CN1212273C - Preparation method of surface modified nano calcium carbonate - Google Patents
Preparation method of surface modified nano calcium carbonate Download PDFInfo
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- CN1212273C CN1212273C CN 01127980 CN01127980A CN1212273C CN 1212273 C CN1212273 C CN 1212273C CN 01127980 CN01127980 CN 01127980 CN 01127980 A CN01127980 A CN 01127980A CN 1212273 C CN1212273 C CN 1212273C
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- calcium carbonate
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- nanometer calcium
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Abstract
The present invention relates to a preparation method of nanometer calcium carbonate with modified surfaces. The present invention is characterized in that calcium oxides and carbon dioxides as raw materials are synthesized into nanometer calcium carbonate; after the nanometer calcium carbonate is carbonized, the surfaces of the nanometer calcium carbonate are modified by two steps; step 1, saturated fatty acid sodium salt whose molecular formula is CH3(CH2)nCOONa(n=10, 12, 14, 16 and 18) is used as surface modifying agents, and the mount accounts for 3 to 6% of the weight of the calcium carbonate; step 2, water-soluble divalent metal salt, such as CaCl2, MgCl2, BaCl2, MgSO4, etc., as surface modifying agents is continuously added, and the amount accounts for 0.5 to 2.5% of the weight of the calcium carbonate. The nanometer calcium carbonate with modified surfaces, which is prepared with the method, has good dispersancy in organic solvents, and is used as strengthening agents which can further improve the performances of plastics, rubber, high molecular resin, etc.
Description
Technical field:
The present invention relates to a kind of preparation method of surface modified nano calcium carbonate.
Background technology:
Nano-calcium carbonate is meant the lime carbonate of median size between 1-100nm, can be used as the strengthening agent of plastics, rubber, macromolecule resin etc., improves the performance of product, improves the quality of product.Usually the calcium carbonate particles surface is hydrophilic, can not disperse well in macromolecular material, need carry out surface modification to improve the consistency of itself and macromolecular material.Mainly adopt Fatty Alcohol(C12-C14 and C12-C18) or lipid acid dispersiveness at present on the industrial production as properties-correcting agent raising lime carbonate, but the dispersed needs that still can not satisfy application.
Summary of the invention:
The present invention is according to the colloidal stability theory, and a kind of preparation method who improves the surface modified nano calcium carbonate of itself and macromolecular material consistency is provided.
Technical scheme of the present invention is:
The first step: under 30-80 ℃ of condition, be the CO that feeds 20-40% concentration in the lime emulsion of 3-10% to CaO content
2, after carburizing reagent is finished, at first adding a kind of saturated fatty acid sodium-salt, its consumption is the 3-6% of weight of calcium carbonate, stirs 20-180min;
Second step: continue to add a kind of water miscible divalent metal salt, consumption is the 0.5-2.5% of weight of calcium carbonate, and after continuing to stir 10-120min, ageing 30-400min filters, and be drying to obtain product under 30-90 ℃ of condition.
The molecular formula of saturated fatty acid sodium salt is CH in the technique scheme
3(CH
2)
nCOONa (n=10,12,14,16,18), water-soluble divalent metal salt can be CaCl
2, MgCl
2, BaCl
2And MgSO
4
Add hard soap in the technical scheme of the present invention, except the hydrophilic and hydrophobic matter that changes particle surface, can also effectively prevent the adhesion that produces owing to collision between particle; Adds the solubility divalent metal salt, the electric charge on calcium carbonate particles surface is increased, the stability of electrostatic double layer is improved, and the divalent ion of absorption is easy to and lipid acid Cheng Jian, thus improve lipid acid particle surface adsorptive capacity and adsorption strength.Nano-calcium carbonate by present method preparation has better dispersiveness in organic solvent, can further improve the performance of products such as plastics, rubber, macromolecule resin as strengthening agent.
Embodiment 1
Get 100gCaO, add the 900ml deionized water, be heated to 60 ℃, fully stir the CO of feeding 35% down
2, speed is 4l/min, stops ventilation after reaction 80min carbonization finishes, with the 6g sodium stearate be dissolved in the 100ml temperature be in 70 ℃ the hot water after, join in the above-mentioned system, after continuing to stir 60min, add 2gCaCl
2, stop behind the 20min stirring, heating, at room temperature place 350min after, filter, and 60 ℃ dry down, obtaining median size is the cube nano-calcium carbonate of the surface modification of 80nm.
Embodiment 2
Get 70gCaO, add the 930ml deionized water, be heated to 40 ℃, fully stir the CO of feeding 25% down
2, speed is 2l/min, stops ventilation after reaction 200min carbonization finishes, with the 3g Sodium pentadecanecarboxylate be dissolved in the 100ml temperature be in 50 ℃ the hot water after, join in the above-mentioned system, stir 180min after, add 0.6gMgSO
4, stop behind the 90min stirring, heating, at room temperature place 40min after, filter, and 80 ℃ dry down, obtain median size is about the surface modification of 1 μ m for 90nm length acicular nanometer lime carbonate.
Embodiment 3
Get 35gCaO, add the 965ml deionized water, be heated to 80 ℃, fully stir the CO of feeding 30% down
2, speed is 1.5l/min, stops ventilation after reaction 70min carbonization finishes, with 3.6g 20 sour sodium be dissolved in the 100ml temperature be in 80 ℃ the hot water after, join in the above-mentioned system, after continuing to stir 30min, add 1.2gBaCl
2, stop behind the 60min stirring, heating, at room temperature place 120min after, filter, and 40 ℃ dry down, obtaining median size is the cube nano-calcium carbonate of the surface modification of 40nm.
Embodiment 4
Change the sodium stearate among the embodiment 1 into sodium laurate, CaCl
2Change MgCl into
2, other conditionally complete is identical.
Embodiment 5
Sodium stearate among the embodiment 1 is changed to TETRADECONIC ACID sodium, and other conditionally complete is identical.
Estimate: the nano-calcium carbonate of the surface modification of embodiment 1 preparation is through sedimentation experiment (the 1g lime carbonate in normal hexane, the 24ml normal hexane), the result shows: only its sedimentation unit diameter of nano-calcium carbonate through the sodium stearate surface modification treatment is 5 μ m, and through sodium stearate and CaCl
2Successively its sedimentation unit diameter of nano-calcium carbonate of surface modification treatment is reduced to 1.8 μ m successively.
The nano-calcium carbonate of the surface modification of embodiment 2 preparations is through sedimentation experiment (the 1g lime carbonate in normal hexane, the 24ml normal hexane), the result shows: only its sedimentation unit diameter of acicular nanometer lime carbonate through the sodium stearate surface modification treatment is 36 μ m, and through Sodium pentadecanecarboxylate and MgSO
4Successively its sedimentation unit diameter of nano-calcium carbonate of surface modification treatment is reduced to 15 μ m successively.
The viscosity that the nano-calcium carbonate 25g of the surface modification of embodiment 3 preparation is dispersed in 75g dibutyl phthalate monitoring mixture changes (DV-1 type viscometer, Shanghai group's long day scientific instrument company limited), the result shows: mixing back viscosity is 20000mPa.s, and viscosity only changes between 20000 ± 2500mPa.s in two weeks.And through 20 sour sodium surface modification treatment without BaCl
2The 40nm cube lime carbonate of surface modification treatment mixes its viscosity of back with dibutyl phthalate under similarity condition be 28000mPa.s, and spread of viscosity is 28000 ± 7000mPa.s in two weeks.
Through the sedimentation experiment (1g lime carbonate, 24ml normal hexane) in normal hexane, the result shows: its sedimentation unit diameters of 80nm cube nano-calcium carbonate through two step surface modification treatment are 2.1 μ m with the nano-calcium carbonate of the surface modification of embodiment 4 preparation.
Through the sedimentation experiment (1g lime carbonate, 24ml normal hexane) in normal hexane, the result shows: its sedimentation unit diameters of 80nm cube nano-calcium carbonate through two step surface modification treatment are 2.0 μ m with the nano-calcium carbonate of the surface modification of embodiment 5 preparation.
Claims (3)
1, a kind of preparation method of surface modified nano calcium carbonate is characterized in that:
The first step: under 30-80 ℃ of condition, be the CO that feeds 20-40% concentration in the lime emulsion of 3-10% to CaO content
2, after carburizing reagent is finished, at first adding a kind of saturated fatty acid sodium-salt, its consumption is the 3-6% of weight of calcium carbonate, stirs 20-180min;
Second step: continue to add a kind of water miscible divalent metal salt, consumption is the 0.5-2.5% of weight of calcium carbonate, and after continuing to stir 10-120min, ageing 30-400min filters, and be drying to obtain product under 30-90 ℃ of condition.
2, according to the preparation method of the described a kind of surface modified nano calcium carbonate of claim 1, it is characterized in that: the molecular formula of saturated fatty acid sodium-salt is CH
3(CH
2) nCOONa, n=10,12,14,16,18.
3, according to the preparation method of the described a kind of surface modified nano calcium carbonate of claim 1, it is characterized in that: water-soluble divalent metal salt can be CaCl
2, MgCl
2, BaCl
2Or MgSO
4
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01127980 CN1212273C (en) | 2001-07-27 | 2001-07-27 | Preparation method of surface modified nano calcium carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01127980 CN1212273C (en) | 2001-07-27 | 2001-07-27 | Preparation method of surface modified nano calcium carbonate |
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| CN1400167A CN1400167A (en) | 2003-03-05 |
| CN1212273C true CN1212273C (en) | 2005-07-27 |
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| CN 01127980 Expired - Fee Related CN1212273C (en) | 2001-07-27 | 2001-07-27 | Preparation method of surface modified nano calcium carbonate |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334166C (en) * | 2005-01-26 | 2007-08-29 | 上海大学 | Method for modifying nano calcium carbonate |
| CN100390064C (en) * | 2005-04-28 | 2008-05-28 | 卢忠远 | Production of superfine calcium carbonate from carbide slag |
| CN102876085A (en) * | 2012-08-29 | 2013-01-16 | 池州凯尔特纳米科技有限公司 | Method for preparing high filling capacity functional powder super-fine calcium carbonate for hard polyvinyl chloride (PVC) |
| CN102876086A (en) * | 2012-08-29 | 2013-01-16 | 池州凯尔特纳米科技有限公司 | Wet-process surface treatment method for superfine heavy calcium carbonate |
| CN104497638B (en) * | 2015-01-07 | 2017-04-26 | 广西大学 | Preparation method of calcium carbonate whiskers by aluminic acid ester and sodium stearate in situ modification |
| CN108658114B (en) * | 2017-03-30 | 2020-07-24 | 北京紫光英力化工技术有限公司 | Preparation method of modified calcium salt |
| CN107235664A (en) * | 2017-07-04 | 2017-10-10 | 合肥市大卓电力有限责任公司 | A kind of light-weight environment-friendly sheet material and preparation method thereof |
| CN107936298A (en) * | 2017-12-12 | 2018-04-20 | 马鞍山市东方仪表有限公司 | A kind of instrument plastic casing filler |
| EP3725851A1 (en) * | 2019-04-16 | 2020-10-21 | Omya International AG | Process for preparing surface-reacted calcium carbonate |
| CN112480714B (en) * | 2020-12-01 | 2021-11-16 | 连州市凯恩斯纳米材料有限公司 | Surface modification method of nano calcium carbonate with particle size less than 20nm |
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