CN103897433A - Calcium carbonate-modifier composition and calcium carbonate surface modification method using the same - Google Patents
Calcium carbonate-modifier composition and calcium carbonate surface modification method using the same Download PDFInfo
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- CN103897433A CN103897433A CN201210575315.XA CN201210575315A CN103897433A CN 103897433 A CN103897433 A CN 103897433A CN 201210575315 A CN201210575315 A CN 201210575315A CN 103897433 A CN103897433 A CN 103897433A
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Abstract
The invention discloses a calcium carbonate-modifier composition and a calcium carbonate surface modification method using the same. The calcium carbonate-modifier composition comprises, by weight, 88-99wt% of calcium carbonate and 1-12wt% of a modifier. The calcium carbonate modifier has appropriate alkalinity. The treated calcium carbonate particles can fill polyethylene, polypropylene and silica gel products. The particle surface is coated uniformly so that the coated particles have good dispersity in the base. The calcium carbonate surface modification method realizes combination of a calcium carbonate surface treatment method and a synthetic calcium carbonate production process, has simple processes, and simultaneously reduces production energy consumption and a product unit cost. The modifier comprises eleaostearic acid, sodium stearate and multiple hydroxy- or amido-containing organic matters. The multiple hydroxy- or amido-containing organic matters have a molecular structural formula shown in the formula (1) of R1-R (1).
Description
Technical field
The present invention relates to composition and the surface modifying method thereof of a kind of calcium carbonate and properties-correcting agent, particularly, relate to and adopt aliphatic amide and fatty alcohol as properties-correcting agent, calcium carbonate to be coated the method for processing.
Background technology
Calcium carbonate is a kind of mineral filler being widely used, may be used in plastics, rubber item, coating, sizing agent etc., particularly nano-calcium carbonate, because particle diameter is little, specific surface area is large, surfactivity is high, add in right amount to the intensity that can improve goods after in body material, modulus, heat-drawn wire, processing flowability etc.But the wetting ability of calcium carbonate is strong, if do not carry out surface modification, poor with the consistency of polymeric matrix in the course of processing of polymer product, be very easy to reunite, even form textural defect because reunite, so calcium carbonate particles, must be to its modifying surface before being applied in polymer materials, complete by wetting ability to oil loving suitable transformation.
The at present known method to the oleophylic processing of calcium carbonate particles surface is existing multiple, a kind of for adopting the method processing of polymer emulsion or solution, as adopted Carboxy or carboxy terminatedpolybutadiene emulsion and calcium carbonate slurry blend in patent documentation CN200910044155, in patent documentation CN02104084.2, adopt PE, PP, the polymkeric substance such as EVA are at benzene, toluene, solution in the organic solvents such as tetrahydrofuran (THF) passes through the method modification of grinding to calcium carbonate particles, in patent documentation CN200810202324, adopt polymethacrylate emulsion etc. and calcium carbonate slurry blending and modifying.Second method is that the method for utilizing monomer to form polymer covering layer at calcium carbonate particles surface aggregate (for example: Shi Jianming, the dispersion of nano-calcium carbonate and polymer overmold, Ph D dissertation is carried out modification; Fourth Feng Xiang etc., microsuspending method CaCO
3surface grafting PMMA and the application in PVC thereof, polymer material science and engineering, 22(6), 192-196).The third method is, with having surface-active material, calcium carbonate particles is coated to modification, such material one end has carboxylic acid, sulfonic acid, phosphoric acid etc. can be connected to the lip-deep polar group of calcium carbonate particles, one end is that lipophilicity segment covers calcium carbonate particles surface in addition, thereby improve the lipophilicity of calcium carbonate particles, as adopted phosphate ester salt to carry out surface modification to calcium carbonate particles in patent documentation CN200510023580, in patent documentation CN200410084711, adopt titanic acid ester salt, Aluminate salt and boric acid ester salt pair calcium carbonate particles to carry out surface modification.In the third method, the most frequently used material is lipid acid or soap, as all adopted stearic acid or salt pair calcium carbonate particles modifying surface in the patent of patent documentation CN200910196953 and CN201110061918, adopting stearic acid or sodium stearate to carry out surface modification to calcium carbonate particles is also in suitability for industrialized production calcium carbonate particles, to apply maximum properties-correcting agent, cheap because of it, effect is better.But above-mentioned method of modifying all has certain limitation, adopt the method for polymer modification generally to need larger add-on, and the cost of polymkeric substance itself is just higher, if be coated again after adopting organic solvent dissolution, also can produce the pollution of organism to empty G&W.The price of phosphoric acid ester, titanic acid ester, Aluminate and boric acid ester and salt is higher, can greatly improve the price of calcium carbonate particles, there is not yet it and applies on a large scale.Although stearic acid and sodium stearate are because having application the most widely in its higher cost performance calcium carbonate particles production field in the world, but poorly soluble due in water of stearic acid, when practical application, need to add a large amount of alkaline matters to be used in conjunction with as sodium hydroxide etc., but on the one hand alkaline matter excessive adds membership and makes the pH value on the calcium carbonate particles surface after modification higher, while application, can bring detrimentally affect in polymkeric substance, on the other hand, the reactive force of hydroxy-acid group and calcium carbonate a little less than, be difficult to form the coated of calcium carbonate surface uniform, between the exposed part of calcium carbonate particles, when dry, can locally reunite, adding and be difficult to man-hour disperse with mixed with polymers, even when the sodium stearate that employing can be water-soluble, because it forms hydrophilic radical micellar structure outwardly in water, doing the used time with calcium carbonate particles, the reactive force that hydroxy-acid group and calcium carbonate are less is also difficult to destroy completely micella, local can form the coated (referring to Shi et.al of polymolecular layer, Onthe Coating of Precipitated Calcium Carbonate with Steric Acid in Aqueous Medium, Langmuir, 2010, 26 (11), 8474-8482), and the hydrophilic radical of outer field stearate outwardly, reduce the lipophilicity of particle, in polymer base material there is certain defect in dispersiveness.
Summary of the invention
The object of the present invention is to provide composition and the calcium carbonate surface modifying method thereof of a kind of calcium carbonate and properties-correcting agent, the defect existing to overcome prior art.
Described calcium carbonate and the composition of properties-correcting agent, be made up of the component of following weight percent:
Calcium carbonate 88～99wt%
Properties-correcting agent 1～12wt%
Preferably, the weight percent of calcium carbonate and modifier composite is:
Calcium carbonate 92～98.5wt%
Properties-correcting agent 1.5～8wt%
More than one in the organism that described properties-correcting agent is stearic acid, sodium stearate, contain hydroxyl or contain amido, the organism that contains hydroxyl or contain amido, has the molecular structural formula shown in formula (1):
R
1-R
（1）
Wherein:
R
1for-OH or-NH
2, the alkyl that R is C4-C30;
Described alkyl comprises line style or branched alkyl chain, preferably 4-28 carbon atom, more preferably 6-20 carbon atom, most preferred is n-hexyl, isohexyl, n-heptyl, different heptyl, n-octyl, iso-octyl, n-nonyl, different nonyl, positive decyl, isodecyl, n-undecane base, different undecyl, dodecyl, Permethyl 99A. base, n-tridecane base, isotridecyl, n-tetradecane base, different tetradecyl, Pentadecane base, different pentadecyl, n-hexadecyl, isocetyl, n-heptadecane base, different heptadecyl, Octadecane base or isooctadecane base,
Calcium carbonate surface modifying method, comprises the steps:
At 30-100 ℃, preferably at 55-80 ℃, calcium carbonate suspension is mixed with described properties-correcting agent, stirring 1-5h, then filters successively and is dried, and can obtain the calcium carbonate of modification;
The add-on of properties-correcting agent is the 1-20wt% of weight of calcium carbonate, preferably 1.5-10wt%;
The state that adds of properties-correcting agent is solid or liquid, or and the mixture of water, if envrionment temperature, below the zero pour of properties-correcting agent, more than being preferably first heated freezing point temperature, joins in calcium carbonate suspension by the mode of pump or gravity trickling with liquid state gradually;
Described calcium carbonate suspension, for the conventional synthetic calcium carbonate suspension of industrial production, the synthetic calcium carbonate suspension that preferably prepared by carborization, its preparation method can be with reference to method preparation patent documentation CN1631789A Instructions Page 3～page 4 step (1)～(3) Suo Shu, the nano-calcium carbonate suspension of preparing for a kind of carborization, wherein, the weight percent content of nano-calcium carbonate is 6～15%, and the median size of nano-calcium carbonate is 0.012～0.10 μ m;
Described synthetic calcium carbonate suspension also can be with reference to the method preparation described in 3rd～4 pages, patent documentation CN11724378A specification sheets, the submicron calcium carbonate suspension of preparing for a kind of carborization, wherein the weight percent of calcium carbonate is 10 ~ 15%, and the median size of calcium carbonate granule is 0.1 ~ 1.0 μ m.
Beneficial effect
Calcium carbonate modifier of the present invention, alkalescence is suitable, calcium carbonate particles after treatment, can be used for being filled in the products such as polyethylene, polypropylene, silica gel, because particle surface is coated evenly, so in matrix good dispersion.Calcium carbonate surface treatment method of the present invention combines with the production process of synthetic calcium carbonate, and process is simple, has reduced the energy consumption of production and the unit cost of product simultaneously.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of embodiment 1 products therefrom;
Fig. 2 is the transmission electron microscope photo of comparative example's 1 products therefrom;
Fig. 3 is the transmission electron microscope photo of comparative example's 2 products therefroms.
Embodiment
The object of following examples just illustrates the present invention, should not be configured to the restriction of forcing on claims.
Embodiment 1
In the stirred autoclave of 7 liters, add 5 liters of concentration 6.22%(calcium hydroxide mass concentrations) starting temperature be the refining lime slurry of 35 ℃, add 5.2g sucrose simultaneously, after stirring, the kiln gas that passes into carbon dioxide content and be 35% (volumetric concentration) starts to carry out carburizing reagent, and kiln gas flow is 25L/h.Be that to obtain temperature at 6.5 o'clock be the nano-calcium carbonate suspension of 55 ℃ to pH of suspension.
Get the nano-calcium carbonate suspension 1000g after carbonization, wherein the mass concentration of calcium carbonate is 8.6wt%, being transferred in 1L round-bottomed flask, keeping 55 ℃ of temperature, using 3.15g(0.13mol) hexadecanol is as properties-correcting agent, disposable joining in calcium carbonate suspension, stir after 2 hours and filter, filter cake is dried 24 hours in 60 ℃ of baking ovens, prepares modified nano calcium carbonate, the pattern of product is shown in accompanying drawing 1, and the water contact angle of modified calcium carbonate and oil-absorption(number) (DOP) are in table 1.
Embodiment 2
Get the nano-calcium carbonate suspension 1000g after the carbonization that embodiment 1 is identical, wherein the mass concentration of calcium carbonate is 8.6wt%, be transferred in 1L round-bottomed flask, keeping 55 ℃ of temperature, using 2.42g(0.13mol) lauryl alcohol is as properties-correcting agent, disposable joining in calcium carbonate suspension, stir after 2 hours and filter, filter cake is dried 24 hours in 60 ℃ of baking ovens, prepares modified nano calcium carbonate, and the water contact angle of modified calcium carbonate and oil-absorption(number) (DOP) are in table 1.
Embodiment 3
Get the nano-calcium carbonate suspension 1000g after the carbonization that embodiment 1 is identical, wherein the mass concentration of calcium carbonate is 8.6wt%, be transferred in 1L round-bottomed flask, being heated to 60 ℃ of insulations, using 3.51g(0.13mol) stearyl alcohol is as properties-correcting agent, and be heated to 65 ℃ and be added drop-wise in calcium carbonate suspension in 20 minutes, stir after 2 hours and filter, filter cake is dried 24 hours in 60 ℃ of baking ovens, prepares modified nano calcium carbonate, and the water contact angle of modified calcium carbonate and oil-absorption(number) (DOP) are in table 1.
Embodiment 4
Get the nano-calcium carbonate suspension 1000g after the carbonization that embodiment 1 is identical, wherein the mass concentration of calcium carbonate is 8.6wt%, be transferred to and in 1L round-bottomed flask, be heated to 70 ℃ and insulation, using 3.50g(0.13mol) stearylamine is as properties-correcting agent, disposable joining in calcium carbonate suspension, stirs after 2 hours and filters, and filter cake is dried 24 hours in 60 ℃ of baking ovens, prepare modified nano calcium carbonate, the water contact angle of modified calcium carbonate and oil-absorption(number) (DOP) are in table 1.
Embodiment 5
Get the nano-calcium carbonate suspension 1000g after the carbonization that embodiment 1 is identical, wherein the mass concentration of calcium carbonate is 8.6wt%, be transferred to and in 1L round-bottomed flask, be heated to 70 ℃ and insulation, using 1.21g(0.065mol) lauryl alcohol and 1.75g(0.065mol) stearylamine is as properties-correcting agent, disposable joining in calcium carbonate suspension, stir after 2 hours and filter, filter cake is dried 24 hours in 60 ℃ of baking ovens, prepare modified nano calcium carbonate, the water contact angle of modified calcium carbonate and oil-absorption(number) (DOP) are in table 1.
Embodiment 6
Get the nano-calcium carbonate suspension 1000g after the carbonization that embodiment 1 is identical, wherein the mass concentration of calcium carbonate is 8.6wt%, be transferred to and in 1L round-bottomed flask, be heated to 80 ℃ and insulation, by sodium stearate 1.99g(0.065mol) be dissolved in 25mL hot water and be added dropwise in calcium carbonate suspension in 30 minutes, stirring after 30 minutes 1.75g(0.065mol) stearylamine is disposable joins in calcium carbonate suspension, stir after 1 hour and filter, filter cake is dried 24 hours in 60 ℃ of baking ovens, prepare modified nano calcium carbonate, the water contact angle of modified calcium carbonate and oil-absorption(number) (DOP) are in table 1.
Comparative example 1
Get the nano-calcium carbonate suspension 1000g after the carbonization that embodiment is identical, wherein the mass concentration of calcium carbonate is 8.6wt%, filter, filter cake is dried 24 hours in 60 ℃ of baking ovens, prepare unmodified calcium carbonate particles, the pattern of product is shown in accompanying drawing 2, and the water contact angle of calcium carbonate and oil-absorption(number) (DOP) are in table 1.
Comparative example 2
Get the nano-calcium carbonate suspension 1000g after the carbonization that embodiment 1 is identical, wherein the mass concentration of calcium carbonate is 8.6wt%, be transferred in 1L round-bottomed flask and be heated to 80 ℃, by 3.98g(0.13mol) sodium stearate is disposable adds in calcium carbonate suspension, stir after 2 hours and filter, filter cake is dried 24 hours in 60 ℃ of baking ovens, prepares modified nano calcium carbonate, the pattern of product is shown in accompanying drawing 3, and the water contact angle of modified calcium carbonate and oil-absorption(number) (DOP) are in table 1.Measure before contact angle, dried sample is placed to one week rear compressing tablet in moisture eliminator, then carry out the measurement of contact angle (water).
Water contact angle and the oil-absorption(number) of table 1 different methods nano-calcium carbonate after treatment
As can be seen from Table 1, alcoholic extract hydroxyl group and amido and calcium carbonate particles can produce good binding ability, the calcium carbonate particles surface after modification from hydrophilicly becoming hydrophobic, oil-absorption(number) reduces greatly, and modification ability is better than sodium stearate.
Claims (9)
1. the composition of calcium carbonate and properties-correcting agent, is characterized in that, is made up of the component of following weight percent:
Calcium carbonate 88～99wt%, properties-correcting agent 1～12wt%;
More than one in the organism that described properties-correcting agent is stearic acid, sodium stearate, contain hydroxyl or contain amido, described in the organism that contains hydroxyl or contain amido, there is the molecular structural formula shown in formula (1):
R
1-R
（1）
Wherein:
R
1for-OH or-NH
2, the alkyl that R is C4-C30.
2. the composition of calcium carbonate according to claim 1 and properties-correcting agent, is characterized in that, the weight percent of calcium carbonate and modifier composite is: calcium carbonate 92～98.5wt%, properties-correcting agent 1.5～8wt%.
3. the composition of calcium carbonate according to claim 1 and 2 and properties-correcting agent, is characterized in that, described alkyl comprises line style or branched alkyl chain.
4. the composition of calcium carbonate according to claim 3 and properties-correcting agent, is characterized in that, described alkyl is 4-28 carbon atom.
5. the composition of calcium carbonate according to claim 4 and properties-correcting agent, is characterized in that, described alkyl is 6-20 carbon atom.
6. the composition of calcium carbonate according to claim 1 and 2 and properties-correcting agent, it is characterized in that, described alkyl is n-hexyl, isohexyl, n-heptyl, different heptyl, n-octyl, iso-octyl, n-nonyl, different nonyl, positive decyl, isodecyl, n-undecane base, different undecyl, dodecyl, Permethyl 99A. base, n-tridecane base, isotridecyl, n-tetradecane base, different tetradecyl, Pentadecane base, different pentadecyl, n-hexadecyl, isocetyl, n-heptadecane base, different heptadecyl, Octadecane base or isooctadecane base.
7. a calcium carbonate surface modifying method, comprises the steps: at 30-100 ℃, and calcium carbonate suspension is mixed with properties-correcting agent described in claim 1～6 any one, stirs 1-5h, then filters successively and is dried; , can obtain the calcium carbonate of modification.
8. method according to claim 7, is characterized in that, the 1-20wt% that the add-on of properties-correcting agent is weight of calcium carbonate.
9. according to the method described in claim 7 or 8, it is characterized in that, the state that adds of properties-correcting agent is solid or liquid, or and the mixture of water, if envrionment temperature is below the zero pour of properties-correcting agent, more than being first heated freezing point temperature, join gradually in calcium carbonate suspension by the mode of pump or gravity trickling with liquid state.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105482500A (en) * | 2015-11-25 | 2016-04-13 | 广西华纳新材料科技有限公司 | Surface modification method of anti-oxidation nanometer calcium carbonate used for silicone sealant |
| CN105778567A (en) * | 2016-04-07 | 2016-07-20 | 安徽江东科技粉业有限公司 | Preparing method for composite calcium carbonate |
| CN105885471A (en) * | 2016-04-07 | 2016-08-24 | 安徽江东科技粉业有限公司 | Preparation method of paste calcium carbonate for papermaking |
| CN107674455A (en) * | 2017-08-30 | 2018-02-09 | 贵州紫云月华新材料有限公司 | A kind of calcium carbonate modifier and its method of modifying |
| CN107699005A (en) * | 2017-08-30 | 2018-02-16 | 贵州紫云月华新材料有限公司 | A kind of modified calcium carbonate production method |
| CN114456564A (en) * | 2022-03-18 | 2022-05-10 | 湖南工程学院 | PLA-PHB blended biodegradable film filled with modified calcium carbonate and preparation method thereof |
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| CN1910226A (en) * | 2004-01-23 | 2007-02-07 | 索尔维公司 | Surface-treated calcium carbonate particles |
| CN101910324A (en) * | 2007-11-02 | 2010-12-08 | 欧米亚发展股份公司 | Use of a surface-reacted calcium carbonate in tissue paper, process to prepare a tissue paper product of improved softness, and resulting improved softness tissue paper products |
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Patent Citations (2)
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| CN1910226A (en) * | 2004-01-23 | 2007-02-07 | 索尔维公司 | Surface-treated calcium carbonate particles |
| CN101910324A (en) * | 2007-11-02 | 2010-12-08 | 欧米亚发展股份公司 | Use of a surface-reacted calcium carbonate in tissue paper, process to prepare a tissue paper product of improved softness, and resulting improved softness tissue paper products |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105482500A (en) * | 2015-11-25 | 2016-04-13 | 广西华纳新材料科技有限公司 | Surface modification method of anti-oxidation nanometer calcium carbonate used for silicone sealant |
| CN105482500B (en) * | 2015-11-25 | 2018-09-14 | 广西华纳新材料科技有限公司 | The surface modifying method of silicone sealant antioxidant nano-calcium carbonate |
| CN105778567A (en) * | 2016-04-07 | 2016-07-20 | 安徽江东科技粉业有限公司 | Preparing method for composite calcium carbonate |
| CN105885471A (en) * | 2016-04-07 | 2016-08-24 | 安徽江东科技粉业有限公司 | Preparation method of paste calcium carbonate for papermaking |
| CN107674455A (en) * | 2017-08-30 | 2018-02-09 | 贵州紫云月华新材料有限公司 | A kind of calcium carbonate modifier and its method of modifying |
| CN107699005A (en) * | 2017-08-30 | 2018-02-16 | 贵州紫云月华新材料有限公司 | A kind of modified calcium carbonate production method |
| CN114456564A (en) * | 2022-03-18 | 2022-05-10 | 湖南工程学院 | PLA-PHB blended biodegradable film filled with modified calcium carbonate and preparation method thereof |
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