WO2013092680A1 - Catalyseur utilisé pour la production de produits d'addition d'époxydes et de composés ayant des atomes d'hydrogène actifs - Google Patents

Catalyseur utilisé pour la production de produits d'addition d'époxydes et de composés ayant des atomes d'hydrogène actifs Download PDF

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Publication number
WO2013092680A1
WO2013092680A1 PCT/EP2012/076107 EP2012076107W WO2013092680A1 WO 2013092680 A1 WO2013092680 A1 WO 2013092680A1 EP 2012076107 W EP2012076107 W EP 2012076107W WO 2013092680 A1 WO2013092680 A1 WO 2013092680A1
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compound
active hydrogen
formula
hydrogen atom
integer
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PCT/EP2012/076107
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English (en)
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Richard Herman Woudenberg
Behrouz Syrous
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Akzo Nobel Chemicals International B.V.
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Publication of WO2013092680A1 publication Critical patent/WO2013092680A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
    • B01J31/0227—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C07F5/069—Aluminium compounds without C-aluminium linkages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/48—Ring-opening reactions

Definitions

  • the present invention relates to a catalyst used for the production of addition products of epoxides and compounds having at least one active hydrogen atom.
  • epoxides such as epichlorohydrin and alkylene oxides
  • compounds having active hydrogen atoms such as alcohols, fatty acids, amines and thiols
  • these reactions may be performed in the presence of various catalysts.
  • the product resulting from the said reaction will normally be a mixture of several addition products where one, two or more epoxides have been added to the compound having at least one active hydrogen atom.
  • catalysts that are acid, such as sulphuric acid, SnCI 4 and BF 3 . These are very selective, but at the same time they are corrosive and may form other side products, such as 1 ,4-dioxane for reactions where the epoxide is ethylene oxide.
  • catalysts that have been described are neutral mineral salts, such as magnesium or zinc perchlorate. These catalysts have good selectivity and are not corrosive, but there is a considerable risk for explosions when using them on a large scale.
  • the alcohol 1_ reacts with epichlorohydrin to yield a first addition product 2, which is the desired product that may be transformed to an alkyl glycidyl ether by reaction with NaOH.
  • the first addition product 2 also has a hydroxyl group and may thus react with one more mole of epichlorohydrin to yield the di-adduct 3.
  • the di- adduct 3 is less desirable, since after reaction with NaOH there will result a glycidyl ether which still contains one chlorine atom.
  • the chlorine-containing glycidyl ether product may give rise to side-products in further syntheses where the glycidyl ether mixture is used.
  • a good catalyst should favour the addition of epichlorohydrin to 1 to give a high ratio of 2 to 3.
  • US 4,543,430 relates to a process for the reaction of an epoxide, e.g. alkylene oxide or epichlorohydrin, and a hydroxylated compound, e.g. an alcohol, in the homogeneous liquid phase, using a catalyst which is a metal salt of trifluoromethane sulphonic acid, such as aluminium triflate.
  • a catalyst which is a metal salt of trifluoromethane sulphonic acid, such as aluminium triflate.
  • the working examples only relate to reactions with ethylene oxide and propylene oxide.
  • US 6,093,793 relates to a process for polyaddition of epoxides to starter compounds having active hydrogen atoms, using a catalyst that is a metal salt of perfluorosulfonic acid.
  • a catalyst that is a metal salt of perfluorosulfonic acid.
  • Other suitable anions may also be present in the salt, but the examples only disclose compounds with triflate anions, such as lanthanum triflate.
  • EP 0 545 576 relates to a catalyst which is a salt of triflic acid or perchloric acid with a metal, e.g. cerium, ytterbium, yttrium or lanthanum.
  • the catalysts are used for reaction between an alcohol and epichlorohydrin.
  • La(OTf) 3 is used.
  • the object of the present invention is to provide a catalyst for the addition reaction of an epoxide to a compound having at least one active hydrogen atom, where the selectivity index between the product formed by addition of one epoxide, and the product where two or more epoxides have been added, is high.
  • a compound comprising a metal ion that is Al 3+ , and two types of anions, where the first type of anion is selected from the group consisting of a perfluorinated C1 -C10 alkylsulfonate and BF 4 " , , and the second type of anion is a C1 -C10 alkylsulfonate, is an excellent catalyst for the addition of an epoxide to a compound having at least one active hydrogen atom.
  • the present invention relates to the use of the aforementioned compound as a catalyst for the addition reaction of an epoxide to a compound having at least one active hydrogen atom.
  • the present invention relates to a process for obtaining an addition product of an epoxide to a compound having at least one active hydrogen atom by addition of the epoxide to the said compound in the presence of the aforementioned catalyst.
  • the present invention relates to specific catalyst compounds per se.
  • an epoxide preferably epichlorohydrin or an alkylene oxide having 2-4 carbon atoms
  • the present invention relates to a specific compound (I) per se having the formula
  • Suitable examples of compounds having formula (I) are AI 3+ (CF 3 S0 3 “ ) n (CH 3 S0 3 “ ) 3 - n (la) and AI 3+ (BF 4 " ) n (CH 3 S0 3 “ ) 3-n (lb), where n is an integer 1 or 2.
  • a compound having an active hydrogen is herein defined as a compound which reacts with methylmagnesium bromide to form metha ne, accord i ng to th e Zerewittenoff process.
  • examples of such compounds include alcohols, carboxylic acids, amines and thiols.
  • R is a hydrocarbyl group having 1 -24 carbon atoms
  • Y is independently H, CH 3 or CH 2 CH 3 , preferably H
  • p 0-10.
  • p is typically 1 -5.
  • Suitable examples of compounds of formula (II) are fatty alcohols that may be saturated or unsaturated, linear or branched, such as n-hexanol, n-octanol, 2-ethylhexanol, n-decanol, isodecanol, 2-propylheptanol, dodecanol, 2-butyloctanol, tetradecanol, hexadecanol, octadecanol, oleyl alcohol, eicosanol, docosanol, erucyl alcohol, tetracosanol, C 9 -Cn alcohol, Cn alcohol, tridecylalcohol, C10-C14 alcohol, C14-C15 alcohol, C12-C14 alcohol and Ci 6 -Ci 8 alcohol.
  • the alkylene oxide having 2-4 carbon atoms could be ethylene oxide, propylene oxide, butylene oxide or mixtures thereof. If more than one alkylene oxide is added, then the ethyleneoxy, propyleneoxy and/or butyleneoxy u n its may be add ed randomly or in blocks. The blocks may be added to the compound having at least one active hydrogen atom, preferably an alcohol, in any order.
  • the invention relates to a process for obtaining an addition product of an epoxide, preferably of epichlorohydrin or an alkylene oxide having 2-4 carbon atoms, to a compound having at least one active hydrogen atom, preferably a compound having formula (II) as described above, by the addition of the epoxide to the said compound having at least one active hydrogen atom in the presence of a compound having formula (I), preferably (la) or (lb), as described above.
  • an epoxide preferably of epichlorohydrin or an alkylene oxide having 2-4 carbon atoms
  • the reaction is carried out in a homogeneous liquid phase at a temperature from 20 to 150°C, preferably from 50 to 120°C and most preferably from 60-105°C, such as from 65 to 100°C.
  • epichlorohydrin is added to a compound having at least one active hydrogen atom, which preferably has the formula (II), in the presence of 0.1 - 2% by weight of a compound having the formula (I), preferably (la) or (lb), where the amount is counted on the compound having at least one active hydrogen atom.
  • the mole ratio between epichlorohydrin and the compound having at least one active hydrogen atom is between 0.9 and 10, preferably between 0.9 and 5, more preferably between 0.9 and 4, and most preferably between 0.9 and 1.2.
  • an alkylene oxide having 2-4 carbon atoms is added to the compound having at least one active hydrogen atom, preferably to a compound having the formula (II), in the presence 0.01 -5% by weight, counted on the compound having at least one active hydrogen atom, of a compound having the formula (I), preferably (la) or (lb).
  • the mole ratio between the alkylene oxide and the compound having at least one active hydrogen atom is between 1 and 10, preferably between 1 and 5.
  • the compound (I) is added to the compound having at least one active hydrogen atom, preferably compound (II), while stirring and heating to obtain the desired temperature. Then the epoxide is slowly added to the mixture of (I) and (II) with continued stirring and heating. When all epoxide has been added, the reaction mixture is further heated and stirred until analysis shows that there is no epoxide left.
  • Examples 1 and 2 could generally be followed for syntheses where other catalysts according to the invention are used , provided appropriate adjustments of reaction times and temperatures are made.
  • the synthesis products of a typical reaction essentially contain three components: unreacted alcohol 1_, chloroglyceryl ether 2 and and chloroglyceryl ether reacted with one more epichlorohydrin 3 (see scheme 1 in the technical background part).
  • the amounts of unreacted alcohol and of the different epoxide adducts were determined by GC analysis of the reaction mixtures.
  • the GC area percentages were approximated to be weight percentages.
  • the selectivity calculations that were performed used only the data for 1_, 2 and 3.
  • the other side-products were disregarded since they were present in amounts lower than 1 %.
  • Neodol 45 (40.0 g, 0.182 mol) was heated to 65°C and then 0.36 g (1 .76 mmol) aluminum triisopropoxide was added and slowly dissolved, after which triflic acid (0.265g, 1 .76 mmol) and methanesulfonic acid (0.335 g, 3.5 mmol) were added immediately).
  • Epichlorohydrin (17.4 g, 0.188 mol) was added dropwise over 30 minutes.
  • the reaction mixture was further heated at 65°C, and the progress of the reaction was followed by GC analysis. When the heating was stopped after a total reaction time of 4 hours the reaction mixture had the composition in table 2 below.
  • the product mixture was also analyzed after heating overnight.
  • Step 2 Ring closure of addition product obtained in step 1 to glycidyl ether
  • the above intermediate product was stirred at a speed of 960 rpm and heated to 80°C. 1 10.5 g of a 31 .2 wt% sodium hydroxide solution in water was added to the reactor over a two hours period of time. The stirring speed was then decreased to 250 rpm, 33 g de-ionized water was added, and the stirring was continued for about 5 min after the addition. The mixture was then transferred to a separating funnel, and after 15 minutes the bottom phase (water phase) was separated from the organic phase (glycidyl ether) and discarded. The amount of glycidyl ether in the organic phase was determined by epoxide titration to be 3.2 mmol/g, which means an active content of 88.2 wt%. The titration method used to determine the amount of epoxide present in the product is described in Analytical Chemistry 36 (1964) p 667.
  • reaction temperature was kept at 75°C, and samples were taken out for analysis at the times indicated in the Table 5 below.
  • the selectivity is about the same at 100 and 75°C, but the conversion is much higher at the higher temperature.
  • the reactor mixture was then heated to 80°C, and 0.7 mole ethylene oxide was added automatically at this temperature with a maximum pressure of 3 bar. The addition time was about one hour and the post reaction time 7 minutes. After evacuation of the autoclave 43.3 g of the product 1 -decanol + 1 EO was discharged from the autoclave for analysis.
  • the reactor mixture was then heated to 100°C, and 27.8 g (0.63 mole) ethylene oxide was added automatically during a 15 minutes period of time. After about 6 minutes a constant pressure of 0.16 bar had been obtained.
  • the temperature in the autoclave was decreased to 30°C and then evacuated. 15.2 g (0.075 mole) of 1 -Decanol+1 EO was discharged from the autoclave for analysis.
  • the above synthesis method was followed using 1 mol% aluminum triflate as catalyst, based on the 1 -decanol.
  • the temperature and the molar ratio of ethylene oxide to 1 -decanol was the same as above, and also the reaction time was about the same.
  • the above synthesis method was followed using 1 mol% boron trifluoride diethyl etherate as catalyst, based on the 1 -decanol.
  • the temperature and the molar ratio of ethylene oxide to 1 -decanol was the same as above, and also the reaction time was about the same. It was no problem adding another mol of EO per mol of 1 -decanol+1 EO using any of the catalysts in this example.
  • the autoclave was flushed with nitrogen gas up to about 4 bar pressure and evacuated by means of a water suction pump. This procedure was repeated three times.
  • the reactor mixture was then heated to 100°C, and 27.7 g ethylene oxide (0.63 mol) was added automatically at this temperature during a 38 minutes period of time. The reaction was allowed to continue until a constant pressure of 0.35 bar was reached. The total reaction time, including the addition time, was 5 hours.
  • the temperature was decreased to 30°C and the autoclave was evacuated. 28 g (0.138 mol) of the product 1 -decanol + 1 EO was discharged from the autoclave for analysis.
  • the autoclave was flushed with nitrogen gas up to about 4 bar pressure and evacuated by means of a water suction pump. This procedure was repeated three times.
  • the reactor mixture was then heated to 100°C, and 27.8 g (0.63 mol) ethylene oxide was added automatically at this temperature during a 10 minutes period of time.
  • the reaction was allowed to continue until a constant pressure of 0.31 bar was reached.
  • the total reaction time, including the addition time, was 5.5 hours.
  • the temperature was decreased to 30°C and the autoclave was evacuated. 12.3 g (0.06 mol) of the product 1 -decanol + 1 EO was discharged from the autoclave for analysis.
  • the reactor mixture was then heated to 100°C, and 27.8 g ethylene oxide (0.63 mol) was added automatically at this temperature during a 18 minutes period of time. The reaction was allowed to continue until a constant pressure of 0.31 bar was reached. The total reaction time, including the addition time, was 31 minutes. The temperature was decreased to 30°C and the autoclave was evacuated. 9.5 g (0.047 mol) of the product 1 -decanol + 1 EO was discharged from the autoclave for analysis.
  • the reactor mixture was then heated to 100°C, and 27.8 g ethylene oxide (0.63 mol) was added automatically at this temperature during a 15 minutes period of time. The reaction was allowed to continue for about 24 hours, after which the pressure was 0.96 bar and still not reaching a constant value. The temperature was then decreased to 30°C and the autoclave was evacuated. A sample of 1 -decanol + 1 EO was discharged from the autoclave for analysis.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
  • Epoxy Compounds (AREA)

Abstract

La présente invention porte sur l'utilisation d'un composé répondant à la formule : Al3+(A1)n(A2)3-n (I) dans laquelle n représente un nombre entier valant 1 ou 2, A1 représente un anion fluoré choisi dans le groupe constitué par les anions répondant aux formules CF3(CF2)ySO3 -, où y = 0 ou un nombre entier de 1 à 9, et BF4 -; et A2 répond à la formule CH3(CH2)zSO3 -, où z = 0 ou un nombre entier de 1 à 9; comme catalyseur pour la réaction d'addition d'un époxyde, de préférence d'épichlorhydrine ou d'un oxyde d'alkylène ayant 2-4 atomes de carbone, sur un composé ayant au moins un atome d'hydrogène actif.
PCT/EP2012/076107 2011-12-22 2012-12-19 Catalyseur utilisé pour la production de produits d'addition d'époxydes et de composés ayant des atomes d'hydrogène actifs WO2013092680A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201161578973P 2011-12-22 2011-12-22
EP11195336.0 2011-12-22
US61/578,973 2011-12-22
EP11195336 2011-12-22

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WO2013092680A1 true WO2013092680A1 (fr) 2013-06-27

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4543430A (en) 1982-11-17 1985-09-24 Bp Chimie Societe Anonyme Process for the preparation of addition products of epoxides and hydroxylated compounds
EP0545576A1 (fr) 1991-11-23 1993-06-09 Ciba-Geigy Ag Procédé pour la glycidylation d'alcools
WO1994009055A2 (fr) 1992-10-21 1994-04-28 E.I. Du Pont De Nemours And Company Polymerisation d'ethers cycliques et depolymerisation pour obtenir lesdits ethers cycliques, a l'aide de la catalyse par des composes metalliques choisis
EP0980869A1 (fr) * 1997-05-01 2000-02-23 Kao Corporation Composes d'aluminium et leur utilisation
US6093793A (en) 1997-01-27 2000-07-25 Bayer Aktiengesellschaft Process for the production of polyether polyols
US20030097026A1 (en) * 1998-10-07 2003-05-22 Uwe Denninger Process for the preparation of polyether polyols
US20050147778A1 (en) 2002-02-26 2005-07-07 Shinji Tai Resin composition and multi-layer structures

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4543430A (en) 1982-11-17 1985-09-24 Bp Chimie Societe Anonyme Process for the preparation of addition products of epoxides and hydroxylated compounds
EP0545576A1 (fr) 1991-11-23 1993-06-09 Ciba-Geigy Ag Procédé pour la glycidylation d'alcools
WO1994009055A2 (fr) 1992-10-21 1994-04-28 E.I. Du Pont De Nemours And Company Polymerisation d'ethers cycliques et depolymerisation pour obtenir lesdits ethers cycliques, a l'aide de la catalyse par des composes metalliques choisis
US6093793A (en) 1997-01-27 2000-07-25 Bayer Aktiengesellschaft Process for the production of polyether polyols
EP0980869A1 (fr) * 1997-05-01 2000-02-23 Kao Corporation Composes d'aluminium et leur utilisation
US20030097026A1 (en) * 1998-10-07 2003-05-22 Uwe Denninger Process for the preparation of polyether polyols
US20050147778A1 (en) 2002-02-26 2005-07-07 Shinji Tai Resin composition and multi-layer structures

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Surfactant Science Series", vol. 72, 1998, MARCEL DEKKER, INC., article "NONIONIC SURFACTANTS Organic Chemistry"
ANALYTICAL CHEMISTRY, vol. 36, 1964, pages 667
D. BRADLEY G. WILLIAMS ET AL: "Aluminium triflate: a remarkable Lewis acid catalyst for the ring opening of epoxides by alcohols", ORGANIC & BIOMOLECULAR CHEMISTRY, vol. 3, no. 18, 1 September 2005 (2005-09-01), pages 3269 - 3272, XP055027543, ISSN: 1477-0520, DOI: 10.1039/b508924g *

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