WO2022076208A1

WO2022076208A1 - Method of making an amphiphilic oxetane oligomer

Info

Publication number: WO2022076208A1
Application number: PCT/US2021/052482
Authority: WO
Inventors: Matthew E. BELOWICH; Mari S. ROSEN; Eric Wasserman
Original assignee: Dow Global Technologies Llc
Priority date: 2020-10-06
Filing date: 2021-09-28
Publication date: 2022-04-14

Abstract

In an aspect, a method for preparing an amphiphilic oxetane oligomer, comprises reacting a reaction mixture comprising oxetane, an alcohol, and a triflate catalyst comprising a rare earth trifluoromethanesulfonate salt to form the amphiphilic oxetane oligomer; wherein a molar ratio of the oxetane to the alcohol is 50:1 to 1:1 or wherein the amphiphilic oxetane oligomer has the formula R(O-(CH2CH2CH2O)n-H)m, wherein n is an integer of 1 to 50, or 2 to 20; m is 1 to 10, or 1 to 4; and R is a fragment of the alcohol.

Description

METHOD OF MAKING AN AMPHIPHILIC OXETANE OLIGOMER

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Patent Application Serial No. 63/088,090 filed October 6, 2020. The related application is incorporated herein in its entirety by reference.

BACKGROUND

[0001] Amphiphilic compounds comprise a more hydrophilic moiety and a more hydrophobic moiety. These compounds are commonly used as surfactants, emollients, and emulsifiers in a variety of different industries. Polyethers, such as polyethylene glycol), are commonly used components that make up the hydrophilic moiety of the amphiphilic compounds. Oligomerization of such components though is difficult to control and the uncontrolled oligomerization to form these components leads to a broad distribution in the molecular weight of the product and the increased concentration of components that add zero or negative performance in the desired application, for example, in cleaning.

[0002] It would be useful to replicate the features of the ethylene oxide and propylene oxide repeat units with the trimethylene oxide repeat unit as the parent diol, 1,3 -propanediol, can be prepared from renewable raw materials. Unfortunately though, the controlled addition of oxetane to fatty alcohols to form amphiphilic materials with a low amount of unwanted side products has proven difficult to obtain. Therefore, improved methods of preparing amphiphilic oxetane compounds are desired.

BRIEF SUMMARY

[0003] Disclosed herein is a process for the preparation of an amphiphilic oxetane compound.

[0004] In an aspect, a method for preparing an amphiphilic oxetane oligomer, comprises reacting a reaction mixture comprising oxetane, an alcohol, and a triflate catalyst comprising a rare earth trifluoromethanesulfonate salt to form the amphiphilic oxetane oligomer; wherein a molar ratio of the oxetane to the alcohol is 50: 1 to 1 : 1 or wherein the amphiphilic oxetane oligomer has the formula R(O-(CH2CH2CH2O)_n-H)_m, wherein n is an integer of 1 to 50, or 2 to 20; m is 1 to 10, or 1 to 4; and R is a fragment of the alcohol. [0005] In another aspect, a reaction product comprising the amphiphilic oxetane oligomer comprises less than or equal to 5 mole percent of oxetane by-products based on the total moles of reaction products in the reaction product.

[0006] The above described and other features are exemplified by the following detailed description and claims.

DETAILED DESCRIPTION

[0007] Amphiphilic compounds of trimethylene oxide, for example, of the formula R-O-(CH2CH2CH2O)_n-H, can be prepared by the condensation polymerization of 1,3 -propanediol (PDO) or by the ring-opening polymerization of oxetane and reacting an end group with a hydroxyl group of a hydrophobic compound. Methods of producing such compounds though generally exhibit poor conversion and/or selectivity values and are unable to produce a more controlled polymerization. For example, condensation oligomerization of 1,3 -propanediol in the presence of R-OH makes a mixture of products that includes molecules having the trimethylene oxide repeat units capped with the R unit. This process though, typically achieved by dehydration at high temperatures using strong acids, also generates a significant amount of byproducts including R-O-R, R-O-(CH2CH2CH2O)_n-R, and HO-(CH2CH2CH2O)_n-H, which are very difficult to remove from the mixture and can detract from the performance of the product. For example, the dimeric monoether from the hydrophobic alcohol is unlikely to be soluble in aqueous formulations and can therefore create an undesirable turbidity. Moreover, prior processes tend to be uncontrolled in that they generally form amphiphilic compounds having a relatively broad distribution in the degree of polymerization, for example, having poly dispersity indexes of 2 or more. Thus, there is a need for a better process to make the oligomer in high purity and with a narrow mass distribution.

[0008] An improved method of preparing amphiphilic oxetane oligomers was discovered. The method includes the ring opening polymerization of oxetane in the presence of an alcohol and a catalyst comprising a rare earth trifluoromethanesulfonate salt (referred to herein as a triflate catalyst). This method can result in both a high selectivity for the amphiphilic oxetane oligomers with a high conversion of the oxetane. The method can result in an amphiphilic oxetane oligomer with a narrower distribution in the molecular weight range. The method can have a more controlled oligomerization and reaction with the alcohol as is observed by a good agreement between the predicted and actual degree of polymerization.

[0009] The method can result in a reduced amount of undesired oxetane by-products that could otherwise have a negative effect on a desired formulation property. For example, if the amphiphilic oligomer is used in a cleaning composition, the presence of oxetane by-products could reduce the desired cleaning ability relative to the same cleaning composition but without the oxetane by-products. Conversely, the oxetane by-product may not affect on the cleaning ability, but its presence may require more of the reaction product to be added in order to obtain a cleaning composition having the same cleaning ability as is the oxetane by-product was not there.

[0010] The tritiate catalyst can comprise a tritiate (i.e. trifluoromethane sulfonate) of the formula M(O3SOCF3)3, where M is at least one of lanthanum, a lanthanide atom taken from elements of atomic number 58-71, scandium, or yttrium in its 3+ oxidation state. M can comprise at least one of lanthanum, scandium, or samarium.

[0011] The alcohol can comprise at least one of an alkyl alcohol, an alkoxylated alcohol, or a polyglycol. The alcohol can comprise a monohydric alcohol, a diol, or a polyol. The alcohol can comprise one or more primary hydroxyl groups.

[0012] The alcohol can comprise the alkyl alcohol. The alkyl alcohol can have the formula: ROH, wherein R is a linear or branched alkyl group containing 4 to 30 carbon atoms, or 8 to 22 carbon atoms, or 8 to 18 carbon atoms. The alkyl alcohol can comprise a linear alkyl alcohol. The alkyl alcohol can comprise 1 or more alkyl alcohols of the formula ROH. The alkyl alcohol can comprise at least one of capryl alcohol, lauryl alcohol, capric alcohol, undecanol, myristyl alcohol, cetyl alcohol, or stearyl alcohol (1 -octadecanol).

[0013] The alcohol can comprise a diol. The diol can have the formula HO-(CH2)_X-OH, where x is an integer of 2 to 20, or 6 to 12. The diol can comprise at least one of a dialkanolamine (for example, diethanolamine or methyl diethanolamine), a cycloalkane diol (for example, cyclohexane diol or a cyclohexanedialkanol), an alkylene glycol (for example, propylene glycol, ethylene glycol, butylene glycol, or hexamethylene glycol), or a branched diol (for example, ethane- 1,1 -diol, propane- 1,2-diol, 2-methyl-butane- 1,3-diol, pentane- 1,4-diol, 2, 2-dimethyl- 1,3 -propanediol, or 2,5-dimethylhexane-l,3-diol).

[0014] The alcohol can comprise a polyol. The polyol can have an average functionality or 2 to 8, or 2 to 5, or 2 to 4. The polyol can have an average hydroxyl number of 20 to 100 milligrams of potassium hydroxide per gram of polyol (mg KOH/g), or 20 to 70 mg KOH/g. The polyol can comprise at least one of a polyester polyol or a polyether polyol. The polyol can comprise a high molecular weight polyol having a weight average molecular weight of greater than 500 grams per mole. The high molecular weight polyol can comprise the reaction product of glycerol and a poly(alkylene glycol) (for example, poly(tetramethylene glycol), polypropylene glycol), or poly(ethylene glycol)). The polyol can comprise a low molecular weight polyol having a molar mass of less than or equal to 500 grams per mole, for example, comprising at least one of glycerol, trimethylolpropane, a hexane triol, meso erythritol, xylitol, pentaerythritol, or triethanolamine.

[0015] The alcohol can comprise an alkoxylated alcohol. The alkoxylated alcohol can have the formula A: RO(CH2CH(CH3)O)_a(CH2CH2O)b(CH2CH(CH3)O)_cH, wherein a is an integer of 0 to 8, b is an integer of 1 to 20, and c is an integer of 0 to 20. The alcohol can comprise a polyglycol. The polyglycol can have the formula B: HO(CHRiCH2)dO(CH2CHR2O)_e(CH2CHRiO)dH, where each d independently is an integer of 0 to 30, e is an integer of 2 to 40, and Ri is a hydrogen atom, a methyl group, or an ethyl group.

[0016] The reaction mixture can comprise at least one of an additional cyclic ether or a residue of an additional cyclic ether. The additional cyclic ether can comprise at least one of tetrahydrofuran, ethylene oxide, propylene oxide, glycidol, or a Ci-8 alkyl glycidyl ether. The additional cyclic ether can be reacted concurrently with the oxetane or can be reacted before or after the reaction of the oxetane in preceding or in subsequent reaction steps.

[0017] The reaction mixture can comprise additional components such as co-catalysts, solvents, or the like so long as they do not adversely affect the reaction. Examples of suitable solvents include ethers (for example, 1,2-dimethoxy ethane) or polar aprotic solvents (for example, dimethyl sulfoxide or hexamethylphosphoramide)

[0018] The reaction mixture can be anhydrous in that the reaction mixture can comprise less than or equal to 10 weight percent, or less than 5 weight percent, or 0 to 2 weight percent of water based on the total weight of the reaction mixture. The reaction can be performed in a nitrogen atmosphere or an argon atmosphere.

[0019] A molar ratio of the oxetane to the alcohol can be 50: 1 to 1 :1, or 10:1 to 1: 1, or 10:1 to 2: 1, where the molar ratio is calculated on the basis of the total moles of the hydroxyl groups of the alcohol. A molar ratio of the oxetane to the alcohol can be 50: 1 to 1 : 1, or 20: 1 to 2: 1, or 5 : 1 to 2: 1, where the molar ratio is calculated on the basis of the total moles of the hydroxyl groups of the alcohol. A molar ratio of the tritiate catalyst to the alcohol can be 1 :20 to 1 :2,000, or 1 :20 to 1 :500, wherein the ratio is calculated on the basis of total moles of hydroxyl groups of the alcohol.

[0020] The order of addition of the components to form the reaction mixture is not particularly limited. For example, the method can include adding the alkyl alcohol and the tritiate catalyst to the reactor and subsequently adding the oxetane. The method can include adding the alkyl alcohol and the oxetane to the reactor and subsequently adding the tritiate catalyst. The method can include adding the oxetane and the tritiate catalyst to the reactor and subsequently adding the alkyl alcohol, though care should be taken in this instance to ensure that oxetane polymerization does not proceed too much before adding the alkyl alcohol. The method can include adding the alkyl alcohol, the oxetane, and the tritiate catalyst simultaneously to the reactor, for example, if the method comprises continuously reacting the reactants.

[0021] The reaction can include agitating the reaction mixture, for example, by stirring. The reaction can occur at a temperature of 20 to 300 degrees Celsius (°C), or 30 to 200 °C, or 85 to 110 °C. The reaction can occur at a pressure of 300 to 1,500 kilopascal (kPa). The reaction can occur at for 0.5 to 72 hours, or 2 to 24 hours, or 4 to 12 hours. After the reaction, the product mixture can be cooled to room temperature, for example, 23 to 26 °C.

[0022] The product mixture can comprise the amphiphilic oxetane oligomer derived from the oxetane and alcohol. The amphiphilic oxetane oligomer can have the formula R-O-(CH2CH2CH2O)_n-H, wherein n is an integer of 1 to 50, or 2 to 20, or 2 to 5; and R is a linear or branched alkyl group containing 8 to 22, or 10 to 15 carbon atoms. The amphiphilic oxetane oligomer can have the formula R-O-(CH2CH2CH2O)_n-H, wherein n is an integer of 1 to 50, or 2 to 20, or 2 to 5; and R is fragment of alcohol. The amphiphilic oxetane oligomer can have the formula R(O-(CH2CH2CH2O)_n-H)_m, wherein n is an integer of 1 to 50, or 2 to 20, or 2 to 5; m is 1 to 10, or 1 to 4; and R is fragment of alcohol.

[0023] The product mixture can comprise less than or equal to 5 mole percent of oxetane by-products based on the total moles of reaction products in the reaction product. As used herein oxetane by-products include the undesired compounds formed from the reaction. For example, the oxetane by-products can include compounds that are made from the condensation of oxetane molecules by dehydration, for example, when RO(CH2CH2CH2O)_nH reacts with RO(CH2CH2CH2O)_n"H to form the oxetane by-product of RO(CH2CH2CH2O)(n₊n')R. [0024] The amphiphilic oxetane oligomer can be converted to a sulfate salt to form an anionic oxetane oligomer. For example, anionic oxetane oligomer can be formed by converting the amphiphilic oligomer to a half ester of sulfuric acid and neutralizing it with a salt, for example, a sodium salt. The anionic oxetane oligomer can have the formula R((OCH2CH₂CH2)n-OSO3X)_m, where R, m, and n are defined above and X is sodium, potassium, ammonium, or magnesium. The anionic oxetane oligomer can have the formula R-(OCH2CH2CH2)_n-OSO3X, where R and n are defined above and X is sodium, potassium, ammonium, or magnesium.

[0025] A method for preparing an amphiphilic oxetane oligomer can comprise reacting a reaction mixture comprising oxetane, an alcohol, and a tritiate catalyst comprising a rare earth trifluoromethanesulfonate salt to form the amphiphilic oxetane oligomer. A molar ratio of the oxetane to the alcohol can be 50: 1 to 1 : 1 or the amphiphilic oxetane oligomer have the formula R(O-(CH2CH2CH2O)_n-H)_m, wherein n is an integer of 1 to 50, or 2 to 20; m is 1 to 10, or 1 to 4; and R is a fragment of the alcohol. The tritiate catalyst can comprise a tritiate of the formula M(O3SOCF3)3, where M is at least one of lanthanum, a lanthanide atom taken from elements of atomic number 58 to 71, scandium, or yttrium in its 3+ oxidation state. M can comprise at least one of lanthanum, scandium, or samarium. A molar ratio of the tritiate catalyst to the alcohol is 1 :20 to 1 :2,000, or 1 :20 to 1 :500, when calculated on the basis of total moles of hydroxyl groups of the alcohol. A molar ratio of the oxetane to the alcohol can be 10: 1 to 1 : 1, or 10: 1 to 2: 1, when calculated on the basis of total moles of hydroxyl groups of the alcohol. The alcohol can comprise an alkyl alcohol having the formula ROH, wherein R is a linear or branched alkyl group containing 4 to 30, or 8 to 22, or 8 to 18 carbon atoms. The alcohol can comprise a linear alkyl alcohol. The alcohol can comprise at least one of capryl alcohol, lauryl alcohol, capric alcohol, undecanol, myristyl alcohol, cetyl alcohol, or stearyl alcohol. The alcohol can comprise at least one of a diol or a polyol (for example, glycerol). The diol can have the formula HO-(CH2)_X-OH, where x is an integer of 2 to 20, or 6 to 12. The alcohol can comprise an alkoxylated alcohol. The alkoxylated alcohol can have the formula A. The alcohol can comprise a polyglycol. The polyglycol can have the formula B. The reaction mixture can further comprise at least one of an additional cyclic ether or a residue of an additional cyclic ether. The additional cyclic ether can comprise at least one of tetrahydrofuran, ethylene oxide, propylene oxide, or a Ci-8 alkyl glycidyl ether. The reaction mixture can comprise less than or equal to 10 weight percent, or less than 5 weight percent, or 0 to 2 weight percent of water based on the total weight of the reaction mixture. The reacting can occur in a nitrogen atmosphere or an argon atmosphere. The reacting can occur under agitation. The amphiphilic oxetane oligomer can comprise an amphiphilic oxetane oligomer having the formula R-O-(CH2CH2CH2O)_n-H; wherein n is an integer of 1 to 50, or 2 to 20, or 2 to 5; and R is a linear or branched alkyl group containing 4 to 30, or 8 to 22, or 8 to 18 carbon atoms. The amphiphilic oxetane oligomer can comprise an amphiphilic oxetane oligomer having the formula R-O-(CH2CH2CH2O)_n-H; wherein n is an integer of 1 to 50, or 2 to 20, or 2 to 5; and R is a residue of a polyol, an alkoxylated alcohol, or a polyglycol. The reacting can occur at a temperature of 20 to 300 °C, or 30 to 200 °C, or 85 to 110 °C. The reacting can occur for 0.5 to 72 hours, or 2 to 24 hours, or 4 to 12 hours. The method can further comprise converting the amphiphilic oxetane oligomer to a sulfate salt.

[0026] The amphiphilic oxetane oligomer can be reacted with a reactant mixture comprising an isocyanate and optionally a polyol to form a polyurethane. The amphiphilic oxetane oligomer can be used as at least one of a solvent, an emollient, an emulsifier, a dispersant, a stabilizer, or a surfactant. The amphiphilic oxetane oligomer can be used as a sensory agent, a foam controlling agent, or a wetting agent. The amphiphilic oxetane oligomer can aide in the dispersion of various particles or pigments in a product formulation. The amphiphilic oxetane oligomer can aide in cleaning a substrate.

[0027] A product formulation can comprise the amphiphilic oxetane oligomer or a fragment thereof. The product formulation can be a personal care product. For example, the personal care product can be a cosmetic (for example, a lipstick), a hair product (for example, a shampoo, a conditioner, a conditioning shampoo, a hair coloring product, a hair relaxer, a styling gel, or a mousse), a shaving cream, a cleanser (for example, a body wash or a bar soap), a skincare product (for example, a lotion, a cream, an ointment, an acne product, a bronzer, or a sunscreen), an antiperspirant, or a deodorant. The product formulation can comprise 1 to 50 weight percent, or 5 to 20 weight percent of the amphiphilic oxetane oligomer or a fragment thereof based on the total weight of the product formulation.

[0028] The personal care product can comprise the amphiphilic oxetane oligomer or a fragment thereof and additional components, for example, at least one of an emollient, a carrier, a surfactant, a preservative, a perfume, a humectant, a solvent, a sunscreen material, an alpha hydroxy acid, an anti-aging additive, an antimicrobial, a vitamin, a skincare agent, a phospholipid, a vesicle-containing formulation, a botanical extract, a skin whitener, a skin repair compound, caffeine, a cooling additive, an insect repellant, an essential oil, a pigment, a dye, or the like.

[0029] The personal care product can be made by conventional emulsification and mixing methods. For example, the personal care product can be formed by adding the amphiphilic oxetane oligomer or a fragment thereof (i) to an oil phase that is then added to the aqueous phase, or (ii) to both the combined oil and water phases, or (iii) to the water phase that is then added to the oil phase. In all of these methods, the resulting mixture can then be emulsified using standard techniques. Vigorous mixing and the use of moderately elevated temperatures can be used before, during, or after the respective adding steps.

[0030] The personal care product can be made by an inverse emulsification method, whereby the amphiphilic oxetane oligomer or a fragment thereof is added to either the oil phase or the aqueous phase, and the aqueous phase is mixed into the oil phase to initially form a water in oil emulsion. Aqueous phase addition is continued until the system inverts to form an oil in water emulsion. Vigorous mixing and the use of moderately elevated temperatures can be combined if desired. Heating can be carried out during or after the addition of the aqueous phase and before, during, or after inversion. High intensity mixing can be carried out during or after the addition of the aqueous phase, and before or during inversion.

[0031] The personal care product can be a microemulsion or a nanoemulsion, for example, having a mean droplet size of 10 to 10,000 nanometers (nm), or 100 to 1,000 nm, or 300 to 600 nm.

[0032] The following examples are provided to illustrate the present disclosure. The examples are merely illustrative and are not intended to limit devices made in accordance with the disclosure to the materials, conditions, or process parameters set forth therein. Examples

[0033] The components used in the examples are listed in Table 1, where all of the components except the oxetane were purchased from SIGMA-ALDRICH and used as received. The oxetane was obtained from ACROS ORGANICS and stored over activated 4 A molecular sieves prior to use.

[0034] In the examples, proton nuclear magnetic resonance (^XH NMR or NMR) spectra were measured on a VARIAN 400 spectrometer. All samples were measured as solutions in deuterated chloroform (CDCh). 'HNMR chemical shifts are measured in parts per million (ppm) relative to tetramethylsilane and referenced against CDCh (7.16 ppm).

[0035] The degree of polymerization (DP) was determined using the ^XH NMR spectra, where the triplet at about 0.8 ppm, which corresponds to the methyl group of 1- or 2-dodecanol, was set to an integral of 3H. The number of oxetane units is one half the integral value of the multiplet at about 1.8 ppm, which corresponds to the methylene group in the -OCH2CH2CH2O- repeat unit.

[0036] Mass spectroscopy (MS) was performed on samples at a concentration of 1 milligram per milliliter tetrahydrofuran (THF). 0.5 milliliters were injected into AGILENT 6538 LC-qTof MS instrument using an AGILENT ECLIPSE column C18 1.8 micrometers, 3x50 millimeters. The mobile phase A was 0.1 volume percent formic acid in water; the mobile phase B was THF; and the post column phase was: 1 gram ammonium formate per liter of water. The temperature of the system was 45 °C. The flow rate: 0.7 milliliters per minute (mL/min), the post column addition flow was 0.1 mL/min, and the ultraviolet light detection was at 220 nanometers. The mass range was 100 to 1,700 m/z in the extended dynamic range mode.

Examples 1-7: Oxetane polymerization using triflate catalysts

[0037] Oxetane was polymerized using a 48-well SYMYX TECHNOLOGIES Parallel Pressure Reactor (PPR). Each of the 48 wells was equipped with an individually weighed glass insert having an internal working liquid volume of approximately 5 milliliters (mL). The wells each contained an overhead paddle stirrer.

[0038] 0.7 milliliters of an initial mixture of the 1-dodecanol and catalyst was charged to each glass insert. Each well was pressurized with 50 pounds per square inch gauge (psig) (344.7 kilopascal (kPa)) of nitrogen and then heated to the polymerization temperature of 100 °C. Upon reaching the polymerization temperature, 50 volume percent of the total volume of oxetane was injected into each well, where it reacted with the 1 -dodecanol in the glass insert. The internal pressure in the headspace of each well was monitored individually throughout the polymerization. One hour after the first injection, the remaining volume of oxetane was injected. Four hours after the first injection, the wells were allowed to cool to about 50 °C and were vented. The glass inserts were allowed to stand under nitrogen at 50 °C to allow residual monomer to volatilize, after which the inserts were weighed to determine the amount of product.

[0039] The specific amounts and the catalysts used are shown in Table 2 as well as the results, where g stands for grams, cat in mol% stands for mole percent of the catalyst based on the total moles of hydroxyl groups of ROH, conv. stands for the conversion, pred. stands for the predicted degree of polymerization, and n.d. means not determined. The molar equivalence (eq.) of the oxetane was determined by dividing the moles of oxetane by the moles of 1 -dodecanol.

[0040] Table 2 shows that both scandium(III) tritiate and samarium(III) tritiate result in good yields, producing more than 1.4 grams of product, with high conversions, of more than 75%. Comparisons of the reproduced Examples 1-4 and 5-7, using scandium(III) tritiate and samarium(III) tritiate, respectively, show that these results are reproducible. Comparing the predicted degree of polymerization of Examples 3 and 6 to those values measured using NMR and MS show that there is good agreement and thus a good selectivity for the desired amphiphilic oxetane oligomer.

Examples 8-11 : Oxetane polymerization using a borane catalyst [0041] Oxetane was polymerized according to procedure of Example 1, except that the polymerization temperature was 60 °C and the mole percent of the amount of tris(pentafluorophenyl)borane was 0.28 mole percent based on the total moles of hydroxyl groups of ROH. It is noted that amount of catalyst used in these examples is slightly lower because this catalyst tends to be more active than the tritiate catalyst, so less is needed to effect reaction. Also, the reaction temperature was reduced as the borane catalyst is less thermally stable and would otherwise decompose at higher temperatures. The reactant details and results are shown in Table 3.

[0042] Table 3 shows that the borane catalyst had variable conversion values ranging from 37 to 100%. Table 3 also shows that the borane catalyst had a poor selectivity for the surfactant.

Examples 12-15: Oxetane polymerization using an anionic coordination catalyst

[0043] Oxetane was polymerized according to the procedure of Example 1, except that the polymerization temperature was 35 °C and the amount of the tris(pentafluorophenyl)borane was 1 mole percent based on the total moles of hydroxyl groups of ROH. Similar to the borane catalyst, the relative amount of the catalyst and the reaction temperature were selected to ensure the optimum reaction conditions. The reactant details and results are shown in Table 4.

[0044] Table 4 shows that the anionic coordination catalyst was essentially inactive, showing very low degrees of polymerization, low conversion values, and low yields. It is noted that the negative predicted DPs and the negative conversion values result when the recovered mass is less than the mass of starter plus catalyst, which can occur when there is a loss of unreacted starter, for example, due to evaporation when the reactors are opened and vented at high temperature.

Examples 16-23: Oxetane polymerization using a boron trifluoride catalyst

[0045] Oxetane was polymerized according to the procedure of Example 1, except that the polymerization temperature was 35 °C and the amount of the boron trifluoride was 0.28 mol% based on the total moles of hydroxyl groups of ROH. Also, the amount of ROH was increased in Examples 20-23, reducing the oxetane equivalence from 6 to 2, relative to that of Examples 16-19. The reactant details and results are shown in Table 5.

[0046] Table 5 shows that the Lewis acid catalyst had a variable conversion, ranging from 31 to 65% in Examples 16-19 and from 28 to 101% in Examples 20-23, where it is noted that the value of 101% is within the measurement error of a 100% conversion. Table 5 also shows that the Lewis acid catalyst had a poor selectivity for the amphiphilic molecule.

[0047] Set forth below are non-limiting aspects of the present disclosure.

[0048] Aspect 1 : A method for preparing an amphiphilic oxetane oligomer, comprising: reacting a reaction mixture comprising oxetane, an alcohol, and a triflate catalyst comprising a rare earth trifluoromethanesulfonate salt to form the amphiphilic oxetane oligomer; wherein a molar ratio of the oxetane to the alcohol is 50: 1 to 1 : 1 or wherein the amphiphilic oxetane oligomer has the formula R(O-(CH2CH2CH2O)_n-H)_m, wherein n is an integer of 1 to 50, or 2 to 20; m is 1 to 10, or 1 to 4; and R is a fragment of the alcohol.

[0049] Aspect 2: The method of Aspect 1, wherein the triflate catalyst comprises a triflate of the formula M(O3SOCF3)3, where M is at least one of lanthanum, a lanthanide atom taken from elements of atomic number 58 to 71, scandium, or yttrium in its 3+ oxidation state.

[0050] Aspect 3: The method of Aspect 2, wherein M comprises at least one of lanthanum, scandium, or samarium.

[0051] Aspect 4: The method of any one of the preceding aspects, wherein a molar ratio of the triflate catalyst to the alcohol is 1 :20 to 1 :2,000, or 1 :20 to 1 :500, when calculated on the basis of total moles of hydroxyl groups of the alcohol.

[0052] Aspect 5: The method of any one of the preceding aspects, wherein a molar ratio of the oxetane to the alcohol is 10: 1 to 1 : 1, or 10: 1 to 2: 1, when calculated on the basis of total moles of hydroxyl groups of the alcohol.

[0053] Aspect 6: The method of any one of the preceding aspects, wherein the alcohol comprises an alkyl alcohol having the formula ROH, wherein R is a linear or branched alkyl group containing 4 to 30, or 8 to 22, or 8 to 18 carbon atoms.

[0054] Aspect 7: The method of any one of the preceding aspects, wherein the alcohol comprises a linear alkyl alcohol.

[0055] Aspect 8: The method of any one of the preceding aspects, wherein the alcohol comprises at least one of capryl alcohol, lauryl alcohol, capric alcohol, undecanol, myristyl alcohol, cetyl alcohol, or stearyl alcohol. [0056] Aspect 9: The method of any one of the preceding aspects, wherein the alcohol comprises at least one of a diol or a polyol (for example, glycerol); wherein the diol optionally has the formula HO-(CH2)_X-OH, where x is an integer of 2 to 20, or 6 to 12.

[0057] Aspect 10: The method of any one of the preceding aspects, wherein the alcohol comprises an alkoxylated alcohol, wherein the alkoxylated alcohol optionally has the formula RO(CH2CH(CH3)O)_a(CH2CH2O)b(CH2CH(CH3)O)_cH, wherein a is an integer of 0 to 8, b is an integer of 1 to 20, and c is an integer of 0 to 20.

[0058] Aspect 11 : The method of any one of the preceding aspects, wherein the alcohol comprises polyglycol, wherein the polyglycol optionally has the formula HO(CHRiCH₂)dO(CH2CHR2O)_e(CH2CHRiO)_dH, where d is an integer of 0 to 30, e is an integer of 2 to 40, and Ri is a hydrogen atom, a methyl group, or an ethyl group.

[0059] Aspect 12: The method of any one of the preceding aspects, wherein the reaction mixture further comprises at least one of an additional cyclic ether or a residue of an additional cyclic ether; wherein the additional cyclic ether optionally comprises at least one of tetrahydrofuran, ethylene oxide, propylene oxide, or a Ci-8 alkyl glycidyl ether.

[0060] Aspect 13: The method of any one of the preceding aspects, wherein the reaction mixture comprises less than or equal to 10 weight percent, or less than 5 weight percent, or 0 to 2 weight percent of water based on the total weight of the reaction mixture.

[0061] Aspect 14: The method of any one of the preceding aspects, wherein the reacting occurs in a nitrogen atmosphere or an argon atmosphere.

[0062] Aspect 15 : The method of any one of the preceding aspects, wherein the reacting occurs under agitation.

[0063] Aspect 16: The method of any one of the preceding aspects; wherein the amphiphilic oxetane oligomer comprises an amphiphilic oxetane oligomer having the formula R-O-(CH2CH2CH2O)_n-H; wherein n is an integer of 1 to 50, or 2 to 20, or 2 to 5; and R is a linear or branched alkyl group containing 4 to 30, or 8 to 22, or 8 to 18 carbon atoms.

[0064] Aspect 17: The method of any one of the preceding aspects; wherein the amphiphilic oxetane oligomer comprises an amphiphilic oxetane oligomer having the formula R-O-(CH2CH2CH2O)_n-H; wherein n is an integer of 1 to 50, or 2 to 20, or 2 to 5; and R is a residue of a polyol, an alkoxylated alcohol, or a polyglycol.

[0065] Aspect 18: The method of any one of the preceding aspects, wherein the reacting occurs at a temperature of 20 to 300 °C, or 30 to 200 °C, or 85 to 110 °C. [0066] Aspect 19: The method of any one of the preceding aspects, wherein the reacting occurs for 0.5 to 72 hours, or 2 to 24 hours, or 4 to 12 hours.

[0067] Aspect 20: The method of any one of the preceding aspects, further comprising converting the amphiphilic oxetane oligomer to a sulfate salt.

[0068] Aspect 21 : A reaction product comprising the amphiphilic oxetane oligomer prepared by the method of any one of the preceding aspects; wherein the reaction product comprises less than or equal to 5 mole percent of oxetane by-products based on the total moles of reaction products in the reaction product.

[0069] The compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed. The compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any materials (or species), steps, or components, that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.

[0070] As used herein, “a,” “an,” “the,” and “at least one” do not denote a limitation of quantity, and are intended to cover both the singular and plural, unless the context clearly indicates otherwise. For example, "an element" has the same meaning as “at least one element," unless the context clearly indicates otherwise. The term “combination” is inclusive of blends, mixtures, alloys, reaction products, and the like. Also, “at least one of’ means that the list is inclusive of each element individually, as well as combinations of two or more elements of the list, and combinations of at least one element of the list with like elements not named.

[0071] The term “or” means “and/or” unless clearly indicated otherwise by context. Reference throughout the specification to “an aspect,” “another aspect,” “some aspects,” and so forth, means that a particular element (e.g., feature, structure, step, or characteristic) described in connection with the aspect is included in at least one aspect described herein, and may or may not be present in other aspects. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various aspects.

[0072] The endpoints of all ranges directed to the same component or property are inclusive of the endpoints, are independently combinable, and include all intermediate points and ranges. For example, ranges of “up to 25 weight percent, or 5 to 20 weight percent” is inclusive of the endpoints and all intermediate values of the ranges of “5 to 25 weight percent,” such as “10 to 23 weight percent,” etc. Moreover, stated upper and lower limits can be combined to form ranges, for example, “5 to 20 weight percent, or 10 to 15 weight percent” can be combined as the ranges “5 to 15 weight percent,” or “10 to 20 weight percent.”

[0073] Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this disclosure belongs. Compounds are described using standard nomenclature

[0074] All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.

[0075] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.

Claims

CLAIMS What is claimed is:

1. A method for preparing an amphiphilic oxetane oligomer, comprising: reacting a reaction mixture comprising oxetane, an alcohol, and a triflate catalyst comprising a rare earth trifluoromethanesulfonate salt to form the amphiphilic oxetane oligomer; wherein a molar ratio of the oxetane to the alcohol is 50: 1 to 1 : 1 or wherein the amphiphilic oxetane oligomer has the formula R(O-(CH2CH2CH2O)_n-H)_m, wherein n is an integer of 1 to 50, or 2 to 20; m is 1 to 10, or 1 to 4; and R is a fragment of the alcohol.

2. The method of Claim 1, wherein the triflate catalyst comprises a triflate of the formula M(O3SOCF3)3, where M is at least one of lanthanum, a lanthanide atom taken from elements of atomic number 58 to 71, scandium, or yttrium in its 3+ oxidation state.

3. The method of any one of the preceding claims, wherein a molar ratio of the triflate catalyst to the alcohol is 1 :20 to 1 :2,000, or 1 :20 to 1 :500, when calculated on the basis of total moles of hydroxyl groups of the alcohol.

4. The method of any one of the preceding claims, wherein a molar ratio of the oxetane to the alcohol is 10: 1 to 1 : 1, or 10: 1 to 2: 1, when calculated on the basis of total moles of hydroxyl groups of the alcohol.

5. The method of any one of the preceding claims, wherein the alcohol comprises an alkyl alcohol having the formula ROH, wherein R is a linear or branched alkyl group containing 4 to 30, or 8 to 22, or 8 to 18 carbon atoms.

6. The method of any one of the preceding claims, wherein the alcohol comprises at least one of a linear alkyl alcohol, capryl alcohol, lauryl alcohol, capric alcohol, undecanol, myristyl alcohol, cetyl alcohol, or stearyl alcohol.

7. The method of any one of the preceding claims, wherein the alcohol comprises at least one of a diol or a polyol (for example, glycerol); wherein the diol optionally has the formula HO-(CH2)_X-OH, where x is an integer of 2 to 20, or 6 to 12.

8. The method of any one of the preceding claims, wherein the alcohol comprises an alkoxylated alcohol, wherein the alkoxylated alcohol optionally has the formula RO(CH2CH(CH3)O)a(CH2CH2O)b(CH₂CH(CH3)O)cH, wherein a is an integer of 0 to 8, b is an integer of 1 to 20, and c is an integer of 0 to 20.

9. The method of any one of the preceding claims, wherein the alcohol comprises polyglycol, wherein the polyglycol optionally has the formula HO(CHRiCH₂)_dO(CH₂CHR₂O)_e(CH₂CHRiO)_dH, where d is an integer of 0 to 30, e is an integer of 2 to 40, and Ri is a hydrogen atom, a methyl group, or an ethyl group.

10. The method of any one of the preceding claims, wherein the reaction mixture comprises less than or equal to 10 weight percent, or less than 5 weight percent, or 0 to 2 weight percent of water based on the total weight of the reaction mixture.

11. The method of any one of the preceding claims, wherein the reacting occurs in a nitrogen atmosphere or an argon atmosphere.

12. The method of any one of the preceding claims, wherein the reacting occurs under agitation; or at a temperature of 20 to 300 °C, or 30 to 200 °C, or 85 to 110 °C; or for 0.5 to 72 hours, or 2 to 24 hours, or 4 to 12 hours.

13. The method of any one of the preceding claims; wherein the amphiphilic oxetane oligomer comprises an amphiphilic oxetane oligomer having the formula R-O-(CH₂CH₂CH₂O)_n-H; wherein n is an integer of 1 to 50, or 2 to 20, or 2 to 5; and R is a linear or branched alkyl group containing 4 to 30, or 8 to 22, or 8 to 18 carbon atoms.

14. The method of any one of the preceding claims; wherein the amphiphilic oxetane oligomer comprises an amphiphilic oxetane oligomer having the formula R-O-(CH₂CH₂CH₂O)_n-H; wherein n is an integer of 1 to 50, or 2 to 20, or 2 to 5; and R is a residue of a polyol, an alkoxylated alcohol, or a polyglycol.

15. A reaction product comprising the amphiphilic oxetane oligomer prepared by the method of any one of the preceding claims; wherein the reaction product comprises less than or equal to 5 mole percent of oxetane by-products based on the total moles of reaction products in the reaction product.