CN107964120A - A kind of rubber function additive calcium sulfate crystal whiskers and the composite modified method of white carbon - Google Patents
A kind of rubber function additive calcium sulfate crystal whiskers and the composite modified method of white carbon Download PDFInfo
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- CN107964120A CN107964120A CN201711447239.3A CN201711447239A CN107964120A CN 107964120 A CN107964120 A CN 107964120A CN 201711447239 A CN201711447239 A CN 201711447239A CN 107964120 A CN107964120 A CN 107964120A
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- Prior art keywords
- white carbon
- calcium sulfate
- sulfate crystal
- crystal whiskers
- rubber
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
The invention belongs to technical field of rubber material, discloses a kind of rubber function additive calcium sulfate crystal whiskers and the composite modified method of white carbon, is carried out in absolute ethyl alcohol, white carbon and calcium sulfate crystal whiskers addition ultrasonic dispersers pre-dispersed；According to weight ratio absolute ethyl alcohol：White carbon and calcium sulfate crystal whiskers=1：7；Absolute ethyl alcohol is added in the tank reactor with stirring and heating system, starts heating and stirring system；Add stearic acid；Stearic acid：Ethanol=1:50.The present invention is used using calcium sulfate crystal whiskers and white carbon both function additives compounding as the supporting material of rubber, white carbon can be further enhanced to rubber mechanics strengthening action, significantly improve the mechanical property of rubber, and then the anti-tensile of rubber, the performance such as wear-resisting is further lifted, and application cost will be greatly reduced.
Description
Technical field
The invention belongs to technical field of rubber material, more particularly to a kind of rubber function additive calcium sulfate crystal whiskers and white carbon
Composite modified method.
Background technology
Currently, it is external both at home and abroad also independent of the relevant report of calcium sulfate crystal whiskers and the common modified rubber material of white carbon
Filler inorganic filler used in rubber industry accounts for 30%, and white carbon accounts for 15%, wherein more than 95% is precipitation method hard charcoal
Black, the white carbon for rubber industry wherein accounts for 63% for sole according to statistics, and tire industry accounts for 15%, and coatings industry accounts for
10%, the chemical product such as toothpaste accounts for 7%, other to account for 5%.In the U.S., white carbon accounts for 16~20% for tire.Therefore market prospects
It is very big.The precipitated silica of one of raw material is hydrophily product.About 3 silanol groups on every square of millimicron of particle surface
Group.Group has compatibility to rubber, rubber molecule and filler grain surface is produced bonding action, therefore its benefit as rubber
Strong agent, can improve rubber tensile strength, its anti-aging and cracking performance is also improved, but unmodified white carbon was being applied
Since there is substantial amounts of hydroxyl on its surface in journey, easily assemble in application process, disperse in a polymer matrix bad, it may appear that with
The combination power of rubber and the problems such as wear no resistance.Another raw material sulphuric acid calcium pyroborate is fibrous monocrystal, has high intensity, height
Modulus, high tenacity, high-insulativity, abrasion performance, high temperature resistant, it is anticorrosive, be easy to surface treatment, easily with polymer (such as rubber, modeling
Material) many excellent physicochemical properties such as compound, nontoxic, inexpensive, as toughened and reinforced material, it can be widely used for rubber, plastics, glue
The industries such as stick and field, can be used as alternative supplement, reinforcing component new fiber materials.Rubber after calcium sulfate whisker modified
Elongation at break, thermal stability and wear-resisting property of product etc. are significantly improved, and application prospect is very wide, particularly exist
High tyre industry is required to have huge application space wearability.But due to calcium sulfate crystal whiskers surface energy relatively
Height, this causes unmodified calcium sulfate crystal whiskers agglomeration than more serious, and calcium sulfate crystal whiskers belong to one kind in inorganic material,
Rubber, plastics are being added to when in organic material as function additive, and there are the scattered uneven and untight problem of combination.
So needing to be modified calcium sulfate crystal whiskers before organic material is added to, it is allowed effectively to play advantageous property.
In conclusion problem existing in the prior art is：White carbon and calcium sulfate crystal whiskers are since surface energy is larger, before modified
It is more serious there are phenomenon for the form of aggregate, and it is all inorganic functional auxiliary agent, when being added in elastomeric material, it may appear that
Reunite, disperse uneven and combine untight problem；It is single that white carbon and calcium sulfate crystal whiskers are modified respectively, it is re-used as
Function additive is used for elastomeric material, can also disperse non-uniform problem in elastomeric material there are both function additives, and then
Cause the existence position deviation of enhanced elastomeric material performance.
The content of the invention
In view of the problems of the existing technology, the present invention provides a kind of rubber function additive calcium sulfate crystal whiskers and white carbon
Composite modified method.
The present invention is achieved in that a kind of rubber function additive calcium sulfate crystal whiskers and the composite modified method of white carbon, should
Method is using efficient (efficiency >=90%), microdispersed (1 μm or so) ultrasonic disperser to raw material white carbon and calcium sulfate
Whisker is pre-dispersed before being modified, its can effectively depolymerization white carbon and calcium sulfate crystal whiskers, improve the activation index of modified product；
This method as decentralized medium, can effectively prevent hydrolysis problem of the calcium sulfate crystal whiskers in modifying process using absolute ethyl alcohol,
Improve the rate of recovery of calcium sulfate crystal whiskers；This method is dried modified product using electromagnetic wave drier, can greatly improve dry
The utilization ratio of dry speed and energy；The rubber function additive calcium sulfate crystal whiskers include following with the composite modified method of white carbon
Step：
Step 1, absolute ethyl alcohol, white carbon and calcium sulfate crystal whiskers add in ultrasonic dispersers carry out it is pre-dispersed；According to quality
Compare absolute ethyl alcohol：White carbon and calcium sulfate crystal whiskers=1：7；It is (living that this method can improve modified product activation index more than 20%
Change index >=90%).
Step 2, absolute ethyl alcohol are added in the tank reactor with stirring and heating system, start heating and stirring system；
Add stearic acid；Stearic acid：Ethanol=1:50 (mass ratioes).
Further, needed after the step 2：
The first step, will add still reaction through the mixed system of pre-dispersed absolute ethyl alcohol, white carbon and calcium sulfate crystal whiskers
In device, after mixture temperature rises to 80~120 DEG C in question response device, start timing；
Second step, after 0.5~4h of material reaction in upper tank reactor, closes heating；By reaction solution, solid-liquid divides while hot
From；
3rd step, Solid Conveying and Melting dry 0.2~1h into electromagnetic wave drier；Solid, which is introduced into air drying air, to be shaken
0.2~1h of depolymerization cooling；This method can save drying time about 2h than conventional kiln dried energy saving 20%；
4th step, packs after 30~50 DEG C of depolymerization cooling.
Another object of the present invention is to provide a kind of functionalization auxiliary agent of above-mentioned composite modified product as elastomeric material.
Whiteness >=90% of the auxiliary agent, fusing point >=400 DEG C, Mohs' hardness 3~4, elasticity modulus/Gpa >=170, tensile strength/Gpa >=
20, apparent density about 0.2g/ml.
Advantages of the present invention and good effect are：Single application calcium sulfate crystal whiskers as supporting material rubbery intensity not
Enough, wearability is fine；Single application white carbon is inadequate as the rubber abrasive-resistance of supporting material, and intensity is fine.Therefore this need to be integrated
The advantages of two kinds of supporting materials, the supporting material using calcium sulfate crystal whiskers and white carbon both function additives compounding as rubber
To use.If be applied to after both raw materials are compounded in rubber, white carbon can be further enhanced to rubber mechanics reinforcement
Effect, significantly improves the mechanical property of rubber and (is broken drawing and stretches intensity ratio single application calcium sulfate crystal whiskers raising >=10%；Rubber
The wear resistance ratio of product is single to reduce≤15% using white carbon；), and then the tensile strength of rubber is improved >=10%, heat-resisting temperature
Spend (temperature in use steady in a long-term) and improve >=20 DEG C, and improve added value >=10% of rubber.
Brief description of the drawings
Fig. 1 is rubber function additive calcium sulfate crystal whiskers provided in an embodiment of the present invention and the composite modified method flow of white carbon
Figure.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
The application principle of the present invention is explained in detail below in conjunction with the accompanying drawings.
As shown in Figure 1, rubber function additive calcium sulfate crystal whiskers provided in an embodiment of the present invention and the composite modified side of white carbon
Method comprises the following steps：
S101：By the absolute ethyl alcohol (absolute ethyl alcohol of certain mass：White carbon and calcium sulfate crystal whiskers=1：7 (mass ratioes)),
White carbon and calcium sulfate crystal whiskers add in ultrasonic dispersers carry out it is pre-dispersed；
S102：The absolute ethyl alcohol of certain mass is added in the tank reactor with stirring and heating system, starts heating
And stirring system, then add a certain amount of modifying agent (stearic acid) (modifying agent thereto again：Ethanol=1:50) modifying agent, is made
Fully dissolving；
S103：Upper still reaction will be added through the mixed system of pre-dispersed absolute ethyl alcohol, white carbon and calcium sulfate crystal whiskers
In device, mixture temperature is risen in 80~120 DEG C after a certain temperature in question response device, starts timing；
S104：After material reaction certain time (0.5~4h) in upper tank reactor, heating is closed；Reaction solution is taken advantage of
Hot separation of solid and liquid；
S105：Obtained Solid Conveying and Melting is dried into 0.2~1h into electromagnetic wave drier；
S106：Obtained solid is introduced into air drying air and shakes 0.2~1h of depolymerization cooling；
S107：Depolymerization is cooled down the pack of the product after (30~50 DEG C).
The application principle of the present invention is further described with reference to specific embodiment.
Embodiment 1：
Step 1, absolute ethyl alcohol, white carbon and calcium sulfate crystal whiskers add in ultrasonic dispersers carry out it is pre-dispersed；According to weight
Compare absolute ethyl alcohol：White carbon and calcium sulfate crystal whiskers=1：7；It is (living that this method can improve modified product activation index more than 20%
Change index >=90%).
Step 2, absolute ethyl alcohol are added in the tank reactor with stirring and heating system, start heating and stirring system；
Add stearic acid；Stearic acid：Ethanol=1:50.
Further, needed after the step 2：
Step 3, will add step 2 through the mixed system of pre-dispersed absolute ethyl alcohol, white carbon and calcium sulfate crystal whiskers
In tank reactor, after mixture temperature rises to 100 DEG C in question response device, start timing；
Step 4, after material reaction 1h in upper tank reactor, closes heating；By reaction solution separation of solid and liquid while hot；
Step 5, Solid Conveying and Melting dry 0.4h into electromagnetic wave drier；Solid, which is introduced into air drying air, shakes solution
Poly- cooling 0.4h；
Step 6, packs after 40 DEG C of depolymerization cooling.Obtained white carbon is activated with the composite modified product of calcium sulfate crystal whiskers
Index can reach more than 90%, and energy consumption takes more than 2h, modified product less than traditional few energy consumption more than 20% of stove formula drying
For common butadiene-styrene rubber functionalization auxiliary agent, the fracture drawing of butadiene-styrene rubber can be made to stretch intensity ratio single application calcium sulfate crystal whiskers and carried
High >=10%；Wear resistance ratio is single to reduce≤15% using white carbon；Tensile strength improves >=10%, heat resisting temperature and improves >=20
℃。
Embodiment 2：By same steps repetitive operation as described in Example 1.Wherein the temperature of step 3 is 110 DEG C；Step
Four time is 1.5h；The drying time of step 5 is 0.8h, obtained white carbon and the composite modified product of calcium sulfate crystal whiskers
Activation index can reach more than 95%, and energy consumption takes more than 1.5h, change less than traditional few energy consumption more than 15% of stove formula drying
Property product be used for common butadiene-styrene rubber functionalization auxiliary agent, can make butadiene-styrene rubber fracture draw stretch intensity ratio single application calcium sulfate
Whisker improves >=12%；Wear resistance ratio is single to reduce≤13% using white carbon；Tensile strength improves >=12%, heat resisting temperature and improves
≥25℃。
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should all be included in the protection scope of the present invention.
Claims (3)
1. a kind of rubber function additive calcium sulfate crystal whiskers and the composite modified method of white carbon, it is characterised in that the rubber function
Auxiliary agent calcium sulfate crystal whiskers comprise the following steps with the composite modified method of white carbon：
Step 1, absolute ethyl alcohol, white carbon and calcium sulfate crystal whiskers add in ultrasonic dispersers carry out it is pre-dispersed；According to mass ratio without
Water-ethanol：White carbon and calcium sulfate crystal whiskers=1:7；
Step 2, absolute ethyl alcohol are added in the tank reactor with stirring and heating system, start heating and stirring system；According to
Mass ratio adds stearic acid；Stearic acid：Ethanol=1:50.
2. rubber function additive calcium sulfate crystal whiskers as claimed in claim 1 and the composite modified method of white carbon, it is characterised in that
Needed after the step 2：
The first step, will add in tank reactor through the mixed system of pre-dispersed absolute ethyl alcohol, white carbon and calcium sulfate crystal whiskers,
After mixture temperature rises to 80~120 DEG C in question response device, start timing；
Second step, after 0.5~4h of material reaction in upper tank reactor, closes heating；By reaction solution separation of solid and liquid while hot；
3rd step, Solid Conveying and Melting dry 0.2~1h into electromagnetic wave drier；Solid, which is introduced into air drying air, shakes depolymerization
Cool down 0.2~1h；
4th step, packs after 30~50 DEG C of depolymerization cooling.
3. one kind is composite modified using rubber function additive calcium sulfate crystal whiskers described in claim 1~2 any one and white carbon
The elastomeric material of method.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711447239.3A CN107964120A (en) | 2017-12-27 | 2017-12-27 | A kind of rubber function additive calcium sulfate crystal whiskers and the composite modified method of white carbon |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711447239.3A CN107964120A (en) | 2017-12-27 | 2017-12-27 | A kind of rubber function additive calcium sulfate crystal whiskers and the composite modified method of white carbon |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110903799A (en) * | 2019-12-02 | 2020-03-24 | 武汉市科达云石护理材料有限公司 | Water-based light-cured stone decorative surface adhesive |
| CN111253637A (en) * | 2020-03-07 | 2020-06-09 | 安陆市全盛粮食机械有限公司 | Preparation method of wear-resistant rice hulling rubber roll |
Citations (3)
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| CN105623175A (en) * | 2016-04-06 | 2016-06-01 | 苏州甫众塑胶有限公司 | Enhanced-type wear-resistant composite plastic material and preparation method thereof |
| CN106431454A (en) * | 2016-09-18 | 2017-02-22 | 广州大学 | Aerogel composite material containing calcium sulfate whiskers and clay and preparation method of aerogel composite material |
| CN106565269A (en) * | 2016-11-08 | 2017-04-19 | 成都新柯力化工科技有限公司 | Method for preparing calcium sulfate whisker-silicon dioxide aerogel through normal-pressure drying |
-
2017
- 2017-12-27 CN CN201711447239.3A patent/CN107964120A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105623175A (en) * | 2016-04-06 | 2016-06-01 | 苏州甫众塑胶有限公司 | Enhanced-type wear-resistant composite plastic material and preparation method thereof |
| CN106431454A (en) * | 2016-09-18 | 2017-02-22 | 广州大学 | Aerogel composite material containing calcium sulfate whiskers and clay and preparation method of aerogel composite material |
| CN106565269A (en) * | 2016-11-08 | 2017-04-19 | 成都新柯力化工科技有限公司 | Method for preparing calcium sulfate whisker-silicon dioxide aerogel through normal-pressure drying |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110903799A (en) * | 2019-12-02 | 2020-03-24 | 武汉市科达云石护理材料有限公司 | Water-based light-cured stone decorative surface adhesive |
| CN110903799B (en) * | 2019-12-02 | 2021-08-17 | 武汉市科达云石护理材料有限公司 | Water-based light-cured stone decorative surface adhesive |
| CN111253637A (en) * | 2020-03-07 | 2020-06-09 | 安陆市全盛粮食机械有限公司 | Preparation method of wear-resistant rice hulling rubber roll |
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Application publication date: 20180427 |
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