CN109651609B - Preparation method of polyether polyol with high EO content - Google Patents
Preparation method of polyether polyol with high EO content Download PDFInfo
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- CN109651609B CN109651609B CN201811471072.9A CN201811471072A CN109651609B CN 109651609 B CN109651609 B CN 109651609B CN 201811471072 A CN201811471072 A CN 201811471072A CN 109651609 B CN109651609 B CN 109651609B
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- 229920000570 polyether Polymers 0.000 title claims abstract description 51
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 50
- 229920005862 polyol Polymers 0.000 title claims abstract description 50
- 150000003077 polyols Chemical class 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003999 initiator Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 30
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 21
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 230000009977 dual effect Effects 0.000 claims description 6
- 229960004063 propylene glycol Drugs 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- QOFLTGDAZLWRMJ-UHFFFAOYSA-N 2-methylpropane-1,1-diol Chemical compound CC(C)C(O)O QOFLTGDAZLWRMJ-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000003860 storage Methods 0.000 description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 6
- 239000000391 magnesium silicate Substances 0.000 description 6
- 229910052919 magnesium silicate Inorganic materials 0.000 description 6
- 235000019792 magnesium silicate Nutrition 0.000 description 6
- 229910001414 potassium ion Inorganic materials 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- -1 alcohol amine Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 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
- C08G65/2603—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
- C08G65/2642—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
- C08G65/2672—Nitrogen 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/58—Ethylene oxide or propylene oxide copolymers, e.g. pluronics
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation method of polyether polyol with high EO content. The invention adopts double initiators, adds the initiators by a segmented charging method, and sequentially and alternately adds propylene oxide and ethylene oxide by a regular interval method under the action of a catalyst to carry out polymerization reaction, thereby preparing the polyether polyol with high EO content. The preparation method of the polyether polyol with the high EO content enables all the initiators to better and uniformly participate in the reaction, the product functionality can be freely mastered, the reaction addition effect is better, the turbidity phenomenon of the polyether polyol product is also improved, the unsaturated value is reduced, and more different use requirements can be met.
Description
Technical Field
The invention belongs to the technical field of polyether polyol synthesis, and particularly relates to a preparation method of polyether polyol with high EO content.
Background
Polyether Polyols (PPG) and polymer polyols (POP) are important raw materials for the Polyurethane (PU) industry. The polyurethane product has excellent physical and mechanical performance, easy processing, various products and wide application. The application field relates to the industries of automobiles, trains, ships, airplanes, aerospace, furniture, household appliances, construction, medicine and health, mines, water power, electric power, electronics, agriculture and the like.
The industrial production of general polyether polyol is mainly based on anion catalyzed ring-opening polymerization, usually potassium hydroxide (or sodium hydroxide) or dimethylamine is used as a catalyst, micromolecular polyol such as glycerol or sucrose or other active hydrogen-containing compounds such as amine and alcohol amine are used as an initiator, Propylene Oxide (PO) or a mixture of the PO and Ethylene Oxide (EO) is used as a monomer, ring-opening polymerization is carried out at a certain temperature and pressure to obtain crude polyether polyol, and then steps such as neutralization and refining are carried out to obtain the finished polyether polyol.
The properties of polyether polyols are closely related to the initiator and also to the oxyalkylene chain length and arrangement in the molecule. The functionality of the polyether polyols depends on the type of initiator chosen for the synthesis and the number of its active hydrogens. The initiator for synthesizing polyether polyol is distinguished according to the properties of active groups and mainly comprises two main classes of compounds containing hydroxyl groups and compounds containing amino groups. The most commonly used starters are propylene glycol, trimethylolpropane, glycerol, mannitol, sorbitol, pentaerythritol, sucrose, xylitol, ethylenediamine, triethanolamine, toluenediamine, and the like. In order to obtain polyether polyols of suitable functionality and viscosity, polyethers are sometimes produced by mixing the initiators. In the production of the mixed initiator polyether polyol, how to enable each initiator to better and uniformly participate in the reaction has important significance for improving the performance of the product.
The monomers usually used for the preparation of polyether polyols are ethylene oxide, propylene oxide or mixtures of ethylene oxide and propylene oxide. Some products require a higher proportion of ethylene oxide as polymerized monomer due to higher requirements for hydrophilicity or the amount of soft segments. However, when the proportion of ethylene oxide is high, whether the ethylene oxide and the propylene oxide are mixed or the ethylene oxide is adopted for blocking, the appearance of the polyether polyol is easily turbid, or the polyether polyol becomes thick paste and even becomes solid at normal temperature.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of polyether polyol with high EO content, which enables all initiators to better and uniformly participate in the reaction, the product functionality can be freely mastered, the reaction addition effect is better, the turbidity phenomenon of the polyether polyol product is improved, the unsaturated value is reduced, and more different use requirements can be met.
The preparation method of the polyether polyol with high EO content adopts a double initiator, adds the initiator by a segmented charging method, sequentially and alternately adds propylene oxide and ethylene oxide by a regular interval method under the action of a catalyst, and carries out polymerization reaction to prepare the polyether polyol with high EO content.
The two starters of the dual starter have different functionalities.
The dual initiator is two of alcohol compounds such as n-octanol, n-decanol, lauryl alcohol, stearyl alcohol, ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, neopentyl glycol, diethylene glycol, 2-methylpropanediol, 1, 6-hexanediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol and the like.
The staged addition process begins with the addition of a low molecular weight, low functionality initiator. When molecular weight and functionality conflict, functionality is a priority.
In the staged addition method, after the small molecular weight low functionality initiator and alkylene oxide (including propylene oxide and ethylene oxide) react smoothly (the pressure shows a tendency to decrease), the large molecular weight high functionality initiator is continuously and slowly added into the reaction vessel.
The mass ratio of ethylene oxide to propylene oxide is 3-20:1, preferably 5-15: 1.
When propylene oxide and ethylene oxide are alternately added in sequence by using a regular interval method, the number of times of alternate addition is 5 to 50 times, preferably 10 to 20 times, and the alternation can be carried out until the pressure is not reduced after the internal pressure reaction is finished after each addition.
The initiators for polyether polyol synthesis have different functionalities and different molecular weights, and therefore, the reactivity of the initiators in addition to alkylene oxides is different, and when polyether is prepared using a mixed initiator, the small molecular weight low functionality initiator is more likely to initiate and the addition of alkylene oxides begins, resulting in more addition of alkylene oxides to such initiators. The method comprises the steps of adding a dual initiator by a segmented charging method, adding a low-molecular-weight low-functionality initiator, and continuously and slowly adding a high-molecular-weight high-functionality initiator into a reaction container through a storage tank through a pipeline, so that a small amount of initiator which just enters the reaction container can easily start to react in the initiated whole large environment, the product functionality can be freely mastered, the reaction addition effect is better, and the product meets more different use requirements.
The monomers usually used for the preparation of polyether polyols are ethylene oxide, propylene oxide or mixtures of ethylene oxide and propylene oxide. Some products require a higher proportion of ethylene oxide as polymerized monomer due to higher requirements for hydrophilicity or the amount of soft segments. However, when the proportion of ethylene oxide is high, no matter the mixture of ethylene oxide and propylene oxide or the end capping of ethylene oxide is adopted, the polyether is easily turbid in appearance or becomes thick paste, and even becomes solid at normal temperature. In order to improve the phenomenon, the adding sequence and the adding mode of the propylene oxide and the ethylene oxide are adjusted except for controlling proper temperature and feeding speed, the propylene oxide and the ethylene oxide are sequentially and alternately added by adopting a regular interval method, the ethylene oxide does not form overlong chain segments due to the interval action of the propylene oxide, the turbidity phenomenon of the polyether polyol product is improved, the side reaction is reduced due to the fact that the addition segments of the propylene oxide are mixed in the ethylene oxide, and the unsaturated value of the polyether polyol product is reduced.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, a segmented charging method is adopted to add the dual initiator, the initiator with small molecular weight and low functionality is added firstly, and then the initiator with large molecular weight and high functionality is continuously and slowly added into the reaction container through the storage tank through the pipeline, so that a small amount of initiator which just enters is easier to start to react in the initiated whole large environment, the functionality of the product can be freely mastered, the reaction addition effect is better, and the product meets more different use requirements;
(2) according to the invention, propylene oxide and ethylene oxide are sequentially and alternately added by adopting a regular interval method, due to the interval effect of the propylene oxide, the ethylene oxide does not form an overlong chain segment, the turbidity phenomenon of the polyether polyol product is improved, and due to the fact that the addition segments of the propylene oxide are mixed in the ethylene oxide, the side reaction is reduced, and the unsaturated value of the polyether polyol product is reduced.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
Adding 50 parts of propylene glycol and 3 parts of potassium hydroxide into a 5L stainless steel reaction kettle, adding 80 parts of glycerol into a storage tank A, adding 1500 parts of ethylene oxide into a storage tank B, adding 150 parts of propylene oxide into a storage tank C, and controlling the temperature to be less than or equal to 40 ℃; stirring the reaction kettle, replacing the reaction kettle with nitrogen for 2-3 times, vacuumizing, bubbling the nitrogen for 2 hours, heating to 105 ℃, adding 80 parts of glycerol into the kettle through a storage tank A, adding 200 parts of ethylene oxide through a storage tank B, adding 20 parts of propylene oxide through a storage tank C, sequentially and alternately adding propylene oxide and ethylene oxide, finally adding 1500 parts of ethylene oxide and 150 parts of propylene oxide, adding 3 hours, controlling the pressure to be 0.1-0.4MPa, controlling the temperature to be 110-115 ℃, and then carrying out internal pressure reaction for 3 hours to obtain crude polyether polyol; after the reaction is finished, adding phosphoric acid and water, adsorbing and crystallizing potassium ions by using magnesium silicate, decompressing and dehydrating, and filtering to obtain the polyether polyol product.
Comparative example 1
Adding 50 parts of propylene glycol and 3 parts of potassium hydroxide into a 5L stainless steel reaction kettle, adding 80 parts of glycerol into a storage tank A, adding 1500 parts of ethylene oxide and 150 parts of propylene oxide into a storage tank B, and keeping the temperature to be less than or equal to 40 ℃; stirring the reaction kettle, replacing the reaction kettle with nitrogen for 2-3 times, vacuumizing, bubbling the nitrogen for 2 hours, heating to 105 ℃, adding 80 parts of glycerol into the kettle through a storage tank A, adding the glycerol for 2 hours, continuously adding a mixture of 1500 parts of ethylene oxide and 150 parts of propylene oxide through a storage tank B, controlling the pressure to be 0.1-0.4MPa, the temperature to be 110-115 ℃, adding the ethylene oxide for 3 hours, and then carrying out internal pressure reaction for 3 hours to obtain crude polyether polyol; after the reaction is finished, adding phosphoric acid and water, adsorbing and crystallizing potassium ions by using magnesium silicate, decompressing and dehydrating, and filtering to obtain the polyether polyol product.
Comparative example 2
Adding 50 parts of propylene glycol, 80 parts of glycerol and 3 parts of potassium hydroxide into a 5L stainless steel reaction kettle, adding 1500 parts of ethylene oxide and 150 parts of propylene oxide into a storage tank, and keeping the temperature to be less than or equal to 40 ℃; starting the reaction kettle for stirring, replacing the nitrogen for 2-3 times, vacuumizing, heating to 110 ℃, and bubbling the nitrogen for 2 hours; continuously adding a mixture of 1500 parts of ethylene oxide and 150 parts of propylene oxide into a storage tank, controlling the pressure to be 0.1-0.4MPa, the temperature to be 110-; after the reaction is finished, adding phosphoric acid and water, adsorbing and crystallizing potassium ions by using magnesium silicate, decompressing and dehydrating, and filtering to obtain the polyether polyol product.
The performance criteria of the polyether polyols prepared in example 1 and comparative examples 1-2 are shown in Table 1.
TABLE 1 Performance indices of polyether polyols prepared in example 1 and comparative examples 1-2
| Performance index | Example 1 | Comparative example 1 | Comparative example 2 |
| Hydroxyl value (mgKOH/g) | 124.0 | 125.1 | 126.8 |
| Viscosity (mPa. s/25 ℃ C.) | 975 | 1003 | 1024 |
| pH | 6.25 | 6.17 | 6.20 |
| H2O(％) | 0.01 | 0.01 | 0.01 |
| Unsaturation number (mol/kg) | 0.008 | 0.014 | 0.020 |
| Appearance of the product | Clear and clear liquid | Colorless, slightly turbid liquid | Colorless, turbid, viscous liquids |
As can be seen from table 1: the actual hydroxyl number of the product in example 1 was closer to the theoretical hydroxyl number (theoretical hydroxyl number of 123.66 mgKOH/g); the viscosity is low, the unsaturated value is low, and the appearance is optimal.
Example 2
Adding 100 parts of lauryl alcohol and 5 parts of potassium hydroxide into a 5L stainless steel reaction kettle, adding 65 parts of diethylene glycol into a storage tank A, adding 2000 parts of ethylene oxide into a storage tank B, adding 400 parts of propylene oxide into a storage tank C, and controlling the temperature to be less than or equal to 40 ℃; stirring the reaction kettle, replacing the reaction kettle with nitrogen for 2-3 times, vacuumizing, heating to 110 ℃, adding 65 parts of diethylene glycol into the kettle through a storage tank A, and finishing the addition within 1.5 hours; adding 200 parts of ethylene oxide through a storage tank B, adding 40 parts of propylene oxide through a storage tank C, sequentially and alternately adding the propylene oxide and the ethylene oxide, finally adding 2000 parts of ethylene oxide and 400 parts of propylene oxide, controlling the pressure to be 0.1-0.4MPa, the temperature to be 110-115 ℃ after adding, and carrying out internal pressure reaction for 3 hours to obtain crude polyether polyol; after the reaction is finished, adding phosphoric acid and water, adsorbing and crystallizing potassium ions by using magnesium silicate, decompressing and dehydrating, and filtering to obtain the polyether polyol product.
Comparative example 3
Adding 100 parts of lauryl alcohol and 5 parts of potassium hydroxide into a 5L stainless steel reaction kettle, adding 65 parts of diethylene glycol into a storage tank A, adding 2000 parts of ethylene oxide and 400 parts of propylene oxide into a storage tank B, and keeping the temperature to be less than or equal to 40 ℃; stirring the reaction kettle, replacing the reaction kettle with nitrogen for 2-3 times, vacuumizing, heating to 110 ℃, adding 65 parts of diethylene glycol into the kettle through a storage tank A for 1.5 hours, continuously adding a mixture of 2000 parts of ethylene oxide and 400 parts of propylene oxide through a storage tank B, controlling the pressure to be 0.1-0.4MPa, the temperature to be 110-115 ℃, completing the addition for 4 hours, and then carrying out internal pressure reaction for 3 hours to obtain crude polyether polyol; after the reaction is finished, adding phosphoric acid and water, adsorbing and crystallizing potassium ions by using magnesium silicate, decompressing and dehydrating, and filtering to obtain the polyether polyol product.
Comparative example 4
Adding 100 parts of lauryl alcohol, 65 parts of diethylene glycol and 5 parts of potassium hydroxide into a 5L stainless steel reaction kettle, adding 2000 parts of ethylene oxide and 400 parts of propylene oxide into a storage tank, and keeping the temperature to be less than or equal to 40 ℃; stirring the reaction kettle, replacing the reaction kettle with nitrogen for 2-3 times, vacuumizing, heating to 110 ℃, continuously adding a mixture of 2000 parts of ethylene oxide and 400 parts of propylene oxide through a storage tank, controlling the pressure to be 0.1-0.4MPa, the temperature to be 110-115 ℃, completing the addition for 4 hours, and then carrying out internal pressure reaction for 3 hours to obtain crude polyether polyol; after the reaction is finished, adding phosphoric acid and water, adsorbing and crystallizing potassium ions by using magnesium silicate, decompressing and dehydrating, and filtering to obtain the polyether polyol product.
The performance criteria for the polyether polyols prepared in example 2 and comparative examples 3-4 are shown in Table 2.
TABLE 2 Performance indices of polyether polyols prepared in example 2 and comparative examples 3 to 4
As can be seen from table 2: the actual hydroxyl number of the product in example 2 was closer to the theoretical hydroxyl number (theoretical hydroxyl number 38.52 mgKOH/g); the viscosity is low, the unsaturated value is low, and the appearance is optimal.
Claims (2)
1. A preparation method of polyether polyol with high EO content is characterized in that: adopting a double initiator, adding the initiator by using a segmented charging method, and sequentially and alternately adding propylene oxide and ethylene oxide by using a regular interval method under the action of a catalyst to carry out polymerization reaction to prepare polyether polyol with high EO content;
in the sectional feeding method, a small molecular weight low functionality initiator is added firstly;
in the sectional feeding method, after the reaction of the initiator with small molecular weight and low functionality and the alkylene oxide is stable, the initiator with large molecular weight and high functionality is continuously and slowly added into a reaction container;
when propylene oxide and ethylene oxide are alternately added in sequence by using a regular interval method, the alternate feeding times are 5 to 50;
the dual initiator is two of n-octanol, n-decanol, lauryl alcohol, stearyl alcohol, ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, neopentyl glycol, diethylene glycol, 2-methylpropanediol, 1, 6-hexanediol, glycerol, trimethylolpropane, pentaerythritol and sorbitol;
the mass ratio of the ethylene oxide to the propylene oxide is 3-20: 1.
2. The process for preparing a high EO content polyether polyol as claimed in claim 1, wherein: the two starters in the dual starter have different functionalities.
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| CN112661952B (en) * | 2020-12-14 | 2023-09-22 | 山东一诺威新材料有限公司 | Preparation method of low-reaction heat polyether polyol |
| CN113105617A (en) * | 2021-04-12 | 2021-07-13 | 山东蓝星东大有限公司 | Preparation method of polyether polyol for high-performance waterproof coating |
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