CN110218375A - Butadiene-styrene rubber/Nano carbon white composite material, vulcanizate and its preparation method and application - Google Patents
Butadiene-styrene rubber/Nano carbon white composite material, vulcanizate and its preparation method and application Download PDFInfo
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- CN110218375A CN110218375A CN201810174524.0A CN201810174524A CN110218375A CN 110218375 A CN110218375 A CN 110218375A CN 201810174524 A CN201810174524 A CN 201810174524A CN 110218375 A CN110218375 A CN 110218375A
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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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
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- C08K2201/011—Nanostructured additives
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Abstract
The present invention relates to rubber material preparation technical field, a kind of butadiene-styrene rubber/Nano carbon white composite material, vulcanizate and its preparation method and application are disclosed.Butadiene-styrene rubber of the invention/Nano carbon white composite material preparation method include: (1) in the presence of water, waterglass is swapped with weak-acid cation-exchange resin and is separated by solid-liquid separation after reacting, Nano carbon white aqueous dispersions are obtained；(2) after being mixed Nano carbon white aqueous dispersions with styrene-butadiene latex, flocculant is added and is condensed, and the product after cohesion is separated by solid-liquid separation.Preparation method of the invention has many advantages, such as that preparation flow is simple, environmental pollution is small and energy saving, meanwhile there is preferable tensile property, tear resistance, wet-sliding resistant performance and low-rolling-resistance by prepared butadiene-styrene rubber/obtained vulcanizate of Nano carbon white composite material.
Description
Technical field
The present invention relates to rubber material preparation technical fields, and in particular to a kind of butadiene-styrene rubber/Nano carbon white composite wood
Material, vulcanizate and its preparation method and application.
Background technique
White carbon black is the important reinforcing filler of rubber, and interparticle force is strong and is easy to reunite, and because surface exists
A large amount of hydroxyl, the interaction between rubber is weaker, is difficult in rubber well divide it using traditional dry method mixing
It dissipates, although silane coupling agent, which is added, can enhance the interaction between white carbon black and rubber and improve its dispersion in rubber,
But silane coupling agent valence is high, limits its application.
Newest loaded rubber hybrid technology is that lotion is compound, and also referred to as wet process is compound, is to make inorganic reinforcing filler and glue
Cream realizes compound process in the liquid phase, can overcome the problems, such as a lot in conventional dry mixing technology, effectively prevents filler
Pollution caused by powder is flown upward can make filler obtain good dispersion, and can significantly reduce the mixing energy consumption and cost of rubber, be
Prepare high-performance rubber/filler composite materials important method.
CN102153792A discloses a kind of preparation method of wet process mixed natural rubber material, specific technical solution
To configure slurry, 15-40% white carbon black siccative being immersed in the deionized water of 60-85%, coupling agent, surface-active is added
Agent is uniformly mixed, and grinding produces latex mixed liquor, takes Heveatex, white carbon black aqueous dispersions are added in latex, and stirring is mixed
Synthetic latex mixed liquor, flocculation, acetic acid is added in mixed liquor, carries out washing glue and dehydration through rubber washing machine, send to rubber comminutor
It is granulated, then sizing material is sent into box-type drying cabinet and is dried.This method, which needs to be added coupling agent, improves white carbon black in rubber
In dispersibility, and the preparation section time is long, is unfavorable for the production of actual industrial metaplasia.
CN105710983A discloses a kind of rubber wet process mixing method for remixing of premix atomization, by liquid processed, atomization,
Diffusion, cohesion, collection, stirring and dry seven steps finally obtain rubber masterbatch.This method not only needs additional atomization
Device, and atomization process parameter tool there are certain requirements, therefore limit the practicability of this method.
Summary of the invention
It is an object of the invention to solve white carbon black in dry method mixing process to be difficult to fine dispersion and need in butadiene-styrene rubber
The high silane coupling agent problem of price is added, to provide a kind of preparation side of butadiene-styrene rubber/Nano carbon white composite material
Method, this method have many advantages, such as that preparation flow is simple, environmental pollution is small and energy saving, meanwhile, by prepared butadiene-styrene rubber/receive
The obtained vulcanizate of off-white carbon black composite material has preferable tensile property, tear resistance, wet-sliding resistant performance and low rolling
Dynamic resistance.
To achieve the goals above, one aspect of the present invention provides a kind of system of butadiene-styrene rubber/Nano carbon white composite material
Preparation Method, method includes the following steps:
(1) in the presence of water, waterglass is swapped with weak-acid cation-exchange resin and is separated by solid-liquid separation after reacting, obtained
To Nano carbon white aqueous dispersions；
(2) after being mixed Nano carbon white aqueous dispersions with styrene-butadiene latex, flocculant is added and is condensed, and will coagulate
Product after poly- is separated by solid-liquid separation.
Second aspect of the present invention provides butadiene-styrene rubber/Nano carbon white composite material that the above method is prepared.
Third aspect present invention provides a kind of vulcanizate, and the vulcanizate is by by butadiene-styrene rubber of the invention/nanometer hard charcoal
Black composite material is kneaded and is vulcanized with vulcanizing agent, vulcanization accelerator, activator and optional auxiliary agent and obtained.
Fourth aspect present invention provides butadiene-styrene rubber of the invention/Nano carbon white composite material and is preparing answering in rubber
With.
Through the above technical solutions, butadiene-styrene rubber/Nano carbon white composite material and preparation method thereof that the present invention uses avoids
The pollution problem that a large amount of fleuts are flown upward in dry method calendering process, makes the calendering process working environment be improved.Secondly,
Due to white carbon black fine dispersion in the composite material, reduce the energy consumption of subsequent compounding procedure, with energy-saving and emission-reduction
Effect.Finally, vulcanizate prepared by the butadiene-styrene rubber/Nano carbon white composite material prepared using this method is shown preferably
Physical mechanical property (have preferable tensile property, tear resistance, wet-sliding resistant performance and low-rolling-resistance).
Detailed description of the invention
Fig. 1 is butadiene-styrene rubber/Nano carbon white composite material NRS2050 scanning electron microscope (SEM) photograph that preparation example 1 is prepared
Piece.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
Butadiene-styrene rubber provided by the invention/Nano carbon white composite material preparation method the following steps are included:
(1) in the presence of water, waterglass is swapped with weak-acid cation-exchange resin and is separated by solid-liquid separation after reacting, obtained
To Nano carbon white aqueous dispersions；
(2) after being mixed Nano carbon white aqueous dispersions with styrene-butadiene latex, flocculant is added and is condensed, and will coagulate
Product after poly- is separated by solid-liquid separation.
Method in accordance with the invention it is preferred that waterglass and weak-acid cation-exchange resin are carried out in step (1)
The mode of exchange reaction are as follows: be respectively fed to carry out in reaction vessel by water glass solution and weak-acid cation-exchange resin anti-
It answers, wherein be continuously introduced into the water glass solution into reaction vessel, and the Subacidity cation exchange tree is added portionwise
Rouge, the time interval that the weak-acid cation-exchange resin is added portionwise are 5 minutes hereinafter, the faintly acid is added portionwise
The time interval meter of cation exchange resin, the water glass solution in terms of sodium metasilicate exchange tree with the Subacidity cation
The feed weight ratio of rouge is 1.3-3.2:1.
According to the method for the present invention, the mode that the water glass solution is continuously introduced into reaction vessel does not limit particularly
It is fixed, such as the water glass solution can be continuously added drop-wise in reaction vessel.The speed of the dropwise addition can be in biggish model
Interior variation is enclosed, such as can be with 5g/ minutes or more, preferably 5-100g/ minutes, more preferably 5-50g/ minutes, more preferably 5-
20g/ minutes, further preferably 6-15g/ minutes.
In the present invention, consider in terms of a certain range makes reacting balance progress from control reacting solution pH value,
The weak-acid cation-exchange resin is added portionwise, and will be added portionwise between the time of the weak-acid cation-exchange resin
Every being set as 5 minutes or less.Preferably, the time interval that the weak-acid cation-exchange resin is added portionwise is 2-3 minutes.
In the present invention, as the specific example example for the time interval that the weak-acid cation-exchange resin is added portionwise
It can such as enumerate: 1 minute, 30 seconds 1 minute, 40 seconds 1 minute, 50 seconds 1 minute, 2 minutes, 10 seconds 2 minutes, 15 seconds, 2 points 2 minutes
Clock 20 seconds, 30 seconds 2 minutes, 40 seconds 2 minutes, 50 seconds 2 minutes, 3 minutes, 10 seconds 3 minutes, 15 seconds 3 minutes, 20 seconds, 3 points 3 minutes
Clock 30 seconds, 40 seconds 3 minutes, 50 seconds 3 minutes, 4 minutes, 10 seconds 4 minutes, 15 seconds 4 minutes, 20 seconds 4 minutes, 30 seconds, 4 points 4 minutes
Clock 40 seconds, 50 seconds 4 minutes or 5 minutes etc..
According to the method for the present invention, the time interval when weak-acid cation-exchange resin is added portionwise can be identical
It can also be different, the weak-acid cation-exchange resin is preferably added portionwise at the same time.
In addition, as described above, in terms of the time interval that the weak-acid cation-exchange resin is added portionwise, with sodium metasilicate
The water glass solution of meter and the feed weight ratio of the weak-acid cation-exchange resin are 1.3-3.2:1；Preferably, with
The time interval meter of the weak-acid cation-exchange resin is added portionwise, the water glass solution in terms of sodium metasilicate with it is described
The feed weight ratio of weak-acid cation-exchange resin is 1.5-3:1；It is highly preferred that the Subacidity cation is added portionwise
The time interval meter of exchanger resin, the water glass solution in terms of sodium metasilicate and the weak-acid cation-exchange resin into
Material weight ratio is 1.6-2.5:1 described by making in the time interval that the weak-acid cation-exchange resin is added portionwise
The charge ratio of water glass solution and the weak-acid cation-exchange resin within the above range, has and stablizes reacting solution pH value
In the effect that a certain range carries out reacting balance.
As the water in terms of the time interval that the weak-acid cation-exchange resin is added portionwise, in terms of sodium metasilicate
The specific example of the feed weight ratio of glass solution and the weak-acid cation-exchange resin, for example: 1.3,
1.4,1.5,1.6,1.7,1.8,1.9,2.0,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9,3.0,3.1 or 3.2
Deng.
According to the method for the present invention, the silicic acid sodium content in the water glass solution can change in a big way, example
It such as can be 20-70 weight %, preferably 30-70 weight %.There is no particular limitation for the preparation method of the water glass solution,
It can adopt and carry out with the conventional methods in the field.Preferably, it by mixing waterglass with water (preferably deionized water), obtains
The water glass solution.
Above-mentioned waterglass is liquid sodium silicate, also referred to as sodium silicate.Molecular formula is Na2O·nSiO2, wherein silica and oxygen
Change the ratio between the gram molecule molal quantity of sodium n and is known as modulus.In preparation method of the invention, the modulus of the waterglass is preferably 2.4-
3.6。
According to the method for the present invention, for the condition of the exchange reaction, there is no particular limitation, can be this field
Normal condition.Preferably, the condition of the exchange reaction includes that reaction temperature is 80-95 DEG C, and the reaction time is 20-120 points
Clock；It is highly preferred that the condition of the exchange reaction includes, reaction temperature is 90-95 DEG C, and the reaction time is 30-80 minutes, into one
Step preferably 30-60 minutes.
According to the method for the present invention, it under the premise of meeting above-mentioned time interval and reaction time, is added portionwise described weak
The number of acid cation exchange resin can be 10-30 times, preferably 10-20 times.Additionally, it is preferred that the faintly acid sun from
Sub-exchange resin last time stops being sent into the water glass solution and the reaction was continued 1-30 minutes, more preferably 3-10 after being added
Minute, further preferably 3-5 minutes.
According to the method for the present invention, for the ease of the progress of reaction, it is (excellent water can be added in the reaction vessel in advance
It is selected as deionized water) or addition water (preferably deionized water) and the part faintly acid are positive in the reaction vessel in advance
Ion exchange resin, the weak-acid cation-exchange resin being previously added are that 10 weight % of total amount are added hereinafter, more excellent
8 weight % are selected as hereinafter, further preferably 6 weight % are hereinafter, be still more preferably 5 weight % or less.By existing in advance
Deionized water is added in the reaction vessel water of reaction system is adjusted, has and adjust reaction solution solid content and glue
The effect of degree.
In the present invention, in the case where water is added in the reaction vessel in advance, the water consumption can be in larger model
Enclose interior variation, it is preferable that the water and the weak-acid cation-exchange resin being added in the reaction vessel in advance are added total
The weight ratio of amount is 1-10:1, preferably 3.5-8.5:1.
In a preferred embodiment of the invention, deionized water and part is added in the reaction vessel in advance
The weak-acid cation-exchange resin, is added deionized water in the reaction vessel in advance and the Subacidity cation is handed over
Changing resin and the weight ratio of total amount is added is 3.5-8.5:1, and the amount of the weak-acid cation-exchange resin of every batch of addition is identical,
And the faintly acid sun of the weak-acid cation-exchange resin being added in the reaction vessel in advance and every batch of addition
The amount of ion exchange resin is identical.
According to the method for the present invention, the addition total amount of the water glass solution in terms of sodium metasilicate and the faintly acid sun from
The weight ratio of the addition total amount of sub-exchange resin is preferably 1.3-3.2:1, more preferably 1.5-3:1, further preferably 1.6-
2.5:1.By making the addition total amount of the water glass solution in terms of sodium metasilicate and the weak-acid cation-exchange resin
Be added total amount weight ratio within the above range, can obtain stable reacting solution pH value a certain range make reacting balance into
Capable effect.
According to the method for the present invention, the weak-acid cation-exchange resin refers to has on cross-linked structure macromolecule matrix
Carboxyl (- COOH) or the (- PO containing phosphonic acid base3H2) ion exchange resin.Dissociation degree is weak and weakly acidic in aqueous solution for it.
It is divided by the pass of ion exchange resin: gel-type ion-exchange resin and macroreticular ion exchange resin.It is handed over by synthesis ion
The monomer for changing resin can be divided into: polystyrene, acrylic acid series, epoxy, phenolic aldehyde system and ureaformaldehyde system etc..The Subacidity cation
Exchanger resin preferably contains carboxyl weak-acid cation-exchange resin, more preferably macroporous type acrylic acid series cation exchange tree
Rouge.As weak-acid cation-exchange resin of the invention include but is not limited to D113 resin, D115 resin, D150 resin,
D151 resin, D152 resin, D154 resin, D155 resin, 110 resins, DK110 resin, SQD80 resin, SQD112 resin,
724 resins and CD180 resin.Weak-acid cation-exchange resin after reaction can be repeated several times use after regeneration treatment.
According to the method for the present invention, this method further includes being separated by solid-liquid separation the product after reaction to obtain Nano carbon white
The step of aqueous dispersions.As the method for separation of solid and liquid, there is no particular limitation, can be the method for this field routine, such as can
To be filtered.It is preferably washed by deionized water after filtering.
Method according to the invention it is possible to by the average grain diameter control of silica in obtained Nano carbon white aqueous dispersions
It is made as in the range of 10-100nm, is preferably controlled in the range of 20-40nm.Additionally, it is preferred that obtained Nano carbon white moisture
The pH value of dispersion liquid is 6-10, and the solid content of Nano carbon white aqueous dispersions is 10-20 weight %.
In the present invention, the styrene-butadiene latex is synthesizing butadiene styrene rubber latex.Specifically, the styrene-butadiene latex includes that lotion is poly-
Close styrene butadiene rubber latex and emulsion polymerization carboxylic styrene-butadiene rubber latex.SBR of emulsion polymerization abbreviation emulsion polymerized styrene butadiene rubber, often
The trade mark seen has 1500,1502,1503,1505,1506,1507,1508,1509,1510,1512 etc..Emulsion polymerization carboxyl fourth
Benzene rubber is the copolymer for adding a small amount of carboxylic acid and other auxiliary agents to generate by emulsion polymerization with butadiene, styrene, common board
Number there are XSBRL-6500, XSBRL-673, XSBRL-46C, XSBRL-45B, Rovene-9410, Rovene-6130, JSR-
0545, JSR-0573 etc..
There is no particular limitation for the solid content of styrene-butadiene latex, such as can be 15-70 weight %, preferably 20-50 weight
Measure %, more preferably 20-25 weight %.
According to the method for the present invention, in step (2), relative to 100 parts by weight of styrene-butadiene latex of solid content meter, to receive
The dosage of the Nano carbon white aqueous dispersions of off-white carbon black meter is 15-100 parts by weight, preferably 30-70 parts by weight.
In the present invention, the effect of the flocculant is the rubber particle that will be suspended in mixed liquor and white carbon black particle buildup connection
Knot forms coarse cotton-shaped granule or agglomerate.The flocculant includes inorganic and organic two class, it is preferable that the flocculant is sulphur
Acid, hydrochloric acid, formic acid, acetic acid, calcium chloride, sodium chloride, zinc chloride, aluminum sulfate, calcium nitrate, ammonium nitrate, zinc nitrate, potassium silicofluoride,
Sodium silicofluoride, polyethylene glycol oxide, polyvinyl pyrrolidone, dicyandiamide formaldehyde condensation products, polyvinyl sulfonate, polyvinylamine, poly- hydroxyl
Base hydroxypropyl methyl ammonium chloride, poly- hydroxypropyl alkyl dimethyl ammonium chloride, poly dimethyl amine Methacrylamide and poly dimethyl amine first
One of base propylacrylamide is a variety of.It is highly preferred that the flocculant is sulfuric acid and/or dicyandiamide formaldehyde condensation products.
According to the present invention, there is no particular limitation for the dosage of the flocculant, can be the conventional amount used of this field, preferably
Ground, relative to being 0.5-15 parts by weight with the dosage of 100 parts by weight of styrene-butadiene latex of solid content meter, the flocculant, preferably
For 6-10 parts by weight.
According to the present invention, white carbon black is evenly dispersed in the Nano carbon white aqueous dispersions being prepared by the above method,
Property is stablized, and generates long-term place without flocculation sedimentation.The dispersion liquid can be mixed with styrene-butadiene latex arbitrary proportion, after flocculation
White carbon black and butadiene-styrene rubber are assembled jointly is detached from water phase, and butadiene-styrene rubber/Nano carbon white composite material can be obtained through being separated by solid-liquid separation.
Above-mentioned separation of solid and liquid is not particularly limited, can be this field routine method, such as can by filter come
Obtain butadiene-styrene rubber/Nano carbon white composite material.Preferably, after separation of solid and liquid, it can also be washed and be dried.Washing
It is conventionally carried out with dry.
The present invention also provides a kind of vulcanizate, which passes through butadiene-styrene rubber/Nano carbon white of the invention is compound
Material is kneaded and is vulcanized with vulcanizing agent, vulcanization accelerator, activator and optional auxiliary agent and obtained.
As the vulcanizing agent for example: sulphur, insoluble sulfur, two thio morpholines and four vulcanization two morphines
Quinoline.They can be used alone, and can also be used in combination.Wherein, the insoluble sulfur is that the homoatomic of sulphur is different
Body does not dissolve in sulfur dioxide and other solvents, is also insoluble in base rubber, exists in base rubber with dispersity.
Generally, relative to the butadiene-styrene rubber in terms of butadiene-styrene rubber/100 parts by weight of Nano carbon white composite material,
The dosage of the vulcanizing agent can be 1-3 parts by weight, preferably 1-2.5 parts by weight.
The promotor can be used for existing various vulcanization time, reduction curing temperature, the reduction vulcanizing agents of capable of shortening
The substance of the physical mechanical property of vulcanized rubber is measured and improves, for example, can be sulfenamide vulcanization accelerator, thiurams
At least one of vulcanization accelerator, thiazoles vulcanization accelerator and guanidine vulcanization accelerator.Preferably, the promotor is selected from
Tetramethylthiuram disulfide, DMDPTD dimethyl diphenylthiuram disulfide and N- oxygen diethylidene -2-[4-morpholinodithio base time sulphonyl
At least one of amine.
Generally, relative to the butadiene-styrene rubber in terms of butadiene-styrene rubber/100 parts by weight of Nano carbon white composite material,
The dosage of the promotor can be 0.5-3 parts by weight, preferably 1-2 parts by weight.
The activator is preferably zinc oxide and/or stearic acid.Relative to the butadiene-styrene rubber in terms of butadiene-styrene rubber/receive
The dosage of 100 parts by weight of off-white carbon black composite material, the zinc oxide can be 0.5-10 parts by weight, preferably 1-3 parts by weight,
Stearic dosage can be 0.5-6 parts by weight, preferably 1-3 parts by weight.
Above-mentioned auxiliary agent can be the existing various auxiliary agents commonly used in vulcanizate, such as can be anti-aging agent, softening agent
And acid-base modifier.
Various anti-aging agents commonly used in the art can be used in the anti-aging agent.Preferably, the anti-aging agent is selected from 2,
2,4- trimethyl -1,2- dihyaroquinoline condensate (anti-aging agent RD), N- isopropyl-N '-diphenyl-para-phenylene diamine (anti-aging agent
4010NA), at least one of N- (1,3- dimethylbutyl)-N '-diphenyl-para-phenylene diamine (antioxidant 4020) and microwax.Phase
For the butadiene-styrene rubber in terms of butadiene-styrene rubber/100 parts by weight of Nano carbon white composite material, the dosage of the anti-aging agent can
Think 0-6 parts by weight.
Various softening agents commonly used in the art can be used in the softening agent.Preferably, the softening agent is selected from ring
Protect at least one of aromatic naphtha, aromatic naphtha, naphthenic oil and paraffin oil.Relative to the butadiene-styrene rubber in terms of butadiene-styrene rubber/
100 parts by weight of Nano carbon white composite material, the dosage of the softening agent can be 0-50 parts by weight.
Various acid-base modifiers commonly used in the art can be used in the acid-base modifier, and activation is played in rubber
White carbon black adjusts the effect of system pH.Preferably, the acid-base modifier is polyethylene glycol.Relative in terms of butadiene-styrene rubber
The butadiene-styrene rubber/100 parts by weight of Nano carbon white composite material, the dosage of the acid-base modifier can be 0-10 weight
Part.
In addition, the method for being kneaded and vulcanizing can use various methods commonly used in the art, not stated herein tired.
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
In following preparation example and embodiment,
Waterglass is purchased from Foshan Ke Ning new material Science and Technology Ltd., modulus 3.6；
Weak-acid cation-exchange resin, D113 resin are purchased from Jining Bai Chuan Chemical Co., Ltd.；
Styrene-butadiene latex, SBR1502, Qilu Petrochemical, 20.5 weight % of solid content；
Flocculant CA (dicyandiamide formaldehyde condensation products), is purchased from Qilu Petrochemical, and concentration is 50 weight %；
White carbon black is purchased from Shanghai Ze Heng Chemical Co., Ltd., Zeosil 1165MP；
8# carbon black is purchased from Beijing Guan Yuan Science and Technology Ltd., model IRB8；
Antioxidant 4010 is purchased from Shanghai Zhu Jiang Chemical Co., Ltd.；
Diphenylguanidine is purchased from Shijiazhuang City Jia Teng Chemical Co., Ltd.；
TDAE is purchased from Shandong Tai Chang petrochemical industry Science and Technology Ltd.；
Accelerator TBBS is purchased from Guangzhou Hong Na Chemical Co., Ltd..
Preparation example 1
This preparation example is for illustrating butadiene-styrene rubber provided by the invention/Nano carbon white composite material and preparation method.
Waterglass is mixed with deionized water, obtains the water glass solution that silicic acid sodium content is 40 weight %.
600g deionized water and 8g weak-acid cation-exchange resin (D113 resin) are added in a kettle, stir and adds
Heat, until 95 DEG C of whens start that above-mentioned water glass solution is added dropwise, drop speed 12g per minute added 8g Subacidity cation every 3 minutes again
Exchanger resin (D113 resin), altogether plus 15 times, last time stops that water glass solution is added dropwise after being added and the reaction was continued 5 minutes.
It filters after being cooled to 40 DEG C and is rinsed with 300g deionized water, finally obtain Nano carbon white aqueous dispersions S20, solid content is
12 weight %.Measuring white carbon black average grain diameter by nano-particle size analysis instrument is 20.2nm.
The aqueous dispersions S20 containing 307.5g white carbon black is added into 3000g styrene-butadiene latex, 50g is added in stirring after five minutes
Flocculant CA.It is filtered after being agglomerated 30 minutes at 25 DEG C, it is 24 hours dry at 60 DEG C after then being washed with deionized water,
Obtain butadiene-styrene rubber/Nano carbon white composite material SBRS2050 (butadiene-styrene rubber content is 66.7 weight %).Fig. 1 is butylbenzene rubber
Glue/Nano carbon white composite material SBRS2050 scanning electron microscopic picture, as shown in Figure 1, Nano carbon white is in butadiene-styrene rubber
In can disperse well, do not reunite.
Preparation example 2
This preparation example is for illustrating butadiene-styrene rubber provided by the invention/Nano carbon white composite material and preparation method.
Waterglass is mixed with deionized water, obtains the water glass solution that silicic acid sodium content is 40 weight %.
600g deionized water and 7.5g weak-acid cation-exchange resin (D113 resin) are added in a kettle, stirring is simultaneously
Heating, until 95 DEG C of whens start that above-mentioned water glass solution is added dropwise, drop speed 12g per minute added 7.5g faintly acid every 2.5 minutes again
Cation exchange resin (D113 resin), altogether plus 15 times, last time stops being added dropwise water glass solution after being added and the reaction was continued 5
Minute.It filters after being cooled to 40 DEG C and is rinsed with 400g deionized water, finally obtain Nano carbon white aqueous dispersions S40, Gu
Content is 13 weight %.Measuring white carbon black average grain diameter by nano-particle size analysis instrument is 41.5nm.
The aqueous dispersions S40 containing 184.5g white carbon black is added into 3000g styrene-butadiene latex, 42g is added in stirring after five minutes
Flocculant CA.It is filtered after being agglomerated 30 minutes at 25 DEG C, it is 24 hours dry at 60 DEG C after then being washed with deionized water,
Obtain butadiene-styrene rubber/Nano carbon white composite material SBRS4030 (butadiene-styrene rubber content is 76.9 weight %).Pass through butylbenzene rubber
Glue/Nano carbon white composite material SBRS4030 scanning electron microscopic picture is it is found that Nano carbon white can be very in butadiene-styrene rubber
Disperse well, does not reunite.
Preparation example 3
This preparation example is for illustrating butadiene-styrene rubber provided by the invention/Nano carbon white composite material and preparation method.
Waterglass is mixed with deionized water, obtains the water glass solution that silicic acid sodium content is 60 weight %.
600g deionized water and 5.4g weak-acid cation-exchange resin (D113 resin) are added in a kettle, stirring is simultaneously
Heating, until 90 DEG C of whens start that above-mentioned water glass solution is added dropwise, drop speed 10g per minute adds 5.4g faintly acid in 15 seconds every 2 points again
Cation exchange resin (D113 resin), altogether plus 15 times, last time stops being added dropwise water glass solution after being added and the reaction was continued 5
Minute.It filters after being cooled to 40 DEG C and is rinsed with 400g deionized water, finally obtain Nano carbon white aqueous dispersions S80, Gu
Content is 13 weight %.Measuring white carbon black average grain diameter by nano-particle size analysis instrument is 82.4nm.
The aqueous dispersions S80 containing 430.5g white carbon black is added into 3000g styrene-butadiene latex, 55g is added in stirring after five minutes
Flocculant CA.It is filtered after being agglomerated 30 minutes at 25 DEG C, it is 24 hours dry at 60 DEG C after then being washed with deionized water,
Obtain butadiene-styrene rubber/Nano carbon white composite material SBRS8070 (butadiene-styrene rubber content is 58.8 weight %).Pass through butylbenzene rubber
Glue/Nano carbon white composite material SBRS8070 scanning electron microscopic picture is it is found that Nano carbon white can be very in butadiene-styrene rubber
Disperse well, does not reunite.
Preparation example 4
This preparation example is for illustrating butadiene-styrene rubber provided by the invention/Nano carbon white composite material and preparation method.
Waterglass is mixed with deionized water, obtains the water glass solution that silicic acid sodium content is 60 weight %.
600g deionized water and 5.4g weak-acid cation-exchange resin (D113 resin) are added in a kettle, stirring is simultaneously
Heating, until 90 DEG C of whens start that above-mentioned water glass solution is added dropwise, drop speed 10g per minute adds 5.4g faintly acid in 15 seconds every 2 points again
Cation exchange resin (D113 resin), altogether plus 15 times, last time stops being added dropwise water glass solution after being added and the reaction was continued 5
Minute.It filters after being cooled to 40 DEG C and is rinsed with 400g deionized water, finally obtain Nano carbon white aqueous dispersions S80, Gu
Content is 13 weight %.Measuring white carbon black average grain diameter by nano-particle size analysis instrument is 82.4nm.
The aqueous dispersions S80 containing 92.3g white carbon black is added into 3000g styrene-butadiene latex, 60g is added in stirring after five minutes
The sulfuric acid solution and 37g flocculant CA that mass fraction is 10%.It is filtered after being agglomerated 30 minutes at 25 DEG C, then uses deionized water
It is 24 hours dry at 60 DEG C after being washed, obtain butadiene-styrene rubber/Nano carbon white composite material SBRS8015 (butadiene-styrene rubber
Content is 87.0 weight %).By butadiene-styrene rubber/Nano carbon white composite material SBRS8015 scanning electron microscopic picture it is found that
Nano carbon white can disperse well in butadiene-styrene rubber, not reunite.
Preparation example 5
The sulfuric acid solution and 18g flocculant CA that 10g mass fraction is 10% are added into 3000g styrene-butadiene latex, at 25 DEG C
Lower cohesion is filtered after 30 minutes, 24 hours dry at 60 DEG C after then being washed with deionized water, obtains butadiene-styrene rubber
SBR。
Embodiment 1
The embodiment is for illustrating butadiene-styrene rubber provided by the invention/Nano carbon white composite material vulcanizate and its preparation
Method.
For rubber compound using two sections of calendering process preparations according to table 1, mixer fill factor is 0.7.One section of mixer
Being kneaded set temperature is 80 DEG C, rotor speed 90r/min.The 30s that plasticates first is added in mixer in whole SBRS2050, later
ZnO is added, is kneaded 150s, stearic acid, antioxidant 4010, PEG4000 and microwax is eventually adding, when the temperature of sizing material reaches
150 DEG C of time discharges after reaching 5min；It parks 4 hours, two-stage mixing set temperature is 40 DEG C, rotor speed 60r/min.
One section of rubber compound is added to and is kneaded 30s in mixer, is added after sulphur, diphenylguanidine and accelerator TBBS are kneaded 240s to go out later
Material；By two-stage mixing glue, longitudinal direction is thin in open mill leads to 3 bottom sheet, and open mill roller is room temperature.Curing temperature is 160 DEG C, pressure
15MPa, the vulcanizate obtained after vulcanization carry out following physical mechanical property tests, and the results are shown in Table 2.
Hardness: using Shore durometer (TH210, Yingkou Material Test Maching Factory), measures Shao by GB/T 531.1-2008
That A type hardness tester.
Mechanical property: tensile property is carried out to material prepared using Material Testing Machine (SHIMADZU, AG-20KNG)
Test characterization.Force snesor selected by Material Testing Machine is 1KN.According to national standard GB/T 528-2008, rate of extension is
500mm/min, test temperature are 23 ± 2 DEG C.The live part length of sample is 25mm, width 6mm.For every group of sample,
5 parallel laboratory tests are carried out, results are averaged.
Dynamic mechanical: temperature scanning is enterprising in German GABO company EPLEXOR 500N dynamic thermomechanical analysis apparatus
Row, using stretching clamp, test frequency 11Hz, temperature range: -80~80 DEG C, 3 DEG C/min of heating rate, static strain
1%, dynamic strain 0.25%.The wet-sliding resistant performance of vulcanized rubber is characterized with (0 DEG C) of tan δ, tan δ (0 DEG C) is bigger, indicates vulcanization
Rubber wet-sliding resistant performance is better；The rolling resistance of vulcanized rubber is characterized with (60 DEG C) of tan δ, tan δ (60 DEG C) is smaller, indicates vulcanization
Rubber rolling resistance is smaller.
Dynamic compression heat build-up: pressing GB/T 1687-1993, using the production of Beijing You Shen Electron equipment Co., Ltd
The dynamic compression heat build-up of RH-2000 type rubber compression heat generation testing machine test sample.Condition is stroke 4.45mm, load
1MPa, 55 DEG C of temperature, time 25min.
Embodiment 2
The embodiment is for illustrating butadiene-styrene rubber provided by the invention/Nano carbon white composite material vulcanizate and its preparation
Method.
For rubber compound using two sections of calendering process preparations according to table 1, mixer fill factor is 0.7.One section of mixer
Being kneaded set temperature is 80 DEG C, rotor speed 90r/min.The 30s that plasticates first is added in mixer in whole SBRS4030, later
ZnO is added, is kneaded 150s, stearic acid, antioxidant 4010, PEG4000 and microwax is eventually adding, when the temperature of sizing material reaches
150 DEG C of time discharges after reaching 5min；It parks 4 hours, two-stage mixing set temperature is 40 DEG C, rotor speed 60r/min.
One section of rubber compound is added to and is kneaded 30s in mixer, is added after sulphur, diphenylguanidine and accelerator TBBS are kneaded 240s to go out later
Material；By two-stage mixing glue, longitudinal direction is thin in open mill leads to 3 bottom sheet, and open mill roller is room temperature.Curing temperature is 160 DEG C, pressure
15MPa, the vulcanizate obtained after vulcanization carry out physical mechanical property test, result such as table 2 according to the identical method of embodiment 1
It is shown.
Embodiment 3
The embodiment is for illustrating butadiene-styrene rubber provided by the invention/Nano carbon white composite material vulcanizate and its preparation
Method.
For rubber compound using two sections of calendering process preparations according to table 1, mixer fill factor is 0.7.One section of mixer
Being kneaded set temperature is 80 DEG C, rotor speed 90r/min.The 30s that plasticates first is added in mixer in whole SBRS8070, later
ZnO is added, is kneaded 150s, stearic acid, antioxidant 4010, PEG4000 and microwax is eventually adding, when the temperature of sizing material reaches
150 DEG C of time discharges after reaching 5min；It parks 4 hours, two-stage mixing set temperature is 40 DEG C, rotor speed 60r/min.
One section of rubber compound is added to and is kneaded 30s in mixer, is added after sulphur, diphenylguanidine and accelerator TBBS are kneaded 240s to go out later
Material；By two-stage mixing glue, longitudinal direction is thin in open mill leads to 3 bottom sheet, and open mill roller is room temperature.Curing temperature is 160 DEG C, pressure
15MPa, the vulcanizate obtained after vulcanization carry out physical mechanical property test, result such as table 2 according to the identical method of embodiment 1
It is shown.
Embodiment 4
The embodiment is for illustrating butadiene-styrene rubber provided by the invention/Nano carbon white composite material vulcanizate and its preparation
Method.
For rubber compound using two sections of calendering process preparations according to table 1, mixer fill factor is 0.7.One section of mixer
Being kneaded set temperature is 80 DEG C, rotor speed 90r/min.The 30s that plasticates first is added in mixer in whole SBRS8015, later
ZnO is added, is kneaded 150s, stearic acid, antioxidant 4010, PEG4000 and microwax is eventually adding, when the temperature of sizing material reaches
150 DEG C of time discharges after reaching 5min；It parks 4 hours, two-stage mixing set temperature is 40 DEG C, rotor speed 60r/min.
One section of rubber compound is added to and is kneaded 30s in mixer, is added after sulphur, diphenylguanidine and accelerator TBBS are kneaded 240s to go out later
Material；By two-stage mixing glue, longitudinal direction is thin in open mill leads to 3 bottom sheet, and open mill roller is room temperature.Curing temperature is 160 DEG C, pressure
15MPa, the vulcanizate obtained after vulcanization carry out physical mechanical property test, result such as table 2 according to the identical method of embodiment 1
It is shown.
Comparative example 1
For comparative example rubber compound using two sections of calendering process preparations according to table 1, mixer fill factor is 0.7.Mixing
One section of mixing set temperature of machine is 80 DEG C, rotor speed 90r/min.First the SBR in whole preparation examples 5 is added in mixer
Plasticate 30s, later be added white carbon black 1165MP and ZnO, be kneaded 150s, be eventually adding 8# carbon black, stearic acid, antioxidant 4010,
PEG4000 and microwax discharge after the time that the temperature of sizing material reaches 150 DEG C reaches 5min；4 hours are parked, two-stage mixing
Set temperature is 40 DEG C, rotor speed 60r/min.One section of rubber compound is added to and is kneaded 30s in mixer, sulphur is added later
Sulphur, diphenylguanidine and accelerator TBBS discharge after being kneaded 240s；By two-stage mixing glue, longitudinal direction is thin in open mill leads to 3 bottom sheet, opens
Mill roller is room temperature.Curing temperature is 160 DEG C, pressure 15MPa, and the vulcanizate obtained after vulcanization is according to the identical side of embodiment 1
Method carries out physical mechanical property test, and the results are shown in Table 2.
Table 1
Table 2
| Project | Comparative example | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Shao Er A type hardness tester/degree | 66 | 70 | 68 | 74 | 67 |
| 300% stress at definite elongation/MPa | 16.5 | 18.8 | 17.9 | 19.6 | 17.2 |
| Tensile strength/MPa | 19.2 | 21.4 | 20.0 | 23.1 | 19.9 |
| Elongation rate of tensile failure/% | 385 | 357 | 362 | 343 | 406 |
| Tearing strength/(kN/m) | 24 | 33 | 31 | 28 | 29 |
| Compression temperature rise/DEG C | 44.2 | 31.5 | 35.4 | 36.2 | 38.5 |
| tanδ(0℃) | 0.2243 | 0.2517 | 0.2483 | 0.2566 | 0.2344 |
| tanδ(60℃) | 0.1219 | 0.1070 | 0.1135 | 0.1086 | 0.1172 |
It can be seen that the butadiene-styrene rubber/Nano carbon white composite wood being prepared using the present invention from the test result of table 2
Expect that obtained vulcanizate, tensile property, tear resistance, wet-sliding resistant performance and low-rolling-resistance etc. are better than comparative example,
And it improves a lot.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (18)
1. a kind of butadiene-styrene rubber/Nano carbon white composite material preparation method, which is characterized in that this method includes following step
It is rapid:
(1) in the presence of water, waterglass is swapped with weak-acid cation-exchange resin and is separated by solid-liquid separation after reacting, received
Off-white carbon black aqueous dispersions；
(2) after being mixed Nano carbon white aqueous dispersions with styrene-butadiene latex, flocculant is added and is condensed, and will be after cohesion
Product be separated by solid-liquid separation.
2. according to the method described in claim 1, wherein, in step (1), by waterglass and weak-acid cation-exchange resin into
The mode of row exchange reaction are as follows: be respectively fed into reaction vessel carry out with weak-acid cation-exchange resin by water glass solution
Reaction, wherein be continuously introduced into the water glass solution into reaction vessel, and the Subacidity cation exchange tree is added portionwise
Rouge, the time interval that the weak-acid cation-exchange resin is added portionwise are 5 minutes hereinafter, the faintly acid is added portionwise
The time interval meter of cation exchange resin, the water glass solution in terms of sodium metasilicate exchange tree with the Subacidity cation
The feed weight ratio of rouge is 1.3-3.2:1.
3. according to the method described in claim 2, wherein, to be added portionwise between the time of the weak-acid cation-exchange resin
Every meter, the feed weight ratio of the water glass solution and the weak-acid cation-exchange resin in terms of sodium metasilicate is 1.5-3:
1。
4. according to the method in claim 2 or 3, wherein be continuously introduced into the side of the water glass solution into reaction vessel
Formula is continuously to be added drop-wise to the water glass solution in reaction vessel.
5. according to the method described in claim 2, wherein, the time interval of the weak-acid cation-exchange resin is added portionwise
It is 2-3 minutes.
6. according to the method described in claim 2, wherein, the content of the sodium metasilicate in the water glass solution is 20-70 weight
Measure %；
Preferably, the modulus of the waterglass is 2.4-3.6.
7. method according to claim 1 or 2, wherein the condition of the reaction includes that reaction temperature is 80-95 DEG C, instead
It is 20-120 minutes between seasonable.
8. the method according to any one of claim 2-7, wherein it is 10-30 times that number, which is added portionwise, preferably
10-20 times.
9. the method according to any one of claim 2-7, wherein in advance in the reaction vessel be added water and/
Or the part weak-acid cation-exchange resin, the weak-acid cation-exchange resin being previously added are the faintly acid
The 10 weight % or less of cation exchange resin addition total amount；
Preferably, it is 1-10:1 that the weight ratio of total amount, which is added, in the water and the weak-acid cation-exchange resin；
It is highly preferred that the water is deionized water.
10. method according to any one of claims 1-7, wherein the water glass solution adds in terms of sodium metasilicate
The weight ratio for entering the addition total amount of total amount and the weak-acid cation-exchange resin is 1.5-3:1.
11. method according to any one of claims 1-7, wherein the weak-acid cation-exchange resin be containing
Carboxyl weak-acid cation-exchange resin；
Preferably, the weak-acid cation-exchange resin is macroporous type acrylic resin.
12. according to the method described in claim 1, wherein, the average grain of silica in the Nano carbon white aqueous dispersions
Diameter is 10-100nm；
Preferably, the pH value of the Nano carbon white aqueous dispersions is 6-10；
Preferably, the solid content of the Nano carbon white aqueous dispersions is 10-20 weight %.
13. according to the method described in claim 1, wherein, the styrene-butadiene latex is synthesizing butadiene styrene rubber latex.
14. according to the method described in claim 1, wherein, in step (2), relative to the styrene-butadiene latex 100 of solid content meter
Parts by weight, the dosage of the Nano carbon white aqueous dispersions in terms of Nano carbon white are 15-100 parts by weight, preferably 30-70
Parts by weight.
15. according to the method described in claim 1, wherein, the flocculant is sulfuric acid, hydrochloric acid, formic acid, acetic acid, calcium chloride, chlorine
Change sodium, zinc chloride, aluminum sulfate, calcium nitrate, ammonium nitrate, zinc nitrate, potassium silicofluoride, sodium silicofluoride, polyethylene glycol oxide, polyethylene pyrrole
Cough up ketone, dicyandiamide formaldehyde condensation products, polyvinyl sulfonate, polyvinylamine, poly- hydroxypropylmethyl ammonium chloride, poly- hydroxypropyl two
One of ammonio methacrylate, poly dimethyl amine Methacrylamide and poly dimethyl amine methyl-propyl acrylamide are a variety of.
16. the butadiene-styrene rubber that method described in any one of claim 1-15 is prepared/Nano carbon white composite material.
17. a kind of vulcanizate, which is characterized in that the vulcanizate is by by butadiene-styrene rubber described in claim 16/nanometer hard charcoal
Black composite material is kneaded and is vulcanized with vulcanizing agent, vulcanization accelerator, activator and optional auxiliary agent and obtained.
18. butadiene-styrene rubber described in claim 16/Nano carbon white composite material is preparing the application in rubber.
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