CN100448915C - Highly pure polyalkylene glycols and production method thereof - Google Patents
Highly pure polyalkylene glycols and production method thereof Download PDFInfo
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- CN100448915C CN100448915C CNB2004800191215A CN200480019121A CN100448915C CN 100448915 C CN100448915 C CN 100448915C CN B2004800191215 A CNB2004800191215 A CN B2004800191215A CN 200480019121 A CN200480019121 A CN 200480019121A CN 100448915 C CN100448915 C CN 100448915C
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- optical whitner
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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
- 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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Abstract
The invention relates to a method for purifying polyalkylene glycols obtained by adding alkylene oxide to alkylene glycol, whereby after addition, the polyalkylene glycol is treated at a pH value of > 7 with a bleaching agent from the group consisting of peroxide, peracids, percarbonates, perborates, peroxide sulfates or oxygen, optionally using a bleach activator. The method is particularly useful for the production of polyethylene glycol with molecular weights ranging from 196 to 203 g/mol, complying with pharmacopoeial requirements.
Description
The present invention relates to a kind of method for preparing highly pure polyalkylene glycols, particularly polyoxyethylene glycol.According to the present invention, bleaching is handled by using, preferred H
2O
2Handle and realize described high purity, and can use the starting raw material of technical grade purity.In the most preferred embodiment, the molar mass of polyoxyethylene glycol is that 190～210g/mol and this polyoxyethylene glycol meet pharmacopeia requirement (being called PEG200 hereinafter).Polyalkylene glycol of the present invention, particularly polyoxyethylene glycol are suitable for medicine and nutritious prod.
Poly suboxygen alkyl glycol (polyoxyalkylene glycol) has the very Application Areas of height change.In some Application Areass, for example in human goods such as food and medicine, exist high request to purity and colour.The poly suboxygen alkyl glycol that is generally used for most these fields is polyoxyethylene glycol PEG.
The example of poly suboxygen alkyl glycol comprises polyoxyethylene glycol PEG, polypropylene glycol PPG and polytetramethylene glycol PBG, and it is made by oxyethane EO, propylene oxide PO and butylene oxide ring BO respectively.The mixed polymer of EO, PO and/or BuO (for example mixed polymer of EP and PO) also is known.Described mixed polymer can be unregulated polymer or block polymer.
Medicine has for example been made regulation among Ph.G (DAB), American Pharmacopeia USP and the European Pharmacopoeia EUP with the requirement of PEG in the most extensive different pharmacopeia.Therefore, according to USP, the PEG aqueous solution of 10% concentration must be clarification and colourless, and according to EUP, as the solution of 25% concentration in water, colour can be no more than 20 APHA.Other requirements are: the maximum sulfate ash oontent is 0.1%, the maximum total content of monoethylene glycol and glycol ether is 0.25% and EO and 1, and the maximum level of 4-diox is 10ppm under situation separately.
Up to now, only there is the method that can prepare high purity poly suboxygen alkyl glycol on a small quantity by the aklylene glycol of technical grade quality with the permission that technical scale is used.
The approach of a kind of PEG of preparation is to make ethylene oxide polymerization by the oxyhydroxide of basic catalyst, for example basic metal and alkaline-earth metal or alkoxide.In addition, add pure, normally specific (gathering) ethylene glycol as initiator, the addition reaction of described oxyethane to this initiator takes place at this.Can prepare other polyalkylene glycols (for example propylene oxide) by corresponding alkylene oxide being added corresponding (gathering) aklylene glycol in another way.
For the polyoxyethylene glycol that meets the high request in food service industry or the medicine trade with the technical scale preparation, use highly purified starting raw material usually, comprise polyoxyethylene glycol.This need carry out complicated purifying in advance to starting raw material, and therefore cost increases.
EP-A 1 245 608 has described use triglycol TEG and has prepared polyoxyethylene glycol.Obtain having the PEG of low monoethylene glycol (MEG) content and glycol ether (DEG) content; Do not provide other details about other requirements.Particularly do not consider the colour and the EO content of resulting product.In addition, from embodiment, can infer,, must strictly carry out drying in order to realize low MEG and DEG content.Therefore, fundamentally, very high-quality TEG mixed with solid KOH and under the pressure that reduces, carry out drying, and make nitrogen by to remove residual water in addition.
RO-B 114 124 has described by use hydrogen peroxide treatment and purifying PEG in the presence of the strongly-acid ion-exchanger.The shortcoming that this method has is to carry out additional processing based on alkaline ion exchanger to remove residual acidity.
CN-A 1 132 194 has described the preparation of poly suboxygen alkyl glycol and has passed through distillation and purifying with it.
RO-A 62 314 has described under base catalysis and has prepared Tetraglycol 99 by TEG and EO.Must be used for purifying by product of distillation.
JP-A 53 046 907 has described the polyalkylene oxide shortening to reduce the colour in the goods.
RD-A 372014 has described by hydrogenation on nickel catalyzator and additional activated carbon purifying subsequently and has removed coloured component in the Tetraglycol 99.
US-A 4,946, and 939 have described preparation poly suboxygen alkyl two pure and mild its passes through membrane filtration and purifying.The shortcoming of this method is that PEG is limited in molar weight is 400 and the membrane filtration of itself complexity.
The purpose of this invention is to provide a kind of method for preparing poly suboxygen alkyl glycol, preferred PEG, preferred especially PEG200, this method begins and adds corresponding alkylene oxide from the aklylene glycol of technical grade quality, obtains the desirable product that quality satisfies color and purity aspect high request.This method can generally be used.Preferably, poly suboxygen alkyl two pure and mild PEG satisfy the requirement in food and the pharmaceutical industries.Especially, satisfy the requirement of stipulating in the different pharmacopeia, for example, enumerated described requirement hereinafter according to the requirement of American Pharmacopeia USP25 for PEG200.
| Standard | USP 25 is desired |
| The outward appearance colour | Clarification and colourless＜20APHA |
| Kinematic viscosity | 3.9-4.8mm 2/s(98.9±0.3℃) |
| Molar weight | The hydroxyl value that obtains by the Tetra hydro Phthalic anhydride method is 535-590mg/g; Be equivalent to M 190-210g/mol |
| pH | 4.5-7.5 |
| Sulfated ash | Maximum 0.1% |
| Heavy metal | Maximum 5ppm |
| EO/1, the 4-diox | Be 10ppm separately to the maximum |
| MEG+DEG | Total is 0.25% to the maximum |
| Volatile organic compounds | Satisfy requirement about benzene, chloroform, methylene dichloride and trieline |
We have found that this purpose can be by means of a kind of to realizing by oxirane being added to the method that the polyalkylene glycol that obtains on the aklylene glycol carries out purifying, this method comprises: after addition is finished, handle the polyalkylene glycol of gained in pH＞7 time with the SYNTHETIC OPTICAL WHITNER that is selected from superoxide, peracid, percarbonate (Percarbonate), perborate (Perborate), peroxydisulfate (Peroxodisulfate) or oxygen, adding or do not adding bleach-activating agent under the situation separately.
According to the present invention, in described addition reaction, can use to change maximum aklylene glycols and polyalkylene glycol as being known as those of initiator, using with poly suboxygen alkyl glycol to be obtained of they is target.The example of suitable initiator comprises monoethylene glycol MEG, glycol ether DEG, triglycol TEG, single propylene glycol MPG, dipropylene glycol DPG, tripropylene glycol TPG, two pure and mild pairs of fourth glycol of only son.
This addition reaction is carried out in the presence of basic catalyst usually.Suitable basic catalyst is known for those skilled in the art and is selected from the oxyhydroxide and the alkoxide of basic metal and alkaline-earth metal usually.The addition of this catalyzer is 0.001～5wt%, preferred 0.01～1wt%, preferred especially 0.01～0.2wt%.Preferred catalyzer is KOH and/or NaOH.
Usually as follows with the reaction of described initiator and oxirane: before adding oxirane,,, and it is reached be higher than 80 ℃ temperature of reaction if suitablely make its drying with initiator and catalyst mix.Add described oxirane then.
After reaction finishes, described SYNTHETIC OPTICAL WHITNER is added in this mixture.Preferably, this carries out in 50～120 ℃, preferred especially 70～100 ℃ temperature range.Cool off this mixture then and described reaction mixture is discharged from reactor.
Suitable SYNTHETIC OPTICAL WHITNER is well known by persons skilled in the art.Example comprises for example H of organic and inorganic peroxide
2O
2Peracid is Peracetic Acid for example; Percarbonate; Perborate; Peroxydisulfate; Oxygen is arranged in addition.Preferred SYNTHETIC OPTICAL WHITNER is oxygen or H
2O
2Especially, use H
2O
2, it is usually to be purchased the form of the aqueous solution (for example 30%).
With respect to described aklylene glycol, the consumption of mentioned SYNTHETIC OPTICAL WHITNER is 0.05～1wt%, is preferably 0.1～0.5wt%, is in particular 0.1～0.25wt%.In this case, SYNTHETIC OPTICAL WHITNER is in particular H
2O
2, aklylene glycol is in particular triglycol.
If use bleach-activating agent in addition, then these are selected from conventional bleaching activator well known by persons skilled in the art.Can use single bleach-activating agent or both or more kinds of mixtures.Preferred bleach-activating agent comprises: tetra acetyl ethylene diamine (TAED), penta-acetyl glucose (PAG), right-different nonanoyl benzene sulfonic acid sodium salt (i-NOBS), 1; 5-diacetyl-2; 4-dioxy six hydrogen-1; 3; the mixed anhydride of 5-triazine (DADHT), tetra-acetylated glykouril (TAGU), N-nonanoyl succinimide (NOSI), Tetra hydro Phthalic anhydride, citric acid and acetate; particularly triple diacetyl oxides of citric acid, and Mn salt.
If suitable, then before the described reaction of oxirane and initiator with initiator and/or catalyzer drying.If obtain single aklylene glycol and two aklylene glycols (dialkeylene glycol) product that residual content is low, then this step is carried out in suggestion.Particularly, oxyethane preparing on the TEG among the PEG by being added to, and can be by dry low-down MEG and the DEG residual content realized.
Can carry out drying by method known to those skilled in the art, for example by vacuumizing, feed the combination of nitrogen, azeotropic drying or 2 kinds or all described methods.Preferably, carry out drying by vacuumizing and/or feed nitrogen.Having been found that particularly in preparation PEG according to the present invention, is fully enough by simply vacuumizing dry initiator and/or catalyzer.
When handling polyalkylene glycol with SYNTHETIC OPTICAL WHITNER, the pH of solution should＞7, be preferably 7.5～10.0, be in particular 8.0～9.0.In many cases, owing to formed carboxylic acid in the addition reaction process, it can reduce pH, but so pH self be adjusted to above-mentioned value.It may be necessary increasing the measure that reduces pH, preferably by acid or acid ion exchangers.Preferred use acid is more preferably acetate, lactic acid and/or phosphoric acid, particularly acetate and/or lactic acid.
The inventive method is suitable for preparation and purifying by corresponding alkylene oxide being added to the polyalkylene glycol that (is accompanied by base catalysis usually) on the initiator and prepares.Employed initiator can exist with enough purity.If yet the initiator of use technical grade quality, advantage of the present invention can be more remarkable.In this case, do not need the technology of complexity or more uncomplicated purifying initiator, although and lack prepurification, the product of high purity and low colour also can be obtained.
Preferably, method of the present invention is used for being prepared by the initiator of technical grade quality the PEG of high purity and low colour.More preferably, initiator is TEG.If carried out drying before addition, the PEG that then obtains also has only a spot of MEG and DEG except low colour.
The PEG quality grade that obtains according to the present invention is applicable to food and medicine.
In a preferred embodiment, adopt method of the present invention by oxyethane and use TEG as initiator, to make molar weight be 150～500g/mol, be preferably 190～300g/mol, more preferably 190～210g/mol, be in particular the PEG of 196～203g/mol.In this embodiment, more preferably, the MEG of PEG and DEG residual content altogether＜0.25wt%, especially altogether≤0.05wt%.Even more preferably, residual ethylene oxide content＜10ppm and 1 of above-mentioned PEG, 4-diox content＜10ppm particularly preferably is ethylene oxide residue content＜0.5ppm and 1,4-diox residual content＜2ppm.
In the most preferred embodiment, method of the present invention is used to use TEG to prepare PEG as initiator by oxyethane, the molar weight of this PEG be 196～203g/mol (determining by hydroxyl value), MEG and DEG residual content by the Tetra hydro Phthalic anhydride method of USP 25 altogether≤0.05wt%, ethylene oxide residue content＜0.5ppm and 1,4-diox content＜2ppm, kinematic viscosity is 3.9～4.8mm under 98.9 ± 0.3 ℃
2The PEG200 aqueous solution of/s, 25wt% concentration is clarification and colourless, colour＜20APHA.
In the preparation of PEG, the inventive method allow to use carbonyl content be＞25ppm is until the initiator of 100ppm.
According to the present invention, can realize colour＜20APHA without a doubt, consequently corresponding PEG satisfies the requirement of USP and/or European Pharmacopoeia.
Make medicine, nutritious prod and the food supplement field that itself can be used for the human and animal and use according to polyalkylene glycol of the present invention, particularly polyoxyethylene glycol.
Embodiment
The Tetra hydro Phthalic anhydride method of employing USP 25 is determined the molar mass of products therefrom by hydroxyl value.
Embodiment 1
600g (4mol) triglycol mixed with the potassium hydroxide solution (is 0.015wt% based on goods) of 0.30g 40% concentration and 80 ℃/＜10 millibars dry 30 minutes down.Then under 150 ℃ with these goods and 200.6g (4.56mol) reacting ethylene oxide.Discharging 804g, colour: 15APHA (25wt% of Yu Shuizhong).
With 0.064g acetate the 500g discharging is adjusted to pH 7.4, adds the hydrogen peroxide of 0.94ml 50wt% concentration and heated this mixture 1 hour down at 80 ℃.This mixture is stripped under 100 ℃/15 millibars with 35g water then and pack described goods.
Outward appearance: colourless
Colour: 1 APHA (25wt% of Yu Shuizhong)
Hydroxyl value: 564mg/g
Viscosity: 98.9 ℃ are 4.106mm down
2/ s
pH：4.5
EO content:＜0.5ppm
1,4-diox content:＜2ppm
Total MEG/DEG:0.05wt%
Water: 0.15wt%
Embodiment 2
600g (4mol) triglycol mixed with the potassium hydroxide solution (is 0.015wt% based on goods) of 0.30g 40% concentration and 80 ℃/＜10 millibars dry 40 minutes down.Then under 150 ℃ with this mixture and 200.6g (4.56mol) reacting ethylene oxide.Discharging 798g, colour: 17APHA (25wt% of Yu Shuizhong).
With 0.06g acetate the 500g discharging is adjusted to pH 8.1, adds the hydrogen peroxide of 0.94ml 50wt% concentration and heated this mixture 1 hour down at 80 ℃.This mixture is stripped under 100 ℃/15 millibars with 35g water then and pack described goods.
Outward appearance: colourless
Colour: 5 APHA (25wt% of Yu Shuizhong)
Hydroxyl value: 564mg/g
Viscosity: 98.9 ℃ are 4.126mm down
2/ s
pH：5.4
EO content:＜0.5ppm
1,4-diox content:＜2ppm
Total MEG/DEG:0.05wt%
Water: 0.15wt%
Embodiment 3
600g (4mol) triglycol mixed with the potassium hydroxide solution (is 0.015wt% based on goods) of 0.30g 40% concentration and 80 ℃/＜10 millibars dry 30 minutes down.Then under 150 ℃ with this mixture and 200.6g (4.56mol) reacting ethylene oxide.Discharging 803g, colour: 13APHA (25wt% of Yu Shuizhong).
With 0.065g acetate the 500g discharging is adjusted to pH 8.4, adds the hydrogen peroxide of 0.94ml 50wt% concentration and this mixture heating up to 80 ℃ is continued 1 hour.This mixture is stripped under 100 ℃/15 millibars with 35g water then and pack described goods.
Outward appearance: colourless
Colour: 3 APHA (25wt% of Yu Shuizhong)
Hydroxyl value: 564mg/g
Viscosity: 98.9 ℃ are 4.107mm down
2/ s
pH：4.7
EO content:＜0.5ppm
1,4-diox content:＜2ppm
Total MEG/DEG:0.05wt%
Water: 0.15wt%
Embodiment 4
600g (4mol) triglycol mixed with the potassium hydroxide solution (is 0.015wt% based on goods) of 0.30g 40% concentration and 80 ℃/＜10 millibars dry 45 minutes down.Then under 150 ℃ with this mixture and 200.6g (4.56mol) reacting ethylene oxide.Discharging 797g, colour: 65APHA (25wt% of Yu Shuizhong).
The hydrogen peroxide of 300g discharging with 0.02g acetate and 0.56ml 50% concentration mixed, and heated 1 hour down at 80 ℃.This mixture is stripped under 100 ℃/15 millibars with 21g water then and pack described goods.
Outward appearance: colourless
Colour: 17 APHA (25wt% of Yu Shuizhong)
pH：5.4
Embodiment 5
600g (4mol) triglycol mixed with the potassium hydroxide solution (is 0.015wt% based on goods) of 0.30g 40% concentration and 80 ℃/＜10 millibars dry 45 minutes down.Then under 150 ℃ with this mixture and 200.6g (4.56mol) reacting ethylene oxide.Discharging 799g, colour: 21APHA (25wt% of Yu Shuizhong).
With 0.04g acetate the 600g discharging is adjusted to pH 9.5.Wherein 300g mixed with the hydrogen peroxide of 0.564ml50wt% concentration and 80 ℃ of heating 1 hour down.This mixture is stripped under 100 ℃/15 millibars with 21g water then and pack described goods.
Outward appearance: colourless
Colour: 10 APHA (25wt% of Yu Shuizhong)
pH：5.2
Other 300g mixed with the hydrogen peroxide of 0.28ml 50wt% concentration and 80 ℃ of heating 1 hour down.This mixture is stripped under 100 ℃/15 millibars with 21g water then and pack described goods.
Outward appearance: colourless
Colour: 15 APHA (25wt% of Yu Shuizhong)
pH：6.1
Embodiment 6
79kg (53mol) triglycol mixed with the potassium hydroxide solution of 35g 45% concentration and 120 ℃/＜20 millibars dry 25 minutes down.Then under 150 ℃ with mixture and 26.5kg (60mol) reacting ethylene oxide.With 7g acetate batch of material is adjusted to pH 9.2, its hydrogen peroxide with 199g 50wt% concentration is mixed and stirred 1 hour down at 80 ℃.Use 7.35kg water under 100 ℃/＜20 millibars, this mixture to be stripped then and pack described goods.
Outward appearance: colourless
Colour: 5 APHA (25wt% of Yu Shuizhong)
Hydroxyl value: 557.6mg/g
Viscosity: 98.9 ℃ are 4.455mm down
2/ s
pH：5.3
EO content:＜0.5ppm
1,4-diox content:＜2ppm
Total MEG/DEG:0.01wt%
Water: 0.13wt%
Embodiment 7
79kg (53mol) triglycol mixed with the potassium hydroxide solution of 35g 45% concentration and 120 ℃/＜20 millibars dry 25 minutes down.Then under 150 ℃ with this mixture and 26.5kg (60mol) reacting ethylene oxide.With 13g acetate batch of material is adjusted to the pH 7.2 (colour of sample: 53 APHA; The 25wt% of Yu Shuizhong).With 9g potassium hydroxide this mixture is adjusted to pH8.6 then, its hydrogen peroxide with 99g 50wt% concentration is mixed and stirred 1 hour down at 80 ℃.Use 7.35kg water under 100 ℃/＜20 millibars, this mixture to be stripped then and pack described goods.
Outward appearance: colourless
Colour: 5 APHA (25wt% of Yu Shuizhong)
Hydroxyl value: 560mg/g
Viscosity: 98.9 ℃ are 4.486mm down
2/ s
pH：6.3
EO content:＜0.5ppm
1,4-diox content:＜2ppm
Total MEG/DEG:0.05wt%
Water: 0.20wt%
Claims (11)
1. one kind is used for purifying by oxirane being added to the method for the polyalkylene glycol that obtains on the aklylene glycol, it comprises: after addition is finished, handle the polyalkylene glycol of gained in pH＞7 time with the SYNTHETIC OPTICAL WHITNER that is selected from organic and inorganic peroxide, peracid, percarbonate, perborate, peroxydisulfate or oxygen, adding or do not adding bleach-activating agent under the situation separately.
2. the method for claim 1, the processing of wherein said use SYNTHETIC OPTICAL WHITNER is carried out under 50～120 ℃ temperature.
3. method as claimed in claim 1 or 2 is wherein used H
2O
2As SYNTHETIC OPTICAL WHITNER.
4. method as claimed in claim 1 or 2, the processing of wherein said use SYNTHETIC OPTICAL WHITNER are to carry out for 7.5～10.0 times at pH.
5. method as claimed in claim 1 or 2 is wherein regulated pH by adding acid or ion-exchanger.
6. method as claimed in claim 1 or 2, wherein said oxirane is added under the existence of basic catalyst that being reflected on the aklylene glycol be selected from the oxyhydroxide of basic metal and alkaline-earth metal and alkoxide carried out.
7. the method for claim 1, wherein the polyalkylene glycol of gained is a polyoxyethylene glycol.
8. method as claimed in claim 7, the aklylene glycol that wherein is used for addition is a triglycol.
9. method as claimed in claim 8, wherein dry described triglycol before addition reaction.
10. method as claimed in claim 7, the molar weight of the polyoxyethylene glycol that wherein obtains by this way are 150～500g/mol.
11. method as claimed in claim 1 or 2, wherein with respect to aklylene glycol, the consumption of described SYNTHETIC OPTICAL WHITNER is 0.05～1wt%.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2003125264 DE10325264A1 (en) | 2003-06-03 | 2003-06-03 | Purification of polyalkylene glycol for use in food and pharmaceuticals, involves treating the crude alkylene oxide-glycol addition product at above pH 7 with a bleaching agent, preferably hydrogen peroxide |
| DE10325264.9 | 2003-06-03 | ||
| DE10339184.3 | 2003-08-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1816582A CN1816582A (en) | 2006-08-09 |
| CN100448915C true CN100448915C (en) | 2009-01-07 |
Family
ID=33482500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800191215A Expired - Fee Related CN100448915C (en) | 2003-06-03 | 2004-06-02 | Highly pure polyalkylene glycols and production method thereof |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN100448915C (en) |
| DE (1) | DE10325264A1 (en) |
| ZA (1) | ZA200509794B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102597189B (en) * | 2009-10-16 | 2014-01-29 | 陶氏环球技术有限责任公司 | Cutting fluids with improved performance |
| CN106432709A (en) * | 2016-04-25 | 2017-02-22 | 桐乡市恒隆化工有限公司 | Production method for preventing fatty alcohol-polyoxyethylene ether from yellowing |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4946939A (en) * | 1989-05-30 | 1990-08-07 | The Dow Chemical Company | High purity polyether polyols |
| US5235114A (en) * | 1991-04-29 | 1993-08-10 | Olin Corporation | Process for purifying and end-capping polyols made using double metal cyanide catalysts |
| EP1245608A1 (en) * | 2001-03-27 | 2002-10-02 | Nof Corporation | Polyethylene glycol and process for producing the same |
-
2003
- 2003-06-03 DE DE2003125264 patent/DE10325264A1/en not_active Withdrawn
-
2004
- 2004-06-02 CN CNB2004800191215A patent/CN100448915C/en not_active Expired - Fee Related
-
2005
- 2005-12-02 ZA ZA200509794A patent/ZA200509794B/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4946939A (en) * | 1989-05-30 | 1990-08-07 | The Dow Chemical Company | High purity polyether polyols |
| US5235114A (en) * | 1991-04-29 | 1993-08-10 | Olin Corporation | Process for purifying and end-capping polyols made using double metal cyanide catalysts |
| EP1245608A1 (en) * | 2001-03-27 | 2002-10-02 | Nof Corporation | Polyethylene glycol and process for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1816582A (en) | 2006-08-09 |
| DE10325264A1 (en) | 2004-12-23 |
| ZA200509794B (en) | 2008-09-25 |
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