CN103804953B - The preparation method of ultra-fine surface modification rhombspar - Google Patents
The preparation method of ultra-fine surface modification rhombspar Download PDFInfo
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- CN103804953B CN103804953B CN201310664396.5A CN201310664396A CN103804953B CN 103804953 B CN103804953 B CN 103804953B CN 201310664396 A CN201310664396 A CN 201310664396A CN 103804953 B CN103804953 B CN 103804953B
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Abstract
The invention discloses a kind of preparation method of ultra-fine surface modification rhombspar, namely the technology of superfine modified rhombspar is prepared by mechanical force and chemical method, concrete technical scheme is after being pulverized by rhombspar, add in ball mill and obtain superfine modified rhombspar powder by properties-correcting agent through dry ball milling, the present invention is to provide a kind of technological method superfine grinding of rhombspar powder and surface modification simultaneously carried out, this method not only simplify production technique, and the product granularity obtained is thin, distribution is concentrated, improve the physicochemical property of ground dolomite surface simultaneously, the good physical strength of material and mechanical property is maintained while strengthening the consistency between rhombspar powder and matrix.
Description
Technical field
The present invention relates to a kind of preparation method of superfine modified rhombspar, relate to a kind of mechanochemical method specifically to reach the object of surface modification while making rhombspar super-refinement.
Background technology
Rhombspar is a kind of common white nonmetal mineral thing, belongs to CaCO
3and MgCO
3compound carbonate mineral, extremely abundant in China's standing stock, be a kind of important calcium magnesium resource.Rhombspar has been widely used in the industries such as plastics, rubber, binding agent as filler.But oarse-grained rhombspar powder can cause the physical strength of material itself as the deterioration of the indices such as tensile resistance and elongation at break in macromolecular material, rhombspar super-refinement is become a kind of inevitable.
At present, physical pulverization method relies on the advantage that its cost is low, production technique is simple and output is large to become production superfine powdery material method the most widely.The research of super-pine crush equipment used mainly contains micronizer mill, mechanical shock pulverizer, ball mill, vibration mill, Ball-stirring mill, colloidal mill etc.The product pulverized out is due to fine size, narrowly distributing, uniform quality, thus have that specific surface area is large, surfactivity is high, chemical reaction velocity is fast, dissolution rate is fast, that sintered compact intensity is large and unique be electrical, magnetic, optical etc., be thus widely used in many technical fields.But, due to superfine powder there is small-size effect, surface and interface effect, macro quanta tunnel effect make it be easy to reunite, and not easily disperses in organic medium, poor with matrix compatibility, directly affects its actual effect.Superfine powder is carried out to one of the most effective approach of dispersion treatment and exactly surface modification is carried out to it, thus reach improve powder physicochemical property, reinforcing filler and matrix consistency, improve object that is dispersed, that improve interfacial property, give particle New function.
At present, carry out surface modification to powder mainly contain surface coverage modification, local chemical modification, mechanical-chemical modification, outer membrane modification, high-energy surface modification and utilize precipitin reaction to carry out surface modification etc.Mechanical-chemical modification refers to by compression, shears, friction, extend, the means such as bending, impact, mechanical energy is applied to material, thus the physicochemical property of bringing out material change, make the method that the material of itself and surrounding reacts.While the surface properties changing product Natural hydrophilic oleophobic, improve its consistency in the polymer, reduce its impact on polymeric articles processing characteristics and mechanical property, even make their over-all propertieies increase.
Technological achievement display past according to this, first roughly grinds rhombspar, carries out mechanical-chemical modification afterwards to it, although the product obtained is good with macromolecular material consistency, but there is the shortcoming that powder granularity is thin not; And first by rhombspar superfine grinding, then carry out wet-process modified to it, there is complex manufacturing, properties-correcting agent and powder surface affinity is poor, adhewsive action is weak and uneven shortcoming.
Summary of the invention
For the deficiency of above-mentioned technology, the present invention proposes a kind of preparation method of super fine bitter spar, technology that a kind of mechanical force and chemical method prepares superfine modified rhombspar, while superfine grinding is carried out to powder, complete the surface active modification of powder.Technical process of the present invention is first pulverized by rhombspar to make rhombspar powder, and then obtain superfine modified powder through properties-correcting agent dry ball milling in ball mill; Concrete technical scheme realizes as follows:
1) rhombspar pulverizing is obtained the rhombspar powder that size is 4-7um;
2) rhombspar powder step 1) obtained joins in the ball grinder of ball mill, then the properties-correcting agent that quality is powder quality 1.5%-5% is added, rotational speed of ball-mill be 200-500r/min, under temperature is the condition of 60-90 DEG C, dry ball milling 100-120min obtains the super fine bitter spar powder of surface modification, and the grinding medium in ball mill is abrading-ball.
Preferably, in the present invention the rhombspar powder described in step 1) obtains with airflow milling fine grinding after Raymond machine corase grind.
Preferably, step 2) described in the number of abrading-ball be 20-60, diameter is between 5mm-10mm, and the ratio that abrading-ball is 15-25 in ratio of grinding media to material adds.
Preferably, step 2 in the present invention) described abrading-ball be two kinds of different sizes abrading-ball mixing, be of a size of any two numerical value of diameter between 5mm-10mm, the number of described abrading-ball is any two numerical value between 10-30, also can be the abrading-ball mixing of multiple different size, the ratio that abrading-ball is 15-25 in ratio of grinding media to material adds.
Preferably, in the present invention described abrading-ball is aluminum oxide or zirconium white.
Preferably, step 2 in the present invention) described in ball mill be planetary ball mill, the present invention utilizes solid material form, the change of crystalline structure thus induction physicochemical change this principle can occur under mechanical force to produce superfine powdery material, and planetary ball mill advantage is that make full use of Mechanosensitive channels carries out surface active modification while carrying out superfine grinding.
Preferably, in the present invention step 2) described in properties-correcting agent be higher fatty acid, higher fatty acid salt or coupling agent.
Preferably, in the present invention the carbonatoms of described higher fatty acid, higher fatty acid salt is between 16-18.
Preferably, in the present invention described coupling agent is titanate coupling agent, boric acid ester coupler, silane coupling agent, aluminum-zirconium coupling agent, aluminate coupling agent, aluminium titanium composite coupler or aluminium zirconium composite coupler.
Step 2 in the present invention) the super fine bitter spar powder median size D50 of described surface modification is 1.0um.
Step 2 in the present invention) described in the super fine bitter spar powder particle diameter D97 of surface modification be 2.0um.
The quality of product modified effect is embodied by activation rate, the specific experiment process of activation rate test is as follows: accurately take the modified sample of 1g in 20ml graduated cylinder, add water to 15ml, vibration shakes up rear standing 30min, at this moment a powder part for modification floats on the upper strata of water, a part sinks to the bottom, reads the upper float sum sinking volume of sample after kept in balance;
Activation rate calculation formula:
V1: floating volume;
V2: sinking volume;
The larger explanation surface modification effect of degree of activation is better, the ratio of modification that what it more embodied is.The characteristic of the hydrophilic oleophobic of unmodified rhombspar surface presentation, carrying out surface modification to it is consistency in order to increase itself and organic phase, thus does not change the mechanical property of material while making it give full play to filler effect.
In order to verify the consistency of modification dolomite and organic phase further, respectively oil absorbency mensuration being carried out to modification and unmodified rhombspar, comparing the change of both oil absorbencies.Detailed process is as follows: take 5g modification and unmodified rhombspar powder respectively on watch-glass, while stir limit drop-burette with glass stick to drip Viscotrol C, records the consumption of Viscotrol C when powder is just bonded to pelletizing.
Oil absorbency formula: oil absorbency=Viscotrol C consumption/powder consumption
Mechanics Performance Testing: by PP(polypropylene) mix in different ratios from rhombspar, melting compound on double roller plastic-making device, mixing even rear tab is taken off, pressurize cooling in chilling press is taken off after hot-forming on vulcanizing press, take out cutting sample preparation, tensile property and impact property test are carried out to it.
Beneficial effect of the present invention: provide a kind of technological method superfine grinding of rhombspar powder and surface modification simultaneously carried out, simplify production technique, the product granularity obtained is thin, distribution is concentrated, improve the physicochemical property of ground dolomite surface, while strengthening the consistency between rhombspar powder and matrix, maintain the good physical strength of material and mechanical property.
accompanying drawing explanationthe preparation method of the ultra-fine surface modification rhombspar of Fig. 1.
Embodiment
Embodiment 1:
In the ball grinder of planetary ball mill, add the rhombspar powder that particle diameter is 5 um, be 100 weight parts with rhombspar, add the stearic acid of 2 deals, ball milling 100min at 60 DEG C, obtain the modification dolomite powder that particle diameter described in the invention is 2um; Sample degree of activation is 99.3% after testing; Modification dolomite powder decreases 12.5% than unmodified ground dolomite oil absorbency; The rhombspar of long time without surface modification joins in PP, and the increase tensile strength with content declines gradually, and when modified rhombspar loading level reaches 2%, tensile strength is maximum; The rhombspar of non-modified joins in PP, and goods impact property reaches maximum 6.5 MPa 1%, and after stearic acid modified, matrix material impact property when modification dolomite loading level is 2% is up to 6.8 MPa.
Embodiment 2:
In the ball grinder of planetary ball mill, add the rhombspar powder that particle diameter is 6 um, be 100 weight parts with rhombspar, add the stearate of 2 deals, ball milling 100 min at 75 DEG C, obtain the modification dolomite powder that particle diameter described in the invention is 2 um; Sample degree of activation is 99.5% after testing; Modification dolomite powder decreases 13.8% than unmodified ground dolomite oil absorbency; Modified rhombspar joins in PP, and when loading level reaches 3%, tensile strength is maximum; Modified through stearate, matrix material impact property when modification dolomite loading level is 3% is up to 7.0 MPa.
Embodiment 3:
The rhombspar powder that particle diameter is 7 um is added in the ball grinder of planetary ball mill, be 100 weight parts with rhombspar, add the silane coupling agent of 2.5 deals, ball milling 120 min at 80 DEG C, obtain the modification dolomite powder that particle diameter described in the invention is 2 um; Sample degree of activation is 99.1% after testing; Modification dolomite powder decreases 12.3% than unmodified ground dolomite oil absorbency; Modified rhombspar joins in PP, and when loading level reaches 3%, tensile strength is maximum; After silane coupling agent surface modification, matrix material impact property when modification dolomite loading level is 3% is up to 7.0 MPa.
Embodiment 4:
The rhombspar powder that particle diameter is 4 um is added in the ball grinder of planetary ball mill, be 100 weight parts with rhombspar, add the titanate coupling agent of 5 deals, ball milling 120 min at 80 DEG C, obtain the modification dolomite powder that particle diameter described in the invention is 2 um.Sample degree of activation is 99.6% after testing; Modification dolomite powder decreases 13.9% than unmodified ground dolomite oil absorbency; Modified rhombspar joins in PP, and when loading level reaches 3%, tensile strength is maximum; After titanate coupling agent surface modification, matrix material impact property when modification dolomite loading level is 3% is up to 7.2MPa.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (7)
1. the preparation method of ultra-fine surface modification rhombspar, is characterized in that, comprise the steps,
1) rhombspar pulverizing is obtained the rhombspar powder that size is 4-7 μm;
2) rhombspar powder step 1) obtained joins in the ball grinder of ball mill, then the properties-correcting agent that quality is powder quality 1.5%-5% is added, rotational speed of ball-mill be 200-500r/min, under temperature is the condition of 60-90 DEG C, dry ball milling 100-120min obtains the super fine bitter spar powder of surface modification, and the grinding medium in ball mill is abrading-ball; The number of described abrading-ball is 20-60, and diameter is between 5mm-10mm, and the ratio that abrading-ball is 15-25 in ratio of grinding media to material adds; Described abrading-ball is aluminum oxide or zirconium white; Described ball mill is planetary ball mill.
2. the preparation method of ultra-fine surface modification rhombspar according to claim 1, is characterized in that, the rhombspar powder described in step 1) is by obtaining with airflow milling fine grinding after Raymond machine corase grind.
3. the preparation method of ultra-fine surface modification rhombspar according to claim 1, it is characterized in that, step 2) described in abrading-ball be two kinds of different sizes abrading-ball mixing, be of a size of any two numerical value of diameter between 5mm-10mm, the number of described abrading-ball is any two numerical value between 20-30, and the ratio that abrading-ball is 15-25 in ratio of grinding media to material adds.
4. the preparation method of ultra-fine surface modification rhombspar according to claim 1, is characterized in that, step 2) described in properties-correcting agent be higher fatty acid, higher fatty acid salt or coupling agent.
5. the preparation method of ultra-fine surface modification rhombspar according to claim 4, is characterized in that, the carbonatoms of described higher fatty acid, higher fatty acid salt is between 16-18.
6. the preparation method of ultra-fine surface modification rhombspar according to claim 4, it is characterized in that, described coupling agent is titanate coupling agent, boric acid ester coupler, silane coupling agent, aluminum-zirconium coupling agent, aluminate coupling agent, aluminium titanium composite coupler or aluminium zirconium composite coupler.
7. the preparation method of ultra-fine surface modification rhombspar according to claim 1, is characterized in that, step 2) described in the particle diameter D50 of super fine bitter spar powder of surface modification be 1.0 μm, D97 is 2.0 μm.
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| CN107418250A (en) * | 2017-08-10 | 2017-12-01 | 青阳县永诚钙业有限责任公司 | A kind of preparation method of modification dolomite |
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| CN113025077A (en) * | 2021-03-01 | 2021-06-25 | 武宣宝丰矿业有限公司 | Preparation method of superfine dolomite powder |
| CN113136108A (en) * | 2021-04-02 | 2021-07-20 | 湖北工业大学 | Preparation method of superfine inorganic micro powder modified asphalt |
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