MXPA00010629A - High molecular weight polyols, process for preparation and use thereof - Google Patents

Abstract

The invention is a high molecular weight polyether polyol prepared by the reaction of one or more compounds having one or more active hydrogen compounds with one or more alkylene oxides in the presence of a catalyst comprising calcium having counterions of carbonate and a C6-10 alkanoate in a solvent or dispersant which does not contain active hydrogen atoms. The polyether polyol prepared preferably has an equivalent weight of from 1,000 to 20,000, a polydispersity of 1.3 or less and a residual catalyst level of from 0 to 2000 parts per million (ppm). In another embodiment the invention is a process for preparing such high molecular weight polyether polyols. The process comprises first, contacting one or more compounds having one or more active hydrogen atoms with one or more alkylene oxides in the presence of a catalyst. The catalyst comprises calcium having counterions of carbonate and a C6-10alkanoate in a solvent, wherein the solvent does not contain active hydrogen atoms. The mixture is exposed to conditions at which the alkylene oxides react with the compound containing more than one active hydrogen atom such that a polyether polyol is prepared which has an equivalent weight of from 1,000 to 20,000, a polydispersity of 1.3 or less and a residual catalyst level of from 0 to 1000 (ppm).

Description

POLYOLS OF HIGH MOLECULAR WEIGHT. PROCESS FOR ITS PREPARATION, AND ITS USE This patent application relates to novel polyether polyols, based on high molecular weight alkylene oxide, and to a process for their preparation. This application further relates to the use of said polyether polyols based on alkylene oxide, of high molecular weight, to prepare useful prepolymers adhesives and high functionality elastomers. This invention further relates to high viscosity polyether polyols, useful as lubricants. The invention is further related to polyether polyols of high molecular weight, useful as thickeners in hydraulic fluids. The polyether polyols used in the preparation of polyurethane derivatives and elastomers are usually prepared by reacting an initiator compound having a plurality of active hydrogen atoms, with an alkylene oxide, in the presence of basic catalysts, such as tertiary amines, hydroxides of sodium and potassium, and sodium; where a sodium derivative, such as alkylate or alkoxide, is formed in situ. However, these catalysts must usually be removed by filtration and / or neutralization, or other methods to remove catalysts, before use; particularly when preparing prepolymers from said polyether polyols. Olstowski and Nafziger, in US Pat. No. 4,282,387, issued August 4, 1981, described the preparation of polyols by reacting alkylene oxides with hydroxyl initiator compounds, in the presence of calcium, strontium or barium salts catalysts, of organic acids . There is no need to remove these catalysts before using the resulting product in the preparation of polyurethanes. Such catalysts are generally available in a mineral spirits solvent, which additionally contains monoether glycols. These monoether glycols contain active hydrogen atoms and act as initiators. This results in the preparation of a mixture of polyoids, where some of the polyols are monofunctional with respect to the hydroxyl group. The presence of monofunctional polyether polyols decreases the physical properties of the elastomers that are formed therefrom. They also form polyether polyols which have low molecular weight species, and which result in high polydispersity. Polydispersity is defined as the weight average molecular weight divided by the number average molecular weight. A high polydispersity indicates that the polyether polyol prepared is a mixture of polyether polyols having a broad scale of molecular weights. High polydispersity and low molecular weight make such polyether polyols unsuitable for high performance applications, such as elastomers and high functionality adhesives. Many of the polyether polyols prepared using said catalyst system are initiated with a monofunctional glycol ether and are monofunctional and, therefore, are not useful in high functionality applications. Yates and co-inventors, US Pat. No. 4,326,047 describe a process for preparing polyols using the catalysts described in Olstowki, where the catalyst is precipitated from, the mineral spirits carrier and the glycol ether coupling agent. The resulting catalyst is solid. To be effective, this catalyst must be dissolved again in the reaction medium. This extra step is delayed and negatively affects the productivity of the reaction and the polydispersity of the product prepared. Hydraulic fluids are generally thickened with polyether polyols. In order to obtain the desired viscosity of said hydraulic fluids, it is frequently necessary to use a high concentration of polyether polyols in water-based hydraulic fluids. A common hydraulic fluid is ISO VG46, a hydraulic fluid that has a viscosity of 46 centistokes at 40 ° C. Most of the polyether polyols used in this application have a relatively low molecular weight. In order to prepare a hydraulic fluid that satisfies this requirement, with these low molecular weight polyethers, a concentration of 30 to 70% by weight of polyether polyol is required. This formulation is expensive, due to the need for a high concentration of polyether polyols These are known polyethylene polyethylene oxide based polyethers used as thickeners in hydraulic fluid, obtainable from Union Carbide under the brand POLYOX WSRN-10 ™, these generally have a molecular weight of 100,000 or more, can be used at low concentration, but exhibit poor shear stability and the fluid containing these polyethers is not stable under shear stress and suffers from a reduction In the viscosity, during use, it would be convenient to have a polyether polyol of high molecular weight, which could thicken the hydraulic fluid at the desired level, at a significantly lower concentration and which would be stable to the shear stress Some lubricants are designed to have certain viscosities at 40 ° C, ISO VG 1000 lubricants demonstrate a viscosity of 1000 centistokes at 40 ° C. ISO VG 2000 manufacturers demonstrate a viscosity of 2,000 centistokes at 40 ° C. Polyether polyols made with basic catalysts generally do not have sufficient molecular weight to achieve the desired viscosities. High molecular weight polyether polyols that have sufficient viscosity to function like those lubricants are convenient. What is needed is that there are high molecular weight polyether polyols, which are useful in high functionality applications. A process is also necessary for the preparation of these high functionality polyether polyols. There is also a need for a prepolymer useful in the preparation of high functionality elastomers and adhesives, prepared from those high molecular weight polyether polyols. Polyether polyols of high molecular weight which can be used as thickeners in water-based hydraulic fluids and which are stable to shear stress under lubrication conditions are also necessary. A polyether polyol of high viscosity is also necessary, which can obtain the desired viscosities ISO VG 1000 and ISO VG 2000. The invention is a polyether polyol of high molecular weight, prepared by reaction of one or more compounds having one or more active hydrogen compounds, with one or more alkylene oxides, in the presence of a catalyst comprising calcium, which has opposite ions of carbonate and an alkanoate of 6 to 10 carbon atoms, in a solvent or dispersant that does not contain hydrogen atoms active. The polyether polyol prepared preferably has an equivalent weight of 1000 to 20,000, a polydispersity of 1.3 or less, preferably 1.2 or less, and a residual catalyst level of 0 to 2000 parts per million (ppm), preferably up to 1000 ppm. . In another embodiment, the invention consists of a process for preparing said polyether polyols of high molecular weight. The process comprises first contacting one or more compounds having more than one active hydrogen atom, with one or more alkylene oxides, in the presence of a catalyst. The catalyst comprises calcium having opposite ions of carbonate and an alkanoate of 6 to 10 carbon atoms, where the solvent does not contain active hydrogen atoms. The mixture is exposed to conditions at which the alkylene oxides react with the compound containing more than one active hydrogen atom, so that a polyether polyol having an equivalent weight of 1,000 to 20,000 and a polydispersity of 1.2 is prepared. or less, and a residual catalyst level of 0 to 2000 ppm. In another embodiment the invention is a hydraulic fluid comprising from 1 to 50 weight percent of a polyether polyol as described above, and 50 to 99 weight percent water. Said polyether polyols allow the preparation of hydraulic fluids having the required viscosities, with a lower concentration of polyether polyols incorporated in said hydraulic fluids, than has been possible until now. These polyether polyols are stable to shear stress under the conditions of use. In yet another embodiment, the invention is a lubricant composition comprising a polyether polyol as described hereinabove. In still another embodiment, the invention is a prepolymer comprising the uct of the reaction of a polyether polyol as described above, with an isocyanato silane having at least one silane moiety having a hydrolysable moiety attached thereto. The invention, in another embodiment, is a ess for preparing a silyl-terminated prepolymer. The ess comprises contacting a polyether polyol, as described herein, with an isocyanato-isan having at least one silane portion having a hydrolysable portion attached thereto. The polyether polyol and the isocyanatosilane react under conditions such that the hydroxy portions of the polyol react with isocyanate portions of the silane in order to place the terminal silane portion in the polyether polyol. The ess is preferably carried out without adding catalyst. The ess of the invention allows the preparation of high molecular weight polyether polyols, which have low polydispersity. Polyether polyols are useful in the preparation of reactive silicone functional polyurethane and prepolymers, which are stable under ambient conditions. Said prepolymers are useful in the preparation of elastomers, sealants and adhesives. Figure 1 illustrates the gel permeation chromatography curves of two polyols; a polyol according to the invention and a second polyol, made in accordance with the prior art closest to the present. The polyether polyols of the invention are generally prepared by reacting an initiator, a compound having one or more active hydrogen atoms, with an alkylene oxide, in the presence of a suitable catalyst, under appropriate conditions so that the alkylene oxide react with the active hydrogen portion of the initiator, so as to increase a series of ether units to the initiators, thereby preparing a polyether polyol. The initiators that are useful in this invention are well known to those skilled in the art. Preferable initiator compounds, which are used to prepare the polyether polyols are compounds having from 1 to 8, preferably from 2 to 8, more preferably from 2 to 4, most preferably 2 or 3, active hydrogens. Preferable initiator compounds include, for example, alcohols, glycols, low molecular weight polyols, glycerin, trimethylolpropane, pentaerythritol, glucosides, sugars, ethylenediamine, diethylenetriamine. Particularly suitable glycols include: ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butyl glycol, 1,2-pentylene glycol, 1,3-penti lengl icol, 1, 4-pentylene glycol, 1,5-pentylene glycol, neopentyl glycol and various hexanediols, and mixtures thereof. The alkylene oxides useful in this invention are well known to those skilled in the art and are described in U.S. Patent 4,326,047 and U.S. Patent 4,282,387. Preferred alkylene oxides include: ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-buylene oxide or hexene oxide. The most preferred alkylene oxides are: ethylene oxide and propylene oxide, the most preferred of all being propylene oxide. It is possible to use combinations of the alkylene oxides mentioned above in random polymers or block polymers. The catalysts used to prepare the polyether polyols of this invention are calcium catalysts containing counter ions of both carbonate and alkanoate of 6 to 10 carbon atoms, and preferably counterions of 8 carbon atoms. The catalyst is dispersed or dissolved in a dispersant or solvent that has no active hydrogen atoms, capable of initiating a polyether. It is preferable that the solvent or dispersant be a hydrocarbon or a mixture of hydrocarbons and be soluble or dispersible in the polyether polyol and the components used to prepare the polyether polyol. In a more preferred embodiment, the solvent or dispersant consists of mineral spirits. It is preferable that the alkanoate counter ions be from 6 to 10 carbon atoms and, more preferably, residues of 8 carbon atoms, of organic carboxylic acids. In a preferred embodiment, the alkanoates are derivatives of substantially pure organic carboxylic acids. Preferably the pure carboxylic acids are synthetic carboxylic acids, since the synthetic ones generally exhibit higher purity. The carbonate counter ions are the result of contacting calcium and the organic carboxylic acid, with carbon dioxide. The ratio of calcium ions to organic acid ions is from 1: 0.2 to 1: 1. It is preferred that the ratio be from 1:03 to 1: 0.7. The catalysts can be prepared by contacting the appropriate ratio of calcium hydroxide with a carboxylic acid of 6 to 10 carbon atoms, and bubbling carbon dioxide through the mixture to form carbonate portions. The use of a solvent without active hydrogen atoms prevents the undesirable initiation of polyols with an undesirable initiator. It is believed that the use of substantially pure organic acids improves the polydispersity and performance of the resulting polyols in the applications described herein. In the preparation of the polyether polyols of the invention, the initiating alkylene oxides and the catalyst are contacted in an appropriate solvent. Typically contact takes place in the absence of oxygen and atmospheric moisture. It is preferred to make contact under an inert atmosphere, as nitrogen or argon. The initiator ratio to alkylene oxide is selected to obtain the desired molecular weight or an equivalent weight of the polyether polyol. The reason can be easily calculated, by whoever is an expert in the field. The amount of catalyst used must be sufficient for the residual catalyst remaining in the polyether polyol when the reaction is complete to be 0 ppm or more, more preferably, 200 ppm or more and, most preferably, 300 ppm or more. It is preferable that the amount of catalyst used be selected such that the amount of catalyst remaining in the polyether polyol upon completion of the reaction is 2000 ppm or less and, more preferably, 1000 ppm or less. In the embodiment in which the polyether polyol is used to prepare elastomers, the resulting, high molecular weight polyether polyol preferably contains a residual amount of catalyst of 200 ppm or more, more preferably, 300 ppm or more and , very preferable, 400 ppm or more. It is preferred that the residual catalyst level be 1000 ppm or less, more preferably, 800 ppm or less, and still more preferably, 600 ppm or less; and what is most preferred, 500 ppm or less. In some embodiments when the polyether polyol is used to prepare elastomers, it may be convenient to remove all of the residual catalyst. In the embodiment in which the polyether polyol is used in a hydraulic fluid or a lubricant, the resulting, high molecular weight polyether polyol contains a residual amount of catalyst of 200 ppm or more, more preferably, 300 ppm or more , and most preferably, 400 ppm or more. It is preferable that the level of residual catalyst is 2000 ppm or less, more preferably, 1000 ppm or less, still more preferable, 800 ppm or less and, most preferably, 600 ppm or less. In some embodiments it may be convenient to remove the residual catalyst from the polyether polyols of the invention. This can be achieved by contacting the polyether polyol of the invention with magnesium silicate or phosphoric acid and filtering the polyol with dimamate earth. The calcium catalyst complex and the additives are removed in the filter material. In those modalities in which calcium is eliminated, the resulting parts per million of catalyst that remain in the polymer can be zero. The reagents are preferably reacted at a temperature of 90 ° C or more, more preferably, 100 ° C or more and, most preferably, 110 ° C or more. The reagents are preferably reacted at a temperature of 150 ° C or less, more preferably, 130 ° C or less and, most preferably, 120 ° C or less. The reagents are contacted for a sufficient time to prepare the desired high molecular weight polyether polyol. The reaction time is controlled by the feed rate, reactor size, catalyst concentration and temperature. Anyone who is an expert in the field can determine the appropriate time, based on these variables. The unreacted alkylene oxides and any solvents can be removed from the reaction by stripping them off using means well known to those skilled in the art. In the embodiment in which the polyether polyol is used to prepare elastomers, the polyether polyol preferably has a weight average molecular weight of 2,000 or more, more preferably, 3,000 or more; even more preferable, 6,000 or more and, most preferable, 10,000 or more. The resulting polyether polyol preferably has a weight average molecular weight of 20,000 or less, more preferably, 16,000 or less and, most preferably, 14,000 or less. In the embodiment in which the polyether polyol is used in a hydraulic fluid, it is preferred that the polyether polyol has the weight average molecular weight of 20,000 or more, more preferably, 25,000 or more, and most preferably, 30,000 or more . The resulting polyol preferably has a molecular weight of 80,000 or less, more preferably, 60,000 or less and, most preferably, 50,000 or less. In the embodiment in which the polyether polyol is used as a lubricant, the polyether polyol preferably has a weight average molecular weight of 1,000 or more, more preferably, 2,000 or more, most preferably, 5,000 or more. Preferably the resulting polyol has a weight average molecular weight of 20,000 or less, more preferably, 16,000 or less and, still more preferably, 12,000 or less; and very preferable, 10,000 or less. The resulting polyether polyol preferably has a polydispersity of 1.20 or less and, more preferably, 1.12 or less. It is preferred that the polyether polyol of the invention correspond to formula 1: R1 - ((CH (R2) CH (R2) 0) m - H), (D wherein: R1 is the residue of a compound having 1 to 8 active hydrogen atoms; R2 is, independently in each occurrence, hydrogen or a saturated or unsaturated hydrocarbon chain, of 1 to 6 carbon atoms; m is independently in each occurrence, such a number, that the equivalent weight of the polyether polyol is from 1,000 to 20,000; and p is independently, in each occurrence, from 1 to 8. It is preferable that R1 is an alkyl or cycloalkyl portion of 1 to 8 carbon atoms, or oxygen. It is more preferred that R1 is an alkyl group of 2 to 4 carbon atoms, or oxygen. It is preferred that R 2 is hydrogen, methyl or ethyl and what is most preferred is that it is hydrogen or methyl. In the embodiment in which the polyether polyol is used to prepare an elastomeric composition, m, independently in each occurrence, is a number such that the equivalent weight of the polyol is from 1,000 to 20,000 and, more preferably, from 5,000 to 8,000. . In the embodiment in which the polyether polyol is used to prepare a hydraulic fluid, m is independently in each occurrence, a number such that the equivalent weight of the polyol is 10,000 to 30,000, and more preferably, 10,000 to 20,000. In the embodiment in which the polyether polyol is used as a lubricant, m is independently in each occurrence, a number such that the equivalent weight of the polyol is from 2,000 to 7,000 and, more preferably, from 3,000 to 5,000; more preferable, from 3,000 to 4,000. It is preferred that p is 4 or less and, more preferably, 3 or less. In the embodiment wherein R1 is oxygen, p must be 2. The polyether polyols of the invention also demonstrate a low level of unsaturation, preferably 0.04 milliequivalents of unsaturation per gram of polyol, or less; and more preferably, 0.02 milliequivalents of unsaturation per gram of polyol, or less. The high molecular weight polyether polyols of this invention can be used to prepare functional prepolymers with reactive silicone. Said prepolymers are prepared by reacting a polyether polyol of high molecular weight, of this invention, with an isocyanatosilane. Said isocyanatosilane requires a silane group with a hydrolysable portion attached thereto. The isocyanate portion of the isocyanatosilane reacts with the active hydrogen atoms of the polyether polyol to place the reactive silicone-containing portion in the polyol. The isocyanatosilanes useful in the invention are described in US Pat. No. 4,618,656, in column 3, lines 24 to 34. It is preferred that said isocyanatosilanes correspond to the following formula. 0 = C = N - Z - wherein: R3 independently at each occurrence, is a hydrolysable portion, R4 independently at each occurrence is hydrogen or a hydrocarbyl portion; a independently in each occurrence is an integer from 0 to 2; Z independently in each occurrence is a divalent hydrocarbyl portion, of 1 to 40 carbon atoms. In the formula mentioned above, Z is preferably a divalent hydrocarbyl portion, of 1 to 20 carbon atoms, more preferably, alkylene of 1 to 8 carbon atoms and, most preferably, alkylene of 1 to 3 carbon atoms. R3 is preferably a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an amino-oxy group, a mercapto group or an alkylenoxy group. Among them, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an amino-oxy group, a mercapto group or an alkenyloxy group are preferred. In particular, an alkoxy group, for example, a methoxy or ethoxy group, was preferred because of the possibility of moderately hydrolyzing it and the ease of handling it. The reaction of an isocyanatosilane with a polyol is well known to those skilled in the art. The process for the preparation of a silyl-terminated prepolymer comprises contacting a polyether polyol with an isocyanato silane having at least one silane portion having a hydrolysable portion attached thereto., under such conditions, that the hydroxy portions of the polyol react with the isocyanate portions of the silane, in order to place a terminal silane moiety in the polyether polyol, where contact is carried out without the addition of catalyst. The reaction of the polyether polyol with an organofunctional syllabus can be carried out using conventional processes, such as those described in U.S. Patent No. 4,625,012. The polyether polyols of the invention allow the preparation of silane-terminated polyethers, by reaction of isocyanatosilanes with the polyether polyols of the invention, without the addition of additional catalysts. The residual calcium catalysts of the reaction sequence for the formation of the polyether polyol are sufficient to catalyze the reaction. After the reaction is complete, the residual calcium catalyst can be neutralized with acid. If desired, a common polyurethane catalyst can be added, such as those described in US Pat. No. 4,625,012, in column 5, lines 14 to 23. It is disadvantageous to add said catalysts, since this can negatively impact the stability of the prepolymer. Prepared It has been found that the prepolymer, if prepared in the absence of ordinary polyurethane catalysts and currents, is stable to condensation, if exposed to atmospheric moisture. Said prepolymer can be used to prepare elastomers and adhesive compositions. Those elastomeric materials in the adhesive compositions demonstrate better stability and better elastomeric properties if they are prepared in the absence of additional polyurethane catalysts. The reaction of the isocyanatosilane with a polyol preferably takes place at a temperature of 0 ° C or more and, more preferably, 25 ° C or more. It is preferred that the reaction take place at a temperature of 150 ° C or less and, more preferably, at 80 ° C or less. It is preferable to carry out this reaction in an inert atmosphere, such as under nitrogen blanket. The reaction is allowed to proceed until the desired silane functionality is obtained. In a preferred embodiment, a sufficient amount of isocyanatosilane is used to react with all of the hydroxyl functionality contained in the polyol. In one embodiment, a polyurethane prepolymer can be prepared from the polyether polyols of the invention. These prepolymers are prepared by reacting the polyether polyols with a polyisocyanate (having two or more isocyanate moieties per molecule) This reaction is well known in the art See 1 Hsieh, US Patent 5,852,137 A prepolymer having functionality is prepared Isocyanate when there is an excess of isocyanate equivalents in the reaction, compared to the active hydrogen-containing portions The prepolymer will be hydroxyl-functional if an excess of polyol is used, compared to the isocyanate The prepolymer can be prepared by any suitable method , such as bulk polymerization and solution polymerization The reaction is carried out to prepare the prepolymer under anhydrous conditions, preferably under an inert atmosphere, such as a blanket of nitrogen, to prevent entanglement of the isocyanate groups by atmospheric moisture. preferably carries out the reaction at a temperature of 0 C or more and more preferably 25 ° C or more. The reaction is preferably carried out at a temperature of 150 ° C or less and, more preferably, 80 ° C or less. The reaction is allowed to proceed until the residual isocyanate content, determined by titration of a sample, is very close to the desired theoretical value. The reaction can be carried out to prepare the prepolymer in the presence of the urethane catalyst. Examples thereof include the stannous salts of carboxylic acids, such as stannous octoate, stannous oleate, stannous acetate and stannous laurate. Dialkyltin dicarboxylates are also known in the art., such as dibutyltin dilaurate and dibutyltin diacetate, as urethane catalysts, as well as tertiary amines and tin mercaptides. It is preferred that the reaction to prepare the prepolymer be catalyzed by stannous octoate. The amount of catalyst employed is generally between 0.005 and 5 weight percent of the catalyzed mixture, depending on the nature of the isocyanate. In a preferred embodiment, the residual catalyst of the polyol synthesis reaction is sufficient to catalyze the preparation of the prepolymer without addition of another polyurethane catalyst. The polyurethane prepolymers can be used in adhesive compositions, as described in Risk, US Pat. No. 4,758,648; Bhat, US Pat. No. 5,603,798; and Hsieh, US Pat. No. 5,852,137. Adhesive compositions containing polyurethane prepolymers, prepared as described herein, without the addition of a polyurethane catalyst, demonstrate improved stability as compared to formulations in which the prepolymer is prepared using a common urethane catalyst. In addition, these polyurethane prepolymers form elastomers when cured by known curing agents or crosslinkers. The interleavers used in this invention include any interleaver which is known and which preferably has an equivalent weight of 200 or less. Interleavers, as used herein, refer to compounds that are also commonly referred to as chain extenders. These crosslinkers are low molecular weight compounds that have two active hydrogen atoms, which react with socianate moieties. Preferred crosslinkers are alkenediols of 3 to 10 carbon atoms, cycloalkylene diols of 3 to 10 carbon atoms, di (beta-hydroxyethyl) ether of hydroquinone, ethoxylated bisphenol A, 4,4'-methylenebis (2-chloroaniline), 4, 4'-methylenebis (3-chloro-2,6-diethylaniline), 3,5-dimethylthio-2,4-toluene-diamine, 3,5-dimethylthio-2,6-toluenediamine, di-p-aminobenzoate of trimethylene glycol and 1,4-bis (beta-hydroxyethoxy) benzene. Examples of alkylene dioxides of 3 to 10 carbon atoms are: 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-eti I- 1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol and 2-b ut i l-2-ethyl-1,3-propanediol. Interlators are preferably present in an amount of 1 percent by weight or more and, more preferably, 5% by weight or more, based on the total weight of the formulation. It is preferred that the crosslinking agent be present in an amount of 30 weight percent or less, based on the total weight of the total formulation and, more preferably, 15 percent or less. Elastomers can be prepared in the presence of normal polyurethane catalysts. Additionally, normal elastomeric additives, such as fillers and antioxidants may be present. The elastomers can be formed at temperatures of 15 ° C or more, more preferably, 20 ° C or more and, most preferably, 25 ° C or more. It is preferred to form the elastomers at a temperature of 100 ° C or less, more preferably, 40 ° C or less. After forming them, the elastomers can be subjected to curing conditions. These curing conditions include curing at 80 ° C or more for one hour or more, and can be further cured at 80 ° C or more and, preferably, at 100 ° C or more, for 12 hours or more, and preferably for 24 hours or more. In another embodiment of the invention, the polyether polyols of the invention can be used as thickeners in water-based hydraulic fluids. In those embodiments the alkylene oxides used to prepare the polyether polyols are preferably ethylene oxide and propylene oxide, and the initiator is preferably a difunctional or trifunctional initiator, more preferably, a trifunctional initiator. In a preferred embodiment the polyether polyol is a mixture of ethylene oxide and propylene oxide units in block form or in random form. It is preferable that the ethylene oxide units be 95 weight percent or less of the polyether polyol and, more preferably, 75 weight percent or less of the polyether polyol. A sufficient amount of the polyether polyol is used to obtain the desired viscosity of the fluid. A normal lubricating quality is ISO VG 46 hydraulic fluid, which has a viscosity of 46 centistokes at 40 ° C. The polyether polyols of the invention exhibit the appropriate viscosity at less than 30 weight percent of the polyether polyol in the formulation. It is preferable that the formulation contains 5 weight percent or more of the polyol of the invention; more preferably, 10 weight percent or more of the polyether polyol and, most preferably, 14 weight percent or more of polyether polyol. It is preferred that the formulation has 30 wt% or less of polyether polyol, more preferably, 29 weight percent or less of polyether polyol, still more preferable, 20 weight percent or less, and most preferably, 16 weight percent or less. It is preferable that the formulation contains 70 weight percent or more water, more preferable, 71 weight percent or more water, more preferable, 80 weight percent or more water, and, most preferably, 84% in weight or more of water. Preferably the formulation has 95 percent by weight or less of water, more preferably, 90 percent by weight or less of water and, most preferably, 86 percent by weight or less of water. At higher ethylene oxide contents in the polyether polyol, the polyether polyol can be phase separated from water at elevated temperatures. Under certain circumstances the polyether polyol will phase-separate from the aqueous base of the hydraulic fluid. In this embodiment of the polyether polyol it is preferred that it has an ethylene oxide content of 75 weight percent or more, more preferably, a polyethylene oxide content of 90 weight percent or less and, most preferably, 80 weight percent. cent in weight or less. This phase separation preferably occurs at a temperature of 50 ° C or more and, most preferably, at 70 ° C or more and, preferably, at 80 ° C or less. This phase separation of the base fluid allows for easy recovery of the polyether polyol from the hydraulic fluid used and is more environmentally friendly. The hydraulic fluids of the invention are more stable to shear stress and the polyether polyols of the invention dissolve in the aqueous solution more easily than conventional polyols, ie, POLYOX, polyols based on polyethylene oxide.

The hydraulic fluids of the invention may additionally contain other components well known to those skilled in the art. The additives used in these hydraulic fluids are described in U.S. Patent No. 4,481,125; in U.S. Patent No. 4,312,768; in U.S. Patent No. 4,093,554; in U.S. Patent 4,391,722; in U.S. Patent 4,686,058; in U.S. Patent 5,326,485 and U.S. Patent 4, 702, 854. In one embodiment, certain polyether polyols of the invention can be used as lubricants. In that embodiment, the polyether polyol comprises the bulk of the lubricant. Common additives, known to those skilled in the art, can be mixed with the polyether polyol to prepare the lubricant. The final lubricant or hydraulic fluid compositions of those embodiments may contain effective amounts of ashless additives, such as antioxidants, corrosion inhibitors, metal deactivators, lubricity additives, extreme pressure additives and viscosity modifiers, as necessary. The polyether polyols used as lubricants are prepared as described above, the viscosity being monitored until the desired viscosity is obtained. Lubricants having a viscosity of 1000 centistokes and 2000 centistokes at 40 ° C can be prepared from the polyether polyols of the invention, as described. Examples of useful ashless antioxidants that could be used here are phenylnaphthylamines, ie both alpha- and beta-naphthylamines; diphenylamine, minodibenzyl; p, p-dibutyl-diphenylamine; p, p-dioctyldiphenylamine and their mixtures. Other suitable antioxidants are hindered phenolics, such as 2-tert-butylphenol, 2,6-di-tert-butylphenol and 4-methyl-2,6-diterbutylphenol. Examples of suitable, ashless, metallic corrosion inhibitors are those commercially available, such as IRGALUBE 349 ™, from Ciba-Geigy. This inhibiting compound is an aliphatic amine salt of the monohexylic ester of phosphoric acid. Other useful metal corrosion inhibitors are NA-SUL DTA ™ and NA-SUL EDS ™ from King Industries, Inc. (dinonylnaphthalene sulfonate, diethylenetriamine dlnonylnaphthalenesulfonate and ethylene diamine dinnaylnaphthalene sulfonate) and Sarcosyl O, N-methylloleosarcosine, from Ciba , Inc. Examples of suitable ashless metal deactivators are imidazole, benzimidazole, pyrazole, benzotriazole, tolutriazole, 2-methylbenzimidazole, 3,5-dimethylpyrazole and methylenebis-benzotriazole. Examples of suitable viscosity modifiers are pentaerythritol tetrapelargonate and tirmetololpropane triheptonate. An effective amount of the foregoing additives, for use in a lubricant or in a hydraulic fluid, will generally be in the range of 0.1 to 5.0 weight percent for the antioxidant, 0.1 to 5.0 weight percent for the corrosion inhibitors, and 0.001 to 0.5 percent by weight for metal deactivators. The above percentages by weight are based on the total weight of the polyether polyols. It should be understood that more or less additive may be used, depending on the circumstances in which the final composition is to be used. Unless otherwise noted, all molecular weights, when used here, are determined by titration to determine the hydroxyl number and calculate the molecular weight according to the formula: molecular weight equals functionality (56.1 x 1000 / OH #). If the molecular weight is designated as the number average molecular weight, it is determined according to gel permeation chromatography. The following examples were included for illustrative purposes only, and are not intended to limit the scope of the invention. Unless stated otherwise, all parts and percentages are based on weight.

EXAMPLE 1 PREPARATION OF A POLYETER DIOL. OF HIGH MOLECULAR WEIGHT It was placed in a pressure reactor, dried, steam-heated and stirred, which was then purged several times with nitrogen, a mixture of 97.3 g of polyglycol P1000, a polyol propylene oxide diol of molecular weight 1000, from which essentially all of the catalyst (KOH) had been removed. , and 9.73 g of 10 percent calcium, CM ALL D10 ™ (50% by weight calcium isooctoate in mineral spirits carrier, and containing no glycol ether stabilizers, obtainable from OMG Americas, Cleveland, Ohio). The mixture was heated to 100 ° C and 1.985 g of propylene oxide was added with rapid stirring. The product was a liquid having an equivalent weight of 5.218, determined by a wet method, for hydroxyl analysis. The average molecular weight of product number was 9.978, as determined by means of gel permeation chromatography, using polyglycol standards and a polydispersity of 1.1, determined by size exclusion chromatography.

EXAMPLE 2 PREPARATION OF AN ISOCYANATE PREPOLIME. OF HIGH MOLECULAR WEIGHT 300.35 g of the polyglycol of Example 1 were mixed with 600 g of toluene and stirred at 23 ° C until it was mixed well. 8.2 ml of toluene diisocyanate was added and heated to 100 ° C with stirring. After two hours the toluene was removed in vacuo. 308 g of a clear, viscous, light yellow liquid was recovered. The IR spectrum of the product isocyanate had peak at 2274. CM-1 and the urethane peak were gradually reduced to 1,650 CM-1 increase, indicating that most of the isocyanate had reacted. This NCO concentration of the mixture was 0.69 percent, when measured by the wet chemical method.

EXAMPLE 3 PREPARATION OF AN ELASTÓMERO DE URETANO DE ELEVADO MOLECULAR WEIGHT 1.7 g of dibutyltin dilaurate (CATACHK 820 ™ from Ferro Chemical Corp.) was added to 170 g of the product of Example 2. The mixture was mixed well. A 30 milliliter film was emptied onto glass plates and allowed to cure overnight at 23 ° C. The film showed good adhesion to the glass plates. The elastomer was cured in a chamber with a relative humidity of 70 percent for four days. The average physical properties of the elastomer (five duplicates) were 2075 kPa of tensile strength, 78.9 kPa of modulus, 0.29 kg of load at tearing and an elongation at break of 934 percent.

EXAMPLE 4 PREPARATION OF SILICONE FINISHED POLYETER. OF HIGH MOLECULAR WEIGHT In a 500 milliliter round bottom flask, mechanically stirred, dried, heated and purged with nitrogen, was added 134.94 g of the product of example 1, 6.33 g of Siliquest A1310, gamma-isocyanatopropyltriethoxysilane and 1.52 g of dilaurate of dibutyltin. The mixture was heated to 100 ° C with stirring and allowed to cool immediately to room temperature. A 30 milliliter film was stretched on glass plates. The film was allowed to cure in the humidity overnight. The film was tack-free in 24 hours. The film was placed in a humidity chamber at 70 percent for 5 days, and then placed in an oven at 50 ° C overnight. the cured film had a tensile strength of 503 kPa, modulus of 241 kPa and an elongation at break of 347 percent.

EXAMPLE 5 PREPARATION OF A LUBRICANT ISO VG 1000 It was placed in a pressure reactor, heated with dry and stirred steam, which was subsequently purged with nitrogen several times, a mixture of 792 g of polyglycol PB200, a monol of polypropylene oxide, of molecular weight 910, initiated with n-butanol, from which essentially all the catalyst (KOH) had been removed, and . 3 g of calcium CEM ALL D10 ™ at 10%. The mixture was heated to 100 ° C and 5.230 g of propylene oxide was added, with rapid stirring. The product was a liquid that had an equivalent weight of 4,968, determined by a wet method for hydroxyl analysis.

The average molecular weight of the product number was 5,000. The polydispersity was 1.26, as determined by size exclusion chromatography. The viscosity at 37 ° C was 1,182 cS (1,182x10'3 m2 / s) and the viscosity at 210 ° C was 162.2 cS (1,622 x 10"4 m2 / s) The viscosity calculated at 40 ° C was 1,182 cS (1,182 x 10"3 m2 / s). This is an ISO viscosity grade of 1000.

EXAMPLE 6 PREPARATION OF A POLYETER TRIOL OF HIGH MOLECULAR WEIGHT, SOLUBLE IN WATER A reactor of 7.57 liters was charged with 92 g of glycerin (1 mol) and 250 g of calcium CM-ALL DIO ™ at 10%. The reactor was purged with nitrogen. 2,480 g of a 75/25 weight / weight mixture of OE / OP (ethylene oxide / propylene oxide) was fed at 100 ° C. Of the 2,823 g present in the reactor, 2,230 g was eliminated. To the remaining 593 g in the reactor, 2.950 g of the mixed oxide was fed at 100 ° C. Of the 3,543 g present in the reactor, 2,985 g was eliminated (the product is referred to hereinafter as example 6, step 2).

To the remaining 558 g in the reactor, 2790 g of mixed oxide was fed at 100 ° C. The contents of the reactor were drained (the product is referred to hereinafter as example 6, step 3). The polymer was so viscous that an accurate mass balance was not possible. EXAMPLE 7 PREPARATION OF A TRIOL OF HIGH MOLECULAR WEIGHT. CORONATED WITH A POLYETHYLENE OXIDE CHAIN The polyether polyol reaction product of Example 6, step 2, was stripped off at 90 ° C to remove the volatiles. A polyether polyol was made by initiating a reaction (500 g) of the product of example 6, step 2, dissolved in 600 g of toluene. 2485 g of EO was added at 100 ° C, to form the OE-crowned polyol. The hydroxyl percentage of the polyether polyols of example 6, operation 2, example 6, operation 3 and example 7 was determined, and the results are compiled in table 1 TABLE 1 * Calculated from the percentage of hydroxyl corrected for b a s i c i d a d. The viscosity of aqueous solutions of several polyols in Cannon-Fensky tubes was determined in a thermostat-controlled bath. The results are compiled in Table 2. TABLE 2 VISCOSITY (cS) AT 40 ° C OF AQUEOUS SOLUTIONS ** Comparison, PG6000 is a polyol based on 50/50 OE / OP, initiated with n-butanol, with a molecular weight of 5,600. Several polyols were used to formulate an ISO VG 46 fluid. The polyol concentrations in water to obtain an ISO VG 46 fluid are compiled in Table 3.

TABLE 3 Synalox 25D700 ™ is a polyol initiated with dipropylene glycol, having a polyether chain comprising 65/35 weight / weight OE / OP and having a molecular weight of 5,500, obtainable from The Dow Chemical Company. Synalox 25-300B ™ is a polyol initiated with dipropylene glycol n-butyl ether, having a polyether chain comprising 75/25 w / w OE / OP and having a molecular weight of 3450, obtainable from The Dow Chemical Company . Synalox 25-220B ™ is a polyol initiated with dipropylene glycol n-butyl ether having a polyether chain comprising 75/25 weight / weight OE / OP and having a molecular weight of 3100, obtainable from The Dow Chemical Company. Terralox HP400 ™ is ethylene oxide polyol initiated with sorbitol, which has an average of 18 moles of ethylene, obtainable from The Dow Chemical Company. Terralox HP670 ™ is propylene oxide polyol initiated with 31/69 w / w glycerin / sucrose, having a molecular weight of 500, obtainable from The Dow Chemical Company. Terralox HP4800 ™ is a propylene oxide polyol initiated with 5/95 glycerin / sucrose in weight / weight, having a molecular weight of 1,000, obtainable from The Dow Chemical Company. PEO 200,000 ™ is a polyethylene oxide having an approximate molecular weight of 200,000, obtainable from Aldrich Chemical. PEO 100,000 ™ is a polyethylene oxide having an approximate molecular weight of 100,000, obtainable from Aldrich Chemical. CARBOWAX 20M ™ is a polyethylene oxide having a molecular weight of 20,000, obtainable from Union Carbide. AQUAZOL 500 ™ is a poly (2-ethyl-2-oxazoline) obtainable from Polymer Laboratories, which has a molecular weight of 500,000. AQUAZOL 200 ™ is a poly (2-ethyl-2-oxazoline) obtainable from Polymer Laboratories, which has a molecular weight of 200,000.

UCON 75H 380,000 ™ is a polyethylene oxide containing 75/25 OE / OP, obtainable from Union Carbide. UCON 75H 90,000 ™ is a polyethylene oxide containing 75/25 OE / OP having a molecular weight of 15,000, obtainable from Union Carbide. PG 6000 ™ is a 50/50 OP / OE polyol, initiated with n-butanol, having a molecular weight of 5600, obtainable from Dow Chemical. The effect of temperature on the viscosity of the polyol solution of operation 3 of Example 6 is illustrated in Table 4.

TABLE 4 The data in Table 4 demonstrate that the polyether polyols of the invention exhibit good ability to maintain viscosity in the face of temperature increase. The polyol of Example 6, step 3, was separated to about 50 ° C (75/25 OE / OP). The 100,000 polyethylene oxide polyols were heated and 200,000, at 90 ° C without any separation of the polymer from the water; Heating was stopped due to boiling. The effect of pH on the viscosity of the solution of the polyol of Example 6, step 3, was determined. After vacuum separation the polyol of Example 6, step 3, gave a neutral pH. HCl was used to acidify and KOH was added to make the polyol basic. The viscosity of the polyols was examined at three pH levels. The results are compiled in table 5.

TABLE 5 Table 5 shows that changes in pH do not affect the viscosity of polyether polyols, as much as it affects the viscosity of poly (2-ethyl-2-oxazoline).

EXAMPLE 8 Experiments were carried out to evaluate the use of solid calcium catalyst, prepared by the method of US Pat. No. 4,329,047, with catalysts made in accordance with this invention.

TABLE 6 COMPOSITION OF THE CATALYST * Both catalysts obtained from OMG Americas Inc. The catalyst of Example 8 contains 50 weight percent calcium isooctanoate, with high purity synthetic isooctanoic acid, and 50 weight percent mineral spirits. The catalyst of Example 8 contains 10 weight percent calcium and contains no glycol ethers. The catalyst of the comparative example contains 35 weight percent calcium naphthenate, 60 weight percent mineral spirits and 5 weight percent 2-ethoxyethanol, a glycol ether. It also contains 4 percent by weight of calcium. It is representative of the catalyst used in Example 1 of the US Patent 4,329,047, and was prepared in accordance with the teachings of that patent. 2928.6 g of acetone was added to a stirred 4 liter beaker. 207.79 g of the catalyst of the comparative example as described in Table 6 was slowly added to prevent agglomeration. The white precipitate was allowed to settle for one hour. The acetone was decanted and the residual volatiles were removed at room temperature, under vacuum. 116.98 g of a semi-solid, thick product was recovered. 98.69 g of Polyglycol P425, a propylene oxide diol of molecular weight 425, was mixed with 15.69 g of the solid catalyst of the comparative example, prepared as described above. The solid catalyst was not soluble in the propylene oxide diol. The mixture was added to a stirred, dry, 7.57 liter, heated steam reactor. The reactor was purged with nitrogen to remove oxygen. 5,740 g of propylene oxide was added during five days, at a temperature of 120 ° C. Almost no reaction was observed during the first two days. 334.1 g of Polyglycol P425 was added to a dry pressure reactor, 18.92 liters, steam heated and stirred. 110.1 g of the catalyst of Example 8 was added to the reactor. The reactor was purged with nitrogen to remove oxygen. 5,740 g of propylene oxide was added for twenty hours at a temperature of 120 ° C. An initial time of slow rust feed rate was observed for two hours.

TABLE 7 PRODUCTION DATA * Actual rust feed times do not include digestion or waiting times. Operations 1 and 2 of Example 8 and operation 1 of the comparative example were carried out in a 18.92 liter reactor. Operation 2 of the comparative example was carried out in a 7.57 liter reactor. The temperature of the reaction was the same for all operations. The unit ratios of active catalyst, initiator and propylene oxide are the same for all operations. Feeding times for solid catalyst operations were longer than for liquid catalyst operations. The initial period of slow oxide addition was also greater for solid catalyst operations. The solid catalyst from the comparative example operations was insoluble in the Polyglycol P425 initiator.

TABLE 8 PROPERTIES OF POLYETER POLYOLS (1)% OH corrected for basicity. (2) Molecular weight calculated for the% OH corrected, assuming that the functionality is 2. (3) Unsaturation, meq / g, corrected for basicity. The polyether polyols made with the solid catalyst (comparative examples) were of lower molecular weight, determined by a wet chemical method, and of higher unsaturation than the polyether polyols made with the liquid catalyst, the catalyst of the invention. The number average molecular weight (Mn) determined by size exclusion chromatography of the polyether polyols made with solid catalyst was lower than that of the polyether polyols made with the liquid catalyst. The polydispersity of the polyether polyols made with the solid catalyst of calcium naphthenate was much higher than that of the polyether polyoids made with the liquid catalyst of calcium isooctanoate. The polyether polyols of example 8, step 2 and the comparative example were tested by size exclusion chromatography, and the results are illustrated in figure 1. The polyether polyol made with the solid catalyst of calcium naphthenate, step 2 of the comparative example, it contained lower molecular weight species than example 8, operation 2, made with the liquid catalyst of calcium isooctanoate. This is shown in Figure 1. The polyether polyol of the comparative example, step 2, made with the solid calcium naphthenate catalyst, contained 22 weight percent of species with molecular weights less than 10,000 dalton. In comparison, example 8, operation 2, made with the calcium catalyst of isooctanoate calcium only had 10 weight percent of species with less than 10,000 dalton. This is the cause of the low molecular weight determination, the high pohdispersity and the low viscosity of the polyether polyol of the comparative example, operation 2. The low molecular weight species adversely affects the elongation properties of an elastomer made with that polyol of polyether The polyether polyol made with calcium isooctanoate (comparative example, operation 1) exhibited the same deficiencies as the polyether polyol prepared with solid calcium naphthenate, although to a lesser extent. The conclusion is that the use of a solid catalyst in the production of high molecular weight polyether polyols has several disadvantages: solid catalysts are difficult to handle in manufacturing plants; solid catalysts have a longer initial time of slow oxide feed, compared to liquid catalysts; solid catalysts have longer feeding times than liquid catalysts; solid catalysts form a polyether polyol with higher polydispersity than liquid catalysts, especially the calcium naphthenate catalyst. Solid catalysts form more species of lower molecular weight than liquid catalysts, especially the calcium naphthenate catalyst.

Claims (6)

1. CLAIMS 1.- A high molecular weight polyol, prepared by reacting one or more compounds having one or more active hydrogen compounds, with one or more alkylene oxides, in the presence of a catalyst consisting of calcium having opposite ions of carbonate and an alkanoate of 6 to 10 carbon atoms, in a solvent that does not contain active hydrogen atoms; wherein the polyol prepared has an equivalent weight of 1,000 to 20,000, a polydispersity of 1.30 or less; a level of unsaturation of 0.02 milliequivalents or less; a weight average molecular weight of 10,000 or more and a residual catalyst level of from 0 to 1,000 ppm.
2. 2. A polyol according to claim 2, further characterized in that the residual catalyst is a calcium salt and is present in an amount of 200 to 1000 ppm, and the polyol has a polydispersity of 1.20 or less.
3. 3. A process for preparing a high molecular weight polyol according to claim 1 or 2, characterized in that it comprises: contacting one or more compounds having more than one active hydrogen atom, with one or more alkylene oxides , in the presence of a catalyst consisting of calcium having opposite ions of carbonate and an alkanoate of 6 to 10 carbon atoms, in a solvent that does not contain active hydrogen atoms; and exposing the mixture to conditions at which the alkylene oxides react with the compound containing more than one active hydrogen atom, such that a polyol with an equivalent weight of 1,000 to 20,000, a polydispersity of 1.20 or less is prepared. and a residual catalyst level of 200 to 2,000 ppm.
4. 4. A hydraulic fluid, characterized in that it comprises from 5 to 30 weight percent of a polyol of claim 1 or 2, and from 95 to 70 weight percent of water.
5. 5. A hydraulic fluid according to claim 4, further characterized in that the polyol has a molecular weight of 20,000 to 80,000. 6. A prepolymer, characterized in that it comprises the product of the reaction of the polyol of claim 1 or 2, with an isocyanatosilane having at least one silane portion having a hydrolysable silane portion attached thereto. 7. A process according to claim 6, for the preparation of a prepolymer terminated in silyl, further characterized in that the contact is effected without the addition catalyst. 8. A lubricant, characterized in that it comprises the polyether polyol according to any of claims 1 or 2. 9. A polyurethane prepolymer, characterized in that it is prepared by contacting a polyether polyol according to claim 1, with one or more polyisocyanates, under conditions in which a polyurethane prepolymer is prepared. 10. An adhesive composition, characterized in that it comprises the polyurethane prepolymer of claim 9, or the silyl-terminated prepolymer of claim
6. 6.