WO2004048440A1 - ポリエーテルポリオールの製造方法 - Google Patents
ポリエーテルポリオールの製造方法 Download PDFInfo
- Publication number
- WO2004048440A1 WO2004048440A1 PCT/JP2003/013650 JP0313650W WO2004048440A1 WO 2004048440 A1 WO2004048440 A1 WO 2004048440A1 JP 0313650 W JP0313650 W JP 0313650W WO 2004048440 A1 WO2004048440 A1 WO 2004048440A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- polyether polyol
- producing
- catalyst
- reaction
- Prior art date
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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
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
Definitions
- the present invention relates to a method for producing a polyether polyol by dehydration condensation reaction of a polyol. More specifically, it relates to a method of carrying out this reaction in the presence of a novel catalyst.
- Polyether polyols are polymers that have a wide range of uses, including materials for soft segments such as elastic fibers and plastic elastomers.
- Polyethylene glycol, poly (1,2-propanediol), polythe 1, lamethylene ether glycol and the like are known as typical polyetherpolyols.
- poly (1,2-propanediol) is widely used because it is liquid at room temperature, easy to handle, and inexpensive.
- poly (1,2-propanediol) has a primary hydroxyl group and a secondary hydroxyl group, the difference in the physical properties of these hydroxyl groups may be a problem depending on the application.
- polytrimethylene ether dacol which is a dehydrated condensate of 1,3-propanediol, has attracted attention in recent years because it has only a primary hydroxyl group and has a low melting point.
- Polyether polyols can generally be produced by the dehydration condensation reaction of the corresponding polyols.
- ethylene glycol, 1,4-butanediol and 1,5-pentanediol etc. form 5- or 6-membered cyclic ethers upon dehydration condensation, ie, 1,4-dioxane, tetrahydrofuran and tetrahydropyran, respectively.
- polyether polyols corresponding to polymers of ethylene glycol and 1,4-butanediol are produced by ring-opening polymerization of corresponding cyclic ethers, ie, ethylene oxide and tetrahydrofuran.
- a polyester corresponding to a polymer of 1, 5-pentanediol One terpolyol is difficult to obtain because the cyclic ether tetrahydropyran is thermodynamically favorable.
- Production of polyether polyols by dehydration condensation reaction of polyols is generally carried out using an acid catalyst.
- the catalyst inorganic acids such as iodine, hydrogen iodide and sulfuric acid, organic acids such as paratoluenesulfonic acid (see Patent Document 1), and resins having perfluoroalkylsulfonic acid groups in the side chain (see Patent Document 2) And the like), sulfuric acid, activated clay, zeolite, organic sulfonic acid, heteropoly acid and the like and a combination of cuprous chloride (see Patent Document 3) and the like.
- the present invention is intended to provide a method for producing a polyether polyol having a high degree of polymerization and less coloring with high yield by dehydrating condensation of the polyether polyol under mild reaction conditions.
- the present inventors have found that the above object can be achieved by using a specific catalyst system, and have completed the present invention. That is, the gist of the present invention is a method for producing a polyether polyol characterized in that the reaction is carried out in the presence of a catalyst comprising an acid and a base when producing a polyether polyol by dehydration condensation reaction of a polyol.
- a catalyst comprising an acid and a base
- any of those conventionally known to form an ether bond by dehydration condensation reaction of alcoholic hydroxyl group can be used.
- the acid may be either dissolved in the reaction system to act as a homogeneous catalyst or one which does not dissolve but acts as a heterogeneous catalyst.
- examples of such an acid include, as the former, heteropoly acids such as sulfuric acid, phosphoric acid, fluorosulfuric acid and phosphotungstic acid; Alkylsulfonic acid whose alkyl chain may be fluorinated, such as 1, 2, 2-tetrafluoroethanesulfonic acid, benzenesulfonic acid which may have alkyl side chain in the benzenesulfonic acid ring.
- Acids for example, arylsulfonic acids such as para-toluenesulfonic acid, and the latter include activated clay, zeolite, metal complex oxides such as silica-alumina and silica-zirconia, and perfluoroalkyl sulfonate groups And the like.
- sulfuric acid, phosphoric acid, benzenesulfonic acid, p-toluenesulfonic acid and the like are preferable in that they are easily available and inexpensive, and among these, sulfuric acid is most preferable.
- an organic base and an alkali metal are preferable, and an organic base is particularly preferable.
- the organic base for the catalyst is preferably a nitrogen-containing organic base, particularly a nitrogen-containing organic base having a tertiary nitrogen atom.
- the organic base is used in an amount less than the equivalent of the acid of the catalyst, that is, in an amount ratio that does not completely neutralize the acid of the catalyst.
- the amount is preferably at least 0.01 equivalents, more preferably at least 0.50 equivalents, preferably at most 0.9 equivalents, more preferably at most 0.5 equivalents, based on the acid of the catalyst. Is good.
- the acid and the organic base may be present separately in the reaction system, or the acid and the organic base may form a salt.
- one in which a salt is formed with an acid and an organic base in advance may be used.
- an alkali metal which is a base of a catalyst Li, Na, K, Cs is preferable and Na is particularly preferable.
- an alkali metal one in which an alkali metal salt is formed by an alkali metal and a catalyst acid is preferably used.
- alkali metal salts include sulfates, hydrogen sulfates, halides, phosphates, hydrogen phosphates, salts of mineral acids such as borates, trifluoromethane sulfonate, para-toluene sulfonate, methane Organic sulfonates such as sulfonates, carboxylates such as formates, acetates and the like.
- an alkali metal salt and a free acid preferably coexist, and in this case, the acid forming the alkali metal salt and the free acid are preferably the same.
- an acid as a catalyst and its alkali metal salt may be used, respectively, carbonates, hydrogen carbonates, hydroxides, simple metals of aluminum metal and the like are reacted with the acid as a catalyst. It is also possible to prepare a catalyst consisting of the desired acid and alkali metal salt.
- a catalyst consisting of the desired acid and alkali metal salt.
- an alkali metal carbonate and sulfuric acid can be reacted in a polyol which is a reaction substrate to form a solution containing sulfuric acid and an alkali metal salt of sulfuric acid.
- the alkali metal salt is preferably at least 0.01 equivalents, more preferably at least 0.5 equivalents, preferably at most 0.9 equivalents, more preferably at least 0.5 equivalents, as the alkali metal, relative to the acid of the catalyst. It is good to use it as follows.
- ethylene glycol, 1,4-butanediol, 1,5-pentanediol and the like produce cyclic ether ethers by the dehydration condensation reaction as described above. Therefore, it is not preferable as a raw material for the method of the present invention.
- these diols are used alone but, if desired, can be used as a mixture of two or more diols. But preferably primary di- O Lumpur this case is to occupy 5 0 mole 0/0 above.
- oligomers of 2- to 9-mers obtained by dehydration condensation reaction of main diols can be used together with these diols.
- triol or higher polyols such as trimethylol ethane, trimethylolpropane and pentaerythritol, or oligomers of these polyols may be used in combination.
- the carbon number is 3 to 1 having two primary hydroxyl groups. The reaction is carried out with a diol of 0 or a mixture of this with another polyol, the proportion of the other polyol being less than 50 mol%.
- the ratio of the other polyol is 50 moles. /. Use less than one for the reaction.
- the production of polyether polyols by the dehydration condensation reaction of polyols according to the process of the present invention can be carried out either batchwise or continuously.
- the raw material polyol, the acid of the catalyst and the base may be charged into the reactor and reacted under stirring.
- the raw material polyol and the catalyst are continuously supplied from one end of a reaction apparatus or flow type reaction apparatus in which a large number of stirring vessels are connected in series, and the apparatus moves in a biston flow or similar manner Let the reaction solution be continuously withdrawn from the other end.
- An expressive method can be used.
- the catalyst acid is usually added to the raw material polyol
- the lower limit is usually 0.1 times by weight or more, preferably 1 times by weight or more, and the upper limit is usually 100 times by weight with respect to the acid generally staying in the reactor.
- the temperature of the dehydration condensation reaction is such that the lower limit is usually 120 ° C. or higher, preferably 140 ° C. or higher, and the upper limit is usually 250 ° C., preferably 20 ° C. or lower That's good.
- the reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon.
- the reaction pressure is arbitrary as long as the reaction system is maintained in the liquid phase, and is usually performed under normal pressure. If desired, the reaction may be conducted under reduced pressure or an inert gas may be passed through the reaction system to promote the elimination of water produced by the reaction from the reaction system.
- the reaction time varies depending on the amount of catalyst used, reaction temperature and desired yield and physical properties of the dehydrating condensation product, but the lower limit is usually 0.5 hours or more, preferably 1 hour or more, and the upper limit is It is usually 50 hours or less, preferably 20 hours or less.
- the reaction is usually carried out without a solvent, but a solvent can also be used if desired.
- the solvent may be appropriately selected from organic solvents used in conventional organic synthesis reactions in consideration of the vapor pressure under the reaction conditions, the stability, the solubility of the raw materials and the like, and the like.
- the separation and recovery of the formed polyether polyol from the reaction system can be carried out by a conventional method.
- an acid that acts as a heterogeneous catalyst first, suspended acid is removed from the reaction solution by filtration or centrifugation. Then remove low-boiling oligomers and bases by distillation or extraction with water etc. Get terpolyol.
- water is first added to the reaction solution to separate the polyether polyol layer and the aqueous layer containing the acid, the base oligomer and the like.
- polyether polyol Since part of the polyether polyol forms an ester with an acid used as a catalyst, water is added to the reaction solution, and then the ester is heated to hydrolyze and then allowed to separate. At this time, hydrolysis can be promoted by using an organic solvent having affinity for both polyether polyol and water together with water.
- an organic solvent that has affinity for the polyether polyol and can be easily separated from the polyether polyol by distillation. .
- the polyether polyol phase obtained by phase separation is distilled to distill off the remaining water and organic solvent to obtain the desired polyether polyol.
- the polyether polyol obtained by the method of the present invention has a weight-average molecular weight (M w) ⁇ lower limit of usually 600 or more, preferably 120 or more, and an upper limit of usually 300 000 or less, preferably 1 5 0 0 0 or less.
- the lower limit of the number average molecular weight (M n) is usually 500 or more, preferably 100 or more, and the upper limit is usually 1000 or less, preferably 500 or less.
- the molecular weight distribution (MwZMn) is preferably as close to 1 as possible, and the upper limit is usually 3 or less, preferably 2.5 or less.
- the Hazen color number is preferably as close to 0 as possible, and the upper limit is usually 120 or less, preferably 100 or less.
- the degree of coloring of the polyether polyol is represented by the Hazen color number defined in the standard of the American Public Health Association (APHA).
- Hazen color number A standard solution prepared by diluting an APHA color number standard solution (NO. 500) manufactured by Kishida Chemical Co., Ltd. was used to determine the colorimetry according to J I S K 007 1- 1.
- reaction solution cooled to room temperature was transferred to a 300 ml eggplant-type flask using 50 g of tetrahydrofuran, to which 50 g of demineralized water was added and gently refluxed for 1 hour to hydrolyze the sulfate.
- the lower layer water layer separated into two layers was removed.
- 50 g of toluene is added and the mixture is heated to 60 ° C., and tetrahydrofuran, water and toluene are distilled off under reduced pressure. I left it.
- Example 2 A polytrimethylene ether glycol was obtained in the same manner as in Example 1 except that pyridine was not added. The results are shown in Table 1.
- Example 2 A polytrimethylene ether glycol was obtained in the same manner as in Example 1 except that pyridine was not added. The results are shown in Table 1.
- Example 5 A polytrimethylene tertericol was obtained in the same manner as in Example 1 except that 0.103 g of 1,8-diazabicyclo [5.4.0] -7-undecene was used instead of pyridine. The results are shown in Table 1.
- Example 5 A polytrimethylene tertericol was obtained in the same manner as in Example 1 except that 0.103 g of 1,8-diazabicyclo [5.4.0] -7-undecene was used instead of pyridine. The results are shown in Table 1.
- Example 5 A polytrimethylene tertericol was obtained in the same manner as in Example 1 except that 0.103 g of 1,8-diazabicyclo [5.4.0] -7-undecene was used instead of pyridine. The results are shown in Table 1.
- Example 5 A polytrimethylene tertericol was obtained in the same manner as in Example 1 except that 0.103 g of 1,8-diazabicyclo [5.4.0] -7-undecene was used instead
- Example 1 2, 173 4, 322 1. 99 64 37. 0 Comparative Example 1 1, 544 2, 830 1. 83 130
- a polyether polyol having a high degree of polymerization and little coloration can be efficiently produced by the reaction under mild conditions.
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- 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)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003280574A AU2003280574A1 (en) | 2002-11-22 | 2003-10-24 | Method for producing polyether polyol |
US11/134,460 US20050272911A1 (en) | 2002-11-22 | 2005-05-23 | Method for producing polyether polyol |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002339507 | 2002-11-22 | ||
JP2002-339507 | 2002-11-22 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/134,460 Continuation US20050272911A1 (en) | 2002-11-22 | 2005-05-23 | Method for producing polyether polyol |
Publications (1)
Publication Number | Publication Date |
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WO2004048440A1 true WO2004048440A1 (ja) | 2004-06-10 |
Family
ID=32375775
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2003/013650 WO2004048440A1 (ja) | 2002-11-22 | 2003-10-24 | ポリエーテルポリオールの製造方法 |
Country Status (4)
Country | Link |
---|---|
US (1) | US20050272911A1 (ja) |
CN (1) | CN1774462A (ja) |
AU (1) | AU2003280574A1 (ja) |
WO (1) | WO2004048440A1 (ja) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006001482A1 (ja) * | 2004-06-29 | 2006-01-05 | Mitsubishi Chemical Corporation | ポリエーテルポリオールの製造方法 |
US7074969B2 (en) | 2004-06-18 | 2006-07-11 | E.I. Du Pont De Nemours And Company | Process for preparation of polytrimethylene ether glycols |
WO2006121111A1 (ja) * | 2005-05-13 | 2006-11-16 | Mitsubishi Chemical Corporation | ポリエーテルポリオールの製造方法 |
US7157607B1 (en) | 2005-08-16 | 2007-01-02 | E. I. Du Pont De Nemours And Company | Manufacture of polytrimethylene ether glycol |
US7161045B1 (en) | 2005-08-16 | 2007-01-09 | E. I. Du Pont De Nemours And Company | Process for manufacture of polytrimethylene ether glycol |
WO2007083519A1 (ja) * | 2006-01-20 | 2007-07-26 | Mitsubishi Chemical Corporation | ポリエーテルポリオールの製造方法 |
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WO2004099110A1 (ja) * | 2003-05-08 | 2004-11-18 | Mitsubishi Chemical Corporation | 1,3−プロパンジオールの製造方法 |
CN101155851B (zh) | 2005-04-15 | 2011-06-22 | 三菱化学株式会社 | 聚醚酯嵌段共聚物 |
EP1940914B1 (en) * | 2005-09-22 | 2009-05-13 | E.I. Du Pont De Nemours And Company | Preparation of polytrimethylene ether glycol and copolymers thereof |
US7164046B1 (en) | 2006-01-20 | 2007-01-16 | E. I. Du Pont De Nemours And Company | Manufacture of polytrimethylene ether glycol |
US7388115B2 (en) | 2006-01-20 | 2008-06-17 | E. I. Du Pont De Nemours And Company | Manufacture of polytrimethylene ether glycol |
US20070203371A1 (en) * | 2006-01-23 | 2007-08-30 | Sunkara Hari B | Process for producing polytrimethylene ether glycol |
EP2064259B1 (en) * | 2006-09-21 | 2013-10-23 | Henkel AG & Co. KGaA | LOW TEMPERATURE curable composition comprising a benzoxazine component |
US7714174B2 (en) * | 2007-03-27 | 2010-05-11 | E. I. Du Pont De Nemours And Company | Lower-color polytrimethylene ether glycol using hydride compounds |
EP2205659B1 (en) * | 2007-11-01 | 2014-06-04 | E. I. du Pont de Nemours and Company | Preparation of polytrimethylene ether glycol or copolymers thereof |
US8114957B2 (en) * | 2009-02-09 | 2012-02-14 | E. I. Du Pont De Nemours And Company | Process for preparing poly(trimethylene ether) glycol and copolymers thereof |
US20100204439A1 (en) * | 2009-02-09 | 2010-08-12 | E.I. Du Pont De Nemours And Company | Processes for making poly(trimethylene ether) glycol using organophosphorous compound |
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US20110112331A1 (en) * | 2009-11-09 | 2011-05-12 | E.I. Du Pont De Nemours And Company | Method for phase separation of polytrimethylene ether glycol in salt solution |
CN102666651B (zh) * | 2009-12-21 | 2014-09-10 | 纳幕尔杜邦公司 | 用于制备聚三亚甲基醚二醇及其共聚物的方法 |
CN114230784B (zh) * | 2021-12-29 | 2023-05-26 | 万华化学集团股份有限公司 | 一种聚醚多元醇的制备方法及其应用 |
CN114316254B (zh) * | 2021-12-29 | 2023-05-30 | 万华化学集团股份有限公司 | 一种聚醚多元醇及其制备方法和应用 |
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US2520733A (en) * | 1946-08-26 | 1950-08-29 | Shell Dev | Polymers of trimethylene glycol |
US3188353A (en) * | 1960-09-17 | 1965-06-08 | Bayer Ag | Method of preparing polyethers |
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US3326985A (en) * | 1964-12-29 | 1967-06-20 | Shell Oil Co | Polytrimethylene glycol |
US5659089A (en) * | 1996-05-22 | 1997-08-19 | Arco Chemical Technology, L.P. | Process for making poly(2-methyl-1,3-propanediol) |
US6683222B2 (en) * | 1999-02-18 | 2004-01-27 | Taiyo Kagaku Co., Ltd. | Polyether-polyol compound |
JP4786847B2 (ja) * | 1999-12-17 | 2011-10-05 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | ポリトリメチレンエーテルグリコールおよびそのコポリマーの生成 |
US6780964B2 (en) * | 2001-08-30 | 2004-08-24 | Hodogaya Chemical Co., Ltd. | Method for preparing polyether polyol copolymer |
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2003
- 2003-10-24 CN CN200380109115.4A patent/CN1774462A/zh active Pending
- 2003-10-24 WO PCT/JP2003/013650 patent/WO2004048440A1/ja active Application Filing
- 2003-10-24 AU AU2003280574A patent/AU2003280574A1/en not_active Abandoned
-
2005
- 2005-05-23 US US11/134,460 patent/US20050272911A1/en not_active Abandoned
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US4551561A (en) * | 1983-12-21 | 1985-11-05 | Hoechst Aktiengesellschaft | Process for the preparation of polyglycerols |
JPS61123630A (ja) * | 1984-11-21 | 1986-06-11 | Asahi Chem Ind Co Ltd | ポリアルキレンエ−テルポリオ−ルの製造法 |
US5403912A (en) * | 1990-11-27 | 1995-04-04 | Commonwealth Scientific And Industrial Research Organization | Process for the production of poly(alkylene oxide) |
US5616679A (en) * | 1993-05-14 | 1997-04-01 | Henkel Kommanditgesellschaft Auf Aktien | Polyalkylene glycol |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7074969B2 (en) | 2004-06-18 | 2006-07-11 | E.I. Du Pont De Nemours And Company | Process for preparation of polytrimethylene ether glycols |
WO2006001482A1 (ja) * | 2004-06-29 | 2006-01-05 | Mitsubishi Chemical Corporation | ポリエーテルポリオールの製造方法 |
WO2006121111A1 (ja) * | 2005-05-13 | 2006-11-16 | Mitsubishi Chemical Corporation | ポリエーテルポリオールの製造方法 |
US7157607B1 (en) | 2005-08-16 | 2007-01-02 | E. I. Du Pont De Nemours And Company | Manufacture of polytrimethylene ether glycol |
US7161045B1 (en) | 2005-08-16 | 2007-01-09 | E. I. Du Pont De Nemours And Company | Process for manufacture of polytrimethylene ether glycol |
WO2007021954A1 (en) * | 2005-08-16 | 2007-02-22 | E. I. Du Pont De Nemours And Company | Manufacture of polytrimethylene ether glycol |
JP2009504880A (ja) * | 2005-08-16 | 2009-02-05 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | ポリトリメチレンエーテルグリコールの製造 |
CN101248104B (zh) * | 2005-08-16 | 2011-03-02 | 纳幕尔杜邦公司 | 聚三亚甲基醚二醇的制造 |
WO2007083519A1 (ja) * | 2006-01-20 | 2007-07-26 | Mitsubishi Chemical Corporation | ポリエーテルポリオールの製造方法 |
Also Published As
Publication number | Publication date |
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US20050272911A1 (en) | 2005-12-08 |
CN1774462A (zh) | 2006-05-17 |
AU2003280574A1 (en) | 2004-06-18 |
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