CN105801898A - Crosslinked polyurea hollow microspheres and preparation method and application thereof - Google Patents
Crosslinked polyurea hollow microspheres and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/02—Polyureas
Abstract
The invention belongs to the technical field of hollow microsphere materials and discloses crosslinked polyurea hollow microspheres and a preparation method and application thereof.The preparation method comprises the steps of conducting a precipitation reaction on a calcium chloride solution and a sodium carbonate solution under the condition of a crystal form control agent, so that calcium carbonate particles are obtained; then modifying the obtained calcium carbonate particles with modifier, so that modified calcium carbonate is obtained; then conducting a reaction on the modified calcium carbonate, a cross-linking agent and isophorone diisocyanate in a mixed solvent medium formed by water and acetone, so that crosslinked polyurea core-shell microspheres are obtained; then dissolving and removing core templates of the crosslinked polyurea core-shell microspheres with hydrochloric acid, so that the crosslinked polyurea hollow microspheres are obtained.According to the crosslinked polyurea hollow microspheres and the preparation method and application thereof, the calcium carbonate particles are modified, and a polyurea material is crosslinked, so that the coating effect of the polyurea material and the calcium carbonate particles is improved; the obtained crosslinked polyurea hollow microspheres have good solvent resistance and acid and alkali resistance and can serve as opacifier to be applied to paint.
Description
Technical field
The invention belongs to hollow microsphere field of material technology, be specifically related to a kind of crosslinking polyureas hollow microsphere and preparation method thereof and application.
Background technology
TiO2Powder body is often used as light screening material in coating, but TiO2Powder body is in solvent seasoning process, and powder body is easily close to each other overlap even occurs, reduces covering power, it is, thus, sought for one light screening material better.
Polymer hollow particles, due to the structure of its internal cavities, causes that the refractive index between inner cavity part with polymer interface is different, and scattering can occur when therefore light passes through, so that this polymer has good light covering effect.The preparation method of hollow microsphere has template, LBL self-assembly method, sol-gal process, emulsion polymerization etc., and wherein template can control pattern and the particle diameter of hollow microsphere preferably.
Template is divided into hard template method and soft template method, and owing to soft template method is not easily controlled size and the pattern of microsphere, therefore, industrial conventional preparation method is generally adopted hard template method.The template particles of hard template method includes polymer particle (polystyrene particle, polymethyl acid particles), inorganic matter (calcium carbonate particle, silicon dioxide granule, TiO 2 particles) etc..The whole spherical face of spherical calcium carbonate particle can be close, and boundary material is easier to carry out sprawling cladding on ball surface, therefore can be used as hard template material, generally can prepare spherical calcium carbonate particle by interpolation chemical additives.Additionally, calcium carbonate raw material is simple and easy to get and cost is low, preparation method maturation, environmental friendliness and repeatability are strong, and After Enucleation residue is environmentally friendly.
Polyurea materials has much excellent characteristic, and polyureas building-up process complete monomer conversion, will not produce noxious substance on the one hand, therefore environmentally friendly；On the other hand, polyurea materials has the physicochemical property of excellence, has the excellent properties such as stronger wearability, anticorrosion, anti-aging.Therefore the polyurea materials boundary material as polymer hollow particles it is considered as.Having invented a kind of calcium carbonate as hard template, polyurea materials is as the crosslinking polyureas hollow microsphere preparation method of interfacial polymerization thing.
But calcium carbonate surface contains calcium ion, hydroxide ion, bicarbonate ion etc., has certain electrostatic interaction, therefore has higher surface energy.Calcium carbonate surface has many hydroxyls, and calcium carbonate is polarity inorganic matter and surface hydrophilic oleophobic, causes that calcium carbonate is not enough with the compatibility of polyureas, and affinity is poor, it is difficult to being formed with polyureas and be firmly chemically or physically combined, the nucleocapsid clad structure of formation is imperfect.Additionally, be by hydrogen bonded between the strand of polyurea microsphere, for linear structure, opposing is acid and other organic solvent properties are poor, limits the application of this microsphere.In order to strengthen interface compatibility and the affinity of calcium carbonate particle and polymer, improve microsphere solvent resistance and resistance to acids and bases, it is necessary to calcium carbonate particle is carried out surface modification treatment and polyureas is carried out cross-linking reaction.It is modified calcium carbonate mainly eliminating particle surface electric charge and then reducing the surface energy of calcium carbonate particle, weaken the surface polarity of calcium carbonate particle, be conducive to the compatibility improving calcium carbonate with polymer after surface modification, improve the integrity of polymer and calcium carbonate particle cladding.Crosslinking polyureas hollow microsphere solvent resistance and resistance to acids and bases can be improved after cross-linking reaction.
Summary of the invention
In order to solve the shortcoming and defect part of prior art, the primary and foremost purpose of the present invention is in that to provide a kind of preparation method cross-linking polyureas hollow microsphere.
Another object of the present invention is to provide a kind of crosslinking polyureas hollow microsphere prepared by said method.
It is still another object of the present invention to provide above-mentioned crosslinking polyureas hollow microsphere as opacifier application in coating.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method cross-linking polyureas hollow microsphere, including following preparation process:
(1) calcium chloride solution is placed in reactor, under ultrasonication, adds chemical additives, add sodium carbonate liquor after being uniformly mixed and carry out precipitation, pelleting centrifugation is washed, obtains calcium carbonate particle；Then it is modified with modifying agent after gained calcium carbonate particle being scattered in water, obtains modified calcium carbonate emulsion, centrifuge washing, obtain modified calcium carbonate particle；
(2) with the mixed solvent of water and acetone for reaction medium, add modified calcium carbonate particle and cross-linking agent, after ultrasonic mix homogeneously, add isophorone diisocyanate (IPDI) and react, product is washed by centrifugation, obtains crosslinking polyureas core-shell particles；Then crosslinking polyureas core-shell particles dissolving with hydrochloric acid is removed calcium carbonate kernel template, obtain described crosslinking polyureas hollow microsphere.
Preferably, described calcium chloride solution refers to the calcium chloride solution that concentration is 0.02～0.4mol/L, and the volume of described sodium carbonate liquor is identical with calcium chloride solution with concentration.
Preferably, the power of described ultrasonication is 120～500W.
Preferably, described chemical additives refer to sodium carboxymethyl cellulose (CMC), kayexalate (PSS), ethanol, isopropanol, 2,4-diethylene glycol, parents notion polystyrene-acrylic acid (PAS), polyacrylic acid, polymethylacrylic acid, polyvinyl alcohol, polyethylene adjoin pyrrolidone (PVP), ethylenediaminetetraacetic acid (EDTA), polymaleic anhydride (PAM), at least one in vinylbenzenesulfonic acid (SS) and sodium tripolyphosphate (STP)；The addition of chemical additives is the 0.02%～1.4% of calcium chloride solution quality.
Preferably, described modifying agent refers at least one in oleic acid, soap, titanate coupling agent, silane coupler and aluminate coupling agent；The addition of described modifying agent is the 1%～5% of calcium carbonate quality.
Preferably, in the mixed solvent of described water and acetone, the quality accounting of acetone is 50%～80%.
Preferably, described cross-linking agent refers to binary amine cross-linking agent or polynary amine cross-linking agent；Described binary amine cross-linking agent includes propane diamine, ethylenediamine (EDA), diphenylmethanediamiand (MOCA), and described polynary amine cross-linking agent includes Diethylenetriamine (DETA), three second tetramines (TETA), tetren (TEPA).
Preferably, described modified calcium carbonate particle, cross-linking agent, mass ratio between isophorone diisocyanate and water and the mixed solvent of acetone are 0.3:(0.1～0.5): (0.3～1.5): 100.
A kind of crosslinking polyureas hollow microsphere, is prepared by above method.
Above-mentioned crosslinking polyureas hollow microsphere is as opacifier application in coating.
Preparation method and the obtained product of the present invention have the advantage that and beneficial effect:
(1) the crosslinking polyureas hollow microsphere cheaper starting materials that prepared by the present invention is easy to get, and preparation condition easily realizes, and reduces the cost preparing hollow microsphere, is conducive to the large-scale production of this technology；
(2) present invention selects cheap and easy to get, nontoxic calcium carbonate as hard template, it is easy to remove calcium carbonate template and residue does not affect crosslinking polyureas hollow microsphere quality；
(3) when the present invention prepares calcium carbonate particle, add chemical additives, it is possible to efficiently control shape and appearance of calcium carbonate so that it is for spherical, be beneficial to polyureas and it is coated with；
(4) calcium carbonate particle surface has been modifiied by the present invention, it is possible to improve polyurea materials and calcium carbonate Interface composites ability, thus improving covered effect；
(5) polyurea materials is cross-linked by the present invention, makes balling ratio significant increase, improves its acid resistance and solvent resistance, it is possible to widen application scenario and the field of crosslinking polyureas hollow microsphere.
Accompanying drawing explanation
Fig. 1 is with unmodified calcium carbonate polyureas compound particle scanning electron microscope (SEM) figure as template in comparative example；
Fig. 2 is the polyureas particle scanning electron microscope diagram in comparative example after salt acid etch；
Fig. 3 uses modified calcium carbonate as the crosslinking polyureas core-shell particles scanning electron microscope diagram of template in embodiment 1；
Fig. 4 is the crosslinking polyureas hollow microsphere scanning electron microscope diagram in embodiment 1 after salt acid etch.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
In example below, unless stated otherwise, percentage ratio (%) is all mass percent, and room temperature refers to 15～30 DEG C.
For measure preparation crosslinking polyureas hollow microsphere mean diameter, adopt observation by light microscope prepare crosslinking polyureas hollow microsphere and to its scale particle size distribution add up, obtain crosslinking polyureas hollow microsphere average-size.
For measuring the resistance to acids and bases of the crosslinking polyureas hollow microsphere of preparation, crosslinking polyureas hollow microsphere particle is dispersed in respectively after acetic acid and sodium hydroxide solution (1.0mol/L) are incubated 12h, adopt its pattern of observation by light microscope, it may be judged whether be dissolved in acetic acid or sodium hydroxide solution (1.0mol/L).
For measuring the degree of cross linking of the crosslinking polyureas hollow microsphere of preparation, with glacial acetic acid for extractant, adopt glass fiber filter cylinder to carry out extracting 10h to crosslinking polyureas hollow microsphere particle, weigh the mass change before and after extracting, calculate surplus after extracting.
For measuring the solvent resistance of the crosslinking polyureas hollow microsphere of preparation, after crosslinking polyureas hollow microsphere particle is dispersed in pyridine, toluene, normal hexane and hexamethylene insulation 12h, adopt its pattern of observation by light microscope, it may be judged whether be dissolved in pyridine, toluene, normal hexane and hexamethylene.
Comparative example
(1) calcium chloride solution and sodium carbonate liquor that molar concentration is 0.1mol/L it are respectively configured, the calcium chloride solution taking 50ml joins in 200ml beaker, under hyperacoustic effect, (120W and 40KHz) is slowly added to the chemical additives CMC of 0.5g, after mixing and stirring, the isocyatic sodium carbonate liquor of equal-volume it is rapidly added under room temperature, 0.5h is reacted under room temperature, then stand to the complete precipitated and separated of system, it is centrifuged products therefrom again separating and washing 3 times respectively with water and ethanol removing chemical additives, obtains calcium carbonate particle.
(2) in the glass reaction bottle of 250ml, add 100g boiling mixed solvent (acetone of 60%), add calcium carbonate particle and 1.0gIPDI prepared by 0.3g step (1), after ultrasonic mix homogeneously, in the constant temperature oscillation water-bath of 30 DEG C, frequency of oscillation is set to 120osc/min, reaction 4h, it is centrifuged products therefrom separating and washing 3 times with above-mentioned boiling mixed solvent removing oligomer, collect precipitation obtain polyureas compound particle, with unmodified calcium carbonate as the polyureas compound particle of template scanning electron microscope diagram as shown in Figure 1.By the polyureas compound particle 0.1mol/L soak with hydrochloric acid 30h of preparation, removing calcium carbonate template, obtain polyureas particle, the scanning electron microscope diagram of the polyureas particle after salt acid etch is as shown in Figure 2.Gained polyureas particle assay result is as shown in table 1.
Embodiment 1
A kind of preparation method cross-linking polyureas hollow microsphere of the present embodiment, concretely comprises the following steps:
(1) calcium chloride solution and sodium carbonate liquor that molar concentration is 0.1mol/L it are respectively configured, the calcium chloride solution taking 50ml joins in 200ml beaker, under hyperacoustic effect, (120W and 40KHz) is slowly added to the chemical additives CMC of 0.5g, after mixing and stirring, the isocyatic sodium carbonate liquor of equal-volume it is rapidly added under room temperature, 0.5h is reacted under room temperature, then stand to the complete precipitated and separated of system, it is centrifuged products therefrom again separating and washing 3 times respectively with water and ethanol removing chemical additives, obtains calcium carbonate particle.Joining in there-necked flask after the calcium carbonate particle of preparation is scattered in water, and add mass percent and be equivalent to the sodium stearate of calcium carbonate quality 1%, at 60 DEG C, quickly stirring 1h can obtain modified calcium carbonate emulsion.Centrifuge washing, obtains modified calcium carbonate particle.
(2) in the glass reaction bottle of 250ml, add 100g boiling mixed solvent (acetone of 60%), add modified calcium carbonate particle and 0.24gTETA cross-linking agent prepared by 0.3g step (1), ultrasonic mix homogeneously, rapid disposable addition 1.0gIPDI, in the constant temperature oscillation water-bath of 30 DEG C, frequency of oscillation is set to 120osc/min, reaction 4h, it is centrifuged products therefrom separating and washing 3 times with above-mentioned boiling mixed solvent removing oligomer, collects precipitation and obtain crosslinking polyureas core-shell particles.With modified calcium carbonate as template crosslinking polyureas core-shell particles scanning electron microscope diagram as shown in Figure 3.By the crosslinking polyureas core-shell particles 0.1mol/L soak with hydrochloric acid 30h of preparation, remove calcium carbonate template, obtain crosslinking polyureas hollow microsphere.The scanning electron microscope diagram of the crosslinking polyureas hollow microsphere after salt acid etch is as shown in Figure 4.Gained crosslinking polyureas hollow microsphere measurement result is as shown in table 1.
Embodiment 2
A kind of preparation method cross-linking polyureas hollow microsphere of the present embodiment, concretely comprises the following steps:
(1) calcium chloride solution and sodium carbonate liquor that molar concentration is 0.4mol/L it are respectively configured, the sodium carbonate liquor taking 50ml joins in 200ml beaker, the chemical additives STP of 0.01g it is slowly added under 800rpm stirring condition, after mixing and stirring, the isocyatic calcium chloride solution of equal-volume it is rapidly added under room temperature, 0.5h is reacted under room temperature, then stand to the complete precipitated and separated of system, it is centrifuged products therefrom again separating and washing 3 times respectively with water and ethanol removing chemical additives, obtains calcium carbonate particle.
Other preparation process is identical with embodiment 1, and gained crosslinking polyureas hollow microsphere measurement result is as shown in table 1.
Embodiment 3
A kind of preparation method cross-linking polyureas hollow microsphere of the present embodiment, concretely comprises the following steps:
(1) calcium chloride solution and sodium carbonate liquor that molar concentration is 0.2mol/L it are respectively configured, the calcium chloride solution taking 50ml joins in 200ml beaker, the chemical additives CMC of 0.7g it is slowly added under 3000rpm stirring condition, after mixing and stirring, the isocyatic sodium carbonate liquor of equal-volume it is rapidly added under room temperature, 0.5h is reacted under room temperature, then stand to the complete precipitated and separated of system, it is centrifuged products therefrom again separating and washing 3 times respectively with water and ethanol removing chemical additives, obtains calcium carbonate particle.
Other preparation process is identical with embodiment 1, and gained crosslinking polyureas hollow microsphere measurement result is as shown in table 1.
Embodiment 4
A kind of preparation method cross-linking polyureas hollow microsphere of the present embodiment, concretely comprises the following steps:
(1) calcium chloride solution and sodium carbonate liquor that molar concentration is 0.02mol/L it are respectively configured, the calcium chloride solution taking 50ml joins in 200ml beaker, under hyperacoustic effect, (500W and 40KHz) is slowly added to the chemical additives PSS of 0.1g, after mixing and stirring, the isocyatic sodium carbonate liquor of equal-volume it is rapidly added under room temperature, 0.5h is reacted under room temperature, then stand to the complete precipitated and separated of system, it is centrifuged products therefrom again separating and washing 3 times respectively with water and ethanol removing chemical additives, obtains calcium carbonate particle.
Other preparation process is identical with embodiment 1, and gained crosslinking polyureas hollow microsphere measurement result is as shown in table 1.
Embodiment 5
A kind of preparation method cross-linking polyureas hollow microsphere of the present embodiment, concretely comprises the following steps:
(1) calcium chloride solution and sodium carbonate liquor that molar concentration is 0.1mol/L it are respectively configured, the calcium chloride solution taking 50ml joins in 200ml beaker, under hyperacoustic effect, (120W and 40KHz) is slowly added to the chemical additives CMC of 0.5g, after mixing and stirring, the isocyatic sodium carbonate liquor of equal-volume it is rapidly added under room temperature, 0.5h is reacted under room temperature, then stand to the complete precipitated and separated of system, it is centrifuged products therefrom again separating and washing 3 times respectively with water and ethanol removing chemical additives, obtains calcium carbonate particle.Joining in there-necked flask after the calcium carbonate particle of preparation is scattered in water, and add mass percent and be equivalent to the sodium stearate of calcium carbonate quality 5%, at 60 DEG C, quickly stirring 1h can obtain modified calcium carbonate emulsion.Centrifuge washing, obtains modified calcium carbonate particle.
(2) in the glass reaction bottle of 250ml, add 100g boiling mixed solvent (acetone of 50%), add the 0.3g modified calcium carbonate particle prepared and 0.5gDETA cross-linking agent, ultrasonic mix homogeneously, 1.5 parts of IPDI of rapid disposable addition, in the constant temperature oscillation water-bath of 30 DEG C, frequency of oscillation is set to 120osc/min, reaction 4h, it is centrifuged products therefrom separating and washing 3 times with above-mentioned boiling mixed solvent removing oligomer, collects precipitation and obtain crosslinking polyureas core-shell particles.By the crosslinking polyureas core-shell particles 0.5mol/L soak with hydrochloric acid 30h of preparation, remove calcium carbonate template, obtain crosslinking polyureas hollow microsphere.Gained crosslinking polyureas hollow microsphere measurement result is as shown in table 1.
Embodiment 6
A kind of preparation method cross-linking polyureas hollow microsphere of the present embodiment, concretely comprises the following steps:
(1) calcium chloride solution and sodium carbonate liquor that molar concentration is 0.1mol/L it are respectively configured, the calcium chloride solution taking 50ml joins in 200ml beaker, under hyperacoustic effect, (120W and 40KHz) is slowly added to the chemical additives CMC of 0.5g, after mixing and stirring, the isocyatic sodium carbonate liquor of equal-volume it is rapidly added under room temperature, 0.5h is reacted under room temperature, then stand to the complete precipitated and separated of system, it is centrifuged products therefrom again separating and washing 3 times respectively with water and ethanol removing chemical additives, obtains calcium carbonate particle.Joining in there-necked flask after the calcium carbonate particle of preparation is scattered in water, and drip mass percent and be equivalent to the oleic acid of calcium carbonate quality 1%, at 60 DEG C, quickly stirring 1h can obtain modified calcium carbonate emulsion.Centrifuge washing, obtains modified calcium carbonate particle.
(2) in the glass reaction bottle of 250ml, add 100g boiling mixed solvent (acetone of 80%), add the 0.3g modified calcium carbonate particle prepared and 0.1gTEPA cross-linking agent, ultrasonic mix homogeneously, 0.3 part of IPDI of rapid disposable addition, in the constant temperature oscillation water-bath of 30 DEG C, frequency of oscillation is set to 120osc/min, reaction 4h, it is centrifuged products therefrom separating and washing 3 times with above-mentioned boiling mixed solvent removing oligomer, collects precipitation and obtain crosslinking polyureas core-shell particles.By the crosslinking polyureas core-shell particles 0.1mol/L soak with hydrochloric acid 30h of preparation, remove calcium carbonate template, obtain crosslinking polyureas hollow microsphere.Gained crosslinking polyureas hollow microsphere measurement result is as shown in table 1.
The each embodiment of table 1 and comparative example location parameter
As can be seen from Table 1: the polyureas hollow microsphere mean diameter of preparation is micron order, in comparative example, is added without cross-linking agent, and the polyureas particle of gained is dissolved in acetic acid, is partially dissolved in pyridine, resistance to acids and bases and solvent resistance poor.The addition of cross-linking agent makes product have good solvent resistance and resistance to acids and bases.
Above-described embodiment is the present invention preferably embodiment; but embodiments of the present invention are also not restricted to the described embodiments; the change made under other any spirit without departing from the present invention and principle, modification, replacement, combination, simplification; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the preparation method cross-linking polyureas hollow microsphere, it is characterised in that include following preparation process:
(1) calcium chloride solution is placed in reactor, under ultrasonication, adds chemical additives, add sodium carbonate liquor after being uniformly mixed and carry out precipitation, pelleting centrifugation is washed, obtains calcium carbonate particle；Then it is modified with modifying agent after gained calcium carbonate particle being scattered in water, obtains modified calcium carbonate emulsion, centrifuge washing, obtain modified calcium carbonate particle；
(2) with the mixed solvent of water and acetone for reaction medium, adding modified calcium carbonate particle and cross-linking agent, after ultrasonic mix homogeneously, add isophorone diisocyanate and react, product is washed by centrifugation, obtains crosslinking polyureas core-shell particles；Then crosslinking polyureas core-shell particles dissolving with hydrochloric acid is removed calcium carbonate kernel template, obtain described crosslinking polyureas hollow microsphere.
2. a kind of preparation method cross-linking polyureas hollow microsphere according to claim 1, it is characterised in that: described calcium chloride solution refers to the calcium chloride solution that concentration is 0.02～0.4mol/L, and the volume of described sodium carbonate liquor is identical with calcium chloride solution with concentration.
3. a kind of preparation method cross-linking polyureas hollow microsphere according to claim 1, it is characterised in that: the power of described ultrasonication is 120～500W.
4. a kind of preparation method cross-linking polyureas hollow microsphere according to claim 1, it is characterized in that: described chemical additives refer to sodium carboxymethyl cellulose, kayexalate, ethanol, isopropanol, 2,4-diethylene glycol, parents notion polystyrene-acrylic acid, polyacrylic acid, polymethylacrylic acid, polyvinyl alcohol, polyethylene adjoin pyrrolidone, ethylenediaminetetraacetic acid, polymaleic anhydride, at least one in vinylbenzenesulfonic acid and sodium tripolyphosphate；The addition of chemical additives is the 0.02%～1.4% of calcium chloride solution quality.
5. a kind of preparation method cross-linking polyureas hollow microsphere according to claim 1, it is characterised in that: described modifying agent refers at least one in oleic acid, soap, titanate coupling agent, silane coupler and aluminate coupling agent；The addition of described modifying agent is the 1%～5% of calcium carbonate quality.
6. a kind of preparation method cross-linking polyureas hollow microsphere according to claim 1, it is characterised in that: in the mixed solvent of described water and acetone, the quality accounting of acetone is 50%～80%.
7. a kind of preparation method cross-linking polyureas hollow microsphere according to claim 1, it is characterised in that: described cross-linking agent refers to binary amine cross-linking agent or polynary amine cross-linking agent；Described binary amine cross-linking agent includes propane diamine, ethylenediamine or diphenylmethanediamiand, and described polynary amine cross-linking agent includes Diethylenetriamine, three second tetramine or tetrens.
8. a kind of preparation method cross-linking polyureas hollow microsphere according to claim 1, it is characterised in that: the mass ratio between described modified calcium carbonate, cross-linking agent, isophorone diisocyanate and water and the mixed solvent of acetone is 0.3:(0.1～0.5): (0.3～1.5): 100.
9. a crosslinking polyureas hollow microsphere, it is characterised in that: prepared by the method described in any one of claim 1～8.
10. the crosslinking polyureas hollow microsphere described in claim 9 is as opacifier application in coating.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN115872432A (en) * | 2022-12-08 | 2023-03-31 | 贺州学院 | Method for preparing spherical calcium carbonate through regulation and control modification and improving specific surface area |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3293231A1 (en) * | 2016-09-09 | 2018-03-14 | Rohm and Haas Company | Aqueous dispersion of keto-functionalized polymer particles and polymer beads |
| CN107805436A (en) * | 2016-09-09 | 2018-03-16 | 罗门哈斯公司 | The aqueous liquid dispersion of ketone group functionalized polymeric particle and polymer beads |
| CN107805436B (en) * | 2016-09-09 | 2021-05-07 | 罗门哈斯公司 | Aqueous dispersion of ketone-based functionalized polymer particles and polymer beads |
| AU2017219037B2 (en) * | 2016-09-09 | 2021-09-30 | Rohm And Haas Company | Aqueous dispersion of keto-functionalized polymer particles and polymer beads |
| CN109054846A (en) * | 2018-06-20 | 2018-12-21 | 上海工程技术大学 | A kind of preparation method of the soil conditioner based on LBL self-assembly microballoon |
| CN108794721A (en) * | 2018-07-03 | 2018-11-13 | 安徽大学 | A kind of preparation method of polyurethane hollow microsphere |
| CN109876744A (en) * | 2019-01-15 | 2019-06-14 | 济南大学 | A method of preparing transparent polyureas mono-dispersion microballoon |
| CN112390244A (en) * | 2019-08-18 | 2021-02-23 | 宋文良 | Hollow polymer microsphere and preparation method of corresponding hollow carbon sphere |
| CN112390244B (en) * | 2019-08-18 | 2023-07-21 | 宋文良 | Hollow polymer microsphere and preparation method of corresponding hollow carbon sphere |
| WO2023074651A1 (en) * | 2021-10-29 | 2023-05-04 | 日本ゼオン株式会社 | Hollow particle, method for producing hollow particle, resin composition, and molded body |
| CN115947386A (en) * | 2022-12-05 | 2023-04-11 | 华鼎国联四川电池材料有限公司 | Ternary cathode material with carbon-coated hollow structure and preparation method thereof |
| CN115872432A (en) * | 2022-12-08 | 2023-03-31 | 贺州学院 | Method for preparing spherical calcium carbonate through regulation and control modification and improving specific surface area |
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