CN111087599B - Process for preparing high molecular weight polyethylene oxides - Google Patents
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- CN111087599B CN111087599B CN201811235290.2A CN201811235290A CN111087599B CN 111087599 B CN111087599 B CN 111087599B CN 201811235290 A CN201811235290 A CN 201811235290A CN 111087599 B CN111087599 B CN 111087599B
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- 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
- C08G65/2612—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 aromatic or arylaliphatic hydroxyl groups
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- 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
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- 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
- C08G65/2669—Non-metals or compounds thereof
- C08G65/2675—Phosphorus or compounds thereof
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- 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
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Abstract
The invention discloses a method for preparing high molecular weight polyethylene oxide by using a phosphonitrile oxide catalyst. Mainly solves the problem that polyoxyethylene prepared by using a phosphazene oxide catalyst in the prior art has lower molecular weight, and adopts the method for preparing the polyoxyethylene with high molecular weight, which comprises the following steps: taking a phosphonitrile oxide compound as a catalyst, ethylene oxide as a raw material and an active hydrogen compound as an initiator to react in a solvent to obtain the high molecular weight polyethylene oxide; wherein the reaction temperature is 40-160 ℃, the reaction pressure is not higher than 4.0MPa, and the reaction time is 8-100 hours; the phosphonitrile oxide compound has the structure shown in the formula (1), so that the problem is solved well, and the phosphonitrile oxide compound can be used in industrial production of high molecular weight polyethylene oxide.
Description
Technical Field
The invention discloses a method for preparing high molecular weight polyethylene oxide by using a phosphonitrile oxide catalyst.
Background
The polyethylene oxide has a plurality of applications in daily chemical products, biological medicine, building industry, steel industry, energy storage and electronics. The ethoxylation catalyst is strong base catalyst such as KOH, naOH, etc., or BF 3 And the like. However, synthesis of high molecular weight polyethylene oxide requires use of flammable organometallic compounds such as aluminum alkyls, which poses a major safety problem in both laboratory and industrial production.
Phosphazene compounds are a class of strong organic bases that can catalyze the ring-opening polymerization of cyclic monomers such as lactones, lactides, cyclic carbonates, cyclic siloxanes, epoxyolefins, etc., and also the free-radical polymerization of polar vinyl monomers such as acrylates, methacrylates, etc. (US 5399662 cn 1200380a: maromol. Rapid commu., 16,449-453 (1995); macromol. Sym., 107,331-340 (1996)).
The invention discloses a method for preparing high molecular weight polyethylene oxide by utilizing a self-made phosphonitrile oxide catalyst.
Disclosure of Invention
The technical problem to be solved by the invention is that the molecular weight of polyoxyethylene prepared by using a phosphazene catalyst is low in the prior art, and the invention provides a method for preparing high molecular weight polyoxyethylene, which has the advantage of high molecular weight of the prepared polyoxyethylene.
In order to solve the technical problems, the invention adopts the following technical scheme: a process for preparing high molecular weight polyethylene oxide comprising the steps of:
taking a phosphonitrile oxide compound as a catalyst, ethylene oxide as a raw material and an active hydrogen compound as an initiator to react in a solvent to obtain the high molecular weight polyethylene oxide; wherein the phosphazene oxide compound has a structure represented by formula (1):
in the formula (1), R 1 、R 2 Each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a phenyl group having 6 to 10 carbon atoms and being unsubstituted or substituted, or a phenylalkyl group having 6 to 10 carbon atoms and being unsubstituted or substituted; x represents the amount of water molecules in a molar ratio, and x =0 to 5.0.
In the technical scheme, the reaction temperature of the reaction is preferably 40-160 ℃, the reaction pressure is preferably not higher than 4.0MPa, and the reaction time is preferably 8-100 hours.
In the above technical solution, the preferable R 1 And R 2 Or R is 1 And R 2 Are bonded to each other to form a ring structure.
In the above technical scheme, R 1 And R 2 Preferably at least one or a mixture of two or more of aliphatic hydrocarbon groups having 1 to 8 carbon atoms.
In the above technical scheme, R 1 、R 2 Each independently selected from alkyl groups having 1 to 10 carbon atoms.
In the above technical scheme, R 1 And R 2 Preferably methyl.
In the above-described embodiment, x =0 to 2.0 is preferable.
In the above technical solution, the active hydrogen compound is preferably selected from water or an organic compound having a structure of-OH or an organic compound having a structure of-NH-.
In the above-mentioned embodiment, the organic compound having the structural formula-OH preferably includes, for example, carboxylic acids having 1 to 20 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, lauric acid, etc.; polycarboxylic acids having 2 to 20 carbon atoms and 2 to 6 carboxylic acids, such as oxalic acid, malonic acid, succinic acid, maleic acid terephthalic acid, etc.; alcohols having 1 to 20 carbon atoms such as methanol, ethanol, phenol, n-propanol, isopropanol, n-butanol, t-butanol, isoamyl alcohol, n-octadecyl alcohol, phenol, substituted phenols and the like; polyhydric alcohols having 2 to 20 carbon atoms and 2 to 8 hydroxyl groups such as ethylene glycol, propylene glycol, glycerin, diglycerin, butylene glycol, pentaerythritol, etc.; saccharides or derivatives thereof such as glucose, sorbitol, fructose, sucrose, bisphenol A and the like, and polyether polyols having 2 to 8 terminal groups and 1 to 8 hydroxyl groups on the terminal groups and having a number average molecular weight of 200 to 30000.
In the above-mentioned embodiments, the organic compound having the structure-NH-preferably includes, for example, primary aliphatic or aromatic amines having 1 to 20 carbon atoms, such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, benzylamine, aniline, etc.; secondary aliphatic or aromatic amines having 2 to 20 carbon atoms such as diethylamine, methylethylamine, di-n-propylamine, diphenylamine and the like; polyamines having 2 to 20 carbon atoms and having 2 to 3 primary or secondary amine groups, such as ethylenediamine, hexamethylenediamine, melamine, N, N' -dimethylethyleneamine, etc.; unsaturated cyclic secondary amines having 4 to 20 carbon atoms, such as 3-pyrroline, pyrrole, indole, carbazole, imidazole, pyrazole, purine, etc.; cyclic polyamines having 4 to 20 carbon atoms and having 2 to 3 secondary amine groups, such as pyrazine, piperazine, etc.; substituted or N-monosubstituted acid amides having 2 to 20 carbon atoms, such as acetamide, propionamide, N-methylpropionamide, 2-pyrrolidone, etc.; and imides of dicarboxylic acids having 4 to 10 carbon atoms, such as succinimide, maleimide, etc.
In the above technical solution, the solvent is selected from aliphatic hydrocarbons, aromatic hydrocarbons, ethers, aprotic solvents; further preferred said aliphatic hydrocarbon is selected from pentane, hexane, heptane, cyclohexane; the aromatic hydrocarbon is preferably selected from benzene, toluene; the ethers are preferably selected from diethyl ether, tetrahydrofuran, anisole; the aprotic solvent is preferably selected from dimethyl sulfoxide, N-dimethylformamide.
Other active hydrides useful in the present invention include polymers having terminal active hydrogen atoms such as polyalkylene oxides, polylactides, polyamides, polycarbonates, polysiloxanes, and copolymers thereof.
In the process of the present invention, the amount of the phosphazene oxide compound represented by the general formula (1) to be used is not particularly limited, but is usually in the range of 1X 10 -10 ～1×10 -1 Preferably 1X 10 -7 ～1×10 -1 mol per mol of epoxy compound.
The type of polymerization reaction in the process of the present invention is not particularly limited. A method of feeding ethylene oxide to a reactor in which a phosphazene oxide compound represented by the general formula (1) or the phosphazene oxide compound and an active hydrogen compound are fed together with a solvent (when used) at a time, intermittently or continuously is generally used. The reaction temperature is between 40 and 160 ℃, preferably in the range of 50 to 150 ℃, more preferably in the range of 60 to 130 ℃. The reaction pressure is not higher than 4.0MPa, preferably in the range of 0.01 to 1.5MPa, more preferably in the range of 0.1 to 1.0 MPa. The reaction time varies depending on the type of substance used, the amount used, the polymerization temperature and the pressure, and is preferably in the range of 8 to 100 hours, more preferably in the range of 8 to 30 hours.
In the process of the present invention, in order to obtain high molecular weight PEO, a solvent is used. The solvent used includes, for example, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane and the like; aromatic hydrocarbons such as benzene, toluene, etc.; ethers such as diethyl ether, tetrahydrofuran, anisole and the like; aprotic solvents such as dimethylsulfoxide, N, N-dimethylformamide and the like. In addition to these, any solvent can be used as long as it does not inhibit the polymerization reaction of the method of the present invention.
The polymerization reaction in the process of the present invention can also be carried out in the presence of an inert gas such as nitrogen, argon, etc., as required.
By adopting the technical scheme of the invention, the prepared polyoxyethylene has high molecular weight, the molecular weight can reach 230000 in GPC test, the molecular weight distribution can be less than 1.07, and better technical effect is achieved.
The present invention will be described in more detail with reference to examples, but the present invention is not to be construed as being limited to the examples.
Detailed Description
[ example 1 ]
Into a 500ml glass three-necked flask equipped with a temperature gauge, a stirring device and a raw material feed port were charged 0.15g (0.001 mol) of 4-ethyl-2-methoxyphenol, 0.40g (0.1 mol) of tris (tetramethylguanidino) phosphonium oxide { [ (Me) 2 N) 2 C＝N] 3 P = O },100ml of toluene, nitrogen substitution, slow addition of 200g of ethylene oxide at 100 degrees, reaction for 20h, draining of solvent and unreacted monomers to give a polymer. GPC measured molecular weight 220000, molecular weight distribution 1.10.
[ example 2 ] A method for producing a polycarbonate
Into a 500ml glass three-necked flask equipped with a temperature gauge, a stirring device and a raw material feed port were charged 0.15g (0.001 mol) of 4-ethyl-2-methoxyphenol, 0.389g (0.1 mol) of tris (tetramethylguanidino) phosphonium oxide { [ (Me) 2 N) 2 C＝N] 3 P = O },100mL of tetrahydrofuran, replaced with nitrogen, at 50 degrees, 200g of ethylene oxide was slowly added over 40 hours, and after cooling to room temperature, the reaction solution was poured into n-hexane, filtered and dried to obtain a polymer. GPC measured molecular weight 230000, molecular weight distribution 1.07.
[ example 3 ]
Into a 500ml glass three-necked flask equipped with a temperature gauge, a stirring device and a raw material feed port, 0.094g (0.001 mol) of phenol, 0.40g (0.1 mol) of tris (tetramethylguanidino) phosphonium oxide { [ (Me) 2 N) 2 C＝N] 3 P = O },100ml toluene, replacing with nitrogen, slowly adding 200g ethylene oxide at 100 ℃, reacting for 30h, and draining the solvent and unreacted monomers to obtainA polymer. GPC measured molecular weight 210000, molecular weight distribution 1.12.
[ example 4 ] A method for producing a polycarbonate
Into a 500ml glass three-necked flask equipped with a temperature gauge, a stirring device and a raw material feed port, 0.094g (0.001 mol) of phenol, 0.40g (0.1 mol) of tris (tetramethylguanidino) phosphonium oxide { [ (Me) 2 N) 2 C＝N] 3 P = O },100ml tetrahydrofuran, replaced with nitrogen, slowly adding 200g of ethylene oxide at 50 ℃, reacting for 30h, cooling to room temperature, pouring the reaction solution into n-hexane, filtering and drying to obtain the polymer. GPC measured molecular weight 220000, molecular weight distribution 1.08.
[ example 5 ]
Into a 500ml glass three-necked flask equipped with a temperature gauge, a stirring device and a raw material feed port, 0.27g (0.001 mol) of n-octadecanol, 0.40g (0.01 mol) of tris (tetramethylguanidino) phosphonium oxide { [ (Me) 2 N) 2 C＝N] 3 P = O },100ml tetrahydrofuran, replacing with nitrogen, slowly adding 200g of ethylene oxide at 100 ℃, reacting for 30h, cooling to room temperature, pouring the reaction solution into n-hexane, filtering and drying to obtain the polymer. GPC measured molecular weight 200000, molecular weight distribution 1.08.
Comparative example 1
100g (0.1 mol) of PEG-1000,5g (1 mol) of KOH are added into a reactor with a temperature meter, a stirring device and a raw material feeding port of 2.5L, nitrogen is replaced, vacuum pumping is carried out for 1h at 100 ℃, ethylene oxide is slowly added, after 1500g of ethylene oxide is added, the pressure is not reduced any more, unreacted monomers are pumped out, and the polymer is discharged. GPC measured molecular weight 13000, molecular weight distribution 1.50.
Comparative example 2
In a 2.5L reactor equipped with a temperature meter, a stirring device and a raw material feed port, 15.22g (0.1 mol) of 4-ethyl-2-methoxyphenol and 3.89g (1 mol) of tris (tetramethylguanidino) phosphonium oxide { [ (Me) 2 N) 2 C＝N] 3 P = O }, replacing with nitrogen, slowly adding 1985g of ethylene oxide at 100 ℃, controlling the pressure below 0.3MPa, and draining unreacted monomers to release the polymer. GPC measurement molecular weight 23000, molecular weight fractionCloth 1.40.
According to the method, the high molecular weight polyethylene oxide can be prepared by a solvent method by utilizing the phosphonitrile oxide catalyst, and the method has high activity and narrow molecular weight distribution.
Claims (10)
1. A process for preparing high molecular weight polyethylene oxide comprising the steps of:
taking a phosphonitrile oxide compound as a catalyst, ethylene oxide as a raw material and an active hydrogen compound as an initiator, and reacting in a tetrahydrofuran solvent at 50 ℃ to obtain the high molecular weight polyethylene oxide; wherein the phosphazene oxide compound has a structure represented by formula (1):
in the formula (1), R 1 、R 2 Each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a phenyl group having 6 to 10 carbon atoms which is unsubstituted or substituted, or a phenylalkyl group having 6 to 10 carbon atoms which is unsubstituted or substituted; x represents the amount of water molecules in molar ratio, x =0 to 5.0;
the amount of the phosphazene oxide compound represented by the general formula (1) used is 1X 10 -10 ～1×10 -1 mol per mol of epoxy compound.
2. The method for producing high molecular weight polyethylene oxide according to claim 1, characterized in that R is 1 And R 2 Are bonded to each other to form a ring structure.
3. The method for producing high molecular weight polyethylene oxide according to claim 1, characterized in that R is 1 And R 2 At least one or a mixture of two or more selected from aliphatic hydrocarbon groups of 1 to 8 carbon atoms.
4. Preparation of high molecular weight according to claim 1 or 2Process for the preparation of polyethylene oxide, characterized in that R is 1 、R 2 Each independently represents an alkyl group having 1 to 10 carbon atoms.
5. The method according to claim 4, wherein R is 1 And R 2 Is methyl.
6. The method for producing high molecular weight polyethylene oxide according to claim 1 or 2, characterized in that the reaction pressure of the reaction is not higher than 4.0MPa and the reaction time is 8 to 100 hours.
7. The method for producing high molecular weight polyethylene oxide according to any one of claims 1 to 3, characterized in that x =0 to 2.0.
8. The method for producing high molecular weight polyethylene oxide according to claim 1, characterized in that the active hydrogen compound is selected from water or an organic compound containing the structure-OH or an organic compound containing the structure-NH-.
9. The method for producing high molecular weight polyethylene oxide according to claim 8, characterized in that the organic compound containing the structural formula-OH is selected from: at least one of carboxylic acids having 1 to 20 carbon atoms, alcohols having 1 to 20 carbon atoms, polyether polyols having 2 to 8 terminal groups and 1 to 8 hydroxyl groups on the terminal groups and having a number average molecular weight of 200 to 30000.
10. The process for preparing high molecular weight polyethylene oxide according to claim 8, characterized in that the organic compound containing the structure-NH-is selected from: at least one of polyamines having 2 to 20 carbon atoms and having 2 to 3 primary or secondary amine groups, and cyclic polyamines having 4 to 10 carbon atoms and having 2 to 3 secondary amine groups.
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| CN103946270A (en) * | 2011-11-22 | 2014-07-23 | 西奥公司 | Synthesis of high molecular weight peo using non-metal initiators |
| CN104448287A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Preparation method of polyether polyol |
| CN104927035A (en) * | 2014-03-17 | 2015-09-23 | 中国石油化工股份有限公司 | Method for preparing polymer through ring opening polymerization of cyclic monomer |
| CN108239265A (en) * | 2016-12-26 | 2018-07-03 | 青岛科技大学 | Organic phosphazenium catalyst and its preparation method and application |
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| CN101942081A (en) * | 2010-08-13 | 2011-01-12 | 浙江大学 | Method for preparing aliphatic polycarbonates by catalyzing by metal cyanide coordination catalyst |
| CN103946270A (en) * | 2011-11-22 | 2014-07-23 | 西奥公司 | Synthesis of high molecular weight peo using non-metal initiators |
| CN104448287A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Preparation method of polyether polyol |
| CN104927035A (en) * | 2014-03-17 | 2015-09-23 | 中国石油化工股份有限公司 | Method for preparing polymer through ring opening polymerization of cyclic monomer |
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