Alkoxylation process using bi-catecholate phosphonium catalysts

Abstract

Polyethers are prepared by polymerizing cyclic oxides in the presence of a starter and certain phosphonium catalysts. The phosphonium catalyst is highly active and effective at such small amounts such that generally no catalyst residue needs to be removed from the product. The phosphonium catalysts are very effective in alkoxylation even in low molecular weight initiators, such as glycerol and sorbitol.

Description

[0001] The present invention relates to an alkoxylation process in which a cyclic oxide is added to a starter compound to produce an ether or polyether.

[0002] Polyethers are produced in large quantities worldwide. For example, polyether polyols are important raw materials for the production of polyurethanes. Among other things, they are used to make high-resistance foams, molded foams or rigid foams. For example, polyether monools are used as surfactants and industrial solvents, among others. Carbonate-modified alkylene oxide polymers and ester-modified alkylene oxide polymers are also found in these and other applications.

[0003] Polyether mono- and polyols are produced via alkoxylation of a starter compound, wherein an active site on the starter reacts with a cyclic oxide in a ring-opening reaction. Terminal hydroxyl groups are produced, which in turn can be used as active sites for subsequent alkoxylation steps, thereby producing polyether chains. The active sites of the starter compound are groups containing active hydrogens, such as hydroxyl or thiol groups. The main function of the starter compound is to provide molecular weight control and determine the number of hydroxyl groups that the alkoxylated product will have.

[0004] Catalysts are required to obtain economical polymerization rates.The most commonly used catalysts are alkali metal hydroxides (such as potassium hydroxide) and the so-called double metal cyanide (DMC) catalyst complexes, of which zinc hexacyanocobaltate catalyst complexes are the commercially most important type.

[0005] Alkali metal hydroxides offer the benefits of low catalyst cost and acceptable alkoxylation rates. They are widely used because they can effectively polymerize many alkylene oxides. Nevertheless, alkali metal hydroxides still have well-known disadvantages. The alkoxylation product must be neutralized and catalyst residues carefully removed. These finishing steps greatly increase both capital and operating costs and generate additional waste streams that must be cleaned and / or disposed of.

[0006] Compared to alkali metal catalysts, DMC catalysts provide fast polymerization rates, even when used at very low catalyst concentrations. An important advantage of DMC catalysts over alkali metal hydroxides is that no neutralization step is required. Unlike when alkali metal hydroxides are used as polymerization catalysts, catalyst residues can usually be left in the product. This can lead to a significant reduction in production costs. Nevertheless, DMC catalysts also have significant disadvantages. DMC catalysts tend to perform poorly in the presence of high concentrations of hydroxyl groups, especially in the presence of low molecular weight starter compounds such as glycerol or sorbitol having hydroxyl groups located in the 1,2-position or 1,3-position relative to each other. Under these conditions, the catalyst is difficult to activate, acts slowly, and is often deactivated before the polymerization is completed. This has placed significant limitations on the widespread adoption of DMC catalysts. It is usually necessary to produce polyethers in two or more separate steps, in which the early stages of the polymerization are carried out in the presence of an alkali metal catalyst and, after cleaning up the resulting intermediate product, the remainder of the polymerization is carried out using a DMC catalyst. This approach requires neutralization and purification of the intermediate (since the DMC catalyst is deactivated by strong bases), thus reintroducing the costs that DMC-catalyzed polymerizations are intended to avoid.

[0007] Some Lewis acids have been evaluated as alkylene oxide polymerization catalysts. These Lewis acids do not require activation time substantially, but rapidly deactivate, and therefore cannot produce high molecular weight polymers or cannot convert alkylene oxide heights into polymers. Another problem with many Lewis acid catalysts is that they deactivate at higher operating temperatures. This makes them unsuitable for use with some solid, sticky or otherwise poorly miscible initiators of cyclic oxides, because in those cases high operating temperatures are required to melt the initiator, reduce its viscosity or promote mixing with the cyclic oxide.

[0008] Various phosphonium compounds have been described in the literature. See, for example, Science 341 1374 (2013), Dalton Trans. 2018, 47, 11411, Chem. Eur. J. 2015, 21, 6491-6500; Dalton Trans. 2016, 45, 5568, Angew. Chem. Int. Ed. 2014, 53, 6538-6541, Chem. Sci. 2015, 6, 2016 and Chem. Commun., 2018, 54, 662-665. Bis-catechol acid phosphonium is described in J. Am. Chem. Soc. 2021, 143, 15845-15851. These phosphonium compounds have been described as catalysts in various reactions such as olefin isomerization, hydrosilylation, dehydrogenative coupling, hydrodefluorination, hydrogenation, and Friedel-Crafts reactions.

[0009] The present invention is an alkoxylation process comprising: (step I) forming a reaction mixture comprising a) a starter compound having at least one hydroxyl or thiol group; b) at least one cyclic oxide; and c) a catalytically effective amount of a phosphonium catalyst having one of the following structures:

[0010]

[0011] wherein each R is independently hydrogen, halogen, unsubstituted or inertly substituted C 1-12 alkoxy, aryloxy, unsubstituted or inertly substituted linear, branched and / or cyclic alkyl and unsubstituted or inertly substituted aryl, and any two R groups can form a ring structure together, A represents a weakly coordinating anion and n represents the valence of A; and (step II) reacting the cyclic oxide with a starter compound in the presence of a biscatecholate phosphonium catalyst to form an alkoxylated starter product.

[0012] The process of the present invention has the advantage of obtaining very high alkoxylation rates using very small amounts of phosphonium catalysts. For this reason, catalyst residues can be left in the product (unlike potassium hydroxide), thereby reducing or even eliminating catalyst deactivation and removal steps. Unlike DMC catalysts, these compounds are highly effective in polymerizing ethylene oxide to very low molecular weight starter compounds. The phosphonium catalysts described herein are particularly useful for alkoxylating low molecular weight starters having 1 to 12 oxyalkylene units per active site.

[0013] Inert substituents do not react with the initiator or the cyclic oxide under the alkoxylation reaction conditions and include, for example, alkyl (linear, branched and / or cyclic), aryl, ether (—O—), ester (—OC(O)—), carbonate (—OC(O)—O))—, halogen (especially F, Cl, Br and / or I), sulfide (—S—), polysulfide (—S—), z -, wherein z>1), amino, silyl, etc. The R group preferably does not contain active sites (such as -OH, -NH, -SH or -COOH) where alkoxylation can occur, and preferably does not contain cyclic oxide structures.

[0014] Examples of R groups in Structure I and Structure II include hydrogen, F, Cl, Br, and I. Other examples of R groups include -OR 1 , where R 1 is an unsubstituted or inertly substituted linear, branched and / or cyclic alkyl group having 1 to 12 carbon atoms (particularly 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl). 1is substituted, then the preferred substituent is halogen, especially F or Cl. 1 Specific examples of the group include -CF 3 , -CCl 3 , perfluoroethyl, perchloroethyl, monochloromethyl, monofluoromethyl, etc.

[0015] Other examples of R groups include -O-Ar, where Ar represents an unsubstituted or inertly substituted aryl group (particularly phenyl). In embodiments where Ar is substituted, preferred substituents include halogen (particularly F and Cl), lower alkyl (such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl) and halogen-substituted alkyl (such as -CF 3 , -CCl 3 , perfluoroethyl, perchloroethyl, monochloromethyl, monofluoromethyl, etc.).

[0016] In embodiments where two or more R groups together form a ring structure (together with the carbon atoms of the phenyl groups to which they are attached), the ring structure may be aliphatic or aromatic and may contain heteroatoms in the ring. When such a ring structure formed by two R groups is aromatic, the ring structure may be fused to the associated phenyl group.

[0017] The anion A is a weakly coordinating anion with a valence of n. n is preferably 1 or 2, and most preferably 1. Weakly coordinating anions are those whose coordination to the associated cation is weaker than that of the surrounding solvent molecules. The coordination strength of the anion is conveniently determined by forming a tri-n-octylammonium salt of the anion, dissolving the salt in carbon tetrachloride, and measuring the NH stretching frequency by infrared spectroscopy using a method such as described in the following literature: J. Am. Chem Soc. 2006, 128, 8500-8508. 3000 cm -1 or larger, especially 3050cm -1 An NH stretching frequency of 100 Å or greater indicates a weakly coordinating anion.

[0018] Examples of weakly coordinating anions include tetrakis[perfluorophenyl]borate, tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triflate (triflate), Al[OC(CF 3 ) 3 ] 4 - 、HCB 11 Me 5 F 6 - , B 12 F 12 2- 、HCB 11 H 5 F 6- , B(OTeF 5 ) 4 - 、Sb(OTeF 5 ) 6 - 、Al[OC(CF 3 ) 3 ] 4 - 、Al[OCH(CF 3 ) 2 ] 4 - and Al[OC(CH 3 )(CF 3 ) 2 ] 4 - .

[0019] Specific examples of phosphonium catalysts include:

[0020]

[0021]

[0022] etc., wherein A is monovalent in each case. + 2 A 2- Also useful are similar compounds of the form wherein Z + represents a phosphonium cation as shown in any one of structures III-XIV and A 2- Represents a divalent weakly coordinating anion.

[0023] In any of the foregoing, A - and A 2- It may be any of the weakly coordinating anions mentioned above, particularly monovalent anions such as tetrakis(perfluorophenyl)borate, tetrakis[3,5-bis(trifluoromethyl)phenyl]borate and triflate (triflate).

[0024] Methods that can be used to prepare phosphonium catalysts of structure I are generally described in J. Am. Chem. Soc. 2021, 143, 15845-15851.

[0025] Generally speaking, symmetrical bis-catechol acid phosphonium catalysts can be prepared by using Catechol or catechol derivatives and PCl 5 In solution in dichloromethane or other suitable solvent to form the corresponding chlorophosphane Reaction with the sodium salt of the A anion or other suitable salt such as sodium tetrakis(pentafluorophenyl)borate produces the phosphonium catalyst.

[0026] The asymmetric phosphonium catalyst of structure I can be prepared by making a catalyst having structure Catechol or catechol derivatives and PCl 5 in solution in dichloromethane or other suitable solvent to produce The compound is further prepared by reacting with a compound having the structure A second but different catechol or catechol derivative is reacted wherein each R 5 Defined in the same way as R to produce chlorophosphine The chlorophosphane is converted to the phosphonium catalyst by reaction with the sodium salt of the A anion or other suitable salt such as sodium tetrakis(pentafluorophenyl)borate.

[0027] Compounds of structure II can be synthesized similarly by reacting an appropriately substituted biphenol with PCl 5 Reaction affords the intermediate phosphorus chloride, which is metathesized by its salt with tetrakis(perfluorophenyl)borate base to provide the desired product.

[0028] Alkoxylation is carried out in the presence of one or more initiator compounds. The initiator compound has one or more functional groups that can be alkoxylated. The initiator can contain any large number of such functional groups. These functional groups can be, for example, primary hydroxyl, secondary hydroxyl or tertiary hydroxyl or thiol. Preferred initiators contain 1 or more such functional groups, preferably 2 or more such functional groups, and can contain up to 12 or more such functional groups.

[0029] In certain embodiments, these functional groups are all hydroxyl groups.In some embodiments, the initiator compound will have 2 to 8, 2 to 6, 2 to 4, or 2 to 3 hydroxyl groups.

[0030] The equivalent weight per functional group of the initiator compound is less than the equivalent weight per functional group of the polyether product. Its equivalent weight can be from 9 g / equivalent (with respect to water) to 6000 g / equivalent or greater. When the initiator compound is a low equivalent alcohol or polyol (e.g., at most 500 g / equivalent, at most 250 g / equivalent, at most 125 g / equivalent and in particular at most 80 g / equivalent) and therefore has a high concentration of hydroxyl groups before alkoxylation, the present invention has particular advantages. The equivalent weight of an alcohol or polyol is conveniently determined using a titration method such as ASTM 4274-16, which produces a hydroxyl number in the form of mg KOH / g polyol, which can be converted into an equivalent weight using the following relationship: equivalent weight = 56,100 ÷ hydroxyl number.

[0031] Suitable initiators include vinyl alcohol, propenyl alcohol, allyl alcohol, acrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, C 1-50 Alkanol, cyclohexanol, water, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butylene glycol, 1,6-hexanediol, 1,8-octanediol, cyclohexanedimethanol, glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, xylitol, mannitol, maltitol, sucralose, phenol, alkylphenol, polyphenol initiator (such as bisphenol A) and 1,1,1-tris(hydroxyphenyl)ethane, etc. If necessary, any two or more of the above initiators can be used together.

[0032] The cyclic oxide is characterized by having at least one 3-membered ring structure, 4-membered ring structure or 5-membered ring structure containing an oxygen atom in the ring structure. Particularly preferred cyclic oxides are ethylene oxides with a three-membered oxygen-containing ring. The cyclic oxide can be, for example, ethylene oxide, 1,2-propylene oxide (commonly referred to herein as "propylene oxide"), oxetane, 1,2-butylene oxide, 2-methyl-1,2-butylene oxide, 2,3-butylene oxide, tetrahydrofuran, epichlorohydrin, hexylene oxide, octane oxide, styrene oxide, divinylbenzene dioxide, glycidyl ether (such as bisphenol A diglycidyl ether), epichlorohydrin or other polymerizable ethylene oxides. In some embodiments, the alkylene oxide is propylene oxide, ethylene oxide or a mixture thereof, including, for example, a mixture of at least 50% by weight (preferably at least 80% by weight) of propylene oxide and correspondingly up to 50% by weight (preferably up to 20% by weight) of ethylene oxide. In some embodiments, two or more alkylene oxides are polymerized simultaneously (to form a random copolymer), and either the composition of the alkylene oxide is changed one or more times throughout the polymerization process, or even continuously, to form block copolymers and / or random / block copolymers.

[0033] The alkoxylation is carried out by combining the initiator and the phosphonium catalyst with the cyclic oxide and optional comonomer and subjecting the resulting reaction mixture to reaction conditions. The catalyst may be added as a solution in a solvent. Such solvents are preferably inert under the conditions of the alkoxylation reaction. Dichloromethane and dichloroethane are useful solvents for the phosphonium catalyst.

[0034] The polymerization is carried out in a temperature range of -100 ° C to 250 ° C or higher. In some embodiments, the reaction temperature is at least 80 ° C, at least 100 ° C, at least 120 ° C, at least 130 ° C or at least 150 ° C. The polymerization temperature is preferably no more than 190 ° C, and more preferably no more than 180 ° C. An important advantage of the phosphonium catalyst used in the present invention is that they perform well at higher temperatures, particularly 150 ° C to 200 ° C or 150 ° C to 180 ° C without premature deactivation. Higher temperatures promote faster reactions. In addition, the ability to operate at these higher temperatures allows the method to be used with initiators and / or cyclic oxides that have a slightly high melting temperature (such as sorbitol, xylitol, mannitol, maltitol and sucralose) and / or are viscous at lower temperatures, or have limited solubility in cyclic oxides at lower temperatures like sorbitol and glycerol.

[0035] The alkoxylation reaction is generally carried out under superatmospheric pressure, but can also be carried out at atmospheric pressure or even subatmospheric pressure.

[0036] Sufficient phosphonium catalyst is used to provide a commercially reasonable alkoxylation rate, but it is generally desirable to use as little phosphonium catalyst as possible consistent with a reasonable alkoxylation rate because this reduces the cost of the catalyst and does not require removal of catalyst residues from the product. The amount of phosphonium catalyst can be, for example, sufficient to provide 10 ppm to 10,000 ppm by weight of phosphonium catalyst based on the weight of the initiator. In a specific embodiment, on the basis of the foregoing, the amount of phosphonium catalyst can be sufficient to provide at least 25 ppm, at least 50 ppm, or at least 100 ppm of catalyst, and also on the basis of the foregoing, can be sufficient to provide up to 1,000 ppm or up to 500 ppm of aluminum. The weight of the phosphonium catalyst includes the weight of both the cation and the associated anion.

[0037] The alkoxylation reaction can be carried out batchwise, semi-continuously (including continuous addition of the starter, as described in US Pat. No. 5,777,177), or continuously.

[0038] The alkoxylation reaction can be carried out in any type of vessel suitable for the pressures and temperatures encountered. The reactor should be equipped with means for supplying and / or removing heat, whereby the temperature of the reaction mixture can be maintained within the desired range. Suitable means include various types of jackets for hot fluids, various types of internal or external heaters, and the like. The cooking step of the continuously withdrawn product is conveniently carried out in a reactor which prevents significant backmixing. Plug flow operation in a pipeline or tubular reactor is a preferred manner for carrying out this cooking step.

[0039] The crude product obtained in any of the foregoing methods may contain unreacted cyclic oxides, small amounts of initiator compounds and their low molecular weight alkoxylates, and small amounts of other organic impurities and / or water. Volatile impurities (including unreacted cyclic oxides) should be flashed or stripped from the product. The crude product usually contains catalyst residues. These residues are usually left in the product, but can be removed if necessary. Water and volatiles can be removed by stripping the alkoxylated product.

[0040] The process of the present invention can be used to prepare alkoxylated products having hydroxyl equivalent weights ranging from as low as about 85 g / equivalent to as high as about 8000 g / equivalent or more. The alkoxylated polyols prepared according to the present invention are useful raw materials for preparing polyurethanes and other polymers prepared by reacting alkoxylated polyols with polyisocyanates. These products include a wide variety of porous and non-porous materials whose physical properties can vary from very rigid to highly flexible. The alkoxylated mono-ols produced according to the present invention can be used as surfactants or industrial solvents, among other things. The alkoxylated polyols and mono-ols can be aminated to produce corresponding amine-terminated materials, which in turn are useful raw materials for preparing a variety of materials, including polyureas and cured epoxy resins.

[0041] In a specific embodiment, the initiator is a polyol having a hydroxyl equivalent weight of 125 g / equivalent or less, particularly 75 g / equivalent or less or even 50 g / equivalent or less, and alkoxylation is continued to produce an alkoxylation product having 1 to 12, particularly 1 to 10, 1 or 5 or 1 to 3 polymerized cyclic oxide units per hydroxyl group on the initiator. The number average molecular weight of the alkoxylation product can be, for example, 100 g / mol to 1000 g / mol, 100 g / mol to 8500 g / mol, 150 g / mol to 800 g / mol or 200 g / mol to 800 g / mol. In such specific embodiments, the cyclic oxide is preferably 1,2-propylene oxide, ethylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, epichlorohydrin or a mixture of any two or more thereof, wherein 1,2-propylene oxide, ethylene oxide or a mixture thereof is particularly preferred. The initiator in such an embodiment is most preferably one or more of glycerol, trimethylolpropane, trimethylolethane, erythritol, pentaerythritol, sorbitol and sucrose. Such products can be used as raw materials for preparing rigid polyurethane and / or polyisocyanurate polymers (including foams).

[0042] In some embodiments, the cyclic oxide is polymerized with one or more copolymerizable monomers that are not cyclic oxides or is polymerized in the presence of it. Examples of such copolymerizable monomers include carbonate precursors that copolymerize with alkylene oxide to produce carbonate bonds in the product. Examples of such carbonate precursors include carbonic acid gas, phosgene, linear carbonates and cyclic carbonates. Other copolymerizable monomers include carboxylic anhydrides that copolymerize with cyclic oxides to produce ester bonds in the product.

[0043] The following examples are provided to illustrate the present invention but are not intended to limit the scope of the present invention. Unless otherwise indicated, all parts and percentages are by weight.

[0044] Examples 1-2 and Comparative Samples AC

[0045] Bis(Catechol)phosphonium tetrakis(pentafluorophenyl)borate (PCat 2 ) was prepared according to the method described in the following document: J.Am.Chem.Soc.2021,143,15845-15851.

[0046] 45 grams of initiator as indicated in Table 1 were charged into a semi-batch reactor equipped with an agitator, a temperature controller, a nitrogen feed line and a monomer feed line, and a vent. The catalyst was added to the initiator as a solid. The type and amount of catalyst (based on the initiator) are as indicated in Table 1. The reactor was purged with nitrogen and heated to the temperature indicated in Table 1 under stirring, and then purged with nitrogen again to remove any solvent from the catalyst addition. While maintaining the same temperature, propylene oxide was then fed into the reactor as needed to try to maintain the target propylene oxide partial pressure as indicated in Table 1. The target amount of propylene oxide to be added was about 103 g for polyols initiated by glycerol and 150 g for polyols initiated by sorbitol; the actual feed amounts are indicated in Table 1. The time required to feed propylene oxide (run time) is indicated in Table 1. Upon completion of the monomer feed, the reactants were digested at 160°C for 2 hours and then cooled to 50°C under a nitrogen purge. After purging with nitrogen at 50 °C for 10 min, the product was collected and the yield was calculated. The M of the product was analyzed by gel permeation chromatography against polystyrene standards. n and polydispersity.

[0047] The activity of the catalysts was compared by calculating the turnover frequency (TOF) in each case. TOF reflects the number of propylene oxide molecules converted per catalytic site per unit time, as follows:

[0048]

[0049] Higher values ​​indicate higher catalyst activity.

[0050] In Table 1, KOH represents potassium hydroxide, and BF 3 ·OEt 2 It stands for boron trifluoride etherate.

[0051] Table 1

[0052]

[0053] * Not an example of the present invention. "ND" means not determined. "Gly" means glycerol. "Sorb" means sorbitol.

[0054] "PO Partial Pressure" is the target PO partial pressure in the reactor during polymerization. "Run Time" indicates the time required to feed the indicated amount of propylene oxide. "PO Feed" indicates the total amount of propylene oxide fed during the indicated run time. "TOF" is the turnover frequency. PDI is the polydispersity index, i.e., the weight average molecular weight divided by the number average molecular weight.

[0055] Molecular weight is measured by GPC relative to polystyrene standards.

[0056] As indicated by the data in Table 1, the catalysts of the present invention are extremely active compared to the controls. The turnover frequency range is about 500 to 650 times that of KOH, an industrial workhorse propylene oxide polymerization catalyst. The greater catalytic activity results in significantly reduced run times, effectively increasing the production capacity of the manufacturing equipment in proportion. The molecular weight and polydispersity are similar to those obtained in the KOH-catalyzed run (Comparative Example A).

[0057] Parallel Pressure Reactor (PPR) Polymerization Procedure

[0058] Ethylene oxide polymerization was performed using a 48-well Symyx Technologies parallel pressure reactor (PPR). Each of the 48 wells was equipped with an individually weighed glass insert with an internal working liquid volume of approximately 5 mL. Each of the wells contained an overhead paddle stirrer.

[0059] 0.7 mL of glycerol / PCat 2 The mixture (containing about 0.72 g of initiator) was loaded into the insert. The mixture provided about 500 ppm by weight of catalyst based on the combined weight of initiator and ethylene oxide used in the polymerization run. The well was pressurized with 50 psig (344.7 kPa) of nitrogen and then heated to a polymerization temperature of 160° C. Upon reaching the polymerization temperature, 0.67 mL of ethylene oxide was injected into the well, where it reacted with the initiator in the glass insert.

[0060] An additional 0.67 mL of ethylene oxide was injected one hour after the start of polymerization and again after the second hour of polymerization. Four hours after the first injection of ethylene oxide, the well was cooled to room temperature and vented. The glass insert was allowed to stand overnight at 40° C. to 50° C. under nitrogen to allow the residual ethylene oxide to volatilize, after which the insert was weighed to determine the amount of product.

[0061] The molecular weight and polydispersity (M) of the obtained products were analyzed by gel permeation chromatography against polystyrene standards. w / M n ).

[0062] Polymerization at 160°C resulted in 82% conversion of ethylene oxide to polymer. The number average molecular weight of the product was 280 and the polydispersity was 1.01.

Claims

1. An alkoxylation method, the alkoxylation method include: (Step I) forming a reaction mixture comprising a) a starter compound having at least one hydroxyl or thiol group; b) at least one cyclic oxide; and c) a catalytically effective amount of a phosphonium catalyst having the following structure: wherein each R is independently hydrogen, halogen, unsubstituted or inertly substituted C 1-12 Alkoxy, aryloxy, unsubstituted or inertly substituted linear, branched and / or cyclic alkyl and unsubstituted or inertly substituted aryl, wherein any two R groups can form a ring structure together, A represents a weakly coordinating anion and n represents the valence of A; and (step II) reacting the cyclic oxide with the initiator compound in the presence of a phosphonium biscatecholate catalyst to form an alkoxylated initiator product.

2. The alkoxylation process according to claim 1, wherein the phosphonium catalyst has any one of the following structures:

3. The alkoxylation process according to claim 1 or 2, wherein A is selected from the group consisting of tetrakis[perfluorophenyl]borate, tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triflate, Al[OC(CF 3 ) 3 ] 4 - 、HCB 11 Me 5 F 6 - 、HCB 11 H 5 F 6 - , B(OTeF 5 ) 4 - 、Sb(OTeF 5 ) 6 - 、Al[OC(CF 3 ) 3 ] 4 - 、Al[OCH(CF 3 ) 2 ] 4 - and Al[OC(CH 3 )(CF 3 ) 2 ] 4 - .

4. The alkoxylation process according to any preceding claim, wherein the phosphonium catalyst is 5. The alkoxylation process according to claim 4, wherein A is tetrakis(perfluorophenyl)borate, tetrakis[3,5-bis(trifluoromethyl)phenyl]borate or triflate.

6. The alkoxylation process according to claim 1, wherein A is B 12 F 12 2- And n is 2.

7. The alkoxylation process according to any preceding claim, wherein the starter compound has an equivalent weight of 80 g / equivalent or less.

8. The alkoxylation process according to any preceding claim, wherein the initiator is one or more of the following: vinyl alcohol, propenyl alcohol, allyl alcohol, acrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, C 1-50 Alkyl alcohol, cyclohexanol, water, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butylene glycol, 1,6-hexanediol, 1,8-octanediol, cyclohexanedimethanol, glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, sucrose, xylitol, mannitol, maltitol, sucralose, phenol, alkylphenols, bisphenol A and 1,1,1-tris(hydroxyphenyl)ethane.

9. The alkoxylation process according to any preceding claim, wherein the cyclic oxide is ethylene oxide.

10. The alkoxylation method according to claim 10, wherein the cyclic oxide is one or more of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide and 2,3-butylene oxide.

11. The alkoxylation process according to any preceding claim, wherein step II is carried out at a temperature of from 150°C to 200°C.

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