CN106349755A - Preparation method of high-reinforcing nano calcium carbonate/one-dimensional mineral composite - Google Patents
Preparation method of high-reinforcing nano calcium carbonate/one-dimensional mineral composite Download PDFInfo
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- CN106349755A CN106349755A CN201610689881.1A CN201610689881A CN106349755A CN 106349755 A CN106349755 A CN 106349755A CN 201610689881 A CN201610689881 A CN 201610689881A CN 106349755 A CN106349755 A CN 106349755A
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- calcium carbonate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
- C09C1/0093—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound whose phases only contain calcium ions, carbonate ions and silicate ions or silica
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
Abstract
The invention relates to a preparation method of a high-reinforcing nano calcium carbonate/one-dimensional mineral composite and belongs to the field of mineral processing and nonmetal mineral materials. The preparation method includes the steps of (1) adding, by weight, 500-1500 parts of one-dimensional mineral, 50-200 parts of quick lime and 5-50 parts of a particle blocking agent into water, and mixing and stirring to obtain a suspension; (2) pumping the suspension of step (1) into a rotational high gravity field, and hydrating at normal temperature; (3), after hydration, introducing CO2 to the rotational high gravity field for reaction, and stopping introduction when pH of reaction liquid is </=8.5+/-0.25 and electrical conductivity is </=0.10+/-0.02 Mus/cm; (4) subjecting reaction product of step (3) to solid-liquid separation to obtain the finished composite. Particle size distribution of nano calcium carbonate particles can be narrowed, reinforcing action of the particles are given to better play, and self-assembly of nano calcium carbonate and one-dimensional minerals is achieved in the high gravity field through heterogeneous nucleating effect.
Description
Technical field
The present invention relates to the use of natural non-metallic mineral and be combined the preparation method preparing macromolecular material filler, especially relate to
And a kind of preparation method of the nano-calcium carbonate of high reinforcing property/one-dimensional mineral composite, belong to mineral processing with nonmetallic
Mineral material field.
Background technology
The nonmetallic minerals such as wollastonite, attapulgite, meerschaum belong to typically one-dimensional ore deposit from grain shape
Thing, has been widely used as the filler of the polymer composites materials such as plastics, rubber at present.The filling capacity master of these mineral fillers
The chemical composition of mineral to be depended on, crystal structure, granularity, grain shape, surface nature etc..Modern New high polymer base is combined
Material does not require nothing more than nonmetal mineral fillers to be had functions that increment and reduces material cost, more importantly requires it can
Significantly improve the performance of packing material or there is the functions such as reinforcement and enhancing.Filler is combined and surface modification is to improve inorganic non-gold
Belong to the important technical of mineral filler filler reinforcement performance.Yet with the defect of above-mentioned natural one-dimensional mineral microstructure,
Good combination interface cannot be formed with matrix resin, some mechanical performance indexs often resulting in composite are unable to reach height
The application requirement of reinforcing function.
Wollastonite belongs to typical one-dimensional chain metasilicate, in threadiness or needle-like.Due to its have excellent, unique
Particle shape, physicochemical characteristicss and processing performance and be widely used in plastics, coating, rubber, papermaking and building, pottery, resistance to
Numerous industrial department such as fiery material, is a kind of feature reinforcer of plastics, rubber Polymer material.Attapulgite is also
One kind typically one-dimensional natural nano structural material, can be effectively improved the combination property of macromolecular material as filler when using.
Meerschaum is a kind of clay mineral of magnesium silicate containing Shuifu County of tool layer chain structure, use as gum filler can play half plus
Gu the effect of filler, the modulus of rubber, tensile strength, hardness, anti-tear power is made to increase, and obtain preferable aging characteristics.
However, above-mentioned one-dimensional mineral surfaces are all poor with the compatibility of organic polymer base material；And due to natural minerals
The color development point impurity that surface often exists, when as plastics, the filler of rubber Polymer material, can have a strong impact on product
Whiteness.Therefore, it is necessary to using before should carry out surface modification to it.For example: patent cn200710151943.4 reports a kind of silicon
The method of lime stone coating alumina silicate nano particle on surface, the method not only remains original performance of wollastonite fibre, but also
Can be with performances such as acidproof, the high whiteness of complex silicate aluminum, high covering powers, but technique is more complicated, and process is wayward, produces into
This is also higher；Patent cn201410335290.5 reports a kind of attapulgite/Calcium Carbonate Composite Fillers for polyurethane leather
Preparation method, the method is worked in coordination with according to filler and is strengthened principle, by attapulgite that is fibrous and having flexibility and graininess and tool
The Calcium Carbonate of rigidity is combined to lift the apparent and mechanical property of polyurethane leather.However, due to being changed using simple physical mixed
Property it is difficult to the densification realizing Calcium Carbonate and attapulgite is combined it is impossible to give full play to the two synergy, and adopt micron order
Ground calcium carbonate is raw material it is impossible to be obviously improved the mechanical property of system.Paper 1(China powder technology, 1999,5(5), 24-
27；Chinese powder technology, 2002,8(1), 1-5) and report a kind of ground calcium carbonate with wollastonite by being simply mixed or grinding
The mode of mixing, synthetic wollastonite/Calcium Carbonate Composite Fillers, above-mentioned technique equally cannot realize the densification of Calcium Carbonate and wollastonite
Compound, and grind and can destroy the original fibre structure of wollastonite.Paper 2(silicate is circulated a notice of, and 2009,28(5), 1076～
1079) report a kind of method that attapulgite/Calcium Carbonate Composite Fillers are prepared using nonhomogen-ous nucleation method, however micro- according to it
See morphology characterization result, the calcium carbonate granule that the method produces there occurs obvious reunion, and the two combines also not tight, this meeting
Affect its practical application effect it is impossible to meet the application requirement of high reinforced filling.
Content of the invention
For above-mentioned the deficiencies in the prior art, the technical problem to be solved in the present invention is to provide a kind of receiving of high reinforcing property
The preparation method of rice Calcium Carbonate/one-dimensional mineral composite, this method can make the Nano particles of calcium carbonate particle size distribution of formation relatively
Narrow, preferably play its toughened and reinforced effect, utilize nonhomogen-ous nucleation to act on simultaneously, super gravity field is realized nano-calcium carbonate
Calcium and the self assembly of one-dimensional mineral.
Realize above-mentioned purpose of the present invention to be adopted the technical scheme that:
1. following components proportioning, one-dimensional mineral 500～1500 weight portion, quick lime 50～200 weight portion, particle barrier 5 are pressed
～50 weight portions are added to the water and carry out mix and blend and obtain suspension；
2. 1. gained suspension will pump into and under room temperature in rotation invariant recognition, carry out hydration reaction；
3., after hydration reaction terminates, rotation invariant recognition is passed through co again2Reaction, when reactant liquor ph≤8.5 ± 0.25, electrical conductivity≤
Stop ventilation during 0.10 ± 0.02 μ s/cm；
4. finished product is obtained to product solid-liquid separation 3..
Described one-dimensional mineral are wollastonite, attapulgite, meerschaum natural non-metallic mineral, draw ratio >=5, purity >=
85%；Described particle barrier is surfactant op-10 or Polyethylene Glycol.
Described rotation invariant recognition uses rotating packed bed reactor, rotational speed regulation to 500～2000rpm,
The liquid that reactor flows out enters external circulation stirring kettle, then pumps into rotating packed bed reactor through pump circulation, and iterative cycles are anti-
Answer 30～100min.
It is passed through co2Reacted product solid-liquid separation adopts centrifuge, and rotating speed is 1000～10000rpm, centrifugation time 5
～50min.
The ultimate principle of the present invention is, by, in aqueous medium, making above-mentioned one-dimensional mineral surfaces equal using hypergravity effect
Even densely coated caco3 nanoparticle, the microcosmic enhancing between one-dimensional mineral and generation nano-calcium carbonate is combined, and is given birth to
The cium carbonate nanoparticles becoming, because specific surface area itself is big, free energy is high, not only can reduce natural mineral fiber surplus color
The impact to material whiteness for the plain impurity, and mineral fibres can be protected not to be destroyed；Additionally, one-dimensional mineral come to micron order
Say, calcium carbonate nano particle passes through load effect, corner angle sharp keen for one-dimensional mineral fiber surfaces can be passivated, reduce stress collection
In, make that smooth Crystal Cleavage face becomes is coarse, and the larger plane of roughness can make contact angle reduce, thus be more likely to poly-
Compound sill is compatible；The calcium carbonate nano particle of area load is easier to form chemisorbed with modifying agent simultaneously, improves one
Tie up the organic surface modifying effect of mineral and improve its dispersibility in high polymer further.Using receiving of gravity Method preparation
Rice Calcium Carbonate coats original performance that above-mentioned one-dimensional mineral not only remain one-dimensional mineral, but also can improve composite Nano carbon
The performances such as the high whiteness of sour calcium rigid particles, high covering power, form the assembling association of nano-calcium carbonate zero dimension material and one-dimensional mineral
Same effect.The present invention is significant for the progress of above-mentioned one-dimensional mineral modified technology and its deep processing and utilization.
Beneficial effects of the present invention are as follows: 1 present invention achieves the preparation of nano-calcium carbonate particles and coating modification process
Carry out simultaneously, compare traditional physics cladding process, the technique of the present invention substantially increases production efficiency and product quality；2 and
The product that the conventional uniform sedimentation method prepare is compared, and is coated in the nano-calcium carbonate/one-dimensional mineral composite of the present invention
Nano-calcium carbonate particles particle diameter is little, narrowly distributing, one-dimensional size can reach 0.5～10nm, and in mineral fiber surfaces distribution
Dense uniform, can give full play to cooperative effect when applying both as reinforced filling.
Specific embodiment
Embodiment 1:
(1) in external circulation stirring kettle, by the wollastonite of certain proportioning, quick lime and particle barrier op-10 be added to the water into
Row dispersed with stirring, mix and blend obtains suspension.Each raw material components proportioning is: wollastonite 600 weight portion, quick lime 60 weight portion,
Particle barrier 10 weight portion.
(2) rotating packed bed reactor, rotational speed regulation to 800rpm are opened, the suspension that step (1) is obtained pumps into
High gravity rotating packed bed carries out hydration reaction, is exported by liquid reactor and flows out, enter after the strengthening mixing of reactant liquor rotated bed
Enter external circulation stirring kettle, in kettle, reactant liquor squeezes into high-gravity rotating bed, so circulation reaction 50min at normal temperatures again through pump.
(3), after hydration reaction terminates, it is passed through co to gravity revolving bed air inlet2, course of reaction needs real-time monitoring ore pulp
Ph and electrical conductivity, control co by the feedback regulation effect of detector2Duration of ventilation, that is, control reaction end；As reactant liquor ph
≤ 8.5 ± 0.25, during the μ s/cm of electrical conductivity≤0.10 ± 0.02, monitoring display instrument is automatically reminded to reaction end, and breather valve is closed.
(4) product is fed centrifuge, rotating speed is 2000rpm, centrifugation time 15min, carries out solid-liquid separation, obtains
Nano-calcium carbonate/grammite composite material.
Embodiment 2:
Same as Example 1, change is:
In step (1), each raw material components proportioning is: wollastonite 800 weight portion, quick lime 70 weight portion, particle barrier op-10
25 weight portions.
Speed of agitator 1200rpm, circular response 65min under room temperature in step (2).
Step (4) centrifuge speed is 3500rpm, centrifugation time 10min.
Embodiment 3:
Same as Example 1, change is:
In step (1), each raw material components proportioning is: wollastonite 1200 weight portion, quick lime 160 weight portion, particle barrier 40 weight
Amount part, particle barrier is changed to Polyethylene Glycol.
Speed of agitator 1600rpm, circular response 80min under room temperature in step (2).
Step (4) centrifuge speed is 6000rpm, centrifugation time 8min.
Embodiment 4:
(1) in external circulation stirring kettle, the attapulgite of certain proportioning, quick lime and particle barrier op-10 are added to the water
It is stirred disperseing, mix and blend obtains suspension.Each raw material components proportioning is: attapulgite 600 weight portion, quick lime 60 weight
Part, particle barrier (op-10) 15 weight portion.
(2) rotating packed bed reactor, rotational speed regulation to 800rpm are opened, the suspension that step (1) is obtained pumps into
High gravity rotating packed bed carries out hydration reaction, is exported by liquid reactor and flows out, enter after the strengthening mixing of reactant liquor rotated bed
Enter external circulation stirring kettle, in kettle, reactant liquor squeezes into high-gravity rotating bed, so circulation reaction 50min at normal temperatures again through pump；
(3), after hydration reaction terminates, it is passed through co to gravity revolving bed air inlet2, course of reaction need real-time monitoring ore pulp ph and
Electrical conductivity, controls co by the feedback regulation effect of detector2Duration of ventilation, that is, control reaction end；When reactant liquor ph≤8.5
± 0.25, during the μ s/cm of electrical conductivity≤0.10 ± 0.02, monitoring display instrument is automatically reminded to reaction end, and breather valve is closed.
(4) product is fed centrifuge, rotating speed is 4000rpm, centrifugation time 10min, carries out solid-liquid separation, obtains
Nano-calcium carbonate/attapulgite composite.
Embodiment 5:
Same as Example 4, change is:
In step (1), each raw material components proportioning is: attapulgite 800 weight portion, quick lime 70 weight portion, particle barrier (op-
10) 25 weight portion；
Speed of agitator 1200rpm, circular response 65min under room temperature in step (2)；
Step (4) centrifuge speed is 5500rpm, centrifugation time 10min.
Embodiment 6:
Same as Example 4, change is:
In step (1), each raw material components proportioning is: attapulgite 1200 weight portion, quick lime 160 weight portion, particle barrier 40
Weight portion, particle barrier is changed to surfactant polyethylene.
Speed of agitator 1600rpm, circular response 80min under room temperature in step (2)；
Step (4) centrifuge speed is 8000rpm, centrifugation time 8min.
Embodiment 7:
(1) in external circulation stirring kettle, by the meerschaum of certain proportioning, quick lime and particle barrier op-10 be added to the water into
Row dispersed with stirring, mix and blend obtains suspension.Each raw material components proportioning is: meerschaum 600 weight portion, quick lime 60 weight portion,
Particle barrier (op-10) 10 weight portion.
(2) rotating packed bed reactor, rotational speed regulation to 1200rpm are opened, the suspension that step (1) is obtained pumps into
High gravity rotating packed bed carries out hydration reaction, is exported by liquid reactor and flows out, enter after the strengthening mixing of reactant liquor rotated bed
Enter external circulation stirring kettle, in kettle, reactant liquor squeezes into high-gravity rotating bed, so circulation reaction 50min at normal temperatures again through pump；
(3), after hydration reaction terminates, it is passed through co to gravity revolving bed air inlet2, course of reaction need real-time monitoring ore pulp ph and
Electrical conductivity, controls co by the feedback regulation effect of detector2Duration of ventilation, that is, control reaction end；When reactant liquor ph≤8.5
± 0.25, during the μ s/cm of electrical conductivity≤0.10 ± 0.02, monitoring display instrument is automatically reminded to reaction end, and breather valve is closed.
(4) product is fed centrifuge, rotating speed is 4000rpm, centrifugation time 10min, carries out solid-liquid separation, obtains
Nano-calcium carbonate/meerschaum composite.
Embodiment 8:
Same as Example 7, change is:
In step (1), each raw material components proportioning is: meerschaum 800 weight portion, quick lime 70 weight portion, particle barrier (op-
10) 25 weight portion；
Speed of agitator 1200rpm, circular response 65min under room temperature in step (2)；
Step (4) centrifuge speed is 5500rpm, centrifugation time 10min.
Embodiment 9:
Same as Example 7, change is:
In step (1), each raw material components proportioning is: meerschaum 1200 weight portion, quick lime 160 weight portion, particle barrier 40 weight
Amount part, particle barrier is changed to surfactant polyethylene；
Speed of agitator 1600rpm, circular response 65min under room temperature in step (2)；
Step (4) centrifuge speed is 8000rpm, centrifugation time 8min.
Table is carried out to the composite of various embodiments above gained using Laboratary type step heated at high speed blender
Face is modified, and modifying agent is hard fatty acids, and consumption is 1.2 w%., loading is 30% situation taking filling polyvinyl chloride (pvc) as a example
Under, the mechanical property of the composite after each embodiment filling is shown in Table 1.
The mechanical property of the filling polyvinyl chloride (pvc) of each compounded mix in table 1 embodiment
The above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not the reality to the present invention
Apply the restriction of mode, for those of ordinary skill in the field, other can also be made on the basis of the above description
The change of multi-form or variation, cannot be exhaustive to all of embodiment here, every technical side belonging to the present invention
Obvious change that case is extended out or change the row still in protection scope of the present invention.
Claims (4)
1. a kind of preparation method of the nano-calcium carbonate of high reinforcing property/one-dimensional mineral composite, is characterized in that including following
Step: 1. press following components proportioning, one-dimensional mineral 500～1500 weight portion, quick lime 50～200 weight portion, particle barrier 5
～50 weight portions are added to the water and carry out mix and blend and obtain suspension；2. 1. room temperature in rotation invariant recognition will be pumped into by gained suspension
Under carry out hydration reaction；3., after hydration reaction terminates, rotation invariant recognition is passed through co again2Reaction, when reactant liquor ph≤8.5 ±
0.25, stop ventilation during the μ s/cm of electrical conductivity≤0.10 ± 0.02；4. finished product is obtained to product solid-liquid separation 3..
2. the preparation method of the nano-calcium carbonate of the high reinforcing property as described in claim 1/one-dimensional mineral composite, it is special
Levying is: described one-dimensional mineral are wollastonite, attapulgite, meerschaum natural non-metallic mineral, draw ratio >=5, purity >=
85%；Described particle barrier is surfactant op-10 or Polyethylene Glycol.
3. the preparation method of the nano-calcium carbonate of the high reinforcing property as described in claim 2/one-dimensional mineral composite, it is special
Levying is: rotation invariant recognition uses rotating packed bed reactor, rotational speed regulation to 500～2000rpm, and reactor flows out
Liquid enter external circulation stirring kettle, then pump into rotating packed bed reactor through pump circulation, iterative cycles reaction 30～
100min.
4. the preparation method of the nano-calcium carbonate of the high reinforcing property as described in claim 2/one-dimensional mineral composite, it is special
Levying is: is passed through co2Reacted product solid-liquid separation adopts centrifuge, and rotating speed is 1000～10000rpm, and centrifugation time 5～
50min.
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| CN201610689881.1A CN106349755A (en) | 2016-08-19 | 2016-08-19 | Preparation method of high-reinforcing nano calcium carbonate/one-dimensional mineral composite |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1371947A (en) * | 2001-02-27 | 2002-10-02 | 盖国胜 | Method for covering nano calcium carbonate on heavy mass calcium carbonate surface |
| CN101392106A (en) * | 2007-09-21 | 2009-03-25 | 中国矿业大学(北京) | Method for coating alumina silicate nano particle on surface of grammite |
| CN101498052A (en) * | 2009-01-04 | 2009-08-05 | 颜鑫 | Grammite raphioid fibre crystal-nano calcium carbonate micro-nano composite powder material and production method |
-
2016
- 2016-08-19 CN CN201610689881.1A patent/CN106349755A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1371947A (en) * | 2001-02-27 | 2002-10-02 | 盖国胜 | Method for covering nano calcium carbonate on heavy mass calcium carbonate surface |
| CN101392106A (en) * | 2007-09-21 | 2009-03-25 | 中国矿业大学(北京) | Method for coating alumina silicate nano particle on surface of grammite |
| CN101498052A (en) * | 2009-01-04 | 2009-08-05 | 颜鑫 | Grammite raphioid fibre crystal-nano calcium carbonate micro-nano composite powder material and production method |
Non-Patent Citations (1)
| Title |
|---|
| 陈大勇 等: "纳米碳酸钙的制备技术与表面改性方法", 《化学工业与工程技术》 * |
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