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CN-116693726-B - Method for preparing scale inhibitor based on olefin functional polymer

CN116693726BCN 116693726 BCN116693726 BCN 116693726BCN-116693726-B

Abstract

The invention provides a method for preparing a scale inhibitor based on an olefin functional polymer, which comprises the steps of introducing low-carbon olefin into a reactor, heating and boosting, adding a functional monomer, an initiator and a solvent into the reactor for polymerization reaction, carrying out gas-solid-liquid separation after the polymerization reaction, recovering the low-carbon olefin, carrying out solid-liquid separation on the rest materials to obtain the olefin functional polymer, carrying out esterification reaction on the olefin functional polymer and alcohols, and then carrying out reaction on the obtained esterified olefin functional polymer and quaternary ammonium salt, alkali or acid to obtain the cationic or anionic polymer scale inhibitor. The invention realizes the same-chain alternating copolymerization of the low-carbon gaseous olefin and the functional monomer by the pressurized reaction of the low-carbon gaseous olefin and the functional monomer, adopts a heterogeneous polymerization mode to improve the monomer concentration and the reaction efficiency, prepares different polymer scale inhibitors by esterification and anion-cation reaction, has good heat stability and excellent water treatment performance, and has the advantages of simple operation, mild condition, easy separation and purification and environmental protection.

Inventors

  • WANG CHENG
  • DING KEHONG
  • WANG GENLIN
  • XU LIN
  • ZHANG LIUQIAO
  • WANG GUICHENG
  • YIN NANA

Assignees

  • 江苏扬农化工集团有限公司

Dates

Publication Date
20260512
Application Date
20230612

Claims (20)

  1. 1. A process for preparing a scale inhibitor based on an olefin functional polymer, characterized in that the process comprises the steps of: (1) After the low-carbon olefin is introduced into a reactor, the temperature and the pressure are raised, and after the reaction temperature and the reaction pressure are reached, raw material liquid prepared from functional monomers, an initiator and a solvent is added into the reactor for polymerization reaction, wherein the functional monomers comprise maleic anhydride; (2) Carrying out gas-solid-liquid separation on the materials obtained after the polymerization reaction in the step (1), recovering the low-carbon olefin, discharging the rest materials, and carrying out solid-liquid separation to obtain a solid-phase olefin functional polymer and a liquid-phase material; (3) Esterifying the olefin functional polymer obtained in the step (2) with alcohols to obtain an esterified olefin functional polymer; (4) And (3) reacting the olefin functional polymer obtained in the step (2) or the esterified olefin functional polymer obtained in the step (3) with quaternary ammonium salt, alkali or acid to obtain the cationic polymer scale inhibitor or the anionic polymer scale inhibitor.
  2. 2. The method of claim 1, wherein the low carbon olefin of step (1) comprises any one or a combination of at least two of ethylene, propylene, butene, or butadiene.
  3. 3. The method according to claim 1, wherein the reactor is evacuated and then replaced by a shielding gas before the light olefins are introduced in step (1).
  4. 4. The method of claim 1, wherein the reactor of step (1) comprises any one of a tank reactor, a tubular reactor, a microchannel reactor, a tower reactor, a fluidized bed reactor, or an ebullated bed reactor.
  5. 5. The method of claim 1, wherein the initiator of step (1) comprises azo-based compounds and/or peroxide-based compounds.
  6. 6. The method according to claim 5, wherein the azo-based compound comprises any one or a combination of at least two of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, azobicyclohexylcarbonitrile, and dimethyl azobisisobutyrate.
  7. 7. The method of claim 5, wherein the peroxide compound comprises any one or a combination of at least two of dibenzoyl peroxide, lauroyl peroxide, dicumyl peroxide, or diisopropyl peroxydicarbonate.
  8. 8. The method of claim 1, wherein the solvent of step (1) comprises any one or a combination of at least two of an organic alkanoate compound, an alkane compound, or an arene compound.
  9. 9. The method according to claim 8, wherein the organic alkanoate compound has a general structural formula of Wherein R1 is any one of H, C-C20 alkyl or C6-C10 aryl, and R2 is any one of C1-C20 alkyl or C6-C10 aryl.
  10. 10. The method of claim 8, wherein the alkane compound comprises any one or a combination of at least two of n-hexane, cyclohexane, n-pentane, n-heptane, n-octane, or n-decane.
  11. 11. The method of claim 8, wherein the aromatic compound comprises any one or a combination of at least two of benzene, toluene, ethylbenzene, or xylene.
  12. 12. The method of claim 1, wherein the molar ratio of the initiator to the functional monomer in step (1) is (0.001-0.2): 1.
  13. 13. The method of claim 1, wherein the mass ratio of the solvent to the functional monomer in the step (1) is (2-50): 1.
  14. 14. The method of claim 1, wherein the feed solution of step (1) is purified and preheated prior to being fed to the reactor.
  15. 15. The method of claim 1, wherein the feed solution in step (1) is pumped into the reactor at a constant speed after being pressurized by a transfer pump.
  16. 16. The method of claim 1, wherein the polymerization reaction in step (1) is carried out at a temperature of 50 to 150 ℃.
  17. 17. The method of claim 1, wherein the polymerization reaction in step (1) is carried out at a pressure of 0.1 to 10mpa.
  18. 18. The method of claim 1, wherein the residence time of the raw material liquid in step (1) is 10s to 10h.
  19. 19. The method of claim 1, wherein the pressure is maintained by continuously introducing the light olefin during the polymerization reaction in step (1).
  20. 20. The method according to claim 1, wherein the low-carbon olefin is discharged and recovered in the gas-solid-liquid separation process of step (2).

Description

Method for preparing scale inhibitor based on olefin functional polymer Technical Field The invention belongs to the technical field of organic polymerization, and relates to a method for preparing a scale inhibitor based on an olefin functional polymer. Background With the continuous development of society, adverse effects caused by a large amount of human activities on water bodies are increasingly aggravated, domestic sewage, industrial wastewater, agricultural discharge runoff and the like can cause continuous deterioration of water quality, and phosphorus-containing compounds pollute the water bodies and cause eutrophication problems, so that the method is one of the important reasons for causing the deterioration of water quality. Aiming at the treatment of polluted water, the chemical treatment method is often used more, and the water is purified by adding sewage treatment agent. The scale inhibitor is a commonly used sewage treatment agent at present, and comprises a natural polymer scale inhibitor and a synthetic polymer scale inhibitor, wherein the natural polymer scale inhibitor and the synthetic polymer scale inhibitor can be divided into carboxylic acid polymers, sulfonic acid polymers, phosphorus-containing polymers and environment-friendly scale inhibitors, and the traditional scale inhibitor is usually phosphorus-containing scale inhibitor, but with the increasing strictness of environmental protection requirements, the development of low-phosphorus and phosphorus-free scale inhibitors becomes a research hot spot. The polycarboxylic acid scale inhibitor is a prior phosphorus-free scale inhibitor, and comprises polyacrylic acid, polymethyl acrylate, polymaleic acid and the like. The olefin functional polymer is used as a functional high polymer material, has wide application in the aspects of engineering plastic chain extension, high-performance composite material, nylon infiltration, ink dispersion, microencapsulation, filtration membrane film formation and the like, and is greatly concerned. The olefin-maleic anhydride polymer can be used as a novel scale inhibitor, and carboxyl in the molecular structure of the olefin-maleic anhydride polymer can form chelate with calcium, magnesium, barium and other ions, so that the olefin-maleic anhydride polymer has good lattice distortion and dispersion effects, has little pollution to the environment, and has the advantages of green and high efficiency. The synthetic raw materials of the olefin functional polymer mainly comprise olefin and functional monomers, and corresponding synthetic processes are needed according to different types of olefin or functional monomers in the synthetic raw materials of the olefin functional polymer. However, conventionally, the polymerization of maleic anhydride as a functional monomer with an olefin is carried out, and the olefin used is usually an olefin of at least C4, and is usually a liquid olefin such as a diolefin, a cycloolefin or an isoolefin, and the polymerization of a gaseous olefin of at most C4 is not involved. CN 1560323a discloses a method for preparing a scale inhibitor of maleic anhydride and vinyl acetate copolymer, which uses maleic anhydride and vinyl acetate as raw materials, uses water as solvent, uses redox system as initiator to perform free radical polymerization, reduces bromine number of product and improves scale inhibition performance through improving initiator system, but the method does not involve the steps of further esterifying olefin functional polymer and ionizing yin and yang to prepare the scale inhibitor, the synthesis of olefin functional polymer is liquid olefin, vinyl acetate can be regarded as functional monomer, and the synthesis process of gaseous olefin and functional monomer is not involved. CN 104262546A discloses an alkenyl polyoxyethylene ether/maleic anhydride/acrylic acid copolymer, a preparation method and application thereof, wherein the copolymer is polymerized by taking maleic anhydride, acrylic acid and alkenyl polyoxyethylene ether as monomers, and carboxylic acid groups and oxyethylene repeating units are introduced, so that polyether groups with stronger hydrophilicity and carboxylate ions capable of chelating calcium and magnesium ions are contained in the copolymer, and the copolymer is a novel water treatment agent. CN 111253516a discloses a preparation method and application of novel polyether scale inhibitor based on carboxylic acid group, ester group and ether, the polymer uses maleic anhydride, fatty alcohol polyoxyethylene ether and sodium hydroxide as raw materials, potassium persulfate as initiator, copolymerization is carried out in aqueous solution, and the polymerization product is green and environment-friendly. In the method, the copolymer is not subjected to esterification reaction after synthesis, and the polymer is not involved in the polymerization process of the low-carbon olefin and the functional monomer. In summary, for the synthesis