CN114672011A - High molecular weight polyethylene glycol bulk polymerization method - Google Patents
High molecular weight polyethylene glycol bulk polymerization method Download PDFInfo
- Publication number
- CN114672011A CN114672011A CN202011551258.2A CN202011551258A CN114672011A CN 114672011 A CN114672011 A CN 114672011A CN 202011551258 A CN202011551258 A CN 202011551258A CN 114672011 A CN114672011 A CN 114672011A
- Authority
- CN
- China
- Prior art keywords
- molecular weight
- polyethylene glycol
- high molecular
- weight polyethylene
- polymerization process
- 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.)
- Granted
Links
- 229920001223 polyethylene glycol Polymers 0.000 title claims abstract description 27
- 239000004705 High-molecular-weight polyethylene Substances 0.000 title claims abstract description 18
- 238000012662 bulk polymerization Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 16
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000004014 plasticizer Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 20
- -1 fatty acid ester Chemical class 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 7
- 150000007530 organic bases Chemical class 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229910052730 francium Inorganic materials 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910007161 Si(CH3)3 Inorganic materials 0.000 claims description 2
- 229910003828 SiH3 Inorganic materials 0.000 claims description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 150000008052 alkyl sulfonates Chemical class 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 10
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 8
- 238000001035 drying Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000006276 transfer reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- 238000010926 purge Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- ZMJJCODMIXQWCQ-UHFFFAOYSA-N potassium;di(propan-2-yl)azanide Chemical compound [K+].CC(C)[N-]C(C)C ZMJJCODMIXQWCQ-UHFFFAOYSA-N 0.000 description 4
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 description 3
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VRRHDQCREAEINR-UHFFFAOYSA-N sodium;bis[tri(propan-2-yl)silyl]azanide Chemical compound [Na+].CC(C)[Si](C(C)C)(C(C)C)[N-][Si](C(C)C)(C(C)C)C(C)C VRRHDQCREAEINR-UHFFFAOYSA-N 0.000 description 2
- IKHKUYNSOCALHY-UHFFFAOYSA-N sodium;dihexylazanide Chemical compound [Na+].CCCCCC[N-]CCCCCC IKHKUYNSOCALHY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 101000611641 Rattus norvegicus Protein phosphatase 1 regulatory subunit 15A Proteins 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2648—Alkali metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2696—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the process or apparatus used
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The application relates to a bulk polymerization method of high molecular weight polyethylene glycol, which comprises the step of carrying out bulk polymerization on ethylene oxide in the presence of an organic weak base catalyst and a plasticizer to obtain the high molecular weight polyethylene glycol. The bulk polymerization method of the high molecular weight polyethylene glycol adopts a high-activity catalyst to reduce the chain transfer reaction in the polyethylene glycol synthesis process through low-temperature polymerization; meanwhile, the viscosity of a polymerization reaction system is reduced by adding the plasticizer, so that the bulk polymerization of the high molecular weight polyethylene glycol is realized, and a series of problems of separation, solvent drying and the like caused by solvent introduction are avoided while a high molecular weight is obtained.
Description
Technical Field
The present invention relates to the field of polyethylene glycol, and in particular to a bulk polymerization method of high molecular weight polyethylene glycol.
Background
Polyethylene glycol is an important chemical product, and is widely applied to the fields of biological medicines, daily chemicals, washing and the like due to good water solubility and biocompatibility, wherein the polyethylene glycol with high molecular weight (the molecular weight is more than 20000) is used as an adhesive and the like to be applied to the fields of biology, medicines and the like due to the advantages of good compatibility, high viscosity and the like. The molecular weight of the traditional polyethylene glycol product is mainly concentrated on 200-. The method is difficult to obtain the polyethylene glycol with the molecular weight more than 20000, which is mainly because the catalyst used in the method needs to initiate the polymerization of ethylene oxide under the high temperature condition, and the strong chain transfer effect exists in the polymerization reaction of the ethylene oxide under the high temperature environment, which leads to the chain scission of polymer molecules, and along with the increase of the molecular weight, the viscosity in a reaction system is increased sharply, the mass and heat transfer are difficult, and the increase of the molecular weight is further hindered. In order to improve the mass transfer and heat transfer problems in the later reaction period, a solvent is added for solution polymerization, but the method needs to remove the solvent after the reaction is finished, so that the energy consumption and pollution are increased, and the viscosity of the system is increased along with the removal of the solvent, so that the solvent is difficult to remove.
Disclosure of Invention
It is a main object of the present invention to provide a bulk polymerization method of a high molecular weight polyethylene glycol (e.g., having a weight average molecular weight of 2 to 5 ten thousand) comprising bulk polymerizing ethylene oxide in the presence of an organic weak base catalyst and a plasticizer to obtain the high molecular weight polyethylene glycol;
wherein the weak organic base catalyst has the following structure:
wherein M is one or more of Li, Na, K, Rb, Cs and Fr; r and R`Same or different, selected from H, C1-C15Alkyl radical, C1-C6Haloalkyl, -SiR1R2R3；
Wherein R is1、R2、R3Each independently selected from H, C1-C6An alkyl group.
In one embodiment, R and R`Same or different, selected from H, -CH3、-CH2CH3、-CH2CH2CH3、-CH2(CH2)2CH3、-CH2(CH2)3CH3、-CH2(CH2)4CH3、-CH2(CH2)5CH3、-CH2(CH2)6CH3、-CH2(CH2)7CH3、-CH2(CH2)8CH3、-CH2(CH2)9CH3、-CH2(CH2)10CH3、-CH(CH3)2、-C(CH3)3、-SiH3、-Si(CH3)3、-Si(CH2CH3)3、-Si[CH(CH3)2]3、-Si[C(CH3)3]3、-CF2CF3。
In one embodiment, the weak organic base catalyst is used in an amount of 0.001% to 0.01%, preferably 0.002% to 0.006%, based on the total mass of ethylene oxide.
In one embodiment, the plasticizer is one or more of phthalate esters, aliphatic dibasic acid esters, fatty acid esters, benzenepolycarboxylic acid esters, polyol esters, epoxy hydrocarbons, alkyl sulfonate esters.
In one embodiment, the plasticizer is used in an amount of 0.1% to 5%, preferably 1% to 3%, of the total mass of ethylene oxide.
In one embodiment, the reaction system further comprises an initiator in an amount of 0.001% to 0.01% by mass of ethylene oxide, wherein 0.002% to 0.05% is preferred.
In one embodiment, the reaction system pressure is from 0.1MPa to 2MPa, with from 0.2MPa to 0.5MPa being preferred.
In one embodiment, the reaction temperature is from 20 ℃ to 80 ℃, with from 40 ℃ to 60 ℃ being preferred.
In one embodiment, the high molecular weight polyethylene glycol has a weight average molecular weight of 2 to 5 million and a molecular weight distribution coefficient PDI < 1.2.
The bulk polymerization method of the high molecular weight polyethylene glycol adopts a high-activity catalyst to reduce the chain transfer reaction in the polyethylene glycol synthesis process through low-temperature polymerization; meanwhile, the viscosity of a polymerization reaction system is reduced by adding the plasticizer, so that the bulk polymerization of the high molecular weight polyethylene glycol is realized, and a series of problems of separation, solvent drying and the like caused by solvent introduction are avoided while a high molecular weight is obtained.
Detailed Description
The application provides a bulk polymerization method of high molecular weight polyethylene glycol, which comprises the steps of carrying out bulk polymerization on ethylene oxide in the presence of an organic weak base catalyst and a plasticizer to obtain the high molecular weight polyethylene glycol;
wherein the weak organic base catalyst has the following structure:
wherein M is one or more of Li, Na, K, Rb, Cs and Fr; r and R`Same or different, selected from H, C1-C15Alkyl radical, C1-C6Haloalkyl, -SiR1R2R3；
Wherein R is1、R2、R3Each independently selected from H, C1-C6An alkyl group.
In this application, C1-C15Alkyl includes but is not limited to-CH3、-CH2CH3、-CH2CH2CH3、-CH2(CH2)2CH3、-CH2(CH2)3CH3、-CH2(CH2)4CH3、-CH2(CH2)5CH3、-CH2(CH2)6CH3、-CH2(CH2)7CH3、-CH2(CH2)8CH3、-CH2(CH2)9CH3、-CH2(CH2)10CH3、-CH(CH3)2、-C(CH3)3And the like. C1-C6Alkyl includes but is not limited to-CH3、-CH2CH3、-CH(CH3)2、-C(CH3)3And the like. C1-C6Haloalkyl includes, but is not limited to, -CF3、-CF2CF3And the like.
The use of the weak organic base catalyst in the process of the present application can realize the polymerization of ethylene oxide under low temperature conditions, and can also reduce chain transfer reaction during the polymerization. In the present application, the weak organic base catalyst is used in an amount of 0.001% to 0.01%, wherein 0.002% to 0.006% is preferred, based on the total mass of ethylene oxide.
In the present application, plasticizers are also used. The viscosity of a polymerization reaction system is reduced by adding the plasticizer, so that the bulk polymerization of the high molecular weight polyethylene glycol is realized, and a series of problems of separation, solvent drying and the like caused by solvent introduction are avoided while a higher molecular weight is obtained. In one embodiment, the plasticizer is one or more of phthalate esters, aliphatic dibasic acid esters, fatty acid esters, benzenepolycarboxylic acid esters, polyol esters, epoxy hydrocarbons, alkyl sulfonate esters. In one embodiment, the plasticizer is used in an amount of 0.1% to 5%, preferably 1% to 3%, of the total mass of ethylene oxide.
In the present application, the reaction system may further comprise an initiator in an amount of 0.001% to 0.01% by mass of ethylene oxide, wherein 0.002% to 0.05% is preferred. The initiator for use herein may be ethylene glycol.
In one embodiment, the polymerization reaction herein has a reaction system pressure of 0.1MPa to 2MPa, with 0.2MPa to 0.5MPa being preferred. In one embodiment, the reaction temperature is from 20 ℃ to 80 ℃, with from 40 ℃ to 60 ℃ being preferred.
Specifically, the bulk polymerization process of the present application can be carried out as follows: adding a certain amount of initiator ethylene glycol, catalyst and plasticizer into a reactor, N2After purging, the temperature is raised to the reaction temperature, ethylene oxide is continuously added, and the pressure of the reaction system is maintained within a set pressure range. After the ethylene oxide is added, the reaction is carried out until the system pressure does not drop any more, and N is discharged2And obtaining the target product.
In one embodiment, the resulting polyethylene glycol has a high molecular weight, which may have a weight average molecular weight of greater than or equal to 2 ten thousand, such as greater than or equal to 25000, such as from 2 ten thousand to 5 ten thousand, such as from 3 ten thousand to 5 ten thousand. The polyethylene glycols obtained also have a narrow molecular weight distribution with a molecular weight distribution coefficient PDI <1.2, in particular less than or equal to 1.1.
Example 1
A2L autoclave was charged with 3g of ethylene glycol, 0.04g of diisopropylamino potassium and 25g of phthalate. Stirring until the diisopropylamino potassium is completely dissolved or uniformly dispersed. N is a radical of2Purging for 3-5 times, and heating to 50 ℃. 1500g of ethylene oxide was continuously added to maintain the pressure in the reaction system at 0.6 MPa. Reacting until the system pressure does not drop any more, discharging N2And cooling to obtain the target product PEG-1#, the weight average molecular weight 31000 and the molecular weight distribution coefficient 1.03.
Example 2
A1L autoclave was charged with 1g of ethylene glycol, 0.02g of sodium dihexylamide, and 10g of C12 fatty acid methyl ester. Stirring until the dihexyl sodium amide is completely dissolved or uniformly dispersed. N is a radical of2Purging for 3-5 times, and heating to 60 ℃. 800g of ethylene oxide was continuously fed to maintain the pressure in the reaction system at 0.5 MPa. Reacting until the system pressure does not drop any more, discharging N2And cooling to obtain the target product PEG-2#, the weight-average molecular weight of 49500 and the molecular weight distribution coefficient of 1.05.
Example 3
A2L autoclave was charged with 4g of ethylene glycol, 0.072g of sodium bis (triisopropylsilyl) amide, and 21g of a benzenepolycarboxylic acid ester. Stirring until the sodium bis (triisopropylsilyl) amide is completely dissolved or uniformly dispersed. N is a radical of2Purging for 3-5 times, and heating to 60 ℃. 1400g of ethylene oxide was continuously fed to maintain the pressure in the reaction system at 0.4 MPa. Reacting until the system pressure does not drop any more, discharging N2And cooling to obtain the target product PEG-3#, the weight average molecular weight 22000 and the molecular weight distribution coefficient 1.08.
Example 4
A500 ml autoclave was charged with 0.5g of ethylene glycol, 0.015g of potassium didodecylaminoate and 4g of dodecylsulfonate. Stirring toAfter the didodecyl amino potassium is completely dissolved or uniformly dispersed. N is a radical of2Purging for 3-5 times, and heating to 60 ℃. 300g of ethylene oxide was continuously fed to maintain the pressure of the reaction system at 0.4 MPa. Reacting until the system pressure does not drop any more, discharging N2And cooling to obtain the target product PEG-4#, the weight average molecular weight 40200 and the molecular weight distribution coefficient 1.1.
Example 5
A1L autoclave was charged with 1.5g of ethylene glycol, 0.02g of diisopropylamino potassium and 18 g of phthalate. Stirring until the diisopropylamino potassium is completely dissolved or uniformly dispersed. N is a radical of2Purging for 3-5 times, and heating to 55 ℃. 700g of ethylene oxide was continuously fed to maintain the pressure in the reaction system at 0.4 MPa. Reacting until the system pressure does not drop any more, discharging N2And cooling to obtain the target product PEG-5#, the weight average molecular weight of 31200 and the molecular weight distribution coefficient of 1.08.
Unless otherwise defined, all terms used herein have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are for illustrative purposes only and are not intended to limit the scope of the present invention, and those skilled in the art may make various other substitutions, alterations, and modifications within the scope of the present invention, and thus, the present invention is not limited to the above-described embodiments but only by the claims.
Claims (9)
1. A bulk polymerization method of high molecular weight polyethylene glycol comprises the steps of carrying out bulk polymerization on ethylene oxide in the presence of an organic weak base catalyst and a plasticizer to obtain the high molecular weight polyethylene glycol;
wherein the weak organic base catalyst has the following structure:
wherein M is one or more of Li, Na, K, Rb, Cs and Fr; r and R`Same or different, selected from H, C1-C15Alkyl radical, C1-C6HalogenatedAlkyl, -SiR1R2R3；
Wherein R is1、R2、R3Each independently selected from H, C1-C6An alkyl group.
2. The polymerization process of claim 1, wherein R and R`Same or different, selected from H, -CH3、-CH2CH3、-CH2CH2CH3、-CH2(CH2)2CH3、-CH2(CH2)3CH3、-CH2(CH2)4CH3、-CH2(CH2)5CH3、-CH2(CH2)6CH3、-CH2(CH2)7CH3、-CH2(CH2)8CH3、-CH2(CH2)9CH3、-CH2(CH2)10CH3、-CH(CH3)2、-C(CH3)3、-SiH3、-Si(CH3)3、-Si(CH2CH3)3、-Si[CH(CH3)2]3、-Si[C(CH3)3]3、-CF2CF3。
3. The polymerization process according to claim 1, wherein the weak organic base catalyst is used in an amount of 0.001% to 0.01%, preferably 0.002% to 0.006%, based on the total mass of ethylene oxide.
4. The polymerization process of claim 1, wherein the plasticizer is one or more of a phthalate, an aliphatic dibasic acid ester, a fatty acid ester, a benzenepolyacid ester, a polyol ester, an epoxy hydrocarbon, an alkyl sulfonate.
5. The polymerization process according to claim 1, wherein the plasticizer is used in an amount of 0.1% to 5%, preferably 1% to 3%, of the total mass of ethylene oxide.
6. The polymerization process according to claim 1, wherein the reaction system further comprises an initiator in an amount of 0.001 to 0.01%, preferably 0.002 to 0.05%, based on the total mass of ethylene oxide.
7. The polymerization process according to claim 1, wherein the reaction system pressure is from 0.1MPa to 2MPa, preferably from 0.2MPa to 0.5 MPa.
8. The polymerization process according to claim 1, wherein the reaction temperature is from 20 ℃ to 80 ℃, wherein preferably from 40 ℃ to 60 ℃.
9. The polymerization process of any one of claims 1-8, wherein the high molecular weight polyethylene glycol has a weight average molecular weight of 2-5 ten thousand and a molecular weight distribution coefficient PDI < 1.2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011551258.2A CN114672011B (en) | 2020-12-24 | 2020-12-24 | High molecular weight polyethylene glycol bulk polymerization method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011551258.2A CN114672011B (en) | 2020-12-24 | 2020-12-24 | High molecular weight polyethylene glycol bulk polymerization method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114672011A true CN114672011A (en) | 2022-06-28 |
| CN114672011B CN114672011B (en) | 2024-01-26 |
Family
ID=82070793
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011551258.2A Active CN114672011B (en) | 2020-12-24 | 2020-12-24 | High molecular weight polyethylene glycol bulk polymerization method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114672011B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013241581A (en) * | 2012-04-23 | 2013-12-05 | Takemoto Oil & Fat Co Ltd | Method of manufacturing polyether |
| CN104370711A (en) * | 2014-11-03 | 2015-02-25 | 上海三瑞高分子材料有限公司 | Alkenyl polyalkaneneglycol monomer, comb copolymer prepared from monomer and preparation method thereof |
| JP2015214605A (en) * | 2014-05-07 | 2015-12-03 | 旭硝子株式会社 | Hydroxyl group-containing polyether production method, hydrolyzable silyl group-containing polyether production method, and urethane prepolymer production method |
-
2020
- 2020-12-24 CN CN202011551258.2A patent/CN114672011B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013241581A (en) * | 2012-04-23 | 2013-12-05 | Takemoto Oil & Fat Co Ltd | Method of manufacturing polyether |
| JP2015214605A (en) * | 2014-05-07 | 2015-12-03 | 旭硝子株式会社 | Hydroxyl group-containing polyether production method, hydrolyzable silyl group-containing polyether production method, and urethane prepolymer production method |
| CN104370711A (en) * | 2014-11-03 | 2015-02-25 | 上海三瑞高分子材料有限公司 | Alkenyl polyalkaneneglycol monomer, comb copolymer prepared from monomer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114672011B (en) | 2024-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100577697C (en) | Method for producing an (meth)acrylate syrup | |
| JP5652691B2 (en) | Polyalkylene glycol derivative and method for producing the same | |
| WO2000004054A1 (en) | Process for producing methacrylic polymer | |
| US9321867B2 (en) | Synthesis of 2,3,3,3-tetrafluoropropene/vinylidene fluoride copolymers | |
| WO2023000871A1 (en) | Method for preparing high molecular weight furan polyamide | |
| KR20010007301A (en) | Polyvinyl alcohol polymer production and polyvinyl alcohol polymer | |
| CN102295718B (en) | Bio-based high-branched polyester and preparation method thereof | |
| CN112898480A (en) | Hydroxyethyl acrylate eutectic solvent, hydroxyethyl acrylate hydrogel, preparation method and application | |
| EP4389785A1 (en) | Method for preparing ethylene-vinyl alcohol copolymer | |
| KR20100100392A (en) | Hexafluoropropylene oxide polymer compositions and preparing method of hexafluoropropylene oxide polymer using hexafluoropropylene oligomer | |
| CN114672011B (en) | High molecular weight polyethylene glycol bulk polymerization method | |
| CN111936548B (en) | Method for producing multi-arm polyethylene glycol derivative | |
| CN111533852A (en) | Solid polycarboxylic acid water reducing agent and preparation method thereof | |
| CN105541625A (en) | Method for preparing acetoacetoxy ethyl methacrylate | |
| EP2280037A1 (en) | Fluorine-containing polyether compound and method for producing the same | |
| JP5716266B2 (en) | Method for producing methacrylic resin | |
| CN102875405B (en) | Polyol of basic amino acid or ester thereof, preparation and application thereof | |
| TWI518100B (en) | Method for producing methacrylic polymer | |
| CN106046238A (en) | Unsaturated polyether monomer and method for synthesizing and preparing polycarboxylate-type water reducing agent | |
| CN112646162A (en) | Preparation method of polyether chain extender for waterborne polyurethane | |
| CN102850481B (en) | Preparation method of (methyl) acrylate polymer with dendritic structure | |
| CN110746529A (en) | Synthesis method of zwitterionic polymer | |
| US2835658A (en) | Process for preparing polystyrene block polymers | |
| JP2001233912A (en) | Manufacturing method of methacrylic polymer | |
| CN113993834B (en) | Process for producing diester |
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 |