CN110885439A - Method for reducing content of volatile organic compounds in polyether polyol - Google Patents
Method for reducing content of volatile organic compounds in polyether polyol Download PDFInfo
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- CN110885439A CN110885439A CN201911153406.2A CN201911153406A CN110885439A CN 110885439 A CN110885439 A CN 110885439A CN 201911153406 A CN201911153406 A CN 201911153406A CN 110885439 A CN110885439 A CN 110885439A
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- polyether polyol
- removing agent
- aldehyde removing
- reaction kettle
- acid
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 79
- 229920000570 polyether Polymers 0.000 title claims abstract description 79
- 229920005862 polyol Polymers 0.000 title claims abstract description 76
- 150000003077 polyols Chemical class 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 92
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 41
- 238000003756 stirring Methods 0.000 claims abstract description 41
- 239000003463 adsorbent Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 8
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 7
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000391 magnesium silicate Substances 0.000 claims description 7
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 7
- 235000019792 magnesium silicate Nutrition 0.000 claims description 7
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 6
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 claims description 6
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- MXLMTQWGSQIYOW-UHFFFAOYSA-N 3-methyl-2-butanol Chemical compound CC(C)C(C)O MXLMTQWGSQIYOW-UHFFFAOYSA-N 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 claims description 4
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 10
- 150000001299 aldehydes Chemical class 0.000 abstract description 36
- 239000000126 substance Substances 0.000 abstract description 13
- 230000005587 bubbling Effects 0.000 abstract description 10
- -1 aldehyde ketone Chemical class 0.000 abstract description 4
- 238000005886 esterification reaction Methods 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract description 2
- 230000008020 evaporation Effects 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 16
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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
- C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
Abstract
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for reducing the content of volatile organic compounds in polyether polyol. Adding polyether polyol to be treated into a reaction kettle, performing nitrogen replacement, stirring and heating, adding an aldehyde removing agent into the reaction kettle under the protection of nitrogen, performing nitrogen replacement after the addition is finished, continuously stirring for 10-120 minutes, adding pure water and a refined adsorbent respectively, stirring, drying, and filtering to obtain a finished product; the aldehyde removing agent comprises an aldehyde removing agent A, an aldehyde removing agent B and an auxiliary agent C, the adding amount of the aldehyde removing agent is 0.01-0.5 per mill of the mass of the polyether polyol to be treated, and the mass ratio of the aldehyde removing agent A to the aldehyde removing agent B to the auxiliary agent C is 1: 1: 1-1: 5: 50. according to the invention, aldehyde ketone substances in polyether polyol to be treated are directly oxidized and decomposed into small molecular substances by a chemical reaction method or removed by an esterification reaction, and volatile organic compounds can be effectively removed by nitrogen bubbling evaporation purification and physical adsorption.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for reducing the content of volatile organic compounds in polyether polyol.
Background
Along with the living standard of peopleThe continuous improvement of the technology, the ecological livable and healthy trip problems cause wide attention of the whole society. The state improves and revises the standards of passenger cars, and releases national standard' air quality evaluation guide in passenger cars (revision GB _ T27630-2011). According to this standard, it is required that the formaldehyde content does not exceed 0.1mg/m3The content of acetaldehyde is not more than 0.2mg/m3The content of acrolein is not more than 0.05mg/m3. The high-end automobile seat transnational production enterprises develop the purchasing standard of the main raw material polyether polyol according to the standard, and the content of formaldehyde, acetaldehyde and acrolein in the polyether polyol product is required to be not higher than 1.0 mg/g. After the standard is issued, the trialdehyde content of most domestic polyether polyol production enterprises cannot meet the standard, the acetaldehyde content of foreign polyether polyol products cannot meet the standard, and automobile seat manufacturers can only reduce the content of aldehyde and ketone substances in polyether polyol by adding an aldehyde removing agent. Therefore, there is an increasing interest in reducing the content of volatile organic compounds in polyether polyols.
Chinese patent CN109096479A discloses a method for reducing propionaldehyde in polyether polyol, which adopts specific peroxide and specific catalyst to convert propionaldehyde in polyether polyol into propionic acid, then reacts with solid alkaline substance, and reduces the propionaldehyde content in polyether in a filtering manner, specifically as follows: the specific peroxide is hydrogen peroxide, the using amount of the specific peroxide is 0.02-0.2% of the mass of the polyether polyol, the specific catalyst is a cobalt metal complex catalyst, and the using amount of the specific catalyst is 0.0005-0.002% of the mass of the polyether polyol; the solid alkaline substance is porous magnesium silicate, and the using amount of the solid alkaline substance is 0.1-1% of the mass of the polyether polyol. The method effectively reduces the content of propionaldehyde in the polyether, is safe and reliable, and saves the cost. However, this method requires a specific catalyst to remove propionaldehyde from polyether polyol, which increases production cost.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method overcomes the defects of the prior art, can completely remove all aldehyde and ketone substances in the polyether polyol to be treated without specific catalytic treatment, saves the production cost and improves the production efficiency.
The method for reducing the content of the volatile organic compounds in the polyether polyol comprises the following steps:
adding polyether polyol to be treated into a reaction kettle, performing nitrogen replacement, stirring and heating, adding an aldehyde removing agent into the reaction kettle under the protection of nitrogen, performing nitrogen replacement after the addition is finished, continuously stirring for 10-120 minutes, adding pure water and a refined adsorbent respectively, stirring, drying, and filtering to obtain a polyether polyol finished product;
the aldehyde removing agent comprises an aldehyde removing agent A, an aldehyde removing agent B and an auxiliary agent C, the adding amount of the aldehyde removing agent is 0.01-0.5 per mill of the mass of the polyether polyol to be treated, and the mass ratio of the aldehyde removing agent A to the aldehyde removing agent B to the auxiliary agent C is 1: 1: 1-1: 5: 50, preferably 1: 1: 1-1: 5: 10;
the aldehyde removing agent A is one or a mixture of more of ethanol, propanol, n-butanol, n-pentanol, hexanol, heptanol, octanol, nonanol, decanol, 3-methyl-2-butanol, tert-butanol, 2-methyl-2-butanol, propylene glycol, ethylene glycol, diethylene glycol, isobutanol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol or glycerol, and preferably ethanol or propanol;
the aldehyde removing agent B is one or a mixture of more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, oxalic acid, hypochlorous acid, sulfurous acid, acetic acid, trifluoroacetic acid, propionic acid, p-toluenesulfonic acid, trifluoroacetic acid, methanesulfonic acid or tert-valeric acid, preferably hydrochloric acid or phosphoric acid;
the assistant C is polyether polyol with 2 functionality, 400-12000 number average molecular weight or polyether polyol with 3 functionality, 400-12000 number average molecular weight, or the mixture of two of the two, preferably polyether polyol with 3 functionality, 5000-6000 number average molecular weight.
The aldehyde removing agent A and the aldehyde removing agent B are uniformly dispersed and dissolved in the auxiliary agent C, and the aldehyde removing agent A and the aldehyde removing agent B can oxidize and decompose aldehyde ketone substances in the polyether to be treated or remove the aldehyde ketone substances through esterification reaction under the synergistic chemical action.
Wherein:
stirring and heating to 50-130 ℃, and adding an aldehyde removing agent into the reaction kettle under the protection of nitrogen.
The adding amount of the pure water is 1-10% of the mass of the polyether polyol to be treated.
The refined adsorbent is one or a mixture of magnesium silicate, aluminum silicate or magnesium aluminum silicate.
The addition amount of the refined adsorbent is 1-10 per mill of the mass of the polyether polyol to be treated.
The step of respectively adding pure water and the refined adsorbent and stirring specifically comprises the following steps: firstly, adding pure water and stirring for 10-120 minutes, then adding the refined adsorbent and stirring for 10-120 minutes.
And replacing the nitrogen until the oxygen content in the reaction kettle is less than or equal to 100 ppm.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the aldehyde removing agent is added into the polyether polyol to be treated, the aldehyde and ketone substances in the polyether polyol to be treated are directly oxidized and decomposed into small molecular substances by a chemical reaction method or are removed by an esterification reaction, and the volatile organic compounds can be effectively removed by a subsequent nitrogen bubbling evaporation purification and physical adsorption mode.
2. The method disclosed by the invention can effectively reduce the content of volatile organic compounds (formaldehyde, acetaldehyde, acrolein, acetone and propionaldehyde) in the polyether polyol, reduce the concentration of harmful gas, meet the requirements of related environmental protection indexes, improve the downstream application quality of the polyether polyol and meet the use requirements of preparing high-end polyurethane products.
3. According to the method, all aldehyde and ketone substances in the polyether polyol to be treated can be completely removed without specific catalytic treatment, so that the production cost is saved, and the production efficiency is improved.
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
Adding 1000g of polyether polyol to be treated into a 5-liter stainless steel reaction kettle, replacing with nitrogen for 3 times (the oxygen content in the reaction kettle is less than or equal to 100ppm), starting the reaction kettle for stirring, heating the materials in the kettle to 50 ℃, adding 0.01g of aldehyde removing agent (propylene glycol: 2 functionality, 400 molecular weight polyether polyol is 1: 1: 1) into the reaction kettle under the protection of nitrogen, keeping the reaction kettle stirrer in a rotating state, replacing with nitrogen (the oxygen content in the reaction kettle is less than or equal to 100ppm), stirring for 10 minutes, then sequentially adding 10g of pure water and 1g of magnesium silicate adsorbent into the reaction kettle, stirring for 10 minutes respectively, bubbling the materials with nitrogen, drying under reduced pressure, and filtering to obtain the polyether polyol finished product.
Example 2
Adding 1000g of polyether polyol to be treated into a 5-liter stainless steel reaction kettle, replacing the polyether polyol with nitrogen for 3 times (the oxygen content in the reaction kettle is less than or equal to 100ppm), starting the reaction kettle to stir, heating the materials in the kettle to 130 ℃, adding 0.5g of aldehyde removing agent (a mixture of ethylene glycol and tert-butyl alcohol in a mass ratio of 1: a mixture of sulfuric acid and nitric acid in a mass ratio of 1: a mixture of 2-functionality polyether polyol and 4000-molecular-weight polyether polyol in a mass ratio of 3-functionality 3000: 1: 5: 50) into the reaction kettle under the protection of nitrogen, keeping the reaction kettle stirrer in a rotating state, replacing the reaction kettle with nitrogen (the oxygen content in the reaction kettle is less than or equal to 100ppm), stirring for 120 minutes, then respectively adding 100g of pure water and 10g of aluminum silicate adsorbent into the reaction kettle, stirring for 120 minutes respectively, then bubbling the materials, drying under reduced pressure, and filtering to obtain polyether polyol product.
Example 3
Adding 1000g of polyether polyol to be treated into a 5-liter stainless steel reaction kettle, replacing with nitrogen for 3 times (the oxygen content in the reaction kettle is less than or equal to 100ppm), starting the reaction kettle for stirring, heating the materials in the kettle to 110 ℃, adding 0.05g of an aldehyde removing agent (ethylene glycol: 3 functionality of sulfuric acid and 3000 molecular weight polyether polyol is 1: 5: 20) into the reaction kettle under the protection of nitrogen, keeping the reaction kettle stirrer in a rotating state, performing nitrogen replacement on the reaction kettle (the oxygen content in the reaction kettle is less than or equal to 100ppm), stirring for 20 minutes, then sequentially adding 20g of pure water and 8g of magnesium aluminum silicate adsorbent into the reaction kettle, stirring for 20 minutes respectively, then bubbling the materials with nitrogen, drying under reduced pressure, and filtering to obtain the polyether polyol finished product.
Example 4
Adding 1000g of polyether polyol to be treated into a 5-liter stainless steel reaction kettle, performing nitrogen replacement for 3 times (the oxygen content in the reaction kettle is less than or equal to 100ppm), starting the reaction kettle for stirring, heating materials in the reaction kettle to 55 ℃, adding 0.3g of aldehyde removing agent (heptanol: hydrochloric acid: 8000 molecular weight polyether polyol with 2 functionality is 1: 3: 10) into the reaction kettle under the protection of nitrogen, keeping the reaction kettle stirrer in a rotating state, performing nitrogen replacement on the reaction kettle (the oxygen content in the reaction kettle is less than or equal to 100ppm), stirring for 90 minutes, then sequentially adding 70g of pure water and 6g of aluminum silicate and magnesium silicate mixed adsorbent into the reaction kettle, respectively stirring for 90 minutes, then performing nitrogen bubbling on the materials, drying under reduced pressure, and filtering to obtain a polyether polyol finished product.
Example 5
Adding 1000g of polyether polyol to be treated into a 5-liter stainless steel reaction kettle, performing nitrogen replacement for 3 times (the oxygen content in the reaction kettle is less than or equal to 100ppm), starting the reaction kettle for stirring, heating the materials in the kettle to 110 ℃, adding 0.05g of an aldehyde removing agent (ethanol: hydrochloric acid: 3 functionality, 5000 molecular weight polyether polyol is 1: 5: 10) into the reaction kettle under the protection of nitrogen, keeping the reaction kettle stirrer in a rotating state, performing nitrogen replacement on the reaction kettle (the oxygen content in the reaction kettle is less than or equal to 100ppm), stirring for 20 minutes, then sequentially adding 20g of pure water and 8g of magnesium aluminum silicate adsorbent into the reaction kettle, stirring for 20 minutes respectively, then performing nitrogen bubbling on the materials, drying under reduced pressure, and filtering to obtain the polyether polyol finished product.
Example 6
Adding 1000g of polyether polyol to be treated into a 5-liter stainless steel reaction kettle, performing nitrogen replacement for 3 times (the oxygen content in the reaction kettle is less than or equal to 100ppm), starting the reaction kettle for stirring, heating the materials in the kettle to 110 ℃, adding 0.05g of an aldehyde removing agent (propanol: 3 functionality and 6000 molecular weight polyether polyol is 1: 5: 10) into the reaction kettle under the protection of nitrogen, keeping the reaction kettle stirrer in a rotating state, performing nitrogen replacement on the reaction kettle (the oxygen content in the reaction kettle is less than or equal to 100ppm), stirring for 20 minutes, then sequentially adding 20g of pure water and 8g of magnesium aluminum silicate adsorbent into the reaction kettle, stirring for 20 minutes respectively, then performing nitrogen bubbling on the materials, drying under reduced pressure, and filtering to obtain the polyether polyol finished product.
Comparative example 1
Adding 1000g of polyether polyol to be treated into a 5-liter stainless steel reaction kettle, replacing with nitrogen for 3 times (the oxygen content in the reaction kettle is less than or equal to 100ppm), starting the reaction kettle for stirring, heating the materials in the kettle to 50 ℃, adding 0.01g of an aldehyde removing agent (phosphoric acid: 2-functionality 400-molecular-weight polyether polyol is 1: 1) into the reaction kettle under the protection of nitrogen, keeping the reaction kettle stirrer in a rotating state, replacing with nitrogen (the oxygen content in the reaction kettle is less than or equal to 100ppm), stirring for 10 minutes, then sequentially adding 10g of pure water and 1g of a magnesium silicate adsorbent into the reaction kettle, stirring for 10 minutes respectively, bubbling the materials with nitrogen, drying under reduced pressure, and filtering to obtain a polyether polyol finished product.
Comparative example 2
Adding 1000g of polyether polyol to be treated into a 5-liter stainless steel reaction kettle, replacing with nitrogen for 3 times (the oxygen content in the reaction kettle is less than or equal to 100ppm), starting the reaction kettle for stirring, heating the materials in the kettle to 50 ℃, adding 0.01g of an aldehyde removing agent (propylene glycol: 2 functionality 400 molecular weight polyether polyol is 1: 1) into the reaction kettle under the protection of nitrogen, keeping the reaction kettle stirrer in a rotating state, performing nitrogen replacement on the reaction kettle (the oxygen content in the reaction kettle is less than or equal to 100ppm), stirring for 10 minutes, then sequentially adding 10g of pure water and 1g of a magnesium silicate adsorbent into the reaction kettle, respectively stirring for 10 minutes, then performing nitrogen bubbling on the materials, drying under reduced pressure, and filtering to obtain a polyether polyol finished product.
Comparative example 3
The polyether polyol to be treated is not subjected to any treatment.
The polyether polyols of examples 1-6 and comparative examples 1-3 were subjected to the aldehyde number test, and the test results are shown in Table 1.
TABLE 1 test results
Claims (7)
1. A method for reducing the content of volatile organic compounds in polyether polyol is characterized by comprising the following steps: the method comprises the following steps:
adding polyether polyol to be treated into a reaction kettle, performing nitrogen replacement, stirring and heating, adding an aldehyde removing agent into the reaction kettle under the protection of nitrogen, performing nitrogen replacement after the addition is finished, continuously stirring for 10-120 minutes, adding pure water and a refined adsorbent respectively, stirring, drying, and filtering to obtain a polyether polyol finished product;
the aldehyde removing agent comprises an aldehyde removing agent A, an aldehyde removing agent B and an auxiliary agent C, the adding amount of the aldehyde removing agent is 0.01-0.5 per mill of the mass of the polyether polyol to be treated, and the mass ratio of the aldehyde removing agent A to the aldehyde removing agent B to the auxiliary agent C is 1: 1: 1-1: 5: 50;
the aldehyde removing agent A is one or a mixture of more of ethanol, propanol, n-butanol, n-pentanol, hexanol, heptanol, octanol, nonanol, decanol, 3-methyl-2-butanol, tert-butanol, 2-methyl-2-butanol, propylene glycol, ethylene glycol, diethylene glycol, isobutanol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol or glycerol;
the aldehyde removing agent B is one or a mixture of more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, oxalic acid, hypochlorous acid, sulfurous acid, acetic acid, trifluoroacetic acid, propionic acid, p-toluenesulfonic acid, trifluoroacetic acid, methanesulfonic acid or tert-valeric acid;
the auxiliary agent C is one or a mixture of two of polyether polyol with the functionality of 2 and the number average molecular weight of 400-12000 or polyether polyol with the functionality of 3 and the number average molecular weight of 400-12000.
2. A process for reducing the volatile organic content of polyether polyols according to claim 1, wherein: stirring and heating to 50-130 ℃, and adding an aldehyde removing agent into the reaction kettle under the protection of nitrogen.
3. A process for reducing the volatile organic content of polyether polyols according to claim 1, wherein: the adding amount of the pure water is 1-10% of the mass of the polyether polyol to be treated.
4. A process for reducing the volatile organic content of polyether polyols according to claim 1, wherein: the refined adsorbent is one or more of magnesium silicate, aluminum silicate or magnesium aluminum silicate.
5. A process for reducing the volatile organic content of polyether polyols according to claim 1, wherein: the addition amount of the refined adsorbent is 1-10 per mill of the mass of the polyether polyol to be treated.
6. A process for reducing the volatile organic content of polyether polyols according to claim 1, wherein: respectively adding pure water and the refined adsorbent and stirring the mixture specifically: firstly, adding pure water and stirring for 10-120 minutes, then adding the refined adsorbent and stirring for 10-120 minutes.
7. A process for reducing the volatile organic content of polyether polyols according to claim 1, wherein: replacing nitrogen until the oxygen content in the reaction kettle is less than or equal to 100 ppm.
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