CN106589345B - A kind of polyether polyol refining methd reducing VOC content and smell - Google Patents
A kind of polyether polyol refining methd reducing VOC content and smell Download PDFInfo
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- CN106589345B CN106589345B CN201611169822.8A CN201611169822A CN106589345B CN 106589345 B CN106589345 B CN 106589345B CN 201611169822 A CN201611169822 A CN 201611169822A CN 106589345 B CN106589345 B CN 106589345B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The present invention relates to a kind of reduction polyether polyol VOC content and the post-processing approach of smell, the polyether polyol is under base metal catalysts effect, it is reacted and is made with oxyalkylene by initiator, this method is that the adsorbent for accounting for crude polyoxyalkylene polyol gross mass 1.0-1.5% is added at 80-120 DEG C, after stirring and adsorbing, it is cooled to 80-90 DEG C, add the water of thick polyethers gross mass 8-10%, after secondary agitation, it opens vacuum system and heats up simultaneously and remove moisture and low-boiling-point substance in crude polyoxyalkylene polyol, filters pressing obtains finished product after analysis moisture is qualified.The present invention reduces the smell and VOC content of polyether polyol while guaranteeing that kalium ion and natrium ion is adsorbed removing.
Description
Technical field
The present invention relates to the purification sides of volatile organic compounds (VOC) content and smell in a kind of reduction polyether polyol
Method.
Background technique
Polyether polyol is the important source material of polyurethane material, and polyurethane material has extensive use in the automotive industry.
Since people increasingly pay close attention to environment protection health, it is desirable that vapour in-car smell wants low, the automobile polyurethane material of common polyether preparation
There is certain smell, is the smell of mainly some aldehyde materials through detection.This is because the synthesis of polyether polyol is adopted substantially
It is initiator with small molecule polyol or amine, is catalyzed propylene oxide using base metal catalysts or epoxyethane ring-expansion polymerization is formed
Macromolecule polyalcohol, the presence containing catalyst metal ion, unreacted monomer and oligomer in the polyether polyol after polymerization,
So these impurity need to be removed by process for refining.Process for refining most commonly used at present is after being neutralized by acid adding using absorption
Agent carries out adsorption filtration processing.Then there can be remaining acid in the polyether polyol after neutralizing, after high temperature dehydration
Smell can be generated, and the side reaction generated in polymerization process is easy to generate some aldehyde materials, refines commonly
It is difficult to remove these impurity in journey, influences the VOC content of polyethers.
101775132 A of Chinese patent CN describes a kind of process for refining for not needing acid adding, at 60-120 DEG C, uses
It accounts for the water of the 0.1-10% of thick ethoxylated polyhydric alcohol gross mass and uses two kinds of adsorbents, carry out 2-3 absorption, low smell is obtained by filtration
Polyether polyol.Adsorbent used in it is magnesium silicate and diatomite.But its absorption number is excessive, and cost is bigger than normal.
Some producers purify polyether polyol with falling film evaporator, but are needed equipment valuableness, and cannot go completely
Except existing polyethers smell.
Summary of the invention
It is an object of the present invention to provide a kind of refining methd of the polyether polyol of low VOC, the polyether polyol is in alkali
Under metallic catalyst effect, is reacted and be made with oxyalkylene by initiator, it is characterized in that, it is first added and accounts in crude polyoxyalkylene polyol
Stirring is opened after the self-control adsorbent of crude polyoxyalkylene polyol gross mass 0.5-2%, after being warming up to predetermined temperature, is stirred 1 hour, drop
After temperature to predetermined temperature, the water of thick polyethers gross mass 0.5-15% is added, is stirred for 1 hour, opens vacuum system and simultaneously
Moisture and low-boiling-point substance in heating removing crude polyoxyalkylene polyol, filters pressing obtains finished product after analysis moisture is qualified.
Optimal technical scheme of the present invention is as follows:
A kind of polyether polyol refining methd reducing volatile organic compounds (VOC) content and smell, it includes such as
Lower step:
Adsorbent is added in step 1 in polyether polyol to be refined, and the adsorbent is that magnesium silicate and alumina silicate are mixed
Object is closed, wherein magnesium silicate accounts for the 35-45% of adsorbent gross mass, and the amount that the adsorbent is added is polyether polyols to be refined
The 1.0-1.5% of alcohol quality；
Step 2, the polyether polyol wait refine are warming up to predetermined temperature after adsorbent is added be 95-115 DEG C, and stirring 1 is small
When；
Step 3 is cooled to 80-90 DEG C of predetermined temperature, and water is added, and the additional amount of water is polyether polyol quality to be refined
8-10%, and this temperature stir 1 hour；
Step 4, heating and vacuum dehydration, dehydration temperaturre are 105-120 DEG C, vacuum degree≤- 0.09MPa.Moisture after dehydration
It is required that≤0.1%, up to the polyether polyol of low volatile organic compound content after filters pressing.
Above-mentioned refining methd, the polyether polyols alcohol functionalities to be refined are 1-6, and oxyalkylene is propylene oxide
Or ethylene oxide or both mixture, polyether polyol number-average molecular weight are 100-12000.
Method of the invention not only can effectively remove the kalium ion and natrium ion in polyether polyol, and can be effectively reduced poly-
The VOC content and smell of ethoxylated polyhydric alcohol.It can be applied to the poly- ammonia of automobile for having compared with being strict with to polyethers smell and VOC content
Ester material.
Specific embodiment
Illustrate the present invention with reference to embodiments, but the present invention is not only limited to these embodiments.
Embodiment 1:
Adsorbent is made by oneself by 10g in 1000g crude polyoxyalkylene polyol a addition 2L stainless steel cauldron (as described below), is added,
Open timing stirring 1h after stirring is warming up to 100 ± 5 DEG C.80g distilled water is sucked after being cooled to 80 DEG C, temperature is kept for 80 ± 5 DEG C
After stirring 1h, vacuum plant and the dehydration that heats up are opened, is filtered after keeping 110 ± 5 DEG C of dehydration 2h of temperature, the polyethers refined is more
First alcohol finished product.
Polyether polyol a is initiator by glycerine in embodiment 1, is made with reacting ethylene oxide, molecular weight 1500,
Catalyst KOH dosage is 0.25%.
Self-control adsorbent is magnesium silicate and silicic acid aluminium mixture used in embodiment 1, and wherein it is total to account for adsorbent for magnesium silicate
The 38% of quality.
Product performance index prepared by table 1
| Test item | Low VOC process for refining | Acid neutralizes process for refining | Testing standard |
| Formaldehyde ug/g | 1.2 | 9.56 | Liquid chromatogram |
| Acetaldehyde ug/g | 1.78 | 11.54 | Liquid chromatogram |
| Methacrylaldehyde ug/g | 0.71 | 7.85 | Liquid chromatogram |
| Moisture/% | ≤0.1 | ≤0.1 | GB12008.6—1989 |
| Potassium, sodium ion/× 10-6 | 1,0 | 1,2 | GB12008.4—1989 |
Embodiment 2:
Adsorbent is made by oneself by 12g in 1000g crude polyoxyalkylene polyol b addition 2L stainless steel cauldron (as described below), is added,
Open timing stirring 1h after stirring is warming up to 105 ± 5 DEG C.100g distilled water is sucked after being cooled to 90 DEG C, temperature is kept for 90 ± 5 DEG C
After stirring 1h, vacuum plant and the dehydration that heats up are opened, is filtered after keeping 115 ± 5 DEG C of dehydration 2h of temperature, the polyethers refined is more
First alcohol finished product.
Polyether polyol b is initiator by propylene glycol in embodiment 2, reacts and is made with propylene oxide, molecular weight 3000,
Catalyst KOH dosage is 0.3%.
Self-control adsorbent is magnesium silicate and silicic acid aluminium mixture used in embodiment 2, and wherein it is total to account for adsorbent for magnesium silicate
The 40% of quality.
Table 2: the product performance index of preparation
| Test item | Low VOC process for refining | Acid neutralizes process for refining | Testing standard |
| Formaldehyde ug/g | 0.89 | 12.42 | Liquid chromatogram |
| Acetaldehyde ug/g | 1.24 | 9.54 | Liquid chromatogram |
| Methacrylaldehyde ug/g | 0.56 | 10.24 | Liquid chromatogram |
| Moisture/% | ≤0.1 | ≤0.1 | GB12008.6—1989 |
| Potassium, sodium ion/× 10-6 | 2,0 | 2,1 | GB12008.4—1989 |
Embodiment 3:
Adsorbent is made by oneself by 15g in 1000g crude polyoxyalkylene polyol c addition 2L stainless steel cauldron (as described below), is added,
Open timing stirring 1h after stirring is warming up to 110 ± 5 DEG C.100g distilled water is sucked after being cooled to 90 DEG C, temperature is kept for 90 ± 5 DEG C
After stirring 1h, vacuum plant and the dehydration that heats up are opened, is filtered after keeping 115 ± 5 DEG C of dehydration 2h of temperature, the polyethers refined is more
First alcohol finished product.
Polyether polyol c is initiator, average functionality 3.5, with epoxy by glycerine and pentaerythrite in embodiment 3
The reaction of propane ethylene oxide mixture is made, and ethylene oxide accounts for the 15% of ethylene oxide propylene oxide gross mass, molecular weight
It is 3000, catalyst KOH dosage is 0.3%.
Self-control adsorbent is magnesium silicate and silicic acid aluminium mixture used in embodiment 3, and wherein it is total to account for adsorbent for magnesium silicate
The 43% of quality.
Table 3: the product performance index of preparation
| Test item | Low VOC process for refining | Acid neutralizes process for refining | Testing standard |
| Formaldehyde ug/g | 1.59 | 21.54 | Liquid chromatogram |
| Acetaldehyde ug/g | 1.03 | 18.64 | Liquid chromatogram |
| Methacrylaldehyde ug/g | 0.86 | 13.24 | Liquid chromatogram |
| Moisture/% | ≤0.1 | ≤0.1 | GB12008.6—1989 |
| Potassium, sodium ion/× 10-6 | 0,0 | 3,2 | GB12008.4—1989 |
Compare formaldehyde, the acetaldehyde, level of acrolein discovery in conventional acid neutralisation treatment polyether polyol, the present invention can have
Kalium ion and natrium ion in the removal polyether polyol of effect, while formaldehyde, acetaldehyde, methacrylaldehyde in polyether polyol can be substantially reduced
Content, and these aldehyde materials are the roots for generating polyethers smell, therefore the present invention can be substantially reduced polyether polyol
VOC content and smell.
Claims (3)
1. volatile organic compounds (VOC) content and the refining methd of smell in a kind of reduction polyether polyol, it is characterized in that
It includes the following steps:
Adsorbent is added in step 1 in polyether polyol to be refined, and the adsorbent is that magnesium silicate is mixed with alumina silicate
Object, wherein magnesium silicate accounts for the 35-45% of adsorbent gross mass, and the amount that the adsorbent is added is polyether polyol to be refined
The 1.0-1.5% of quality；
Step 2, the polyether polyol wait refine are warming up to predetermined temperature after adsorbent is added be 95-115 DEG C, is stirred 1 hour；
Step 3 is cooled to 80-90 DEG C of predetermined temperature, and water is added, and the additional amount of water is the 8- of polyether polyol quality to be refined
10%, and stirred 1 hour in this temperature；
Step 4, heating and vacuum dehydration, dehydration temperaturre are 105-120 DEG C, moisture requirement≤0.1% after dehydration, after filters pressing to obtain the final product
The polyether polyol of low volatile organic compound content.
2. refining methd according to claim 1, it is characterized in that: the vacuum degree of vacuum dehydration described in step 4≤-
0.09Mpa。
3. refining methd according to claim 1 or 2, it is characterized in that: the polyether polyols alcohol functionalities to be refined
For 1-6, oxyalkylene is propylene oxide or ethylene oxide or both mixture, and polyether polyol number-average molecular weight is 100-
12000。
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| 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 |
| CN107586383B (en) * | 2017-10-20 | 2020-05-15 | 江苏钟山化工有限公司 | Refining method for reducing VOC content and odor in polyether polyol |
| CN108311097A (en) * | 2018-02-06 | 2018-07-24 | 四川润和催化新材料股份有限公司 | A kind of thick ether treating adsorbent and preparation method thereof and the thick ether process for purification based on the adsorbent |
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| CN111318311B (en) * | 2020-04-22 | 2022-09-06 | 上海多纶化工有限公司 | Cocatalyst, catalyst and application thereof |
| CN111763309B (en) * | 2020-07-22 | 2023-01-13 | 万华化学（烟台）容威聚氨酯有限公司 | Refining method for reducing aldehyde content and odor in polyether polyol |
| CN114602536B (en) * | 2020-12-03 | 2023-07-11 | 万华化学集团股份有限公司 | Preparation method of catalyst and method for reducing VOC content in polyether polyol |
| CN112876666B (en) * | 2021-01-14 | 2023-04-14 | 长华化学科技股份有限公司 | Low-aldehyde and low-odor polyether polyol and preparation method and application thereof |
| CN113214053B (en) * | 2021-05-20 | 2022-08-05 | 上海多纶化工有限公司 | Method for refining fatty alcohol polyoxyalkylene ether |
| CN114395107A (en) * | 2022-01-21 | 2022-04-26 | 江苏斯德瑞克化工有限公司 | Environment-friendly low-VOC polyether and production process thereof |
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| CN101775132A (en) * | 2010-02-03 | 2010-07-14 | 山东蓝星东大化工有限责任公司 | Method for refining low-odor polyether polyol |
| CN101962441B (en) * | 2010-10-09 | 2013-05-08 | 南京理工大学 | Purification method of polyether polyol with low degree of unsaturation |
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