CN107011539A - A kind of method of quadripolymer surface modified nano calcium carbonate - Google Patents
A kind of method of quadripolymer surface modified nano calcium carbonate Download PDFInfo
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- CN107011539A CN107011539A CN201710223818.3A CN201710223818A CN107011539A CN 107011539 A CN107011539 A CN 107011539A CN 201710223818 A CN201710223818 A CN 201710223818A CN 107011539 A CN107011539 A CN 107011539A
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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
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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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
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Abstract
A kind of method of quadripolymer surface modified nano calcium carbonate, by quick lime, ashing, except iron, digestion adds chemical additives carbonization, obtain nano-calcium carbonate slurries, using the quadripolymer prepared by acrylamide, acrylic acid, octadecylene, maleic anhydride as modifying agent, add in nano-calcium carbonate concentrated slurry, obtain surface modified nano calcium carbonate slurry.This method need not be carried out repeatedly to nano-calcium carbonate, substep surface is modified, activation, the activation rate of obtained surface modified nano calcium carbonate can reach more than 95%, the Effective Regulation particle diameter distribution and activity of product, drastically increases the compatibility between nano-calcium carbonate and organic polymer.
Description
Technical field
The present invention relates to a kind of preparation method of calcium carbonate, particularly a kind of quadripolymer surface modified nano calcium carbonate
Method.
Background technology
Nano-calcium carbonate is widely used in rubber industry, plastics industry, paper industry, coatings industry, medical industry etc..Answering
With in engineering, nano-calcium carbonate is required to be well dispersed in organic media, so that target material has homogeneous property,
However, because the characteristic of nano-calcium carbonate itself causes nano-calcium carbonate the problem of application aspect has certain, for example, a side
Face, nano grain surface can be high, in thermodynamics unsteady state, it is easy to reunite；On the other hand, calcium carbonate system common at present
It is in hydrophily more the calcium carbonate surface that Preparation Method is obtained, is difficult to reach dispersed effect when in organic media disperseing, with
Adhesion is low between polymer, results in boundary defect, influences polymer performance.Therefore, people for improve nano-powder with
The compatibility of medium interface and the dispersiveness of powder have carried out substantial amounts of trial and effort.Using polymer to nano-calcium carbonate
Compatibility of the nano-calcium carbonate with polymeric matrix in application process can be improved by carrying out surface modification, be conducive to nano-calcium carbonate
Calcium is scattered in polymeric matrix, can also improve nano-calcium carbonate stability in organic media.
The content of the invention
The technical problem to be solved in the present invention is the compatibility and stability for improving nano-calcium carbonate in organic media, is carried
Surface modification is carried out to it for a kind of method for preparing nano-calcium carbonate, and using quadripolymer.
For solve the present invention technical problem, the technical scheme used for：
A kind of method of quadripolymer surface modified nano calcium carbonate, comprises the following steps：
1）Weigh low-grade quick lime, ashing, except iron；
2）Add in digestion reactor filled with hot water, stir, carry out digestion reaction, stand cooling, filtering, slurries ageing；
3）It is passed through carbon dioxide in slurries to be carbonized, carbonisation adds chemical additives, carbonization to pH value is 12-13, is obtained
To nano-calcium carbonate slurries,
4）By step 3）Obtained nano-calcium carbonate slurries ageing, sedimentation concentration；
5）Quadripolymer is prepared by acrylamide, acrylic acid, octadecylene, maleic anhydride；Copolymerization is obtained quarternary copolymerized
Modifying agent is dissolved in the in the mixed solvent of water and ethanol by thing as modifying agent, standby；
6）Modifier solution is added in nano-calcium carbonate concentrated slurry, is modified, the time is 20-30 minutes, obtains surface
Modified nano calcium carbonate slurry；
7）By step 6）Obtained surface modified nano calcium carbonate slurry drying, you can obtain surface modified nano calcium carbonate powder
Body.
Further, the consumption of quadripolymer is the 2-10% of nano-calcium carbonate quality.
Further, prepare in copolymer process, acrylamide, acrylic acid, octadecylene, maleic anhydride raw material mass mixture ratio
For：20-30 parts of acrylamide, 50-70 parts of acrylic acid, 0.5-3 parts of octadecylene, 30-60 parts of maleic anhydride.
Further, it is modified and is carried out at 50-60 DEG C.
Further, step 5）Reclaimed water and the volume ratio of ethanol are 1:4-6.
Further, the carburizing temperature is 20-30 DEG C.
Further, by step 4）Nano-calcium carbonate slurries after concentration carry out secondary carbonization, then carry out surface modification work
Change.
Further, the method for preparing quadripolymer is as follows：Acrylamide, acrylic acid, octadecylene, maleic anhydride are added
Enter in reactor, it is 6.8-7.3 to adjust pH value with sodium hydroxide solution, it is the water-soluble of 15-25% to be made into monomer gross mass concentration
Liquid；Propane diamine is added, is stirred, initiator ammonium persulfate solution and solution of sodium bisulfite is added, is continually fed into nitrogen,
Temperature be 30-40 DEG C under the conditions of react 6-8h；Wash, dry by ethanol, crushing and can obtain quadripolymer.
Further, the mol ratio of initiator ammonium persulfate solution and sodium hydrogensulfite is 1:1.
Further, initiator addition is 0.6-0.8% of monomer gross mass or so.
Beneficial effect：
The present invention uses quadripolymer as modifying agent, and optimizes the composition and proportioning of monomer in quadripolymer, only adopts
The modification to nano-calcium carbonate surface, activation are can reach with once modified, it is not necessary to multiple, substep is carried out to nano-calcium carbonate
Surface is modified, activation, and the activation rate that the present invention obtains surface modified nano calcium carbonate can reach more than 95%, Effective Regulation
The particle diameter distribution and activity of product.The compatibility and stability between nano-calcium carbonate and organic polymer are drastically increased,
Compatibility of the nano-calcium carbonate with polymeric matrix in application process is improved, is conducive to nano-calcium carbonate in polymeric matrix
In it is scattered.
Embodiment
A kind of method of quadripolymer surface modified nano calcium carbonate, comprises the following steps：
1）Weigh low-grade quick lime, ashing, except iron；
2）Add in digestion reactor filled with hot water, stir, carry out digestion reaction, stand cooling, filtering, slurries ageing；
3）It is passed through carbon dioxide in slurries to be carbonized, carbonisation adds chemical additives, carbonization to pH value is 12-13, is obtained
To nano-calcium carbonate slurries,
4）By step 3）Obtained nano-calcium carbonate slurries ageing, sedimentation concentration；
5）Quadripolymer is prepared by acrylamide, acrylic acid, octadecylene, maleic anhydride；Copolymerization is obtained quarternary copolymerized
Modifying agent is dissolved in the in the mixed solvent of water and ethanol by thing as modifying agent, standby；
6）Modifier solution is added in nano-calcium carbonate concentrated slurry, is modified, the time is 20-30 minutes, obtains surface
Modified nano calcium carbonate slurry；
7）By step 6）Obtained surface modified nano calcium carbonate slurry drying, you can obtain surface modified nano calcium carbonate powder
Body.
Further, the consumption of quadripolymer is the 2-10% of nano-calcium carbonate quality.
Further, prepare in copolymer process, acrylamide, acrylic acid, octadecylene, maleic anhydride raw material mass mixture ratio
For：20-30 parts of acrylamide, 50-70 parts of acrylic acid, 0.5-3 parts of octadecylene, 30-60 parts of maleic anhydride.
Further, it is modified and is carried out at 50-60 DEG C.
Further, step 5）Reclaimed water and the volume ratio of ethanol are 1:4-6.
Further, the carburizing temperature is 20-30 DEG C.
Further, by step 4）Nano-calcium carbonate slurries after concentration carry out secondary carbonization, then carry out surface modification work
Change.
Further, the method for preparing quadripolymer is as follows：Acrylamide, acrylic acid, octadecylene, maleic anhydride are added
Enter in reactor, it is 6.8-7.3 to adjust pH value with sodium hydroxide solution, it is the water-soluble of 15-25% to be made into monomer gross mass concentration
Liquid；Propane diamine is added, is stirred, initiator ammonium persulfate solution and solution of sodium bisulfite is added, is continually fed into nitrogen,
Temperature be 30-40 DEG C under the conditions of react 6-8h；Wash, dry by ethanol, crushing and can obtain quadripolymer.
Further, the mol ratio of initiator ammonium persulfate solution and sodium hydrogensulfite is 1:1.
Further, initiator addition is 0.6-0.8% of monomer gross mass or so.
Embodiment 1
1）Weigh low-grade quick lime, ashing, except iron；
2）Add in digestion reactor filled with hot water, stir, carry out digestion reaction, stand cooling, filtering, slurries ageing；
3）It is passed through carbon dioxide in slurries to be carbonized, carbonisation adds chemical additives, 20-30 DEG C of carbonization to pH value is
13, nano-calcium carbonate slurries are obtained,
4）By step 3）Obtained nano-calcium carbonate slurries ageing, sedimentation concentration；
5）Quadripolymer is prepared by acrylamide, acrylic acid, octadecylene, maleic anhydride, wherein, acrylamide, propylene
Acid, octadecylene, maleic anhydride raw material mass mixture ratio are：25 parts of acrylamide, 60 parts of acrylic acid, 1 part of octadecylene, maleic anhydride 40
Part；Copolymerization is obtained to quadripolymer as modifying agent, modifying agent is dissolved in the in the mixed solvent of water and ethanol, it is standby, wherein
The volume ratio of water and ethanol is 1:4-6；
6）Modifier solution is added in nano-calcium carbonate concentrated slurry, is modified at 50-60 DEG C, the time is 20-30 points
Clock, obtains surface modified nano calcium carbonate slurry, and the consumption of quadripolymer is the 2% of nano-calcium carbonate quality；
7）By step 6）Obtained surface modified nano calcium carbonate slurry drying, you can obtain surface modified nano calcium carbonate powder
Body.
Embodiment 2
1）Weigh low-grade quick lime, ashing, except iron；
2）Add in digestion reactor filled with hot water, stir, carry out digestion reaction, stand cooling, filtering, slurries ageing；
3）It is passed through carbon dioxide in slurries to be carbonized, carbonisation adds chemical additives, 20-30 DEG C of carbonization to pH value is
13, nano-calcium carbonate slurries are obtained,
4）By step 3）Obtained nano-calcium carbonate slurries ageing, sedimentation concentration；
5）Quadripolymer is prepared by acrylamide, acrylic acid, octadecylene, maleic anhydride, wherein, acrylamide, propylene
Acid, octadecylene, maleic anhydride raw material mass mixture ratio are：25 parts of acrylamide, 60 parts of acrylic acid, 1 part of octadecylene, maleic anhydride 40
Part；Copolymerization is obtained to quadripolymer as modifying agent, modifying agent is dissolved in the in the mixed solvent of water and ethanol, it is standby, wherein
The volume ratio of water and ethanol is 1:4-6；
6）Modifier solution is added in nano-calcium carbonate concentrated slurry, is modified at 50-60 DEG C, the time is 20-30 points
Clock, obtains surface modified nano calcium carbonate slurry, and the consumption of quadripolymer is the 4% of nano-calcium carbonate quality；
7）By step 6）Obtained surface modified nano calcium carbonate slurry drying, you can obtain surface modified nano calcium carbonate powder
Body.
Embodiment 3
1）Weigh low-grade quick lime, ashing, except iron；
2）Add in digestion reactor filled with hot water, stir, carry out digestion reaction, stand cooling, filtering, slurries ageing；
3）It is passed through carbon dioxide in slurries to be carbonized, carbonisation adds chemical additives, 20-30 DEG C of carbonization to pH value is
13, nano-calcium carbonate slurries are obtained,
4）By step 3）Obtained nano-calcium carbonate slurries ageing, sedimentation concentration；
5）Quadripolymer is prepared by acrylamide, acrylic acid, octadecylene, maleic anhydride, wherein, acrylamide, propylene
Acid, octadecylene, maleic anhydride raw material mass mixture ratio are：25 parts of acrylamide, 60 parts of acrylic acid, 1 part of octadecylene, maleic anhydride 40
Part；Copolymerization is obtained to quadripolymer as modifying agent, modifying agent is dissolved in the in the mixed solvent of water and ethanol, it is standby, wherein
The volume ratio of water and ethanol is 1:4-6；
6）Modifier solution is added in nano-calcium carbonate concentrated slurry, is modified at 50-60 DEG C, the time is 20-30 points
Clock, obtains surface modified nano calcium carbonate slurry, and the consumption of quadripolymer is the 6% of nano-calcium carbonate quality；
7）By step 6）Obtained surface modified nano calcium carbonate slurry drying, you can obtain surface modified nano calcium carbonate powder
Body.
Embodiment 4
1）Weigh low-grade quick lime, ashing, except iron；
2）Add in digestion reactor filled with hot water, stir, carry out digestion reaction, stand cooling, filtering, slurries ageing；
3）It is passed through carbon dioxide in slurries to be carbonized, carbonisation adds chemical additives, 20-30 DEG C of carbonization to pH value is
13, nano-calcium carbonate slurries are obtained,
4）By step 3）Obtained nano-calcium carbonate slurries ageing, sedimentation concentration；
5）Quadripolymer is prepared by acrylamide, acrylic acid, octadecylene, maleic anhydride, wherein, acrylamide, propylene
Acid, octadecylene, maleic anhydride raw material mass mixture ratio are：25 parts of acrylamide, 60 parts of acrylic acid, 1 part of octadecylene, maleic anhydride 40
Part；Copolymerization is obtained to quadripolymer as modifying agent, modifying agent is dissolved in the in the mixed solvent of water and ethanol, it is standby, wherein
The volume ratio of water and ethanol is 1:4-6；
6）Modifier solution is added in nano-calcium carbonate concentrated slurry, is modified at 50-60 DEG C, the time is 20-30 points
Clock, obtains surface modified nano calcium carbonate slurry, and the consumption of quadripolymer is the 8% of nano-calcium carbonate quality；
7）By step 6）Obtained surface modified nano calcium carbonate slurry drying, you can obtain surface modified nano calcium carbonate powder
Body.
Embodiment 5
1）Weigh low-grade quick lime, ashing, except iron；
2）Add in digestion reactor filled with hot water, stir, carry out digestion reaction, stand cooling, filtering, slurries ageing；
3）It is passed through carbon dioxide in slurries to be carbonized, carbonisation adds chemical additives, 20-30 DEG C of carbonization to pH value is
13, nano-calcium carbonate slurries are obtained,
4）By step 3）Obtained nano-calcium carbonate slurries ageing, sedimentation concentration；
5）Quadripolymer is prepared by acrylamide, acrylic acid, octadecylene, maleic anhydride, wherein, acrylamide, propylene
Acid, octadecylene, maleic anhydride raw material mass mixture ratio are：25 parts of acrylamide, 60 parts of acrylic acid, 1 part of octadecylene, maleic anhydride 40
Part；Copolymerization is obtained to quadripolymer as modifying agent, modifying agent is dissolved in the in the mixed solvent of water and ethanol, it is standby, wherein
The volume ratio of water and ethanol is 1:4-6；
6）Modifier solution is added in nano-calcium carbonate concentrated slurry, is modified at 50-60 DEG C, the time is 20-30 points
Clock, obtains surface modified nano calcium carbonate slurry, and the consumption of quadripolymer is the 10% of nano-calcium carbonate quality；
7）By step 6）Obtained surface modified nano calcium carbonate slurry drying, you can obtain surface modified nano calcium carbonate powder
Body.
Embodiment 6
1）Weigh low-grade quick lime, ashing, except iron；
2）Add in digestion reactor filled with hot water, stir, carry out digestion reaction, stand cooling, filtering, slurries ageing；
3）It is passed through carbon dioxide in slurries to be carbonized, carbonisation adds chemical additives, 20-30 DEG C of carbonization to pH value is
13, nano-calcium carbonate slurries are obtained,
4）By step 3）Obtained nano-calcium carbonate slurries ageing, sedimentation concentration；
5）Quadripolymer is prepared by acrylamide, acrylic acid, octadecylene, maleic anhydride, wherein, acrylamide, propylene
Acid, octadecylene, maleic anhydride raw material mass mixture ratio are：25 parts of acrylamide, 60 parts of acrylic acid, 1 part of octadecylene, maleic anhydride 40
Part；Copolymerization is obtained to quadripolymer as modifying agent, modifying agent is dissolved in the in the mixed solvent of water and ethanol, it is standby, wherein
The volume ratio of water and ethanol is 1:4-6；
6）Modifier solution is added in nano-calcium carbonate concentrated slurry, is modified at 50-60 DEG C, the time is 20-30 points
Clock, obtains surface modified nano calcium carbonate slurry, and the consumption of quadripolymer is the 1% of nano-calcium carbonate quality；
7）By step 6）Obtained surface modified nano calcium carbonate slurry drying, you can obtain surface modified nano calcium carbonate powder
Body.
Embodiment 7
1）Weigh low-grade quick lime, ashing, except iron；
2）Add in digestion reactor filled with hot water, stir, carry out digestion reaction, stand cooling, filtering, slurries ageing；
3）It is passed through carbon dioxide in slurries to be carbonized, carbonisation adds chemical additives, 20-30 DEG C of carbonization to pH value is
13, nano-calcium carbonate slurries are obtained,
4）By step 3）Obtained nano-calcium carbonate slurries ageing, sedimentation concentration；
5）Quadripolymer is prepared by acrylamide, acrylic acid, octadecylene, maleic anhydride, wherein, acrylamide, propylene
Acid, octadecylene, maleic anhydride raw material mass mixture ratio are：25 parts of acrylamide, 60 parts of acrylic acid, 1 part of octadecylene, maleic anhydride 40
Part；Copolymerization is obtained to quadripolymer as modifying agent, modifying agent is dissolved in the in the mixed solvent of water and ethanol, it is standby, wherein
The volume ratio of water and ethanol is 1:4-6；
6）Modifier solution is added in nano-calcium carbonate concentrated slurry, is modified at 50-60 DEG C, the time is 20-30 points
Clock, obtains surface modified nano calcium carbonate slurry, and the consumption of quadripolymer is the 11% of nano-calcium carbonate quality；
7）By step 6）Obtained surface modified nano calcium carbonate slurry drying, you can obtain surface modified nano calcium carbonate powder
Body.
Embodiment 8
1）Weigh low-grade quick lime, ashing, except iron；
2）Add in digestion reactor filled with hot water, stir, carry out digestion reaction, stand cooling, filtering, slurries ageing；
3）It is passed through carbon dioxide in slurries to be carbonized, carbonisation adds chemical additives, 20-30 DEG C of carbonization to pH value is
13, nano-calcium carbonate slurries are obtained,
4）By step 3）Obtained nano-calcium carbonate slurries ageing, sedimentation concentration；
5）Quadripolymer is prepared by acrylamide, acrylic acid, octadecylene, maleic anhydride, wherein, acrylamide, propylene
Acid, octadecylene, maleic anhydride raw material mass mixture ratio are：15 parts of acrylamide, 60 parts of acrylic acid, 1 part of octadecylene, maleic anhydride 40
Part；Copolymerization is obtained to quadripolymer as modifying agent, modifying agent is dissolved in the in the mixed solvent of water and ethanol, it is standby, wherein
The volume ratio of water and ethanol is 1:4-6；
6）Modifier solution is added in nano-calcium carbonate concentrated slurry, is modified at 50-60 DEG C, the time is 20-30 points
Clock, obtains surface modified nano calcium carbonate slurry, and the consumption of quadripolymer is the 4% of nano-calcium carbonate quality；
7）By step 6）Obtained surface modified nano calcium carbonate slurry drying, you can obtain surface modified nano calcium carbonate powder
Body.
Embodiment 9
1）Weigh low-grade quick lime, ashing, except iron；
2）Add in digestion reactor filled with hot water, stir, carry out digestion reaction, stand cooling, filtering, slurries ageing；
3）It is passed through carbon dioxide in slurries to be carbonized, carbonisation adds chemical additives, 20-30 DEG C of carbonization to pH value is
13, nano-calcium carbonate slurries are obtained,
4）By step 3）Obtained nano-calcium carbonate slurries ageing, sedimentation concentration；
5）Quadripolymer is prepared by acrylamide, acrylic acid, octadecylene, maleic anhydride, wherein, acrylamide, propylene
Acid, octadecylene, maleic anhydride raw material mass mixture ratio are：40 parts of acrylamide, 60 parts of acrylic acid, 1 part of octadecylene, maleic anhydride 40
Part；Copolymerization is obtained to quadripolymer as modifying agent, modifying agent is dissolved in the in the mixed solvent of water and ethanol, it is standby, wherein
The volume ratio of water and ethanol is 1:4-6；
6）Modifier solution is added in nano-calcium carbonate concentrated slurry, is modified at 50-60 DEG C, the time is 20-30 points
Clock, obtains surface modified nano calcium carbonate slurry, and the consumption of quadripolymer is the 4% of nano-calcium carbonate quality；
7）By step 6）Obtained surface modified nano calcium carbonate slurry drying, you can obtain surface modified nano calcium carbonate powder
Body.
Embodiment 10
1）Weigh low-grade quick lime, ashing, except iron；
2）Add in digestion reactor filled with hot water, stir, carry out digestion reaction, stand cooling, filtering, slurries ageing；
3）It is passed through carbon dioxide in slurries to be carbonized, carbonisation adds chemical additives, 20-30 DEG C of carbonization to pH value is
13, nano-calcium carbonate slurries are obtained,
4）By step 3）Obtained nano-calcium carbonate slurries ageing, sedimentation concentration；
5）Quadripolymer is prepared by acrylamide, acrylic acid, octadecylene, maleic anhydride, wherein, acrylamide, propylene
Acid, octadecylene, maleic anhydride raw material mass mixture ratio are：25 parts of acrylamide, 40 parts of acrylic acid, 1 part of octadecylene, maleic anhydride 40
Part；Copolymerization is obtained to quadripolymer as modifying agent, modifying agent is dissolved in the in the mixed solvent of water and ethanol, it is standby, wherein
The volume ratio of water and ethanol is 1:4-6；
6）Modifier solution is added in nano-calcium carbonate concentrated slurry, is modified at 50-60 DEG C, the time is 20-30 points
Clock, obtains surface modified nano calcium carbonate slurry, and the consumption of quadripolymer is the 4% of nano-calcium carbonate quality；
7）By step 6）Obtained surface modified nano calcium carbonate slurry drying, you can obtain surface modified nano calcium carbonate powder
Body.
Embodiment 11
1）Weigh low-grade quick lime, ashing, except iron；
2）Add in digestion reactor filled with hot water, stir, carry out digestion reaction, stand cooling, filtering, slurries ageing；
3）It is passed through carbon dioxide in slurries to be carbonized, carbonisation adds chemical additives, 20-30 DEG C of carbonization to pH value is
13, nano-calcium carbonate slurries are obtained,
4）By step 3）Obtained nano-calcium carbonate slurries ageing, sedimentation concentration；
5）Quadripolymer is prepared by acrylamide, acrylic acid, octadecylene, maleic anhydride, wherein, acrylamide, propylene
Acid, octadecylene, maleic anhydride raw material mass mixture ratio are：25 parts of acrylamide, 80 parts of acrylic acid, 1 part of octadecylene, maleic anhydride 40
Part；Copolymerization is obtained to quadripolymer as modifying agent, modifying agent is dissolved in the in the mixed solvent of water and ethanol, it is standby, wherein
The volume ratio of water and ethanol is 1:4-6；
6）Modifier solution is added in nano-calcium carbonate concentrated slurry, is modified at 50-60 DEG C, the time is 20-30 points
Clock, obtains surface modified nano calcium carbonate slurry, and the consumption of quadripolymer is the 4% of nano-calcium carbonate quality；
7）By step 6）Obtained surface modified nano calcium carbonate slurry drying, you can obtain surface modified nano calcium carbonate powder
Body.
Embodiment 12
1）Weigh low-grade quick lime, ashing, except iron；
2）Add in digestion reactor filled with hot water, stir, carry out digestion reaction, stand cooling, filtering, slurries ageing；
3）It is passed through carbon dioxide in slurries to be carbonized, carbonisation adds chemical additives, 20-30 DEG C of carbonization to pH value is
13, nano-calcium carbonate slurries are obtained,
4）By step 3）Obtained nano-calcium carbonate slurries ageing, sedimentation concentration；
5）Quadripolymer is prepared by acrylamide, acrylic acid, octadecylene, maleic anhydride, wherein, acrylamide, propylene
Acid, octadecylene, maleic anhydride raw material mass mixture ratio are：25 parts of acrylamide, 60 parts of acrylic acid, 0.3 part of octadecylene, maleic anhydride
40 parts；Copolymerization is obtained to quadripolymer as modifying agent, modifying agent is dissolved in the in the mixed solvent of water and ethanol, it is standby, its
Reclaimed water and the volume ratio of ethanol are 1:4-6；
6）Modifier solution is added in nano-calcium carbonate concentrated slurry, is modified at 50-60 DEG C, the time is 20-30 points
Clock, obtains surface modified nano calcium carbonate slurry, and the consumption of quadripolymer is the 4% of nano-calcium carbonate quality；
7）By step 6）Obtained surface modified nano calcium carbonate slurry drying, you can obtain surface modified nano calcium carbonate powder
Body.
Embodiment 13
1）Weigh low-grade quick lime, ashing, except iron；
2）Add in digestion reactor filled with hot water, stir, carry out digestion reaction, stand cooling, filtering, slurries ageing；
3）It is passed through carbon dioxide in slurries to be carbonized, carbonisation adds chemical additives, 20-30 DEG C of carbonization to pH value is
13, nano-calcium carbonate slurries are obtained,
4）By step 3）Obtained nano-calcium carbonate slurries ageing, sedimentation concentration；
5）Quadripolymer is prepared by acrylamide, acrylic acid, octadecylene, maleic anhydride, wherein, acrylamide, propylene
Acid, octadecylene, maleic anhydride raw material mass mixture ratio are：25 parts of acrylamide, 60 parts of acrylic acid, 4 parts of octadecylene, maleic anhydride 40
Part；Copolymerization is obtained to quadripolymer as modifying agent, modifying agent is dissolved in the in the mixed solvent of water and ethanol, it is standby, wherein
The volume ratio of water and ethanol is 1:4-6；
6）Modifier solution is added in nano-calcium carbonate concentrated slurry, is modified at 50-60 DEG C, the time is 20-30 points
Clock, obtains surface modified nano calcium carbonate slurry, and the consumption of quadripolymer is the 4% of nano-calcium carbonate quality；
7）By step 6）Obtained surface modified nano calcium carbonate slurry drying, you can obtain surface modified nano calcium carbonate powder
Body.
Embodiment 14
1）Weigh low-grade quick lime, ashing, except iron；
2）Add in digestion reactor filled with hot water, stir, carry out digestion reaction, stand cold filtration, slurries ageing；
3）It is passed through carbon dioxide in slurries to be carbonized, carbonisation adds chemical additives, 20-30 DEG C of carbonization to pH value is
13, nano-calcium carbonate slurries are obtained,
4）By step 3）Obtained nano-calcium carbonate slurries ageing, sedimentation concentration；
5）Quadripolymer is prepared by acrylamide, acrylic acid, octadecylene, maleic anhydride, wherein, acrylamide, propylene
Acid, octadecylene, maleic anhydride raw material mass mixture ratio are：25 parts of acrylamide, 60 parts of acrylic acid, 1 part of octadecylene, maleic anhydride 20
Part；Copolymerization is obtained to quadripolymer as modifying agent, modifying agent is dissolved in the in the mixed solvent of water and ethanol, it is standby, wherein
The volume ratio of water and ethanol is 1:4-6；
6）Modifier solution is added in nano-calcium carbonate concentrated slurry, is modified at 50-60 DEG C, the time is 20-30 points
Clock, obtains surface modified nano calcium carbonate slurry, and the consumption of quadripolymer is the 4% of nano-calcium carbonate quality；
7）By step 6）Obtained surface modified nano calcium carbonate slurry drying, you can obtain surface modified nano calcium carbonate powder
Body.
Embodiment 15
1）Weigh low-grade quick lime, ashing, except iron；
2）Add in digestion reactor filled with hot water, stir, carry out digestion reaction, stand cooling, filtering, slurries ageing；
3）It is passed through carbon dioxide in slurries to be carbonized, carbonisation adds chemical additives, 20-30 DEG C of carbonization to pH value is
13, nano-calcium carbonate slurries are obtained,
4）By step 3）Obtained nano-calcium carbonate slurries ageing, sedimentation concentration；
5）Quadripolymer is prepared by acrylamide, acrylic acid, octadecylene, maleic anhydride, wherein, acrylamide, propylene
Acid, octadecylene, maleic anhydride raw material mass mixture ratio are：25 parts of acrylamide, 60 parts of acrylic acid, 1 part of octadecylene, maleic anhydride 70
Part；Copolymerization is obtained to quadripolymer as modifying agent, modifying agent is dissolved in the in the mixed solvent of water and ethanol, it is standby, wherein
The volume ratio of water and ethanol is 1:4-6；
6）Modifier solution is added in nano-calcium carbonate concentrated slurry, is modified at 50-60 DEG C, the time is 20-30 points
Clock, obtains surface modified nano calcium carbonate slurry, and the consumption of quadripolymer is the 4% of nano-calcium carbonate quality；
7）By step 6）Obtained surface modified nano calcium carbonate slurry drying, you can obtain surface modified nano calcium carbonate powder
Body.
Quadripolymer and acrylamide, acrylic acid, octadecylene, maleic anhydride consumption, proportioning, institute in embodiment 1-15
Surface modified nano calcium carbonate activation rate is obtained referring to table 1.
The surface modified nano calcium carbonate activation rate of table 1
The embodiment 16-18 surface modified nano calcium carbonate activation rates of table 2
The method that embodiment 16-18 uses embodiment 2, only uses polyacrylic acid, poly or poly- third respectively by quadripolymer
Olefin(e) acid and poly mixture（Wherein polyacrylic acid and poly weight ratio are 60:40）Instead of gained surface is modified and received
Rice calcium carbonate activation rate is referring to table 2.
Claims (10)
1. a kind of method of quadripolymer surface modified nano calcium carbonate, it is characterised in that：Comprise the following steps：
1）Weigh low-grade quick lime, ashing, except iron；
2）Add in digestion reactor filled with hot water, stir, carry out digestion reaction, stand cooling, filtering, slurries ageing；
3）It is passed through carbon dioxide in slurries to be carbonized, carbonisation adds chemical additives, carbonization to pH value is 12-13, is obtained
To nano-calcium carbonate slurries；
4）By step 3）Obtained nano-calcium carbonate slurries ageing, sedimentation concentration；
5）Quadripolymer is prepared by acrylamide, acrylic acid, octadecylene, maleic anhydride；The quaternary that copolymerization is obtained is total to
Modifying agent is dissolved in the in the mixed solvent of water and ethanol by polymers as modifying agent, standby；
6）Modifier solution is added in nano-calcium carbonate concentrated slurry, is modified, the time is 20-30 minutes, obtains surface
Modified nano calcium carbonate slurry；
7）By step 6）Obtained surface modified nano calcium carbonate slurry drying, you can obtain surface modified nano calcium carbonate powder
Body.
2. the method as described in claim 1, it is characterised in that：The consumption of quadripolymer is the 2- of nano-calcium carbonate quality
10%。
3. the method as described in claim 1, it is characterised in that：Prepare in copolymer process, acrylamide, acrylic acid, 18
Alkene, maleic anhydride raw material mass mixture ratio are：20-30 parts of acrylamide, 50-70 parts of acrylic acid, 0.5-3 parts of octadecylene, maleic acid
30-60 parts of acid anhydride.
4. the method as described in claim 1, it is characterised in that：It is modified to be carried out at 50-60 DEG C.
5. the method described in claim 1, it is characterised in that：Step 5）Reclaimed water and the volume ratio of ethanol are 1:4-6.
6. the method as described in claim 1, it is characterised in that：The carburizing temperature is 20-30 DEG C.
7. the method as described in claim 1, it is characterised in that：By step 4）Nano-calcium carbonate slurries after concentration carry out secondary
Carbonization, then carry out surface modified active.
8. the method as described in claim 1, it is characterised in that：The method for preparing quadripolymer is as follows：By acrylamide, third
Olefin(e) acid, octadecylene, maleic anhydride are added in reactor, and it is 6.8-7.3 to adjust pH value with sodium hydroxide solution, is made into the total matter of monomer
Measure the aqueous solution that concentration is 15-25%；Propane diamine is added, is stirred, initiator ammonium persulfate solution and sodium hydrogensulfite is added
Solution, is continually fed into nitrogen, and 6-8h is reacted under the conditions of temperature is 30-40 DEG C；Wash, dry by ethanol, crushing and can obtain four
Membered copolymer.
9. method as claimed in claim 8, it is characterised in that：The mol ratio of initiator ammonium persulfate solution and sodium hydrogensulfite
For 1:1.
10. method as claimed in claim 8, it is characterised in that：Initiator addition is left for the 0.6-0.8% of monomer gross mass
It is right.
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