CN107652479A - A kind of tennis sizing material of beta-type silicon carbide whisker and rubber blending and preparation method thereof - Google Patents
A kind of tennis sizing material of beta-type silicon carbide whisker and rubber blending and preparation method thereof Download PDFInfo
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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
- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
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- C08J3/203—Solid polymers with solid and/or liquid additives
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2307/00—Characterised by the use of natural rubber
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
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- 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
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- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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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
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Abstract
The invention discloses tennis sizing material of a kind of beta-type silicon carbide whisker and rubber blending and preparation method thereof：Beta-type silicon carbide whisker and butadiene rubber mixing are first prepared into beta-type silicon carbide whisker/butadiene rubber elastomeric compound；Beta-type silicon carbide whisker and natural rubber mixing are prepared into beta-type silicon carbide whisker/natural rubber elastomeric compound again, beta-type silicon carbide whisker/butadiene rubber and beta-type silicon carbide whisker/natural rubber are finally kneaded to the tennis sizing material that beta-type silicon carbide whisker and rubber blending is prepared.The present invention has the characteristics of extreme hardness, modulus of elasticity are very big, tensile strength is very big and heat resisting temperature is high to strengthen the performance of tennis sizing material using beta-type silicon carbide whisker；There is the characteristics of the characteristics of excellent cold resistance, wearability and elasticity and natural rubber combination property itself are good after also using butadiene rubber vulcanization, two kinds of rubber are learnt from other's strong points to offset one's weaknesses and are used for preparing tennis sizing material；Obtained tennis sizing material has the advantages that intensity is high, resilience is good and stress at definite elongation is high.
Description
Technical field
The present invention relates to technical field of polymer materials, the net of more particularly to a kind of beta-type silicon carbide whisker and rubber blending
Ball sizing material and preparation method thereof.
Background technology
Natural rubber has excellent combination property as the important raw material of industry and strategic materials, such as high viscoplasticity, good
Good insulating properties, wearability, air-tightness and flexible resistance energy, therefore it is widely used in space flight and aviation, defence and military, automotive wheels
The fields such as tire, aero tyre and medical elastomer.But the intensity and modulus of natural rubber in itself is relatively low, it usually needs uses charcoal
The reinforcing materials such as black, white carbon, fiber, nano-powder material and crystal whisker materials, which are modified, just has actual application value.
Butadiene rubber is the synthetic rubber of the compound with regular structure formed by polymerizing butadiene, and butadiene rubber is to be only second to butylbenzene rubber
The second largest synthetic rubber of glue.Compared with natural rubber and butadiene-styrene rubber, its cold resistance, wearability and bullet after butadiene rubber vulcanization
Property can become especially excellent, and ageing-resistant performance also improves.Butadiene rubber can show certain soft at high temperature
It is soft and elastic, can machine-shaping, and have preferable compatibility with natural rubber, under the effect of the vulcanizing agents such as Sulfur, can produce
Sulfurization, realize alternate crosslinking.But butadiene rubber has the shortcomings that tensile strength and low tearing strength, therefore, to allow along fourth
Rubber has actual application value, must just improve its tensile strength and tearing strength.
Silicon carbide whisker is a kind of defect seldom and has the mono-crystlling fibre of certain draw ratio, and it is to have synthesized so far
Hardness highest, modulus of elasticity maximum, tensile strength maximum and heat resisting temperature highest crystal whisker products in the whisker gone out.Carborundum
Whisker is generally divided into two kinds of forms of α types and β types, and wherein β types performance is better than α types.Beta-type silicon carbide whisker has higher compared with α types
Hardness (Mohs' hardness up to more than 9.5), and toughness, electric conductivity, wear resistence, heat-resisting quantity, shock resistance, corrosion resistance and
Radiation resistance etc. is more excellent.Therefore in numerous crystal whisker materials, can effectively be strengthened from beta-type silicon carbide whisker suitable
The mechanical strength of the compound elastomeric compound of buna/natural rubber.
Tennis occupies an important position in ball game, to produce meet international networks association standard tennis it is usual
With very big difficulty because high-quality tennis needs to meet high stress at definite elongation and elastomeric feature, but this 2 points
Contradict to a certain extent：High stress at definite elongation requires that tennis sizing material keeps less degree of deformation under the effect of larger external force；
And high resiliency then requires that sizing material produces larger elastic deformation under smaller external force.Therefore, a rational tennis sizing material is designed
Formula and preparation method thereof is necessary, and can so significantly improve the stress at definite elongation of tennis sizing material, and do not influence it
Elasticity.
The content of the invention
It is an object of the invention to provide a kind of beta-type silicon carbide whisker and the tennis sizing material of rubber blending and its preparation side
Method.In order to reach above-mentioned purpose, solution of the invention is：
A kind of tennis sizing material of beta-type silicon carbide whisker and rubber blending, the composition of the sizing material are by mass fraction：β type carbon
85 parts of SiClx whisker dosage；300 parts of butadiene rubber dosage；1000 parts of natural rubber dosage；3 parts of stearic acid dosage；Zinc oxide is used
62 parts of amount；14 parts of rubber accelerator DM dosages；2 parts of rubber accelerator TT dosages；30 parts of sulfur consumption；Rubber accelerator D dosages
10 parts；5 parts of rubber accelerator TMTD dosages.
Preferably, a diameter of 0.05~0.2 μm of described beta-type silicon carbide whisker, average length are 10~40 μm.
Preferably, described butadiene rubber is the butadiene rubber of high-cis structure.
Preferably, described natural rubber is caouttchouc.
A kind of preparation method of the tennis sizing material of beta-type silicon carbide whisker according to claim 1 and rubber blending, bag
Include following steps：
1) it is on a mill, that 300 parts of butadiene rubber is plasticated by mass fraction, temperature is 40 DEG C, and the time is
3min, after its bag roller, 3 parts of stearic acid, 12 parts of zinc oxide, 25 parts of beta-type silicon carbide whiskers, 4 are sequentially added according to mass fraction
Part rubber accelerator DM, 2 parts of rubber accelerator TT and 10 parts of sulphur are kneaded, and temperature is 160 DEG C, time 12min, is obtained
Beta-type silicon carbide whisker/butadiene rubber elastomeric compound；
2) it is on a mill, that 1000 parts of natural rubbers are plasticated by mass fraction, temperature is 50 DEG C, and the time is
3min, after its bag roller, sequentially add 50 parts of zinc oxide, 60 parts of beta-type silicon carbide whiskers, 10 parts of rubber according to mass fraction and promote
Agent D, 10 parts of rubber accelerator DM, 5 parts of rubber accelerator TMTD and 20 parts of sulphur are kneaded, and temperature is 130 DEG C, and the time is
15min, obtain beta-type silicon carbide whisker/natural rubber elastomeric compound；
3) on a mill, by the beta-type silicon carbide whisker being prepared in step 1)/butadiene rubber elastomeric compound and step 2)
In beta-type silicon carbide whisker/natural rubber elastomeric compound for being prepared be kneaded, temperature is 75 DEG C, time 10min, obtains β
Type silicon carbide whisker/butadiene rubber-compound elastomeric compound of beta-type silicon carbide whisker/natural rubber；
4) beta-type silicon carbide whisker/butadiene rubber-beta-type silicon carbide whisker/natural rubber that will be prepared in step 3)
Compound elastomeric compound determines its sulfurizing time t90 with vulcameter, then is vulcanized with vulcanizing press, you can described β is made
The tennis sizing material of type silicon carbide whisker and rubber blending.
Preferably, the curing temperature described in step 4) is 135 DEG C.
Relative to the existing method for preparing tennis sizing material, the present invention has advantages below：
(1) the tennis sizing material of the beta-type silicon carbide whisker prepared by the present invention and rubber blending is first added with beta-type silicon carbide whisker
Enter in butadiene rubber to improve the tensile strength of butadiene rubber and tearing strength, obtain beta-type silicon carbide whisker/butadiene rubber and mix
Refining glue；Added again with beta-type silicon carbide whisker in natural rubber to improve the intensity and modulus of natural rubber, obtain beta-type silicon carbide
Whisker/natural rubber elastomeric compound；Finally by beta-type silicon carbide whisker/butadiene rubber elastomeric compound and beta-type silicon carbide whisker/natural rubber
Glue elastomeric compound is kneaded, and prepares tennis sizing material；Here extreme hardness, the modulus of elasticity pole of beta-type silicon carbide whisker are taken full advantage of
Greatly, the characteristic that tensile strength is very big and heat resisting temperature is high, prepared tennis sizing material is compared with existing tennis sizing material, power
Learn performance and heat resistance is significantly improved.
(2) the tennis sizing material of the beta-type silicon carbide whisker prepared by the present invention and rubber blending using butadiene rubber with it is natural
Rubber blending, its cold resistance after being vulcanized using butadiene rubber, the characteristics of wearability and elasticity are all especially excellent and natural rubber
The characteristics of combination property itself is good, two kinds of rubber are learnt from other's strong points to offset one's weaknesses and are used in combination, so as to further increase prepared tennis glue
Cold resistance, wearability, modulus of elasticity and the stress at definite elongation of material.
(3) preparation method of the invention also has that technique is simple, can have strong operability and be adapted to the excellent of large-scale industrial production
Point.Would generally be first by pure butadiene rubber and pure natural compounding rubber, then by strengthening material according to existing tennis sizing material preparation method
Material is added in the blend compounds after butadiene rubber/natural rubber is kneaded, but this can face how to select butadiene rubber/natural rubber
It is kneaded the problem of blend compounds compounding ingredient.In addition, the existing available compounding ingredient species of technique is various, when formulating sizing compound formula,
Not only will be in view of existing chemical reaction between every kind of compounding ingredient, existing chemical reaction between compounding ingredient and reinforcing material,
Also need to consider that compounding ingredient can promote its vulcanization in pure butadiene rubber, but whether can in butadiene rubber/natural rubber elastomeric compound
The problems such as promoting its vulcanization.Change of the chemism more than compounding ingredient in a kind of rubber during compounding ingredient is rubber mixed at two kinds
Learn mechanism and want the more of complexity, this will make troubles to the property grasped of preparation method.The preparation method of the present invention is by beta-type silicon carbide
For whisker respectively as butadiene rubber and the reinforcing material of natural rubber, beta-type silicon carbide whisker is added to pure suitable fourth by this than directly
Rubber/pure natural rubber mixed, operability is stronger, and technique is also simpler.
(4) the tennis sizing material of the beta-type silicon carbide whisker prepared by the present invention and rubber blending also complies fully with tennis sizing material
It is required that high rigidity, high stress at definite elongation and elastomeric feature, have a wide range of applications in the preparation and production of tennis.
Embodiment
Further below in conjunction with the embodiments to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to is interpreted as limiting the scope of the invention, specific quality, reaction time in example
Also only it is an example in OK range with temperature, technological parameter etc., those skilled in the art is above-mentioned according to the present invention's
Some nonessential modifications and adaptations that content is made belong to protection scope of the present invention.
Embodiment：
Agents useful for same is bought be not further purified just directly from the market as being commercial reagents without particularly pointing out
Connect use.
The preparation method of the tennis sizing material of beta-type silicon carbide whisker and rubber blending, specifically comprises the following steps：
(1) on a mill, by the butadiene rubber of 300g high-cis structures in 40 DEG C of 3min that plasticate, after its bag roller successively
Add 3g stearic acid, 12g zinc oxide, 25g beta-type silicon carbide whiskers, 4g rubber accelerators DM, 2g rubber accelerator TT and 10g sulphur
Sulphur is kneaded 12min at 160 DEG C, obtains beta-type silicon carbide whisker/butadiene rubber elastomeric compound；
(2) on a mill, 1000g caouttchoucs are sequentially added into 50g oxygen in 50 DEG C of 3min that plasticate after its bag roller
Change zinc, 60g beta-type silicon carbide whiskers, 10g rubber accelerators D, 10g rubber accelerator DM, 5g rubber accelerator TMTD and 20g sulphur
Sulphur is kneaded 15min at 130 DEG C, obtains beta-type silicon carbide whisker/natural rubber elastomeric compound.
(3) on a mill, by obtained beta-type silicon carbide whisker/butadiene rubber elastomeric compound in step (1) and step (in)
Obtained beta-type silicon carbide whisker/natural rubber elastomeric compound is kneaded 10min at 75 DEG C, obtains beta-type silicon carbide whisker/suitable fourth rubber
Glue-compound the elastomeric compound of beta-type silicon carbide whisker/natural rubber.This compound elastomeric compound is determined into its sulfurizing time with vulcameter again
T90, vulcanized with vulcanizing press at 135 DEG C, you can the tennis glue of the beta-type silicon carbide whisker and rubber blending is prepared
Material
To synthesized tennis sizing material according to GB/T528-2009《Vulcanize rubber or thermoplastic elastomer tensile stress-strain
The measure of energy》Tensile property test is carried out, according to GB/T531.1-2008《Vulcanize rubber or the experiment of thermoplastic elastomer penetration hardness
Method part 1：Shore durometer (Shao Er hardness)》Carry out hardness to be tested, instrument is：Shao Er A type rubber hardnesses
Count LX-A；Impact rebound degree is surveyed using rubber rebound test instrument；As a result show：Beta-type silicon carbide whisker produced by the present invention and rubber
Glue and tennis sizing material compared with pure butadiene rubber/pure natural rubber mix sizing material, matched in butadiene rubber and natural rubber
In the case of identical, there is following remarkable result：
1st, 200% stress at definite elongation brings up to 9.39Mpa by 8.08Mpa,
2nd, 300% stress at definite elongation brings up to 9.52Mpa by 8.29Mpa,
3rd, tensile strength brings up to 16.77Mpa by 13.58Mpa,
4th, break extension rate and bring up to 338% by 299%,
5th, Shao Er A type hardness testers bring up to 70 degree by 58 degree,
6th, impact rebound degree brings up to 72% by 65%.
Tennis sizing material prepared by the present invention is being prepared with intensity in the high, tennis that resilience is good and stress at definite elongation is high
Have broad application prospects.
Claims (6)
1. the tennis sizing material of a kind of beta-type silicon carbide whisker and rubber blending, it is characterised in that the composition of the sizing material presses mass fraction
For：85 parts of beta-type silicon carbide whisker dosage；300 parts of butadiene rubber dosage；1000 parts of natural rubber dosage；3 parts of stearic acid dosage；
62 parts of zinc oxide dosage；14 parts of rubber accelerator DM dosages；2 parts of rubber accelerator TT dosages；30 parts of sulfur consumption；Rubber promotes
10 parts of agent D dosages；5 parts of rubber accelerator TMTD dosages.
2. the tennis sizing material of beta-type silicon carbide whisker according to claim 1 and rubber blending, it is characterised in that described β
A diameter of 0.05~0.2 μm of type silicon carbide whisker, average length are 10~40 μm.
3. the tennis sizing material of beta-type silicon carbide whisker according to claim 1 and rubber blending, it is characterised in that described
Butadiene rubber is the butadiene rubber of high-cis structure.
4. the tennis sizing material of beta-type silicon carbide whisker according to claim 1 and rubber blending, it is characterised in that described
Natural rubber is caouttchouc.
5. a kind of preparation method of the tennis sizing material of beta-type silicon carbide whisker according to claim 1 and rubber blending, it is special
Sign is to comprise the following steps：
1) on a mill, the butadiene rubber that mass fraction is 300 parts is plasticated, temperature is 40 DEG C, time 3min, is treated
After its bag roller, sequentially add 3 parts of stearic acid, 12 parts of zinc oxide, 25 parts of beta-type silicon carbide whiskers, 4 parts of rubber according to mass fraction and promote
Enter agent DM, 2 parts of rubber accelerator TT and 10 parts of sulphur to be kneaded, temperature is 160 DEG C, time 12min, obtains the carbonization of β types
Silicon wafer palpus/butadiene rubber elastomeric compound；
2) it is on a mill, that 1000 parts of natural rubbers are plasticated by mass fraction, temperature is 50 DEG C, time 3min, is treated
After its bag roller, 50 parts of zinc oxide, 60 parts of beta-type silicon carbide whiskers, 10 parts of rubber accelerator D, 10 are sequentially added according to mass fraction
Part rubber accelerator DM, 5 parts of rubber accelerator TMTD and 20 parts of sulphur are kneaded, and temperature is 130 DEG C, time 15min, is obtained
To beta-type silicon carbide whisker/natural rubber elastomeric compound；
3) on a mill, will be made in the beta-type silicon carbide whisker being prepared in step 1)/butadiene rubber elastomeric compound and step 2)
Standby obtained beta-type silicon carbide whisker/natural rubber elastomeric compound is kneaded, and temperature is 75 DEG C, time 10min, obtains β type carbon
SiClx whisker/butadiene rubber-compound elastomeric compound of beta-type silicon carbide whisker/natural rubber；
4) it is the beta-type silicon carbide whisker/butadiene rubber-beta-type silicon carbide whisker/natural rubber being prepared in step 3) is compound
Elastomeric compound determines its sulfurizing time t90 with vulcameter, then is vulcanized with vulcanizing press, you can described β type carbon is made
The tennis sizing material of SiClx whisker and rubber blending.
6. the preparation method of the tennis sizing material of beta-type silicon carbide whisker according to claim 5 and rubber blending, its feature exist
In the curing temperature described in step 4) is 135 DEG C.
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Cited By (2)
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| CN109400971A (en) * | 2018-09-20 | 2019-03-01 | 天长市富宝橡塑制品有限公司 | A kind of elastic preferably pet tennis and preparation method thereof |
| JP2020097674A (en) * | 2018-12-18 | 2020-06-25 | 住友ゴム工業株式会社 | Rubber composition for tennis ball |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400971A (en) * | 2018-09-20 | 2019-03-01 | 天长市富宝橡塑制品有限公司 | A kind of elastic preferably pet tennis and preparation method thereof |
| JP2020097674A (en) * | 2018-12-18 | 2020-06-25 | 住友ゴム工業株式会社 | Rubber composition for tennis ball |
| JP7275559B2 (en) | 2018-12-18 | 2023-05-18 | 住友ゴム工業株式会社 | Rubber composition for tennis balls |
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| CN107652479B (en) | 2020-06-02 |
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