, reach
Resist to raising tyre surface and collapse the performance for using up block；
(3) modification of aramid fiber is used, anti-cut, the chunking resistance of the tire tread of tyre surface are further improved, to adapt to underground
The road conditions of very severe；
(4) anti-recovery agent is used, cross-linked network can be formed with rubber, so as to compensate the vulcanizate caused by aging
The destruction for the cross-linked network that middle sulfide linkage is formed with rubber, so that it is too fast to keep vulcanizate physical property to be unlikely to decline.
(5) using full butadiene-styrene rubber as rubber system, while using anti-tear crack resin, modification of aramid fiber and sulfuration resistant
The advantages of agent of reverting is compounded, and performance above raw material are in downhole well applications engineering tire tread rubber composition, while gram
Harmful effect caused by above-mentioned raw material is used alone in clothes.
Embodiment
Embodiment and component in comparative example rubber composition and source are as follows：
Butadiene-styrene rubber, E-SBR1502, Shen Hua chemical industry Co., Ltd product；
Carbon black N115, carbon black N1220, carbon black N234, are Cabot (China) Investment Co., Ltd product；
Zinc oxide, Hebei great plan Xin Ye Co., Ltds product；
Stearic acid, Feng Yi oil chemistries Co., Ltd product；
Antioxidant 4020, Jiangsu Sheng'Ao Chemical Technology Co., Ltd's product；
Anti-aging agent RD, Tianjin Ke Mai Chemical Co., Ltd.s product；
Crystallite protection wax, Rhein chemistry Qingdao Co., Ltd product；
Accelerator NS, Tianjin Ke Mai Chemical Co., Ltd.s product；
Altax, Tianjin Ke Mai Chemical Co., Ltd.s product；
Anti-scorching agent CTP, Yanggu Hua Tai chemical inc product；
Anti-tear crack resin SL6903, Hua Qi (China) Chemical Co., Ltd. product；
Modification of aramid fiber Sulfron3001, Japanese Di Ren Te Weilong Co., Ltds product, the auspicious limited public affairs of man of virtue and ability's economy and trade in Shanghai
Department provides；
Anti-recovery agent SR-008, Zun Yi Si Purui science and technology limited Company products；
Key instrument equipment：
FR-103C rubber tensile testing machines, Jiangsu Fa Rui instruments Science and Technology Ltd. product；
Roller abrasiometer, Taiwan high ferro Products；
Dynamic cutting test machine, the safe general Products in the U.S.；
Dynamic mechanical analyzer (DMA), plum Teller Products；
Performance test
1. tensile property is tested
According to the stress at definite elongation of the testing standard GB/T528-2009 tests vulcanization rubber, tensile strength, pull apart elongation
Rate：
100% stress at definite elongation --- sample is stretched to the tensile stress recorded during 100% elongation, units MPa；
Tensile strength --- sample is stretched to the tensile stress of fracture moment record, units MPa；
Elongation of elongation at break --- the sample when breaking, unit %；
According to the tearing strength of the national standard GB/T529-2008 tests vulcanization rubber；
Tearing strength --- with tensile testing machine, to thering is scarfing or sample without scarfing to be carried out under defined speed continuously
Stretching, until the maximum, force needed for sample fracture.Tearing strength unit is KN/m, and tearing strength is big, represents the tear-proof of rubber
Performance is good.
2. the test of shore hardness
According to the shore hardness of rubber composition after standard GB/T531.1-2008 assessment vulcanizations, hardness number is bigger, represents
The rigidity of rubber composition is higher.
3.DIN is worn away
Vulcanization rubber phase is tested to volume worn amount, unit mm according to standard GB/T9867-20083, relative volume abrasion
Measure smaller, show that wearability is better.
4. Cut Resistance Test
Using dynamic cutting test machine using certain specific cutter head, with certain rotating Round Wheel of energy repeated stock
Rubbery sample, simulation tire tread uses up the situation of block by collapsing of occurring of stone impact, cutting in actual use, with rubber
Glue sample impacted, cut after it is of poor quality with the ratio of initial mass characterization coupon results, which is known as " weightlessness ", with hundred
Divide than representing, it is weightless smaller, show that sample belt cutting-resisting property is better.
5. dynamic mechanical properties
Rubber dynamic mechanical properties is tested using dynamic mechanical analyzer (DMA), using the sample of standard wider
Certain shearing force is applied to sample in frequency and temperature range and carries out follow-on test, to obtain the dynamic mechanical of material
Frequency spectrum or TEMPERATURE SPECTROSCOPY.Apply sinusoidal mechanical stress when DMA is measured to sample, the amplitude of measurable power, displacement (deformation) are shaken
Width and phase shift, measure the fuel factor based on modulus or damping behavior change, and the dynamic of rubber is characterized with loss angle Tan δ
Can, Tan δ are smaller, and the elasticity of rubber is better, and heat is low.
Embodiment 1：
Formed according to embodiment 1 in table 1 Suo Shi, the Tire tread rubber composition of the present invention is prepared with following process：
(1) one section of mixing：By 100 parts of environment-friendly type butadiene-styrene rubbers, 2.5 parts of antioxidant 4020s, 3.5 parts of zinc oxide, 1.5 parts of tristearin
Acid, 8 parts of anti-tear crack resin SL6903,3 parts of aramid fiber Sulfron3001 put into internal mixer mixing chamber and are kneaded 30s, and rotor turns
Speed is 45rmp, and temperature carries bolt when reaching 100 DEG C, then add 60 parts of hard carbon black N220, rotor speed 30rmp, temperature
Carry bolt when reaching 125 DEG C and press bolt again, be kneaded to sizing material temperature be 155 DEG C when dumping, be cooled to room by one section of rubber master batch is disposed within
Temperature；
(2) two-stage mixing：By in one section of rubber master batch input mixer mixing room described in (1), 60s is kneaded, rotor speed is
35rmp, carries bolt and presses bolt again, continues to be kneaded 60s under same rotating speed, dumping when sizing material temperature reaches 150 DEG C, two sections of rubber master batch are put
It is cooled to room temperature in interior；
(3) refining eventually：By two sections of rubber master batch described in (2), 1.65 parts of sulphur, 1.3 parts of accelerator NSs, 0.5 part of altax,
2.5 parts of crystallite protection waxes, 0.1 part of antiscorching agent, 1.5 parts of anti-recovery agent SR-008 are put into mixer mixing rooms, and rotor turns
Speed is 20rmp, carries bolt, pressure bolt three times, is respectively kneaded 30s, dumping when sizing material temperature reaches 105 DEG C, obtains environment-friendly type downhole well applications
Engineering tire tread rubber composition.
The physical mechanical property of gained sizing material is shown in Table 2.
Comparative example 1：
The step of repeating embodiment 1, difference is in the composition using comparative example 1 in table 1.The physical machine of gained sizing material
Tool performance is shown in Table 2.
Comparative example 2
The step of repeating embodiment 1, difference is in the composition using comparative example 2 in table 1.The physical machine of gained sizing material
Tool performance is shown in Table 2.
Comparative example 3
The step of repeating embodiment 1, difference is in the composition using comparative example 3 in table 1.The physical machine of gained sizing material
Tool performance is shown in Table 2.
Comparative example 4
The step of repeating embodiment 1, difference is in the composition using comparative example 4 in table 1.The physical machine of gained sizing material
Tool performance is shown in Table 2.
Comparative example 5
The step of repeating embodiment 1, difference is in the composition using comparative example 5 in table 1.The physical machine of gained sizing material
Tool performance is shown in Table 2.
Comparative example 6
The step of repeating embodiment 1, difference is in the composition using comparative example 6 in table 1.The physical machine of gained sizing material
Tool performance is shown in Table 2.
Comparative example 7
The step of repeating embodiment 1, difference is in the composition using comparative example 7 in table 1.The physical machine of gained sizing material
Tool performance is shown in Table 2.
Table 1
Table 2
Conditions of vulcanization：150 DEG C of 60min@, aging condition：48h@100℃
Embodiment 1 can be seen that compared with comparative example 1, while add anti-tear crack resin SL6903, aramid fiber
Sulfron3001, anti-recovery agent SR-008 are into sizing material, and 19.8% He has been respectively increased in tensile strength before and after aging
19.9%, 35% and 72.7% has been respectively increased in 100% stress at definite elongation before and after aging, and aging posterior tear intensity is respectively increased
52.3% and 46.2%, 50% and 80% has been respectively increased in wear-resisting property before and after aging, and belt cutting-resisting property carries respectively before and after aging
It is high by 29.0% and 34.7%.
By embodiment 1 compared with comparative example 2~7, by anti-tear crack resin SL6903, aramid fiber Sulfron3001,
Anti-recovery agent SR-008 is added in sizing material at the same time, and respectively by anti-tear crack resin SL6903, aramid fiber
Sulfron3001, anti-recovery agent SR-008 are separately added in sizing material, and two kinds in above-mentioned three kinds of raw materials are added
It is compared into sizing material, while adds the sizing material of above-mentioned three kinds of raw materials, tensile strength, 100% is stretched surely before and after the aging of sizing material
Stress, tearing strength, wear-resisting property and belt cutting-resisting property have obtained raising by a relatively large margin.It is it can thus be seen that of the invention
Anti-tear crack resin SL6903, aramid fiber Sulfron3001, anti-recovery agent SR-008 are added into sizing material at the same time, three kinds
Raw material can produce synergistic effect, and the tearing strength of sizing material, wear-resisting property, belt cutting-resisting property are remarkably improved.
Obviously, above-described embodiment is only intended to clearly illustrate example of the present invention, and is not the reality to the present invention
Apply the restriction of mode.For those of ordinary skill in the field, can also make on the basis of the above description other
Various forms of changes or variation.There is no necessity and possibility to exhaust all the enbodiments.And these belong to the present invention
Spiritual changes and variations that derived from still in protection scope of the present invention among.
Claims (10)
1. a kind of environment-friendly type downhole well applications engineering tire tread rubber composition, it is characterised in that by weight by following groups
Divide and form：100 parts of butadiene-styrene rubber, 30~70 parts of hard carbon black, 1~10 part of anti-tear crack resin, 1~5 part of modification of aramid fiber, sulfur resistive
Change revert 0.5~2 part of agent, 1~3 part of sulphur, 3~7 parts of antioxidant, 2~4 parts of accelerating agent, 1~4 part of crystallite protection wax, zinc oxide
1~10 part, 1~5 part of stearic acid, 0.05~0.5 part of antiscorching agent.
2. rubber composition according to claim 1, it is characterised in that the butadiene-styrene rubber is environment-friendly type butadiene-styrene rubber 1502.
3. rubber composition according to claim 1, it is characterised in that the anti-tear crack resin is SL6903.
4. rubber composition according to claim 1, it is characterised in that the modification of aramid fiber is Sulfron3001.
5. rubber composition according to claim 1, it is characterised in that the anti-recovery agent is SR-008.
6. rubber composition according to claim 1, it is characterised in that the hard carbon black for N220 hard carbon blacks,
One or both of N234 hard carbon blacks, N115 hard carbon blacks.
7. rubber composition according to claim 1, it is characterised in that the antioxidant is N- (1,3- dimethyl butyrates
Base)-N'- diphenyl-para-phenylene diamines, one or both of 2,2,4- trimethyl -1,2- dihyaroquinoline condensates.
8. rubber composition according to claim 1, it is characterised in that the accelerating agent is the N- tert-butyl group -2- benzo thiophenes
One or both of azoles sulfenamide, 2,2'- dithio-bis-benzothiazoles.
9. rubber composition according to claim 1, it is characterised in that the antiscorching agent is N- cyclohexyl thio neighbours benzene two
Carboximide.
10. a kind of preparation method of environment-friendly type downhole well applications engineering tire tread rubber composition as described in claim 1-9,
It is characterised in that it includes following steps：
(1) one section of mixing：100 parts of butadiene-styrene rubbers, 1~5 part of modification of aramid fiber, 1~10 part of anti-tear crack resin, 3~7 parts are prevented old
Agent, 1~10 part of zinc oxide, 1~5 part of stearic acid put into internal mixer mixing chamber and are kneaded 30~40s, rotor speed for 40~
50rmp, temperature carry bolt when reaching 90~100 DEG C, then add 50~70 parts of hard carbon blacks, and rotor speed is 30~40rmp,
Temperature carries bolt when reaching 120~130 DEG C and presses bolt again, be kneaded to sizing material temperature be 150~155 DEG C when dumping, one section of rubber master batch is put
It is cooled to room temperature in interior；
(2) two-stage mixing：By in one section of rubber master batch input mixer mixing room described in (1), 45~60s, rotor speed are kneaded
For 30~40rmp, carry bolt and press bolt again, continue 45~60s of mixing under 30~40rmp rotating speeds, sizing material temperature reaches 150~155
DEG C when dumping, be cooled to room temperature two sections of rubber master batch are disposed within；
(3) refining eventually：By two sections of rubber master batch described in (2) and 0.5~2 part of anti-recovery agent, 1~3 part of sulphur, 2~4 parts of promotions
Agent, 1~4 part of crystallite protection wax, 0.05~0.5 part of antiscorching agent are put into mixer mixing room, rotor speed for 20~
25rmp, carries bolt, pressure bolt, is respectively kneaded 30~40s, dumping when sizing material temperature reaches 100~110 DEG C, obtains environment-friendly type underground three times
Purposes engineering tire tread rubber composition.
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| CN110028705A (en) * | 2019-04-09 | 2019-07-19 | 江苏通用科技股份有限公司 | Hard Mine Area Engineering tire tread glue and preparation method thereof |
| CN111825895A (en) * | 2020-07-30 | 2020-10-27 | 江苏通用科技股份有限公司 | Tire bead protection rubber and preparation method thereof |
| CN112831100A (en) * | 2021-03-05 | 2021-05-25 | 山东玲珑橡胶科技有限公司 | Pure electric bus tire tread rubber composition |
| CN114133632A (en) * | 2021-12-15 | 2022-03-04 | 泰凯英(青岛)专用轮胎技术研究开发有限公司 | Mining cold-resistant tire tread rubber and preparation method thereof |
| CN115160659A (en) * | 2022-06-23 | 2022-10-11 | 泰凯英(青岛)专用轮胎技术研究开发有限公司 | Low-heat-generation high-wear-resistance tear-resistant engineering tire tread rubber and preparation method thereof |
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Denomination of invention: Environmental protection type underground engineering tire tread rubber composition and its preparation method Effective date of registration: 20220127 Granted publication date: 20200121 Pledgee: Agricultural Bank of China Limited Qingdao Branch Business Department Pledgor: Taikaiying (Qingdao) special tire technology research and Development Co.,Ltd. Registration number: Y2022370010021 |
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Denomination of invention: Environmental friendly underground engineering tire tread rubber composition and its preparation method Effective date of registration: 20230421 Granted publication date: 20200121 Pledgee: Agricultural Bank of China Limited Qingdao Branch Business Department Pledgor: Taikaiying (Qingdao) special tire technology research and Development Co.,Ltd. Registration number: Y2023370010040 |
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