EP0237521A1 - Formation of polyols - Google Patents
Formation of polyolsInfo
- Publication number
- EP0237521A1 EP0237521A1 EP19850905849 EP85905849A EP0237521A1 EP 0237521 A1 EP0237521 A1 EP 0237521A1 EP 19850905849 EP19850905849 EP 19850905849 EP 85905849 A EP85905849 A EP 85905849A EP 0237521 A1 EP0237521 A1 EP 0237521A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- reaction
- catalyst
- koh
- oxide
- polyhydric alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/02—Acyclic radicals, not substituted by cyclic structures
- C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- 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
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- 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
- C08G18/487—Polyethers containing cyclic groups
- C08G18/4883—Polyethers containing cyclic groups containing cyclic groups having at least one oxygen atom in the ring
-
- 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
Definitions
- glycol glucoside has been achieved at atmospheric pressure at 130-1 0°C in N-methyl pyrollidone (NMP).
- the new process has the following advantages over that described in UK-A-2106506. a) A single-stage, more easily controlled process is employed. b) The overall time for production of the final, purified/dry polyol is approximately 1/20 that required in the previous method. c) An autoclave is not required. The process can be carried out in a conventional reactor at atmospheric pressure. d) There is more control over the molecular weights attainable; the amount of alkylene oxide (e.g. propylene oxide (PO)) added controls the final molecular weight obtained. e) The molecular weight and the unsaturation levels of the PE polyols produced are similar to those obtained previously. f) The process is more reproducible. g) The catalyst (e.g.
- KOH is in solution and present at for example 4 mol% cf 20 mol% used previously, thereby lessening corrosion problems in the case where the catalyst is KOH. h)
- the process may be easily adapted for continuous production.
- the present invention relates to the formation of polyols by the oxyalkylation of polyhydric alcohols.
- a method of producing a polyol comprising reacting a polyhydric alcohol selected from glycerol, pentaerythritol, sucrose, sorbitol, a glucoside, and 1, 2, 6 - hexane triol with an alkylene oxide in nitrogen-containing heterocyclic solvent in the presence of a basic catalyst.
- a polyhydric alcohol selected from glycerol, pentaerythritol, sucrose, sorbitol, a glucoside, and 1, 2, 6 - hexane triol
- the alkylene oxide may be, for example, ethylene oxide or propylene oxide.
- the catalyst is preferably used in an amount of 1-10 mole ⁇ more preferably 4-8 mole , based on the polyol.
- suitable catalysts are KOH and amines.
- the solvent is N-methylpyrollidone.
- reaction is effected at a temperature of 130-1 0°C.
- a principal objective of the oxyalkylation reaction is to liquify intractable solid polyhydric alcohols to make them suitable for example for use in polyurethane (PU) forming reactions with diisocyanates; their liquid nature making them suitable for PU production including their use in Reaction Injection Moulding (RIM) and Reinforced Reaction Injection Moulding (RRIM).
- RIM Reaction Injection Moulding
- RRIM Reinforced Reaction Injection Moulding
- the catalyst was then neutralised (to pH7) using about 70g of a cationic exchange resin (Zeocarb 226) or by addition of 0.1M HC1.
- the contents of the flask were filtered and subjected to rotary-film evaporation (3 hr/ 80°C/ 1mm Hg) to remove volatiles. 0 MP was then removed by distillation at 145°C/ 1mm Hg.
- the OPPE product was a dark-red coloured liquid. It was mixed with its own volume of water and shaken. The pH of the mixture was again checked and if necessary adjusted to a value of 7 by the addition of 5 0.1 M HC1.
- the water-OPPE mixture was poured into a separating funnel and sufficient P0 (about an equal volume) added to produce the formation of an aqueous layer at the bottom of the funnel.
- the solvent and unreacted alkylene oxide may be recycled.
- Example 1 The invention will be further described by way of examply only with reference to the following Examples.
- Example 1 The invention will be further described by way of examply only with reference to the following Examples.
- Propylene Oxide (PO) was subjected to reflux distillation over potassium hydroxide for three hours and then fractionally distilled at atmospheric pressure. The fraction boiling at 34°C was collected. It was stored in a desiccator in a freezer.
- NMP N-Methyl Pyrrolidone
- PE aerythritol
- KOH Potassium Hydroxide
- the resulting solution was a pale yellow colour or colourless. If coloured, it was treated with activated charcoal and filtered several times, finally using a Millipore filter (FALP 0025 - 1nm). The solution was then subjected to rotary - film evaporation at 80°C/ mm Hg. The rotary - film evaporation was repeated several times and the product was finally heated to 40°C/lmm Hg under nitrogen for 8 hrs (If traces of water and other volatiles can be tolerated in the product, the repeated rotary- film evaporation and final heating under nitrogen can be omitted.) • The OPPR product obtained was a colourless or very pale yellow liquid. The weight of PO reacted was found by weighing the final product.
- Table 1 specifies the reaction mixtures investigated using the foregoing procedure.
- the amounts of PO added (columns 6 and 7) i.e. was determined by weighing the reaction flask before and after the reaction.
- the amount of P0 reacted (column 8) was determined from the amount of OPPE product finally obtained.
- the amounts of reactants are given in units of moles (columns 2, 3 and 4).
- the ratio of P0 reacted to base moles of PE (column 5) gives the average number of moles of P0 reacted with each mole of PE added.
- the values of Mn in column 6 were obtained as (column 5 x 58) + 136.
- the catalyst level was 4 mol % KOH/OH compared with 20 mol % in the patent.
- the lower catald t level reduces problems of corrosion which may be encountered in metal or glass rea ⁇ tors.
- An approximately constant % of the added - PO undergoes reaction the value (65-67%) used and on the length of time the reaction mixture is maintained at the reaction temperature after addition of all the PO. In the reported examples, the mixture was immediately allowed to cool to room temperature. The % reacted can be increased by maintaining the reaction temperature for a long time.
- Mn increases approximately in proportion to the moles of PO added. Thus, control. of Mn is easily achieved. Due to side reactions, there will no doubt be some limit to the maximum value of Mn which may be realised. However, it should be possible to match the range of molar masses achieved in the patent (up to 5600) by the addition of further PO, extension of the reaction time, and/or variation of the reaction temperature.
- the preparation is a one-stage, solution polymlerisation. The total time to obtaining crude product is first the reaction time (say 4 hr). In the patent, a two stage preparation was necessary to achieve products of similar molar masses (say 4-5 days including the purification of the first-stage product).
- Solvent and PO can be recycled. In the patent method, PO could be recycled.
- the present method is adaptable to continuous operation as the PO is added continuously throughout a reaction.
- continuous addition of PO/PE/KOH/NMP may be used together with continuous withdrawal of product after a certain residence time, depending on the molar mass required.
- the method can be used with other polyhydric alcohols which are soluble in NMP, such as sucrose, glucose, serbitol and glycerol.
- Alternative catalyst systems may have been employed.
- EGG is a mixture of compounds, and may be respresented by the idealised structure (I) ro
- composition varies but generally it consists of a mixture of predominantly ⁇ and glucosides, some bis glucoside, oligomeric material and residual ethylene glucol and glucose.
- the material used in the preparation was an amber glass which yielded a syrup. at - ⁇ >s 100°C. It had an equivalent weight (by acetylation) of 47.3 which compares favourably with that calculated for the monoglucoside of 44.8.
- EGG (200g), KOH (4g) were dissolved in distilled NMP (200ml) contained in a 1 litre flask equipped with a mechanical stirrer, thermometer, pressure equalising dropping funnel and a condenser.
- a length of rubber-tubing connected the condenser to a mineral-oil bubbler which indicated the rate of loss of unreacted PO.
- the contents of the flask were raised to 140°C and PO added dropwise at a rate of ' 150ml per hour.
- Initial addition of PO caused the temperature to rise to *-—-*-155 0 C and the reaction was sufficiently exothermic to maintain the reaction temperature at 130-140° with only minimal external heating. At temperatures below 130°c the PO failed to react.
- PO addition (425ml) was complete, oxygeu-free nitrogen was passed through the reaction solution to drive off unreacted PO.
- the flask was then cooled and weighed to determine PO addition (323g 90% conversion of PO).
- Methyl ethyl Ketone (MEK) 400 ml
- Zerolit DM-F resin (70g) were then added and the slurry mechanically stirred until pH 7 was attained.
- the suspension was filtered and MEK removed from the filtrate using a rotary film evaporator (water bath 30°C) under water-pump vacuum.
- the solution was then transferred into a flask for vacuum distillation to remove NMP. (0.01 mm Hg; maximum flask temperature 150°C).
- the product (513g) w s a clear, amber, viscous liquid at room temperature, mobile above 40°C.
- the object of the preparation was: a) to prepare a liquid polyol from solid EGG. (EGG although producing a syrup at •-*»—100°C is not mixible with MDI and its viscosityis too high to process easily by RIM) b) to maximise the carbolydrate content of the resultant polyol by the minimum addition of PO.
- the method may however be used to prepare a range of EGG/PO adducts by varying the amount of PO added as in the case of PE.
- OPEGG has been employed alone and or in admixture with the commercially available polyether, polytetra- methylene oxide (PTHF) to produce polyurethanes by reaction with 4,4' diphenyl methane diisocyanate (MDI). Viscosity studies on these polyol blends in the temperature range 20-60°C indicate that their
- the polyurethanes produced ranged from a clear amber glass (from OPEGG/MDI) to clear yellow elastomers.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyethers (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Saccharide Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Des polyols sont produits par oxyalkylation d'un alcool polyhydrique sélectionné parmi le glycérol, le pentaérythritol, le sucrose, le sorbitol, un glucoside ou 1, 2, 6 - hexane triol avec un oxyde d'alkylène (p. ex. l'oxyde d'éthylène ou l'oxyde de propylène) dans un solvant hétérocyclique contenant de l'azote (p. ex. NMP) en présence d'un catalyseur basique (p. ex. KOH).Polyols are produced by oxyalkylation of a polyhydric alcohol selected from glycerol, pentaerythritol, sucrose, sorbitol, a glucoside or 1, 2, 6 - hexane triol with an alkylene oxide (e.g. oxide ethylene or propylene oxide) in a heterocyclic solvent containing nitrogen (eg NMP) in the presence of a basic catalyst (eg KOH).
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8427886 | 1984-11-03 | ||
GB8427886A GB8427886D0 (en) | 1984-11-03 | 1984-11-03 | Formation of polyols |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0237521A1 true EP0237521A1 (en) | 1987-09-23 |
Family
ID=10569241
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19850905849 Withdrawn EP0237521A1 (en) | 1984-11-03 | 1985-11-04 | Formation of polyols |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0237521A1 (en) |
JP (1) | JPS62501005A (en) |
GB (1) | GB8427886D0 (en) |
WO (1) | WO1986002635A1 (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63152393A (en) * | 1986-07-03 | 1988-06-24 | Takeda Chem Ind Ltd | Glycosyl derivative |
GB8829033D0 (en) * | 1988-12-13 | 1989-01-25 | Univ Manchester | Formation of polyether polyols |
EP0512270B1 (en) * | 1991-04-08 | 1999-11-03 | Kao Corporation | Cosmetic composition |
US5268510A (en) * | 1992-10-08 | 1993-12-07 | Vista Chemical Company | Process for purification of alkoxylated alcohols |
DE4318962A1 (en) * | 1993-06-08 | 1994-12-15 | Basf Ag | Process for the production of rigid polyurethane foams |
ATE226966T1 (en) * | 1995-04-14 | 2002-11-15 | Kazunori Kataoka | POLYETHYLENE OXIDES HAVING A SACCHARIDE GROUP AT ONE END AND ANOTHER FUNCTIONAL GROUP AT THE OTHER END AND METHOD FOR THE PRODUCTION THEREOF |
WO1996036582A1 (en) * | 1995-05-19 | 1996-11-21 | The Dow Chemical Company | Alkoxylation of alcohols |
DE10061496A1 (en) * | 2000-12-08 | 2002-08-01 | Cce Composites And Compounds E | molding compound |
SE523934C2 (en) * | 2001-09-24 | 2004-06-01 | Perstorp Specialty Chem Ab | Process for alkoxylation of di-, tri- and polyalcohols |
USRE46234E1 (en) | 2009-03-27 | 2016-12-13 | Actamax Surgical Materials, Llc | Tissue adhesive and sealant comprising polyglycerol aldehyde |
US9290620B2 (en) * | 2009-10-21 | 2016-03-22 | Nalco Company | Production and composition of glycerol based polyols |
JP6465475B2 (en) * | 2014-09-25 | 2019-02-06 | 第一工業製薬株式会社 | Method for purifying alkylene oxide adducts of sugars |
CN116096696A (en) * | 2020-10-19 | 2023-05-09 | 奥克西泰诺工业和贸易公司 | Compositions, agrochemicals, methods for increasing water and nutrient availability and improving pest control in plants and seeds, and uses of said compositions and said agrochemicals |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3102114A (en) * | 1961-04-03 | 1963-08-27 | Komori Saburo | Polyoxyethylene derivatives of esters of sucrose with long-chain fatty acids |
US3370056A (en) * | 1963-04-04 | 1968-02-20 | Takeda Chemical Industries Ltd | Production of polyoxyalkylene ethers |
FR1460152A (en) * | 1964-11-09 | 1966-06-17 | Union Carbide Corp | New catalysts for the production of alkylene oxide adducts with hydroxy organic compounds |
US4332936A (en) * | 1978-10-16 | 1982-06-01 | Mobay Chemical Corporation | Method of making polyether polyols from solid hydroxyl containing initiators |
GB2106506B (en) * | 1981-07-04 | 1985-05-09 | Univ Manchester | Production of polymeric polyols |
-
1984
- 1984-11-03 GB GB8427886A patent/GB8427886D0/en active Pending
-
1985
- 1985-11-04 WO PCT/GB1985/000500 patent/WO1986002635A1/en not_active Application Discontinuation
- 1985-11-04 JP JP50509685A patent/JPS62501005A/en active Pending
- 1985-11-04 EP EP19850905849 patent/EP0237521A1/en not_active Withdrawn
Non-Patent Citations (1)
Title |
---|
See references of WO8602635A1 * |
Also Published As
Publication number | Publication date |
---|---|
GB8427886D0 (en) | 1984-12-12 |
WO1986002635A1 (en) | 1986-05-09 |
JPS62501005A (en) | 1987-04-23 |
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Legal Events
Date | Code | Title | Description |
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PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
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17P | Request for examination filed |
Effective date: 19870428 |
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AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): DE FR GB IT |
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17Q | First examination report despatched |
Effective date: 19880325 |
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STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
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18D | Application deemed to be withdrawn |
Effective date: 19910604 |
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RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: STILL, RICHARD, HEYWOOD Inventor name: CAWSE, JOHN, LESLIE Inventor name: STANFORD, JOHN, LAWRENCE |