CN108148190B - Preparation method of high-activity low-volatile polyether polyol - Google Patents
Preparation method of high-activity low-volatile polyether polyol Download PDFInfo
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- CN108148190B CN108148190B CN201611096960.8A CN201611096960A CN108148190B CN 108148190 B CN108148190 B CN 108148190B CN 201611096960 A CN201611096960 A CN 201611096960A CN 108148190 B CN108148190 B CN 108148190B
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 95
- 229920000570 polyether Polymers 0.000 title claims abstract description 95
- 229920005862 polyol Polymers 0.000 title claims abstract description 95
- 150000003077 polyols Chemical class 0.000 title claims abstract description 92
- 230000000694 effects Effects 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 9
- 238000007670 refining Methods 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 239000003999 initiator Substances 0.000 claims abstract description 3
- -1 polyol compound Chemical class 0.000 claims abstract description 3
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 31
- 230000003247 decreasing effect Effects 0.000 claims description 30
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 16
- 239000005416 organic matter Substances 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 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 claims description 2
- 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 2
- 229930195725 Mannitol Natural products 0.000 claims 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 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- 229930182478 glucoside Natural products 0.000 claims description 2
- 150000008131 glucosides Chemical class 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 235000010356 sorbitol Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000811 xylitol Substances 0.000 claims description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 2
- 235000010447 xylitol Nutrition 0.000 claims description 2
- 229960002675 xylitol Drugs 0.000 claims description 2
- 239000003039 volatile agent Substances 0.000 claims 8
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000012855 volatile organic compound Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 34
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- 230000005587 bubbling Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 229920005830 Polyurethane Foam Polymers 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 239000011496 polyurethane foam Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- 241001550224 Apha Species 0.000 description 4
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229910001414 potassium ion Inorganic materials 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000013518 molded foam Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- 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
- C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
-
- 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
- C08G2101/00—Manufacture of cellular products
Landscapes
- 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 activity and low volatile matter. The method comprises the following steps: (1) synthesizing polyether polyol oligomer with high-efficiency catalytic activity by using a polyol compound as an initiator and an alkali metal aqueous solution as a catalyst; (2) taking the polyether polyol oligomer with high catalytic activity prepared in the step (1) as basic polyether, firstly adding propylene oxide to react under the pressure of 0-0.5 MPa and the temperature of 80-150 ℃, then carrying out internal pressure reaction after adding, then adding ethylene oxide to react, and then carrying out internal pressure reaction after adding to prepare a high-activity polyether polyol crude polymer; (3) and (3) refining the high-activity polyether polyol crude polymer prepared in the step (2) to obtain the high-activity low-volatile polyether polyol. The invention can obviously shorten the production period of the product, and the produced product has the characteristics of high activity, low content of volatile organic compounds and small smell.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation method of polyether polyol with high activity and low volatile matter.
Background
The advantages of primary hydroxyl terminated polyether polyols are more pronounced in the preparation of polyurethane articles than secondary hydroxyl terminated polyether polyols. First, the primary hydroxyl group is significantly higher than the secondary hydroxyl group in view of reactivity with isocyanate group, and the reaction speed can be increased. Polyether polyols terminated with secondary hydroxyl groups are mostly prepared by homopolymerization of propylene oxide, and have been largely limited in many applications, such as polyurethane bulk high resilience foams, molded foams, and the like. In addition, secondary hydroxyl terminated polyether polyols have limited utility in polyurethane elastomers and prepolymer foams primarily because the presence of secondary hydroxyl groups increases molding processing time, which necessarily results in increased costs. In summary, in applications for making polyurethane articles, polyether polyols having a relatively high content of terminal primary hydroxyl groups should be selected.
Pure polyether polyol has no pungent smell, but most polyether polyols have pungent smell in practical application, which is mainly mixed with byproducts or auxiliaries in the production process, and the byproducts or the auxiliaries can belong to volatile organic matters, so that the polyether polyol has certain smell in practical application. Although the pungent smell does not affect the chemical performance of the polyether polyol in application, with the continuous pursuit of people for high living quality, green and environment-friendly novel polyether polyol products are favored, the demand is continuously expanded, especially the application of industries such as automobiles, clothes, furniture and the like closely related to the daily life of people has higher requirements on the quality of the polyether polyol, and most of similar products still need to improve the quality of the polyether polyol so as to meet the market demand.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of polyether polyol with high activity and low volatile matter.
The preparation method of the polyether polyol with high activity and low volatile matter comprises the following steps:
(1) synthesizing polyether polyol oligomer with high-efficiency catalytic activity by using a polyol compound as an initiator and an alkali metal aqueous solution as a catalyst;
(2) taking the polyether polyol oligomer with high catalytic activity prepared in the step (1) as basic polyether, firstly adding propylene oxide to react under the pressure of 0-0.5 MPa and the temperature of 80-150 ℃, then carrying out internal pressure reaction after adding, then adding ethylene oxide to react, and then carrying out internal pressure reaction after adding to prepare a high-activity polyether polyol crude polymer;
(3) and (3) refining the high-activity polyether polyol crude polymer prepared in the step (2) to obtain the high-activity low-volatile polyether polyol.
Wherein:
the propylene oxide is firstly added for reaction, then the internal pressure reaction is carried out after the addition, and the process of adding the propylene oxide and the process of the internal pressure reaction are random copolymerization processes.
And adding ethylene oxide for reaction, and performing internal pressure reaction after the addition is finished, wherein the process of adding the ethylene oxide and the process of the internal pressure reaction are end-capping polymerization processes.
The polyalcohol compound is one or a mixture of more of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerol, trimethylolpropane, pentaerythritol, xylitol, sorbitol, mannitol, sucrose or glucoside according to any proportion.
The alkali metal water solution is a mixture of one or more of sodium methoxide, sodium ethoxide, potassium hydroxide or sodium hydroxide according to any proportion; the concentration of the alkali metal aqueous solution is 30-50 wt%.
In the polyether polyol oligomer with high catalytic activity, the content of alkali metal is 3-10 wt%.
The propylene oxide is added in four stages, wherein 10-20% of the total mass of the propylene oxide is added in the first stage, 10-20% of the total mass of the propylene oxide is added in the second stage, 10-20% of the total mass of the propylene oxide is added in the third stage, and the rest of the propylene oxide is added in the fourth stage; wherein the content of the first and second substances,
the first stage is as follows:
the feeding flow is increased from 0t/h to 7-15 t/h;
the feeding temperature is decreased from 130 ℃ to 128-124 ℃, and the decreasing rate is 0.03-0.1 ℃/min.
And a second stage:
the feeding flow is kept at 7-15 t/h;
the feeding temperature is decreased from 128-124 ℃ to 123-115 ℃, and the decreasing rate is 0.15-0.25 ℃/min.
And a third stage:
the feeding flow is decreased from 7 to 15t/h to 3 to 6 t/h;
the feeding temperature is decreased from 123-115 ℃ to 114-98 ℃, and the decreasing rate is 0.10-0.44 ℃/min.
A fourth stage:
the feeding flow is kept at 3-6 t/h;
the feeding temperature is decreased from 114-98 ℃ to 97-85 ℃, and the decreasing rate is 0.03-0.08 ℃/min.
The propylene oxide is added for reaction, and then the internal pressure reaction is carried out, wherein the internal pressure reaction time is 60-120 minutes, the temperature is 110-140 ℃, and the pressure is-0.02-0.5 MPa.
The temperature of adding the ethylene oxide is 80-140 ℃.
And adding ethylene oxide for reaction, and performing internal pressure reaction after the addition is finished, wherein the internal pressure reaction time is 10-40 minutes, the temperature is 110-140 ℃, and the pressure is-0.02-0.5 MPa.
The mass fraction of the ethylene oxide is 10-22% of the high-activity low-volatile polyether polyol prepared in the step (3).
The refining treatment is sequentially carried out neutralization, adsorption, crystallization, filtration and separation treatment by a volatile organic matter treatment device, wherein the operating pressure of the volatile organic matter treatment device is-0.090-0.098 MPa, and the temperature is 100-150 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1. the polyether polyol is produced by adopting the preparation method of the polyether polyol with high activity and low volatile matter, the production period of the polyether polyol product can be obviously shortened, and the produced product has the characteristics of high activity, low content of volatile organic matters and small smell. Meanwhile, the prepared polyurethane foam has the characteristics of high indentation strength, high compression ratio and the like, and can meet the relevant requirements of medium-high grade automobile seat products on the polyurethane foam.
2. The feeding flow, the reaction temperature and the reaction pressure of the propylene oxide feeding process are controlled in a segmented mode, so that the polymerization reaction efficiency can be effectively improved, the generation of side reactions is reduced, and the preparation of the high-activity high-molecular-weight low-unsaturation polyether polyol is facilitated.
3. The preparation method is scientific, reasonable, simple and feasible.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Example 1
(1) Preparation of polyether polyol oligomers
At 15m32460kg of glycerin and 100kg of 45% aqueous potassium hydroxide solution were added to a stainless steel reactor, and nitrogen substitution was carried out, and the amount of oxygen contained in the reactor was measured to be less than 100 ppm. Raising the temperature to 80 ℃, and carrying out nitrogen bubbling and reduced pressure dehydration. The temperature in the kettle is kept at 90 +/-2 ℃ and the pressure is kept at 0.1 +/-0.02 MPa, 9540kg of propylene oxide is continuously added, the internal pressure is kept for reaction for 30 minutes, and the reaction temperature is 90 +/-2 ℃. And then pumping 700kg of 45% potassium hydroxide aqueous solution in a sealed way, heating to 100 +/-2 ℃, carrying out nitrogen bubbling and reduced pressure dehydration to obtain polyether polyol oligomer with high catalytic activity, wherein the water content is less than 0.12 wt%, and cooling and discharging to obtain the polyether polyol oligomer.
(2) Preparation of high-activity polyether polyol crude polymer
At 15m32.98t of the polyether polyol oligomer is added into the stainless steel reaction kettle, nitrogen replacement is carried out, and the oxygen content in the reaction kettle is measured to be lower than 100 ppm. Adding 21.98t of propylene oxide into a reaction kettle in four stages, wherein the propylene oxide is added in the first stage by 10 percent of the total mass of the propylene oxide, and the propylene oxide is added in the second stage10 percent of the total mass of the alkane, 10 percent of the total mass of the propylene oxide is added in the third stage, the rest propylene oxide is added in the fourth stage, wherein,
the first stage is as follows:
the feeding flow is increased from 0t/h to 7t/h, and the flow increase is regulated by a commercial DCS control system;
the feed temperature was ramped down from 130 ℃ to 128 ℃ at a ramp rate of 0.03 ℃/min.
And a second stage:
the feeding flow is kept at 7 t/h;
the feed temperature was ramped from 128 ℃ to 123 ℃ at a ramp rate of 0.15 ℃/min.
And a third stage:
the feeding flow is decreased from 7t/h to 3t/h, and the flow is decreased gradually and is adjusted by a commercial DCS control system;
the feed temperature was ramped from 123 ℃ to 114 ℃ at a ramp rate of 0.225 ℃/min.
A fourth stage:
the feeding flow is kept at 3 t/h;
the feed temperature was ramped from 114 ℃ to 97 ℃ at a ramp rate of 0.06 ℃/min.
After the feeding is finished, internal pressure reaction is carried out, the reaction time is 60 minutes, the reaction pressure is 0.2 +/-0.1 MPa, and the temperature is 112 +/-2 ℃. Then 7.04t of ethylene oxide is continuously added into the reaction kettle, the reaction temperature is controlled to be 90 +/-2 ℃, the pressure is 0.3 +/-0.1 MPa, internal pressure reaction is carried out after the feeding is finished, the temperature is 112 +/-2 ℃, the pressure is 0.3 +/-0.1 MPa, and the time is 10 minutes.
(3) Purification of polyether polyol crude Polymer
The polyether polyol crude polymer is subjected to neutralization, adsorption, crystallization, filtration and separation treatment by a volatile organic matter treatment device to obtain the polyether polyol with high activity and low volatile matter, wherein the operating pressure of the volatile organic matter treatment device is-0.090 MPa, and the temperature is 105 +/-2 ℃.
The analytical indices are as follows, hydroxyl number: 35mgKOH/g, viscosity: 870mpa.s, unsaturation value: 0.04mol/kg, water content: 0.01 wt%, potassium ion: 1ppm, color (APHA): 12, acid value: 0.02 mgKOH/g.
Example 2
(1) Preparation of polyether polyol oligomers
At 15m3Into a stainless steel reactor (2) was charged 2050kg of trimethylolpropane and 266kg of an aqueous solution of a mixture of sodium hydroxide and potassium hydroxide having a mass concentration of 30%, and nitrogen substitution was carried out, and the amount of oxygen contained in the reactor was measured to be less than 100 ppm. The temperature was raised to 105 ℃ and nitrogen bubbling and reduced pressure dehydration were carried out. Keeping the temperature in the kettle at 100 +/-2 ℃ and the pressure at 0.2 +/-0.02 MPa, continuously adding 7950kg of propylene oxide, and reacting for 40 minutes under internal pressure at the reaction temperature of 100 +/-2 ℃. And then, pumping 1400kg of 30% potassium hydroxide aqueous solution in a sealed manner, heating to 100 +/-2 ℃, carrying out nitrogen bubbling and reduced pressure dehydration to obtain polyether polyol oligomer with high catalytic activity, wherein the water content is less than 0.12 wt%, and cooling and discharging to obtain the polyether polyol oligomer.
(2) Preparation of high-activity polyether polyol crude polymer
At 15m32.98t of the polyether polyol oligomer is added into the stainless steel reaction kettle, nitrogen replacement is carried out, and the oxygen content in the reaction kettle is measured to be lower than 100 ppm. Adding 23.58t of propylene oxide into a reaction kettle in four stages, wherein the first stage is added with 20 percent of the total mass of the propylene oxide, the second stage is added with 20 percent of the total mass of the propylene oxide, the third stage is added with 20 percent of the total mass of the propylene oxide, the fourth stage is added with the rest propylene oxide,
the first stage is as follows:
the feeding flow is increased from 0t/h to 15t/h, and the flow increase is regulated by a commercial DCS control system;
the feed temperature was ramped from 130 ℃ to 124 ℃ at a ramp rate of 0.1 ℃/min.
And a second stage:
the feeding flow is kept at 15 t/h;
the feed temperature was ramped down from 124 ℃ to 115 ℃ at a ramp rate of 0.25 ℃/min.
And a third stage:
the feeding flow is decreased from 15t/h to 6t/h, and the flow is decreased gradually and is adjusted by a commercial DCS control system;
the feed temperature was ramped from 115 ℃ to 110 ℃ at a ramp rate of 0.125 ℃/min.
A fourth stage:
the feeding flow is kept at 6 t/h;
the feed temperature was decreased from 110 ℃ to 85 ℃ at a rate of 0.08 ℃/min.
After the feeding is finished, internal pressure reaction is carried out, the reaction time is 120 minutes, the reaction pressure is 0.1 +/-0.12 MPa, and the temperature is 130 +/-2 ℃. Then, 5.44t of ethylene oxide is continuously added into the reaction kettle, the reaction temperature is controlled to be 100 +/-2 ℃, the pressure is controlled to be 0.4 +/-0.1 MPa, and the internal pressure reaction is carried out after the feeding is finished, the temperature is controlled to be 130 +/-2 ℃, the pressure is controlled to be 0.2 +/-0.1 MPa, and the time is 40 minutes.
(3) Purification of polyether polyol crude Polymer
And (3) neutralizing, adsorbing, crystallizing, filtering and separating the polyether polyol crude polymer by using a volatile organic matter treatment device to obtain the polyether polyol with high activity and low volatile matter, wherein the operating pressure of the volatile organic matter treatment device is-0.098 MPa, and the temperature is 145 +/-2 ℃.
The analytical indices are as follows, hydroxyl number: 34mgKOH/g, viscosity: 890mpa.s, unsaturation value: 0.06mol/kg, moisture: 0.02 wt%, potassium ion: 2ppm, color (APHA): 15, acid value: 0.01 mgKOH/g.
Example 3
(1) Preparation of polyether polyol oligomers
At 15m31829kg of a mixture of glycerin and propylene glycol and 180kg of an aqueous solution of a mixture of sodium methoxide and potassium hydroxide having a mass concentration of 50% were charged into a stainless steel reactor, and nitrogen substitution was carried out, and the amount of oxygen contained in the reactor was measured to be less than 100 ppm. Raising the temperature to 110 +/-2 ℃, and carrying out nitrogen bubbling and reduced pressure dehydration. Keeping the temperature in the kettle at 110 +/-2 ℃ and the pressure at 0.1 +/-0.02 MPa, continuously adding 7155kg of propylene oxide, and reacting for 30 minutes under internal pressure at the reaction temperature of 110 +/-2 ℃. And then pumping 900kg of 50% potassium hydroxide aqueous solution in a sealed way, heating to 110 +/-2 ℃, bubbling nitrogen, decompressing and dehydrating, measuring the moisture content to be less than 0.12 wt%, and cooling and discharging to obtain the polyether polyol oligomer with high catalytic activity.
(2) Preparation of high-activity polyether polyol crude polymer
At 15m32.98t of the polyether polyol oligomer is added into the stainless steel reaction kettle, nitrogen replacement is carried out, and the oxygen content in the reaction kettle is measured to be lower than 100 ppm. Adding 24.22t of propylene oxide into a reaction kettle in four stages, wherein 15 percent of the total mass of the propylene oxide is added in the first stage, 15 percent of the total mass of the propylene oxide is added in the second stage, 15 percent of the total mass of the propylene oxide is added in the third stage, the rest of the propylene oxide is added in the fourth stage,
the first stage is as follows:
the feeding flow is increased from 0t/h to 10t/h, and the flow increase is regulated by a commercial DCS control system;
the feed temperature was ramped from 130 ℃ to 124 ℃ at a ramp rate of 0.09 ℃/min.
And a second stage:
the feeding flow is kept at 10 t/h;
the feed temperature was ramped from 124 ℃ to 120 ℃ at a ramp rate of 0.20 ℃/min.
And a third stage:
the feeding flow is decreased from 10t/h to 6t/h, and the flow is decreased gradually and is adjusted by a commercial DCS control system;
the feed temperature was decreased from 120 ℃ to 100 ℃ at a rate of 0.40 ℃/min.
A fourth stage:
the feeding flow is kept at 6 t/h;
the feeding temperature is decreased from 100 ℃ to 90 ℃ at a decreasing rate of 0.03 ℃/min.
After the feeding is finished, internal pressure reaction is carried out, the reaction time is 90 minutes, the pressure is 0.25 +/-0.1 MPa, and the temperature is 125 +/-2 ℃. Then 4.8t of ethylene oxide is continuously added into the reaction kettle, the reaction temperature is controlled to be 110 +/-2 ℃, the pressure is controlled to be 0.25 +/-0.1 MPa, the internal pressure reaction is carried out after the feeding is finished, the temperature is 125 +/-2 ℃, the pressure is 0.25 +/-0.1 MPa, and the time is 20 minutes.
(3) Purification of polyether polyol crude Polymer
The polyether polyol crude polymer is subjected to neutralization, adsorption, crystallization, filtration and separation treatment by a volatile organic matter treatment device to obtain the polyether polyol with high activity and low volatile matter, wherein the operating pressure of the volatile organic matter treatment device is-0.095 MPa, and the temperature is 130 +/-2 ℃.
The analytical indices are as follows, hydroxyl number: 36mgKOH/g, viscosity: 850mpa.s, unsaturation value: 0.05mol/kg, moisture: 0.01 wt%, potassium ion: 1ppm, color (APHA): 9, acid value: 0.02 mgKOH/g.
Example 4
(1) Preparation of polyether polyol oligomers
At 15m31640kg of glycerol, 200kg of an aqueous solution of a mixture of 48% by mass of potassium hydroxide and sodium ethoxide, was added to the stainless steel reactor, and nitrogen substitution was carried out, and the oxygen content in the reactor was measured to be less than 100 ppm. Raising the temperature to 115 +/-2 ℃, and carrying out nitrogen bubbling and reduced pressure dehydration. Keeping the temperature in the kettle at 115 +/-2 ℃ and the pressure at 0.1 +/-0.05 MPa, continuously adding 6360kg of propylene oxide, and reacting for 40 minutes under internal pressure at 115 +/-2 ℃. And then pumping 800kg of 48% potassium hydroxide aqueous solution in a sealed way, heating to 115 +/-2 ℃, carrying out nitrogen bubbling and reduced pressure dehydration until the moisture content is less than 0.12 wt%, and cooling and discharging to obtain the polyether polyol oligomer with high catalytic activity.
(2) Preparation of high-activity polyether polyol crude polymer
At 40m32.98t of the polyether polyol oligomer is added into the stainless steel reaction kettle, nitrogen replacement is carried out, and the oxygen content in the reaction kettle is measured to be lower than 100 ppm. Adding 25.82t of propylene oxide into a reaction kettle in four stages, wherein the first stage is added with 16 percent of the total mass of the propylene oxide, the second stage is added with 16 percent of the total mass of the propylene oxide, the third stage is added with 16 percent of the total mass of the propylene oxide, the fourth stage is added with the rest propylene oxide, wherein,
the first stage is as follows:
the feeding flow is increased from 0t/h to 8t/h, and the flow increase is regulated by a commercial DCS control system;
the feed temperature was ramped down from 130 ℃ to 126 ℃ at a ramp rate of 0.1 ℃/min.
And a second stage:
the feeding flow is kept at 8 t/h;
the feed temperature was ramped from 126 ℃ to 118 ℃ at a ramp rate of 0.18 ℃/min.
And a third stage:
the feeding flow is decreased from 8t/h to 5t/h, and the flow is decreased gradually and is adjusted by a commercial DCS control system;
the feed temperature was ramped from 118 ℃ to 110 ℃ at a ramp rate of 0.40 ℃/min.
A fourth stage:
the feeding flow is kept at 5 t/h;
the feed temperature was ramped from 110 ℃ to 92 ℃ at a ramp rate of 0.05 ℃/min.
After the feeding is finished, internal pressure reaction is carried out, the reaction time is 110 minutes, the pressure is 0.15 +/-0.1 MPa, and the temperature is 120 +/-2 ℃. Then 3.2t of ethylene oxide is continuously added into the reaction kettle, the reaction temperature is controlled to be 120 +/-2 ℃, the pressure is 0.15 +/-0.1 MPa, internal pressure reaction is carried out after the feeding is finished, the temperature is 120 +/-2 ℃, the pressure is 0.15 +/-0.1 MPa, and the time is 30 minutes.
(3) Purification of polyether polyol crude Polymer
The polyether polyol crude polymer is subjected to neutralization, adsorption, crystallization, filtration and separation treatment by a volatile organic matter treatment device to obtain the polyether polyol with high activity and low volatile matter, wherein the operating pressure of the volatile organic matter treatment device is-0.093 MPa, and the temperature is 120 +/-2 ℃.
The analytical indices are as follows, hydroxyl number: 35mgKOH/g, viscosity: 860mpa.s, unsaturation value: 0.04mol/kg, water content: 0.02 wt%, potassium ion: 2ppm, color (APHA): 9, acid value: 0.02 mgKOH/g.
Comparative example
(1) Preparation of polyether polyol oligomer comparative example
At 15m32460g of glycerol and 215kg of potassium hydroxide with the purity of 95% are added into a stainless steel reaction kettle, nitrogen replacement is carried out, and the oxygen content in the reaction kettle is measured to be lower than 100 ppm. The temperature is raised to 115 ℃, and nitrogen bubbling and reduced pressure dehydration are carried out. And keeping the temperature in the kettle at 100 +/-2 ℃ and the pressure at 0.2 +/-0.02 MPa, continuously adding 9540g of propylene oxide, reacting for 30 minutes under internal pressure, and cooling and discharging to obtain the polyether polyol oligomer in the comparative example.
(2) Preparation of comparative polyether polyol
At 40m32.98t of the polyether polyol oligomer is added into the stainless steel reaction kettle, nitrogen replacement is carried out, and the oxygen content in the reaction kettle is measured to be lower than 100 ppm. Keeping the temperature in the kettle at 110 +/-2 ℃ and the pressure at 0.1 +/-0.02 MPa, continuously adding 24.22t of propylene oxide into the reaction kettle, and then carrying out internal pressure reaction for 30 minutes. And then continuously adding 4.8t of ethylene oxide into the reaction kettle, controlling the reaction temperature to be 110 +/-2 ℃ and the pressure to be 0.2 +/-0.1 MPa, then carrying out internal pressure reaction for 30 minutes, cooling and discharging to obtain the polyether polyol crude polymer in the comparative example. And neutralizing, crystallizing and filtering the polyether polyol crude polymer to obtain the polyether polyol of the comparative example.
The high activity low volatile polyether polyols obtained in examples 1 to 4 and the polyether polyol obtained in comparative example were tested for primary hydroxyl group content, formaldehyde content, acetaldehyde content, polymerization time and odor, respectively, and the results are shown in table 1.
TABLE 1 polyether polyol test results
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example |
| Primary hydroxyl group content (%) | 79 | 81 | 79 | 82 | 73 |
| Formaldehyde (ppm) | 0.1 | 0.3 | 0.7 | 1 | ＞10 |
| Acetaldehyde (ppm) | 5 | 8 | 15 | 17 | ＞20 |
| Polymerization time (h) | 9 | 9.5 | 10 | 10 | 24 |
| Smell(s) | Small | Small | Small | Small | Big (a) |
Polyurethane foams were prepared by the same process using the high activity low volatile polyether polyols prepared in examples 1-4 and a commercially available polyether polyol as one of the raw materials, and the test indexes of the prepared polyurethane foams are shown in table 2.
TABLE 2 polyurethane foam test results
Claims (9)
1. A preparation method of polyether polyol with high activity and low volatile matter is characterized by comprising the following steps: the method comprises the following steps:
(1) synthesizing polyether polyol oligomer with high-efficiency catalytic activity by using a polyol compound as an initiator and an alkali metal aqueous solution as a catalyst;
(2) taking the polyether polyol oligomer with high catalytic activity prepared in the step (1) as basic polyether, firstly adding propylene oxide to react under the pressure of 0-0.5 MPa and the temperature of 80-150 ℃, then carrying out internal pressure reaction after adding, then adding ethylene oxide to react, and then carrying out internal pressure reaction after adding to prepare a high-activity polyether polyol crude polymer;
(3) refining the high-activity polyether polyol crude polymer prepared in the step (2) to obtain high-activity low-volatile polyether polyol;
the propylene oxide is added in four stages, wherein 10-20% of the total mass of the propylene oxide is added in the first stage, 10-20% of the total mass of the propylene oxide is added in the second stage, 10-20% of the total mass of the propylene oxide is added in the third stage, and the rest of the propylene oxide is added in the fourth stage; wherein the content of the first and second substances,
the first stage is as follows:
the feeding flow is increased from 0t/h to 7-15 t/h;
the feeding temperature is decreased from 130 ℃ to 128-124 ℃, and the decreasing rate is 0.03-0.1 ℃/min;
and a second stage:
the feeding flow is kept at 7-15 t/h;
the feeding temperature is decreased from 128-124 ℃ to 123-115 ℃, and the decreasing rate is 0.15-0.25 ℃/min;
and a third stage:
the feeding flow is decreased from 7 to 15t/h to 3 to 6 t/h;
the feeding temperature is decreased from 123-115 ℃ to 114-98 ℃, and the decreasing rate is 0.10-0.44 ℃/min;
a fourth stage:
the feeding flow is kept at 3-6 t/h;
the feeding temperature is decreased from 114-98 ℃ to 97-85 ℃, and the decreasing rate is 0.03-0.08 ℃/min.
2. The process for the preparation of high activity low volatiles polyether polyols of claim 1, characterized in that: the polyalcohol compound is one or a mixture of more of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerol, trimethylolpropane, pentaerythritol, xylitol, sorbitol, mannitol, sucrose or glucoside according to any proportion.
3. The process for the preparation of high activity low volatiles polyether polyols of claim 1, characterized in that: the alkali metal water solution is a mixture of one or more of sodium methoxide, sodium ethoxide, potassium hydroxide or sodium hydroxide according to any proportion; the concentration of the alkali metal aqueous solution is 30-50 wt%.
4. The process for the preparation of high activity low volatiles polyether polyols of claim 1, characterized in that: in the polyether polyol oligomer with high catalytic activity, the content of alkali metal is 3-10 wt%.
5. The process for the preparation of high activity low volatiles polyether polyols of claim 1, characterized in that: the propylene oxide is added for reaction, and then the internal pressure reaction is carried out, wherein the internal pressure reaction time is 60-120 minutes, the temperature is 110-140 ℃, and the pressure is-0.02-0.5 MPa.
6. The process for the preparation of high activity low volatiles polyether polyols of claim 1, characterized in that: the temperature of adding the ethylene oxide is 80-140 ℃.
7. The process for the preparation of high activity low volatiles polyether polyols of claim 1, characterized in that: and adding ethylene oxide for reaction, and performing internal pressure reaction after the addition is finished, wherein the internal pressure reaction time is 10-40 minutes, the temperature is 110-140 ℃, and the pressure is-0.02-0.5 MPa.
8. The process for the preparation of high activity low volatiles polyether polyols of claim 1, characterized in that: the mass fraction of the ethylene oxide is 10-22% of the high-activity low-volatile polyether polyol prepared in the step (3).
9. The process for the preparation of high activity low volatiles polyether polyols of claim 1, characterized in that: the refining treatment is sequentially carried out neutralization, adsorption, crystallization, filtration and separation treatment by a volatile organic matter treatment device, wherein the operating pressure of the volatile organic matter treatment device is-0.090-0.098 MPa, and the temperature is 100-150 ℃.
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