WO2003046048A1 - Process for alkylation of an alkoxylated mono di, tri or polyhydric compound - Google Patents

Process for alkylation of an alkoxylated mono di, tri or polyhydric compound Download PDF

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WO2003046048A1
WO2003046048A1 PCT/SE2002/002202 SE0202202W WO03046048A1 WO 2003046048 A1 WO2003046048 A1 WO 2003046048A1 SE 0202202 W SE0202202 W SE 0202202W WO 03046048 A1 WO03046048 A1 WO 03046048A1
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tri
propanediol
process according
alkyl
dioxane
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PCT/SE2002/002202
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French (fr)
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Keith Ogemark
Mircea Manea
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Perstorp Specialty Chemicals Ab
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Priority to AU2002353747A priority Critical patent/AU2002353747A1/en
Publication of WO2003046048A1 publication Critical patent/WO2003046048A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
    • 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
    • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal 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
    • 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
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/322—Polymers modified by chemical after-treatment with inorganic compounds containing hydrogen

Definitions

  • the present invention refers to a process for production of an alkyl ether of an alkoxylated mono, di, tri or polyhydric compound.
  • Alkyl ether is hereinafter to be understood as including alkenyl and alkynyl ethers and the process is accordingly hereinafter referred to as an alkylation.
  • Said alkylation comprises that at least one alkoxylated mono, di, tri or polyhydric compound, at least one reduction agent and at least one alkylation precursor are charged to a reaction vessel, mixed and heated to a suitable and effective reaction temperature.
  • the present invention refers to the use of an allyl or methallyl ether obtainable by the process of the present invention.
  • alkyl ethers such as methyl and allyl ethers, of hydroxyl functional compounds and processes for their preparation have been reported in the chemical literature.
  • the most versatile method of preparing such ethers is the Williamson ether synthesis, particularly in the preparation of unsymmetrical alkyl ethers.
  • the reaction of alcohols or alkali metal alcoholates with alkyl, including alkenyl or alkynyl, halides for instance yields the ethers RO m R' wherein R and R' each independently is linear or branched alkyl, alkenyl or alkynyl and wherein m is an integer and at least 1.
  • Alkyl sulfates can replace the halides, and this modification is especially useful for the preparation of phenolic ethers.
  • Alcohols can be dehydrated with strong acid catalysts and high reaction temperatures to produce ethers. This method is particularly useful for the preparation of symmetrical lower alkyl ethers, such as ethyl ether.
  • Alkyl tertiary alkyl ethers can be prepared by the addition of an alcohol or phenol to a tertiary olefin under acid catalysis (Reycler reaction).
  • Sulfuric acid, phosphoric acid, hydrochloric acid and boron trifluoride have all been used as catalysts.
  • sulfonic acid ion-exchange resins are used in fixed-bed reactors to make tertiary alkyl ethers.
  • Ether production from the reaction of monohydric alcohols with linear olefins has also been demonstrated under more severe conditions using a zeolite-type catalyst system.
  • Simple alkyl ethers of polyalcohols such as trimethylolpropane and pentaerythritol are produced on direct reaction of the polyol and the required alkyl halide in the presence of for instance an alkaline catalyst, such as sodium hydroxide or a quaternary alkylamine bromide.
  • Allyl halide produces for instance trimethylolpropane diallyl ether or pentaerythritol triallyl ether in high yield by this method.
  • AUylation reactions using an organometallic derivative of the compound being allylated, or a strongly electropositive metal in conjunction with the reactants, are known in the art.
  • Alkyl ethers are used for organic reactions and extractions, as plasticizers, as vehicles for other products, as anesthetics, and octane and oxygen enhancers in gasoline. Most ethers have very low solubility in water, but dissolve most organic compounds, and therefore have found wide application in paint and varnish removers as high boiling solvents for gums, resins, and waxes, in lubricating oils, as extraction solvents in the fragrance industry and as inert reaction media in the pharmaceutical industry. Much research has been directed toward the preparation of air-drying prepolymers or oligomers. Thus allyl groups have been introduced into low molecular weight polyesters, polyurethanes and formaldehyde condensates. Some examples include copolymers of for instance trimethylolpropane diallyl ether with unsaturated polyesters in UN curable coatings and the use of polyalcohol allyl ethers as curing agents in acrylic photolacquers.
  • Alkyl ethers of alkoxylated mono, di, tri and polyhydric compounds, such as alkoxylated mono, di, tri and polyalcohols, are rarely reported in the chemical literature. Exceptions include European Patent 158 053, European Patent Application 066 179 and German Patent 41 38 166. EP 158 053 discloses among sulphonated polyoxyalkylene ethers also allyl and methallyl ethers of ethoxylated and/or propoxylated polyalcohols, such as glycerol, trimethylolpropane and trimethylbutane and teaching a process for preparation thereof.
  • the process disclosed in EP 158 053 comprises reacting an acetal or ketal of said polyalcohol with ethylene and/or propylene oxide, reacting obtained polyether with an alkali metal or its alcoholate obtaining an alkali polyether, reacting said alkali polyether with an allyl or methallyl halide and finaly splitting the acetal or ketal by the action of an acid.
  • EP 066 179 teaches a process for preparation of polyoxyalkylene monoallyl or monomethallyl ethers in which polyoxyalkylene ethers are first prepared by stoichiometric polymerisation of alkylene oxides in the presence of alkali metal alkoxides and this intermediate is then reacted with an allyl or methallyl halide in a conventional manner.
  • DE 41 38 166 discloses a process for production of (meth)allyl polyalkoxyalkylene ethers comprising reating an alcohol of formula
  • CH 2 CRCH 2 (OCpenH2 radical) r ⁇ OH with excess ⁇ aOCH 3 or NaOH and simultaneously distilling off formed methanol or water. An excess of sodium chloride is then added to react with the sodium alcoholate produced.
  • Known and commonly used processes for alkylation of mono, di, tri and polyhydric compounds can typically be disclosed as follows.
  • the mono, di, tri or polyhydric compound is charged to a reaction vessel and heated to for instance 120°C followed by gradual and continuous charging of an alkylation precursor, such as an alkyl halide, together with a catalyst, such as an alkali metal hydroxide, to said mono, di, tri or polyhydric compound.
  • the alkylation precursor and the catalyst are normally charged simultaneously and at a rate maintaining the reaction temperature at for instance said 120°C.
  • Using such a process for production of alkyl ethers of alkoxylated mono, di, tri and polyhydric compounds frequently results in said heavy discolouration (see also Example 8 comparative).
  • Alkoxylated mono, di, tri and polyhydric compounds offer many advantages over corresponding non-alkoxylated species, why there is a demand for a simple and relayable process yielding alkyl ether, such as methyl and allyl ethers, not being heavely discoloured.
  • the present invention provides quite unexpectadly a novel process for alkylation of an alkoxylated mono, di, tri and polyhydric compound. Said process yields mono, di, tri or polyalkyl, alkenyl or alkynyl ethers having low colour values.
  • the process of the present invention comprises that a) at least one alkoxylated mono, di, tri or polyhydric compound, b) an effective amount of at least one reduction agent, c) at least one alkylation precursor in an amount corresponding to at least 0.1 mole on 1 mole of hydroxyl groups in said mono, di, tri or polyhydric compound, d) an effective amount, such as 1-3 moles on 1 mole of said alkoxylated mono, di, tri or polyhydric compound, of at least one alkaline catalyst, and optionally e) at least one solvent, are charged to a reaction vessel and mixed, that obtained mixture under stirring is heated, optionally in steps or gradually, to a temperature of 30-180°C, such as 40-150°C or 60-120°C, or reflux temperature until said alkylation is completed.
  • the process comprises in preferred embodiments that at least one alkoxylated mono, di, tri or polyhydric compound (a), an effective amount of at least one reduction agent (b), and optionally at least one solvent (e) are charged to a reaction vessel and under stirring heated to a temperature of 20-180°C, such as 30-120°C, that an effective amount, such as 1-3 moles on 1 mole of said alkoxylated mono, di, tri or polyhydric compound, of at least one alkaline catalyst (d) is added to and mixed into obtained mixture followed by addition of at least one alkylation precursor (c) in an amount corresponding to at least 0.1 mole on 1 mole of hydroxyl groups in said mono, di, tri or polyhydric compound, that obtained reaction mixture under stirring is heated, optionally i steps or gradually, to or kept at a temperature of 30-180°C, such as 40-150°C or 60-120°C, or reflux temperature until said alkylation is completed and that formed reaction water continuously is distilled off from said reaction mixture.
  • the molar ratio hydroxyl groups, in said alkoxylated mono, di, tri or polyhydric compound (a), to alkylation precursor (c) is most preferably between 1:0.8 and 1 :1.2, and said at least one reduction agent (b) is likewise most preferably present in an amount of 0.01-0.5%, such as 0.05-0.2%, by weight calculated on charged amount of said alkoxylated mono, di, tri or polyhydric compound.
  • Said at least one alkoxylated mono, di, tri or polyhydric compound is preferaby at least one hydroxyfunctional ether obtainable by reaction between at least one alkylene oxide, such as ethylene oxide, propylene oxide, 1,3-butylene oxide, 2,4-butylene oxide, cyclohexene oxide, butadiene monoxide and/or phenylethylene oxide, and at least one mono, di, tri och polyhydric compound at a molar ratio said alkylene oxide to said mono, di, tri or polyhydric compound of for instance between 0.1 to 1 and 20 to 1.
  • alkylene oxide such as ethylene oxide, propylene oxide, 1,3-butylene oxide, 2,4-butylene oxide, cyclohexene oxide, butadiene monoxide and/or phenylethylene oxide
  • mono, di, tri och polyhydric compound at least one mono, di, tri och polyhydric compound at a molar ratio said alkylene oxide to said mono, di, tri or
  • Said at least one alkoxylated mono, di, tri or polyhydric compound is in preferred embodiments of the process of the present invention an alkoxylated Cj-C 24 -alkanol, l, ⁇ -diol, 5-hydroxy-l,3-dioxane, 5-hydroxyalkyl-l,3-dioxane, 5-alkyl-5-hydroxyalkyl-l,3-dioxane,
  • Said at least one alkoxylated mono, di, tri or polyhydric compound is in further preferred embodiments of the present invention a dimer, trimer or polymer of an alkoxylated l, ⁇ -diol, 5-hydroxy-l,3-dioxane, 5-hydroxyalkyl-l,3-dioxane, 5-alkyl-5-hydroxyalkyl-l,3-dioxane, 5,5-di(hydroxyalkyl)-l,3-dioxane, 5-carboxy-l,3-dioxane, a 5-carboxyalkyl-l,3-dioxane, 5-alkyl-5-carboxy-l,3-dioxane, 5-alkyl-5-carboxyalkyl-l,3-dioxane, 2-alkyl-l,3-propanediol, 2,2-dialkyl-l,3-propanediol, 2-hydroxy-l
  • Said at least one alkoxylated mono, di, tri or polyhydric compound is in yet further preferred embodiments of the present invention an alkoxylated dimer, trimer or polymer of a
  • Said at least one alkoxylated mono, di, tri or polyhydric compound is most preferably alkoxylated, such as ethoxylated and/or propoxylated, ethanol, n-butanol, ⁇ o-butanol, 5ec-butanol, n-propanol, iso-propanol, octanol, tso-octanol, 2-ethyl-hexanol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 ,6-cyclohexanedimethanol, 5,5-dihydroxymethyl- 1,3-dioxane, 2-methyl- 1,3 -propanediol, 2-methyl-2-ethyl-l,3-propanediol, 2-ethyl-2-butyl- -1,3-propanediol, neopen
  • alkoxylated mono, di, tri and polyhydric compounds suitably alkylated, such as methylated or allylated, by the process of the present invention includes alkoxylate compounds, produced from for instance one or more of said alkylene oxides, such as di, tri or polyethylene glycols, di, tri or polypropylene glycols, hydroxylated di, tri or polybutadienes and epoxidised hydroxylated di, tri or polybutadienes.
  • Polyethylene, polypropylene and polybutadiene is preferably low molecular species.
  • Said at least one alkylation precursor is in especially preferred embodiments of the subject process at least one alkyl, alkenyl or alkynylhalide, such as a compound of formula R'X 2 wherein R 1 is C ⁇ -C 24 - lkyl, C 2 -C 24 -alkenyl or C 2 -C 24 -alkynyl and wherein X is Cl, Br or I.
  • Said halides can suitably be exemplified by compounds such as methylchloride, methyliodide, allylchloride, allylbromide, methallylcloride or methallylbromide.
  • Said at least one reduction agent is in various preferred embodiments at least one hydride and most preferably a hydride of formula BH 4 , R 1 BH 4 , R 1 BH 3 R 2 , R 1 BH 2 (R 2 ) 2 , R'BHCR 2 )-), A1H 4 ,
  • Li, K or Na and R 2 is CN or OC p H p+ i wherein/? is an integer and at least 1, such as an integer between 1 and 5 inclusive.
  • Further embodiments of the process of the present invention include alkali metal or alkaline earth metal hydrides, group 13 (IIIA) or transition metal borohydrides or borohydrides having a formula of (R 3 ) 4 NBH 4 , (R 3 ) 3 R 4 NBH 4 ,
  • At least one alkaline catalyst is in embodiments of the present process most preferably a hydroxide, carbonate or alkoholate, such as a methylate or ethylate, of at least one alkali or alkaline earth metal, such as lithium, potassium, sodium and/or calcium. Further suitable catalysts include lithium, potassium, sodium and/or calcium as elemental metals.
  • Said at least one optional solvent is a compound inert to alkylation and suitably selected from the group consisting of toluene, xylene, methyl isobutyl ketone and/or methyl ethyl ketone.
  • the alkylation of the subject process is in especially preferred embodiments an allylation of at least one alkoxylated di, tri or polyhydric compound, such ethoxylated and/or propoxylated 5,5-dihydroxymethyl-l,3-dioxane, 2-methyl-l,3-propanediol, 2-methyl-2-ethyl-l,3-
  • -propanediol 2-ethyl-2-butyl-l,3-propanediol, neopentyl glycol, dimethylolpropane, 1,1-dimethylolcyclohexane, glycerol, trimethylolethane, trimethylolpropane, diglycerol, di(trimethylolethane), di(trirnethylolpropane), pentaerythritol, di(pentaerythritol), hydroxypivalic acid, dimethylolpropionic acid, 3-methyl-3-(hydroxymethyl)oxetane, 3-ethyl-3-(hydroxymethyl)oxetane and/or 3,3-di(hydroxymethyl)oxetane.
  • alkoxylated mono, di, tri and polyhydric compounds suitably allylated, by the process of the present invention includes alkoxylate compounds, such as di, tri or polyethylene glycols, di, tri or polypropylene glycols, hydroxylated di, tri or polybutadienes and epoxidised hydroxylated di, tri or polybutadienes.
  • alkoxylate compounds such as di, tri or polyethylene glycols, di, tri or polypropylene glycols, hydroxylated di, tri or polybutadienes and epoxidised hydroxylated di, tri or polybutadienes.
  • the alkylation precursor used in said especially preferred embodimets is allylchloride, methallylchloride, allylbromide and/or methallylbromide and the reduction agent is a compound of formula BH 4 , R ⁇ H ⁇ R'BH 3 R 2 , R 1 BH 2 (R 2 ) 2 , R ] BH(R 2 ) 3 A1H 4 , R ⁇ IH 4 ,
  • Na and R 2 is CN or OC p ⁇ . p+ ⁇ wherein ? is an integer and at least 1, such as an integer between 1 and 5 inclusive.
  • ? is an integer and at least 1, such as an integer between 1 and 5 inclusive.
  • the preferred alkali catalyst and the preferred optional solvent are as previously disclosed.
  • the product yielded, in the process of the present invention, is in said especially preferred embodimets a mono, di, tri or poly(allyl) ether or a mono, di, tri or poly(methallyl) ether of alkoxylated 5,5-dihydroxy-methyl-l,3-dioxane, 2-methyl-l,3-propanediol, 2-methyl-2-ethyl- -1,3-propanediol, 2-ethyl-2-buty 1-1, 3 -propanediol, neopentyl glycol, dimethylolpropane, 1,1-dimethylolcyclohexane, glycerol, trimethylolethane, trimethylolpropane, diglycerol, di(trimethylolethane), di(trimethylolpropane), pentaerythritol, di(pentaerythritol), hydroxypivalic acid, dimethylolprop
  • the present invention refers a the use of an allyl or methallyl ether of an alkoxylated mono, di, tri or polyhydric compound, whereby said allyl or methallyl ether is obtainable by and yielded in the process as disclosed above.
  • Preferred embodiments of said use includes the use of said allyl or methallyl ether as peroxide carrier in two component radical curing of unsaturated polyester systems, as crosslinker for acrylic polymers in super absorbants, as wetting additive, optionally copolymerised with acrylic monomers, for concrete, inorganic pigments and inorganic fillers and as oxygen scanvenger in radiation curing systems or in production of unsaturated esters and polyesters, in production of silanes by siloxane addition to double bonds, in production of mono, di, tri and polyepoxides by oxidation of at least one double bond to corresponding oxirane group and in production of thickerners by copolymisation with at least one alkali metal allyl or methallyl sulphonate.
  • Polyol PP 50TM ethoxylated pentaerythritol having a nominal ethoxylation degree of 5 moles of ethylene oxide on 1 mole of pentaerythritol, Perstorp Specialty Chemicals AB,
  • Polyol NS 20TM propoxylated neopentyl glycol having a nominal propoxylation degree of 2 moles of propylene oxide on 1 mole of neopentyl glycol, Perstorp Specialty
  • Polyol PP 50TM ethoxylated pentaerythritol having a nominal ethoxylation degree of 5 moles of ethylene oxide on 1 mole of pentaerythritol, Perstorp Specialty Chemicals AB,

Abstract

A process for alkylation yielding a mono, di, tri or polyalkyl, alkenyl or alkynyl ether of an alkoxylated mono, di, tri or polyhydric compound. The process comprises that at least one alkoxylated mono, di, tri or polyhydric compound, at least one reduction agent, at least one alkylation precursor, at least one alkaline catalyst and optionally at least one solvent are charged to a reaction vessel and mixed and that obtained reaction mixture under stirring is heated, optionally in steps or gradually, to a temperature of 30-180°C or to reflux temperature and maintained until said alkylation is completed. In a further aspect the present invention refers to the use of a mono, di, tri or polyallyl or methallyl ether yielded in said process.

Description

PROCESS FOR ALKYLATION OF AN ALKOXYLATED MONO DI, TRI OR POLYHYDRIC COMPOUND
The present invention refers to a process for production of an alkyl ether of an alkoxylated mono, di, tri or polyhydric compound. Alkyl ether is hereinafter to be understood as including alkenyl and alkynyl ethers and the process is accordingly hereinafter referred to as an alkylation. Said alkylation comprises that at least one alkoxylated mono, di, tri or polyhydric compound, at least one reduction agent and at least one alkylation precursor are charged to a reaction vessel, mixed and heated to a suitable and effective reaction temperature. In a further aspect the present invention refers to the use of an allyl or methallyl ether obtainable by the process of the present invention.
Various alkyl ethers, such as methyl and allyl ethers, of hydroxyl functional compounds and processes for their preparation have been reported in the chemical literature. The most versatile method of preparing such ethers is the Williamson ether synthesis, particularly in the preparation of unsymmetrical alkyl ethers. The reaction of alcohols or alkali metal alcoholates with alkyl, including alkenyl or alkynyl, halides for instance yields the ethers ROmR' wherein R and R' each independently is linear or branched alkyl, alkenyl or alkynyl and wherein m is an integer and at least 1. Alkyl sulfates can replace the halides, and this modification is especially useful for the preparation of phenolic ethers. Alcohols can be dehydrated with strong acid catalysts and high reaction temperatures to produce ethers. This method is particularly useful for the preparation of symmetrical lower alkyl ethers, such as ethyl ether.
The reaction gives poor yields of ethers with secondary and tertiary alcohols. Dehydration to form the corresponding olefin is a more favorable reaction. The reaction fails for the production of diaryl ethers from phenols. Alkyl tertiary alkyl ethers can be prepared by the addition of an alcohol or phenol to a tertiary olefin under acid catalysis (Reycler reaction).
Sulfuric acid, phosphoric acid, hydrochloric acid and boron trifluoride have all been used as catalysts. Commercially, sulfonic acid ion-exchange resins are used in fixed-bed reactors to make tertiary alkyl ethers. Ether production from the reaction of monohydric alcohols with linear olefins has also been demonstrated under more severe conditions using a zeolite-type catalyst system.
Simple alkyl ethers of polyalcohols such as trimethylolpropane and pentaerythritol are produced on direct reaction of the polyol and the required alkyl halide in the presence of for instance an alkaline catalyst, such as sodium hydroxide or a quaternary alkylamine bromide. Allyl halide produces for instance trimethylolpropane diallyl ether or pentaerythritol triallyl ether in high yield by this method. AUylation reactions, using an organometallic derivative of the compound being allylated, or a strongly electropositive metal in conjunction with the reactants, are known in the art. Alkyl ethers are used for organic reactions and extractions, as plasticizers, as vehicles for other products, as anesthetics, and octane and oxygen enhancers in gasoline. Most ethers have very low solubility in water, but dissolve most organic compounds, and therefore have found wide application in paint and varnish removers as high boiling solvents for gums, resins, and waxes, in lubricating oils, as extraction solvents in the fragrance industry and as inert reaction media in the pharmaceutical industry. Much research has been directed toward the preparation of air-drying prepolymers or oligomers. Thus allyl groups have been introduced into low molecular weight polyesters, polyurethanes and formaldehyde condensates. Some examples include copolymers of for instance trimethylolpropane diallyl ether with unsaturated polyesters in UN curable coatings and the use of polyalcohol allyl ethers as curing agents in acrylic photolacquers.
Alkyl ethers of alkoxylated mono, di, tri and polyhydric compounds, such as alkoxylated mono, di, tri and polyalcohols, are rarely reported in the chemical literature. Exceptions include European Patent 158 053, European Patent Application 066 179 and German Patent 41 38 166. EP 158 053 discloses among sulphonated polyoxyalkylene ethers also allyl and methallyl ethers of ethoxylated and/or propoxylated polyalcohols, such as glycerol, trimethylolpropane and trimethylbutane and teaching a process for preparation thereof. The process disclosed in EP 158 053 comprises reacting an acetal or ketal of said polyalcohol with ethylene and/or propylene oxide, reacting obtained polyether with an alkali metal or its alcoholate obtaining an alkali polyether, reacting said alkali polyether with an allyl or methallyl halide and finaly splitting the acetal or ketal by the action of an acid. EP 066 179 teaches a process for preparation of polyoxyalkylene monoallyl or monomethallyl ethers in which polyoxyalkylene ethers are first prepared by stoichiometric polymerisation of alkylene oxides in the presence of alkali metal alkoxides and this intermediate is then reacted with an allyl or methallyl halide in a conventional manner. DE 41 38 166 discloses a process for production of (meth)allyl polyalkoxyalkylene ethers comprising reating an alcohol of formula
CH2=CRCH2(OC„H2„)røOH with excess ΝaOCH3 or NaOH and simultaneously distilling off formed methanol or water. An excess of sodium chloride is then added to react with the sodium alcoholate produced.
Known and commonly used processes for alkylation of mono, di, tri and polyhydric compounds can typically be disclosed as follows. The mono, di, tri or polyhydric compound is charged to a reaction vessel and heated to for instance 120°C followed by gradual and continuous charging of an alkylation precursor, such as an alkyl halide, together with a catalyst, such as an alkali metal hydroxide, to said mono, di, tri or polyhydric compound. The alkylation precursor and the catalyst are normally charged simultaneously and at a rate maintaining the reaction temperature at for instance said 120°C. Using such a process for production of alkyl ethers of alkoxylated mono, di, tri and polyhydric compounds frequently results in said heavy discolouration (see also Example 8 comparative).
Alkoxylated mono, di, tri and polyhydric compounds offer many advantages over corresponding non-alkoxylated species, why there is a demand for a simple and relayable process yielding alkyl ether, such as methyl and allyl ethers, not being heavely discoloured. The present invention provides quite unexpectadly a novel process for alkylation of an alkoxylated mono, di, tri and polyhydric compound. Said process yields mono, di, tri or polyalkyl, alkenyl or alkynyl ethers having low colour values.
The process of the present invention comprises that a) at least one alkoxylated mono, di, tri or polyhydric compound, b) an effective amount of at least one reduction agent, c) at least one alkylation precursor in an amount corresponding to at least 0.1 mole on 1 mole of hydroxyl groups in said mono, di, tri or polyhydric compound, d) an effective amount, such as 1-3 moles on 1 mole of said alkoxylated mono, di, tri or polyhydric compound, of at least one alkaline catalyst, and optionally e) at least one solvent, are charged to a reaction vessel and mixed, that obtained mixture under stirring is heated, optionally in steps or gradually, to a temperature of 30-180°C, such as 40-150°C or 60-120°C, or reflux temperature until said alkylation is completed.
The process comprises in preferred embodiments that at least one alkoxylated mono, di, tri or polyhydric compound (a), an effective amount of at least one reduction agent (b), and optionally at least one solvent (e) are charged to a reaction vessel and under stirring heated to a temperature of 20-180°C, such as 30-120°C, that an effective amount, such as 1-3 moles on 1 mole of said alkoxylated mono, di, tri or polyhydric compound, of at least one alkaline catalyst (d) is added to and mixed into obtained mixture followed by addition of at least one alkylation precursor (c) in an amount corresponding to at least 0.1 mole on 1 mole of hydroxyl groups in said mono, di, tri or polyhydric compound, that obtained reaction mixture under stirring is heated, optionally i steps or gradually, to or kept at a temperature of 30-180°C, such as 40-150°C or 60-120°C, or reflux temperature until said alkylation is completed and that formed reaction water continuously is distilled off from said reaction mixture.
The molar ratio hydroxyl groups, in said alkoxylated mono, di, tri or polyhydric compound (a), to alkylation precursor (c) is most preferably between 1:0.8 and 1 :1.2, and said at least one reduction agent (b) is likewise most preferably present in an amount of 0.01-0.5%, such as 0.05-0.2%, by weight calculated on charged amount of said alkoxylated mono, di, tri or polyhydric compound.
By charging the full amount of all raw materials before commencing the alkylation, instead of, as in prior art, gradually charging alkylation precursor and catalyst to the mono, di, tri or polyhydric compound during the alkylation, and by using a reduction agent, above disclosed problem with heavely discoloured products is eliminated or substantially reduced.
Said at least one alkoxylated mono, di, tri or polyhydric compound is preferaby at least one hydroxyfunctional ether obtainable by reaction between at least one alkylene oxide, such as ethylene oxide, propylene oxide, 1,3-butylene oxide, 2,4-butylene oxide, cyclohexene oxide, butadiene monoxide and/or phenylethylene oxide, and at least one mono, di, tri och polyhydric compound at a molar ratio said alkylene oxide to said mono, di, tri or polyhydric compound of for instance between 0.1 to 1 and 20 to 1.
Said at least one alkoxylated mono, di, tri or polyhydric compound is in preferred embodiments of the process of the present invention an alkoxylated Cj-C24-alkanol, l,ω-diol, 5-hydroxy-l,3-dioxane, 5-hydroxyalkyl-l,3-dioxane, 5-alkyl-5-hydroxyalkyl-l,3-dioxane,
5,5-di(hydroxyalkyl)-l,3-dioxane, 5-carboxy-l,3-dioxane, 5-carboxyalkyl-l,3-dioxane,
5-alkyl-5-carboxy-l,3-dioxane, 5-alkyl-5-carboxyalkyl-l,3-dioxane, 2-alkyl-l,3-propanediol,
2,2-dialkyl-l,3-propanediol, 2-hydroxy-l,3-propanediol, 2-hydroxy-2-alkyl-l,3-propanediol,
2-hydroxyalkyl-2-alkyl-l,3-propanediol, 2,2-di(hydroxyalkyl)-l,3-propanediol, 2-carboxy-l ,3- propanediol, 2-carboxyalkyl-l,3-propanediol, 3-alkyl-3-(hydroxyalkyl)oxetane and/or
3,3-di(hydroxyalkyl)oxetane.
Said at least one alkoxylated mono, di, tri or polyhydric compound is in further preferred embodiments of the present invention a dimer, trimer or polymer of an alkoxylated l,ω-diol, 5-hydroxy-l,3-dioxane, 5-hydroxyalkyl-l,3-dioxane, 5-alkyl-5-hydroxyalkyl-l,3-dioxane, 5,5-di(hydroxyalkyl)-l,3-dioxane, 5-carboxy-l,3-dioxane, a 5-carboxyalkyl-l,3-dioxane, 5-alkyl-5-carboxy-l,3-dioxane, 5-alkyl-5-carboxyalkyl-l,3-dioxane, 2-alkyl-l,3-propanediol, 2,2-dialkyl-l,3-propanediol, 2-hydroxy-l,3-propanediol, 2-hydroxy-2-alkyl-l,3-propanediol, 2-hydroxyalkyl-2-alkyl-l,3-propanediol, 2,2-di(hydroxyalkyl)-l,3-propanediol, 2-carboxy-l, 3- propanediol, 2-carboxyalkyl-l,3-propanediol, 3-alkyl-3-(hydroxyalkyl)oxetane and/or 3,3-di(hydroxyalkyl)oxetane.
Said at least one alkoxylated mono, di, tri or polyhydric compound is in yet further preferred embodiments of the present invention an alkoxylated dimer, trimer or polymer of a
Cι-C24-alkanol, l,ω-diol, 5-hydroxy-l,3-dioxane, 5-hydroxyalkyl-l,3-dioxane, 5-alkyl- -5-hydroxyalkyl-l,3-dioxane, 5,5-di(hydroxyalkyl)-l,3-dioxane, 5-carboxy-l,3dioxane, 5-carboxyalkyl-l,3-dioxane, 5-alkyl-5-carboxy-l,3-dioxane, 5-alkyl-5-carboxyalkyl-
-1,3-dioxane, 2-alkyl-l,3-propanediol, 2,2-dialkyl- 1,3 -propanediol, 2-hydroxy-l,3- propanediol, 2-hydroxy-2-alkyl- 1 ,3 -propanediol, 2-hydroxyalkyl-2-alkyl- 1 ,3-propanediol, 2,2-di(hydroxyalkyl)-l,3-propanediol, 2-carboxy-l ,3-propanediol, 2-carboxyalkyl- 1 ,3- propanediol, 3-alkyl-3-(hydroxyalkyl)oxetane and/or 3,3-di(hydroxyalkyl)oxetane.
Said at least one alkoxylated mono, di, tri or polyhydric compound is most preferably alkoxylated, such as ethoxylated and/or propoxylated, ethanol, n-butanol, ώo-butanol, 5ec-butanol, n-propanol, iso-propanol, octanol, tso-octanol, 2-ethyl-hexanol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 ,6-cyclohexanedimethanol, 5,5-dihydroxymethyl- 1,3-dioxane, 2-methyl- 1,3 -propanediol, 2-methyl-2-ethyl-l,3-propanediol, 2-ethyl-2-butyl- -1,3-propanediol, neopentyl glycol, dimethylolpropane, 1,1-dimethylolcyclohexane, glycerol, trimethylolethane, trimethylolpropane, diglycerol, di(trimethylolethane), di(trimethylolpropane), pentaerythritol, di(pentaerythritol), anhydroenneaheptitol, sorbitol, mannitol, hydroxypivalic acid, dimethylolpropionic acid, 3-methyl-3-(hydroxymethyl)oxetane, 3 -ethyl-3 -(hydroxymethyl)oxetane and/or 3 ,3 -di(hydroxymethyl)oxetane.
Further alkoxylated mono, di, tri and polyhydric compounds suitably alkylated, such as methylated or allylated, by the process of the present invention includes alkoxylate compounds, produced from for instance one or more of said alkylene oxides, such as di, tri or polyethylene glycols, di, tri or polypropylene glycols, hydroxylated di, tri or polybutadienes and epoxidised hydroxylated di, tri or polybutadienes. Polyethylene, polypropylene and polybutadiene is preferably low molecular species.
Said at least one alkylation precursor is in especially preferred embodiments of the subject process at least one alkyl, alkenyl or alkynylhalide, such as a compound of formula R'X2 wherein R1 is Cι-C24- lkyl, C2-C24-alkenyl or C2-C24-alkynyl and wherein X is Cl, Br or I. Said halides can suitably be exemplified by compounds such as methylchloride, methyliodide, allylchloride, allylbromide, methallylcloride or methallylbromide.
Said at least one reduction agent is in various preferred embodiments at least one hydride and most preferably a hydride of formula BH4, R1BH4, R1BH3R2, R1BH2(R2)2, R'BHCR2)-), A1H4,
R1A1H4, R1A1H3R2, R1A1H2(R2)2 or RΑlH(R2)3 wherein R1 is an alkali metal ion, such as
Li, K or Na and R2 is CN or OCpHp+i wherein/? is an integer and at least 1, such as an integer between 1 and 5 inclusive. Further embodiments of the process of the present invention include alkali metal or alkaline earth metal hydrides, group 13 (IIIA) or transition metal borohydrides or borohydrides having a formula of (R3)4NBH4, (R3)3R4NBH4,
(R3)2(R4)2NBH4 or R3(R4)3NBH4, wherein R3 and R4 is linear or branched alkyl individually having 1 to 24 carbon atoms. Said at least one alkaline catalyst is in embodiments of the present process most preferably a hydroxide, carbonate or alkoholate, such as a methylate or ethylate, of at least one alkali or alkaline earth metal, such as lithium, potassium, sodium and/or calcium. Further suitable catalysts include lithium, potassium, sodium and/or calcium as elemental metals.
Said at least one optional solvent is a compound inert to alkylation and suitably selected from the group consisting of toluene, xylene, methyl isobutyl ketone and/or methyl ethyl ketone.
The alkylation of the subject process is in especially preferred embodiments an allylation of at least one alkoxylated di, tri or polyhydric compound, such ethoxylated and/or propoxylated 5,5-dihydroxymethyl-l,3-dioxane, 2-methyl-l,3-propanediol, 2-methyl-2-ethyl-l,3-
-propanediol, 2-ethyl-2-butyl-l,3-propanediol, neopentyl glycol, dimethylolpropane, 1,1-dimethylolcyclohexane, glycerol, trimethylolethane, trimethylolpropane, diglycerol, di(trimethylolethane), di(trirnethylolpropane), pentaerythritol, di(pentaerythritol), hydroxypivalic acid, dimethylolpropionic acid, 3-methyl-3-(hydroxymethyl)oxetane, 3-ethyl-3-(hydroxymethyl)oxetane and/or 3,3-di(hydroxymethyl)oxetane. Further alkoxylated mono, di, tri and polyhydric compounds suitably allylated, by the process of the present invention includes alkoxylate compounds, such as di, tri or polyethylene glycols, di, tri or polypropylene glycols, hydroxylated di, tri or polybutadienes and epoxidised hydroxylated di, tri or polybutadienes.
The alkylation precursor used in said especially preferred embodimets is allylchloride, methallylchloride, allylbromide and/or methallylbromide and the reduction agent is a compound of formula BH4, R^H^ R'BH3R2, R1BH2(R2)2, R]BH(R2)3 A1H4, RΑIH4,
R'A1H3R2, R1A1H2(R2)2 or R1A1H(R2)3, wherein R1 is an alkali metal ion, such as Li, K or
Na and R2 is CN or OCpΗ.p+\ wherein ? is an integer and at least 1, such as an integer between 1 and 5 inclusive. The preferred alkali catalyst and the preferred optional solvent are as previously disclosed.
The product yielded, in the process of the present invention, is in said especially preferred embodimets a mono, di, tri or poly(allyl) ether or a mono, di, tri or poly(methallyl) ether of alkoxylated 5,5-dihydroxy-methyl-l,3-dioxane, 2-methyl-l,3-propanediol, 2-methyl-2-ethyl- -1,3-propanediol, 2-ethyl-2-buty 1-1, 3 -propanediol, neopentyl glycol, dimethylolpropane, 1,1-dimethylolcyclohexane, glycerol, trimethylolethane, trimethylolpropane, diglycerol, di(trimethylolethane), di(trimethylolpropane), pentaerythritol, di(pentaerythritol), hydroxypivalic acid, dimethylolpropionic acid, 3-methyl-3-(hydroxymethyl)oxetane, 3 -ethyl-3 -(hydroxymethyl)oxetane and/or 3 ,3 -di(hydroxymethyl)oxetane. In a further aspect the present invention refers a the use of an allyl or methallyl ether of an alkoxylated mono, di, tri or polyhydric compound, whereby said allyl or methallyl ether is obtainable by and yielded in the process as disclosed above. Preferred embodiments of said use includes the use of said allyl or methallyl ether as peroxide carrier in two component radical curing of unsaturated polyester systems, as crosslinker for acrylic polymers in super absorbants, as wetting additive, optionally copolymerised with acrylic monomers, for concrete, inorganic pigments and inorganic fillers and as oxygen scanvenger in radiation curing systems or in production of unsaturated esters and polyesters, in production of silanes by siloxane addition to double bonds, in production of mono, di, tri and polyepoxides by oxidation of at least one double bond to corresponding oxirane group and in production of thickerners by copolymisation with at least one alkali metal allyl or methallyl sulphonate.
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilise the present invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative and not limitative of the remainder of the disclosure in any way whatsoever. In the following, Examples 1-6 illustrate embodiments of the subject process and Example 7 is a comparative prior art example. Properties of products obtained in Examples 1-6 are given in Table 1.
Example 1
255.7 g of Polyol TP 70™ (ethoxylated trimethylolpropane having a nominal ethoxylation degree of 7 moles of ethylene oxide on 1 mole of trimethylolpropane, Perstorp Specialty
Chemicals AB, Sweden), 255.7 g of xylene and 0.26 g of NaBH4 were charged to a 1-litre reaction flask, provided with an agitator, a cooler, a Dean-Stark separator and a heating device, and heated under stirring to 30°C and kept at said temperature for 30 minutes. 173.1 g of
NaOH (49.9% aq) was now added and 20 minutes later 151.5 g of allylchloride. Obtained mixture was heated to 40°C (weak exotherm) and after 1 hour at said temperature to 60°C. The reaction mixture was kept at 60°C for 2 hours and then further heated to reflux and water separation. Reflux was maintained under gradual temperature increase until water evaporation ceased. The final temperature was 110°C and the total reaction time, from initial charging, was
16 hours. Obtained reaction mixture was finaly cooled to room temperature.
400 ml of water was, in order to dissolve formed NaCl, added to obtained reaction product and excess NaOH was neutralised using HCl (10% aq). The product phase was collected and washed with 3 x 200 ml of water. Yield: 304.1 g of Polyol TP 70™ allyl ether was after evaporation at 60°C and 10 mm Hg recovered.
Product properties are given in Table 1.
Example 2
The procedure of Example 1 was repeated with the following charging:
206.5 g of Polyol PP 50™ (ethoxylated pentaerythritol having a nominal ethoxylation degree of 5 moles of ethylene oxide on 1 mole of pentaerythritol, Perstorp Specialty Chemicals AB,
Sweden), 206.5 g of xylene, 0.21 g of NaBH4, 230.9 g of NaOH (49.9% aq) and 202.0 g of allylchloride.
Yield: 273.1 g of Polyol PP 50™ allyl ether was after removal of formed NaCl, neutralisation and evaporation as in Example 1 recovered.
Product properties are given in Table 1.
Example 3
The procedure of Example 1 was repeated with the following charging:
225.6 g of Polyol TP 30™ (ethoxylated trimethylolpropane having a nominal ethoxylation degree of 3 moles of ethylene oxide on 1 mole of trimethylolpropane, Perstorp Specialty
Chemicals AB, Sweden), 225.6 g of xylene, 0.23 g of NaBH4, 230.9 g of NaOH (49.9% aq) and 202.0 g of allylchloride.
Yield: 286.6 g of Polyol TP 30™ allyl ether was after removal of formed NaCl, neutralisation and evaporation as in Example 1 recovered.
Product properties are given in Table 1.
Example 4
The procedure of Example 1 was repeated with the following charging:
267.5 g of Polyol PP 150™ (ethoxylated pentaerythritol having a nominal ethoxylation degree of 15 moles of ethylene oxide on 1 mole of pentaerythritol, Perstorp Specialty Chemicals AB, Sweden), 267.5 g of xylene, 0.27 g of NaBH4, 138.5 g of NaOH (49.9% aq) and 121.2 g of allylchloride.
Yield: 240.5 g of Polyol PP 150™ allyl ether was after removal of formed NaCl, neutralisation and evaporation as in Example 1 recovered.
Product properties are given in Table 1.
Example 5
The procedure of Example 1 was repeated with the following charging:
216.2 g of Polyol NS 20™ (propoxylated neopentyl glycol having a nominal propoxylation degree of 2 moles of propylene oxide on 1 mole of neopentyl glycol, Perstorp Specialty
Chemicals AB, Sweden), 216.2 g of xylene, 0.22 g of NaBH4, 192.4 g of NaOH (49.9% aq) and 168.3 g of allylchloride.
Yield: 262.3 g of Polyol NS 20™ allyl ether was after removal of formed NaCl, neutralisation and evaporation as in Example 1 recovered.
Product properties are given in Table 1.
Example 6
The procedure of Example 1 was repeated with the following charging:
154.9 g of Polyol PP 50™ (ethoxylated pentaerythritol having a nominal ethoxylation degree of 5 moles of ethylene oxide on 1 mole of pentaerythritol, Perstorp Specialty Chemicals AB,
Sweden), 154.9 g of xylene, 0.15 g of NaBH4, 173.1 g of NaOH (49.9% aq) and 274.0 g of 1-butylbromide.
Yield: 222.0 g of Polyol TP 30™ butyl ether was after removal of formed NaBr, neutralisation and evaporation as in Example 1 recovered.
Product properties are given in Table 1. Example 7 - Comparative
900.0 g of Polyol TP 70™ (ethoxylated trimethylolpropane having a nominal ethoxylation degree of 7 moles of ethylene oxide on 1 mole of trimethylolpropane, Perstorp Specialty Chemicals AB, Sweden) was charged to a reaction flask, provided with an agitator, a cooler, a Dean-Stark separator, inlets for charging of alkylation precursor and catalyst, and a heating device, and heated under stirring to 120°C. Allylchloride and NaOH were now simultaneously and gradually pumped into the reaction vessel at a rate maintaining a temperature of 115-125°C. The cooler was kept at a temperature of -5°C. The synthesis was finalised when all allylchloride and NaOH were charged. A total amount of 644.6 g of allylchloride and 1051.2 g of NaOH (28.9%) aq) were charged.
Low boiling by-products was after the synthesis evaporated at atmospheric pressure and the remain was at room temperature filtered to reduce the NaCl content.
Yielded reaction product, Polyol TP 70™ allyl ether, was heavily discoloured (coffee coloured) having Gardner colour value of > 12.
The same discolouration was the result when the alkaline catalysts KOH and Ca(OH)2 was used instead of NaOH.
Table 1
Figure imgf000011_0001
n.a. = Not applicable
* Calculated on hydroxyl groups available for alkylation.

Claims

1. A process for alkylation yielding a mono, di, tri or polyalkyl, alkenyl or alkynyl ether of an alkoxylated mono, di, tri or polyhydric compound characterised in, that at least one alkoxylated mono, di, tri or polyhydric compound, an effective amount of at least one reduction agent, at least one alkylation precursor in an amount coπesponding to at least 0.1 mole on 1 mole of hydroxyl groups in said mono, di, tri or polyhydric compound, an effective amount of at least one alkaline catalyst and optionally at least one solvent are charged to a reaction vessel and mixed, that obtained mixture under stirring is heated, optionally in steps or gradually, to a temperature of 30-180°C, such as 40-150°C or 60-120°C, or reflux temperature until said alkylation is completed.
2. A process according to Claim 1 characterised in, that at least one alkoxylated mono, di, tri or polyhydric compound, an effective amount of at least one reduction agent and optionally at least one solvent are charged to a reaction vessel and under stirring heated to a temperature of 20-180°C, such as 30-120°C, that an effective amount of at least one alkaline catalyst is added to and mixed into obtained mixture followed by addition of at least one alkylation precursor in an amount corresponding to at least 0.1 mole on 1 mole of hydroxyl groups in said mono, di, tri or polyhydric compound, that obtained reaction mixture under stirring is heated, optionally in steps or gradually, to or kept at a temperature of 30-180°C, such as 40-150°C or 60-120°C, or reflux temperature until said alkylation is completed and that formed reaction water is distilled off from said reaction mixture.
3. A process according to Claim 1 or 2 characterised in, a molar ratio hydroxyl groups in said alkoxylated mono, di, tri or polyhydric compound to alkylation precursor of between 1:0.8 and 1:1.2.
4. A process according to any of the Claims 1-3 characterised in, that said at least one reduction agent is present in an amount of 0.01-0.5%, such as 0.05-0.2%, by weight, calculated on charged amount of said alkoxylated mono, di, tri or polyhydric compound.
5. A process according to any of the Claims 1-4 characterised in, that said at least one alkaline catalyst is present in an amount coπesponding to 1-3 moles on 1 mole of said alkoxylated mono, di, tri or polyhydric compound.
6. A process according to any of the Claims 1-5 characterised in, that said at least one alkoxylated mono, di, tri or polyhydric compound is at least one hydroxyfunctional ether obtainable by reaction between at least one alkylene oxide and at least one mono, di, tri och polyhydric compound.
7. A process according to Claim 6 ch aracterised in, that said at least one alkoxylated mono, di, tri or polyhydric compound is obtainable at a molar ratio said alkylene oxide to said mono, di, tri or polyhydric compound of between 0.1 to 1 and 20 tol.
8. A process according to Claim 6 or 7 characterised in, that said at least one alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, 1,3-butylene oxide, 2,4-butylene oxide, cyclohexene oxide, butadiene monoxide and/or phenylethylene oxide.
9. A process according to any of the Claims 1-8 characterised in, that said at least one alkoxylated mono, di, tri or polyhydric compound is an alkoxylated
Cι-C24-alkanol, l,ω-diol, 5-hydroxy-l,3-dioxane, 5-hydroxyalkyl-l,3-dioxane, 5-alkyl-5-hydroxyalkyl-l,3-dioxane, 5,5-di(hydroxyalkyl)-l,3-dioxane, 5-carboxy-l,3-
-dioxane, 5-carboxyalkyl-l,3-dioxane, 5-alkyl-5-carboxy-l,3-dioxane, 5-alkyl-5-
-carboxyalkyl-l,3-dioxane, 2-alkyl- 1,3 -propanediol, 2,2-dialkyl-l,3-propanediol,
2-hydroxy- 1,3 -propanediol, 2-hydroxy-2-alkyl-l,3-propanediol, 2-hydroxyalkyl-
-2-alkyl- 1 ,3-propanediol, 2,2-di(hydroxyalkyl)- 1 ,3-propanediol, 2-carboxy- 1 ,3-
-propanediol, 2-carboxyalkyl- 1,3 -propanediol, 3-alkyl-3-(hydroxyalkyl)oxetane and/or
3 ,3 -di(hydroxyalkyl)oxetane.
10. A process according to any of the Claims 1-8 characterised in, that said at least one alkoxylated mono, di, tri or polyhydric compound is a dimer, trimer or polymer of an alkoxylated Cι-C24-alkanol, l,ω-diol, 5-hydroxy-l,3-dioxane, 5-hydroxyalkyl-l,3-dioxane, 5-alkyl-5-hydroxyalkyl-l,3-dioxane, 5,5-di(hydroxyalkyl)-
-1,3-dioxane, 5-carboxy-l,3-dioxane, a 5-carboxyalkyl-l,3-dioxane, 5-alkyl-5-
-carboxy-l,3-dioxane, 5-alkyl-5-carboxyalkyl-l,3-dioxane, 2-alkyl- 1,3-propanediol,
2,2-dialkyl-l,3-propanediol, 2-hydroxy- 1,3-propanediol, 2-hydroxy-2-alkyl-
-1,3-propanediol, 2-hydroxyalkyl-2-alkyl- 1,3 -propanediol, 2,2-di(hydroxyalkyl)-l,3-
-propanediol, 2-carboxy-l, 3 -propanediol, 2-carboxyalkyl-l,3-propanediol, 3-alkyl-3-
-(hydroxyalkyl)oxetane and/or 3,3-di(hydroxyalkyl)oxetane.
11. A process according to any of the Claims 1-8 characterised in, that said at least one alkoxylated mono, di, tri or polyhydric compound is alkoxylated dimer, trimer or polymer of a Cj-C24-alkanol, l,ω-diol, 5-hydroxy-l,3-dioxane, 5-hydroxyalkyl-l,3-dioxane, 5-alkyl-5-hydroxyalkyl-l ,3-dioxane, 5,5-di(hydroxyalkyl)-
-1,3-dioxane, 5-carboxy-l,3-dioxane, a 5-carboxyalkyl-l,3-dioxane, 5-alkyl-5-carboxy-
-1,3-dioxane, 5-alkyl-5-carboxyalkyl-l,3-dioxane, 2-alkyl- 1,3-propanediol, 2,2-dialkyl- - 1 ,3-propanediol, 2-hydroxy- 1 ,3-propanediol, 2-hydroxy-2-alkyl- 1 ,3-propanediol, 2-hydroxyalkyl-2-alkyl-l ,3-propanediol, 2,2-di(hydroxyalkyl)-l ,3-propanediol,
2-carboxy- 1,3-propanediol, 2-carboxyalky 1-1, 3 -propanediol, 3-alkyl-3-(hydroxyalkyl)- oxetane and/or 3,3-di(hydroxyalkyl)oxetane.
12. A process according to any of the Claims 1-11 characterised in, that said at least one alkoxylated mono, di, tri or polyhydric compound is alkoxylated ethanol, «-butanol, wo-butanol, sec-butanol, «-propanol, wo-propanol, octanol, tsø-octanol, 2-ethyl-hexanol, 1 ,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6-cyclohexane- dimethanol, 5,5-dihydroxymethyl-l,3-dioxane, 2-methyl- 1,3 -propanediol, 2-methyl- -2-ethyl- 1,3-propanediol, 2-ethyl-2-butyl- 1,3 -propanediol, neopentyl glycol, dimethylolpropane, 1,1-dimethylolcyclohexane, glycerol, trimethylolethane, trimethylolpropane, diglycerol, di(trimethylolethane), di(trimethylolpropane), pentaerythritol, di(pentaerythritol), anhydroenneaheptitol, sorbitol, mannitol, hydroxypivalic acid, dimethylolpropionic acid, 3-methyl-3-(hydroxymethyl)oxetane, 3 -ethyl-3 -(hydroxymethyl)oxetane and/or 3 ,3 -di(hydroxymethyl)oxetane.
13. A process according to any of the Claims 1-8 characterised in, that said at least one alkoxylated mono, di, tri or polyhydric compound is a di, tri or polyethylene glycol, a di, tri or polypropylene glycol, a hydroxylated di, tri or polybutadiene and an epoxidised hydroxylated di, tri or polybutadiene.
14. A process according to any of the Claims 1-13 characterised in, that said at least one alkylation precursor is at least one alkyl, alkenyl or alkynylhalide.
15. A process according to Claim 14 characterised in, that said at least one alkyl, alkenyl and/or alkynylhalide is a compound of formula R^2 wherein R1 is C]-C24-alkyl, C2-C24-alkenyl or C2-C24-alkynyl and wherein X is Cl, Br or I.
16. A process according to Claim 14 or 15 characterised in, that said at least one alkyl, alkenyl and/or alkynylhalide is methylchloride, methyliodide, allylchloride, allylbromide, methallylcloride and/or methallylbromide.
17. A process according to any of the Claims 1-16 characterised in, that said at least one reduction agent is at least one hydride.
18. A process according to Claim 17 characterised in, that said at least one hydride is a compound of formula BH4, R1BH4, R]BH3R2, R1BH2(R2) and/or
R1BH(R2)3 wherein R1 is an alkali metal ion, such as Li, K or Na and R2 is CN or
OCpϊip+\, wherein p is an integer and at least 1, such as an integer between 1 and 5 inclusive.
19. A process according to Claim 17 characterised in, that said at least one hydride is a compound of formula A1H4, RΑIH4, R^l^R2, R1A1H2(R2)2 and/or
R1A1H(R2)3, wherein R1 is an alkali metal ion, such as Li, K or Na and R2 is CN or
OCpHp+i, wherein p is an integer and at least 1, such as an integer between 1 and 5 inclusive.
20. A process according to Claim 17 characterised in, that said at least one hydride is an alkali metal and/or alkaline earth metal hydride.
21. A process according to Claim 17 characterised in, that said at least one hydride is a group 13 (III A) and/or transition metal borohydride.
22. A process according to Claim 17 characterised in, that said at least one hydride is a compound of formula (R3)4NBH4, (R3)3R4NBH4, (R3)2(R4)2NBH4 and/or
R3(R4)3NBH4, wherein R3 and R4 is individually is linear or branched alkyl having 1 to 24 carbon atoms.
23. A process according to any of the Claims 1-22 characterised in, that said at least one alkaline catalyst is a hydroxide, carbonate or alkoholate, such as a methylate or ethylate, of at least one alkali and/or alkaline earth metal.
24. A process according to any of the Claims 1-22 characterised in, that said at least one alkaline catalyst is an elemental alkali and/or alkaline earth metal.
25. A process according to Claim 23 or 24 characterised in, that said at least one alkali metal or alkaline earth metal is potassium, sodium, lithium and/or calcium.
26. A process according to any of the Claims 1-25 characterised in, that said at least one optional solvent is toluene, xylene methyl isobutyl ketone and/or methyl ethyl ketone.
27. A process according to any of the Claims 1-5 characterised in, that said alkylation is an allylation of at least one alkoxylated di, tri or polyhydric compound.
28. A process according to Claims 27 characterised in, that said at least one alkoxylated di, tri or polyhydric compound is ethoxylated and/or propoxylated 5,5-dihydroxymethyl-l,3-dioxane, 2-methyl- 1,3-propanediol, 2-methyl-2-ethyl- -1,3-propanediol, 2-ethyl-2-butyl- 1,3-propanediol, neopentyl glycol, dimethylolpropane, 1,1-dimethylolcyclohexane, glycerol, trimethylolethane, trimethylolpropane, diglycerol, di(trimethylolethane), di(trimethylolpropane), pentaerythritol, di(pentaerythritol), hydroxypivalic acid, dimethylolpropionic acid, 3-methyl-3-(hydroxymethyl)oxetane, 3-ethyl-3-(hydroxymethyl)oxetane and/or 3, 3-di(hydroxymethyl)oxetane.
29. A process according to Claims 27 or 28 characterised in, that said at least one alkylation . precursor is allylchloride, methallylchloride, allylbromide and/or methallylbromide.
30. A process according to any of the Claims 27-29 characterised in, that said at least one reduction agent is a compound of formula BH4, RΕH4, R'BH^2, R'BH2(R2)2 and/or R]BH(R2)3, wherein R1 is an alkali metal ion, such as Li, K or Na and R2 is CN or OCpHp+ wherein/? is an integer and at least 1, such as an integer between 1 and 5 inclusive.
31. A process according to any of the Claims 27-29 characterised in, that said at least one hydride is a compound of formula A1H4, RΑIH4, R^ffl^R2, R1A1H (R2)2 or
R]A1H(R2) wherein R1 is an alkali metal ion, such as Li, K or Na and R2 is CN or
OCpΑp+i wherein p is an integer and at least 1, such as an integer between 1 and 5 inclusive.
32. A process according to any of the Claims 27-31 characterised in, that said at least one alkaline catalyst is lithium, potassium, sodium and/or calcium hydroxide, carbonate and/or alkoholate.
33. A process according to any of the Claims 27-32 characterised in, that yielded product is a mono, di, tri or poly(allyl) ether or a mono, di, tri or poly(methallyl) ether of alkoxylated 5,5-dihydroxymethyl-l,3-dioxane, 2-methyl- 1,3-propanediol, 2-methyl- -2-ethyl-l,3-propanediol, 2-ethyl-2-butyl- 1,3 -propanediol, neopentyl glycol, dimethylolpropane, 1,1-dimethylolcyclohexane, glycerol, trimethylolethane, trimethylolpropane, diglycerol, di(trimethylolethane), di(trimethylolpropane), pentaerythritol, di(pentaerythritol), hydroxypivalic acid, dimethylolpropionic acid, 3-methyl-3-(hydroxymethyl)oxetane, 3-ethyl-3-(hydroxymethyl)oxetane and/or 3 , 3 -di(hy droxymethy l)oxetane .
34. A process according to any of the Claims 27-32 characterised in, that said at least one alkoxylated mono, di, tri or polyhydric compound is a di, tri or polyethylene glycol, a di, tri or polypropylene glycol, a hydroxylated di, tri or polybutadiene and/or an epoxidised hydroxylated di, tri or polybutadiene.
35. Use of a mono, di, tri or poly(allyl) ether or a mono, di, tri or poly(methallyl) ether of an alkoxylated mono, di, tri or polyhydric compound, said mono, di, tri or poly(allyl) ether or mono, di, tri or poly(methallyl) ether being obtainable by and yielded in the process of any of the Claims 27-34.
36. Use according to Claim 35, as peroxide carrier in two coponent radical curing of unsaturated polyester systems.
37. Use according to Claim 35, as crosslinker for acrylic polymers in super absorbants.
38. Use according to Claim 35, as wetting additive, optionally copolymerised with acrylic monomers, for concrete, inorganic pigments and inorganic fillers.
39. Use according to Claim 35, as oxygen scanvenger in radiation curing systems.
40. Use according to Claim 35 in production of unsaturated esters and polyesters.
41. Use according to Claim 35, in production of silanes by siloxane addition to double bonds.
42. Use according to Claim 35, in production of mono, di, tri and polyepoxides by oxidation of at least one double bond to corresponding oxirane group.
43. Use according to Claim 35, in production of thickemers by copolymisation with at least one alkali metal allyl or methallyl sulphonate.
PCT/SE2002/002202 2001-11-30 2002-11-29 Process for alkylation of an alkoxylated mono di, tri or polyhydric compound WO2003046048A1 (en)

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CN114015013A (en) * 2021-11-16 2022-02-08 广东十辰十新材料有限公司 Yellowing-resistant self-decoloring UV resin and application thereof in UV glue dripping

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CN113354516B (en) * 2021-07-07 2022-11-04 浙江皇马科技股份有限公司 Preparation method of glyceryl ether gas drying agent

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