Methods of forming polymers using a catalyst composition

Abstract

Method of forming alcohol ethoxylate polymers using a catalyst. The method comprising reacting an ethylene oxide; and an alcohol which can be selected from butanol, octanol, decanol, docosanol and non

Description

Technical Field The present invention relates to a method of forming high value alcohol ethoxylate polymers by reacting ethylene oxide (EO) with an alcohol in the presence of a catalyst composition. The method of the invention allows alcohol ethoxylates to be formed via an environmentally favourable method. Background Optimising chemical reactions by reducing environmentally taxing reaction processes is currently at the forefront of industrial and academic research. Due to the poor environmental health of the planet, finding sustainable alternatives in processes for the manufacture of high value and widely used chemicals is desirable. Alcohol ethoxylates are a class of non-ionic surfactant polymers formed by an alkoxylation reaction utilised in the chemical industry, ethoxylation. Alcohol ethoxylates find use in a wide range of applications, from household cleaners and laundry detergents to agricultural products, textiles and paints. Alcohol ethoxylates are obtained by chemical synthetic processes, for example by the reaction of an alcohol with EO in the presence of a homogeneous potassium hydroxide (KOH) catalyst. Ethoxylation is an environmentally demanding process and suffers from many drawbacks. This reaction is demanding in energy, for example requiring high reaction temperatures, typically in the range of 160 - 180°C. Pooling is also an issue with conventional ethoxylation processes. Pooling occurs when EO dissolves and accumulates in the reaction medium but does not readily react. This is recognised as a health and safety concern pertaining to for example the KOH catalysed ethoxylation reaction, as the quantity of EO that has reacted with the growing polymer chain is unknown. The progress of such ethoxylation reactions are typically monitored via the pressure within the reactor. Pooling is known to have occurred when the pressure of the reactor spikes during a reaction, signalling that dissolved EO has rapidly evaporated into the gas phase, increasing the pressure within the reactor. Furthermore, a drawback associated with the use of conventional catalysts, for example KOH, is that the polymer product formed as a result of the ethoxylation reaction requires neutralisation using acids, for example acetic, lactic or sulphuric acids. A separation step, to separate salts formed during the neutralisation step, is also necessitated following neutralisation in some instances. Not only do these neutralisation / separation steps significantly increase the cost of performing these reactions on an industrial scale, but they also lend to a decreased environmentally favourable profile of the reaction due to energy and chemical requirements. It would be advantageous to provide a less environmentally taxing route for the synthesis of alcohol ethoxylates. It would be advantageous to provide a synthetic route for the synthesis of alcohol ethoxylates requiring less energy. Furthermore, it would be advantageous to provide a method of ethoxylation that progresses efficiently at a lower temperature. It would also be advantageous to provide a route for the synthesis of alcohol ethoxylates which was not associated with the problem of pooling. It would also be advantageous to provide a route for the synthesis of alcohol ethoxylates which did not require a neutralisation / separation step. It is an aim of the invention to obviate or mitigate one or more of the disadvantages associated with ethoxylation reactions. For instance, it is an aim of this invention to reduce energy requirements; and / or to reduce reaction temperatures; and / or to reduce reaction pressures; and / or to reduce reaction lengths; or any combination thereof. It is an aim of the invention to provide a synthetic method, with a more environmentally favourable synthetic profile, for the production of high value alcohol ethoxylates that is less environmentally demanding. It is an aim of this invention to provide an energy efficient method for the production of alcohol ethoxylate polymers. Summary of the Invention According to a first aspect of the present invention, there is provided a method of forming a polymer which does not have CO2 incorporated in the structure of the polymer, the method comprising reacting ethylene oxide and an alcohol in the presence of a catalyst, wherein the catalyst is a composition comprising a bulk material; and at least one surface; the bulk material comprising ions of a metal M bonded to one another via linker groups; the surface comprising ions of a metal M' bonded to one another via linker groups; the metals M and M' being the same or different; the surface comprising at least one first site A and at least one second, different site B; the site A having a hydroxyl bonded thereto; said site B being a Lewis acid site; said site A being capable of interacting with the EO and alcohol; said site B being capable of interacting with the ethylene oxide and alcohol. As a skilled person would appreciate, an alcohol is defined as an organic compound containing at least one hydroxyl group attached directly to a carbon atom. In an embodiment, the alcohol comprises a C4-C22 hydrocarbon chain. The alcohol may be of the formula R1OH, in which R1 is an optionally substituted C4-C22 hydrocarbon chain, or is a C4-Cs cyclic group or a C4-C8 aromatic group substituted with an optionally substituted C4-C22 hydrocarbon chain. The term "substituted" refers to moieties having substituents replacing a hydrogen atom on one or more non-hydrogen atoms of the molecule. It will be understood that "substitution" or "substituted with" includes the implicit proviso that such substitution is in accordance with permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound, e.g., which does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, etc. Substituents can include for example one or more of hydroxyl and C1-8 alkyl groups. The hydrocarbon chain may be linear or branched. In an embodiment, R1 is a C4-C22 hydrocarbon chain. In an embodiment, R1 is a Cs-Cis hydrocarbon chain. In an embodiment, R1 is a C10-C116 hydrocarbon chain. In an embodiment, R1 is a C12-C14 hydrocarbon chain. In an embodiment the hydrocarbon chain is a linear alkyl chain. Advantageously, linear hydrocarbon chains readily produce micelles which are critical for surfactant behaviour. In an embodiment, the C4-C22 hydrocarbon chain comprises a cyclic or aromatic moiety. For example, the C4-C22 hydrocarbon chain may comprise a pendant cyclic or aromatic moiety. In an embodiment, the cyclic or aromatic moiety is substituted. Examples of alcohols comprising a linear hydrocarbon chain include 1-butanol, 2-butanol, pentanol, hexanol, 1-octanol, 2-octanol, decanol, dodecanol, hexadecanol, docosanol, and nonyl phenol. In an embodiment, the hydrocarbon chain is unsubstituted. In an embodiment, the alcohol may be selected from the group consisting of 1-butanol; 1-octanol; 2-octanol; 1-dodecanol; 1-docosanol; nonyl phenol. In an embodiment, the method comprises: adding the alcohol and the catalyst to a reactor; heating the reactor to an initial reacting temperature; and adding the EO sequentially to maintain a working temperature and reacting to form a polymer. In an embodiment the EO is added portion-wise to the reactor via a mass flow controller from a pre-pressurised EO vessel. The rate of EO addition is controlled to maintain a suitable reactor pressure, for example not exceeding approximately 5 barg. In an embodiment, the initial reacting temperature is between 80°C to 110°C. In an embodiment, the initial reacting temperature is between 85°C to 100°C. In an embodiment, the working temperature is maintained between 80°C to 135°C. In an embodiment, the working temperature is maintained between 90°C to 110°C. In an embodiment, the reacting is carried out for between 1.5 hours and 3.5 hours. In an embodiment, the reacting is carried out for between 2 and 2.5 hours. For the purposes of this method, the reacting is considered to start when the EO is added to the reactor. In an embodiment, the molar ratio of EO to alcohol (EO:alcohol) is from 2:1 to 12:1. In an embodiment, the molar ratio of EO to alcohol (EO:alcohol) is from 4:1 to 10:1. In an embodiment, the mass ratio of the catalyst to alcohol (catalyst:alcohol) is from 0.0005:1 to 0.005:1. In an embodiment, the mass ratio of the catalyst to alcohol (catalyst:alcohol) is from 0.001:1 to 0.004:1. The method of the invention is carried out in the presence of a catalyst. Suitable catalysts for use in the invention, as well as methods of their preparation, are described in detail in WO2021 / 123701 Al and WO2021 / 123761 Al. The general structure of the bulk material and surface structure of the catalyst composition is represented in Figure 2. In an embodiment of the invention, the metal ions M and M' of the catalyst are selected from Sc3+, Cr3+, Al3+and Fe3+. In an embodiment of the invention, the linker groups of the catalyst are of the structure T(R)xy(H)z wherein: T is a multivalent organic moiety; R is a functional group capable of coordinating metal ions M and M'; the functional group being other than H; x is 2 to 6; y is 0 to 4; and z is a number sufficient to occupy the remaining valencies on T. In an embodiment T may be a cycloalkyl, heterocycloalkyl, aryl or heteroaryl ring. In an embodiment, R is CO2H. In an embodiment, the distance d between the site A and site B is such that EO and the alcohol can polymerise on the surface to form the polymer product. In an embodiment, the distance d is between 0.3 and 1 nm. In an embodiment, the distance d is between 0.3 and 0.8 nm. Advantageously, when the distance d between the A site and the B site is between 0.3 and 1 nm, the proximity of the reaction starting materials (EO and alcohol) favours polymerisation in high yields. The distance d can be measured by suitable methods such as X-ray crystallography, as discussed in more detail below. In an embodiment, the catalyst composition has the general formula [Sc3O(OH)(BTC)2] where BTC is benzene-l,3,5-tricarboxylic acid. Advantageously, the inventors have determined that the method of the invention requires less energy (i.e. lower temperature and / or reduced reaction time) in comparison to conventional methods. Brief Description of the Drawings Embodiments of the present invention will now be described by way of example only with reference to the accompanying drawings where like parts are provided with corresponding reference numerals and in which: Figure 1 is a 45Sc magic angle spinning (MAS) NMR spectrum of the catalyst composition prepared in Example 1.1; Figure 2 illustrates the general structure of the bulk material and surface structure of a hybrid platform catalyst composition useful in the methods of the invention, wherein the metal ions M and M' (shown in the Figure as M) are linked by trivalent linkers and showing unoccupied Lewis acid sites B. Figure 3 is an LC-MS spectrum of the EO / C4 polymer prepared according to Example 2.1; Figure 4 is an LC-MS spectrum of the EO / Cs polymer prepared according to Example 2.2; Figure 5 is an LC-MS spectrum of the EO / Cs polymer prepared according to Example 2.3; Figure 6 is an LC-MS spectrum of the EO / C12 polymer prepared according to Example 2.4; Figure 7 is an LC-MS spectrum of the EO / C22 polymer prepared according to Example 2.5; and Figure 8 is an LC-MS spectrum of the EO / nonyl phenol polymer prepared according to Example 2.6. Detailed Description The present invention relates to methods of forming alcohol ethoxylate polymers comprising reacting EO with an alcohol in the presence of the catalyst. The alcohol may be of the formula R1OH and comprise a hydrocarbon chain from C4 - C22. The hydrocarbon chain may be linear or branched. Selection of the alcohol can afford desired properties of the final product; very generally for example, hydrophobicity increasing with increasing alkyl chain length. Polymers with hydrocarbon chains may lead to hydrophobic end-groups being present, which are desirable due to their surfactant-like properties. The inventors have also demonstrated that the method of the invention is applicable and gives desired results when the alcohol has a different R1 group such a cyclic or aromatic group substituted with a hydrocarbon chain. Many of the alcohol ethoxylate polymers formed via this reaction have surfactant-like properties which makes them highly desirable as ingredients for use in a wide range of both consumer and industrial products. The surfactant properties of the polymers can advantageously be adjusted for the intended application, by appropriate selection of the alcohol reactant. For instance, a polymer with increased hydrophobicity can be obtained by increasing the length of the hydrocarbon chain of the alcohol reactant. Conversely, decreasing the length of the hydrocarbon chain of the alcohol, can impart a lower degree of hydrophobicity on the resultant polymer. The polymers formed may be used as replacements for the petrochemically-derived intermediates and products currently used in many applications, for example in the formulation of industrial, personal care and household products. The method of the invention can therefore be used as an environmentally favourable means of producing these high value chemicals. The process of the present invention advantageously provides a method for accessing a wide range of alcohol ethoxylate polymers, whilst production of these materials is carried out in an environmentally friendly manner. The process of the invention requires less energy than traditional ethoxylation processes, e.g. those which use KOH as catalyst, for example by using lower reaction temperatures and / or shorter reaction times. The catalyst used in the process of the invention may also be recycled, unlike conventional catalysts, further adding to the environmentally friendly profile of the process. As the catalyst is a heterogeneous catalyst, it may be recycled multiple times without appreciable loss in catalyst performance. The invention provides a method of forming a polymer which does not have CO2 incorporated in the structure of the polymer, comprising reacting ethylene oxide and an alcohol in the presence of a catalyst, wherein the catalyst is a composition comprising a bulk material; and at least one surface; the bulk material comprising ions of a metal M bonded to one another via linker groups; the surface comprising ions of a metal M' bonded to one another via linker groups; the metals M and M' being the same or different; the surface comprising at least one first site A and at least one second, different site B; the site A having a hydroxyl bonded thereto; said site B being a Lewis acid site; said sites A and B being capable of interacting with the EO and the alcohol. The catalyst composition is described in detail in WO2021 / 123701 Al and WO2021 / 123761 Al, along with methods of its preparation. The catalyst composition may be a crystallite composition. The composition used in the present invention may be in the form of individual, single crystals with control over crystallite size and particle morphology. The catalyst composition comprises a bulk material. Typically, the bulk material comprises ions of a metal M bonded to one another via linker groups, this forming a framework or scaffold. As used herein, the term "crystallite" generally means a small single crystal (i.e., a small single solid material in which the crystal lattice of the material is continuous and unbroken, with no grain boundaries). Single crystal materials should be contrasted with polycrystalline or agglomerate materials which comprise a collection of crystals adhered together. The metal M may be any metal capable of forming ions to which a linkergroup may coordinate to form the bulk material. Examples of such metals include: transition metals, including first 15 row transition metals such as Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn; second row transition metals such as Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag and Cd; third row transition metals such as Hf, Ta, W, Re, Os, Ir, Pt, Au and Hg; lanthanides such as La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu; and p-block metals such as Al, Ga, Ge, In, Sn, TI, Pb and Bi. The metal may be Sc, Cr, Al, or Fe. In an embodiment, the metal is Sc. The metal ions M which coordinate with the linker groups to form the bulk material may be the same or different. In one embodiment, the bulk material comprises ions of only one metal M. In another embodiment, the bulk material comprises ions of a mixture of more than one (preferably 2 to 4, more preferably 2 or 3, most preferably 2) different metals M. In an embodiment, only one metal is used. The metal M may be Sc. In an embodiment, two metals are used (M and M'). The main function of the hydroxyl group of the catalyst, positioned on the surface of the catalyst, is to interact with the epoxide (EO) and the alcohol. In particular, as an epoxide is present, the -OH group of the catalyst, positioned on the surface of the catalyst composition facilitates ring opening of the epoxide group to enable polymerisation to occur on the surface of the catalyst. In addition, the site A is capable of interacting with EO and / or alcohol. The surface of the composition is provided with a sufficient number of hydroxyl groups in sufficient proximity to the B-sites on the surface to enhance the activity of the catalyst towards the polymerisation reactions. As a skilled person would appreciate, the -OH group of the catalyst, positioned on the surface of the catalyst composition, can facilitate ring-opening of the cyclic monomer, allowing the polymer chain to grow therefrom. In the catalyst composition, site B is a Lewis acidic site. In this specification "Lewis acid" takes its normal meaning in the art of an electron pair acceptor. Depending on the intended use of the composition, the Lewis acidic site B may be vacant (unoccupied) or may have a Lewis base bound thereto. The site B is capable of binding the alcohol and the EO. In an embodiment, the Lewis acidic site B is unoccupied. In this embodiment the metal ion is therefore coordinatively unsaturated. By "coordinatively unsaturated" it is meant that not all of the usual coordination sites of the metal ion are occupied. Typically, 1, 2 or 3, in one embodiment 1 or 2, in one embodiment 1 coordination site is unoccupied. By way of example, in the particularly preferred case of the compounds having the general formula [Sc3O(OH)(BTC)2], the Sc3+ ion having a site B on the surface is 5-coordinated rather than the usual 6. Fig. 2 illustrates the general structure of the bulk material and surface structure of a composition for use in the methods of the invention. In this embodiment, the metal ions M and M' are linked by trivalent linkers. The surface metal ions (M') are labelled A and B to illustrate the difference between the sites. In this embodiment, the Lewis acid sites B are unoccupied. The distance d between the A and B sites is important, as explained in more detail below. In the catalyst composition, the distance between sites A and B should be sufficiently close together to allow, in use, the bound EO / alcohol to interact with one another. Therefore, the distance (designated d in Fig. 2) between the metal atom at site A, carrying the hydroxyl group, and the metal atom at site B is such that the EO and alcohol can react together on the surface to form an alcohol ethoxylate polymer. The distance d may vary depending on the nature of the alcohol, the linker group, and the metal ions M' on the surface. In an embodiment, the distance d is between 0.3 and 1 nm. This distance may be measured by known techniques. For example, the distance d may be calculated based on solid-state NMR measurements, for example using the methods and chemical shift standards described in S. Hayashi and K. Hayamizu, Bull. Chern. Soc. Jpn., 1991, 64, 685-687. In one embodiment, the distance d may be determined based on crystallographic data by means of a suitable computational method. As is known to those skilled in the art, suitable crystallographic methods for obtaining the data include X-ray crystallography. One such suitable X-ray crystallographic method is powder diffraction (PDF) analysis. One specific method for carrying out PDF analysis is shown below. In this specific example, the PDF analysis was carried out on a Rigaku R-Axis 3-circle Spider goniometer equipped with a curved Fujifilm® image plate mounted at the window of a graphite monochromated sealed tube silver (Ag Kal / Ka2 = 0.56094 A) generator operating at 1.2 kW (40kV, 30mA). A borosilicate capillary of diameter 1 mm with a 0.01 mm wall thickness was used. A fixed capillary to detector distance of 127.4mm and an exposure time of 84 s per degree w of oscillation. An oscillation w of 84° was used, giving a total collection time of 117.6 minutes. The collected 2D powder pattern was integrated to a ID total scattering pattern using Rigaku 2DP software and transformed to a pair distribution function utilising GudrunX. This is described in more detail in Bi Hinge, S. J. L. Z. Fur Krist. - Cryst. Mater. 2004, 219 (3), 117-121, and in Egami, T. and Billinge, S. J. L. Underneath the Bragg Peaks: Structural Analysis of Complex Materials, Second edition; Pergamon Materials Series; Elsevier: Amsterdam, 2012. Once the crystallographic data has been obtained, the distance d can be obtained from these data using a suitable computational method. One example of such a computational method uses density functional theory (DFT). As is known to the person skilled in the art, in the context of computational materials science, ab initio (from first principles) DFT calculations allow the prediction and calculation of material behaviour on the basis of quantum mechanical considerations, without requiring higher-order parameters such as fundamental material properties. In contemporary DFT techniques, the electronic structure is evaluated using a potential acting on the system's electrons. This DFT potential is constructed as the sum of external potentials Vext, which is determined solely by the structure and the elemental composition of the system, and an effective potential Veff, which represents interelectronic interactions. Thus, a problem for a representative supercell of a material with n electrons can be studied as a set of n one-electron Schrbdinger-like equations, which are also known as Kohn-Sham equations, as described, for example, in Hanaor, D. et al., Computational Mechanics. 2012 50 (2): 185-194. By way of example, the interatomic distances may be calculated using a Gaussian 16 program at the density functional theory (DFT) level with the hybrid functionals B3LYP, as described in M. J. Frisch, et al., Gaussian 16 Rev. B.01, Wallingford, CT, 2016, and in A. D. Becke, J. Chern. Phys., 1993, 98, 5648-5652. For light atoms, the Dunning's correlated-consistent cc-pVDZ basis set may be used. Metal atoms may be described by effective core potentials and related basis set, as described in P. J. Hay and W. R. Wadt, J. Chern. Phys., 1985, 82, 299- 310. Dispersion energies were included in all the calculations with the atom-atom semiempirical method and parameters proposed by Grimme etal.,]. Chern. Phys., 2010,132,154104. When computing coordination energies, Boys' counterpoise correction was applied to compensate the basis set superposition error (BSSE). The catalyst composition for use in the method of the invention can be prepared by reacting a source of metal ions M and M' with a source of linkergroupsand a source of hydroxyl groups, and a modulator, and subjecting the composition to conditions such that the surface of the composition has first sites A to which the hydroxyl groups are bound, and second sites B which are Lewis acidic. The source of metal ions M and M' may be any substance capable of producing the metals M and M' in the requisite ionic form. Typically, these comprise metal salts in which the metal is in ionic form with a suitable counter-ion, examples of which include halide (fluoride, chloride, bromide, iodide), hydroxide, alkoxide, sulfate, nitrate, phosphate, alkylsulfonate, arylsulfonate, alkylphosphonate, arylphosphonate (the alkyl and aryl parts of these counterions being as defined and exemplified above). The source of linker groups may be any substance capable of producing the linker groups in a form capable of coordinating to the metal ion. The source of linker groups comprises a compound which is a conjugate acid of the linkergroup as present in the final composition, such that the linker group which is coordinated to the metal ion is its conjugate base (i.e., it differs from the compound which is the source of the linker group by at least 1, preferably 1, 2, or 3, protons). Typically, the source of linker groups is an organic acid, such as a carboxylic acid. For instance, the source of linker groups may be a dicarboxylic acid. Alternatively, the source of linker groups may be a tricarboxylic acid. The source of linker groups may be benzene, 1,4-dicarboxylic acid or benzene-l,3,5-tricarboxylic acid. The source of hydroxyl groups may be any compound capable of reacting so as to produce a composition wherein hydroxyl groups are present at the sites A on the surface of the composition. Examples of such sources include water. A modulator may be added to the composition. As described in detail in WO2021 / 123761 Al, the addition of the modulator to the reaction mixture facilitates formation of compositions having the surface properties described herein which makes the compositions particularly active as catalysts. Without wishing to be bound by theory, it is believed that the modulator binds to the metal salts used in the synthesis and competes with the linker during formation of the composition. As used herein, the term "modulator" means a small organic molecule capable of binding to a metal ion. The modulator is a different organic molecule from the organic molecule which provides the source of linker groups. Typically, the modulator has a molecular weight of 30 to 900 Da. In one embodiment, the modulator has a molecular weight of 40 to 750 Da. In one embodiment, the modulator has a molecular weight of 50 to 600 Da. In one embodiment, the modulator has a molecular weight of 60 to 500 Da. In one embodiment, the modulator has a molecular weight of 70 to 400 Da. In one embodiment, the modulator has a molecular weight of 80 to 350 Da. In one embodiment, the modulator has a molecular weight of 90 to 300 Da. In one embodiment, the modulator has a molecular weight of 100 to 250 Da. In one embodiment, the modulator has a molecular weight of 60 to 180 Da. In one embodiment, the modulator has a molecular weight of 100 to 170 Da . In one embodiment, the modulator has a molecular weight of 110 to 200 Da. The metal ions M and M' may be the same and a modulator may be added to the composition. For instance, the metal ions M and M' may both be Sc3+ and a modulator is added to the composition during its preparation. When preparing the catalyst composition, the stoichiometric ratio of the source of metal ions to the modulator may be between 1:0.001 and 1:1000, or between 1:0.1 and 1:500. The stoichiometric ratio of the source of metal ions to the modulator may be between 1:0.2 and 1:250, or between 1:0.4 and 1:150. Typical modulators include organic acids (including but not limited to carboxylic acids, phosphonic acids, phosphoric acids, phosphinic acids, sulfonic acids, sulfinic acids, sulfenic acids), alcohols and amines. The stoichiometric ratio of the modulator to the source of linker groups may be between 50:1 and 1:5. The stoichiometric ratio of the modulator to the source of linker groups may be between 20:1 and 1:2. The stoichiometric ratio of the modulator to the source of linker groups may be between 15:1 and 5:1. The stoichiometric ratio of the modulator to the source of linker groups may be between 12:1 and 8:1. The stoichiometric ratio of the modulator to the source of linkergroups may be between 11:1 and 9:1. The stoichiometric ratio of the modulatortothe source of linker groups may be 10:1. The stoichiometric ratio of the modulator to the source of linker groups may be between 2:1 and 1:2. The stoichiometric ratio of the modulator to the source of linker groups may be between 1.5:1 and 1:1.5. The stoichiometric ratio of the modulator to the source of linker groups may be between 1.2:1 and 1:1.2. The stoichiometric ratio of the modulator to the source of linker groups may be 1:1. The source of linker groups may be benzene-l,3,5-tricarboxylic acid and the stoichiometric ratio of the modulator to benzene-l,3,5-tricarboxylic acid may be between 15:1 and 5:1. The source of linker groups may be benzene-l,3,5-tricarboxylic acid and the stoichiometric ratio of the modulator to benzene-l,3,5-tricarboxylicacid maybe between 12:1 and 8:1. The source of linker groups may be benzene-l,3,5-tricarboxylic acid and the stoichiometric ratio of the modulator to benzene-l,3,5-tricarboxylic acid may be between 11:1 and 9:1. The source of linker groups may be benzene-l,3,5-tricarboxylic acid and the stoichiometric ratio of the modulator to benzene-l,3,5-tricarboxylic acid may be 10:1. The source of linker groups may be benzene-l,3,5-tricarboxylic acid and the stoichiometric ratio of the modulator to benzene-l,3,5-tricarboxylic acid may be between 2:1 and 1:2. The source of linker groups may be benzene-l,3,5-tricarboxylic acid and the stoichiometric ratio of the modulator to benzene-l,3,5-tricarboxylic acid may be between 1.5:1 and 1:1.5. The source of linker groups may be benzene-l,3,5-tricarboxylic acid and the stoichiometric ratio of the modulator to benzene-l,3,5-tricarboxylic acid may be between 1.2:1 and 1:1.2. The source of linker groups may be benzene-l,3,5-tricarboxylic acid and the stoichiometric ratio of the modulator to benzene-l,3,5-tricarboxylic acid may be 1:1. The source of linker groups may be benzene-l,3,5-tricarboxylic acid, the modulator may be benzoic acid and the stoichiometric ratio of benzoic acid to benzene-l,3,5-tricarboxylic acid may be between 15:1 and 5:1. The source of linker groups may be benzene-l,3,5-tricarboxylic acid and the modulator may be benzoic acid and the stoichiometric ratio of benzoic acid to benzene-l,3,5-tricarboxylic acid may be between 12:1 and 8:1. The source of linker groups may be benzene-l,3,5-tricarboxylic acid, the modulator may be benzoic acid and the stoichiometric ratio of benzoic acid to benzene-l,3,5-tricarboxylic acid may be between 11:1 and 9:1. The source of linker groups may be benzene-l,3,5-tricarboxylic acid the modulator may be benzoic acid and the stoichiometric ratio of benzoic acid to benzene-1,3,5-tricarboxylic acid may be 10:1. The source of linker groups may be benzene-l,3,5-tricarboxylic acid, the modulator may be trichloroacetic acid and the stoichiometric ratio of trichloroacetic acid to benzene-1,3,5-tricarboxylic acid may be between 15:1 and 5:1. The source of linker groups may be benzene-1,3,5-tricarboxylic acid, the modulator may be trichloroacetic acid and the stoichiometric ratio of trichloroacetic acid to benzene-l,3,5-tricarboxylic acid may be between 12:1 and 8:1. The source of linker groups may be benzene-l,3,5-tricarboxylic acid, the modulator may be trichloroacetic acid and the stoichiometric ratio of trichloroacetic acid to benzene-1,3,5-tricarboxylic acid may be between 11:1 and 9:1. The source of linker groups may be benzene-1,3,5-tricarboxylic acid the modulator may be trichloroacetic acid and the stoichiometric ratio of trichloroacetic acid to benzene-l,3,5-tricarboxylic acid may be 10:1. The source of linker groups may be benzene-l,3,5-tricarboxylic acid and the stoichiometric ratio of the modulator to benzene-l,3,5-tricarboxylic acid may be between 2:1 and 1:2. The source of linker groups may be benzene-l,3,5-tricarboxylic acid and the stoichiometric ratio of the modulator to benzene-l,3,5-tricarboxylic acid may be between 1.5:1 and 1:1.5. The source of linker groups may be benzene-l,3,5-tricarboxylic acid and the stoichiometric ratio of the modulator to benzene-l,3,5-tricarboxylic acid may be between 1.2:1 and 1:1.2. The source of linker groups may be benzene-l,3,5-tricarboxylic acid and the stoichiometric ratio of the modulator to benzene-l,3,5-tricarboxylic acid may be 1:1. The source of linker groups may be benzene-l,3,5-tricarboxylic acid, the modulator may be trifluoroacetic acid and the stoichiometric ratio of trifluoroacetic acid to benzene-1,3,5-tricarboxylic acid may be between 2:1 and 1:2. The source of linker groups may be benzene-1,3,5-tricarboxylic acid, the modulator may be trifluoroacetic acid and the stoichiometric ratio of trifluoroacetic acid to benzene-l,3,5-tricarboxylic acid may be between 1.5:1 and 1:1.5. The source of linker groups may be benzene-l,3,5-tricarboxylic acid, the modulator may be trifluoroacetic acid and the stoichiometric ratio of trifluoroacetic acid to benzene-1,3,5-tricarboxylic acid may be between 1.2:1 and 1:1.2. The source of linker groups may be benzene-l,3,5-tricarboxylic acid, the modulator may be trifluoroacetic acid and the stoichiometric ratio of trifluoroacetic acid to benzene-l,3,5-tricarboxylic acid may be 1:1. The source of linker groups may be benzene-l,3,5-tricarboxylic acid, the modulator may be trichloroacetic acid and the stoichiometric ratio of trichloroacetic acid to benzene-1,3,5-tricarboxylic acid may be between 2:1 and 1:2. The source of linker groups may be benzene-1,3,5-tricarboxylic acid, the modulator may be trichloroacetic acid and the stoichiometric ratio of trichloroacetic acid to benzene-l,3,5-tricarboxylic acid may be between 1.5:1 and 1:1.5. The source of linker groups may be benzene-l,3,5-tricarboxylic acid, the modulator may be trichloroacetic acid and the stoichiometric ratio of trichloroacetic acid to benzene-1,3,5-tricarboxylic acid, may be between 1.2:1 and 1:1.2. The source of linker groups may be benzene-l,3,5-tricarboxylic acid, the modulator may be trichloroacetic acid and the stoichiometric ratio of trichloroacetic acid to benzene-l,3,5-tricarboxylic acid may be 1:1. The stoichiometric ratio of the source of metal ions to the modulator may be between 1:0.1 and 1:500. The stoichiometric ratio of the source of metal ions to the modulator may be between 1:0.2 and 1:200. The method of preparing the catalyst composition may include the following sequential steps (a) and (b): (a) mixing the source of metal ions with the modulator; and (b) adding the linker to the mixture formed in step (a). Step (a) may be carried out with stirring. Step (b) may be carried out with stirring. The synthesis reaction may be carried out at elevated temperature, typically by heating the mixture formed in step (b). Typically, the reaction is carried out at a temperature between 50°C and 250°C. Preferably, the reaction is carried out at a temperature between 100°C and 200°C. More preferably, the reaction is carried out at a temperature between 130°C and 170°C. The reaction time may be 12 to 120 hours. The reaction time may be 24 to 96 hours. The method may further comprise removing the modulator from the catalyst composition following its synthesis, typically by washing. Without wishing to be bound by theory, it is believed that removing the modulator by washing leaves behind a composition having multiple hydroxyl groups on the A sites of the surface of the composition. The washing may be carried out using any liquid capable of removing the modulator. Typical substances used include water, alcohols (typically alcohols having 1 to 4 carbon atoms) and mixtures thereof. A particularly preferred example is a mixture of ethanol and water. An amount of the modulator may remain in the composition following its synthesis. For instance, a maximum of 10% of the modulator may remain in the composition following its synthesis. Alternatively, a maximum of 5%, 3%, 2% or 1% of the modulator remains in the composition following its synthesis. A maximum of 0.5% of the modulator may remain in the composition following its synthesis. A maximum of 0.3% of the modulator may remain in the composition following its synthesis. A maximum of 0.2% or a maximum of 0.1% of the modulator may remain in the composition following its synthesis. These percentages are calculated by weight based on the total weight of the composition. The method of catalyst formation may be carried out in a solvent. Typical examples of suitable solvents include polar aprotic solvents, examples of which include N,N-dimethylformamide and dimethyl sulfoxide. The polar aprotic solvent may be present in a mixture with water. The solvent may be N,N-dimethylformamide. The stoichiometric ratio of the source of metal ions to the solvent may be between 1:10 and 1:200. Following reaction of the metal ion source and the linker source, the reaction mixture may be cooled to a temperature of less than 10°C, typically between -10°C and 10°C. This step is particularly preferred, as rapid cooling of the composition following the reaction results in a composition having particularly favourable surface properties. Typically, the cooling rate is from 2°C to 20°C per minute. The cooling rate may be from 5°C to 15°C per minute. The cooling rate may be from 8°C to 12°C per minute. The method may further comprise removal of water, so as to cause the sites B to become Lewis acidic. Ethoxylation according to the present invention As previously described, the invention relates to ethoxylation by reacting EO with an alcohol in the present of a catalyst, wherein the catalyst is as described in detail previously. Scheme 1 illustrates generally the reaction of an alcohol with EO in the presence of a catalyst. Scheme 1: Preparation of alcohol ethoxylate polymers from EO and an alcohol The use of the catalyst (as illustrated generally in Fig. 2) in the ethoxylation reaction results in an alcohol ethoxylate polymer. In the process of the invention, the ring structure of the EO, allows for a ring opening reaction on the surface of the catalyst for reaction with the alcohol. Polymer growth is initiated when an EO moiety is inserted, by use of the catalyst, onto the hydroxy moiety of the alcohol, forming an ether linkage. The epoxide moiety can form further ether linkages, and in this way the polymer chain grows. The polymer formed contains the R1 group of the alcohol reactant, which can be used to tailor the properties of the resultant polymer, for instance based on the intended application of the polymer. Variation in the length of the R1 group, within the hydrophobic moiety of the polymer leads to the ability to tune the Hydrophilic-Lipophilic balance (HLB) of the polymers, leading to different properties. For instance, a longer R1 group can provide a lower HLB value, producing polymers that find use as anti-foaming agents and water-in-oil emulsifying agents. A shorter R1 group can provide a higher HLB value, producing polymers that find use as solubilising agents, detergents and oil-in-water emulsifiers. In this way the polymer composition can be tailored to high value end products. Various further features and aspects of the invention are defined in the claims. The invention is now described in more detail below with reference to the following illustrative Examples. Examples Example 1: Synthesis of catalyst compositions for use in the process of the invention Example 1.1 Scandium nitrate hydrate (0.240 g) was dissolved into DMF (4 mL) and stirred vigorously at room temperature until dissolved. To the solution was added benzoic acid (0.550 g). The solution was stirred once again until homogeneous. To the solution was added benzene-1, 3, 5-tricarboxylic acid (0.091 g) and DMF (4 mL). The solution was stirred until homogeneous. The resulting solution was sealed inside a 23 mLTeflon®-lined autoclave and heated in an oven at 150°C for 48 hours, after which the autoclaves were removed and rapidly cooled (at a rate of approximately 10°C per minute) to less than 10°C. The synthesised composition was filtered and washed with ethanol and water. Example 1.2 Scandium nitrate (0.688 mmol) and chromium nitrate hexahydrate (0.172 mmol) were stirred in a 0.108 M solution of acetic acid in DMF (4 mL) at room temperature. Once homogenised, benzene-1,3,5-tricarboxylic acid (BTC, 0.430 mmol) in DMF was added and the solution was stirred further. The resulting solution was sealed inside a 23 mL Teflon®-lined autoclave and heated to 150 °C for 48 hours, after which autoclaves were removed from the oven and rapidly cooled (at a rate of approximately 10 °C per minute) to less than 10°C. The synthesised heterogeneous catalyst was collected by filtration and washed with deionized water, then ethanol. The catalyst compositions prepared in Examples 1.1 and 1.2 were analysed by XRD, NMR, N2 adsorption, SEM and TEM, and the NMR results for Example 1.1 are shown in Figure 2. Fig. 2 shows a 45Sc magnetic angle spinning NMR spectrum confirming the presence of A and B sites on the surface of a catalyst composition for use in the methods of the invention. Magic Angle Spinning Nuclear Magnetic Resonance (MAS-NMR) measurements were collected at the UK 850 MHz Solid State NMR Facility on a wide bore 20.0 T Bruker A VANCE III spectrometer at the University of Warwick with a Neo Console, using a 4.0 mm HXY probe in doubleresonance mode. The sample was loaded into 4.0 mm zirconium oxide Bruker NMR rotors with vespel turbines under an N2 atmosphere. 45Sc spectra (45Sc Larmor frequency = 206.51 MHz) were referenced to a 1 mmol ScCh in D2O, using 192 scans and a pulse delay (dl) of 1 second. N2 was used for the drive, bearing and purge. Measurements were carried out with a 13.5 kHz spin-rate. Example 2: Ethoxylation according to the method of the invention 2.1: Alcohol ethoxylate synthesis from ethylene oxide (EO) and 1-butanol (C4) To the main reactor vessel was added 1-butanol (100.0 g, 1.34 moles) and the catalyst (0.4 wt%). The reactor was sealed, evacuated and heated to 85°C. To the reactor, N2 was added until a pressure of 0.2 barg was achieved. EO was added continuously to the reactor via mass flow controller from a pre-pressurised EO vessel, the pressure of which was controlled so to provide a 5 bar differential between the prepressurisation vessel and the main reactor vessel. The rate of EO addition was controlled by mass flow controller so to maintain a reaction temperature of 100-105°C (typically between 120-400 grams / hour) until the total quantity of EO (475g, 10.8 moles, 8 eq.) was added to the reactor. During EO addition, the pressure of the reactor vessel did not exceed 3.5 barg. The reaction was completed in a time of 2.0 hours, after which the main reactor was evacuated to vacuum and cooled. Nitrogen was added to bring the vessel back to atmospheric pressure. The product was removed from the reactor (98%) and analysed via NMR spectroscopy, LC-MS, Gel Permeation Chromatography (GPC) and headspace Gas Chromatography (GC). The product obtained exhibited an average molecular mass of 426 g / mol, and PDI of 1.28. The pH of an aqueous lwt% solution of the polymer product was measured to be 6-7. GC analysis showed that the product contained <3ppm of 1,4-dioxane. GPC Mn = 782 g / mol (in THF vs. polystyrene calibrants) LC-MS = Major Product = 426 g / mol (Peak at 427.5= M+H+) LC-MS Data: 1:MS2 ES+ c (150.0-1500.0) [20v] RT: 1.5474 minutes, Scan 442, NL 1.00e+2 2.2 Alcohol ethoxylate synthesis from ethylene oxide (EO) and primary alcohol, 1-octanol (Cs) To the main reactor vessel was added 1-octanol (100.0 g, 0.77 moles) and the catalyst (0.05 wt% w.r.t to the Cs alcohol). The reactor was sealed, evacuated and heated to 100°C. To the main reactor, N2 was added until a pressure of 0.2 barg was achieved. EO was added continuously to the reactor via mass flow controller from a pre-pressurised EO vessel, the pressure of which was controlled so to provide a 5 bar differential between the prepressurisation vessel and the main reactor vessel. The rate of EO addition was controlled by mass flow controller so to maintain a reaction temperature of 100-105°C (typically between 60-220 grams / hour) until the total quantity of EO (135.1 g, 3.07 moles, 4 eq.) was added to the reactor. During EO addition, the pressure of the reactor vessel did not exceed 4 barg. The reaction was completed in a time of 2.0 hours, after which the main reactor was evacuated to vacuum and cooled. Nitrogen was added to bring the vessel back to atmospheric pressure. The product was collected from the reactor (99% yield) and analysed via NMR spectroscopy, LC-MS, Gel Permeation Chromatography (GPC) and headspace Gas Chromatography (GC). The product obtained exhibited an average molecular mass of 306 g / mol, and PDI of 1.34. The pH of an aqueous 1 wt% solution of the polymer product was measured to be 6-7. GC analysis showed that the product contained <lOppm of 1,4-dioxane. GPC Mn = 653 g / mol (in THF vs. polystyrene calibrants) LC-MS = Major Product = 306 g / mol (Peak at 307.4 = M+H+) LC-MS Data: 1: MS2 ES+ c (150.0-1500) [20v] RT: 2.1531 minutes, Scan 615, NL 1.00e+2 2.3: Alcohol ethoxylate synthesis form ethylene oxide (EO) and secondary alcohol, 2-octanol (C8) To the main reactor vessel was added 2-octanol (100.0 g, 0.77 moles) and the catalyst (0.05 wt% w.r.t the C8 alcohol). The reactor was sealed, evacuated and heated to 100°C. To the main reactor, N2 was added until a pressure of 0.2 barg was achieved. EO was added continuously to the reactor via mass flow controller from a pre-pressurised EO vessel, the pressure of which was controlled so to provide a 5 bar differential between the prepressurisation vessel and the main reactor vessel. The rate of EO addition was controlled by mass flow controller so to maintain a reaction temperature of 100-105°C (typically between 60-220 grams / hour) until the total quantity of EO (135.1 g, 3.07 moles, 4 eq.) was added to the reactor. During EO addition, the pressure of the reactor vessel did not exceed 5 barg. The reaction was completed in a time of 2.5 hours, after which the main reactor was evacuated to vacuum and cooled. Nitrogen was added to bring the vessel back to atmospheric pressure. The product was collected from the reactor (95% yield) and analysed via NMR spectroscopy, LC-MS, Gel Permeation Chromatography (GPC) and headspace Gas Chromatography (GC). The product obtained exhibited an average molecular mass of 306 g / mol, and PDI of 1.31. The pH of an aqueous 1 wt% solution of the polymer product was measured to be 6-7. GC analysis showed that the product contained <lOppm of 1,4-dioxane. GPC Mn = 900 g / mol (in THF vs. polystyrene calibrants) LC-MS = Major Product = 306 g / mol (Peak at 307.4 = M+H+, peak at 329.5 = M+Na+) LC-MS Data: 1: MS2 ES+c (150.0-1500.0) [20v] RT: 2.1076 minutes, Scan 602, NL 1.00e+2 2.4: Alcohol ethoxylate synthesis from ethylene oxide (EO) and 1-dodecanol (C12) To the main reactor vessel was added 1-Dodecanol (100.0 g, 0.53 moles) and the catalyst (0.1 wt% w.r.t to the dodecanol). The reactor was sealed, evacuated and heated to 88°C. To the main reactor, N2 was added until a pressure of 0.2 barg was achieved. EO was added portion-wise (23.2 g, 0.53 moles) to the main reactor via mass flow controller from a pre pressurised EO vessel, the pressure of which was controlled so to provide a 5 bar differential between the pre-pressurisation vessel and the main reactor vessel. The rate of EO addition was controlled by mass flow controller so to maintain a reaction temperature of 85-105°C (typically between 100-220 grams / hour) without the pressure of the reactor vessel exceeding 4 barg. Upon each successful addition of one portion of EO to the main reactor the addition was ceased and the main reactor pressure was observed to drop rapidly before stabilising. The addition of EO was continued until the total quantity of EO (232 g, 5.3 moles, 10 eq.) was added to the reactor. The reaction was completed in a time of 3.25 hours, after which the main reactor was evacuated to vacuum and cooled. Nitrogen was added to bring the vessel back to atmospheric pressure. The product was collected from the reactor (99% yield) and analysed via NMR spectroscopy, LC-MS, Gel Permeation Chromatography (GPC) and headspace Gas Chromatography (GC). The product obtained exhibited an average molecular weight of 626 g / mol and PDI of 1.27. GC analysis showed that the product contained <5ppm of 1,4-dioxane. The pH of an aqueous 1 wt% solution of the polymer product was measured to be 6-7. GPC Mn = 915 g / mol (vs. polystyrene calibrants) LC-MS = Major Product = 626g / mol (Peak at 649.7 = M+Na+) LC-MS Data : 1 : MS2 ES+c (150.0-1500.0) [20v] RT: 2.6292 minutes, Scan 751, NL 1.00e+2 2.5: Alcohol ethoxylate synthesis from ethylene oxide (EO) and 1-docosanol (C22) To the main reactor vessel was added 1-docosanol (100.0 g, 0.31 moles) and the catalyst (0.2 wt% w.r.t to the C22 alcohol). The reactor was sealed, evacuated and heated to 95°C. To the main reactor, N2 was added until a pressure of 0.2 barg was achieved. EO was added portion-wise (13.5 g, 0.31 moles) to the reactor via mass flow controller from a prepressurised EO vessel, the pressure of which was controlled so to provide a 5 bar differential between the pre-pressurisation vessel and the main reactor vessel. The rate of EO addition was controlled by mass flow controller so to maintain a reaction temperature of 95-110°C (typically between 100-220 grams / hour) without the pressure of the reactor vessel exceeding 3 barg. Upon each successful addition of one portion of EO to the main reactor the addition was ceased and the main reactor pressure was observed to drop rapidly before stabilising. The addition of EO was continued until the total quantity of EO (80.8 g, 1.84 moles, 6 eq.) was added to the reactor. The reaction was completed in a time of 2.0 hours, after which the main reactor was evacuated to vacuum and cooled. Nitrogen was added to bring the vessel back to atmospheric pressure. The product was collected from the reactor (99% Yield) and analysed via NMR spectroscopy, LC-MS and Gel Permeation Chromatography (GPC). The product obtained exhibited an average molecular weight of 591 g / mol, and PDI of 1.6. GC analysis showed that the product contained <6ppm of 1,4-dioxane. The pH of an aqueous 1 wt% solution of the polymer product was measured to be 6-7. GPC Mn = 989 g / mol (vs. polystyrene calibrants) LC-MS = Major Product = 591g / mol (Peak at 613.8 = M+Na+) LC-MS Data: 1: MS2 ES+c (150.0-1500.0) [20v] RT: 3.7076 minutes, Scan 1059, NL 1.00e+2 2.6: Alcohol ethoxylate synthesis from ethylene oxide (EO) and nonyl phenol To the main reactor vessel was added Nonyl Phenol (93.0 g, 0.42 moles) and the catalyst (0.16 wt% w.r.t to the nonyl phenol). The reactor was sealed, evacuated and heated to 100°C. To the main reactor, N2 was added until a pressure of 0.2 barg was achieved. EO was added portion-wise (18.6 g, 0.42 moles) to the reactor via mass flow controller from a prepressurised EO vessel, the pressure of which was controlled so to provide a 5 bar differential between the pre-pressurisation vessel and the main reactor vessel. The rate of EO addition was controlled by mass flow controller so to maintain a reaction temperature of 100-131°C (typically between 100-220 grams / hour) without the pressure of the reactor vessel exceeding 5 barg. Upon each successful addition of one portion of EO to the main reactor the addition was ceased and the main reactor pressure was observed to drop rapidly before stabilising. The addition of EO was continued until the total quantity of EO (74.2 g, 1.69 moles, 4 eq.) was added to the reactor. The reaction was completed in a time of 3.5 hours, after which the main reactor was evacuated to vacuum and cooled. Nitrogen was added to bring the vessel back to atmospheric pressure. The product was collected from the reactor (93% yield) and analysed via NMR spectroscopy, LC-MS and Gel Permeation Chromatography (GPC). The product obtained exhibited an average molecular mass of 396 g / mol, and PDI of 2.60. GC analysis showed that the product contained <23ppm of 1,4-dioxane. The pH of an aqueous lwt% solution of the polymer product was measured to be 6-7. GPC Mn = 465 g / mol (vs. polystyrene calibrants) LC-MS = Major Product = 396 g / mol (Peak at 397.5 = M+H+) LC-MS Data: 1: MS2 ES+c (150.0-1500.0) [20v] RT: 2.5697 minutes, Scan 734, NL 1.00e+2 2.7 Control Experiment using KOH as catalyst It is demonstrated that the minimal energy requirements used in the method of the invention are not sufficient when a traditional KOH catalyst is used. To the main reactor vessel was added 1-Dodecanol (100.0 g, 0.53 moles), followed by KOH (0.1 wt% w.r.t to the dodecanol). The reactor was sealed, evacuated and heated to 88°C. To the main reactor, N2 was added until a pressure of 0.2 barg was achieved. EO was added (23.2 g, 0.53 moles, 1 eq.) to the reactor via mass flow controller from a pre-pressurised EO vessel, the pressure of which was controlled so to provide a 5 bar differential between the pre-pressurisation vessel and the main reactor vessel. The reactor pressure was observed to stabilise at ca. 3.5 barg, where the pressure remained for 15 minutes. After this time, the temperature was increased incrementally to 135°C, during which the pressure increased to ca. 5.4 barg and stabilised. No reaction was observed. The main reactor was cooled and evacuated to vacuum. Nitrogen was added to bring the vessel back to atmospheric pressure.

Claims

1. A method of forming a polymer which does not have CO2 incorporated in the structure of the polymer, the method comprising reacting ethylene oxide and an alcohol in the presence of a catalyst, wherein the catalyst is a composition comprising a bulk material; and at least one surface;the bulk material comprising ions of a metal M bonded to one another via linker groups; the surface comprising ions of a metal M' bonded to one another via linker groups; the metals M and M' being the same or different;the surface comprising at least one first site A and at least one second, different site B;the site A having a hydroxyl bonded thereto;said site B being a Lewis acid site;said sites A and B being capable of interacting with the ethylene oxide and the alcohol.

2. The method according to claim 1, wherein the alcohol is of the formula R1OH, in which R1 is a C4 - C22 hydrocarbon chain.

3. The method according to claim 2, wherein the hydrocarbon chain is a linear alkyl chain.

4. The method according to claim 2, wherein the C4-C22 hydrocarbon chain comprises acyclic or aromatic moiety.

5. The method according to claim 4, wherein the cyclic or aromatic moiety is substituted.

6. The method according to any preceding claim, wherein the alcohol is selected from 1-butanol; 1-octanol; 2-octanol; 1-dodecanol; 1-docosanol; and nonyl phenol.

7. The method according to any preceding claim, the method comprising:- adding the alcohol and the catalyst to a reactor;- heating the reactor to an initial reacting temperature; and- adding the ethylene oxide sequentially to maintain a working temperature and reacting to form a polymer.

8. The method according to claim 7 wherein the initial reacting temperature is between 80°C and 110°C.

9. The method according to claim 8 wherein the initial reacting temperature is between 85°Cand 100°C.

10. The method according to claim 7 wherein the working temperature is maintained between 80°C and 135°C.

11. The method according to claim 10, wherein the working temperature is maintained between 90°C and 110°C.

12. The method according to any preceding claim, wherein the reacting is carried out for between 1.5 hours and 3.5 hours.

13. The method according to claim 12, wherein the reacting is carried out for between 2 and 2.5 hours.

14. The method according to any preceding claim wherein the molar ratio of ethylene oxide to alcohol (ethylene oxide:alcohol) is from 2:1 to 12:1.

15. The method according to any preceding claim wherein the mass ratio of the catalyst to alcohol (catalyst:alcohol) is from 0.0005:1 to 0.005:1.

16. The method according to claim 1, wherein the metal ions M and M' are selected from Sc3+, Cr3+, Al3+and Fe3+.

17. The method of any preceding claim, wherein the linker groups are of the structure T(R)xy(H)z wherein: T is a multivalent organic moiety; R is a functional group capable of coordinating metal ions M and M'; the functional group being other than H; x is 2 to 6; y is 0 to 4; and z is a number sufficient to occupy the remaining valencies on T.

18. The method according to claim 17, wherein T is a cycloalkyl, heterocycloalkyl, aryl or heteroaryl ring.

19. The method according to claim 17, wherein in the catalyst composition, R is -CO2H.

20. The method of any preceding claim, wherein the catalyst composition has the generalformula [Sc3O(OH)(BTC)2], in which BTC is benzene-l,3,5-tricarboxylic acid.Application No: GB2416084.8Examiner:Dr Albert MthuphaClaims searched: 1-20Date of search: 18 December 2024Patents Act 1977: Search Report under Section 17Documents considered to be relevant:Category Relevant to claims Identity of document and passage or figure of particular relevance X 1-5, 7, 16- 20. CA 2531162 Al (BASF AG), see para. [0001], [0002], [0005], [0570], the claims, disclosing forming a polymer (based on ethylene oxide) in the presence of metal-organic framework with BTC ligands that is benzene-1,3,5-tricarboxylic acid as catalyst and an alcohol. Y 1-5, 7, 16- 20. US 2023 / 0062611 Al (RAJA et al.), note particularly para. [0320], claims 1, 9, disclosing forming a cyclic ether polymer (based on ethylene oxide) in the presence of [Sc3O(OH)(BTC)2] where BTC is benzene-1,3,5-tricarboxylic acid catalyst. Y 1-5, 7, 16- 20. WO 2008 / 066293 Al (KOREA RES INST CHEM TECH), see para. [64]-[65], claims 18, 27, disclosing Fe-BTC (benzenetricarboxylate) for epoxidation. Y 1-5, 7, 16- 20. US 5012012 A (NAKAMURA et al.), see whole document, note particularly the claims, disclosing an ethoxylation reaction comprising reacting ethylene oxide, an alcohol and a catalyst with metal ions. Y 1-5, 7, 16- 20. CN 111344331 A (UNIV NORTHWESTERN), see EPO Translation, , disclosing an ethoxylation reaction comprising reacting ethylene oxide, an alcohol and a Lewis acid catalyst.Categories:X Document indicating lack of novelty or inventive step A Document indicating technological background and / or state of the art. Y Document indicating lack of inventive step if combined with one or more other documents of same category. P Document published on or after the declared priority date but before the filing date of this invention. & Member of the same patent family E Patent document published on or after, but with priority date earlier than, the filing date of this application.Field of Search:Search of GB, EP, WO &US patent documents classified in the following areas of the UKCX :The following online and other databases have been used in the preparation of this search reportwww.gov.uk / ipoSEARCH-PATENTInternational Classification:Subclass Subgroup Valid From C08G 0065 / 26 01 / 01 / 2006 B01J 0020 / 22 01 / 01 / 2006 C08G 0065 / 28 01 / 01 / 2006 cud 0001 / 00 01 / 01 / 2006www.gov.uk / ipo

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