WO2012034998A1 - Production method of polyether polyol by hydrolyzing alkylene oxide to form alkylene glycol and subsequently adding alkylene oxide - Google Patents
Production method of polyether polyol by hydrolyzing alkylene oxide to form alkylene glycol and subsequently adding alkylene oxide Download PDFInfo
- Publication number
- WO2012034998A1 WO2012034998A1 PCT/EP2011/065831 EP2011065831W WO2012034998A1 WO 2012034998 A1 WO2012034998 A1 WO 2012034998A1 EP 2011065831 W EP2011065831 W EP 2011065831W WO 2012034998 A1 WO2012034998 A1 WO 2012034998A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alkylene oxide
- alkylene
- polyether polyol
- production method
- weight
- Prior art date
Links
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
- C08G65/04—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 only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
- C08G65/10—Saturated oxiranes characterised by the catalysts used
-
- 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
- C08G65/2642—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 characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2648—Alkali metals or compounds thereof
-
- 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
- C08G65/2642—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 characterised by the catalyst used
- C08G65/2669—Non-metals or compounds thereof
- C08G65/2678—Sulfur or compounds thereof
-
- 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
- C08G65/2696—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 characterised by the process or apparatus used
Definitions
- polyol has been produced by using a specific metal catalyst (see Patent document 1 , Patent document 2) .
- these metal catalysts are expensive compared with alkali metal hydroxide catalysts or acid catalysts.
- As an initiator for polyol with active hydrogen (functional group number) of 2, propylene glycol and ethylene glycol are used. These alkylene glycols are produced by hydrolysis of their corresponding alkylene oxides and purification.
- the present invention shows that polypropylene glycol (PPG) can be produced through a simplified process by reacting propylene oxide in the presence of water without using propylene glycol as a starting raw material. It is possible to synthesize polyethylene glycol (PEG) by using ethylene oxide in place of propylene oxide, and polybutylene glycol by using butylene oxide. Other alkylene oxides or mixtures of alkylene oxides can also be used. By this method, polyol with cost competitiveness can be produced by a production method of less environmental burden.
- PPG polypropylene glycol
- the suitable reaction temperature in the hydrolysis reaction process is 20 to 90°C, preferably, 30 to 50°C.
- the reaction time is 1 to 15 hours, for example, 2 to 10 hours.
- the reaction proceeds by adding alkylene oxide to a reaction mixture, continuously where necessary.
- pressure of the gas phase is preferably 1 to 5 barometric pressures.
- Comparative example 1 To an autoclave of 1 L, 100 parts by weight ( 100 g) of water and 2.3 parts by weight of potassium hydroxide were added, it was pressurized with nitrogen to 2 barometric pressures, and 670 parts by weight of propylene oxide was continuously added thereto at 110°C taking 30 hours. Thereafter, 70 parts by weight of water and 2.0 parts by weight of sulfuric acid were added at 80°C, and mixed for 2 hours to complete a neutralization reaction. Further, under a reduced pressure of 0.01 barometric pressures, dehydration was carried out at 100°C for 2 hours, and filtration was conducted using a filter paper, thereby to obtain polyol C. Table 1
- Example 2 From the result of Table 1, in Example 1, compared with the case where propylene oxide undergoes addition by an alkali metal hydroxide catalyst using propylene glycol as a direct raw material, by concomitant use of acid and alkali metal hydroxide catalysts and continuously adding propylene oxide, polyol with a targeted hydroxyl value was able to be synthesized without increasing the reaction time a lot. In Example 2, it has been found that by adding other starting raw material before adding an alkali metal hydroxide catalyst, and after adding it, by adding propylene oxide continuously, the present invention can apply to synthesis of polyol having a plurality of starting materials including water.
- Comparative example 1 only an alkali metal hydroxide catalyst was used as a catalyst. Under this condition, when propylene oxide is added in a short time, 2 hours for example, propylene oxide hardly reacts and evaporates, being exhausted through a pressure control valve. Hence, propylene oxide was slowly added taking 30 hours for propylene oxide to react sufficiently. In this way, in the case of synthesizing polyol only with an alkali metal hydroxide catalyst, it takes a lot of time.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
In synthesizing polyether polyol, not using alkylene glycol as raw material but using water as raw material, energy necessary in a purification process of alkylene glycol, and waste are eliminated, thereby contributing to environmental improvement of the earth. Provided is a production method of polyol, where alkylene oxide is subjected to hydrolysis reaction with an acid catalyst, and an alkali metal hydroxide catalyst is added into the reaction mixed liquid to undergo addition of alkylene oxide appropriately.
Description
PRODUCTION METHOD OF POLYETHER POLYOL BY HYDROLY ING ALKYLENE OXIDE TO FORM ALKYLENE GLYCOL AND SUBSEQUENTLY ADDING ALKYLENE OXIDE
The present invention relates to a production method of polyether polyol (hereinafter abbreviated to polyol) useful as a raw material of polyurethane.
Polyol is generally produced by adding alkyl ene oxide to an active hydrog en compound in the presence of a catalyst. As catalysts, alkali metal hydroxides such as potassium hydroxide, acid catalysts such as sulfuric acid or metal catalysts like DMC catalysts can be used. Among these, in an ordinary industrial production, an alkali metal hydroxide catalyst is used (see Non-patent document 1 ) . On the other hand, an acid catalyst is not used in an industrial production of polyol because hydrolysis reaction of alkylene oxide comes before addition reaction. Hence, the acid catalyst is used as a catalyst for producing propylene glycol by hydrolyzing propylene oxide in the presence of a lot of water. In recent years, polyol has been produced by using a specific metal catalyst (see Patent document 1 , Patent document 2) . However, these metal catalysts are expensive compared with alkali metal hydroxide catalysts or acid catalysts. As an initiator, for polyol with active hydrogen (functional group number) of 2, propylene glycol and ethylene glycol are used. These alkylene glycols are produced by hydrolysis of their corresponding alkylene oxides and purification.
Therefore , two kinds of separated production processe s of alkylene glycol from alkylene oxide and of polyol from alkylene glycol are necessary in order to obtain polyol from alkylene oxide. Relevant prior art is e.g. disclosed in Japanese Unexamined Patent Publication No. 2002-302544, Japanese Unexamined Patent Publication No. 10-212348 and "Outline of polyurethane raw material industry, third edition" page 1 1 , Urethane Raw Materials Association.
It was therefore object of the present invention to provide a process in order to produce
„
- 2 - polyol directly from alkylene oxide. By providing a process combining two kinds of separated production processes of alkylene glycol from alkylene oxide and of polyol from alkylene glycol, it becomes possible not only to get a cost merit of cutting down production costs due to simplification of production process industrially, but also to eliminate energy necessary in a purification process of alkylene glycol and wastes, thus contribute to environmental improvement of the earth as well.
The present inventors studied the method for producing polyol by addition reaction of alkylene oxide, as a result, they have found that polyol with a predetermined molecular weight can be produced by hydrolyzing alkylene oxide using an acid catalyst to synthesize glycol of low molecular weight, subsequently, by adding an alkali metal hydroxide catalyst thereto to undergo addition of alkylene oxide, and accomplished the present invention. The present invention is to solve the above-described problems, and provides polyol obtained in such a manner that alkylene oxide is subjected to hydrolysis reaction with an acid catalyst, and an alkali metal hydroxide catalyst is added into the reaction mixed liquid to undergo addition of alkylene oxide appropriately, and a production method thereof.
The present invention provides a production method of polyether polyol characterized by
( 1) a process for producing alkylene glycol by hydrolyzing alkylene oxide with carbon numbers of 2 to 4 in the presence of an acid catalyst, and
(2) a process for obtaining polyether polyol by adding alkylene oxide with carbon numbers of 2 to 4 to the alkylene glycol.
The present invention shows that polypropylene glycol (PPG) can be produced through a simplified process by reacting propylene oxide in the presence of water without using propylene glycol as a starting raw material. It is possible to synthesize polyethylene
glycol (PEG) by using ethylene oxide in place of propylene oxide, and polybutylene glycol by using butylene oxide. Other alkylene oxides or mixtures of alkylene oxides can also be used. By this method, polyol with cost competitiveness can be produced by a production method of less environmental burden.
In synthesizing polyether polyol, by using water as a raw material without using alkylene glycol as a direct raw material, energy and wastes necessary in a purification process of alkylene glycol are eliminated, thereby contributing to environmental improvement of the earth as well.
The method of the present invention is composed of ( 1) a hydrolysis reaction process and then, (2) an addition reaction process.
With regard to hydrolysis reaction process :
In the present invention, first water and an acid catalyst are weighed in a reactor, and then alkylene oxide is charged therein to implement the hydrolysis reaction of the alkylene oxide. In this process, although hydrolysis reaction is a main reaction, an oligomer of alkylene glycol (for example, dipropylene glycol and tripropylene glycol) is produced partly along with alkylene glycol.
Alkylene oxide has the carbon number of 2 to 4. As specific examples of the alkylene oxide, there are ethylene oxide, propylene oxide, butylene oxide, and a mixture of two kinds or more thereof.
In a hydrolysis reaction process, an alkali metal hydroxide catalyst is not preferable because hydrolysis reaction of alkylene oxide hardly proceeds. A preferable catalyst among acid catalysts used is a mineral acid (inorganic acid), for example, hydrochloric acid, nitric acid, pho sphoric acid, sulfuric acid, and boric acid, and particularly
Λ
- 4 - preferably, sulfuric acid. The acid catalyst can be handled in a form of a mixture with water (for example, aqueous solution) . In a mixture of acid catalyst and water, the weight ratio of acid and water is 1 : 99 to 99 : 1 , and particularly preferably, 10 : 90 to 80 :20.
The suitable amount of the acid catalyst used in hydrolysis reaction is 0.005 to 0.5 parts by weight relative to 100 parts by weight of water, preferably, 0.01 to 0. 1 parts by weight. The suitable amount of alkylene oxide used in hydrolysis reaction is 10 to 1000 parts by weight relative to 100 parts by weight of water, for example, 100 to 500 parts by weight, preferably, 300 to 400 parts by weight.
The suitable reaction temperature in the hydrolysis reaction process is 20 to 90°C, preferably, 30 to 50°C. The reaction time is 1 to 15 hours, for example, 2 to 10 hours. The reaction proceeds by adding alkylene oxide to a reaction mixture, continuously where necessary. In the case that alkylene oxide is gas at the reaction temperature, pressure of the gas phase is preferably 1 to 5 barometric pressures.
Since the hydrolysis reaction proceeds smoothly, the proceeding degree of reaction can be confirmed by measuring water content in a mixture . Thi s reaction proceeds smoothly till water content is 10 weight % to the whole system, but, when it becomes less than that, the reaction rate drops extremely, and the residual amount of unreacted alkylene oxide in the mixture increases. Therefore, it is preferable to consider that the reaction is terminated when water content becomes 10 weight % or less. Alkylene glycol obtained in the hydrolysis reaction process (alkylene glycol and oligomer of alkylene glycol when water is used as an initiator) acts as an initiator in the following addition reaction process.
Addition reaction process :
After completion of hydrolysis reaction, the mixture is transferred to another reactor,
or the next step is done in the same reactor. A base catalyst, in particular, an alkali metal hydroxide or alkaline earth metal hydroxide, preferably potassium hydroxide or its aqueous solution is added thereto in excess, further, alkylene oxide is additionally put therein to undergo addition reaction, thereby synthesizing polyol with a target hydroxyl value.
In the addition reaction process, addition of alkylene oxide occurs while the alkylene glycol and oligomer of alkylene glycol obtained by hydrolysis act as an initiator. The base catalyst is preferably alkali metal hydroxide, alkaline earth metal hydroxide, or a compound having an amino group (amine compound), and specific examples thereof include potassium hydroxide , sodium hydroxide , ce sium hydroxide , magnesium hydroxide, and dimethylamine . The base catalyst can be handled in a form of a mixture with water (for example, aqueous solution) . In a mixture of base catalyst and water, the weight ratio of base and water is 1 : 99 to 99 : 1 , and particularly preferably 20 : 80 to 80 :20. By adding a base catalyst in excess, the acid catalyst is over-neutralized and the reaction mixture (hydrolysis reaction process ( 1 ) terminated) turns basic. The pH of the reaction mixture may be , for example , 8 or more , particularly 10 or more.
Alkylene oxide used in addition reaction generally has the carbon number of 2 to 8, particularly of 2 to 4. Specific examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and a mixture of two kinds or more thereof. Alkylene oxide additionally put in the addition reaction process may be the same as or different from the alkylene oxide used in the hydrolysis reaction process.
The suitable amount of a base catalyst used in addition reaction is 0. 1 to 10 parts by weight relative to 100 parts by weight of an initiator, preferably, 0.5 to 5 parts by weight. The base catalyst is used by an amount higher than that needed for neutralizing the acid catalyst used in the hydrolysis reaction process.
Alkylene oxide may or may not be additionally put in addition reaction. The additional amount of alkylene oxide is, for example, 5 to 5000 parts by weight relative to 100 parts by weight of an initiator, for example, may be 100 to 2000 parts by weight.
In the addition reaction of alkylene oxide, additional raw materials (compounds) having hydroxyl groups or amino groups may be added. Compounds having functional groups such as a hydroxyl groups or amino groups are preferably compounds with a molecular weight of 30 to 600, for example, 40 to 400, in particular, 90 to 350. Specific examples of such compounds having hydroxyl groups include sucrose, pentaerythritol, sorbitol, glycerin, and trimethylolpropane . Specific examples of compounds having amino groups include monoethylamine, ethylenediamine, diethanolamine , triethanolamine , to ly 1 e ne di am ine , diaminodiphenylmethane, and diethylenetriamine. The amount of compounds having hydroxyl groups or amino groups is 50 to 2000 parts by weight relative to 100 parts by weight of an initiator, for example, may be 80 to 650 parts by weight. The compounds having hydroxyl groups or amino groups undergo addition reaction along with alkylene oxide. In the case that a compound having an amino group is used (as a co-starter), in order to advance the reaction of amine and alkylene oxide, it is preferable that base is added first to neutralize the acid (a preferable amount of base is 0.90 to 1.0 equivalents relative to one equivalent of acid.) and to conduct the reaction of amine and alkylene oxide. Then,, additional base is put therein, carrying out addition polymerization of alkylene oxide.
In the addition reaction, the suitable reaction temperature is 100 to 150°C, preferably, 105 to 115°C. The reaction time is 1 to 50 hours, for example, 3 to 30 hours. In the case that alkylene oxide is gas at the reaction temperature, pressure of the gas phase is preferably 1 to 5 barometric pressures.
In the addition reaction of alkylene oxide, by adding other starting raw materials, it becomes possible to synthesize polyol having various characteristics from a plurality of starting raw materials. It is preferable that other starting raw materials are added right before an alkali metal hydroxide catalyst is added, or simultaneously.
In the present invention, polyether polyol obtained using water as a raw material is a polyol having two hydroxyl groups similar to a polyol obtained by addition of alkylene oxide using alkylene glycol as an initiator, and the molecular weight is generally 1 10 to 4000 (hydroxyl value of 28 to 1000 mgKOH/g).
In the addition reaction of alkylene oxide, by adding other starting raw materials, it becomes possible to synthesize polyol having various characteristics from a plurality of starting raw materials . It is preferable that other starting raw materials are added right before an alkali metal hydroxide catalyst is added, or simultaneously.
Examples :
Hereinafter, the present invention is explained specifically by means of Examples and Comparative examples. The present invention's scope is not limited to the examples.
Example 1
To an autoclave of 1 L, 100 parts by weight ( 100 g) of water and 0.04 parts by weight of sulfuric acid were added, it was pressurized with nitrogen to 2 barometric pressures, and then 340 parts by weight of propylene oxide was continuously added thereto at
50°C taking 2 hours. To the mixture, 2.1 parts by weight of potassium hydroxide was added, and under 2 barometric pressures, 300 parts by weight of propylene oxide was continuously added thereto at 110°C taking 2 hours. Thereafter, 1 .7 parts by weight of sulfuric acid was added at 80°C, and mixed for 2 hours to complete a neutralization reaction. Further, under a reduced pressure of 0.01 barometric pressures, dehydration was carried out at 110°C for 2 hours, and filtration was conducted using a filter paper,
thereby to obtain polyol A.
Example 2 To an autoclave of 10 L, 100 parts by weight ( 100 g) of water and 0.04 parts by weight of sulfuric acid were added, it was pressurized with nitrogen to 2 barometric pressures, and then 340 parts by weight of propylene oxide was continuously added thereto at 50°C taking 2 hours. To the mixture, 1500 parts by weight of sucrose and 18.3 parts by weight of potassium hydroxide were added, and under 2 barometric pressures, 3900 parts by weight of propylene oxide was continuously added thereto at 110°C taking 30 hours. Thereafter, 500 parts by weight of water and 15.9 parts by weight of sulfuric acid were added at 80°C, and mixed for 2 hours to complete a neutralization reaction. Further, under a reduced pressure of 0.01 barometric pressures, dehydration was carried out at 100°C for 2 hours, and filtration was conducted using a filter paper, thereby to obtain polyol B.
Comparative example 1 To an autoclave of 1 L, 100 parts by weight ( 100 g) of water and 2.3 parts by weight of potassium hydroxide were added, it was pressurized with nitrogen to 2 barometric pressures, and 670 parts by weight of propylene oxide was continuously added thereto at 110°C taking 30 hours. Thereafter, 70 parts by weight of water and 2.0 parts by weight of sulfuric acid were added at 80°C, and mixed for 2 hours to complete a neutralization reaction. Further, under a reduced pressure of 0.01 barometric pressures, dehydration was carried out at 100°C for 2 hours, and filtration was conducted using a filter paper, thereby to obtain polyol C.
Table 1
From the result of Table 1, in Example 1, compared with the case where propylene oxide undergoes addition by an alkali metal hydroxide catalyst using propylene glycol as a direct raw material, by concomitant use of acid and alkali metal hydroxide catalysts and continuously adding propylene oxide, polyol with a targeted hydroxyl value was able to be synthesized without increasing the reaction time a lot. In Example 2, it has been found that by adding other starting raw material before adding an alkali metal hydroxide catalyst, and after adding it, by adding propylene oxide continuously, the present invention can apply to synthesis of polyol having a plurality of starting materials including water.
In Comparative example 1, only an alkali metal hydroxide catalyst was used as a catalyst. Under this condition, when propylene oxide is added in a short time, 2 hours for example, propylene oxide hardly reacts and evaporates, being exhausted through a pressure control valve. Hence, propylene oxide was slowly added taking 30 hours for propylene oxide to react sufficiently. In this way, in the case of synthesizing polyol only with an alkali metal hydroxide catalyst, it takes a lot of time.
The polyol obtained in Comparative example 1 was different from that obtained in Example 1. It is thought that this is because when hydrolysis reaction is conducted with an alkali metal hydroxide catalyst, the reaction speed is slow and the amount of polypropylene glycol produced by hydrolysis reaction is small, thus the amount of propylene oxide undergoing addition per one molecule of propylene glycol is large.
Polyether polyol obtained by the present invention can be used in various fields, and in particular, it is useful as a raw material of polyurethane.
Claims
1. A production method of polyether polyol characterized by
( 1) a process for producing alkylene glycol by hydrolyzing alkylene oxide with carbon numbers of 2 to 4 in the presence of an acid catalyst, and
(2) a process for obtaining polyether polyol by adding alkylene oxide with carbon numbers of 2 to 4 to the alkylene glycol obtained in process ( 1)
2. The production method of polyether polyol according to claim 1 , wherein in process ( 1 ), the acid catalyst is an inorganic acid.
3. The production method of polyether polyol according to claim 1 or 2,
characterized in that in process (2), an alkali metal hydroxide catalyst is added, and alkylene oxide is subjected to addition reaction.
4. The production method of polyether polyol according to any one of claims 1 to 3, characterized in that in the addition reaction of alkylene oxide (2), raw materials having hydroxyl groups or amino groups are added, and alkylene oxide is subjected to addition reaction.
5. Polyether polyol produced by the production method according to claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010209788A JP5685033B2 (en) | 2010-09-17 | 2010-09-17 | Method for producing polyether polyol using water as a raw material |
| JP2010-209788 | 2010-09-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2012034998A1 true WO2012034998A1 (en) | 2012-03-22 |
Family
ID=44720863
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2011/065831 WO2012034998A1 (en) | 2010-09-17 | 2011-09-13 | Production method of polyether polyol by hydrolyzing alkylene oxide to form alkylene glycol and subsequently adding alkylene oxide |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5685033B2 (en) |
| WO (1) | WO2012034998A1 (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2472417A (en) * | 1942-10-15 | 1949-06-07 | Solvay | Process of manufacture of glycol |
| US4129718A (en) * | 1977-12-01 | 1978-12-12 | Basf Wyandotte Corporation | Process for the removal of catalyst from polyether polyol |
| EP0183028A2 (en) * | 1984-11-24 | 1986-06-04 | Degussa Aktiengesellschaft | Process for the continuous preparation of vicinal diols |
| EP0226799A2 (en) * | 1985-11-18 | 1987-07-01 | MITSUI TOATSU CHEMICALS, Inc. | Method for preparing ethylene glycol and/or propylene glycol |
| EP0369487A2 (en) * | 1988-11-18 | 1990-05-23 | The Dow Chemical Company | Process for the preparation of polyether polyols with reduced unsaturation |
| EP0855417A1 (en) * | 1997-01-27 | 1998-07-29 | Bayer Ag | Process for preparing polyether polyols |
| JP2002302544A (en) | 2001-04-04 | 2002-10-18 | Lion Corp | Polyalkylene glycol and method for producing the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0257243B1 (en) * | 1986-08-23 | 1991-10-23 | Degussa Aktiengesellschaft | Process for the preparation of vicinal diols |
| JP2006089581A (en) * | 2004-09-24 | 2006-04-06 | Sanyo Chem Ind Ltd | Method for producing polyether polyol |
| US20070149634A1 (en) * | 2005-12-22 | 2007-06-28 | Haider Karl W | Long chain polyether polyols |
| US20070149631A1 (en) * | 2005-12-22 | 2007-06-28 | Haider Karl W | Base-catalyzed alkoxylation in the presense of polyoxyethylene-containing compounds |
-
2010
- 2010-09-17 JP JP2010209788A patent/JP5685033B2/en not_active Expired - Fee Related
-
2011
- 2011-09-13 WO PCT/EP2011/065831 patent/WO2012034998A1/en active Application Filing
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2472417A (en) * | 1942-10-15 | 1949-06-07 | Solvay | Process of manufacture of glycol |
| US4129718A (en) * | 1977-12-01 | 1978-12-12 | Basf Wyandotte Corporation | Process for the removal of catalyst from polyether polyol |
| EP0183028A2 (en) * | 1984-11-24 | 1986-06-04 | Degussa Aktiengesellschaft | Process for the continuous preparation of vicinal diols |
| EP0226799A2 (en) * | 1985-11-18 | 1987-07-01 | MITSUI TOATSU CHEMICALS, Inc. | Method for preparing ethylene glycol and/or propylene glycol |
| EP0369487A2 (en) * | 1988-11-18 | 1990-05-23 | The Dow Chemical Company | Process for the preparation of polyether polyols with reduced unsaturation |
| EP0855417A1 (en) * | 1997-01-27 | 1998-07-29 | Bayer Ag | Process for preparing polyether polyols |
| JPH10212348A (en) | 1997-01-27 | 1998-08-11 | Bayer Ag | Production of polyether polyol |
| JP2002302544A (en) | 2001-04-04 | 2002-10-18 | Lion Corp | Polyalkylene glycol and method for producing the same |
Non-Patent Citations (1)
| Title |
|---|
| "Outline of polyurethane raw material industry", URETHANE RAW MATERIALS ASSOCIATION, pages: 11 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5685033B2 (en) | 2015-03-18 |
| JP2012062295A (en) | 2012-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2032523B1 (en) | Process for preparation of alkoxylated alkylamines / alkyl ether amines with peaked distribution | |
| ES2388757T3 (en) | Procedure for the preparation of polyols | |
| KR20110079629A (en) | Polyalkylene glycol producing catalyst, and method for producing polyalkylene glycol using same | |
| CN101775129B (en) | Method for preparing polyether carbonate polyol | |
| CN101250115B (en) | Method for synthesizing 3-amido-1,2-propanediol by pipe reactor | |
| JP2005163022A (en) | Single reactor synthesis of koh-capped polyol based on dmc-synthesized intermediate | |
| ES2388990T3 (en) | Procedure for the production of polyols | |
| US11485695B2 (en) | Alkoxylated secondary alcohol | |
| CN102002157A (en) | Aromatic polyester modified polyether polyol and preparation method thereof | |
| CA2443117A1 (en) | Processes for preparing ethylene oxide-capped polyols | |
| EP2611769B1 (en) | Reactive recovery of dimethyl carbonate from dimethyl carbonate/methanol mixtures | |
| CN103289073A (en) | Preparation method of polycarboxylate water-reducing agent macromonomer methylallyl alcohol polyethenoxy ether | |
| WO2012034998A1 (en) | Production method of polyether polyol by hydrolyzing alkylene oxide to form alkylene glycol and subsequently adding alkylene oxide | |
| CN102126966B (en) | Method for synthesizing N,N-diethyl ethanolamine | |
| JP6350103B2 (en) | Polyalkylene glycol production catalyst | |
| JPH05287071A (en) | Production of liquid water-soluble polyoxyalkylenepolyamine | |
| CN103113241A (en) | Synthetic method of diethylaminoethoxyethanol | |
| JP6520012B2 (en) | Alkylene oxide polymerization catalyst and method for producing polyalkylene oxide using the same | |
| KR101617230B1 (en) | Method and Catalyst of Preparing High Pure Glycerol Carbonate | |
| CN105967983B (en) | The production method of low molecular polyether polyalcohol | |
| JPH0940769A (en) | Production of polyoxyalkylene compound | |
| JPH03181448A (en) | Preparation of polyoxyalkyleneglycolamine | |
| KR102089402B1 (en) | Preparation method of methylol alkanal | |
| CN118201904A (en) | Method for producing alkoxylated etheramines and use thereof | |
| CN104755466A (en) | Preparation of dihydroxyethyl piperazine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11763884 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 11763884 Country of ref document: EP Kind code of ref document: A1 |