CN114106271A - Preparation method of polymer grafted and coated anhydrous phosphogypsum composite microspheres - Google Patents
Preparation method of polymer grafted and coated anhydrous phosphogypsum composite microspheres Download PDFInfo
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- CN114106271A CN114106271A CN202111594878.9A CN202111594878A CN114106271A CN 114106271 A CN114106271 A CN 114106271A CN 202111594878 A CN202111594878 A CN 202111594878A CN 114106271 A CN114106271 A CN 114106271A
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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
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/10—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to inorganic materials
Abstract
The invention discloses a preparation method of a composite microsphere of polymer grafted and coated anhydrous phosphogypsum. The invention selects phosphogypsum solid waste residue as a raw material, puts the phosphogypsum solid waste residue into a gradient furnace for calcination, then grinds and sieves to obtain anhydrous phosphogypsum, hydroxylates the anhydrous phosphogypsum by sodium hydroxide and sodium sulfate to obtain hydroxylated phosphogypsum, introduces C = C double bond on the surface of the hydroxylated phosphogypsum, then prepares the composite microsphere of the long-chain polymer coated anhydrous phosphogypsum by in-situ polymerization with (methyl) acrylate monomers, can be used as filler in high molecular materials such as plastics or rubber and the like to prepare composite materials, improves the dispersibility of the phosphogypsum in a high molecular matrix and enhances the interface action and compatibility of the phosphogypsum and the matrix, and the composite microsphere of the polymer coated anhydrous phosphogypsum can better transmit stress when stressed, thereby improving the comprehensive performance of the high molecular composite materials.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a preparation method of a composite microsphere of polymer grafted and coated anhydrous phosphogypsum.
Background
The phosphogypsum is solid waste residue generated when phosphorite is treated by sulfuric acid in the production of phosphoric acid by a wet process technology adopted by phosphorus chemical enterprises, and the by-product of phosphogypsum is about 5t when 1t of phosphoric acid is produced by the wet process. The main component of the phosphogypsum is calcium sulfate dihydrate. Phosphogypsum stockpiling occupies a large amount of cultivated land, and simultaneously, a large amount of pollutants are generated due to the impurities such as fluoride, phosphorus pentoxide, phosphate and the like, so that the ecological environment of the earth surface is destroyed. The comprehensive utilization of the solid waste phosphogypsum is imperative.
At present, the comprehensive utilization modes of phosphogypsum at home and abroad mainly comprise: the phosphogypsum is used as a cement retarder to replace natural gypsum to prepare building material gypsum such as gypsum blocks, gypsum plates, plastering gypsum, alpha-type high-strength gypsum and the like. The phosphogypsum has the characteristics of low cost, wide sources, good thermal stability and chemical stability, high mechanical strength and the like. Therefore, the phosphogypsum can replace part of light calcium carbonate and heavy calcium carbonate to be used as a filler of plastic or rubber to prepare a composite material in a high polymer material, and can be used as a large way for comprehensively utilizing the phosphogypsum. However, the application of the phosphogypsum in the field of high polymers has the following problems: the ardealite and polymer have large difference of interface performance, are directly blended and easily agglomerated, are not uniformly dispersed in a high polymer material matrix, and are easily peeled and agglomerated in the stress process, so that the toughening effect cannot be achieved, and the performance of the organic-inorganic composite materials is reduced.
In order to solve the problem of compatibility of the phosphogypsum and a polymer, the phosphogypsum can be uniformly dispersed in a polymeric matrix, and the key is to improve the compatibility between the phosphogypsum and the matrix. At present, the phosphogypsum is organically modified by mainly adopting a silane coupling agent, a titanate coupling agent, stearic acid (calcium) and the like. Although the modified phosphogypsum such as the small-molecule coupling agent can improve the comprehensive performance of the polymer/phosphogypsum composite material, the organic chain of the small-molecule coupling agent is short, so that the van der Waals force action of the phosphogypsum and a polymer matrix of a high-molecular material is small, and the small-molecule coupling agent tends to migrate from the interface of the composite material to the surface, so that the improvement of the comprehensive performance of the composite material is not ideal. The inorganic particles coated by the long-chain polymer have better interface compatibility in a high molecular material matrix and are more tightly wound with a molecular chain of the high molecular material matrix. Therefore, the long-chain polymer is grafted and coated on the phosphogypsum to prepare the composite microsphere, the affinity of the phosphogypsum and a high polymer material is increased, the long chain of the polymer grafted to the surface of the phosphogypsum can promote the uniform dispersion of the phosphogypsum in the high polymer material, so that the stress can be better transferred to phosphogypsum particles, the comprehensive performance of the composite material is obviously improved, and the toughening and reinforcing effects are achieved. Therefore, the long-chain polymer is grafted and coated with the phosphogypsum and then is used as a filler applied to plastics or rubber and the like, so that the problems of dispersion performance and interface of the phosphogypsum in a high polymer material matrix can be effectively solved.
Disclosure of Invention
The invention aims to provide a preparation method of a composite microsphere of polymer graft-coated anhydrous phosphogypsum, which aims to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a polymer grafted and coated anhydrous phosphogypsum composite microsphere comprises the following steps:
placing the phosphogypsum waste residue into a gradient furnace for calcining, grinding and screening to obtain anhydrous phosphogypsum, and hydroxylating the anhydrous phosphogypsum by using sodium hydroxide and sodium sulfate to obtain hydroxylated phosphogypsum;
heating the KH570 ethanol aqueous solution to 30-70 ℃ in a nitrogen atmosphere, and then stirring and mixing with the hydroxylated phosphogypsum to obtain a mixed solution; sequentially filtering, washing and drying the mixed solution to obtain KH570 modified anhydrous phosphogypsum;
mixing KH570 modified anhydrous phosphogypsum, deionized water, polyvinyl alcohol, (methyl) acrylate monomer and initiator to obtain a mixture; dispersing the mixture for 30-60min under nitrogen atmosphere, and heating to 60-80 ℃ for reaction to obtain reaction liquid; and sequentially filtering, washing and drying the reaction solution to obtain the polymer grafted and coated anhydrous phosphogypsum composite microspheres.
As a further scheme of the invention: the phosphogypsum is solid waste residue in a phosphorus chemical wet process.
As a further scheme of the invention: the calcination temperature of the phosphogypsum is 400-650 ℃, and the calcination time is 3-6 h.
As a further scheme of the invention: the mass ratio range of the hydroxylated phosphogypsum to the KH570 is 10: 1 to 40: 1.
as a further scheme of the invention: the (methyl) acrylate monomer is methyl methacrylate; the initiator is azobisisobutyronitrile or benzoyl peroxide or lauroyl peroxide;
as a further scheme of the invention: the mass ratio range of the acrylate monomer to the KH570 modified anhydrous phosphogypsum is 2.5: 1 to 25: 1.
the embodiment of the invention also aims to provide the composite microsphere coated with the polymer grafted anhydrous phosphogypsum prepared by the preparation method.
Another object of the embodiment of the present invention is that the surface of the composite microsphere of the polymer graft-coated anhydrous phosphogypsum is coated with polymethyl methacrylate.
Another object of the embodiment of the present invention is to provide the composite microsphere coated with anhydrous phosphogypsum by polymer grafting, which is used as a filler of a high molecular material.
Compared with the prior art, the invention has the beneficial effects that:
the invention selects the phosphogypsum solid waste residue as the raw material, obtains the anhydrous phosphogypsum through pretreatment, firstly introduces C ═ C double bonds on the surface of the anhydrous phosphogypsum, then prepares the composite microspheres of the long-chain polymer coated anhydrous phosphogypsum through in-situ polymerization with (methyl) acrylate monomers, can be used as fillers in high molecular materials such as plastics or rubber and the like to prepare composite materials, improves the dispersibility of the phosphogypsum in a high molecular matrix and enhances the interface action and compatibility of the phosphogypsum and the matrix, and the composite microspheres of the polymer coated anhydrous phosphogypsum can better transmit stress when stressed, thereby improving the comprehensive performance of the high molecular composite materials.
Drawings
FIG. 1 is a morphology of the composite microspheres of polymer graft coated anhydrous phosphogypsum prepared in example 1;
FIG. 2 is a sectional view of the composite microsphere of polymer graft coated with anhydrous phosphogypsum prepared in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1-2, example 1:
a preparation method of a polymer grafted and coated anhydrous phosphogypsum composite microsphere comprises the following steps:
s1, putting the phosphogypsum waste residue into a gradient furnace, calcining for 4 hours at 650 ℃, putting into a ball mill for ball milling, and carrying out ball milling for 60 minutes at the rotation speed of 500rpm to obtain the anhydrous phosphogypsum. Stirring and mixing phosphogypsum, sodium hydroxide and sodium sulfate aqueous solution under nitrogen atmosphere to obtain mixed solution; and sequentially filtering, washing and drying the mixed solution to obtain the hydroxylated phosphogypsum.
S2, adding 2.7g of silane coupling agent KH570 and 7.5mL of deionized water into 150mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 8min to obtain a mixture, and placing the mixture into a four-neck flask with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device. Introducing nitrogen into the mixture, stirring at the speed of 400rpm, heating the mixture to 60 ℃, adding 30g of the hydroxylated phosphogypsum, and mixing for 20 min; keeping the temperature to react for 3 hours to obtain a mixed solution.
S3, filtering the mixed solution, taking a solid, washing the solid with ethanol for multiple times, and drying to obtain the KH570 modified anhydrous phosphogypsum.
S4, adding 0.5g of lauroyl peroxide and 6g of the KH570 modified anhydrous phosphogypsum into 40g of methyl methacrylate solution for ultrasonic treatment for 5min to obtain an oil phase. 0.5g of polyvinyl alcohol was added to 160g of deionized water to obtain an aqueous phase. And the oil phase and the water phase are placed in a four-neck flask with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device.
S5, introducing nitrogen into the flask, stirring at the speed of 400rpm, and dispersing for 40 min; then, the mixture was heated to 70 ℃ and then reacted for 6 hours while maintaining the temperature to obtain a reaction solution.
S6, filtering the reaction liquid, taking a solid, washing the solid for multiple times by using ethanol and deionized water, and drying to obtain the polymer grafted and coated anhydrous phosphogypsum composite microsphere.
Example 2:
a preparation method of a polymer grafted and coated anhydrous phosphogypsum composite microsphere comprises the following steps:
s1, putting the phosphogypsum waste residue into a gradient furnace, calcining for 4.5h at 600 ℃, putting into a ball mill for ball milling, and ball milling for 60min at the rotation speed of 500rpm of the ball mill to obtain the anhydrous phosphogypsum. Stirring and mixing phosphogypsum, sodium hydroxide and sodium sulfate aqueous solution under nitrogen atmosphere to obtain mixed solution; and sequentially filtering, washing and drying the mixed solution to obtain the hydroxylated phosphogypsum.
S2, adding 2.5g of silane coupling agent KH570 and 7.5mL of deionized water into 150mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 8min to obtain a mixture, and placing the mixture into a four-neck flask with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device. Introducing nitrogen into the mixture, stirring at the speed of 400rpm, heating the mixture to 60 ℃, adding 30g of the hydroxylated phosphogypsum, and mixing for 20 min; keeping the temperature to react for 3 hours to obtain a mixed solution.
S3, filtering the mixed solution, taking a solid, washing the solid with ethanol for multiple times, and drying to obtain the KH570 modified anhydrous phosphogypsum.
S4, adding 0.6g of benzoyl peroxide and 4g of the KH570 modified anhydrous phosphogypsum into 40g of methyl methacrylate solution for ultrasonic treatment for 5min to obtain an oil phase. 0.4g of polyvinyl alcohol was added to 180g of deionized water to obtain an aqueous phase. And the oil phase and the water phase are placed in a four-neck flask with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device.
S5, introducing nitrogen into the flask, stirring at the speed of 450rpm, and dispersing for 30 min; then, the mixture was heated to 65 ℃ and then reacted for 6 hours while maintaining the temperature to obtain a reaction solution.
S6, filtering the reaction liquid, taking a solid, washing the solid for multiple times by using ethanol and deionized water, and drying to obtain the polymer grafted and coated anhydrous phosphogypsum composite microsphere.
Example 3:
a preparation method of a polymer grafted coated modified anhydrous phosphogypsum composite microsphere comprises the following steps:
s1, putting the phosphogypsum waste residue into a gradient furnace, calcining for 4.5h at 600 ℃, putting into a ball mill for ball milling, and ball milling for 60min at the rotation speed of 500rpm of the ball mill to obtain the anhydrous phosphogypsum. Stirring and mixing phosphogypsum, sodium hydroxide and sodium sulfate aqueous solution under nitrogen atmosphere to obtain mixed solution; and sequentially filtering, washing and drying the mixed solution to obtain the hydroxylated phosphogypsum.
S2, adding 2.8g of silane coupling agent KH570 and 7.5mL of deionized water into 150mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 8min to obtain a mixture, and placing the mixture into a four-neck flask with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device. Introducing nitrogen into the mixture, stirring at the speed of 400rpm, heating the mixture to 50 ℃, adding 30g of the hydroxylated phosphogypsum, and mixing for 20 min; keeping the temperature to react for 4 hours to obtain a mixed solution.
S3, filtering the mixed solution, taking a solid, washing the solid with ethanol for multiple times, and drying to obtain the KH570 modified anhydrous phosphogypsum.
S4, adding 0.4g of azobisisobutyronitrile and 5g of the KH570 modified anhydrous phosphogypsum into 50g of methyl methacrylate solution for ultrasonic treatment for 5min to obtain an oil phase. 0.5g of polyvinyl alcohol was added to 120g of deionized water to obtain an aqueous phase. And the oil phase and the water phase are placed in a four-neck flask with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device.
S5, introducing nitrogen into the flask, stirring at the speed of 420rpm, and dispersing for 30 min; then, the mixture was heated to 65 ℃ and then reacted for 8 hours while maintaining the temperature to obtain a reaction solution.
S6, filtering the reaction liquid, taking a solid, washing the solid for multiple times by using ethanol and deionized water, and drying to obtain the polymer grafted and coated anhydrous phosphogypsum composite microsphere.
Experimental example:
firstly, the morphology and the section of the composite microsphere of the polymer grafted and coated anhydrous phosphogypsum prepared in the example 1 are observed by a scanning electron microscope, and the analysis of the composition of the section of the composite microsphere is carried out by X-ray energy spectrum analysis, and the results are respectively shown in figures 1 and 2 and table 1. The results show that the composite microspheres of the polymer grafted and coated anhydrous phosphogypsum are successfully prepared.
Table 1: an X-ray energy spectrum analyzer analyzes the composition of the section of the composite microsphere;
| element(s) | Weight percent (%) | Atomic percent (%) |
| C | 64.21 | 73.22 |
| O | 27.73 | 23.74 |
| S | 3.36 | 1.44 |
| Ca | 4.70 | 1.61 |
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (8)
1. A preparation method of a composite microsphere of polymer grafted and coated anhydrous phosphogypsum is characterized by comprising the following steps:
step 1, placing phosphogypsum waste residues into a gradient furnace for calcination, then grinding and screening to obtain anhydrous phosphogypsum, and hydroxylating the anhydrous phosphogypsum by using sodium hydroxide and sodium sulfate to obtain hydroxylated phosphogypsum;
step 2, heating the KH570 ethanol aqueous solution to 30-70 ℃ in a nitrogen atmosphere, and then stirring and mixing with the hydroxylated phosphogypsum to obtain a mixed solution; sequentially filtering, washing and drying the mixed solution to obtain KH570 modified anhydrous phosphogypsum;
step 3, mixing the KH570 modified anhydrous phosphogypsum, deionized water, polyvinyl alcohol, (methyl) acrylate monomer and an initiator to obtain a mixture; dispersing the mixture for 30-60min under nitrogen atmosphere, and heating to 60-80 ℃ for reaction to obtain reaction liquid; and sequentially filtering, washing and drying the reaction solution to obtain the polymer grafted and coated anhydrous phosphogypsum composite microspheres.
2. The method for preparing the composite microspheres coated with the anhydrous phosphogypsum by polymer grafting according to claim 1, wherein the phosphogypsum is solid waste residue of a phosphorus chemical wet process.
3. The preparation method of the composite microsphere coated with the polymer grafted anhydrous phosphogypsum according to claim 1, which is characterized in that the calcination temperature of the phosphogypsum is 400-650 ℃, and the calcination time is 3-6 h.
4. The preparation method of the composite microsphere of polymer graft-coated anhydrous phosphogypsum according to claim 1, wherein the mass ratio of the hydroxylated phosphogypsum to the KH570 is 10: 1 to 40: 1.
5. the preparation method of the composite microsphere of polymer graft-coated anhydrous phosphogypsum according to claim 1, wherein the (meth) acrylate monomer is methyl methacrylate; the initiator is azobisisobutyronitrile or benzoyl peroxide or lauroyl peroxide; the mass ratio range of the (methyl) acrylate monomer to the KH570 modified anhydrous phosphogypsum is 2.5: 1 to 25: 1.
6. a composite microsphere of polymer graft-coated anhydrous phosphogypsum, which is characterized by being prepared by the method of any one of claims 1 to 5.
7. The composite microsphere of polymer graft-coated anhydrous phosphogypsum according to claim 6, wherein the surface graft-coated polymer is polymethyl methacrylate.
8. A high molecular material, characterized in that the composite microspheres of polymer graft-coated anhydrous phosphogypsum as claimed in claim 6 or 7 are used as filler.
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