Boron-based catalysts

Related Patent application

This Patent application relates to the same date with the present Patent application to co-pending Patent application of No. [agent CL4291 file number ] and co-pending Patent application [agent file number 4555] No..

Invention field

The invention relates to boron-based catalyst and the method of their preparation. The catalyst is suitable for the use of alkylene epoxides mellow alkoxyl.

Background of the invention

Containing alkoxylates material has been widely used for various industrial applications, such as non-ionic surface active agent. They usually through mellow and Asia alkyl epoxides such as ethylene oxide (in other words oxa cyclopropane) or epoxy propane (i.e. 2-methyl oxa cyclopropane) in one or more the presence of a catalyst prepared by the reaction. By introducing the fluorinated alkyl alkyl epoxides mellow and Asia prepared by the reaction of the fluorinated alkyl alkoxylate is a kind of important material. Fluorinated alkyl alkane oxide can especially be used for a number of industrial applications, including in the PVC film, electrochemical battery and various photosensitive coating as in the manufacture of non-ionic surface active agent.

For fluorinated mellow alkoxyl known catalyst system and method including the use of Lewis acid, such as boron trifluoride or silicon tetrafluoride, with individual metal hydride, fluoride, alkyl or alkoxide mixed. Such an acidic substance in the alkyl alkoxylated period also catalytic reaction, dimerization alkyl epoxides if Asia form II Alkanes. Because of the reason, many method use of a strong alkaline catalyst to an alkoxylated alcohol. However, some of the alcohol of the alkali is not stable. For example, the presence of the strong alkali, some hydrofluorocarbon easy defoaming HF and form the fluorinated olefin. Halohydrin known XCR₂ CR₂ OH formed in the presence of an alkali epoxide, therefore be used for the synthesis of the olefin into epoxide.

Halling and Huang in United States Patent 5,608,116 disclosed in the method of preparing fluoro base alkane oxide, wherein the iodine source and an alkali metal borohydride such as NaBH₄ (expensive material, due to the safety problem of flammability and) the presence of the catalyst system, will have the general formula structure R_f CH₂ CH₂ OH perfluoroalkyl group of ethanol, commercially available mixture alkoxylated.

Invention overview

One aspect of the invention comprises compound MB (OR⁷)_x (X)_4-x composition, wherein: R⁷ is optionally substituted with 2 to 20 carbon atoms of straight-chain, branched, cyclic, acyclic, or aromatic hydrocarbon group; X is a fluoride ion, bromide, or iodide ion; M is alkali metal cation Na⁺, K⁺, Li⁺, or R² R³ R⁴ R⁵ N⁺ or R² R³ R⁴ R⁵ P⁺-type cation, wherein R², R³, R⁴ and R⁵ is independently has 1 to 20 carbon atoms in the hydrocarbyl group; and for x 1 to 4.

Another aspect of the present invention is to prepare compound MB (OR⁷)_x (X)_4-x method, wherein for x 1-3, the method comprises making B (OR⁷)₃ and MX mixed in in the suitable solvent, wherein said B (OR⁷)₃ and the MX to about the 1 [...] 3 to about 3 the [...] 1 molar ratio of mixing.

Invention details

As used herein, the term "alkyl" means straight-chain, branched, or cyclic arrangement of carbon atoms, the carbon atom through a carbon-carbon single bond, double bond, triple bond or aromatic carbon-carbon bond-connection and/or through the ether linkage is connected, and a hydrogen atom is substituted. Such hydrocarbyl group may be an aliphatic and/or aromatic. Hydrocarbyl examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methyl cyclohexyl, benzyl, phenyl, O-tolyl, m-tolyl, P-tolyl, xylyl, vinyl, allyl, butenyl, cyclohexenyl, ring-based, cyclo dialkylene and butynyl.

"Optional" or "optionally" means that may or may not exist events or circumstances described subsequently, and the stated states the description including the examples of the event or condition does not occur, and among them, examples of the events or circumstances. For example, the phrase "optionally substituted" refers to the moiety may be substituted or may not be substituted, and the stated states the description including not substituted part and the part of the not substituted.

When the group or part is in this text is referred to as "substituted", it refers to the group or portion contains one or more substituents, the substituents of the compound containing these groups experienced by is inert under the process conditions (e.g., an inert functional group, see below). Substituent can be connected to the original part of the pendant group, replacing the stated part of or may be in one or a plurality of atomic. And, substituents also substantially not adversely affecting the method described herein. Comprising one or more hetero atom if nitrogen , oxygen and/or sulfur in chain or link the meaning of "substituted" in. In substituted hydrocarbyl, all the hydrogen is even can be substituted, such as trifluoromethyl.

Refer to "inert functional group" is not hydrocarbyl or substituted hydrocarbyl group, said group in the compound containing the group experienced by is inert under the process conditions. Moreover, the functional groups described herein substantially does not affect the presence of the functional group of the compounds of any of the methods can be used. Functional group examples include halogen (fluorine, chlorine, bromine) and ether.

Only "alkyl" means a monovalent hydrocarbon group containing a single bond.

"Alkylene" means the divalent hydrocarbyl group containing only single bond.

"Fluorinated" means that at least one of directly bonding with carbon is substituted hydrogen already.

"Fluorinated alkyl" means partially or completely fluorinated alkyl.

Described herein is a method for preparing alkyl alkoxylates, in particular the use of the boron-based catalyst, by the epoxidation reaction method of preparing fluoro alkoxy compound. The catalyst may be used with various mellow same place.

In one embodiment, the method comprises: in about 60 the [...] to about 200 the temperature and environment [...] atmospheric pressure to about 1035KPa pressure; alcohol in the presence of a catalyst with the catalyst about 200 to 15 molar ratio of, the formula R¹ OH many kinds of mellow a or with one or more have the formula Q (O) of the 1, 2-alkylene epoxides contact, in order to form the formula R¹ O (QO)_m H alkyl alkoxylate, wherein m is 1 to 20, wherein Q in formula C_y H_2y of alkyl linear chain Asia , wherein for y 2 to 10 integer, and R¹ is optionally substituted with 1 to 30 carbon atoms straight chain, branched chain, cyclic, or aromatic hydrocarbyl; wherein said catalyst is the MB (OR¹)_x (X)_4-x or B (OR¹)₃/MX, wherein the M Na⁺, K⁺, Li⁺, R² R³ R⁴ R⁵ N⁺, or R² R³ R⁴ R⁵ P⁺, and R², R³, R⁴ and R⁵ is independently hydrocarbyl, and for x 1 to 3.

R¹ can be having 1 to 30 carbon atoms, or aryl such as phenyl. R¹ functional group can optionally be substituted, said functional group not but iflimited to ether , amide, ester, halogen, sulfur, nitriles, precondition that the functional group will not affect the alkoxylation reaction. It may also be partially fluorinated, or for C_y F_2y+1 CH₂ CH₂-type straight-chain fluoroalkyl, wherein for y 2 to 20 integer. R¹ can be one or more alkyl mixture, a mixture of such as a fluoro alkyl group.

In one embodiment, in the stated method formula R¹ OH the mixture of alcohols of 1, 2-alkylene epoxides contact, generation of the corresponding alkyl alkoxylate mixture, the mixture can be used for the telomerization mixture. Formula Q (O) of the 1, 2-alkylene epoxides can be ethylene oxide, propylene oxide, 1, 2-epoxy butane, 2, 3-epoxy butane, and styrene oxide, or their mixture, and is usually ethylene oxide or propylene oxide.

In the method disclosed herein the catalyst includes MB (OR¹)_x (X)_4-x or B (OR¹)₃/MX. B (OR¹)₃/MX is that two component catalyst, it is B (OR¹)₃ and a mixture of MX. The two components separately or at the same time any sequence can be added to the method. R¹ defined as above. In the formula MB (OR¹)_x (X)_4-x in, x can be 1 to 3, but is usually 3. It is believed that, B (OR¹)₃/MX catalyst in situ formation formula MB (OR¹)₃ X composition, the composition is used as the catalytic material. R¹ defined as above.

M is alkali metal cation Na⁺, K⁺, Li⁺, or R² R³ R⁴ R⁵ N⁺ or R² R³ R⁴ R⁵ P⁺-type cation, wherein R², R³, R⁴ and R⁵ is independently has 1 to 20 carbon atoms of the alkyl. Usually, R², R³, R⁴ and R⁵ is independently having 1-4 carbon alkyl, such as butyl, and can be the same or different. In one embodiment, for M R² R³ R⁴ R⁵ N⁺.

X is a fluoride ion, bromide ion or iodide ion, but is usually I.

The catalyst can be commercial purchase access to, or by the field prepared by any method known, such as the method disclosed below.

In one embodiment, the method comprises an alcohol in the presence of the catalyst in contact with the epoxy alkane. And at the same time or catalyst can be in any order in the added to the epoxy alkane. Usually the catalyst is added to the pure alcohol, or in pure mellow produces , the alcohol is also used as the reaction solvent. May additionally use of one or a plurality of a co-solvent, the precondition of one or more solvents for all reagent and product is substantially inert. Then with the high temperature epoxy alkane treatment catalyst and alcohol reaction mixture, until reaching the desired conversion.

Catalyst relative to the amount of alcohol is about 0.1 mole % to about 11 mole %, typically about 0.5% to about 8%, more typically in the range of about 1 mole % to about 6%. Usually the catalyst is added and alcohol, epoxy alkane in liquid or steam form is added to the catalyst/alcoholic solution. In addition to providing the required minimum amount to provide a final product in the desired number of alkoxy units, is added to the reaction mixture of epoxy alkane quantity in is not crucial.

The amount of the epoxy alkane is variable, and the desired physical characteristics of the product alcohol alcoxylates decision. Therefore, in some cases, each that corresponded raw material alcohol is reacted to the average alkoxyl base relatively low, for example 2 to 6, and in the case of other conditions, notably to a relatively high average alkoxyl base such as 8 to 30 or higher.

Many epoxy alkane in view of the flammability for reasons of security, the method usually in an inert atmosphere such as nitrogen or other inert gas. Because the water is usually oxyalkylates, so as to produce contaminants, under anhydrous conditions in the implementation of the method. Water may also inhibit or poison some catalyst.

The reaction temperature can be changed, and can be at about 60 the [...] to about 180 the within [...] , and is preferably about 80 the to [...] the 140 [...]. The desired temperature is mainly composed of a permissible reaction time is decided, a relatively low temperature to obtain a relatively long reaction time, while higher temperature to obtain a relatively short reaction time.

During the reaction the reaction is carried out under the pressure generated, the pressure is usually about 0 to about 200psig, or about 0 to about 100psig.

Stirring is not needed, but usually provide stirring, in order to help to uniformly mixed and is beneficial to heat transfer.

The method disclosed herein are alkyl alkoxylate may have any desired number of alkoxy, can custom characteristics of the desired final use. Alkoxy unit content according to the alkyl group by weight of an alkoxylate composition is usually between about 10% to about 90% ; more typical is about 20% to about 70%.

In one embodiment, mixture telomerization method for forming, its also called the telomer. When the principal chain (C) is added to the telogen (AB) to form a telomer, by the mixture low degree of polymerization to form a polymer, by formula A (C)_m B expressed (wherein m general in the 1 to 20 range). As used herein, telomerization mixture m is defined as its degree of polymerization of telomer a plurality of different to each other. Therefore, in some embodiments, can be prepared by the method disclosed herein the formula R¹ O (QO)_m H of the mixture the telomerization of alkyl alkoxy compound, said alkyl alkoxylate having different m value. The methods described herein provide for the average degree of polymerization is especially suitable for producing the 1-20, more typically a 2-8 of the telomer.

The method can also optionally include the recovery or separation of one or more alkyl alkoxylate. This can be known in the field to any method, such as distillation, decantation, recrystallization, or extraction.

The invention further provides a MB (OR⁷)_x (X)_4-x compound, wherein R⁷ is optionally substituted with 2 to 20 carbon atoms of straight-chain, branched chain, cyclic, or aromatic hydrocarbyl;

X is fluorine, bromide, or iodide ion; M is alkali metal cation Na⁺, K⁺, Li⁺, or R² R³ R⁴ R⁵ N⁺ or R² R³ R⁴ R⁵ P⁺-type cation, wherein R², R³, R⁴ and R⁵ is independently has 1 to 20 carbon atoms in the hydrocarbyl group; and for x 1 to 4.

Said compound can be used as catalyst, in particular in the alkoxylation reaction.

R⁷ can be having 1 to 30 carbon atoms, or aryl such as phenyl. It can optionally be replaced by a functional group, the functional group is not but iflimited to ether , amide, ester, halogen, sulfur, nitriles, precondition that the functional group will not affect the alkoxylation reaction. It may also be partially fluorinated, or for C_y F_2y+1 CH₂ CH₂-type straight-chain fluoroalkyl, wherein y=2 to 20, in particular when the x 4 time. R⁷ mixture of the group, such as a mixture of fluorinated alkyl. X to the 4 time, R⁷ may be partially or fully fluorinated the fluorinated alkyl.

In the formula MB (OR⁷)_x (X)_4-x in, x can be 1 to 3, but is usually 3.

M is alkali metal cation Na⁺, K⁺, Li⁺, or R² R³ R⁴ R⁵ N⁺ or R² R³ R⁴ R⁵ P⁺-type cation, wherein R², R³, R⁴ and R⁵ is independently has 1 to 20 carbon atoms of the alkyl. Usually, R², R³, R⁴ and R⁵ is independently having 1-4 carbon alkyl, such as butyl, and can be the same or different. In one embodiment, for M R² R³ R⁴ R⁵ N⁺.

X is a fluoride ion, bromide ion or iodide ion, but usually is iodine ion.

X to the 4 time, four alkoxy boric acid radical B (OR)₄^- can be prepared by various methods. For example, by the B (OH)₃ started by the two-step method described Malkowsky 2006 years "  Chemistry   Journal   Inorganic   of European" section 1690 page. The compounds may also be use for example B (OMe)₄^- or other four mellow roots , prepared by alcohol exchange. Furthermore, NaBO₂ or other anionic borate with alcohol, to remove water to obtain the shows four alkoxide :

NaBO₂ + 4ROH      <AOX1AAO >NaB (OR)₄ + 2H₂ O

Can be through the neutral borate B (OR)₃ and M⁺ X^- mixing, to prepare compound MB (OR)_x (X)_4-x, wherein x is 1 to 3. Formed in the 1st step B (OR)₃, then added in the MX 2nd step. As the other option, can be through the MX and B (OH)₃ or B₂ O₃ underwaterly in alcohol ROH, then optionally detachment water , prepared in a one-step in MB (OR)_x (X)_4-x.

Can be through B (OH)₃ or B₂ O₃ and HOR reaction, water is removed at the same time, to obtain B (OR)₃. As the other option, they can be from halogenated boron like BCl₃ prepared with alcohol, HCl produced at the same time. Alkali for removing the generated HCl. B (OR)₃ prepared compound can be independent, or may be carried out in which the alkoxylated generated in the same reactor. In addition to water is the optional, but usually implemented arefaction in order to avoid generating poly (alkylene glycol), poly (alkylene glycol) is composed of the alkoxylated of the water formed. If in the product mellow alkoxyl presence of poly (alkylene glycol) is not acceptable, the alkoxylation is carried out should be before the removal.

Embodiment

Use the following abbreviation: refers rises "L" is, "mol" is refers to the mole , "ml" means milliliter, " %" means percentage, refer to "ca." approximately, "g" refers to grams, "h" refers to hours, "EO" refers to ethylene oxide.

All B (OR)₃ compound is prepared by the method previously disclosed, such as described for Cotton, F.A. ; Wilkinson, g. The "  Chemistry   Inorganic Advanced" 5th Edition (Wiley-Interscience: New   York, 1988, paragraph 168 page and 171 page); the Malkowsky "Eur.J.Inorg.Chem." (2006, 1690) (wherein including oxygen boron substances such as B (OH)₃ or B₂ O₃ with suitable alcohol) those in. The reaction in the solvent (usually as the backflow of toluene) in. By the standard for continuous removal of water, in order to ensure that the ester is totally transformed including oxygen boron material B (OR)₃. These compound is formed by multi-nuclear NMR (1H, 13C, 19F), mass spectrometry and element analysis to characterization. The following is a representative reaction.

Embodiment 1

B (OCH₂CH₂C₆F₁₃)₃

The B₂ O₃ (1.60g feinmahltechnik powder, 46.0mmol) and 52.8g (145mmol, 3 . 15 equivalent) HOCH₂ CH₂ C₆ F₁₃ underwaterly to 75 ml in toluene. Reflux under nitrogen the mixture, and using the Dean-Stark water separator to remove the water. About 1 hour later, water almost completely desorbed; re-sustained backflow 2h in order to ensure complete reaction. Collecting total 1.2 ml, to 100% the theoretical value. Filtering the product, and then the lifting bucket rotary evaporimeter, colorless liquid product is obtained. Yield: 50.36g, 100%.

NMR display product containing about 94% of B (OR_f)₃ and 6% the HOR_f.¹ H   NMR (d8-THF): 4.15 (t, 6.3Hz, 6H), 2.47 (tt, 19.0Hz, 6 . 2Hz, 6H).

F-+B (OR)₃the NMR characterization

To B (OCH₂ CH₂ CF₂ CH₂ C₄ F₉)₃ (0.189g, 0 . 19mmol) the 2 ml ethyl ether solution, adding Bu₄ NF a hydrate (0.062g, 0 . 22mmol) of 2 ml ether slurry. After stirring a few minutes, crystalline Bu₄ NF dissolved to obtain colorless solution. After stirring overnight, the stripping ether vacuum. The resulting soluble oil again CD₂ Cl₂ in, and by¹⁹ F   NMR detection, showing the 1 [...] the 1 [...] the 1 [...] 1 four heavy peaks of (-144.9ppm, J_B-F = 17.3Hz), this is the characteristic of the fluoro-boron material, and attributable to the anionic B (OCH₂ CH₂ CF₂ CH₂ C₄ F₉)₃ F^-.

This shows that B (OR)₃ and X^- to mix in solution form after B (OR)₃ X^-.

Embodiment 2

NaB (OR)₄synthesis of

These compound is NaB (OCH₃)₄is suitable mellowly prepared by the reaction of. The reaction releases the methanol, and the reaction mixture is heated under vacuum or nitrogen purging to remove methanol. The compound is formed by element analysis and¹ H   NMR to characterization. The following is representative.

The NaB (OCH₃)₄ (1.00g, 6 . 3mmol) and HOCH₂ CH₂ OCF₂ CFHOCF₂ CF₂ CF₃ (9.35g, 28 . 5mmol) mixed, and in 70 the heating [...] obtain pale yellow liquid. 3 hours later, the mixture is cooled to the room temperature, and the release of vacuum to move downwards in addition to the methanol. The product is then in the vacuum and 100 the heating [...] 2 hours. The product and drying with ether washing several times.

¹ H   NMR (CD₃ OD): apart from HOCH₂ CH₂ OCF₂ CFHOCF₂ CF₂ CF₃ and outside the resonance, also detect a small amount of residual HOCH₃ (3 mol %).

Elemental analysis: C₂₈ H₂₀ BF₄₀ NaO₁₂ calculated value: C, 25.06% ; H, 1.50% ; F, 56.62%. Content: C, 24.80% ; H, 1.63% ; F, 56.58%.

Comparative embodiment 1

For treatment of NaH C₆F₁₃CH₂CH₂OH

Adding to a small bottle 0.259g (0.71mmol) C₆ F₁₃ CH₂ CH₂ OH, 4 mg (0.17mmol) NaH and the stirring rod. Immediately escape of gas. The mixture is heated under stirring to 100 the [...]. Initially colorless solution turned deep amber. 75 minutes, then cooling the mixture to room temperature. GCMS analysis shows that, in addition to unreacted mellow outside , quality 344 of the corresponding new peak dissolved in the alcohol (quality = 364) lose HF (quality = 20). Other than olefinic products in addition to other trace, 1H   NMR analysis (CDCl₃) also shown attributable to C₅ F₁₁ CF=CHCH₂ OH olefin resonance. Instantiates the implementation, ethoxylate produces mellowly mellowly for sodium hydride method of the catalyst tends to defoaming fluoride Fluoridize and form the olefin and failure.

Comparative embodiment 2

KOH treatment for C₆F₁₃CH₂CH₂OH

Adding to a small bottle 0.251g (0.69mmol) C₆ F₁₃ CH₂ CH₂ OH, 12 mg (0.21mmol) KOH and the stirring rod. The mixture is heated under stirring to 100 the [...]. Initially colorless mixture into a deep amber. 75 minutes, then cooling the mixture to room temperature. GCMS analysis shows that, in addition to unreacted mellow outside , quality 344 of the corresponding new peak dissolved in the alcohol (quality = 364) lose HF (quality = 20). Other than olefinic products in addition to other trace, 1H   NMR analysis (CDCl₃) also shown attributable to C₅ F₁₁ CF=CHCH₂ OH olefin resonance.

Instantiates the implementation, processing by potassium hydroxide because produces mellowly mellowly ethoxylate catalyst tends to cancel out the method of forming a fluoride and Fluoridize olefin and failure.

Embodiment 3-34

Ethoxylation reaction-general method

In a stainless steel reactor ethoxylated. In some cases, the use of glass lining. In adding to the reactor, magnetic stirring rod, catalyst component (MB (OR)₄ or B (OR)₃ and MX), sealing, and then is connected to the gas manifold. When the catalyst is B (OR₁)₃/MX form, to join together two components. The reactor is evacuated, and then the the 0-5 under [...] , to the/ol EO 4 to 10 the predictive quantitative of the ratio of reactor condensation in EO. When the transfer is complete EO, about for 1psig nitrogen backfill system, and close to the valve. Placing the reactor in the heating part, and reach the reaction temperature, and magnetic stirring. Close attention by monitoring the pressure of the reaction process. At higher catalyst concentration (about 6 mole %)lower, gas absorption usually in 3-6 hours. A relatively low concentration of a catalyst needs a long period of time, and usually make it go on, throughout the night, in order to ensure completely consumed ethylene oxide.

For analysis and processing, ice cooling to the reactor the 0-3 [...]. Via a vacuum to remove unreacted EO (if it exists), and -196 the collection in[...] in the cold trap. By the GC and various other technical (HPLC, MS, NMR) analysis of the ethoxylated product.

Ethoxylated results in conclusion in the schedule. "EO#" average of ethylene oxide unit is inserted into, e.g., RO (CH₂ CH₂ O)_n H in the average of the n. Designated ethoxylation reaction n value in general due to the ratio of the ethylene oxide with an alcohol and conversion rate decision.

Embodiment 34

The catalyst separation-free C₆F₁₃CH₂CH₂OH ethoxylated

Adding to the reactor C₆ F₁₃ CH₂ CH₂ OH (12 molar equivalent) and boron oxide (B₂ O₃, 1 molar equivalent, corresponding to 2 molar equivalents of boron). The mixture is heated to the 80 [...] , at the same time stirring and purged with nitrogen. Frozen to flow into the nitrogen in the cold trap, the water collecting in the observed. 3 hours after the dissolved boric oxide, and water-collecting end, to obtain a clear colorless solution. The sample shows titration analysis Karl-Fischer 100 PPM water content. Taken out from the solution and the sample¹ H   NMR (CDCl₃) analysis, its shown C₆ F₁₃ CH₂ CH₂ OH and B (OCH₂ CH₂ C₆ F₁₃)₃ of the 3 [...] 1 molar mixture, confirmed B₂ O₃ quantitative conversion ester.

To the resulting solution by adding 0.6 molar equivalent of and additional NaI 24 molar equivalent C₆ F₁₃ CH₂ CH₂ OH. Adding 117 molar equivalent of ethylene oxide (EO and C₆ F₁₃ CH₂ CH₂ OH ratio = 9.8), and will be reflected in the 120 [...] lower heating. Observation of the pressure quickly drops. At the end of the consumption EO, and by cooling the reactor GC analysis product, its shown average ethoxylation degree is about 9 the ethoxylate and 0.7% of unreacted C₆ F₁₃ CH₂ CH₂ OH mixture.

Embodiment 35

The catalyst separation-free C₆F₁₃CH₂CH₂OH ethoxylated

Adding boron oxide to the reactor (B₂ O₃, 1 molar equivalent), sodium iodide (1 molar equivalent) and C₆ F₁₃ CH₂ CH₂ OH (17 mol equivalent). The mixture at 80 the heating [...] , nitrogen blowing for stirring and at the same time. 30 minutes later, Karl-Fischer titration analysis shown 3000 PPM water content. The heating and a nitrogen purging longer sustained 60 minutes, at this moment the titration shown water content dropped to 12 PPM.

To the mixture by adding 7.2 mole equivalents of ethylene oxide. The reactor is heated to 120 the [...] , and maintained at this temperature, until completely consumed EO. By cooling and the reactor GC analysis product, its shown average ethoxylation degree is about 6 and ethoxylate of 2% of unreacted C₆ F₁₃ CH₂ CH₂ OH mixture.

Comparative embodiment 3

Under the situation of presence of a halogenide not B (ORf)₃ethoxylated: C4VDF ol

Adding to the reactor 0.888g the B (OCH₂ CH₂ CF₂ CH₂ C₄ F₉)₃ (0.895mmol, based on 80%)and 5.7g (17.5mmol) the HOCH₂ CH₂ CF₂ CH₂ C₄ F₉. Then adding ethylene oxide (5 ml, 0 . 10mol), and the reactor is heated to 125 the [...]. Heating 17 hours later, pressure drop is no longer observed. Cooling and removing the unreacted ethylene oxide, GC analysis shows only 3% of an alcohol into 1-mole ethoxylate, the remaining 97% unreacted alcohol.

Comparative embodiment 4

Under the situation of presence of a halogenide not B (ORf)₃ethoxylated: C6 alcohol

Adding to the reactor B (OCH₂ CH₂ C₆ F₁₃)₃ (4.1 mol %)the HOCH₂ CH₂ C₆ F₁₃ solution. Adding oxirane (25 mole equivalent), and in the reactor the 125 [...] lower heating 18 hours. Cooling to room temperature and after removing the unreacted ethylene oxide, chromatographic analysis of the solution by the gas phase, unreacted alcohol only is shown, and there is no can be ethoxylated product pieces.

Adding to the reactor B (OCH₂ CH₂ C₆ F₁₃)₃ (9.5 mol %)the HOCH₂ CH₂ C₆ F₁₃ solution. Adding oxirane (25 mole equivalent), and in the reactor the 125 [...] lower heating 18 hours. Cooling to room temperature and after removing the unreacted ethylene oxide, the solution by the gas-phase chromatographic analysis, shown> 95% of the unreacted alcohol and trace ethoxylated product.

Comparative embodiment 5

The use of ethoxylated propyl butyl-carbinolxin Chunna

The propyl butyl-carbinol at room temperature (1.31g, 0 . 010mole) and 11 mg   NaH (0.46mmole, 4.6 mol %)mixed, stir at the same time. Immediately escape of gas, and in the 5 end within minutes, sodium octanol solution is obtained. The solution with 5 ml (4.4g, 0 . 10mol) added to the above-mentioned ethoxylated with ethylene oxide in the reactor. The reactor is heated to the 100 [...]. Judge by monitoring the reactor pressure, the reaction of 2 hours. After cooling to room temperature, isolate 5.20g (91%)product. GC analysis shows the average EO 6, the polydispersivity 1.07 the ethoxylate and 7.8% of unreacted alcohol mixture.

Embodiment 36

Using B (O-n-C₈H₁₇)₃and Bu₄NI of ethoxylated propyl butyl-carbinol

Added to the above-mentioned ethoxylated reactor propyl butyl-carbinol (1.30g, 0 . 010mole), Bu₄ NI (0.148g, 0 . 40mmol, 4 mol %)and B (O-n-C₈ H₁₇)₃ (0.159g, 0 . 40mmol, 4 mol %). Adding oxirane (5.0 ml, 0 . 10mol), and the reactor is heated to the 100 [...]. Immediate attention to the gas absorption. The reaction carried out at night, at this time by monitoring the pressure judging, complete conversion of ethylene oxide. After cooling to room temperature, isolate 5.47g (91%)product. GC analysis shows the average EO 5.5, the polydispersivity 1.04 of the ethoxylate and 0.1% of unreacted alcohol mixture.

This embodiment and comparative example 5 shows that, compared with the catalyst of the present invention, alkali metal alkoxide is derived from ethoxylated catalyst was more widely distributed ethoxylated product and is significantly more a large amount of the unreacted alcohol.

Embodiment 37

Low catalyst loading (0.6 weight %)of under C₆F₁₃CH₂CH₂OH ethoxylated

The NaI (0.016g, 0 . 11mmol, 0.6 mol %)soluble in 0.16g   C₆ F₁₃ CH₂ CH₂ O (CH₂ CH₂ O)_n OH (average n=4) and 0.49g   C₆ F₁₃ CH₂ CH₂ OH in the mixture. With this solution B (OCH₂ CH₂ C₆ F₁₃)₃ (0.133g, 0.6 mol %)and 6.50g   C₆ F₁₃ CH₂ CH₂ OH (co -19mmol alcohol) added to together with ethoxylated in the reactor as described above. Then added to the reactor 0.08mol oxirane (EO: alcohol = 4), and in 115 the heating [...] 14 hours, in 125 the heating [...] 8 hours, and then the the 135 heating [...] 14 hours, the pressure is dropped to 0psig, and judge complete absorption EO. Cooling the reactor, and 9.8g nocolor ethoxylate to isolate the product. GC analysis shows 5.5 weight % unreacted alcohol, average EO number is 4, the dispersion and 1.03.

Embodiment 38

2-chloro ethyl alcohol ethoxylated

Adding to the reactor 2-chloro ethanol (0.805g, 0 . 01mol), Bu₄ NI (0.148g, 0 . 4mmol) and B (OCH₂ CH₂ Cl)₃ (0.0997g, 0 . 4mmol). Adding ethylene oxide (5 ml, 0 . 1mol), then the reactor is heated to the 100 [...] , and the pressure to rise to 125psig. After stirring overnight, pressure is dropped to 0psig, shows complete consumption of ethylene oxide. The reactor cooling, and collected into the 5.19 fusional protein. The confirmed product LCMS, its shown Cl (CH₂ CH₂ O)_n OH oligomer mixture, the n 1 to 30 in the range of, approximately n=11 and the peak at.