CN101775132A - Method for refining low-odor polyether polyol - Google Patents
Method for refining low-odor polyether polyol Download PDFInfo
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- CN101775132A CN101775132A CN201010104631A CN201010104631A CN101775132A CN 101775132 A CN101775132 A CN 101775132A CN 201010104631 A CN201010104631 A CN 201010104631A CN 201010104631 A CN201010104631 A CN 201010104631A CN 101775132 A CN101775132 A CN 101775132A
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Abstract
The invention relates to a method for refining low-odor polyether polyol. The polyether polyol is catalyzed and synthesized by using alkali metal. The method is characterized by comprising the following steps of: adsorbing, crystallizing and filtering for 1-5 times at 60-120 DEG C by using pure water which accounts for 0.1-10 percent of the total mass of rough polyether polyol and two adsorbents to obtain the low-odor polyether polyol, wherein the adsorbents are hydrated magnesium silicate and kieselguhr with the mass proportion of 1;1, and the total adding amount of the adsorbents accounts for 0.1-3 percent of the total mass of the rough polyether polyol. The invention can effectively remove the content of potassium and sodium ions in the polyether polyol, prevents the generation of a by-product generating odor to the greatest extent while effectively removing the potassium and sodium ions in polyether and enables the polyether polyols to hardly have odor, thereby fundamentally reducing the odor of the polyether.
Description
Technical field
The invention belongs to process for purification, particularly a kind of process for purification of low-odor polyether polyol to polyether glycol.
Background technology
Polyether glycol (abbreviation polyethers) is a main raw material of producing urethane resin.The synthetic basic small molecules polyvalent alcohol or the polyamine of adopting of polyether glycol is as initiator, adopt alkali-metal oxide compound or oxyhydroxide as catalyzer (the most frequently used catalyzer is a potassium hydroxide), propylene oxide or oxyethane react as polymerization single polymerization monomer and form the macromole liquid polymers.Polyether glycol after the polymerization contains catalyzer potassium hydroxide and part potassium alcoholate, unreacted monomer and oligopolymer thereof, so thick polyethers need carry out purifying treatment and remove these impurity.The removal method of these impurity is known, what use was maximum at present is to use sorbent material to carry out the adsorption filtration processing by adding acid neutralization back, yet contain about 0.05-0.2% (weight) residual water by neutralization, absorption back gained polyether glycol, contain the material of scent of with other, for example aldehydes, dioxolane, dioxane, vinyl carbinol and, two and the tripropylene glycol allyl ester, although the amount of odoriferous substance only is a small amount of usually, however they give polyether glycol with uniqueness, the intensive aromatic odour.
Thereby, developed and described method in the art, be used for from polyether glycol, removing the undesirable by product that in it is produced, produces.For example DE-A2755089 has described a kind of method of removing tedious by product.This method is particularly related to screw and vertical tube evaporator and removes less water and solvent and low molecular weight diols and the material that overpowering odor is arranged.Yet a shortcoming of this method is to remove the organic solvent of existence fully, and can only remove the material of overpowering odor on very low degree.Another shortcoming of the method for describing in this German Patent is to need expensive equipment.
Also can use falling film evaporator to come the purifying polyether glycol in principle.But it also has and the identical shortcoming of the described method of utilizing screw and vertical tube evaporator to carry out purifying of above-mentioned German Patent.
Japanese patent application 56/104936 has been described a kind of method of purifying polyether glycol, wherein under the condition of pH＞6.5,1) with crude polyoxyalkylene polyol underpressure distillation at high temperature, perhaps 2) under decompression and high temperature, water, steam or nitrogen are passed through polyether glycol similarly.Yet, with comparison shows that of the embodiment 2 of this Japanese patent application, when making water pass through the crude polyoxyalkylene polyol compound, not enough to the removal degree of tedious odoriferous substance.This can show by corresponding analytical results and odor test.In addition, poor by the polyether glycol persistence that comparative example 2 obtains, promptly the aldehyde of polyether glycol increases, and has produced undesirable odor.
CN 1145372A has described a kind of method of purifying polyether glycol, and this method can be removed the by product that can produce smell in the polyether glycol effectively, makes almost odorlessness of these polyether glycols.Yet, this method has been carried out strict restriction to the particle diameter of metering, distillatory temperature, pressure and the current of the water of purifying, if do not observe predetermined distillation condition, then can not from polyether glycol, remove the material that produces smell fully, thereby cause this method to use on a large scale.
Summary of the invention
The process for purification that the purpose of this invention is to provide a kind of polyether glycol, it is the polyethers synthetic system of catalyzer that this method is mainly used in basic metal, effectively remove the potassium sodium ions content in the polyether glycol, and avoided producing the by product of smell to the full extent, make almost odorlessness of these polyether glycols, thereby fundamentally reduced the smell of polyethers.
The process for purification of a kind of low-odor polyether polyol of the present invention, described polyether glycol is for using basic metal catalysis synthetic polyether glycol, it is characterized in that under 60-120 ℃, pure water and two kinds of sorbent materials of use with the 0.1-10% that accounts for the crude polyoxyalkylene polyol total mass, carry out 1-5 absorption, crystallization, filtration and obtain low-odor polyether polyol, described sorbent material is hydrated magnesium silicate and diatomite, the two mass ratio is 1: 1, and the interpolation total amount of sorbent material accounts for the 0.1-3% of crude polyoxyalkylene polyol total mass.
Wherein optimized technical scheme is:
Extraction temperature is 70-110 ℃.
The pure water addition is the 0.3-3% of crude polyoxyalkylene polyol total mass.
The interpolation total amount of sorbent material accounts for the 1-3% of crude polyoxyalkylene polyol total mass.
Described absorption, crystallization, filtration number of times are 2-3 time.
The molecular weight of described polyether glycol is 100-18000, preferred 200 to 12000,230-8000 most preferably.
In this article, molecular weight is meant number-average molecular weight.It can easily calculate according to following formula based on Qi Kong value and functionality:
Wherein:
MW represents the number-average molecular weight of polyether glycol,
F represents the functionality of polyether glycol,
OHV represents polyether glycol De Kong value.
Desire to carry out the synthetic synthetic method that is use basic metal known in the art as the polyether glycol of catalyzer of purified polyether glycol according to the present invention.Preferred polyether glycol is based on oxyethane and/or propylene oxide and contains 1-8 hydroxyl and the polyether glycol of molecular weight in the scope that above provides.
Advantage of the present invention:
The present invention can effectively remove the potassium sodium ions content in the polyether glycol, the small molecular weight polyether glycol that is difficult to remove at the potassium sodium ion particularly, and this method effect is obvious.In the potassium sodium ion of effectively removing in the polyethers, can also avoid producing the by product of smell to the full extent, make almost odorlessness of these polyether glycols, thereby fundamentally reduced the smell of polyethers.Such product can also be applicable to that except satisfying them the requirement of producing polyurethane soft foamed plastics cosmetic industry, food packaging industry and pharmaceutical industry etc. are to the more strict field of polyethers smell requirement.
Low-odor polyether polyol of the present invention can be used for from the synthetic low smell polymkeric substance of polyether glycol, and for example urethane, particularly polyurethane soft foamed plastics or elastomerics perhaps are used for producing makeup, medicine and food product pack product.
Embodiment
Following embodiment is used for further specifying the present invention, but is not intended to be used for limiting the present invention.Except as otherwise noted, all umbers and percentage number average be by weight in an embodiment.
Embodiment 1-4:
In the following embodiments, stainless steel cauldron with the various crude polyoxyalkylene polyols of 1000g (as described below) adding 3L is heated to 70 ℃, adds 10g pure water and 10g hydrated magnesium silicate, stirred 30 minutes, use cloth formula funnel to filter, will filter back gained polyether glycol and add again in the reactor, add 10g pure water and 10 gram diatomite, stir after 30 minutes, carried out vacuum hydro-extraction 1 hour, temperature keeps 105 ± 2 ℃, uses cloth formula funnel to filter then and obtains the purified polyether glycol.
The present invention is to removal effect such as the table 1 and the table 2 of impurity in the used polyether glycol.Analysis is to be undertaken by the stratographic analysis of liquid phase gas.
Polyether glycol 1: by the ethylene oxide/propylene oxide polyethers of glycerol preparation, it is a side chain, and the OH value is about 21, molecular weight 8000, KOH%=0.3%.
Polyether glycol 2: by the propylene oxide polyethers of propylene glycol preparation, it is a straight chain, and the OH value is about 112, molecular weight 1000, KOH%=0.3%.
Polyether glycol 3: by the propylene oxide polyethers of propylene glycol preparation, it is a straight chain, and the OH value is about 37.5, molecular weight 3000, KOH%=0.3%.
Polyether glycol 4: by the propylene oxide polyethers of TriMethylolPropane(TMP) preparation, it is a side chain, and the OH value is about 387, molecular weight 440, KOH%=0.3%
Table 1
| Foreign matter content in the polyether glycol | Embodiment 1 (polyether glycol 1) | Embodiment 2 (polyether glycol 2) |
| The potassium sodium ion | ??3 | Do not measure |
| Acetaldehyde | Do not measure | Do not measure |
| Vinylcarbinol | Do not measure | Do not measure |
| The allyl oxidation propyl alcohol | Do not measure | Do not measure |
| The propylene glycol allyl ethers | ??5 | ??3 |
| Propionic aldehyde | Do not measure | Do not measure |
| Other volatile compounds | ??1 | ??1 |
Table 2
| Foreign matter content in the polyether glycol | Embodiment 3 (polyether glycol 3) | Embodiment 4 (polyether glycol 4) |
| The potassium sodium ion | Do not measure | ??3 |
| Acetaldehyde | Do not measure | Do not measure |
| Vinylcarbinol | Do not measure | Do not measure |
| The allyl oxidation propyl alcohol | Do not measure | Do not measure |
| The propylene glycol allyl ethers | ??4 | ??7 |
| Propionic aldehyde | Do not measure | Do not measure |
| Other volatile compounds | ??1 | ??1 |
(unit of all data is ppm in the table)
Comparative example 1-4:
In following comparative example, the stainless steel cauldron that the various crude polyoxyalkylene polyols of 1000g (as embodiment 1-4) is added 3L, be heated to 85 ℃, add 50g pure water and phosphoric acid (85%) 6g, the 2g hydrated magnesium silicate stirred 30 minutes, carried out vacuum hydro-extraction 2 hours, temperature keeps 105 ± 2 ℃, uses cloth formula funnel to filter then and obtains the purified polyether glycol.
Comparative example 1-4 statement be existing general polyethers process for purification, in the polyethers potassium ion and other impurity removal result such as table 3 and table 4.
Table 3
| Foreign matter content in the polyether glycol | Comparative example 1 (polyether glycol 1) | Comparative example 2 (polyether glycol 2) |
| The potassium sodium ion | ??15 | ??3 |
| Acetaldehyde | ??15 | ??10 |
| Vinylcarbinol | ??0.5 | ??1 |
| The allyl oxidation propyl alcohol | ??150 | ??120 |
| Foreign matter content in the polyether glycol | Comparative example 1 (polyether glycol 1) | Comparative example 2 (polyether glycol 2) |
| The propylene glycol allyl ethers | ??10 | ??17 |
| Propionic aldehyde | ??400 | ??180 |
| Other volatile compounds | ??50 | ??40 |
Table 4
| Foreign matter content in the polyether glycol | Comparative example 3 (polyether glycol 3) | Comparative example 4 (polyether glycol 4) |
| The potassium sodium ion | ??10 | ??40 |
| Acetaldehyde | ??12 | ??7 |
| Vinylcarbinol | ??0.7 | ??1 |
| The allyl oxidation propyl alcohol | ??135 | ??65 |
| The propylene glycol allyl ethers | ??6 | ??8 |
| Propionic aldehyde | ??340 | ??220 |
| Other volatile compounds | ??31 | ??28 |
(unit of all data is ppm in the table)
By relatively finding out significantly, the present invention can remove the potassium sodium ion in the polyether glycol effectively, simultaneously can remove undesirable impurity, and one of harm of these impurity is to produce smell, therefore can significantly reduces the smell of polyether glycol by the present invention.
Claims (8)
1. the process for purification of a low-odor polyether polyol, described polyether glycol is for using basic metal catalysis synthetic polyether glycol, it is characterized in that under 60-120 ℃, pure water and two kinds of sorbent materials of use with the 0.1-10% that accounts for the crude polyoxyalkylene polyol total mass, carry out 1-5 absorption, crystallization, filtration and obtain low-odor polyether polyol, described sorbent material is hydrated magnesium silicate and diatomite, the two mass ratio is 1: 1, and the interpolation total amount of sorbent material accounts for the 0.1-3% of crude polyoxyalkylene polyol total mass.
2. process for purification according to claim 1 is characterized in that extraction temperature is 70-110 ℃.
3. process for purification according to claim 1 is characterized in that the pure water addition is the 0.3-3% of crude polyoxyalkylene polyol total mass.
4. process for purification according to claim 1 is characterized in that described absorption, crystallization, filtration number of times are 2-3 time.
5. process for purification according to claim 1, the interpolation total amount that it is characterized in that sorbent material is the 1-3% of crude polyoxyalkylene polyol total mass.
6. process for purification according to claim 1 is characterized in that described polyether glycol is for based on oxyethane and/or propylene oxide and contain 1-8 hydroxyl, the polyether glycol of number-average molecular weight between 100-18000.
7. process for purification according to claim 6, the number-average molecular weight that it is characterized in that described polyether glycol is 200-12000.
8. process for purification according to claim 6, the number-average molecular weight that it is characterized in that described polyether glycol is 230-8000.
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Cited By (16)
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| CN104119523A (en) * | 2014-08-06 | 2014-10-29 | 山东蓝星东大化工有限责任公司 | Method for synthesizing polyether polyol for waterproof coating |
| CN104151541A (en) * | 2014-08-14 | 2014-11-19 | 上海多纶化工有限公司 | Polyether refinement method |
| CN104151540A (en) * | 2014-08-06 | 2014-11-19 | 山东蓝星东大化工有限责任公司 | Preparation method of polyether polyol for low-VOC-content high-resilience polyurethane foam |
| CN105111428A (en) * | 2015-08-31 | 2015-12-02 | 句容宁武新材料发展有限公司 | Preparation method of low-odor polyether polyol |
| CN105860051A (en) * | 2016-06-29 | 2016-08-17 | 句容宁武新材料股份有限公司 | Method for preparing low-odor polyether for polyurethane foam and application of prepared products |
| CN106117537A (en) * | 2016-06-29 | 2016-11-16 | 句容宁武新材料股份有限公司 | The polyurethane foam preparation method of low volatile matter polyethers and the application of prepared product |
| CN106589345A (en) * | 2016-12-16 | 2017-04-26 | 江苏钟山化工有限公司 | Polyether polyol refining method capable of reducing VOC (volatile organic compound) content and odor |
| CN106753181A (en) * | 2017-03-16 | 2017-05-31 | 广东普赛达密封粘胶有限公司 | A kind of odorlessness, low TVOC polyurethane sealants for automotive trim and its preparation method and application |
| CN106832249A (en) * | 2017-02-06 | 2017-06-13 | 山东诺威新材料有限公司 | The process for purification of low smell polyether polyol with high activity |
| CN106892799A (en) * | 2017-02-27 | 2017-06-27 | 江苏钟山化工有限公司 | Continuously depressurize four sections of methods of the rectified purified polyethers propane diols of temperature control |
| CN107057052A (en) * | 2017-02-06 | 2017-08-18 | 山东诺威新材料有限公司 | Castor oil group polyether glycol and its polyurethane soft foamed plastics of preparation |
| CN107586383A (en) * | 2017-10-20 | 2018-01-16 | 江苏钟山化工有限公司 | The process for purification of VOC content and smell in a kind of reduction PPG |
| CN108484896A (en) * | 2018-04-13 | 2018-09-04 | 航锦科技股份有限公司 | A kind of preparation method of low VOC high-activity high molecular weight polyether polyols |
| CN113773486A (en) * | 2020-06-09 | 2021-12-10 | 中国石油化工股份有限公司 | Refining method of polyether polyol, product and application thereof |
| CN114763410A (en) * | 2021-01-14 | 2022-07-19 | 长华化学科技股份有限公司 | Refining method of polyethylene glycol |
| CN115894260A (en) * | 2022-12-15 | 2023-04-04 | 红宝丽集团股份有限公司 | Co-production method of amino-terminated polyether and diol compounds |
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2010
- 2010-02-03 CN CN201010104631A patent/CN101775132A/en active Pending
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| CN104119523A (en) * | 2014-08-06 | 2014-10-29 | 山东蓝星东大化工有限责任公司 | Method for synthesizing polyether polyol for waterproof coating |
| CN104151540A (en) * | 2014-08-06 | 2014-11-19 | 山东蓝星东大化工有限责任公司 | Preparation method of polyether polyol for low-VOC-content high-resilience polyurethane foam |
| CN104151540B (en) * | 2014-08-06 | 2016-08-17 | 山东蓝星东大化工有限责任公司 | The preparation method of low VOC content high resilience polyurethane foam polyether polyol |
| CN104151541A (en) * | 2014-08-14 | 2014-11-19 | 上海多纶化工有限公司 | Polyether refinement method |
| CN104151541B (en) * | 2014-08-14 | 2016-08-24 | 上海多纶化工有限公司 | The process for purification of polyethers |
| CN105111428A (en) * | 2015-08-31 | 2015-12-02 | 句容宁武新材料发展有限公司 | Preparation method of low-odor polyether polyol |
| CN105860051A (en) * | 2016-06-29 | 2016-08-17 | 句容宁武新材料股份有限公司 | Method for preparing low-odor polyether for polyurethane foam and application of prepared products |
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| CN106589345A (en) * | 2016-12-16 | 2017-04-26 | 江苏钟山化工有限公司 | Polyether polyol refining method capable of reducing VOC (volatile organic compound) content and odor |
| CN106832249A (en) * | 2017-02-06 | 2017-06-13 | 山东诺威新材料有限公司 | The process for purification of low smell polyether polyol with high activity |
| CN107057052A (en) * | 2017-02-06 | 2017-08-18 | 山东诺威新材料有限公司 | Castor oil group polyether glycol and its polyurethane soft foamed plastics of preparation |
| CN106832249B (en) * | 2017-02-06 | 2019-05-10 | 山东一诺威新材料有限公司 | The refining methd of low smell polyether polyol with high activity |
| CN107057052B (en) * | 2017-02-06 | 2019-07-12 | 山东一诺威新材料有限公司 | Castor oil group polyether glycol and its polyurethane soft foamed plastics of preparation |
| CN106892799A (en) * | 2017-02-27 | 2017-06-27 | 江苏钟山化工有限公司 | Continuously depressurize four sections of methods of the rectified purified polyethers propane diols of temperature control |
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| CN108484896A (en) * | 2018-04-13 | 2018-09-04 | 航锦科技股份有限公司 | A kind of preparation method of low VOC high-activity high molecular weight polyether polyols |
| CN113773486A (en) * | 2020-06-09 | 2021-12-10 | 中国石油化工股份有限公司 | Refining method of polyether polyol, product and application thereof |
| CN113773486B (en) * | 2020-06-09 | 2024-06-28 | 中国石油化工股份有限公司 | Refining method of polyether polyol, and product and application thereof |
| CN114763410A (en) * | 2021-01-14 | 2022-07-19 | 长华化学科技股份有限公司 | Refining method of polyethylene glycol |
| CN114763410B (en) * | 2021-01-14 | 2023-06-02 | 长华化学科技股份有限公司 | Polyethylene glycol refining method |
| CN115894260A (en) * | 2022-12-15 | 2023-04-04 | 红宝丽集团股份有限公司 | Co-production method of amino-terminated polyether and diol compounds |
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