CN108250346B - Synthesis method of diacetone acrylamide and acrylic acid copolymer - Google Patents

Synthesis method of diacetone acrylamide and acrylic acid copolymer Download PDF

Info

Publication number
CN108250346B
CN108250346B CN201810046550.5A CN201810046550A CN108250346B CN 108250346 B CN108250346 B CN 108250346B CN 201810046550 A CN201810046550 A CN 201810046550A CN 108250346 B CN108250346 B CN 108250346B
Authority
CN
China
Prior art keywords
acrylic acid
diacetone acrylamide
bisulfite
persulfate
reaction kettle
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810046550.5A
Other languages
Chinese (zh)
Other versions
CN108250346A (en
Inventor
兰平
吕佳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiaxing University
Original Assignee
Jiaxing University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiaxing University filed Critical Jiaxing University
Priority to CN201810046550.5A priority Critical patent/CN108250346B/en
Publication of CN108250346A publication Critical patent/CN108250346A/en
Application granted granted Critical
Publication of CN108250346B publication Critical patent/CN108250346B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/40—Redox systems
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses a method for synthesizing a diacetone acrylamide-acrylic acid copolymer, which takes carbon dioxide as a medium and a persulfate and bisulfite redox system as an initiator to carry out precipitation polymerization on a diacetone acrylamide-acrylic acid comonomer at a critical temperature and a critical pressure of the carbon dioxide to obtain a water-free diacetone acrylamide-acrylic acid copolymer. The concentration of the initial dosage of the initiator is 0.05-0.5 mol/l; the initial concentration of the total monomers of diacetone acrylamide and acrylic acid is 1-8 mol/l. In the initiator, the persulfate is one of potassium persulfate, sodium persulfate and ammonium persulfate, and the bisulfite is one of potassium bisulfite, sodium bisulfite and ammonium bisulfite. Because the invention adopts the nontoxic and pollution-free medium supercritical carbon dioxide to replace the organic solvent, the pollution to the environment caused by using the toxic, harmful, volatile and flammable organic solvent is avoided, and the effects of environmental protection, energy conservation and resource conservation can be realized.

Description

Synthesis method of diacetone acrylamide and acrylic acid copolymer
Technical Field
The invention relates to a method for synthesizing a diacetone acrylamide-acrylic acid copolymer, in particular to a method for synthesizing the diacetone acrylamide-acrylic acid copolymer by using supercritical carbon dioxide as a solvent.
Background
The existing method for synthesizing the diacetone acrylamide and acrylic acid copolymer generally adopts solution polymerization or aqueous phase precipitation polymerization in water. In the solution polymerization, the solvent recovery step is added, and the organic or inorganic solvent used is likely to cause environmental pollution and contamination of the polymerization product. And by adopting a water phase precipitation method, reaction products need to be diluted by deionized water, and are precipitated by acetone, washed and dried, so that a large amount of energy is consumed, the process is complicated, and the production cost is increased.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for synthesizing the diacetone acrylamide-acrylic acid copolymer by using supercritical carbon dioxide instead of the traditional solvent, so as to avoid the pollution of the organic solvent to the environment and meet the requirements of environmental protection, energy conservation and resource conservation.
In order to solve the technical problem, the synthesis method of the diacetone acrylamide-acrylic acid copolymer provided by the invention is characterized in that carbon dioxide is used as a medium, a persulfate and bisulfite redox system is used as an initiator, and the diacetone acrylamide-acrylic acid comonomer is subjected to precipitation polymerization at a critical temperature and pressure of the carbon dioxide to obtain the water-free diacetone acrylamide-acrylic acid copolymer.
The synthesis method of the diacetone acrylamide and acrylic acid copolymer comprises the following steps: adding diacetone acrylamide, acrylic acid monomers and an initiator into a reaction kettle, and sealing the reaction kettle, wherein the concentration of the initial dosage of the initiator is 0.05-0.5 mol/l; introducing carbon dioxide to exhaust air in the reaction kettle, enabling the initial concentration of the total monomers of the diacetone acrylamide and the acrylic acid to be 1-8 mol/l, then closing an inlet valve and an outlet valve of the reaction kettle, and heating; the pressure in the reaction kettle continuously rises along with the rise of the temperature, and when the reaction temperature reaches 32-40 ℃, the pressure in the reaction kettle (namely the pressure of carbon dioxide in the kettle) is controlled to be more than 8MPa and less than 45 MPa; at the moment, starting the stirrer, and reacting for 3-20 hours until the reaction is finished.
According to the synthesis method of the diacetone acrylamide-acrylic acid copolymer, the persulfate in the redox system is one of potassium persulfate, sodium persulfate and ammonium persulfate.
In the above method for synthesizing the diacetone acrylamide-acrylic acid copolymer, the bisulfite in the redox system is one of potassium bisulfite, sodium bisulfite and ammonium bisulfite.
According to the synthesis method of the diacetone acrylamide-acrylic acid copolymer, the diacetone acrylamide accounts for 0-70 mol% (excluding 0%) of the two monomers.
According to the synthesis method of the diacetone acrylamide-acrylic acid copolymer, the acrylic acid accounts for 30-100 mol% (excluding 100%) of the two monomers.
According to the synthesis method of the diacetone acrylamide-acrylic acid copolymer, the initial concentration of the total monomer of the diacetone acrylamide and the acrylic acid is 2-6 mol/l.
According to the method for synthesizing the diacetone acrylamide-acrylic acid copolymer, the molar ratio of the initial dosage of the persulfate to the initial dosage of the bisulfite in the initiator is 1:1, and the initial dosage concentration of the initiator is 0.08-0.3 mol/l.
According to the synthesis method of the diacetone acrylamide and acrylic acid copolymer, the pressure in the reaction kettle is 20-30 MPa.
According to the synthesis method of the diacetone acrylamide and acrylic acid copolymer, the reaction temperature is controlled to be 33-38 ℃.
According to the synthesis method of the diacetone acrylamide and acrylic acid copolymer, the reaction time is 4-10 hours.
According to the synthesis method of the diacetone acrylamide and acrylic acid copolymer, after the reaction is finished, cooling water is introduced to cool the reaction kettle to room temperature; and opening an air outlet valve of the reaction kettle, reducing the pressure to normal pressure, and taking out a product, namely a water-free white product, namely the diacetone acrylamide and acrylic acid copolymer.
The invention adopts the technical scheme that the nontoxic and pollution-free medium supercritical carbon dioxide is used for replacing an organic solvent, and the temperature and the pressure of the carbon dioxide are higher than the critical temperature and the critical pressure of the carbon dioxide. At the moment, the supercritical carbon dioxide has the properties of both liquid and gas, and the solubility of the supercritical carbon dioxide can be changed by changing the pressure of the supercritical carbon dioxide, so that the supercritical carbon dioxide can be used for replacing toxic, harmful, volatile and flammable organic solvents, and the serious pollution of the chemical organic solvent to the environment is avoided. Because carbon dioxide is a byproduct generated in a plurality of industries at present, the carbon dioxide can be obtained from the environment, can return to the environment after being used in a chemical process, has no any byproduct, and has the advantages of incombustibility, innocuity, good chemical stability, low price, easy obtaining and the like, the carbon dioxide can be used for synthesizing the diacetone acrylamide-acrylic acid copolymer, thereby avoiding the pollution to the environment caused by using toxic, harmful, volatile and flammable organic solvents, and realizing the effects of environmental protection, energy conservation and resource conservation.
Detailed Description
Embodiment 1 a method for synthesizing a diacetone acrylamide-acrylic acid copolymer, comprising the steps of:
Figure 590801DEST_PATH_IMAGE002
acrylic acid with the concentration of 2.1mol/l, diacetone acrylamide with the concentration of 1.9mol/l and an initiator with the concentration of 0.1 mol/l (a mixture of ammonium persulfate and sodium bisulfite with the mixing molar ratio of 1: 1) are respectively added into a reaction kettle and sealed. Wherein, the mol percentage of diacetone acrylamide in the two monomers is 47.5%, and the mol percentage of acrylic acid in the two monomers is 52.5%.
Figure 773521DEST_PATH_IMAGE004
Carbon dioxide was introduced for 25 minutes to exhaust the air in the reaction vessel so that the initial concentration of the total monomer of diacetone acrylamide and acrylic acid was 4 mol/l.
Figure 818837DEST_PATH_IMAGE006
Then the inlet and outlet valves of the reaction kettle are closed and heated. When the temperature rises to 30 ℃, a high-pressure pump of the reaction kettle and an inlet valve of the reaction kettle are opened, and a certain amount of carbon dioxide is supplemented. The pressure in the reactor was continuously increased with the increase of the temperature, and when the temperature reached the desired reaction temperature of 35 ℃, the pressure in the reactor was controlled to be maintained at the desired pressure of 20MPa, at which time the stirrer was started and the time at which the reaction started was recorded. After 6 hours of reaction, the reaction kettle was cooled to room temperature.
Figure 479626DEST_PATH_IMAGE008
And opening an air outlet valve of the reaction kettle, and reducing the pressure to normal pressure. The resulting product was a largely white product (as a water-free diacetone acrylamide acrylic acid copolymer).
Embodiment 2 a method for synthesizing a diacetone acrylamide-acrylic acid copolymer, comprising the steps of:
Figure 559577DEST_PATH_IMAGE002
the concentration is 3.5mol/lRespectively adding acrylic acid, diacetone acrylamide with the concentration of 0.9mol/l and an initiator (a mixture of sodium persulfate and potassium bisulfite with the mixing molar ratio of 1: 1) with the concentration of 0.2 mol/l into a reaction kettle, and sealing. Wherein, the mol percentage of the diacetone acrylamide in the two monomers is 20.45 percent, and the mol percentage of the acrylic acid in the two monomers is 79.55 percent.
Figure 647619DEST_PATH_IMAGE004
Carbon dioxide was introduced for 25 minutes to exhaust the air in the reaction vessel so that the initial concentration of the total monomer of diacetone acrylamide and acrylic acid was 4.4 mol/l.
Figure 180232DEST_PATH_IMAGE006
Then the inlet and outlet valves of the reaction kettle are closed and heated. When the temperature rises to 30 ℃, a high-pressure pump of the reaction kettle and an inlet valve of the reaction kettle are opened, and a certain amount of carbon dioxide is supplemented. The pressure in the reactor was continuously increased with the increase of the temperature, and when the temperature reached the desired reaction temperature of 33 ℃, the pressure in the reactor was controlled to be maintained at the desired pressure of 25MPa, at which time the stirrer was started and the time at which the reaction started was recorded. After 7 hours of reaction, the reaction kettle was cooled to room temperature.
Figure 910290DEST_PATH_IMAGE008
And opening an air outlet valve of the reaction kettle, and reducing the pressure to normal pressure. The resulting product was a largely white product (no diacetone acrylamide and acrylic acid copolymer).
Embodiment 3 a method for synthesizing a diacetone acrylamide-acrylic acid copolymer, comprising the steps of:
Figure 844748DEST_PATH_IMAGE002
acrylic acid at a concentration of 1.3mol/l, diacetone acrylamide at a concentration of 2.9mol/l and an initiator at a concentration of 0.3mol/l (potassium persulfate andthe mixture of ammonium bisulfite is added into a reaction kettle respectively according to the mixing molar ratio of 1: 1) and sealed. Wherein, the mol percentage of the diacetone acrylamide in the two monomers is 69.05%, and the mol percentage of the acrylic acid in the two monomers is 30.95%.
Figure 103691DEST_PATH_IMAGE004
Carbon dioxide was introduced for 25 minutes to exhaust the air in the reaction vessel so that the initial concentration of the total monomer of diacetone acrylamide and acrylic acid was 4.2 mol/l.
Figure 123600DEST_PATH_IMAGE006
Then the inlet and outlet valves of the reaction kettle are closed and heated. When the temperature rises to 30 ℃, a high-pressure pump of the reaction kettle and an inlet valve of the reaction kettle are opened, and a certain amount of carbon dioxide is supplemented. The pressure in the reactor was continuously increased with the increase of the temperature, and when the temperature reached the desired reaction temperature of 37 ℃, the pressure in the reactor was controlled to be maintained at the desired pressure of 30MPa, at which time the stirrer was turned on and the time at which the reaction started was recorded. After 4 hours of reaction, the reaction kettle was cooled to room temperature.
Figure 126191DEST_PATH_IMAGE008
And opening an air outlet valve of the reaction kettle, and reducing the pressure to normal pressure. The resulting product was a largely white product (no diacetone acrylamide and acrylic acid copolymer).
In the method of the invention, the initiator is formed by mixing a persulfate and a bisulfite, wherein the persulfate has an oxidizing effect and the bisulfite has a reducing effect, so that a redox system is formed.

Claims (1)

1. A method for synthesizing a diacetone acrylamide-acrylic acid copolymer is characterized in that carbon dioxide is used as a medium, a persulfate and bisulfite redox system is used as an initiator, and the diacetone acrylamide-acrylic acid comonomer is subjected to precipitation polymerization at a critical temperature and a critical pressure of the carbon dioxide to obtain a water-free diacetone acrylamide-acrylic acid copolymer, and specifically comprises the following steps: adding diacetone acrylamide, acrylic acid monomers and an initiator into a reaction kettle, sealing, wherein the molar percentage of the diacetone acrylamide in the two monomers is more than 0 and less than or equal to 70 percent, the molar percentage of the acrylic acid in the two monomers is more than or equal to 30 and less than 100 percent, the persulfate in the redox system is one of potassium persulfate, sodium persulfate or ammonium persulfate, the bisulfite is one of potassium bisulfite, sodium bisulfite or ammonium bisulfite, the molar ratio of the initial dosage of the persulfate to the bisulfite is 1:1, and the concentration of the initial dosage of the initiator is 0.08-0.3 mol/l; introducing carbon dioxide to exhaust air in the reaction kettle, enabling the initial concentration of the total monomers of the diacetone acrylamide and the acrylic acid to be 2-6 mol/l, then closing an inlet valve and an outlet valve of the reaction kettle, and heating; the pressure in the reaction kettle continuously rises along with the rise of the temperature, and when the reaction temperature reaches 33-38 ℃, the pressure in the reaction kettle is controlled to be 20-30 MPa; at the moment, starting the stirrer, and reacting for 4-10 hours until the reaction is finished; after the reaction is finished, introducing cooling water to cool the reaction kettle to room temperature; and opening an air outlet valve of the reaction kettle, reducing the pressure to normal pressure, and taking out a product, namely a water-free white product, namely the diacetone acrylamide and acrylic acid copolymer.
CN201810046550.5A 2018-01-18 2018-01-18 Synthesis method of diacetone acrylamide and acrylic acid copolymer Active CN108250346B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810046550.5A CN108250346B (en) 2018-01-18 2018-01-18 Synthesis method of diacetone acrylamide and acrylic acid copolymer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810046550.5A CN108250346B (en) 2018-01-18 2018-01-18 Synthesis method of diacetone acrylamide and acrylic acid copolymer

Publications (2)

Publication Number Publication Date
CN108250346A CN108250346A (en) 2018-07-06
CN108250346B true CN108250346B (en) 2021-03-26

Family

ID=62740734

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810046550.5A Active CN108250346B (en) 2018-01-18 2018-01-18 Synthesis method of diacetone acrylamide and acrylic acid copolymer

Country Status (1)

Country Link
CN (1) CN108250346B (en)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZM14374A1 (en) * 1973-10-05 1976-10-21 Ici Australia Ltd Processes and products
CN101974122B (en) * 2010-09-29 2012-07-04 太原理工大学 Method for preparing solid acrylic acid copolymer

Also Published As

Publication number Publication date
CN108250346A (en) 2018-07-06

Similar Documents

Publication Publication Date Title
CN102863582B (en) Preparation method of ultra-high molecular weight cationic polyacrylamide
CN102731699B (en) Preparation method of ultra high molecular weight anionic polyacrylamide
CN108314750B (en) Method for synthesizing diacetone acrylamide and acrylamide copolymer
CN102746834B (en) Polymer filtrate reducer and preparation method thereof
CN108250346B (en) Synthesis method of diacetone acrylamide and acrylic acid copolymer
CN102492414A (en) Synthesis of thickening agent for methanol-based fracturing fluid
CN108314751B (en) Method for synthesizing diacetone acrylamide and sodium acrylate copolymer
CN108299597B (en) Method for synthesizing diacetone acrylamide and sodium alginate copolymer
CN111040059A (en) High alkali-resistant 1, 1-difluoroethylene polymer and preparation method thereof
CN103073676B (en) A kind of preparation method of terpolymer anti-phase emulsion
CN105801728B (en) Molten terminator of polyvinyl chloride resin oil and preparation method thereof
CN111892682B (en) Small-molecule salt-resistant polymer and preparation method thereof
CN111363070B (en) Medium-low temperature gel for stratum plugging based on cationic cross-linking agent
CN104232058B (en) A kind of preparation method of the tartaric acid aluminium crosslinking agent for polymer water-based fracturing
CN111100238A (en) Salt water resistant plugging agent and preparation method thereof
CN108424490B (en) Acrylamide copolymer and preparation method and application thereof
CN109021222B (en) Preparation method of high-collapse-resistance polyether monomer
CN103755857B (en) Low-temperature resistant fluorubber, and preparation method thereof
CN114874112B (en) Surface active monomer containing sodium sulfonate group, and preparation method and application thereof
CN110819072A (en) La-Schiff base complex super-hydrophobic epoxy resin antibacterial material and preparation method thereof
CN117820547B (en) Polyacrylamide for oil displacement and preparation method thereof
CN103724525A (en) Novel preparation process of thickening agent
CN114907520B (en) Fracturing thickening agent for oilfield reinjection water and preparation method thereof
CN109503745A (en) A kind of continuous production method of hydrolysis of polymaleic anhydride
CN104649940A (en) Acrylamide monomer and its preparation method and use

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant