Method of preparing polyethercyclicpolyols.

0001This invention relates to polyethercyclicpolyols having high molecular weights and to the preparation thereof. In particular, the invention relates to the preparation of polyethercyclicpolyols which, due to improved molecular properties and characteristics, permit the preparation of improved drilling fluids which inhibit formation of gas hydrates, prevent shale dispersion, reduce swelling of the formation to improve wellbore stability, reduce fluid loss, and reduce filter cake thickness. Drilling muds incorporating the polyethercyclicpolyols of this invention are excellent substitutes for oil base muds in many applications.

0002Water-based drilling fluids comprise water, clays or polymers, and various treating agents which control the physical, chemical and/or rheological properties of drilling fluids in wellbores. In order to perform their function as drilling fluid additives, it is theorized, although the invention is not limited to this theory, that the polyethercyclicpolyol mixtures contain large water soluble molecules and have relatively limited crosslinking in view of their high molecular weight. It is difficult to produce polymeric molecules of this type of high molecular weight which do not have extensive crosslinking. Accordingly, the present invention provides a process which overcomes these and other problems in the art as more particularly disclosed hereinafter, and which produces polyethercyclicpolyols of significantly improved characteristics as drilling mud additives.

0003The purpose of the present invention is to form polyethercyclicpolyols by a thermal condensation reaction and copolymerization. This purpose is achieved by heating a reaction mixture comprising a reactant selected from the group consisting of (a) a polyol having at least three hydroxyl groups of which at least two of the hydroxyl groups are vicinal; (b) precursors of the polyol, (c) cyclic derivatives of the polyol, and (d) mixtures thereof, which heating initiates the thermal condensation; removing water formed during the thermal condensation; continuing the thermal condensation until a predetermined quantity of moles of water per mole of reactant are removed, wherein the condensation goes to completion without incurring degeneration, including substantial undesirable crosslinking or carbonization, and prior to the condensation going to completion, admixing with the reaction mixture an epoxy resin.

0004In another embodiment, the purpose of the invention is carried out by heating a reaction mixture comprising a reactant selected from the group consisting of (a) a polyol having at least three hydroxyl groups of which at least two of the hydroxyl groups are vicinal, (b) precursors of the polyol, (c) cyclic derivatives of the polyol, and (d) mixtures thereof, which heating initiates the thermal condensation; removing water formed during the thermal condensation; and continuing the thermal condensation, which is initially endothermic, until the condensation becomes essentially thermally neutral, prior to the reaction becoming exothermic which would lead to substantial undesirable degeneration, i.e., crosslinking or carbonization, and prior to the condensation going to completion, admixing with the reaction mixture an epoxy resin.

0005In yet another embodiment, the purpose of this invention is realized by heating a reaction mixture comprising a reactant selected from the group consisting of (a) a polyol having at least three hydroxyl groups of which at least two of the hydroxyl groups are vicinal, (b) precursors of the polyol, (c) cyclic derivatives of the polyol, and (d) mixtures thereof, which heating initiates the thermal condensation; removing water formed during the thermal condensation; continuing the thermal condensation to completion while controlling the temperature and pressure of the reaction within predetermined ranges to avoid substantial undesirable degeneration and to maximize molecular weight, and prior to the condensation going to completion, admixing with the reaction mixture an epoxy resin.

0006Another embodiment of the invention achieves the purpose thereof by heating a reaction mixture comprising a reactant selected from the group consisting of (a) a polyol having at least three hydroxyl groups of which at least two of the hydroxyl groups are vicinal, (b) precursors of the polyol, (c) cyclic derivatives of the polyol, and (d) mixtures thereof, which heating initiates the thermal condensation; removing water formed during the thermal condensation; continuing the thermal condensation while adding additional reactant in such a manner that the reaction proceeds to completion at a rate faster than the additional reactant is being introduced, thereby maximizing molecular weight of the polyethercyclicpolyol, and (d) prior to the condensation going to completion, admixing with the reaction mixture an epoxy resin.

0007An additional embodiment of the invention achieves its purpose by heating a reaction mixture comprising a basic catalyst and a reactant selected from the group consisting of (a) a polyol having at least three hydroxyl groups of which at least two of the hydroxyl groups are vicinal, (b) precursors of the polyol, (c) cyclic derivatives of the polyol, and (d) mixtures thereof, which heating initiates the thermal condensation; removing water formed during the thermal condensation; continuing the thermal condensation to completion while controlling the temperature and pressure of the reaction within predetermined ranges to avoid substantial undesirable degeneration and to maximize molecular weight, and prior to the condensation going to completion, admixing with the reaction mixture an epoxy resin.

0008The above stated purpose of the invention may also be realized by heating a reaction mixture comprising a reactant selected from the group consisting of (a) a polyol having at least three hydroxyl groups of which at least two of the hydroxyl groups are vicinal, (b) precursors of the polyol, (c) cyclic derivatives of the polyol, and (d) mixtures thereof, which heating initiates the thermal condensation; removing water formed during the thermal condensation; continuing the thermal condensation and adding a final quantity of additional reactant to the reaction mixture when the thermal condensation is within a preselected degree of completion, thereby buffering the condensation and preventing undesirable degeneration, i.e., or carbonization, and prior to the condensation going to completion, admixing with the reaction mixture an epoxy resin.

0009Suitably the amount of epoxy resin is 0.5 to 10 % by weight of the total reactant mixture. The epoxy resin is suitably selected from the group consisting of diglycidyl ethers, triglycidyl ethers and tetraglycidyl ethers.

0010The invention further relates to a polyethercyclicpolyol of a reactant mixture comprising from 99.5 to 90 % by weight of a reactant selected from the group consisting of (1) a polyol having at least three hydroxyl groups of which at least two of the hydroxyl groups are vicinal, (2) precursors of the polyol, (3) cyclic derivatives of the polyol, and (4) mixtures thereof, and from 0.5 to 10% by weight of an epoxy resin, having a weight average molecular weight of 50 000 to 300 000.

0011Polyethercyclicpolyols are those having at least 6 carbon atoms, at least 2 hydroxyl groups, and at least 2 ether linkages, but no more than 1 800 carbon atoms, 450 hydroxyl groups, and 600 ether linkages. More preferably, polyethercyclicpolyols are those having at least 15 carbon atoms, 5 ether linkages, and at least 5 hydroxyl groups, or at least 15 carbon atoms, at least 7 ether linkages, and at least 3 hydroxyl groups. Most preferably, polyethercyclicpolyols are those having at least 18 carbon atoms, at least 6 hydroxyl groups, and at least 6 ether linkages but preferably no more than 1 200 carbon atoms, 300 hydroxyl groups, and 400 ether linkages. Weight average molecular weights, M_w, (defined infra) preferably range from 50 000 to 200 000. Hereinafter "poly" is used to mean two or more, "mono" is used to mean one, "cyclic" is used to mean one or more rings, "ether" is used to mean one or more ether linkages, and polyethercyclicpolyol may also be called PECP or polycyclicpolyetherpolyol.

0012Polyethercyclicpolyols are prepared by polycondensation of the reactants selected from the group consisting of (a) a polyol having at least three hydroxyl groups of which at least two of the hydroxyl groups are vicinal; (b) pre-cursors of the polyol, (c) cyclic derivatives of the polyol, and (d) mix-tures thereof, in chemical processes which are accompanied by significant expulsion of water molecules from the polymer-izing compounds. The number of ether linkages equals the number of water molecules expelled.

0013Useful reactants are polyols that are at least trihydric and have at least two hydroxyl groups in a vicinal position are required. Nonlimiting examples include monomers, oligomers and telomers of polyhydric alcohols (or their precursors, or combinations thereof) such as glycerol (which is a suitable feedstock), telomers of glycerol such as diglycerols, triglycerols, tetraglycerols, penta-glycerols, and hexaglycerols, mixtures of glycerol and telomers of glycerol such as diglycerol and triglycerols, mixtures of telomers of glycerol, 1,5,6,9-decanetetrol, 1,2,4,5-cyclohexanetetra-methanol, 1,2,4,7-heptanetetrol, 1,2,3,5-heptanetetrol, 4,4-dimethyl-1,2,3-pentanetriol, 1,3,4-cycloheptanetriol, 1,2,3-pentanetriol, 1,2,4-pentanetriol, 2,3,4-pentanetriol, 1,2,3-cyclopentanetriol, 1,2,3-hexane-triol, 1,2,4-hexanetriol, 1,2,3,4-hexanetetrol, 1,2,4-cyclohexane-triol, 1,2,5-cyclohexanetriol, 1,2,3,4-cyclohexanetetrol, 1,2,3,5-cyclo-hexane-tetrol, butanetriols, such as 1,2,4-butanetriol and copolymers of ethylene glycol and propylene glycols with the preceding alcohols.

0014An important class of polyhydric alcohols with straight carbon chains and four or more hydroxyl groups, called sugar alcohols, can also be used in pre-paring additive formulations containing cyclic polyethers. Sorbitol and mannitol are two such well known polyhydric alcohols.

0015Precursors of trihydric polyols are suitable feeds. For example, glycidol, an epoxy alcohol which is a precursor of glycerol, reacts by simple addition not involving dehydration or requiring the presence of catalysts such as sodium hydroxide and sodium acetate. Other examples are epichalohydrin, such as epichlorhydrin which, upon reaction with water and an alkali metal base, such as sodium hydroxide, hydrolyzes to give glycerol and alkali metal halide. This latter mixture then can be thermally con-densed to yield polyethercyclicpolyols.

0016Representative structures of precursors of the polyols of interest as feeds in this invention are all epoxides which satisfy the criterion of possessing at least one epoxide and one or more hydroxyl groups. Hence, such precursors include glycidol derivatives with an alkyl or aryl subtituent.

0017Derivatives of polyols are also useful feeds. For example, derivatives of glycerol, including linear and cyclic dimers, such as cis or trans- 2,5-bis(hydroxymethyl)-p-dioxane, cis- or trans-2,6-bis-(hydroxymethyl)-p-dioxane, and the glycerine acetal of hydracryl-aldehyde can separately, or in combination, dimerize or can react with glycerol to produce poly-ethercyclicpolyols.

0018Other trihydric alcohols may yield cyclicetherdiols. Further polycondensation of the cyclicetherdiols will yield poly-cyclicetherpolyols with structures which depend on which hydroxyl groups are involved in the condensation reaction.

0019Known commercial mixtures of bis(hydroxy-methyl)-p-dioxanes and polyols can react to produce polyethercyclicpolyols. Polyols, e.g., poly-glycerols, of a degree of dehydration corresponding from 0.5 to 1.0 moles water per mole of polyol are suitable feedstock. Such polyol mixtures comprise cyclic ethers. Footstill bottoms (heavy ends from the manufacture of glycerol) are mixtures of glycerol, bis(hydroxy-methyl)-p-dioxanes, linear poly-glycerols, and small amounts of low molecular weight polyether-cyclicpolyols, are useful feedstock.

0020Byproduct or effluent streams from other existing processes for which the principal products are resins, soaps, and the like, can be excellent feedstocks. Exemplary are process streams of glycerol/glycidol mixtures which may also contain other components, for example, mixtures of glycerol, glycidol, epichlorohydrin, dimethyl ketone, isopropyl alcohol, and/or sodium chloride made in the manufacture of resins. Such streams may first be processed to remove the nonglycerol-related material, for example, sodium chloride. Effluent streams from processes such as resin manufacture fit this category of feedstock. Such streams may contain predominantly water and salt (10 to 15 percent by weight) with also small amounts of glycerol, glycidol, bis(hydroxymethyl)p-dioxanes, and polyethercyclicpolyols of low molecular weight (and therefore initially ineffective for the use in drilling fluids). For example, in an existing plant, the components of an effluent stream are 12 to 15 percent by weight sodium chloride, 0.3 to 2 percent by weight glycerol, 0.3 to 1.2 percent by weight glycidol, and less than 0.5 percent by weight polyglycerols, bis(hydroxymethyl)-dioxanes, and low molecular weight polyethercyclicpolyols, with the balance being water.

0021In a typical preparation in accordance with the invention, a polyol such as glycerol (which is a suitable feedstock) containing small amounts of catalyst such as sodium hydroxide, preferably along with small amounts of sodium acetate, are reacted in distillation apparatus under conditions which allow water to be removed overhead, but not substantial amounts of glycerol or its dimers and trimers. The catalyst, alkali metal hydroxide, preferably sodium hydroxide, is in a suitable concentration of 0.5 to 1.5 percent by weight of the reaction mixture and alkali metal acetate, preferably sodium acetate, in like or smaller amounts. Other suitable catalysts include potassium, lithium or calcium hydroxide or other condensation catalysts, such as sodium tungstate or tin (IV) chloride.

0022The starting pH for the condensation reaction ranges from 5 to 13.5 and is preferably from 8 to 10. The pH gradually declines during the process to 5 to 9.5 and preferably to 6.5 to 9. The materials removed overhead in the distillation are acidic to neutral and have a pH ranging from 3 to 7.

0023Reference is now made to Figure 1 showing temperature-time plot of a glycerol condensation reaction, wherein the horizontal axis gives the time in hours and the vertical axis the temperature in °C.

0024The reaction mixture is heated under a pressure of at least 100 mm Hg, and preferably between 150 and 300 mm Hg (indicated with reference numeral 1). For glycerol, more preferably 160 to 230 mm Hg is used. Under these conditions, any free water, which is often present in very small amounts even in dry glycerol, will be distilled off. Moreover, water produced by the condensation reactions will be distilled off continuously, allowing the equilibrium-limited condensation reaction to proceed further and to completion. Water removal may be facilitated by bubbling an inert gas, such as nitrogen, through the mixture. Such bubbling will also ensure thorough mixing. The mixture may also be continuously stirred to ensure thermal equilibrium throughout. The dry glycerol will then begin to rise in temperature to about 210 to 230°C at 150 to 300 mm Hg, at which temperature the mixture refluxes, indicating the onset of reactions which produce water by condensation of the glycerol (indicated with reference numeral 2). By maintaining a pressure of at least 160 mm Hg, the glycerol, which may volatilize along with the water, is condensed in an overhead condenser, which is preferably cooled by a coolant such as water/glycol mixtures. The glycerol and its linear and cyclic dimers, which form in the course of the volatilization process, are thus condensed and refluxed to the reacting mixture. Gradually the procedure results in an increase in the boiling point of the mixture, brought about by the continuous removal of water of condensation and by the increase of the molecular weight of the mixture.

0025As the degree of the polymerization increases, and the amount of water removed from the glycerol feed increases, the pressure over the mixture is gradually decreased externally, either in a continuous, preferably gradual, mode, or at selected reaction temperatures. For example, it is possible to reduce the pressure to 120 mm Hg (indicated with reference numeral 3) when the mixture reaches 250°C at a pressure of 180 mm Hg. Or alternatively, it is possible to control the pressure to diminish gradually by known mechanical means. Figure 1 discloses a stepwise pressure reduction: 180 mm Hg to 120 mm Hg to 80 mm Hg to 60 mm Hg.

0026The degree of dehydration during the procedure is monitored in terms of moles of water removed per mole of glycerol left in the product. As the ratio of moles of water removed per mole of glycerol in the product increases, the degree of polymerization of glycerol increases, and the number average molecular weight of the mixture increases. Particularly important is the discovery of the strong relationship between the weight average molecular weight (M_w) and the performance of the product as a drilling fluid additive.

0027The number average molecular weight M_n is determined by the formula: <maths id="math0001" num=""><math display="inline"><mrow><msub><mrow><mtext>M</mtext></mrow><mrow><mtext>n</mtext></mrow></msub><msub><mrow><mtext> = Σ</mtext></mrow><mrow><mtext>i</mtext></mrow></msub><msub><mrow><mtext> (n</mtext></mrow><mrow><mtext>i</mtext></mrow></msub><msub><mrow><mtext>M</mtext></mrow><mrow><mtext>i</mtext></mrow></msub><msub><mrow><mtext>)/Σ</mtext></mrow><mrow><mtext>i</mtext></mrow></msub><msub><mrow><mtext> (n</mtext></mrow><mrow><mtext>i</mtext></mrow></msub><mtext>)</mtext></mrow></math><img file="EP0505000A2_D0001.tif" /></maths> , wherein i= all molecules in the sample, n_i = the number of molecules, and M_i = the molecular mass of each molecule. This is the average molecular weight obtained when the total weight of the sample is divided by the number of molecules in the sample. This molecular weight determines the effect of the sample composition on the osmotic pressure and hence, the effect of the sample composition on the freezing point or other colligative properties of the total mixture.

0028The weight average molecular weight M_w is determined by the formula: <maths id="math0002" num=""><math display="inline"><mrow><msub><mrow><mtext>M</mtext></mrow><mrow><mtext>w</mtext></mrow></msub><msub><mrow><mtext> = Σ</mtext></mrow><mrow><mtext>i</mtext></mrow></msub><msub><mrow><mtext> (n</mtext></mrow><mrow><mtext>i</mtext></mrow></msub><msub><mrow><mtext>M</mtext></mrow><mrow><mtext>i</mtext></mrow></msub><msub><mrow><mtext>²)/Σ</mtext></mrow><mrow><mtext>i</mtext></mrow></msub><msub><mrow><mtext> (n</mtext></mrow><mrow><mtext>i</mtext></mrow></msub><msub><mrow><mtext>M</mtext></mrow><mrow><mtext>i</mtext></mrow></msub><mtext>)</mtext></mrow></math><img file="EP0505000A2_D0002.tif" /></maths> . This molecular weight number weighs molecules proportionally to their molecular weight in the averaging process; that is, the molecular weight M_i is multiplied by the weight n_i*M_i of material of that molecular weight rather than by the number of molecules. This type of average reflects the effect of the sample composition on those properties which depend on the size of the individual molecules, such as effectiveness in light scattering, or ability of the molecule to penetrate into small openings or plug or cover such openings. Thus, a high M_w would be beneficial if penetration of the molecules into the interplanar structure of layered clays in the formulation is to be avoided. While the invention is not limited by this theory, it is believed that when polyethercyclicpolyols of this invention are used in drilling fluids, the presence of molecules possessing large volumes minimizes the swelling of clay components in the wellbore, thereby improving wellbore stability.

0029The centrifuge molecular weight is determined by the formula: <maths id="math0003" num=""><math display="inline"><mrow><msub><mrow><mtext>M</mtext></mrow><mrow><mtext>z</mtext></mrow></msub><msub><mrow><mtext> = Σ</mtext></mrow><mrow><mtext>i</mtext></mrow></msub><msub><mrow><mtext> (n</mtext></mrow><mrow><mtext>i</mtext></mrow></msub><msub><mrow><mtext>M</mtext></mrow><mrow><mtext>i</mtext></mrow></msub><msub><mrow><mtext>³)/Σ</mtext></mrow><mrow><mtext>i</mtext></mrow></msub><msub><mrow><mtext> (n</mtext></mrow><mrow><mtext>i</mtext></mrow></msub><msub><mrow><mtext>M</mtext></mrow><mrow><mtext>i</mtext></mrow></msub><mtext>²).</mtext></mrow></math><img file="EP0505000A2_D0003.tif" /></maths>

0030The ratios M_w/M_n and M_z/M_w are also an indication of the spread or polydispersity in the molecular weight of molecules present in the sample, and by definition M_w ≧ M_n. The ratio M_w/M_n ranges from 50 to 500, and most preferably, in the best formulations of polyethercyclicpolyol, it ranges from 100 to 300. The ratio of M_z/M_w ranges from 1 to 100, and in the most suitable formulations it ranges from 2 to 20. The polydispersity of molecular weights is 2underscored by the appearance of a characteristic binodal molecular weight distribution in virtually all thermal polyethercyclicpolyol samples.

0031In order to attain high M_w values it is necessary to carry out dehydration as far as possible. By dehydration under gradually decreasing pressure it is possible to achieve a degree of dehydration which approaches and exceeds 1 mole of water per mole of glycerol. At this point, theoretically the glycerol feed could have polymerized to yield a single molecule of infinitely high molecular weight. However, in the course of distillation of glycerol from a basic medium, extensive cyclization takes place, which yields compounds such as cis- or trans-2,5-bis(hydroxymethyl)-p-dioxane, cis- or trans-2,6-bis(hydroxymethyl)-p-dioxane and the glycerine acetal of hydracrylaldehyde, or other 5-, 6-, or 7-membered ring structures of which the first two are predominant. The polycondensation of such cyclic structures with linear or branched polyglycerols yields polyethercyclicpolyols. Excellent polyethercyclicpolyols for drilling fluid applications can be obtained by dehydrating to the extent of 1.15 to 1.2 moles of water per mole of glycerol in the product.

0032Polyethercyclicpolyols are characterized by the presence of at least one and usually more than one 5- to 7-membered ring structures per individual molecule in at least 80 percent of the molecular mass. Moreover, a minimum of 20 percent, preferably 30 percent, and most preferably 40 percent, of all molecules of reactant participating in the formation of polyethercyclicpolyols are involved in cyclic structures.

0033A suitable way to achieve such extensive dehydration without undesirable degeneration and gelation of the polyethercyclicpolyols is by the addition of small amounts of polyol, e.g., glycerol, at a later stage of the reaction, for example, when the reaction medium temperature has reached 270 to 280°C at a pressure of 50 to 100 mm Hg, preferably 60 to 90 mm Hg. At least 3 percent by weight of polyol should be added to that effect, although more typically larger aliquots are added not once but several times (indicated with reference numerals 4, 5, 6 and 7). Upon addition of 2 to 6 percent by weight of polyol, e.g., glycerol, (basis final weight of polyol added) at a point after removal, for example, of 0.8 moles of water per mole of polyol, a drop in the temperature of the reacting mixture occurs, the drop being several degrees Centigrade. The drop is caused by the lower temperature of the polyol being added, but more importantly indicates the endothermic nature of the reaction between polyol molecules, or preferably between added polyol molecules and reactive sites in the prepolymerized mixture. For better effectiveness, the added polyol, e.g., glycerol, may be presaturated with alkali metal hydroxide, e.g., sodium hydroxide. Figure 1 shows stepwise addition of polyol with corresponding temperature changes. In general the stepwise addition of glycerol should be initiated when the reaction is at least 40 percent complete (basis the amount of reactant present at the end of the reaction).

0034Upon continued input of heat from an external source, the temperature of the reacting mixtures rises to the previous highest level, or to a higher level, or to a somewhat lower level than the first high temperature, depending upon the molecular weight distribution of polyethercyclicpolyols in the mixture. This results in at least some of the polymerized polyol compounds achieving higher and higher molecular weights. Since the M_w values are very sensitive to the presence of even small amounts of large molecules, this procedure results in increasing M_w values which, generally results in improved performance in drilling mud formulations. This procedure of incremental polyol addition can be repeated any number of times, three being a convenient number. With three additions of polyol the experimental reaction time usually takes 6.5 to 7 hours, and when optimally performed, excellent polyethercyclicpolyols are obtained.

0035The final M_w values obtained are a strong function of the maximum temperature used in the polymerization reaction. Typical maximum temperatures range from 250°C to 295°C at a pressure 40 to 80 mm Hg, preferably 270°C to 295°C, and most preferably 275°C to 285°C.

0036As the reaction approaches 85 percent completion, it is suitable to combine polyol additions with further reductions of pressure, going down to 30 mm Hg, or even lower. This results in deeper dehydration at a given temperature and therefore in higher M_w and M_n values.

0037As the reaction of the present invention approaches completion, it turns from being highly endothermic to being more thermally neutral, and at a dehydration approaching and exceeding 1.2 moles of water per mole of polyol it can become exothermic. This is a reflection of the propensity of the mixture to undergo rapid degeneration of the complex polyethercyclicpolyol structures. In order to avoid the occurrence of such an undesirable degeneration it is preferred to buffer the reaction by adding a small amount of monomeric polyol such as glycerol, for example, 0.2 to 2 percent, and preferably 0.3 to 0.9 percent by weight total (indicated with reference numeral 7). Preferably, there is added 0.5 percent by weight of polyol at a selected time such as when reaction is at least 90 percent complete, or preferably at a point where the reaction is 95 percent complete, i.e., after removal of 1.12 to 1.15 moles of water per mole of polyol in the reaction medium.

0038Figure 1 shows reaction end point control. The dotted line 8 shows what could happen to temperature without a final addition of polyol, as the reaction becomes exothermic, leading to substantial degeneration and the formation of sludge. After reaction is terminated (indicated with reference numeral 9) the polyethercyclicpolyol is removed from the reaction kettle by dilution with at least 20%w water.

0039The below table gives the extent of the reaction and the relative amounts of water removed (in moles water removed per mole of glycerol) from reaction mixture at the stages in the reaction indicated by the reference numerals in Figure 1. <tables id="tabl0001" num="0001"><table frame="all"><title>Table</title><tgroup cols="6" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="26.25mm" /><colspec colnum="2" colname="col2" colwidth="26.25mm" /><colspec colnum="3" colname="col3" colwidth="26.25mm" /><colspec colnum="4" colname="col4" colwidth="26.25mm" /><colspec colnum="5" colname="col5" colwidth="26.25mm" /><colspec colnum="6" colname="col6" colwidth="26.25mm" /><thead valign="top"><row><entry namest="col1" nameend="col6" align="center">Extend of the reaction and relative amount of water removed of the condensation reaction.</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">4</entry><entry namest="col3" nameend="col3" align="center">5</entry><entry namest="col4" nameend="col4" align="center">6</entry><entry namest="col5" nameend="col5" align="center">7</entry><entry namest="col6" nameend="col6" align="center">9</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Glycerol addition (in %)</entry><entry namest="col2" nameend="col2" align="char" char=".">4</entry><entry namest="col3" nameend="col3" align="char" char=".">4</entry><entry namest="col4" nameend="col4" align="char" char=".">4</entry><entry namest="col5" nameend="col5" align="char" char=".">0.5</entry><entry namest="col6" nameend="col6" /></row><row><entry namest="col1" nameend="col1" align="left">Extent of reaction (in %)</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" /><entry namest="col5" nameend="col5" /><entry namest="col6" nameend="col6" /></row><row><entry namest="col1" nameend="col1" align="left">Basis glycerol present</entry><entry namest="col2" nameend="col2" align="char" char=".">76</entry><entry namest="col3" nameend="col3" align="char" char=".">78</entry><entry namest="col4" nameend="col4" align="char" char=".">83</entry><entry namest="col5" nameend="col5" align="char" char=".">96</entry><entry namest="col6" nameend="col6" align="char" char=".">100</entry></row><row><entry namest="col1" nameend="col1" align="left">Basis final total glycerol</entry><entry namest="col2" nameend="col2" align="char" char=".">66</entry><entry namest="col3" nameend="col3" align="char" char=".">71</entry><entry namest="col4" nameend="col4" align="char" char=".">79.5</entry><entry namest="col5" nameend="col5" align="char" char=".">96</entry><entry namest="col6" nameend="col6" align="char" char=".">100</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Water removed</entry><entry namest="col2" nameend="col2" align="char" char=".">0.78</entry><entry namest="col3" nameend="col3" align="char" char=".">0.91</entry><entry namest="col4" nameend="col4" align="char" char=".">1.12</entry><entry namest="col5" nameend="col5" align="char" char=".">1.15</entry><entry namest="col6" nameend="col6" align="char" char=".">1.2</entry></row></tbody></tgroup></table></tables>

0040With glycerol as the primary reaction medium, it is preferable to remove at least 1.05 and more preferably at least approximately 1.12 moles of water per mole of glycerol. Most preferably 1.15 to 1.25 moles of water per mole of glycerol in the product should be removed. If the feed contains an appreciable amount of predehydrated glycerol polymers, then the remaining dehydration will be less than 1.2 moles per mole of glycerol. As an example, for a known commercial product which typically contains 15 percent by weight of bis(hydroxymethyl)-dioxanes, and 85 percent by weight of glycerol the dehydration can be calculated as follows. For approximately 100 grams of feed there are 85 grams of glycerol (0.99 moles) and 15 grams of bis(hydroxymethyl)-dioxane (0.1014 moles). The glycerol component will have to lose 0.92 X 1.2 = 1.104 moles of water. The 0.1014 moles of bis(hydroxymethyl)-dioxane is derived from 0.2028 moles of glycerol by removal of 0.2028 moles of water; 1.2 total moles water per mole of glycerol should be removed, i.e., 0.2028 * 1.2 = 0.2434 moles. Thus, it is necessary to remove 0.2434 - 0.2028 = 0.0406 moles of water. The total to be removed is 1.104 moles from the glycerol + 0.0406 moles from the bis(hydroxymethyl)- dioxane = 1.1496 moles water (or approximately 1.145 moles) from the 100 grams of the known commercial product.

0041Therefore it is necessary to remove close to 1.2 moles of water for each mole of glycerol which enters into the condensation of an initially partially dehydrated glycerol feed stream. Alternatively, in most cases involving complex feed streams, it would be appropriate to carry out the reaction and select a final maximum reaction temperature at set pressure conditions, such as is known from previous experience to yield satisfactory polyethercyclicpolyol preparations.

0042Certain prehydrated glycerol feeds are not suitable for preparation of good quality polyethercyclicpolyol. An example is an extensively degenerated footstill bottoms (heavy ends from glycerol manufacture). In such cases, an acceptable feed may still be recovered from such materials by proper separation/purification. For example, extraction of the lower molecular weight fraction of a footstill bottom product by use of a low molecular weight alcohol, followed by recovery and reuse of the extracting alcohol. Alternatively, however, small amounts of extensively dehydrated polyglycerols can be used as additive components of the glycerol-rich feed, provided they are not unduly degenerated to yield essentially gel-like compositions.

0043Molecular weights referred to below have been determined using a three-column gel permeation chromatographic technique using three Ultrahydrogel columns: a Linear column, a 250 angstrom column, and a 120 angstrom column in series, using water solvent at 30°C. Using this technique, polyethercyclicpolyols produced by the methods described herein range from M_w values of 20 000 to 300 000. Preferred polyethercyclicpolyols have M_w values in the range of 50 000 to 200 000.

0044In accordance with the present invention it has been found that the addition of minor amounts of epoxy resins are beneficial. Epoxy resins are characterized by the presence of a three-membered cyclic ether group commonly referred to as an epoxy group, 1,2-epoxide, or oxirane. Suitable epoxy resins are diglycidyl ethers, triglycidyl ethers, and tetraglycidyl ethers which, in the reacting glycerol or polyol medium, result in the formation of higher molecular weight polyethercyclicpolyols with substantially improved properties in connection with drilling fluid performance.

0045A particularly useful epoxy is a difunctional glycidyl ether such as "EPON 828" (a trademark of Shell Oil Company, diglycidylether of 2,2-bis(4-hydroxyphenyl) propane) which significantly increases the molecular weight of a significant fraction of the polyethercyclicpolyols preparation. Thus, addition of 3 weight percent of "EPON 828" could result in doubling the molecular weight of between 10 and 20 percent of the preparation. By thus increasing the molecular weight of a significant portion of the preparation, the copolymerization of "EPON 828" results in significantly boosting the M_w value of the sample, with attendant significant improvements in the performance of the resulting polyethercyclicpolyols polymer/polyethercyclicpolyols-diglycidyl ether copolymer mixture. In order to obtain polyethercyclicpolyols with maximum coverage potential, it is suitable to use tri- and tetraglycidyl ethers which will direct polymerization along more than one direction in a planar configuration. It is theorized, although the invention is not limited to this theory, that the use of such epoxies facilitates the coverage of openings in the clay surface of an oil well through which water can enter the clay. Thus, it is believed that molecules which are substantially planar in structure are most useful with the invention when it is employed as part of a drilling fluid additive. Additionally, the attachment of several polyethercyclicpolyols onto the same central molecule of polyglycidyl ether, allows multiple coordination of cationic species to occur through the electron donating oxygen atoms in the ether linkages, which results in formation of large molecular aggregates that can inhibit the migration of water molecules from the aqueous phase of the water-based drilling mud onto the hydrophilic clay solids of the formation. Conventional drilling muds containing polyethercyclicpolyols act essentially in a manner similar to that of oil-based muds. This theory, of course, is not limiting of the application of this invention.

0046Experimental results as shown hereinafter show that the impact of using multifunctional glycidyl ethers on the values of M_w and on the performance, particularly as regards swelling of clays when the invention is used as a drilling fluid additive, is truly significant. Thus, when using 3 weight percent "EPON 828" and 3 weight percent "EPON 1031" (tradename of Shell Oil Company, tetraglycicylether of 1,1,2,2,-tetra(4-hydroxyphenyl)-ethane), the M_w values are correspondingly 78,015 and 151,000, and the swelling inhibition is the highest with "EPON 1031", with good performance also observed on inhibition of fluid loss and dispersion.

0047Although the observation of binodal distribution of molecular weights in GPC (three-column chromotography) does not require the presence of epoxies, nevertheless, incorporation of epoxies into the polyethercyclicpolyols structure has a significant impact on the relative amounts of "large" molecules in the polyethercyclicpolyol production, increasing the ratio of large volume molecules/small volume molecules.

0048The following other epoxies are considered useful in the present invention: triglycidylether of tris(4-hydroxyphenyl) methane ("TACTIX 742, trade name for epoxy manufactured by Dow Chemical Company); diglycidylether of 1,4-dihydroxybutane ("HELOXY 67", trade name for epoxy manufactured by Rhône-Poulenc); diglycidylether of 1,4-dihydroxybenzene ("HELOXY 69", trade name for epoxy manufactured by Rhône-Poulenc); diglycidylether of 1,4(dihydroxymethyl)-benzene ("HELOXY 107", trade name for epoxy manufactured by Rhône-Poulenc); and triglycidylether of 2,2(dihydroxymethyl)-1-propanol ("HELOXY 5044", trade name for epoxy manufactured by Rhône-Poulenc).

0049With respect to "EPON 828", it is preferred to add the material in two or three aliquots, generally observing the layer addition until about 40 to 50 percent of the reaction is complete.

0050With "EPON 1031", it is suitable to add all the material at the beginning of the condensation reaction. It is suitable to add a larger amount of "EPON 828" than of "EPON 1031" because of the lower molecular weight of "EPON 828". It is preferred to avoid adding "EPON 828" at temperatures in excess of 270°C, due to risk of premature polymerization. The addition of more volatile polyglycidyl ethers must be carried out with caution due to their potential toxicity and relatively higher volatilities.

0051The invention will now be described in more detail by way of example with reference to the examples.

0052Example 1. Copolymerization of glycerol and diglycidyl ethers to high performance PECP drilling mud additives.

0053About 750g of glycerol were placed in a 2-litre round bottom distillation flask along with 5.8g of sodium hydroxide and 3.6g of sodium acetate and the pressure of the unit was brought to 180mm Hg using a N₂ blanket. The pressure was controlled by a bleed and makeup device using a low pressure N₂ source. The temperature was then raised gradually to 227°C kettle temperature, at which point reflux was obtained through a 1-inch diameter, 15-inch high Vigreaux column, equivalent to ca. 10 plates, connected to the distillation flask. The column was not insulated. A magnetically controlled variable reflux distillation head was used to control the reflux ratio at 1:1 and water-rich overhead was obtained. Under these conditions, the loss of glycerol to the overhead was kept at a minimum and a water-rich overhead was continuously removed as the polycondensation reaction proceeded. An amount of 5cc of liquid "EPON-828", a difunctional glycidyl ether, was added to the mixture immediately after the mixture started refluxing at 227°C to 228°C. By allowing the aqueous overhead to reach a volume of 60cc (about 62g), the boiling temperature of the partially polymerized glycerol mixture reached 248°C at 180mm Hg. The reaction continued to a boiling point of 250°C at 180mm Hg, at which point the pressure was adjusted to 100mm Hg. As a result the kettle temperature was reduced to about 239°C at 100mm Hg. At that point 5cc of liquid "EPON-828" was added. The reaction was continued, and an additional 60cc of aqueous overhead was removed by the time the kettle temperature reached 260°C at 100mm Hg. The pressure was readjusted to 80mm Hg, with a resulting temperature drop to 258°C. At 260°C a final 11cc of "EPON-828" was added. No cooling results upon addition of the "EPON-828" due to the exothermicity of the addition reaction between the epoxy group of "EPON-828" and the hydroxyl groups of the polyethercyclicpolyol present. The reaction was allowed to proceed to 285°C at 80mm Hg, at which point 28cc (36g) of NaOH-saturated glycerol was added. The temperature experienced a drop to 271°C, and rose again to 280°C. The third overhead 60cc fraction was taken about that time. A second addition of 28cc of glycerol (NaOH-saturated) was also made at 280°C, the temperature dropping to 269°C at 80mm Hg. When the temperature rose again to 280°C, the pressure was adjusted to 60mm Hg and after a small temperature reduction of 1°C, there was added a third aliquot of NaOH-saturated glycerol at 280°C. When 50cc of overhead were collected in the fourth overhead fraction, a final addition was made of NaOH-free glycerol (4cc) to prevent the onset of an exothermic reaction. The reaction mixture at this point was 285°C, and a final pressure adjustment to 40mm Hg was made. The reaction was stopped shortly thereafter. The cooled reaction mixture was then diluted with water to 50 weight percent. A determination of the viscosities of this mixture yielded 153 cP at 25°C, and 58 cP at 60°C. The GPC determination of molecular weight using three Ultrahydrogel columns (Linear, 250 angstroms, and 125 angstroms), and using water solvent at 30°C yielded M_n = 380, M_w = 78 000 and M_z = 390 000. The performance of this material as a drilling mud additive was very good.

0054Example 2. Copolymerization of glycerol and triglycidyl ethers into high performance polyethercyclicpolyol drilling mud additives.

0055About 752g of glycerol, 5.4g of sodium hydroxide and 3.6g sodium acetate were placed in the same unit described above. Along with these reagents there was added 21.1g of a Dow triglycidyl ether, trade name "TACTIX-742", prior to heating the mixture. The mixture was then heated and polycondensed as described in Example 1, the first 60cc overhead fraction being obtained at 248°C. No "EPON 828" was added during this run. The reaction proceeded as expected, the kettle temperature rising gradually to 250°C at 180mm Hg, at which point the pressure was adjusted to 100mm Hg. A second 60cc overhead fraction was obtained at 261°C and 100mm Hg, and the pressure was adjusted to 80mm Hg. At 280°C kettle temperature the first addition was made of 28cc (36g) of NaOH-saturated glycerol. A second addition of glycerol was made at 276°C after the mixture was reheated from a minimum of 265°C following the first glycerol addition. The third overhead fraction was taken at 274°C and a pressure adjustment was made at 276°C and the final 28cc of glycerol (NaOH-saturated) was added at 276°C. The temperature was reduced to 262°C by the glycerol addition. At 285°C, a final pressure adjustment was made to 40mm Hg. At 50cc overhead in the receiver a final 4cc addition was made of NaOH-free glycerol to prevent exothermicity. The reaction was stopped at 276°C and 40mm Hg. A total of 1.19 moles of water were removed per mole of glycerol left in the product. The molecular weights measured as in Example 1 were M_n = 375, M_w = 125 000, and M_z - 563 000. The performance of the produced polyethercyclicpolyol with excellent performance in inhibition of fluid loss, cuttings dispersion and swelling in drilling muds. The viscosities of a 50 weight percent water-polyethercyclicpolyol solution for this preparation were 261 cP at 25°C and 93 cP at 60°C.

0056Example 3. Copolymerization of glycerol and tetraglycidyl ethers into high performance drilling fluid additives.

0057About 751g of glycerol, 5.4g of sodium hydroxide, 3.6g of sodium acetate, and 21g of the tetrafunctional glycidyl ether "EPON 1031" were heated in the unit described in Examples 1 and 2 above in a temperature-pressure profile very similar to those described in the above two examples. Addition of glycerol aliquots were made at 280°C, 275°C, and 275°C respectively, and the final addition of a small amount of glycerol (NaOH-free, 4cc) was made at 273°C at 40mm Hg. The resulting polyethercyclicpolyol from this preparation exhibited a viscosity of 483 cP at 25°C and 122 cP at 60°C, when dissolved in a 50 weight percent aqueous solution. The performance characteristics of this material as a drilling fluid additive were outstanding. The M_n, M_w, and M_z values of this product were 460, 151 000 and 575 000.

0058Example 4. Copolymerization of glycerol with mixed glycidyl ethers.

0059In this preparation, both "EPON 828" and "EPON 1031" were used to increase the molecular weights of polyethercyclicpolyols. The "EPON 1031" (11g) was mixed in the feed prior to heating of the mixture. The "EPON-828", on the other hand, was added when the mixture had been gradually heated to 260°C at 80mm Hg. Further delay of the "EPON 828" addition was avoided to prevent any premature curing (due to high temperature) of the glycidyl ether prior to reaction with the polyethercyclicpolyol. The preparation was otherwise quite similar to those described in Examples 1, 2 and 3 above. The resulting product has a viscosity of 270 cP as a 50 weight percent solution at 25°C. The M_n, M_w and M_z values were 391, 148 000 and 700 000. The product is an excellent drilling mud additive, simultaneously inhibiting fluid loss, swelling and dispersion of cuttings.

0060Example 5. Upgrading polyethercyclicpolyols by post-polymerization of low molecular weight polyethercyclicpolyol using glycidyl ethers.

0061In Examples 1 through 4 the multifunctional glycidyl ethers were incorporated into the polyethercyclicpolyol structure by reacting simultaneously the resulting low and high molecular weight cyclic polyethers with the reactive epoxy groups of the glycidyl ethers present or added to the mixture during the reaction. In the present example the glycidyl ethers are used to bind or fuse preformed polyethercyclicpolyols after the dehydration has already taken place. An advantage of this technique is that the polycondensation reaction of the glycerol can be stopped short of the 1.18 moles of water per mole of glycerol left in the product, thus further minimizing the risk of undesirable, and even exothermic, crosslinking and carbonization. In this example, 750g of glycerol, 5.4g of sodium hydroxide and 3.6g of sodium acetate are polycondensed in the 2-litre reactive distillation flask/Vigreaux column assembly in a manner similar to that described in examples 1 through 4. A total of 109g of NaOH-saturated glycerol is added in three aliquots as per examples 1 through 4, and 245g of aqueous overhead is taken. However, no glycidyl ether is added to the mixture either before or during the reaction. Furthermore, the reaction is stopped at about 1.04 moles of water removed per mole of glycerol left in the product. The M_n, M_w and M_z values of the product are 220, 24 000 and 115 000 respectively. The performance of the resulting polyethercyclicpolyol product as a drilling mud additive is acceptable but not outstanding.

0062The 614g of polyethercyclicpolyol product is divided into four equal parts, placed in four separate 500cc Erlenmeyer flasks, and labelled as Samples 5-A, 5-B, 5-C and 5-D. Of these, 5-A is left unreacted to serve as a reference. To sample 5-B, which contains 153g of anhydrous polyethercyclicpolyol, there is added 3.8g of "EPON-828". To 5-C there is added 3.8g of "TACTIX-742", and to 5-D there is added 3.8g of "EPON 1031". The samples are then provided with a magnetic stir bar, blanketed with N₂ gas from a N₂ gas source, and placed in three silicone oil baths, each heated by a hot plate equipped with a magnetic stirrer. The magnetic stirrers are activated when the temperatures in the three samples reach about 190°C, and the mixture is kept at 200°C ± 10°C for ca. 3 hours. After this period, the reaction is stopped and the following observations are made: First, the water-insoluble "EPON 828" phase is no longer visible as a separate phase in 5-B. The solids "EPON 1031" and "TACTIX-742" are likewise not visible as separate phases in 5-C and 5-D. Molecular weight determinations by GPC on Samples 5-B, 5-C and 5-D show substantial increases in the M_n, M_w and M_z values, even though no evidence of polycondensation is seen (no water production). The M_n, M_w and M_z values are approximately as follows: <tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="4" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="39.37mm" /><colspec colnum="2" colname="col2" colwidth="39.37mm" /><colspec colnum="3" colname="col3" colwidth="39.37mm" /><colspec colnum="4" colname="col4" colwidth="39.37mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="center">Sample Designation</entry><entry namest="col2" nameend="col2" align="left">M_n</entry><entry namest="col3" nameend="col3" align="center">M_w</entry><entry namest="col4" nameend="col4" align="center">M_z</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="right">5-A</entry><entry namest="col2" nameend="col2" align="right">220</entry><entry namest="col3" nameend="col3" align="right">24 000</entry><entry namest="col4" nameend="col4" align="right">115 000</entry></row><row><entry namest="col1" nameend="col1" align="right">5-B</entry><entry namest="col2" nameend="col2" align="right">330</entry><entry namest="col3" nameend="col3" align="right">75 000</entry><entry namest="col4" nameend="col4" align="right">360 000</entry></row><row><entry namest="col1" nameend="col1" align="right">5-C</entry><entry namest="col2" nameend="col2" align="right">350</entry><entry namest="col3" nameend="col3" align="right">110 000</entry><entry namest="col4" nameend="col4" align="right">500 000</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="right">5-D</entry><entry namest="col2" nameend="col2" align="right">420</entry><entry namest="col3" nameend="col3" align="right">120 000</entry><entry namest="col4" nameend="col4" align="right">550 000</entry></row></tbody></tgroup></table></tables> The performance of the four samples improves as the molecular weight of the polyethercyclicpolyols increases from 5-A to 5-B to 5-C and to 5-D.