CN112029085A - Method for preparing polyether polyol by adopting solution polymerization method - Google Patents
Method for preparing polyether polyol by adopting solution polymerization method Download PDFInfo
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- CN112029085A CN112029085A CN202010804074.6A CN202010804074A CN112029085A CN 112029085 A CN112029085 A CN 112029085A CN 202010804074 A CN202010804074 A CN 202010804074A CN 112029085 A CN112029085 A CN 112029085A
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- polyether polyol
- solution polymerization
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 71
- 229920000570 polyether Polymers 0.000 title claims abstract description 71
- 229920005862 polyol Polymers 0.000 title claims abstract description 64
- 150000003077 polyols Chemical class 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000010528 free radical solution polymerization reaction Methods 0.000 title claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000008234 soft water Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000004593 Epoxy Substances 0.000 claims description 21
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 18
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical group CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000007872 degassing Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 35
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000017525 heat dissipation Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 238000001816 cooling Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- -1 alcohol amine Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000010198 maturation time Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Classifications
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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
- C08G65/2618—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 nitrogen
- C08G65/2621—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 nitrogen containing amine groups
- C08G65/2624—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 nitrogen containing amine groups containing aliphatic amine groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/04—Breaking emulsions
- B01D17/047—Breaking emulsions with separation aids
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Polyethers (AREA)
Abstract
According to the method for preparing the polyether polyol by adopting the solution polymerization method, the solvent consumption in the solution polymerization method is 10-50 wt% of the theoretical yield of the polyether polyol. According to the method for preparing the polyether polyol by adopting the solution polymerization method, the temperature runaway phenomenon in the polymerization process can be effectively prevented by limiting the using amount of the solvent; the reaction temperature is low, the energy consumption is low, and the reaction rate and the temperature are easy to control; and the prepared polyether polyol has low chroma and wide application range. If the dosage of the solvent is less than 10 wt% of the theoretical yield of the polyether polyol, the heat dissipation effect is poor, and the chromaticity of the product is poor; if the solvent dosage exceeds 50 wt% of the theoretical yield of the polyether polyol, the later desolventizing time is too long, which also causes poor product chromaticity, long period, low yield and high cost.
Description
Technical Field
The invention relates to the technical field of polyether polyol, in particular to a method for preparing polyether polyol by adopting a solution polymerization method.
Background
Polyether polyol (polyether for short) is prepared by the polyaddition reaction of an initiator (compound containing active hydrogen groups) and an epoxy compound in the presence of a catalyst. The prior production of polyether polyol is mainly anion catalyzed ring-opening polymerization. Usually, potassium hydroxide (or sodium hydroxide), bimetallic catalyst or dimethylamine is used as catalyst, micromolecular polyalcohol such as glycerin or sucrose or other active hydrogen-containing compounds such as amine and alcohol amine are used as initiator, propylene oxide, ethylene oxide or the mixture thereof is used as epoxy compound, ring-opening polymerization is carried out at certain temperature and pressure to obtain crude polyether, and the crude polyether is neutralized and refined to obtain the finished polyether. The polyether polyol can be widely used for manufacturing polyurethane foam plastics, adhesives and elastomers, and can also be used as a defoaming agent, a surfactant, an oilfield sewage treatment agent and the like.
For example, chinese patent document CN103739837A discloses a block polyether oilfield sewage treatment agent using N ' N-dimethylethanolamine as an initiator, and a preparation method thereof, wherein the block polyether oilfield sewage treatment agent uses N ' N-dimethylethanolamine as an initiator, and obtains the block polyether oilfield sewage treatment agent using N ' N-dimethylethanolamine as an initiator through ring-opening polymerization of propylene oxide and ethylene oxide under high-temperature and high-pressure conditions. The oilfield sewage treatment agent disclosed in the above document has a good oil-water separation effect on polymer-containing sewage generated after oilfield polymer flooding. However, the polyether polyol prepared by the method has poor chroma, so that the application range of the polyether polyol is severely limited.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of high chromaticity and limited use of polyether polyol synthesized by taking N' N-dimethylethanolamine as an initiator in the prior art, so that the method for preparing polyether polyol by adopting a solution polymerization method is provided.
Therefore, the invention provides the following technical scheme:
a process for preparing polyether polyols by solution polymerization, the amount of solvent used in the solution polymerization being from 10 to 50% by weight of the theoretical yield of the polyether polyol.
Further, under the inert gas atmosphere, introducing an epoxy compound into a system comprising an initiator and a solvent, and curing and degassing to obtain the polyether polyol.
Further, the initiator is N, N-dimethylethanolamine.
Further, the solvent is at least one of liquid aromatic hydrocarbon, ketone and ether.
The aromatic hydrocarbon is liquid aromatic hydrocarbon at normal temperature such as toluene, xylene or propylbenzene;
the ketones are butanone, methyl isobutyl ketone or cyclohexanone which are liquid at normal temperature;
the ethers are ethers which are liquid at normal temperature, such as ethylene glycol butyl ether or propylene glycol methyl ether acetate.
Further, the method comprises the step of mixing soft water with the initiator and the solvent.
Further, the soft water is used in an amount of 5 to 30 wt% based on the initiator.
Preferably, the soft water is used in an amount of 10 wt% of the initiator.
Further, the introduction temperature of the epoxy compound is 40-80 ℃; preferably, the epoxide compound is passed at a temperature of 50 ℃;
the introducing pressure of the epoxy compound is less than or equal to 0.60 MPa; preferably, the introduction pressure of the epoxy compound is less than or equal to 0.40 MPa;
the curing temperature is 40-80 ℃, preferably, the curing temperature is 50 ℃;
the degassing temperature is 90-150 ℃. The degassing is to remove the solvent, soft water and unreacted epoxy compound according to different boiling points; the solvent can be recycled after being collected, and the cost is saved.
Further, the oxygen content in the inert gas atmosphere is < 100 ppm;
preferably, the oxygen content in the inert gas atmosphere is < 50 ppm.
The inert gas is nitrogen, helium or argon. Preferably, the inert gas is nitrogen.
Further, the epoxy compound is at least one of ethylene oxide, propylene oxide (methyl ethylene oxide), butylene oxide and epichlorohydrin. The epoxy compounds are not limited to those listed above, and conventional epoxy compounds used for preparing polyether polyols are satisfactory.
The invention also provides polyether polyol prepared by the method for preparing polyether polyol by adopting the solution polymerization method.
The invention also provides the application of the polyether polyol prepared by the method for preparing the polyether polyol by adopting the solution polymerization method in coating dispersants, oil field demulsifiers or printing ink raw materials.
The technical scheme of the invention has the following advantages:
1. according to the method for preparing the polyether polyol by adopting the solution polymerization method, the solvent consumption in the solution polymerization method is 10-50 wt% of the theoretical yield of the polyether polyol. According to the method for preparing the polyether polyol by adopting the solution polymerization method, the temperature runaway phenomenon in the polymerization process can be effectively prevented by limiting the using amount of the solvent; the reaction temperature is low, the energy consumption is low, and the reaction rate and the temperature are easy to control; and the prepared polyether polyol has low chroma and wide application range. If the dosage of the solvent is less than 10 wt% of the theoretical yield of the polyether polyol, the heat dissipation effect is poor, and the chromaticity of the product is poor; if the solvent dosage exceeds 50 wt% of the theoretical yield of the polyether polyol, the later desolventizing time is too long, which also causes poor product chromaticity, long period, low yield and high cost.
2. According to the method for preparing polyether polyol by adopting the solution polymerization method, N, N-dimethylethanolamine is used as an initiator, and the N, N-dimethylethanolamine also plays a role in autocatalysis while participating in a reaction; and the combination of the addition of a limited amount of solvent, the prepared polyether polyol has low chroma, and polyether polyols with different requirements can be prepared by adjusting the proportion of the epoxy compound and the initiator.
3. According to the method for preparing polyether polyol by adopting the solution polymerization method, soft water is mixed with the initiator and the solvent, and the hydrogen bond forming capability and polarity of the water are favorable for the polymerization reaction of the epoxy compound and the N, N-dimethylethanolamine, so that the polymerization reaction activity is high, the selectivity of the N, N-dimethylethanolamine is high, the soft water can play a role of a cocatalyst, the polymerization reaction rate is effectively improved, the production period is shortened, and the cost is reduced. The soft water is used instead of other water, so that the metal ions in the water can be effectively prevented from influencing the cocatalyst effect and the polymerization reaction rate of the water.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
The introduction rate in each of the examples and comparative examples means the introduction rate of the epoxy compound, and the epoxy compound is introduced, and if the pressure is not changed, it is considered that the introduced epoxy compound has reacted; in the reaction process, the pressure is gradually increased, but the introduction rate of the epoxy compound in the whole introduction process is fluctuated when the pressure is controlled within a certain pressure range; the reaction period is the sum of the introduction time and the curing time of the epoxy compound.
Example 1
This example provides a method for preparing polyether polyol, including the following steps:
adding 89g of N, N-dimethylethanolamine, 8.9g of soft water and 158.6g of toluene into a 2L reaction kettle, and introducing nitrogen for replacement to remove residual air in the kettle, wherein the oxygen content of the replaced system is 40 ppm; and (2) introducing 704g of ethylene oxide under the conditions that the reaction temperature is controlled to be 50 ℃ and the pressure is 0.50MPa, continuing curing at the temperature of 50 ℃ after the introduction is finished until the system pressure is stable, heating to 120 ℃, removing soft water, toluene and residual ethylene oxide in vacuum, and then cooling to 50 ℃ to obtain the polyether polyol. The feeding rate is about 40-50g/10min, and the reaction period is 4h (wherein the curing time is 1 h).
Example 2
This example provides a method for preparing polyether polyol, including the following steps:
adding 89g of N, N-dimethylethanolamine, 26.7g of soft water and 166.08g of xylene into a 2L reaction kettle, introducing nitrogen for replacement to remove residual air in the kettle, wherein the oxygen content of the replaced system is 90 ppm; and (3) introducing 580g of propylene oxide under the conditions that the reaction temperature is controlled to be 80 ℃ and the pressure is 0.60MPa, continuing curing at 80 ℃ after the introduction is finished until the system pressure is stable, heating to 150 ℃, removing soft water, xylene and residual propylene oxide in vacuum, and then cooling to 50 ℃ to obtain the polyether polyol. The feeding rate is 30-40g/10min, and the reaction period is 5h (wherein the curing time is 2 h).
Example 3
This example provides a method for preparing polyether polyol, including the following steps:
adding 89g of N, N-dimethylethanolamine, 4.45g of soft water and 381.7g of butanone into a 2L reaction kettle, introducing nitrogen for replacement to remove residual air in the kettle, wherein the oxygen content of the replaced system is 50 ppm; controlling the reaction temperature to be 40 ℃ and the pressure to be 0.30MPa, introducing 865.3g of butylene oxide, continuing curing at 40 ℃ after the introduction is finished until the system pressure is stable, heating to 90 ℃, removing soft water, butanone and residual butylene oxide in vacuum, and then cooling to 50 ℃ to obtain the polyether polyol. The feeding rate is 20-30g/10min, and the reaction period is about 10h (wherein the curing time is 4 h).
Example 4
This example provides a method for preparing polyether polyol, including the following steps:
adding 89g of N, N-dimethylethanolamine, 17.8g of soft water and 194g of methyl isobutyl ketone into a 5L reaction kettle, and introducing nitrogen for replacement to remove residual air in the kettle, wherein the oxygen content of the replaced system is 60 ppm; controlling the reaction temperature to be 60 ℃ and the pressure to be 0.40MPa, introducing 1850.4g of epoxy chloropropane, continuing curing at 60 ℃ after the introduction is finished until the system pressure is stable, heating to 120 ℃, removing soft water, methyl isobutyl ketone and residual epoxy chloropropane in vacuum, and then cooling to 55 ℃ to obtain the polyether polyol. The feeding rate is 60-70g/10min, and the reaction period is 8h (wherein the curing time is 3 h).
Example 5
This example provides a method for preparing polyether polyol, including the following steps:
adding 89g of N, N-dimethylethanolamine and 462g of ethylene glycol butyl ether into a 2L reaction kettle, and introducing nitrogen for replacement to remove residual air in the kettle, wherein the oxygen content of the replaced system is 20 ppm; controlling the reaction temperature to be 70 ℃ and the pressure to be 0.50MPa, sequentially and continuously introducing 660.7g of Ethylene Oxide (EO) and 175g of Propylene Oxide (PO), after the introduction is finished, continuously curing at 70 ℃ until the system pressure is stable, heating to 150 ℃, removing soft water, ethylene glycol monobutyl ether and residual ethylene oxide in vacuum, and then cooling to 50 ℃ to obtain the polyether polyol. The EO section introduction rate is 35-45g/10min, and the PO section introduction rate is 25-35g/10 min; the reaction period was 7.5h (with a maturation time of 3.5 h).
Example 6
This example provides a method for preparing polyether polyol, including the following steps:
adding 89g of N, N-dimethylethanolamine and 185.3g of propylene glycol monomethyl ether acetate into a 2L reaction kettle, introducing nitrogen for replacement to remove residual air in the kettle, wherein the oxygen content of a system after replacement is 10 ppm; and (2) introducing 440.5g of ethylene oxide under the conditions that the reaction temperature is controlled to be 50 ℃ and the pressure is 0.30MPa, continuing curing at 50 ℃ after the introduction is finished until the system pressure is stable, heating to 150 ℃, removing soft water, propylene glycol monomethyl ether acetate and residual ethylene oxide in vacuum, and then cooling to 60 ℃ to obtain the polyether polyol. The feeding rate is 20-30g/10min, and the reaction period is about 4.5h (wherein the curing time is 1.5 h).
Comparative example 1
The present comparative example provides a process for the preparation of a polyether polyol comprising the steps of:
adding 89g of N, N-dimethylethanolamine and 8.9g of soft water into a 2L reaction kettle, introducing nitrogen for replacement to remove residual air in the kettle, wherein the oxygen content of the replaced system is 40 ppm; and (2) introducing 704g of ethylene oxide under the conditions that the reaction temperature is controlled to be 50 ℃ and the pressure is 0.50MPa, continuing curing at 50 ℃ after introduction is finished until the system pressure is stable, heating to 120 ℃, removing soft water and residual ethylene oxide in vacuum, and then cooling to 50 ℃ to obtain the polyether polyol. The feeding rate is 50-60g/10min, and the reaction period is about 3.5h (wherein the curing time is 1 h).
Comparative example 2
The present comparative example provides a process for the preparation of a polyether polyol comprising the steps of:
adding 89g of N, N-dimethylethanolamine, 8.9g of soft water and 63g of toluene into a 2L reaction kettle, introducing nitrogen for replacement to remove residual air in the kettle, wherein the oxygen content of the replaced system is 40 ppm; and (2) introducing 704g of ethylene oxide under the conditions that the reaction temperature is controlled to be 50 ℃ and the pressure is 0.50MPa, continuing curing at the temperature of 50 ℃ after the introduction is finished until the system pressure is stable, heating to 120 ℃, removing soft water, toluene and residual ethylene oxide in vacuum, and then cooling to 50 ℃ to obtain the polyether polyol. The feeding rate is 40-50g/10min, and the reaction period is about 4h (wherein the curing time is 1 h).
Comparative example 3
The present comparative example provides a process for the preparation of a polyether polyol comprising the steps of:
adding 89g of N, N-dimethylethanolamine, 8.9g of soft water and 420.3g of toluene into a 2L reaction kettle, and introducing nitrogen for replacement to remove residual air in the kettle, wherein the oxygen content of the replaced system is 40 ppm; and (2) introducing 704g of ethylene oxide under the conditions that the reaction temperature is controlled to be 50 ℃ and the pressure is 0.50MPa, continuing curing at the temperature of 50 ℃ after the introduction is finished until the system pressure is stable, heating to 120 ℃, removing soft water, toluene and residual ethylene oxide in vacuum, and then cooling to 50 ℃ to obtain the polyether polyol. The feeding rate is 20-30g/10min, and the reaction period is about 7h (wherein the curing time is 2 h).
Examples of the experiments
The polyether polyols obtained in the examples and the comparative examples were respectively subjected to visual inspection and color measurement, wherein the color measurement was carried out according to GB/T3143-1982 (color measurement for liquid chemical products), and the specific results are shown in Table 1.
TABLE 1 appearance and color test results
| Appearance of the product | Color intensity | |
| Example 1 | Colorless to pale yellow liquid | 20Pt-Co |
| Example 2 | Colorless to pale yellow liquid | 20Pt-Co |
| Example 3 | Colorless to pale yellow liquid | 20Pt-Co |
| Example 4 | Colorless to pale yellow liquid | 20Pt-Co |
| Example 5 | Colorless to pale yellow liquid | 20Pt-Co |
| Example 6 | Colorless to pale yellow liquid | 20Pt-Co |
| Comparative example 1 | Brown liquid | 3GD |
| Comparative example 2 | Light yellow liquid | 60Pt-Co |
| Comparative example 3 | Light yellow liquid | 30Pt-Co |
As can be seen from the data in the above table, the polyether polyol prepared by the method of the present invention by limiting the amount of the solvent used has excellent appearance and low color.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. A method for preparing polyether polyol by adopting a solution polymerization method is characterized in that the using amount of a solvent in the solution polymerization method is 10-50 wt% of the theoretical yield of the polyether polyol.
2. The method of claim 1, wherein the polyether polyol is prepared by introducing an epoxy compound into a system comprising an initiator and a solvent under an inert gas atmosphere, and aging and degassing the mixture.
3. The method of claim 2, wherein the initiator is N, N-dimethylethanolamine.
4. The method of claim 2 or 3, wherein the solvent is at least one of liquid aromatic hydrocarbons, ketones and ethers.
5. The method of claim 4 further comprising the step of mixing soft water with the initiator and the solvent.
6. The method of claim 5, wherein the amount of the soft water is 5-30 wt% of the initiator.
7. The method for producing polyether polyol by solution polymerization according to any one of claims 2 to 6, wherein the epoxy compound is introduced at a temperature of 40 to 80 ℃;
the introducing pressure of the epoxy compound is less than or equal to 0.60 MPa;
the curing temperature is 40-80 ℃;
the degassing temperature is 90-150 ℃.
8. The method for producing polyether polyol by the solution polymerization method according to any one of claims 2 to 7, wherein the epoxy compound is at least one of ethylene oxide, propylene oxide, butylene oxide and epichlorohydrin.
9. Polyether polyol obtainable by a process for the preparation of polyether polyol according to any of claims 1 to 8 by solution polymerization.
10. Use of a polyether polyol obtained by the method of producing a polyether polyol by a solution polymerization process according to any one of claims 1 to 8 in a coating dispersant, an oil field demulsifier or an ink raw material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115594836A (en) * | 2022-09-29 | 2023-01-13 | 上海抚佳精细化工有限公司（Cn） | Preparation method of hard foam polyether polyol |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0347832A (en) * | 1989-04-20 | 1991-02-28 | Mitsui Toatsu Chem Inc | Production of polyether polyol |
| US20060258832A1 (en) * | 2003-08-12 | 2006-11-16 | Basf Aktiengesellschaft | Device for producing polyether alcohols |
| US20070203319A1 (en) * | 2006-02-27 | 2007-08-30 | Dexheimer Edward M | Process of forming a polyol |
| CN103755884A (en) * | 2013-12-20 | 2014-04-30 | 西南石油大学 | Reverse-phase demulsifying agent for treating polymer flooding produced liquid of oil fields and preparation method thereof |
-
2020
- 2020-08-12 CN CN202010804074.6A patent/CN112029085A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0347832A (en) * | 1989-04-20 | 1991-02-28 | Mitsui Toatsu Chem Inc | Production of polyether polyol |
| US20060258832A1 (en) * | 2003-08-12 | 2006-11-16 | Basf Aktiengesellschaft | Device for producing polyether alcohols |
| US20070203319A1 (en) * | 2006-02-27 | 2007-08-30 | Dexheimer Edward M | Process of forming a polyol |
| CN103755884A (en) * | 2013-12-20 | 2014-04-30 | 西南石油大学 | Reverse-phase demulsifying agent for treating polymer flooding produced liquid of oil fields and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115594836A (en) * | 2022-09-29 | 2023-01-13 | 上海抚佳精细化工有限公司（Cn） | Preparation method of hard foam polyether polyol |
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