CN1079099C - Method for preparing polyacrylic acid in supercritical carbon dioxide medium - Google Patents
Method for preparing polyacrylic acid in supercritical carbon dioxide medium Download PDFInfo
- Publication number
- CN1079099C CN1079099C CN98122224A CN98122224A CN1079099C CN 1079099 C CN1079099 C CN 1079099C CN 98122224 A CN98122224 A CN 98122224A CN 98122224 A CN98122224 A CN 98122224A CN 1079099 C CN1079099 C CN 1079099C
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- China
- Prior art keywords
- polyacrylic acid
- initiator
- supercritical
- acid
- molecular weight
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- 238000000034 method Methods 0.000 title claims abstract description 20
- 229920002125 Sokalan® Polymers 0.000 title claims abstract description 18
- 239000004584 polyacrylic acid Substances 0.000 title claims abstract description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title 2
- 229910002092 carbon dioxide Inorganic materials 0.000 title 1
- 239000001569 carbon dioxide Substances 0.000 title 1
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 230000000977 initiatory effect Effects 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000012966 redox initiator Substances 0.000 claims description 5
- 230000002829 reductive effect Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 150000003384 small molecules Chemical class 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- -1 polypropylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 238000000194 supercritical-fluid extraction Methods 0.000 abstract description 2
- 238000007789 sealing Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000007664 blowing Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000006837 decompression Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
- C08F20/00—Homopolymers and 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
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/04—Acids, Metal salts or ammonium salts thereof
- C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a method of preparing polyacrylic acid in supercritical CO2 mediums by using an oxidation-reduction initiating system. In the prior art, the molecular weight of the prepared polyacrylic acid is low, and the purifying work is complicated. The oxidation-reduction initiating system provided by the present invention adopts oxidation-reduction initiator and a technique of supercritical fluid extraction for purifying; therefore, the polyacrylic acid with high molecular weight and high purity is obtained. The content of reaction products is improved to 99.2% from 80%; the viscosity-average molecular weight can reach about 1500000; CO2 can be circularly used in a sealing pipe.
Description
The present invention relates to oxidation-reduction initiating system at supercritical CO
2Prepare the high-molecular weight polyacrylic acid in the medium and improve polyacrylic purity with supercritical liquid extraction technique.
Polyacrylic acid and the traditional purposes of acrylic copolymer with vinylformic acid production are as water conditioners such as dispersion agent, flocculation agent and thickening materials.In the later stage seventies, polyacrylic acid and acrylic copolymer two brand-new application market-High hydrophilous resins occurred and have helped washing composition etc.When the polyacrylic acid molecular weight was too low, the polyacrylic acid molecular chain was shorter relatively, this will certainly impact polypropylene acid as the effect of High hydrophilous resin and flocculation agent etc.Bibliographical information is at supercritical CO at present
2The preparation polyacrylic acid all adopts AIBN (Diisopropyl azodicarboxylate) as initiator in the medium, the polyacrylic molecular weight that obtains is the highest also to be had only tens0000 (reference is: T.J.Romack, E.E.Maury and J.M.Desimone Macromolecules1995,8:912-915).In addition, if polyacrylic acid is used for industries such as daily use chemicals, food, then require purity very high.Prepare polyacrylic acid with traditional methods such as inverse suspension polymerization method and water solution polymerization process, reaction needs drying to dewater after finishing, and it is very big to consume energy, and removing small-molecule substances such as organic solvent, tensio-active agent and residual monomer simultaneously also is a loaded down with trivial details job.
The present invention uses water soluble oxidized one reduction initiating system and oil soluble oxygenant-water-soluble reductive agent initiator system, make viscosity-average molecular weight respectively and be about 1,230,000 and 1,500,000 polyacrylic acid, and product is water-soluble fine.Need not dry just can obtain the white powder of solid state after reaction finishes, use supercritical extraction technique simultaneously, the content of reaction product is brought up to about 99.2% by 80%.And CO
2Can in airtight pipeline, recycle.
The invention provides a kind of method for preparing the acid of high molecular high purity polypropylene in supercritical fluid media, this method is that vinylformic acid and initiator adding are had supercritical CO
2Carry out polymerization in the autoclave that medium exists, it is characterized in that adopting redox initiation system, the acrylic acid concentration of monomer is 10-30%, initiator concentration is monomeric 0.2-1%, polyreaction 8-10 hour, obtain high-molecular weight polyacrylic acid powder, use supercritical liquid extraction technique extracting unreacted small molecule monomer completely again, thereby further obtain highly purified polyacrylic acid.
The process of the method for the invention comprises: at first vinylformic acid and initiator are added autoclave, used initiator system is a redox initiation system, mainly contains following two kinds: water soluble oxidized reduction initiating system K
2S
2O
8And NaHSO
3And oil soluble oxygenant-water-soluble reductive agent initiator system BPO and NaHSO
3, initiator concentration is monomeric 0.2-1%, and wherein the molar ratio range of Oxidizing and Reducing Agents is 1: 0.6-1: 1.3.The acrylic acid concentration of monomer is 10-30%, and airtight then nitrogen blowing 10 minutes is got rid of the oxygen that remains in the still, with CO in the steel cylinder
2Charge into reactor, open high-pressure pump when being heated to 35 ℃ again and make CO in the still
2Boost to supercritical state, monomer is fully dissolved, keep-up pressure at last and be that 9-20MPa, temperature are 40-60 ℃, stirring reaction 8-10 hour, open air outlet valve Deng after the reaction end, use high-pressure pump to make the still internal pressure keep 10-20MPa, the temperature of autoclave remains on 40-100 ℃, and the resolver temperature is 50-70 ℃, slowly resolve, make the CO that flows through wet flow indicator
2Flow is 10-80 liter (atmospheric pressure state), closes the parsing valve after having resolved, on one side cooling, slowly CO is emitted in decompression on one side
2, can obtain the highly purified polyacrylic acid white powder of high molecular.
Example 1: in 100 milliliters of autoclaves, add 10 milliliters of vinylformic acid and K
2S
2O
8: NaHSO
3: H
2The O mol ratio is 1: 1.3: 151 0.1 milliliter of a solution, and airtight and nitrogen blowing was got rid of oxygen in 10 minutes.Heat up and charge into CO with high-pressure pump
2Make to reach 50 ℃, 14MPa, stirring reaction 8 hours, last cooling decompression obtains white moistening block, records viscosity-average molecular weight with viscosimetry and is about 1,230,000.
Example 2: in 100 milliliters of autoclaves, add 10 milliliters of vinylformic acid, 25 milligrams of BPO and 12 milligrams of NaHSO
3(mol ratio is 1: 1.1), airtight and nitrogen blowing was got rid of oxygen in 10 minutes.Heat up and charge into CO with high-pressure pump
2Make to reach 50 ℃, 9MPa, stirring reaction 8 hours, last cooling decompression obtains white moistening block, records viscosity-average molecular weight with viscosimetry and is about 1,500,000.
Add 20 milliliters of vinylformic acid and 50 milligrams of BPO and 24 milligrams of NaHSO in the example 3:100 milliliter autoclave
3(mol ratio is 1: 1.1), airtight and nitrogen blowing was got rid of the oxygen that remains in the still in 10 minutes, heated up and charged into CO
2, equitemperature is raised to 65 ℃, and after pressure reached 14MPa, stirring reaction 10 hours was opened air outlet valve, injects CO with high-pressure pump
2, keep-uping pressure is that 11MPa, resolver temperature are 55 ℃, autoclave temp is 50 ℃, slowly resolves the CO that makes by wet flow indicator
2Flow is 40 liters (atmospheric pressure states).Last cooling is on one side slowly reduced pressure on one side, and it is 99.2% white solid powder that the result obtains product content.
Add 10 milliliters of vinylformic acid and 25 milligrams of BPO and 12 milligrams of NaHSO in the example 4:100 milliliter autoclave
3(mol ratio is 1: 1.1), airtight and nitrogen blowing was got rid of the oxygen that remains in the still in 10 minutes, heated up and charged into CO
2, equitemperature is raised to 65 ℃, and after pressure reached 14MPa, stirring reaction 10 hours was opened air outlet valve, injects CO with high-pressure pump
2, keep-uping pressure is that 13MPa, resolver temperature are 65 ℃, autoclave temp is 60 ℃, slowly resolves the CO that makes by wet flow indicator
2Flow is 10 liters (atmospheric pressure states).Last cooling is on one side slowly reduced pressure on one side, and it is 92.6% white solid powder that the result obtains product content.
Claims (4)
1, a kind of method for preparing the acid of high molecular high purity polypropylene in supercritical fluid media, this method are that vinylformic acid and initiator adding are had supercritical CO
2Carry out polymerization in the autoclave that medium exists, it is characterized in that adopting redox initiation system, the acrylic acid concentration of monomer is 10-30%, initiator concentration is monomeric 0.2-1%, polyreaction 8-10 hour, obtain high-molecular weight polyacrylic acid powder, use supercritical liquid extraction technique extracting unreacted small molecule monomer completely again, thereby further obtain highly purified polyacrylic acid; Wherein said redox system is water soluble oxidized reduction initiating system K
2S
2O
8And NaHSO
3Or oil soluble oxygenant-water-soluble reductive agent initiator system BPO and NaHSO
3
2, according to the method described in the claim 1, it is characterized in that described redox initiator, the molar ratio range of Oxidizing and Reducing Agents is 1: 0.6-1: 1.3.
3,, it is characterized in that CO in the described redox initiation system polyreaction according to the method described in the claim 1
2Medium temperature is 40-60 ℃, and pressure is 9-20MPa.
4, according to the method described in the claim 1, it is characterized in that the described supercritical liquid extraction technique extracting small molecule monomer of using, autoclave temp is 40-100 ℃, and pressure is 10-20MPa, and the resolver temperature is 50-70 ℃, flows through the CO of wet flow indicator
2Flow under atmospheric pressure state is the 10-80 liter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98122224A CN1079099C (en) | 1998-11-26 | 1998-11-26 | Method for preparing polyacrylic acid in supercritical carbon dioxide medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98122224A CN1079099C (en) | 1998-11-26 | 1998-11-26 | Method for preparing polyacrylic acid in supercritical carbon dioxide medium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1228441A CN1228441A (en) | 1999-09-15 |
| CN1079099C true CN1079099C (en) | 2002-02-13 |
Family
ID=5227680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98122224A Expired - Fee Related CN1079099C (en) | 1998-11-26 | 1998-11-26 | Method for preparing polyacrylic acid in supercritical carbon dioxide medium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1079099C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3862489B2 (en) | 1999-12-14 | 2006-12-27 | 日東電工株式会社 | Re-peeling adhesive sheet |
| CN102030850B (en) * | 2010-10-29 | 2012-05-09 | 华南理工大学 | Method for preparing environmentally-friendly anhydrous phase paper coating |
| CN105585650B (en) * | 2014-10-21 | 2018-11-30 | 中国石油化工股份有限公司 | A kind of preparation method of high molecular weight polyacrylamide |
| CN105542067B (en) * | 2016-02-19 | 2017-10-31 | 山东省计量科学研究院 | One kind is based on supercritical CO2The method for preparing N vinyl formamides and acrylonitrile copolymer |
| CN108314751B (en) * | 2018-01-18 | 2020-06-19 | 嘉兴学院 | Method for synthesizing diacetone acrylamide and sodium acrylate copolymer |
| CN114316123B (en) * | 2021-12-28 | 2023-04-21 | 宁波南大光电材料有限公司 | Method for polymerizing photoresist resin by using supercritical carbon dioxide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1274942A (en) * | 1985-09-20 | 1990-10-02 | Wilfred G. Sertage, Jr. | Acrylic acid polymerization |
| CN1096792A (en) * | 1992-09-28 | 1994-12-28 | 罗姆和哈斯公司 | The method for preparing low-molecular weight polymer |
-
1998
- 1998-11-26 CN CN98122224A patent/CN1079099C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1274942A (en) * | 1985-09-20 | 1990-10-02 | Wilfred G. Sertage, Jr. | Acrylic acid polymerization |
| CN1096792A (en) * | 1992-09-28 | 1994-12-28 | 罗姆和哈斯公司 | The method for preparing low-molecular weight polymer |
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| Publication number | Publication date |
|---|---|
| CN1228441A (en) | 1999-09-15 |
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