CN109369994A - A kind of low zinc rubber composition - Google Patents
A kind of low zinc rubber composition Download PDFInfo
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- CN109369994A CN109369994A CN201811363285.XA CN201811363285A CN109369994A CN 109369994 A CN109369994 A CN 109369994A CN 201811363285 A CN201811363285 A CN 201811363285A CN 109369994 A CN109369994 A CN 109369994A
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C08L23/283—Halogenated homo- or copolymers of iso-olefins
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- 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
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- 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
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- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- 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
Abstract
The invention discloses a kind of low zinc rubber compositions, it is characterised in that it includes the rubber composition of at least one diene elastomer, the zinc for being 0.5~1phr containing content, phr refers to the number of every 100 parts of rubber, and the rubber composition is based at least: a kind of filler systems；A kind of cross-linking system based on sulphur, the cross-linking system include it is a kind of using zinc hydroxide particle be the high-specific area nano zinc oxide of carrier as vulcanizing activator, also comprising a kind of adjuvant system.Such vulcanizing activator is in sediment decomposable process, by nano zine oxide uniform load in zinc hydroxide particle surface, chemical activity is high, good dispersion, and the superperformance of product is also ensured that in the case where being reduced service condition, reduces the residual volume of the zinc in rubber product.Applied to tire product and its environmental-protecting performance is improved, reduces tire bring zinc pollution problem.
Description
Technical field
Invention belongs to tyre stock production technical field, and in particular to a kind of low zinc rubber composition.
Background technique
Zinc compound, especially zinc oxide will be used in the production of nearly all rubber product.Usual dosage is sizing material
The 2% of total amount is about as much as 3~5phr zinc oxide.In European Union, about 100,000 tons of zinc oxide and slightly a small amount of its every year
He is used for rubber industry by zinc compound, this probably accounts for the 40% of zinc oxide total amount consumed, and the annual zinc oxide consumption in China is big
About 18~300,000 tons.In sulfur sulfide system, zinc oxide is mainly used as activating agent, in addition, it can be also added to peroxide
In compound vulcanizing system, crosslinking agent use can also be made in the rubber containing halogen and carboxyl.It is also used as latex
White dye also functions as half reinforced filling once in a while, and zinc oxide can also improve heat transfer performance, other zinc impregnations for being used for sizing material are closed
Object includes zinc soap, curing carbaminate, benzothiazole -2- mercaptan zinc, benzimidazole -2- mercaptan zinc.
Although zinc using very extensive.However, when zinc is released in environment, when into streams, river and ocean,
The alloy of certain zinc can poison microorganism and aquatile.Studies have shown that zinc is more than that a certain concentration can block each interlayer in fish body
Channel hinders respiratory movement, body growth and maturation, and mankind's activity, which is arranged, to be influenced also caused by the zinc to aquatic ecosystem in mistake
It is gradually displayed in 30 years gone.1993, Dutch national health and Study on Environmental Protection institute proposed one about zinc
" unified standard ", it is proposed that zinc concentration is 9 μ g/L in water, and maximum acceptable concentration is 25 μ g/L.Nineteen ninety-five, in Sweden's environmental protection
In the rubber compound list of mechanism of organizations, zinc and zinc compound are listed in main matter, it is proposed that being substituted or being limited makes
With.In the same year, in the assessment of risks project of European Union, zinc and zinc oxide are put into again in the second class harmful substance list.2004 4
Month, zinc oxide is formally divided into the substance " to environment nocuousness " by EU Committee instruction 2004/73/EC, and hazard class is
R50/53 " very harmful to aquatile, long-term adverse effect can be generated to aquatic ecosystem ", " should avoid being discharged into life
In state environment ".3 the end of month in 2016, California, USA propose a bill SB1260, it is proposed that being limited in tire makes
With zinc or zinc oxide, while it may forbid sale to contain the tire product of certain zinc, cause zinc oxide and tire production
The highest attention of enterprise.The bill is it also hold that outdoor rubber material is the main source of zinc pollution in environment.All in all,
Under the present circumstances, it is a kind of watchful for accelerating green product upgrading to Tire production enterprise for the proposition of bill.Zinc pollution is true
Property presence, and due to global rubber industry to environmental requirement be continuously improved, actively find and exploitation zinc oxide substitution produce
Product are got more and more attention, and zinc decrement research is trend of the times.
It is the metal to be obtained by smelting currently, generalling use indirect process zinc oxide in each position sizing compound formula of tire
Zinc ingot metal or cadmia are raw material, and zinc fume is converted under 1000 DEG C of high temperature, the air oxidation then blasted at zinc oxide, and
It collects after the cooling period and obtains Zinc oxide particles.Indirect process zinc oxide simple production process, particle diameter is on 0.1~10 micron of left side
The right side, specific surface area is in 3~7m2/g.(the zinc oxide product such as Figure of description 1 of indirect method production)
Since indirect oxidation zinc specific surface area is small, the only small part effect that really plays vulcanizing activator is generally used
Number is 3~5phr, and the dosage of common zinc oxide may be up to 8phr in privileged sites such as steel belt glue formula.These contain zinc
Measure high sizing material and automobile tire be made by a series of production processes, in vehicle travel process, zinc with tire abrasion, useless
It abandons and enters in surrounding enviroment and soil, river, adverse effect is caused to the ecosystem.Nano zine oxide is because have nanoparticle
The distinctive advantage of son, therefore dosage can be reduced in use, but nanoparticle is easy to reunite, and limits the hair of nano effect
It waves.In order to solve the dispersion of nano zine oxide, people attempt that dispersing agent, lubrication are added in nano zine oxide production process
Agent, or using nanoclay, silica as core or carrier, thereon by oxide coated by zinc, but all loss a part activity.
By the end of the year 2017, continuous 9 years ranking the first in the world, auto industry are China's wheel fetal hairs to China's automobile volume of production and marketing
The huge motive force of exhibition, as the exploitation of Domestic Automotive Industry product restructuring, especially new-energy automobile will drive significantly
The exploitation of the advanced concept tires such as China's green tire, energy conservation and environmental protection tire.Development and application green tire make to tire is improved
With performance, realize energy-saving and emission-reduction, environmentally protective with important strategic importance.Therefore, it is white how to research and develop a kind of low rolling resistance of low zinc
Black filled rubber composition is related to tyre stock production field, is applied to the low rolling of low zinc and hinders green tire technology, has important
Realistic meaning.
Summary of the invention
It is easy the technical issues of reunion leads to zinc pollution for nanoparticle existing in the prior art, the purpose of invention exists
In providing a kind of low zinc rubber composition, formula while the advantage that Zn content is low, rolling resistance is low is had both.
Invent the technical solution taken are as follows:
A kind of low zinc rubber composition, which is characterized in that the rubber composition including at least one diene elastomer contains
Having content is the zinc of 0.5~1phr, and phr refers to the number of every 100 parts of rubber, and the rubber composition is based at least:
A kind of filler systems；
A kind of cross-linking system based on sulphur, the cross-linking system include a kind of using zinc hydroxide particle as the Gao Bibiao of carrier
Area nanometer zinc oxide is as vulcanizing activator；
It include also vulcanization accelerator, such as thiazoles, sulfenamide, thiurams, dithiocarbamates and two
Benzene guanidine etc.；Vulcanizing agent, such as common sulphur powder, insoluble sulfuy.
Adjuvant system.
Further, nano zine oxide mass fraction 80 ± 5% in the vulcanizing activator, zinc hydroxide mass fraction are
20 ± 5%.
Further, the vulcanizing activator the preparation method comprises the following steps: using wet production principle, it is molten in the soluble-salt of zinc
(soluble salt solutions of common zinc have ZnCl to liquid2、ZnSO4、Zn(NO3)2Deng) in be added precipitating reagent, the precipitating reagent be ammonia
Water, urea or sodium hydroxide decompose zinc hydroxide precipitation object is made under the high temperature conditions, can under heating, mechanical agitation
Soluble zinc salt and precipitating reagent are cooperated by certain mol proportion example, by adjusting solution hydrolysising reacting temperature, hydrolysis time, pH
Value, feed molar proportion, the type and ratio of surfactant, obtain presoma Zn (OH)2Precipitating；Pass through secondary distilled water again
It repeatedly washs, filter, being dried to obtain Zn (OH)2Powder.Then sediment is filtered, washed, dry after thermally decompose again,
It roasts under hot conditions, by adjusting maturing temperature and calcining time, obtains using certain mass number zinc hydroxide as carrier
Nano zine oxide.
Further, the hot conditions roasting refers to 170 DEG C ± 30 DEG C.
Further, the nano zine oxide has larger aperture distribution and its specific surface area is 20~80m2/g。
Further, the filler systems include one of carbon black, graphene, carbon nanotube or inorganic filler or more
Kind.
Further, the inorganic filler is in white carbon black, titanium dioxide, nanoclay, calcium carbonate or magnesium carbonate
It is one or more.
Further, the diene elastomer is polybutadiene (BR), synthetic polyisoprenes (IR), natural rubber
(NR), butadiene-styrene (SBR) copolymer, isobutylene-isoprene (butyl rubber IIR) copolymer and its halobutyl
One or more blends of rubber.
Further, all main vulcanization accelerators of the cross-linking system and time vulcanization accelerator content be 0.5~
5.0phr。
Further, the adjuvant system includes operation oil, includes aromatic naphtha, environment-friendly aromatic oil, heavy naphthenic oils, cycloalkanes
Oil, paraffin oil etc.；Anti-aging agent includes the anti-aging agents such as quinolines, amine, triazines, naphthylamines class；It in addition may include plasticizer, modeling
Solve well known auxiliary agent in the rubber industries such as agent, silane coupling agent, homogenizing agent, dispersing agent, tackifying resin, antiscorching agent.
Advantageous effect of the invention are as follows:
Zinc oxide mass fraction 80 ± 5% in cross-linking system based on sulphur of the invention, zinc hydroxide mass fraction are 20
± 5%.Such vulcanizing activator is in sediment decomposable process, by nano zine oxide uniform load in zinc hydroxide particle table
Face.Nano zine oxide itself is easy to reunite, and zinc hydroxide then has of a relatively loose stacking states, in process of production, nanometer
Zinc oxide is uniformly supported on of a relatively loose zinc hydroxide particle, can effectively reduce the reunion between nano zine oxide
Degree.And in rubber mixing process, even if there is the particle of some reunions not disperse, when melting temperature reaches 125 DEG C or more, hydrogen
Zinc oxide is heated to decompose, i.e., aggregate structure is deteriorated because of the decomposition of zinc hydroxide, forms new small zinc oxide fragment,
And further disperse under the effect of mixer mechanical shearing.Therefore, vivid can think, zinc hydroxide is the structure of aggregate
Disintegrating agent.This high, the good dispersion using zinc hydroxide as the nano zine oxide chemical activity of carrier, and in decrement service condition
Under also ensure that the superperformance of product, it is possible to reduce the residual volume of the zinc in rubber product.
The present invention designs to obtain that a kind of Zn content is low, rubber composition of excellent combination property, is applied to tire product simultaneously
Its environmental-protecting performance is improved, while guaranteeing and optimizing tyre performance, Zn content can reduce by 50~80%, to reduce tire belt
The zinc pollution problem come.
Detailed description of the invention
Fig. 1 is the zinc oxide product figure of indirect method preparation in the prior art；
Fig. 2 is to meet GB/T 19589-2004 requirement, zinc oxide content >=99.0%, specific surface area 45m2/ g's is general
Lead to nano oxidized zinc product figure, there are obvious reunions；
Fig. 3 is in the application using zinc hydroxide as the high-specific area nano zinc oxide product figure of carrier；
Fig. 4 is that can be reduced to make in rubber as the high-specific area nano zinc oxide of carrier using zinc hydroxide in the application
Schematic diagram.In Fig. 4 ● zinc hydroxide is represented, ● zinc oxide is represented, black curve represents rubber macromolecule.
Specific embodiment
Invention is further illustrated with reference to the accompanying drawing.
Zinc oxide applies existing one-hundred-year history as vulcanizing activator in rubber, it can accelerate curingprocess rate but also mention
High-sulfurized degree.Zinc oxide is big to the affinity of electronics, also big to the effect of promotor adsorption, is active in metal oxide
A kind of strongest activating agent.Zinc oxide and stearic acid are that the classics of vulcanization of rubber activating agent combine, with thiazole accelerator (with
XSH general formula indicates) for, the mechanism of action is as follows:
1) in the presence of conditions of vulcanization and fatty acid, zinc oxide first generates promotor zinc salt with XSH effect
ZnO+2XSH→XS-Zn-SX
2) promotor zinc salt and the effect of 8 ring body of sulphur generate more sulphur zinc salts
XS-Zn-SX+2Sm→XS-Sm-Zn-Sm-SX
3) more sulphur zinc salts and rubber reaction generate and are crosslinked pre- precursor XSnR
XS-Sm-Zn-Sm-SX+RH→XS-Sm-R+ZnS+HSm-1X
4) it is crosslinked pre- precursor XSSmR is acted on rubber molecule complete crosslinking again
XS-Sm-R+RH→R-Sm-1-R+XSH
By reaction equation (2) as it can be seen that each Zn atom and 2 cyclic annular sulphur (Sm) effect.It is calculated by reaction equation (2), Zn and S
Atomicity ratio be 1:16.Such as with 3 parts of sulphur, zinc oxide dosage should be 81.36 × 3/ (32.06 × 16)=0.48 part.
A.Chapmlln is based on the analysis conventional vulcanized to natural rubber, and the product after finding zinc oxide reaction is as follows, and 0.6 part is converted into
Zinc sulphide；0.2 part is converted into stearic acid；≤ 0.1 part is converted into zinc-promotor complex compound.It can thus be seen that in general oxygen
Change in 4 parts of zinc dosage of conventional formulation, only 1 part is used effectively, so the space for reducing zinc oxide dosage is very big, still
It should be taken into account that the cross-bond in rubber reticular structure is not entirely polysulfide bond, there are also a small amount of monosulfidic bonds and cystine linkage, and
The influence of various other factors.Researcher is studying always the problem of reducing zinc oxide dosage for many years, and finds different
Zinc oxide substitute generallys use the mode of addition processing aid, but its effect is not obvious as vulcanizing activator.
A kind of low zinc rubber composition, which is characterized in that the rubber composition including at least one diene elastomer contains
Having content is the zinc of 0.5~1phr, and phr refers to the number of every 100 parts of rubber, and the rubber composition is based at least:
A kind of filler systems, for improving the processing performance, mechanical property, wear hardness of rubber matrix；
A kind of cross-linking system based on sulphur, the cross-linking system include a kind of using zinc hydroxide particle as the Gao Bibiao of carrier
Area nanometer zinc oxide is as vulcanizing activator；
It include also vulcanization accelerator, such as thiazoles, sulfenamide, thiurams, dithiocarbamates and two
Benzene guanidine etc.；Vulcanizing agent, such as common sulphur powder, insoluble sulfuy.Effect is to make linear macromolecule chain by chemical crosslinking
With three-dimensional space net structure is formed, so that basic change occurs for the physical property of rubber, dynamic property, wear hardness etc., in fact
Its existing wider purposes.
Adjuvant system, main purpose are such as led to improve the processing performances such as the mixing of rubber, calendering, extrusion, molding
It crosses chemistry modeling solution effect and interrupts rubber macromolecule chain, reduce sizing material mooney viscosity；It is big by the way that physics lubricant increase rubber is added
Strand mobility improves processing performance；Half parts-moulding viscosity is improved by the way that tackifying resin is added；It is anti-scorch by being added
Agent improves sizing material process safety etc..
The diene elastomer is polybutadiene (BR), synthetic polyisoprenes (IR), natural rubber (NR), butadiene-
Styrene (SBR) copolymer, isobutylene-isoprene (butyl rubber IIR) copolymer and its halogenated butyl rubber one kind or
A variety of blends.
Further, nano zine oxide mass fraction 80 ± 5% in the vulcanizing activator, zinc hydroxide mass fraction are
20 ± 5%.
Further, the vulcanizing activator the preparation method comprises the following steps: using wet production principle, be with the soluble-salt of zinc
Precipitating reagent is added in raw material, and under water bath with thermostatic control heating, mechanical agitation, soluble zinc salt and precipitating reagent press certain mol proportion
Example cooperation, by adjusting solution hydrolysising reacting temperature, hydrolysis time, pH value, feed molar proportion, the kind of surfactant
Class and ratio obtain presoma Zn (OH)2Precipitating；It repeatedly washs, filter, being dried to obtain Zn (OH) by secondary distilled water again2Powder
End.It roasts, by adjusting maturing temperature and calcining time, obtains with certain mass number zinc hydroxide as load under the high temperature conditions
The nano zine oxide of body.
Further, the soluble salt solutions of the zinc can be ZnCl2、ZnSO4、Zn(NO3) 2 it is equal in precipitating is added
Agent.
Further, the precipitating reagent is ammonium hydroxide, urea or sodium hydroxide.
Further, the hot conditions roasting refers to 170 DEG C ± 30 DEG C.
Further, described by the nano zine oxide specific surface area of carrier of zinc hydroxide is 20~80m2/g。
Further, the filler systems include one of carbon black, graphene, carbon nanotube or inorganic filler or more
Kind.
Further, the inorganic filler is in white carbon black, titanium dioxide, nanoclay, calcium carbonate or magnesium carbonate
It is one or more.
Further, the diene elastomer is polybutadiene (BR), synthetic polyisoprenes (IR), natural rubber
(NR), butadiene-styrene (SBR) copolymer, isobutylene-isoprene (butyl rubber IIR) copolymer and its halobutyl
One or more blends of rubber.
Further, all main vulcanization accelerators of the cross-linking system and time vulcanization accelerator content be 0.5~
5.0phr。
Filler systems include one of carbon black, graphene, carbon nanotube or inorganic filler or a variety of.
Especially commonly used in HAF, ISAF, SAF, FEF, GPF type in tire, the non-limiting reality of this carbon black
Example is it can be mentioned that N115, N134, N234, N330, N339, N347, N375, N550, N660 carbon black.
The inorganic filler is one of white carbon black, titanium dioxide, nanoclay, calcium carbonate or magnesium carbonate or a variety of.
, it is preferable to use the precipitated silica of high dispersive, is precipitated as this high dispersive in the case of using white carbon black
The non-limiting example of method white carbon black, it can be mentioned that the Ultrasil 7000 of Evonic；The Zeosil200MP of Soilve,
1165MP, 1115MP white carbon black；Hi-Sil EZ150G silica of PPG etc..
It is well known in the art to utilize when white carbon black, need to establish between filler and elastomer using coupling agent
Bonding.
Common nano zine oxide is easy to reunite, the more difficult effect for playing vulcanizing activator of the zinc oxide at reunion center.At present
The carrier zinc oxide that the country occurs is usually to load or be coated on inert substance (such as nano clay, silica for zinc oxide
Deng) on, this inertia core species activity is low.And vulcanizing activator used in the present invention is using zinc hydroxide as carrier or core
The heart continues the effect for playing sulfurate activity its advantage is that zinc hydroxide can resolve into zinc oxide at a certain temperature, is to have one
Fixed active carrier.As shown in figure 4, such vulcanizing activator is uniformly to bear nano zine oxide in sediment decomposable process
It is loaded in zinc hydroxide particle surface.Nano zine oxide itself is easy to reunite, and zinc hydroxide then has of a relatively loose stacking states,
In process of production, nano zine oxide is uniformly supported on of a relatively loose zinc hydroxide particle, can effectively reduce nanometer
Degree of aggregation between zinc oxide improves dispersibility of the nano zine oxide in rubber.And in rubber mixing process, even if having
The particle of some reunions does not disperse, and when melting temperature reaches 125 DEG C or more, zinc hydroxide is heated to decompose, that is, knot of reuniting
Structure forms new small zinc oxide fragment because the decomposition of zinc hydroxide is deteriorated, and under the effect of mixer mechanical shearing into
The dispersion of one step.Therefore, can image think that zinc hydroxide is the structural collapse agent of aggregate, principle is similar to effervescent tablet.With
Zinc hydroxide is that the nano zine oxide chemical activity of carrier is high, good dispersion, and also ensures that system in the case where being reduced service condition
The superperformance of product, it is possible to reduce the residual volume of the zinc in rubber product.
The rubber composition also may include all or part of elastic compositions it is generally desirable to for manufacturing tire
In typical additives, such as plasticizer or fill oily (no matter the latter is aromatic or non-aromatic), functional resin,
Protective reagent such as ozone-resistant wax, chemical antiozonant, antioxidant, antifatigue etc..
The rubber composition further includes vulcanizing system, is preferably based on sulphur, and be based on main vulcanization accelerator, is based especially on
The promotor of thiazoles, sulfenamide type, such as 2-mercaptobenzothiazole based bisulfide (referred to as " MBTS "), N- hexamethylene
Base -2-[4-morpholinodithio base sulfenamide (referred to as " CBS "), N, N- dicyclohexyl -2-[4-morpholinodithio base sulfenamide is (referred to as
" DCBS "), N- tert-butyl -2-[4-morpholinodithio base sulfenamide (referred to as " TBBS "), N- tert-butyl -2-[4-morpholinodithio base time sulphur
The mixture of acid imide (referred to as " TBSI ") and these compounds.
The rubber composition can be used in each rubber components of tire, such as tyre surface (including crown and base portion
Glue), sidewall, triangle rubber, chafer, air/tight layer rubber etc..
Embodiment 1
Indirect process zinc oxide meets national standard GB/T3185-2016 and requires, zinc oxide content >=99.7%, as shown in Fig. 1,
As can be seen that indirect process zinc oxide is mostly rock sugar shape irregular square.
Common nano zine oxide A: meeting GB/T 19589-2004 requirement, zinc oxide content >=99.0%, and specific surface area is
45m2/ g has obvious agglomeration as shown in Figure 2.
Nano zine oxide B: using zinc hydroxide as the nano zine oxide of carrier, specific surface area 45m2/ g, wherein zinc oxide
Mass fraction is 80.2%, and zinc hydroxide mass fraction is 19.5%, i.e., nano zine oxide of the invention, as shown in Figure 3.
Formula:
Performance:
Zinc oxide in vulcanization of rubber crosslinking and ageing process other than playing the role of vulcanizing activator, in the vulcanization of rubber
Positive effect can also be played in ageing process: in vulcanization and ageing process, cross-bond especially polysulfide crosslink bond is easy hair
Raw fracture, the sulfydryl for being broken generation can make rubber molecule generate cyclized structure, and zinc oxide can be acted on sulfydryl, is broken
Cross-bond recombine as new cross-bond, avoiding problems the generations of the reduction of cross-bond and cyclized structure；Sizing material exists
In vulcanization and ageing process, especially under the high temperature conditions, hydrogen sulfide may be generated, polysulfide bond can be decomposed, make to be crosslinked bond number
Reduce, when there is zinc oxide, it can be acted on hydrogen sulfide, to prevent the fracture of polysulfide bond；In addition, zinc oxide can be with polysulfide bond
Effect deviates from the sulphur atom in polysulfide bond, becomes the cross-bond of less sulphur atom, the thermal stability of vulcanizate is improved.Cause
This, whether zinc oxide is well dispersed, and whether dosage is suitable, and whether activity meets the requirements, most important for rubber compounding performance.
R97 refers on curing curve the time required for peak torque MH decline 3%, and characterization is that the sulfuration resistant of sizing material is returned
Originality energy, the R97 time is longer, and characterization anti-reversion behaviour is better.As can be seen that using the comparative formula of indirect process zinc oxide
The R97 of 1-1 is 49min14sec, but its zinc dosage is more；It is dropped using zinc dosage in the comparative formula 1-2 of common nano zine oxide A
Low 67%, but R97 shortens 5min49sec, reversion resistance decline simultaneously；And use the embodiment 1 of nano zine oxide B not only
Zinc dosage is reduced more than 67%, and anti-reversion behaviour still is able to be maintained.
It is pulled apart before tensile strength * aging before elongation at break/aging after ageing-resistant coefficient=aging post-tensioning intensity * aging
Elongation * 100%.Ageing-resistant coefficient is bigger, and characterization sizing material ageing-resistant performance is better.As can be seen that compared to indirect method oxygen is used
The comparative formula 1-1 for changing zinc declines 14.7% using the comparative formula 1-2 ageing-resistant performance of common nano zine oxide A；And make
It still is able to be maintained with 1 ageing-resistant performance of embodiment of nano zine oxide B.
In conclusion nano zine oxide B used in the present embodiment has preferable anti-reversion behaviour and ageing-resistant
Performance.This is mainly due to common nano zine oxide A to reunite seriously, the more difficult dispersion in sizing material.And nano zine oxide is with hydrogen-oxygen
Change zinc is carrier, when melting temperature reaches 125 DEG C or more, it may occur that point of chemical breakdown, i.e. aggregate structure because of zinc hydroxide
Solution is deteriorated, and forms new small zinc oxide fragment, and further disperse under the effect of mixer mechanical shearing, and play sulphur
Change the effect of activating agent.
Embodiment 2
Nano zine oxide B in embodiment 2: using zinc hydroxide as the nano zine oxide of carrier, specific surface area 45m2/ g,
Wherein zinc oxide mass fraction is 80.2%, and zinc hydroxide mass fraction is 19.5%, i.e., nano zine oxide of the invention is such as schemed
Shown in 3.
The indirect process zinc oxide used in comparative formula 2-1 meets national standard GB/T3185-2016 and requires, and zinc oxide content >=
99.7%, as shown in Figure 1, it can be seen that indirect process zinc oxide is mostly rock sugar shape irregular square.
The nano zine oxide C used in comparative formula 2-2 are as follows: by above-mentioned using zinc hydroxide as the nano zine oxide B of carrier,
It is heat-treated 2h at 150 DEG C, so that zinc hydroxide resolves into zinc oxide completely, obtains nano zine oxide C.
Formula:
| Formula constituent | Comparative formula 2-1 | 2-2 is matched in comparison | Embodiment 2 |
| Oil-filled emulsion polymerized styrene butadiene rubber | 110.0 | 110.0 | 110.0 |
| Natural rubber | 20.0 | 20.0 | 20.0 |
| High-dispersion white carbon black 200MP | 70.0 | 70.0 | 70.0 |
| N339 carbon black | 5.0 | 5.0 | 5.0 |
| Silane coupling agent Si75 | 6.4 | 6.4 | 6.4 |
| Stearic acid | 1.8 | 1.8 | 1.8 |
| Indirect process zinc oxide | 3.0 | ||
| Nano zine oxide B | 0.9 | ||
| Nano zine oxide C | 0.9 | ||
| Environment-friendly aromatic oil | 6.0 | 6.0 | 6.0 |
| Antioxidant 4020 | 2.2 | 2.2 | 2.2 |
| Anti-aging agent RD | 1.8 | 1.8 | 1.8 |
| Protection wax | 1.5 | 1.5 | 1.5 |
| Diphenylguanidine PG | 1.8 | 1.8 | 1.8 |
| Accelerator NS | 1.8 | 1.8 | 1.8 |
| Insoluble sulfur HD OT 20 | 2.0 | 2.0 | 2.0 |
Performance:
As can be seen that the use of the R97 of the comparative formula 2-1 of indirect process zinc oxide being 47min24sec, but its zinc dosage is more；
70% is reduced using zinc dosage in the comparative formula 2-2 of nano zine oxide C, but R97 shortens 5min42sec simultaneously, sulfuration resistant is returned
Originality decline；And using the embodiment 2 of nano zine oxide B, not only zinc dosage is reduced more than 70%, and anti-reversion behaviour is still
It can be maintained.
The ageing-resistant ageing-resistant coefficient of coefficient is bigger, and characterization sizing material ageing-resistant performance is better.As can be seen that compared to using indirect
The comparative formula 2-1 of method zinc oxide declines 9.5% using the comparative formula 2-2 ageing-resistant performance of nano zine oxide C；And it uses
2 ageing-resistant performance of embodiment of nano zine oxide B still is able to be maintained.
For nano zine oxide B after Overheating Treatment, zinc hydroxide is decomposed into zinc oxide, and losing in structure can be heated
The carrier zinc hydroxide that chemical breakdown occurs, is unfavorable for dispersing, therefore comparative formula 2-2 anti-reversion behaviour and resistance to ag(e)ing
It can decline.Nano zine oxide B used in embodiment 2 is using zinc hydroxide as carrier, and aggregate structure can be because of the height of zinc hydroxide
Warm chemical breakdown is deteriorated, and forms new small zinc oxide fragment, and further disperse under the effect of mixer mechanical shearing,
Its activity is set to be not fully exerted, therefore the formula of embodiment 2 shows preferable anti-reversion behaviour and ageing-resistant performance.
Embodiment 3-5
The indirect process zinc oxide used in comparative formula 3 meets national standard GB/T3185-2016 and requires, and zinc oxide content >=
99.7%, as shown in Figure 1, it can be seen that indirect process zinc oxide is mostly rock sugar shape irregular square.
Nano zine oxide B in embodiment 3,4,5: using zinc hydroxide as the nano zine oxide of carrier, specific surface area 45m2/
G, wherein zinc oxide mass fraction is 80.2%, and zinc hydroxide mass fraction is 19.5%, i.e., nano zine oxide of the invention, such as
Fig. 3.
Formula:
| Formula constituent | Comparative formula 3 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Brombutyl | 80.0 | 80.0 | 90.0 | 70.0 |
| Natural rubber | 20.0 | 20.0 | 10.0 | 30.0 |
| N660 carbon black | 64.0 | 58.0 | 55.0 | 45.0 |
| N550 carbon black | 8.0 | 13.0 | 20.0 | |
| Homogenizing agent | 8.0 | 10.0 | 6.0 | 8.0 |
| Naphthenic oil | 4.0 | 7.0 | ||
| Paraffin oil | 8.0 | 6.0 | ||
| Stearic acid | 1.0 | 0.8 | 0.8 | 1.0 |
| Indirect process zinc oxide | 3.0 | |||
| Nano zine oxide B | 0.8 | 0.9 | 1.0 | |
| Altax | 1.5 | 1.4 | 1.3 | 1.6 |
| Accelerator NS | 0.8 | 0.9 | ||
| Accelerant CZ | 0.9 | 1.0 | ||
| Common Sulfur | 0.5 | 0.5 | 0.6 | 0.7 |
Performance:
As can be seen that zinc dosage maximum can reduce by 70% left side for the formula system based on brombutyl
It is right.
Embodiment 6
The vulcanizing activator used in comparative formula 4 is to compare table using nanoclay as core or the activated zinc oxide of carrier
Area is 65m2/ g, zinc oxide mass fraction are 75.2%, and nanoclay mass fraction is 24.5%.
Nano zine oxide D is using zinc hydroxide as carrier in embodiment 6, specific surface area 65m2/ g, wherein zinc oxide quality
Score is 75.0%, and zinc hydroxide mass fraction is 24.6%.
Formula:
| Formula constituent | Comparative formula 4 | Embodiment 6 |
| Natural rubber | 40.0 | 40.0 |
| Butadiene rubber | 60.0 | 60.0 |
| N330 carbon black | 35.0 | 35.0 |
| N660 carbon black | 20.0 | 20.0 |
| Naphthenic oil | 4.0 | 4.0 |
| Stearic acid | 2.0 | 2.0 |
| Activated zinc oxide | 0.8 | |
| Nano zine oxide D | 0.8 | |
| Accelerator NS | 0.8 | 0.8 |
| Common Sulfur | 2.2 | 2.2 |
Performance:
Compared to comparative formula 4,6 sizing material R97 of embodiment extends 2min19sec, and anti-reversion behaviour is promoted；After aging
Tensile strength, elongation at break improve, and ageing-resistant coefficient improves about 15%, and sizing material ageing-resistant performance is improved.This is because,
It is using zinc hydroxide as carrier or the nano zine oxide of core, when melting temperature is super in mixing process used in embodiment 6
When crossing 125 DEG C, zinc hydroxide is decomposed, and generates the zinc oxide with sulfurate activity.And active oxygen used in comparative formula 4
Change zinc using inert nanoclay as carrier or core, nanoclay does not have sulfurate activity.
The above is not the limitation to invention, it should be pointed out that: for those skilled in the art,
Under the premise of not departing from invention essential scope, several variations, modifications, additions or substitutions can also be made, these are improved and profit
Decorations also should be regarded as the protection scope of invention.
Claims (9)
1. a kind of low zinc rubber composition, which is characterized in that the rubber composition including at least one diene elastomer contains
Content is the zinc of 0.5~1phr, and phr refers to the number of every 100 parts of rubber, and the rubber composition is based at least:
A kind of filler systems；
A kind of cross-linking system based on sulphur, the cross-linking system include a kind of using zinc hydroxide as the high-specific area nano of carrier
Zinc oxide is as vulcanizing activator；
Adjuvant system.
2. a kind of low zinc rubber composition according to claim 1, which is characterized in that nano oxidized in the vulcanizing activator
Zinc mass fraction 80 ± 5%, zinc hydroxide mass fraction are 20 ± 5%.
3. a kind of low zinc rubber composition according to claim 1, which is characterized in that the preparation method of the vulcanizing activator
Are as follows: wet production principle is used, precipitating reagent is added in the soluble salt solutions of zinc, decomposes hydroxide is made under the high temperature conditions
Zinc sediment, then sediment is filtered, washed, dry after thermally decompose again, and generate receiving using zinc hydroxide as carrier
Rice zinc oxide.
4. a kind of low zinc rubber composition according to claim 3, which is characterized in that the nano zine oxide specific surface area is
20~80m2/g。
5. a kind of low zinc rubber composition according to claim 1, which is characterized in that the filler systems include carbon black, stone
One of black alkene, carbon nanotube or inorganic filler are a variety of.
6. a kind of low zinc rubber composition according to claim 5, which is characterized in that the inorganic filler is white carbon black, two
One of titanium oxide, nanoclay, calcium carbonate or magnesium carbonate are a variety of.
7. a kind of low zinc rubber composition according to claim 1, which is characterized in that the diene elastomer is polybutadiene
(BR), synthetic polyisoprenes (IR), natural rubber (NR), butadiene-styrene (SBR) copolymer, isobutylene-isoprene
One or more blends of (butyl rubber IIR) copolymer and its halogenated butyl rubber.
8. a kind of low zinc rubber composition according to claim 1, which is characterized in that the cross-linking system of the sulphur also includes sulphur
Change promotor, vulcanizing agent, the vulcanization accelerator is thiazoles, sulfenamide, thiurams, dithiocarbamates
Or one of hexichol guanidine vulcanization accelerator；The vulcanizing agent is sulphur powder or insoluble sulfuy.
9. a kind of low zinc rubber composition according to claim 1, which is characterized in that the adjuvant system includes operation oil,
The operation oil is one of aromatic naphtha, environment-friendly aromatic oil, heavy naphthenic oils, naphthenic oil or paraffin oil；It further include anti-aging agent,
The anti-aging agent is one of quinolines, amine, triazines or naphthylamines class or a variety of anti-aging agents；Additionally comprise plasticizer, modeling
Solve agent, silane coupling agent, homogenizing agent, dispersing agent, tackifying resin or antiscorching agent.
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| CN113755031A (en) * | 2021-10-22 | 2021-12-07 | 安徽锦华氧化锌有限公司 | Dispersing and activating treatment method for zinc oxide |
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