CN114316632A - Preparation method of polymer-coated phosphogypsum composite master batch - Google Patents
Preparation method of polymer-coated phosphogypsum composite master batch Download PDFInfo
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- CN114316632A CN114316632A CN202210097323.1A CN202210097323A CN114316632A CN 114316632 A CN114316632 A CN 114316632A CN 202210097323 A CN202210097323 A CN 202210097323A CN 114316632 A CN114316632 A CN 114316632A
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Abstract
The invention provides a preparation method of a polymer-coated phosphogypsum composite master batch, and relates to the technical field of hydrophobic modification of inorganic fillers and preparation of composite materials. The method comprises the following steps: the method comprises the steps of adopting phosphogypsum waste residues as raw materials, calcining in a gradient furnace, grinding and screening to obtain anhydrous phosphogypsum, treating the anhydrous phosphogypsum with sodium hydroxide and anhydrous sodium sulfate to obtain hydroxylated phosphogypsum, carrying out surface modification on the hydroxylated phosphogypsum with a modifier to obtain modified phosphogypsum, and carrying out in-situ suspension polymerization on the modified phosphogypsum, vinyl monomers and reaction assistants to obtain the hydrophobic polymer coated phosphogypsum composite master batch. The polymer-coated phosphogypsum composite master batch can be used as a filler in high polymer materials such as plastics or rubber and the like, can obviously enhance the molecular winding and interface action between phosphogypsum and a high polymer matrix, and obviously improves the comprehensive performance of the high polymer composite material. Meanwhile, the invention has important significance for resource utilization of the phosphogypsum, and can widen the application range of the phosphogypsum.
Description
Technical Field
The invention relates to the technical field of inorganic filler modification and composite material preparation, in particular to a preparation method of a polymer-coated phosphogypsum composite master batch.
Background
Phosphogypsum is the main solid waste residue generated in the wet process of phosphoric acid, and the phosphogypsum residue with the main component of CaSO can be generated as a byproduct of about 5t every 1t of phosphoric acid is produced4·2H2O, and impurities such as undecomposed phosphate ore, fluoride, phosphoric acid, organic matter, and acid-insoluble matter. The comprehensive utilization rate of the phosphogypsum is low, the annual yield of the phosphogypsum in China is 7000 ten thousand t, and the comprehensive utilization rate is about 40 percent, so that the stockpiling of the phosphogypsum causes huge pressure on the ecological environment. The phosphogypsum accounts for about 4000m per 1 ten thousand t of the stacked phosphogypsum in the open air2The land is easy to cause dust weather and pollute the atmosphere after weathering, and the breathing health of people is influenced, wherein soluble phosphorus, fluorine, organic matters and the like are soaked into soil and underground water under the washing of rainwater, so the sustainable strategy of the phosphorus chemical industry in China is severely restricted, and therefore, the improvement of the comprehensive utilization rate of the phosphogypsum is very urgent.
The crystal morphology of the phosphogypsum is mainly flaky, contains a small amount of fibrous and spherical crystals, and can improve the stability, rigidity, hardness and the like of materials when being applied to plastic products, so that the phosphogypsum can replace part of light calcium carbonate and heavy calcium carbonate to be used as fillers of high polymer materials such as plastics or rubber and the like. However, the ardealite and the polymer have large difference in interface performance, are directly blended and easily agglomerate with each other, are unevenly dispersed in a high polymer material matrix, and are easily peeled and agglomerated from the matrix in a stress process. Therefore, pretreatment and surface modification of phosphogypsum are required. Generally, silane, phthalate ester and other coupling agents and stearic acid and the like are adopted to react with hydroxyl on the surface of inorganic particles for modification, but the modifying agents have short molecular chains and cannot extend into a polymer matrix, and a coating layer is thin, so that the improvement on the mechanical property of a polymer material is limited.
Disclosure of Invention
The invention aims to provide a preparation method of a polymer-coated phosphogypsum composite master batch, 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-coated phosphogypsum composite master batch comprises the following steps:
putting the phosphogypsum waste residue into a gradient furnace for calcination, then grinding and screening to obtain anhydrous phosphogypsum, and treating the anhydrous phosphogypsum by using sodium hydroxide and anhydrous sodium sulfate to obtain hydroxylated phosphogypsum;
stirring the hydroxylated phosphogypsum, the modifier and the ethanol aqueous solution at 30-70 ℃ in a nitrogen atmosphere, mixing to obtain a mixed solution, and sequentially filtering, washing and drying to obtain the modified phosphogypsum;
and (3) dispersing the mixture of the modified phosphogypsum, deionized water, a dispersing agent, a vinyl monomer and an initiator for 30-60min in a nitrogen atmosphere, heating to 50-75 ℃ for suspension polymerization reaction to obtain a reaction mixture, and sequentially filtering, washing and drying to obtain the hydrophobic polymer-coated phosphogypsum composite master batch.
As a further technical scheme of the invention, the phosphogypsum is solid waste residue in a phosphoric acid wet process.
As a further technical scheme of the invention, the calcination temperature of the phosphogypsum is 450-800 ℃, and the calcination time is 0.5-3 h.
As a further technical scheme of the invention, the modifier is preferably one of titanate, stearic acid, calcium stearate, sodium oleate, aluminate and silane coupling agent.
As a further technical scheme of the invention, the mass ratio range of the hydroxylated phosphogypsum to the modifier is 9: 1 to 40: 1.
as a further technical scheme of the invention, the dispersing agent is one or more of hydroxypropyl methyl cellulose, polyvinyl alcohol and polyvinylpyrrolidone.
In a further embodiment of the present invention, the vinyl monomer is one or more selected from methyl methacrylate, ethyl methacrylate, isobornyl methacrylate, methyl acrylate, and styrene.
In a further embodiment of the present invention, the initiator is an organic peroxide or an azo compound, preferably one of dibenzoyl peroxide, lauroyl peroxide, didecanoic acid peroxide, tert-butyl peracetate, tert-butyl peraurate or azobisisobutyronitrile, and 2, 2' -bis-azo- (2, 4-dimethyl pentanitrile).
As a further technical scheme of the invention, the mass ratio range of the vinyl monomer to the modified phosphogypsum is 2.5: 1 to 25: 1; the mass ratio of the vinyl monomer to the initiator is in the range of 30: 1 to 100: 1; the mass ratio of the vinyl monomer to the dispersant ranges from 30: 1 to 75: 1.
the filler of the high molecular material is prepared by coating the phosphogypsum composite master batch with the polymer.
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 carries out hydroxylation treatment on the anhydrous phosphogypsum to improve the hydroxyl number on the surface of the phosphogypsum, and then prepares the long-chain polymer coated phosphogypsum composite master batch through in-situ polymerization of the modified phosphogypsum and a vinyl monomer by a modifier, and the long-chain polymer coated phosphogypsum composite master batch can be used as a filler of a high polymer material, can obviously improve the dispersibility of the phosphogypsum in a high polymer matrix, and enhances the interface action and compatibility of the phosphogypsum and the high polymer matrix, thereby obviously improving the comprehensive performance of the high polymer composite material. Meanwhile, the invention has important significance for resource utilization of the phosphogypsum, and can widen the application range of the phosphogypsum.
Drawings
FIG. 1 is a diagram of the composite masterbatch product of the present invention.
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.
Example 1:
a preparation method of a polymer-coated phosphogypsum composite master batch comprises the following steps:
s1, putting the phosphogypsum waste residue into a gradient furnace, calcining for 2h at 600 ℃, putting into a ball mill for ball milling, wherein the rotation number of the ball mill is 500rpm, the ball milling is 60min, and screening to obtain the anhydrous phosphogypsum. And stirring and mixing the anhydrous phosphogypsum, sodium hydroxide and sodium sulfate aqueous solution under the nitrogen atmosphere to obtain a mixed solution, and sequentially filtering, washing and drying to obtain the hydroxylated phosphogypsum.
S2, adding 2.0g of neoalkoxy tri (dioctyl pyrophosphato acyloxy) titanate (TCA-L38) and 7.5mL of deionized water into 150mL of absolute ethyl alcohol for ultrasonic treatment for 8min to obtain a mixture, placing the mixture into a four-neck flask with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device, introducing nitrogen, stirring at the speed of 300rpm, heating to 60 ℃, adding 30g of the hydroxylated phosphogypsum, and carrying out heat preservation reaction for 3h to obtain a mixed solution. And filtering the mixed solution, taking a solid, washing the solid with ethanol for multiple times, and drying to obtain the TCA-L38 modified phosphogypsum.
S3, adding 0.65g of lauroyl peroxide and 8g of TCA-L38 modified phosphogypsum into 40g of methyl methacrylate solution for ultrasonic treatment for 5min to obtain an oil phase. 0.6g of hydroxypropylmethylcellulose was added to 160g of deionized water to obtain an aqueous phase. Placing the oil phase and the water phase in a four-neck flask with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device, introducing nitrogen, stirring at the speed of 400rpm, dispersing for 35min, heating to 70 ℃, carrying out heat preservation reaction for 6h to obtain a reaction mixture, filtering, taking a solid, washing the solid for multiple times by using ethanol and deionized water, and drying to obtain the polymer-coated phosphogypsum composite master batch.
Example 2:
a preparation method of a polymer-coated phosphogypsum composite master batch comprises the following steps:
s1, putting the phosphogypsum waste residue into a gradient furnace, calcining for 3h at 550 ℃, putting into a ball mill for ball milling, wherein the rotation number of the ball mill is 500rpm, ball milling is carried out for 60min, and screening is carried out to obtain the anhydrous phosphogypsum. And stirring and mixing the anhydrous phosphogypsum, sodium hydroxide and sodium sulfate aqueous solution under the nitrogen atmosphere to obtain a mixed solution, and sequentially filtering, washing and drying to obtain the hydroxylated phosphogypsum.
S2, adding 3.0g of TCA-L38 and 7.5mL of deionized water into 150mL of absolute ethyl alcohol for ultrasonic treatment for 8min to obtain a mixture, placing the mixture into a four-neck flask with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device, introducing nitrogen, stirring at the speed of 400rpm, heating to 50 ℃, adding 30g of hydroxylated phosphogypsum, and carrying out heat preservation reaction for 4h to obtain a mixed solution. And filtering the mixed solution, taking a solid, washing the solid with ethanol for multiple times, and drying to obtain the TCA-L38 modified phosphogypsum.
S3, adding 0.9g of azobisisobutyronitrile and 8g of TCA-L38 modified phosphogypsum into 50g of styrene solution for ultrasonic treatment for 5min to obtain an oil phase. 0.35g of hydroxypropylmethylcellulose and 0.35g of methylcellulose were added to 220g of deionized water to obtain an aqueous phase. And placing the oil phase and the water phase in a four-neck flask with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device, introducing nitrogen, stirring at the speed of 420rpm, dispersing for 30min, heating to 65 ℃, preserving heat, reacting for 8h to obtain a reaction mixture, filtering, taking a solid, washing the solid for multiple times by using ethanol and deionized water, and drying to obtain the polymer-coated phosphogypsum composite master batch.
Example 3:
a preparation method of a polymer-coated phosphogypsum composite master batch comprises the following steps:
s1, putting the phosphogypsum waste residue into a gradient furnace, calcining for 2h at 600 ℃, putting into a ball mill for ball milling, wherein the rotation number of the ball mill is 500rpm, the ball milling is 60min, and screening to obtain the anhydrous phosphogypsum. And stirring and mixing the anhydrous phosphogypsum, sodium hydroxide and sodium sulfate aqueous solution under the nitrogen atmosphere to obtain a mixed solution, and sequentially filtering, washing and drying to obtain the hydroxylated phosphogypsum.
S2, adding 2.5g of TCA-L38 and 7.5mL of deionized water into 200mL of absolute ethyl alcohol, and carrying out ultrasonic treatment for 8min to obtain a mixture. And (3) placing the mixture into a four-neck flask with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device, introducing nitrogen, stirring at the speed of 320rpm, simultaneously heating to 60 ℃, adding 30g of the hydroxylated phosphogypsum, and carrying out heat preservation reaction for 3 hours to obtain a mixed solution. And filtering the mixed solution, taking a solid, washing the solid with ethanol for multiple times, and drying to obtain the TCA-L38 modified phosphogypsum.
S3, adding 0.8g of lauroyl peroxide and 6g of TCA-L38 modified phosphogypsum into a mixed solution of 25g of methyl methacrylate and 15g of methyl acrylate for ultrasonic treatment for 5min to obtain an oil phase. 0.6g of hydroxypropylmethylcellulose was added to 180g of deionized water to obtain an aqueous phase. And placing the oil phase and the water phase in a four-neck flask with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device, introducing nitrogen, stirring at 450rpm, dispersing for 30min, heating to 70 ℃, carrying out heat preservation reaction for 6h to obtain a reaction mixture, filtering, taking a solid, washing the solid for multiple times by using ethanol and deionized water, and drying to obtain the polymer-coated phosphogypsum composite master batch.
Example 4:
a preparation method of a polymer-coated phosphogypsum composite master batch comprises the following steps:
and S1, putting the phosphogypsum waste residue into a ball mill for ball milling, wherein the rotation speed of the ball mill is 500rpm, the ball milling is carried out for 60min, then putting the phosphogypsum waste residue into a gradient furnace, calcining for 1.5h at 650 ℃, and screening to obtain the anhydrous phosphogypsum. And stirring and mixing the anhydrous phosphogypsum, sodium hydroxide and sodium sulfate aqueous solution under the nitrogen atmosphere to obtain a mixed solution, and sequentially filtering, washing and drying to obtain the hydroxylated phosphogypsum.
S2, adding 2.0g of stearic acid into 180mL of absolute ethyl alcohol, performing ultrasonic treatment for 8min to obtain a mixture, placing the mixture into a four-neck flask with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device, introducing nitrogen, stirring at the speed of 300rpm, heating to 60 ℃, adding 30g of the hydroxylated phosphogypsum, and performing heat preservation reaction for 3h to obtain a mixed solution. And filtering the mixed solution, taking a solid, washing the solid with ethanol for multiple times, and drying to obtain the stearic acid modified phosphogypsum.
S3, adding 0.6g of dibenzoyl peroxide and 7g of the stearic acid modified phosphogypsum into 45g of methyl methacrylate solution for ultrasonic treatment for 5min to obtain an oil phase. 0.9g of polyvinyl alcohol was added to 170g of deionized water to obtain an aqueous phase. And placing the oil phase and the water phase in a four-neck flask with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device, introducing nitrogen, stirring at 415rpm, dispersing for 50min, heating to 70 ℃, preserving heat, reacting for 6h to obtain a reaction mixture, filtering, taking a solid, washing the solid for multiple times by using ethanol and deionized water, and drying to obtain the polymer-coated phosphogypsum composite master batch.
Example 5:
a preparation method of a polymer-coated phosphogypsum composite master batch comprises the following steps:
and S1, putting the phosphogypsum waste residue into a ball mill for ball milling, wherein the rotation speed of the ball mill is 500rpm, the ball milling is carried out for 50min, then putting the phosphogypsum waste residue into a gradient furnace, and calcining the phosphogypsum waste residue for 0.5h at 800 ℃ to obtain the anhydrous phosphogypsum. And stirring and mixing the phosphogypsum, sodium hydroxide and sodium sulfate aqueous solution under the nitrogen atmosphere to obtain mixed solution, and sequentially filtering, washing and drying to obtain the hydroxylated phosphogypsum.
S2, adding 2.5g of stearic acid into 200mL of absolute ethyl alcohol for ultrasonic treatment for 8min to obtain a mixture, placing the mixture into a four-neck flask with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device, introducing nitrogen, stirring at the speed of 350rpm, simultaneously heating to 60 ℃, adding 30g of the hydroxylated phosphogypsum, and carrying out heat preservation reaction for 3h to obtain a mixed solution. And filtering the mixed solution, taking a solid, washing the solid with ethanol for multiple times, and drying to obtain the stearic acid modified phosphogypsum.
S3, adding 0.6g of lauroyl peroxide and 8g of stearic acid modified phosphogypsum into a mixed solution of 40g of methyl methacrylate and 10g of isobornyl methacrylate, and carrying out ultrasonic treatment for 5min to obtain an oil phase. 1g of polyvinyl alcohol was added to 200g of deionized water to obtain an aqueous phase. And placing the oil phase and the water phase in a four-neck flask with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device, introducing nitrogen, stirring at the speed of 450rpm, dispersing for 30min, heating to 70 ℃, preserving heat, reacting for 6h to obtain a reaction mixture, filtering, taking a solid, washing the solid for multiple times by using ethanol and deionized water, and drying to obtain the polymer-coated phosphogypsum composite master batch.
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 (10)
1. The preparation method of the polymer-coated phosphogypsum composite master batch is characterized by comprising the following steps:
putting the phosphogypsum waste residue into a gradient furnace for calcination, then grinding and screening to obtain anhydrous phosphogypsum, and treating the anhydrous phosphogypsum by using sodium hydroxide and anhydrous sodium sulfate to obtain hydroxylated phosphogypsum;
stirring the hydroxylated phosphogypsum, the modifier and the ethanol aqueous solution at 30-70 ℃ in a nitrogen atmosphere, mixing to obtain a mixed solution, and sequentially filtering, washing and drying to obtain the modified phosphogypsum;
and (3) dispersing the mixture of the modified phosphogypsum, deionized water, a dispersing agent, a vinyl monomer and an initiator for 30-60min in a nitrogen atmosphere, heating to 50-75 ℃ for suspension polymerization reaction to obtain a reaction mixture, and sequentially filtering, washing and drying to obtain the hydrophobic polymer-coated phosphogypsum composite master batch.
2. The preparation method of the polymer-coated phosphogypsum composite masterbatch according to claim 1, wherein the phosphogypsum is solid waste residue in a phosphoric acid wet process.
3. The preparation method of the polymer-coated phosphogypsum composite master batch according to claim 1, which is characterized in that the calcination temperature of the phosphogypsum is 450-800 ℃, and the calcination time is 0.5-3 h.
4. The preparation method of the polymer-coated phosphogypsum composite master batch according to claim 1, wherein the modifier is preferably one of titanate, stearic acid, calcium stearate, sodium oleate, aluminate ester and silane coupling agent.
5. The preparation method of the polymer-coated phosphogypsum composite masterbatch according to claim 1, wherein the mass ratio of the hydroxylated phosphogypsum to the modifier is in the range of 9: 1 to 40: 1.
6. the preparation method of the polymer-coated phosphogypsum composite master batch according to claim 1, wherein the dispersing agent is one or more of hydroxypropyl methylcellulose, polyvinyl alcohol and polyvinylpyrrolidone.
7. The preparation method of the polymer-coated phosphogypsum composite masterbatch according to claim 1, wherein the vinyl monomer is one or more of methyl methacrylate, ethyl methacrylate, isobornyl methacrylate, methyl acrylate and styrene.
8. The method for preparing the polymer-coated phosphogypsum composite masterbatch according to claim 1, wherein the initiator is an organic peroxide or an azo compound, preferably one of dibenzoyl peroxide, lauroyl peroxide, didecanoic acid peroxide, tert-butyl peracetate, tert-butyl peraurate or azobisisobutyronitrile and 2, 2' -bisazo- (2, 4-dimethyl valeronitrile).
9. The preparation method of the polymer-coated phosphogypsum composite masterbatch according to claim 1, wherein the mass ratio of the vinyl monomer to the modified phosphogypsum is within the range of 2.5: 1 to 25: 1; the mass ratio of the vinyl monomer to the initiator is in the range of 30: 1 to 100: 1; the mass ratio of the vinyl monomer to the dispersant ranges from 30: 1 to 75: 1.
10. a filler of high molecular material, characterized in that the polymer according to any one of claims 1-9 is used to coat the phosphogypsum composite masterbatch.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116285670A (en) * | 2023-03-28 | 2023-06-23 | 贵州大学 | Preparation method of beta-semi-hydrated phosphogypsum surface hybridization nano silicon dioxide hydrophobic self-cleaning coating |
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| CN1129004A (en) * | 1994-04-19 | 1996-08-14 | M·西基威茨 | Method for mfg. polymeric material having high chemical and mechanical resistance |
| CN113527911A (en) * | 2021-07-22 | 2021-10-22 | 贵州大学 | Phosphogypsum surface hydroxylation and hydrophobic modification method and phosphogypsum |
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2022
- 2022-01-27 CN CN202210097323.1A patent/CN114316632A/en active Pending
Patent Citations (2)
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| CN1129004A (en) * | 1994-04-19 | 1996-08-14 | M·西基威茨 | Method for mfg. polymeric material having high chemical and mechanical resistance |
| CN113527911A (en) * | 2021-07-22 | 2021-10-22 | 贵州大学 | Phosphogypsum surface hydroxylation and hydrophobic modification method and phosphogypsum |
Non-Patent Citations (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116285670A (en) * | 2023-03-28 | 2023-06-23 | 贵州大学 | Preparation method of beta-semi-hydrated phosphogypsum surface hybridization nano silicon dioxide hydrophobic self-cleaning coating |
| CN116285670B (en) * | 2023-03-28 | 2023-08-29 | 贵州大学 | Preparation method of beta-semi-hydrated phosphogypsum surface hybridization nano silicon dioxide hydrophobic self-cleaning coating |
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