MXPA96006314A

MXPA96006314A - Method for manufacturing polyolet polyoles from bajainsaturac

Info

Publication number: MXPA96006314A
Application number: MXPA/A/1996/006314A
Authority: MX
Inventors: L Fishback Thomas; J Reichel Curtis; M Aviles Gladys
Original assignee: Basf Corporation
Priority date: 1995-12-29
Filing date: 1996-12-11
Publication date: 1998-07-03

Abstract

The present invention relates to an isocyanate-reactive polyoxyalkylene polyether polymer having a structure in the following manner: the core of an initiator compound, an inner block of oxypropylene groups, and a second block of oxyalkylene groups; Inner of oxypropylene groups lies between the core of the initiator and the second block, the second block contains at least some oxyalkylene groups derived from at least one alkylene oxide of 4 or more carbon atoms. This structure allows a polyether polymer to be produced which has a low degree of unsaturation, adjust the degree of hydrophobicity to a broad scale of values and can simply be manufactured without relying on the use of exotic catalysts. The amount of the internal block of oxypropylene groups is advantageously from 25 weight percent to 80 weight percent based on the weight of the oxyalkylene groups and the initiator compound. The amount of the second block containing higher alkali oxide 4-atom must be effective to reduce the unsaturation of the polyether polyol to 0.06 milliequivalent KOH per gram of polyol or men

Description

"METHOD FOR MANUFACTURING LOW INSATURATION POLYETER POLYOLS" FIELD OF THE INVENTION The present invention relates to polyoxyalkylene polyether polyols, polyol compositions made with these polyols; with sealing compounds, adhesives and elastomers made with these polyoxyalkylene polyols and with the methods for preparing each product. More particularly, sealants, adhesives and elastomers are made with polyoxyalkylene polyether polyol having an internal polyoxypropylene block attached to the core of the initiator molecule, followed by at least one alkylene oxide of 4 carbon atoms or more, an amount sufficient to reduce the degree of unsaturation of the polyol to 0.06 milliequivalent per gram of the polyol or less.

BACKGROUND OF THE INVENTION Methods for preparing elastomers are well known in the art. In general, an elastomer is prepared by reacting a polyoxyalkylene polyether polyol with an organic isocyanate in the presence of a chain-lengthening agent. The chain-lengthening agent may be a diol or a mixture of triols and diols such that the total functionality of the mixture is generally less than 2.3. The polyoxyalkylene polyether polyols used in the preparation of elastomers generally have molecular weights ranging from 2,000 to 5,000. For the preparation of the sealing compounds, the chain elongation agent may be a triol or a mixture of diols, triols, and / or tetranels, such that the total functionality of the mixture ranges from more than 2.3 to 3.0. The polyoxyalkylene polyether polyols used in the preparation of polyurethane elastomers are usually prepared by reacting an initiator compound with an alkylene oxide in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide, tertiary amine, or a alkoxide These catalysts are useful in the preparation of polyoxypropylene polyols until the equivalent weight of the polyol reaches from about 1,000 to 1,200, at which point an excess of the allylic terminal unsaturation begins to develop. The formation of the unsaturation is believed to be a consequence of the propylene oxide which is isomerized in allyl alcohol, which subsequently reacts with the propylene oxide to form allyl (2-propenyl) ethers of the polyoxypropylene. The point at which the unsaturation begins to develop and the unsaturation regime can be influenced by variables such as temperature, pressure, catalyst concentration, and type of catalyst used. Beyond certain equivalent weights, it is difficult if it is not impossible to manufacture a polyoxypropylene polyether polyol having suitable functionality using conventional catalysts. Thus, as discussed further below, many attempts have been made to solve the problem of unsaturation by varying the kinds of catalysts used in the preparation of the polyol. The disadvantage that the polyether polyols have high levels of unsaturation is that the allylic terminal unsaturation reduces the functionality of the polyol and terminates the growth of the chain in the final polyurethane, thereby reducing the equivalent weight of the polyol and expanding its distribution of polyol. molecular weight. Employing a polyether polyol with less than anticipated functionality and a high level of unsaturation in the manufacture of polyurethane and elastomer sealing compounds results in the degradation of mechanical properties, such as hardness, and tensile strength. Even though the level of unsaturation can be maintained low by producing a polyol of very low equivalent weight, elastomers and sealing compounds must be made with high weight equivalent polyols to improve their elasticity. Therefore, it is highly desirable to manufacture a polyether polyol of high equivalent weight suitable in the manufacture of sealing compounds, adhesives and elastomers, which approximates the functionality of the initiator as much as possible. Various attempts have been made to reduce the unsaturation of the polyoxyalkylene polyether polyols by experimenting with classes of catalysts used in their preparation. For example, US Patents Numbers 5,136,010; 5,185,420; 5,266,681; 5,116,931; 5,096,993; No. 4,985,491, teach the preparation of polyether polyols using a double metal cyanide (DMC) catalyst to reduce the level of unsaturation to about 0.04 equivalent per gram of polyol or less. The disadvantages of using DMC catalysts to prepare polyols are that these catalysts are quite expensive; and as disclosed in US Pat. No. 4,355,188, the polyols containing the DMC catalyst residues are less stable during storage, can provide an odor to the polyol and cause undesirable side reactions during the manufacture of the products. of polyurethane. In the manufacture of a block polyether polyol having an oxyethylene block, it is usually necessary to remove the used DMC catalyst to prepare the block of the oxypropylene groups before polymerizing the oxyethylene oxide block, because the residual catalyst DMC would prevent the uniform addition of ethylene oxide through all the functional sites in the growing polymer. Therefore, the DMC must be removed and a normal catalyst such as KOH added as additional processing steps when the blocks of the oxyethylene groups are polymerized. U.S. Patent Nos. 4,902,834 and 4,764,567 describe the use of an alternative catalyst, cesium hydroxide, to reduce the unsaturation of the polyoxyethylene polyether polyols. These patents, however, lack the general teachings on the manner and which of the catalysts would be effective in reducing the unsaturation of the polyoxypropylene polyether polyols. In addition, it would be desirable to manufacture a polyether polyol with its level of unsaturation that does not depend on a specific catalyst. In addition to the catalysts based on double metal cyanide and cesium to decrease the unsaturation of polyether polyols, US Patent Nos. 5,010,187 and 5,070,125 also describe the use of barium or strontium based catalysts to reduce unsaturation. As with the cesium and DMC catalysts described above, it would be desirable to make a polyether polyol of low unsaturation that does not depend on a catalyst. U.S. Patent No. 4,687,851 discloses a polyether polyol having an unsaturation level of 0.06 milliequivalent per gram or less, made with conventional tertiary amines or with sodium and potassium hydroxides. To obtain the low unsaturation, the polyether polyol must be initiated with an amine. There continues to be a need for the manufacture of polyether polyols that have a low degree of unsaturation that are not limited to a specific initiator, and that can be manufactured in the presence of conventional catalysts or other low cost catalysts. In this regard, we begin to investigate the decrease in the degree of unsaturation through methods other than the improvement of processing techniques or the development of new catalysts. We arrived at a trajectory that was not believed as a means to diminish unsaturation. By altering the structure of the polyol molecule, we discovered that the degree of unsaturation could be significantly decreased regardless of what kind of catalyst was used. The structure of the polyether polyols can vary widely depending on the desired application. For example, conjugated or block polymers of ethylene oxide and propylene oxide that are reacted towards an initiator molecule are known to impart unique properties in a specific application depending on the order of the oxide addition. U.S. Patent Nos. 3,036,118 and 3,036,130 each disclose conjugated block polymers of polyether polyols having an internal oxyethylene block followed by a block of oxypropylene groups for use as nonionic surfactants. The North American Patent Number 4No. 738,993 also discloses a polyether polyol having an internal block of oxyethylene groups useful in the manufacture of RIM polyurethane elastomers. Polyether polyols having an internal block of oxyethylene groups have also found use for improving the air flow and load carrying properties of polyurethane foams, as disclosed in US Patent Number 4,487,854. Reversing the order of the addition of ethylene oxide and propylene oxide is also a known technique. For example, the surfactant, the detergent and the anti-foam polyether polyols having an internal block of oxypropylene groups followed by a chain of oxyethylene groups are already known in accordance with the teachings of U.S. Patent Nos. 2,674,619 and 2,948,757. These polyols have also found use in the manufacture of flexible polyurethane foams in accordance with U.S. Patent No. 3,865,762. The polyether polyols having a heteric structure, wherein a mixture of alkylene oxides are added to the initiator molecule such that the oxyalkylene groups are distributed randomly in each molecule, are likewise known according to the teachings of the different patents. According to these patents, suitable alkylene oxides usually include ethylene oxide, propylene oxide and butylene oxide. For example, U.S. Patent No. 4,812,350 discloses the manufacture of an ether polyether polyol having certain weight proportions of ethylene oxide and either butyrene oxide and / or propylene oxide to be used as an adhesion enhancer in panels. of polyurethane foam covered. U.S. Patent Number 2,733,272 recommends using a polyoxyethylene-polyoxyether >Etheric glycerol cipropylene as a lubricant, especially in brake fluids. Etheric polyether diols are also disclosed in U.S. Patent Number 2,425,845; and U.S. Patent No. 4,301,110 discloses the manufacture of a polyether polyol having an ether structure of oxyethylene and oxybutylene groups, optionally blocked with a block of oxyethylene groups, useful in the manufacture of reaction injection molded parts. There are also polyether polyols that have both an etheric and blocked structure. For example, U.S. Patent No. 4,487,854 discloses a polyether polyol having an internal block of oxyethylene groups followed by an ether mixture of ethylene oxide, butylene oxide and / or propylene oxide, optionally followed by a block of oxypropylene or oxybutylene groups as a terminal terminal block. The polyester polyol is said to deteriorate the good air flow properties and the load carrying properties of a polyurethane foam. None of these patents, however, discloses the concept of reducing allylic unsaturation by altering the structure of the polyether polymer, or the manner in which this alteration must be made to effect the decrease of the degree of unsaturation. In addition, most of these polyether polyols are too hydrophilic to make useful in applications of an elastomeric sealant and an adhesive.

COMPENDIUM OF THE INVENTION It would be desirable to have a polyether polyol of high equivalent weight containing a block of oxypropylene groups with reduced unsaturation. It would also be highly desirable that this polyether polyol could be prepared using an economical catalyst and whose method of preparation does not depend on employing a specific catalyst in order to achieve a reduction in unsaturation. It is also desired to produce a reduced unsaturation polyether polyol whose degree of unsaturation does not depend on the kind of initiator used and specifically yields a polyether polyol of reduced unsaturation which can be initiated with functional hydroxyl initiators. In addition, these polyether polyols should be suitable for the manufacture of prepolymers for use in polyurethane elastomers, sealants and adhesives, implying that a significant portion of the polyether polyols should be hydrophobic. Hydroxyl isocyanate-terminated prepolymers manufactured from a polyether polymer having a structure are now provided in the following manner: the core of an initiator compound, an oxypropylene group internal block and a second block of oxyalkylene groups; the internal block of the oxypropylene groups is placed between the core of the initiator and the second block, the second block containing at least certain oxyalkylene groups derived from at least one alkylene oxide of four carbon atoms or higher This structure allows that a polyether polymer having a low degree of unsaturation is produced, adjust the degree of hydrophobicity to a broad scale of values and can be manufactured simply without relying on the use of exotic catalysts. The amount of the internal block of oxypropylene groups is advantageously from 25 weight percent to 80 weight percent based on the weight of all the oxyalkylene groups and the initiator. The amount of the second block containing an alkylene oxide of four carbon atoms or higher must be effective to reduce the unsaturation of the polyether polyol to 0.06 milliequivalent KOH per gram of polyol or less. The preferred four-carbon alkylene oxide or higher is 1,2-butylene oxide.

In another embodiment there is provided a method for producing the polyoxyalkylene polyether polyol by reacting, in the presence of a catalyst, an initiator compound having at least two sites reactive with alkylene oxide directly or indirectly in order of sequence, the propylene to form an internal block of oxypropylene groups, followed by reacting directly or indirectly to the block of oxypropylene groups, one or more of the second oxide compounds, at least one of which is an alkylene oxide of 4 higher carbon atoms, to form a second block of oxyalkylene groups. Also, the amount of propylene oxide that is advantageously added from 25 weight percent to 80 weight percent, based on the weight of all the oxyalkylene compounds added to the initiator and initiator compound, and the amount of one or more of the second oxide compounds, at least one of which is an alkylene oxide of 4 higher carbon atoms, must be effective to reduce the unsaturation of the polyether polyol to 0.06 milliequivalent KOH per gram of polyol or less. In a further embodiment of the invention, there is provided a polyether polyol and a method for producing this polyether polyol wherein the propylene oxide is added directly to the initiator compound in order to form a reaction product having at least one weight equivalent of 800, after which one more types of the second oxides, at least one of which is an alkylene oxide of 4 carbon atoms or greater, are added to the resulting internal block of the oxypropylene groups. This second block of oxyalkylene groups may comprise a random mixture of oxyalkylene groups (i.e., heteric block) or may comprise one or more different blocks of each oxyalkylene group. In another embodiment of the invention, one or more of the second oxide compounds added to the inner block of oxypropylene groups constitutes a mixture of ethylene oxide and 1, 2-butylene oxide. In another advantageous embodiment of the invention, the polyether polyol described above is terminated with a block of oxyalkylene groups that would yield primary hydroxyl functionalities, such as ethylene oxide. Other especially preferred embodiments and scales are discussed in detail below. The polyether polyols of the invention have at least one of the following advantages and, in the preferred embodiments, simultaneously have all of the following advantages: they have a degree of unsaturation of 0.06 milliequivalent per gram of polyol or less, do not depend on the kind of catalyst or the kind of initiator used to achieve the reduction manifested in the degree of unsaturation, the polyethers used in sealant applications have a Cl of 25 ° C or less, the polyethers have equivalent weights of at least 1500 , and are suitable for the preparation of elastomers, sealants, and adhesives having high resistance to elongation and modulus of 100 to 300 percent elongation.

DETAILED DESCRIPTION OF THE INVENTION The polyoxyalkylene polyethers of the invention contain a core of an initiator compound, an internal block of oxypropylene groups, and a second block of oxyalkylene groups containing an oxyalkylene group derived from an alkylene oxide of four carbon atoms or higher , in the order in manifested sequence. The polyoxyalkylene polyethers of the invention have a degree of unsaturation of 0.06 milliequivalent of KOH per gram of polyol or less.

Surprisingly, this low degree of unsaturation can be achieved in the manufacture of high equivalent weight polyethers (such as an equivalent weight of less than 1,500) in the presence of conventional catalysts such as sodium and potassium hydroxides. Before discussing the structure and od of preparation of the polyethers of the invention, a brief overview of some terms used throughout the specification and means for performing the calculations are now explained in greater detail. The polyoxyalkylene polyether polymers of this invention are mixtures of compounds that can be defined by the equivalent weight and the weight percentage of the oxyalkylene groups. If the amount of alkylene oxide reacting to an initiator is relatively large, uniform molecular compounds having the same defined number of oxyalkylene groups are not obtained; but rather, a mixture of closely related homologs is obtained wherein the statistical average number of oxyalkylene groups is equal to the number of moles of alkylene oxide added in the manufacturing process. Therefore, a means for calculating the weight percentage of the oxyalkylene groups in the polyoxyalkylene polyether is adding the number of moles or the weight of the specific alkylene oxide added to create the desired block. The equivalent weight of a chain within a polyether polymer can also be calculated by adding the total weight of the charged specific alkylene oxide divided by the functionality of the initiator molecule. The polyoxyalkylene polyethers of this invention are "block" polymers of alkylene oxides. The polyethers of this invention contain a block of oxyalkylene groups in a chain connected to a block of different oxyalkylene groups in the chain to provide a structure of a conjugated unit necessary to impart both hydrophobic and hydrophilic properties to the polymer. A block of typical polyoxyalkylene groups is believed to contain the same type of oxyalkylene residues, for example, a block of pure oxypropylene groups or a block of pure oxyethylene groups. In this invention, however, a "block" of a mixture of different oxyalkylene groups distributed in random order can be provided. The different oxyalkylene groups are distributed randomly, however, within the parars of a discrete block rather than through the entire polymer chain. The degree of unsaturation can be determined by reacting the polyether polymer in mercuric acetate and anol in a anolic solution to liberate the oxy, acetoxymercuric compounds and the acetic acids. Any remaining mercuric acetate is treated with sodium bromide to convert mercuric acetate to bromide. The acetic acid in the solution can then be titrated with potassium hydroxide and the degree of unsaturation can be calculated for a number of moles of the acetic acid titrated. More specifically, 30 grams of the polyether polymer sample can be weighed in a sample flask and 50 milliliters of the reactive-class mercury acetate in anol are added to a sample flask and to a blank flask. The sample is stirred until the content dissolves. The sample and blank flasks are allowed to stand for thirty (30) minutes with occasional shaking. Subsequently, 8 to 10 grams of sodium bromide are added to each and stirred for two (2) minutes, after which one (1) milliliter of the phenolphthalein indicator is added to each vial and assessed as a standard. of normal anolic KOH from 0.1 to a pink color end point. The degree of unsaturation is calculated and expressed as milliequivalents per gram: (ml of KOH sample - ml of K0H blank) XN KOH Acidity (A) as a sample weight of milliequivalents per gram Acidity correction is made only if the acid number of the sample is greater than 0.04 in which case se - 1! divide between 56.1 to provide the milliequivalents per gram. The hydroxyl number of the polyether polyol can be measured experimentally by normal titration methods. Once the hydroxyl number has been measured by titration, the average molecular weight of the resulting polyether polymer can be calculated by the expression: OH = (f) 56, 100 / M.W. wherein f is the nominal functionality of the polymer based on the functionality of the initiator molecule. The compatibility index is measured by heating the polyether polymer in a 50:50 weight ratio of water to a solution of reactive-grade isopropanol. 25 grams of the polyether polymer are added to a test tube. Then, 25 milliliters of the water / isopropanol solution is added and the test tube is immersed in a water bath. The test tube mixture is stirred at 300 revolutions per minute. If the mixture in the test tube is cloudy at room temperature, the water bath is replaced with a dry ice-isopropanol bath until the mixture in the test tube is rinsed. For Cl at less than 15 ° C, the test tube is allowed to warm up in air.

If the expected Cl is greater than 15 ° C, a water bath is used which is heated at a rate such that the temperature of the bath is about 3 ° C higher than the temperature of the mixture in the test tube. In any case, as the Cl value approaches, the mixture in the test tube will become cloudy. Shortly after the nebulosity, the mixture will become turbid or will form discrete particles of separate phase. This is the Cl temperature. Within the structure of the polyoxyalkylene polyether, a core of an initiator compound is first provided. The initiator compound contains at least two hydrogen atoms reactive to the alkylene oxides. Specifically, the reactive hydrogen atoms in the initiator compound must be sufficiently labile to open the epoxide ring of the ethylene oxide. The initiator compound has a relatively low molecular weight, generally less than 400, and more preferably less than 150. The initiator compound usually has from 2 to 6 carbon atoms. Examples of initiator compounds useful in the practice of this invention include, but are not limited to: ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2,3-butylene glycol, 1,3-butylene glycol, 1,5-pentanediol, 1, 6 hexanediol, glycerol, trimethylol propane, sorbitol, sucrose, glycerin (glycerol), pentaerythritol and the like and mixtures of any of these. Another class of reactive hydrogen compounds that can be used are alkyl amines and alkylene polyamines having at least two reactive hydrogen atoms, such as methylamine, ethylamine, propylamine, butylamine, hexylamine, ethylenediamine, diethylene diamine, 1-6. hexandiamine, diethylenetriamine, and the like. Also, these cyclisamines such as piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine and TDA can also be used. The amides constitute an additional class of these reactive hydrogen compounds, such as acetamide, succinamide and benzene sulfonamide. A still further class of these reactive hydrogen compounds are the di- and polycarboxylic acids, such as adipic acid, succinic acid, glutaric acid, aconitic acid, diglycolic acid, and the like. The initiator is also one which contains different functional groups which also have reactive hydrogen atoms, such as citric acid, glycolic acid ethanolamine and the like. One of the advantages of the invention lies in the preparation of low unsaturation polyoids using functional hydroxyl initiator compounds. In the preparation of sealants, adhesives and elastomers, it is preferred that the initiator compound have two or three active hydrogen atoms; and it is especially preferred that these active hydrogen atoms are of hydroxyl functionalities. A mixture of initiator compounds can be used to adjust the functionality of the primer to a number between the integers. In the preparation of elastomers, it is desirable to employ an initiator having a functionality as close to 2 as possible; while in the preparation of sealing compounds, it is desirable to employ an initiator having functionality within the range of 2.3 to 3.0. Therefore, if it is desired to manufacture an elastomer having only a slight degree of crosslinking, a high proportion of an initiator having a functionality of 2, to which relatively small amounts of trifunctional or higher functionality starter compounds are added can be mixed together to get to an initiator that has an average functionality next 2, such as from 2.0 to less than 2.3. On the other hand, a larger proportion of the tri-functional or higher functionality starter compounds can be mixed with a difunctional initiator compound when a greater degree of crosslinking is desired such as in the preparation of sealants and adhesives. As can be seen in the foregoing, it is especially preferred that all of these functionalities be hydroxyl functionalities. The polyether of the invention can be prepared by the addition reaction between an appropriate initiator compound directly or indirectly with a defined amount of propylene oxide so as to form an internal block of oxypropylene groups, followed by additional direct or indirect addition of one. or more second oxides comprising an alkylene oxide of 4 carbon atoms or more. In one embodiment of the invention, the propylene oxide is added and reacted directly with a di-functional initiator or higher functionality, through reactive hydrogen atom sites to form an internal block of polyoxypropylene groups. The structure of this intermediate compound can be represented according to the following formula: R [(C3H60) w] -z where R is the initiator core, w is an integer representing the number of oxypropylene groups in the block such that the weight of the oxypropylene groups is from 25 percent to 80 percent by weight, based on the weight of the alkylene oxides added and the initiator, and z is an integer of 2 or more representing the number of reactive sites in the initiator molecule to which the chains of the oxypropylene groups join. The internal block of the oxypropylene groups imparts hydrophobic characteristics to the polymer, which is essential to repel water and prevent swelling and degradation of elastomers, sealants and adhesives made with the polyether polymer. The hydrophobic characteristic of the polymer can be measured by a compatibility index. The block of oxypropylene groups is internal with respect to the polyoxyalkylene polyether polymer. By internal block it is meant that the block of oxypropylene groups must be structurally placed between the core of the initiator compound and another block of one or more different classes of oxyalkylene groups. It is within the scope of the invention to interpose a block of different oxyalkylene groups between the initiator core and the block of oxypropylene groups, especially if the different oxyalkylene groups are also hydrophobic. In a preferred embodiment, however, the internal block of the oxypropylene groups is attached directly to the core of the initiator compound through its reactive hydrogen sites. This preferred embodiment can be carried out by directly reacting the initiator compound with propylene oxide. The internal block of oxypropylene groups consists essentially of oxypropylene groups, implying that essentially all of the alkylene oxides added to form the internal block are propylene oxide compounds. It is within the spirit and scope of the invention that the internal block of oxypropylene groups may contain a small number of different oxyalkylene groups such as oxyethylene or oxybutylene groups. The internal block of the oxypropylene groups is designed to impart hydrophobic characteristics to the polyoxyalkylene polyether polymer in order to repel water, and reduce the swelling and degradation of the elastomers, sealants and adhesives made with these polyethers. Although the alkylene oxides which would impart hydrophilic properties to the polyether polymer can be tolerated in small amounts, they should be avoided to the extent that the hydrophobicity of the polymer deteriorates such that the resulting adhesive elastomers or sealing agents manufactured therewith show signs of swelling in water and degradation. Furthermore, even when the oxybutylene groups are hydrophobic, a commercial advantage is achieved by using as much as possible of propylene oxide without significantly decreasing the functionality of the polyether polymer. Generally, 5 weight percent or less of all the propylene oxide added as an internal block may be in the form of different alkylene oxides, such as ethylene oxide, butylene oxide, tetrahydrofuran, etc. In a particularly preferred embodiment, less than 2 weight percent based on the internal block is made up of oxyalkylene groups which are different from the oxypropylene groups. In the especially preferred embodiment, the internal block consists solely of oxypropylene groups. The polyoxyalkylene polyether polymer may comprise more than one internal block of oxypropylene groups. Whatever the number of internal blocks of oxypropylene groups placed in the polyether polymer structure, the total weight of the polyoxypropylene groups is advantageously from 25 weight percent to 80 weight percent based on the weight of the compounds of oxyalkylene added to the initiator and the initiator itself. In the method of the invention, an initiator compound is reacted in sequence order with the propylene oxide followed by a reaction with one or more second oxides. By the term "sequential order" is meant only that at least one block of the internal oxypropylene groups must appear to the polyether polymer, followed by adding directly to the internal block one or more second oxides as defined in present, indirectly adding to the internal block of oxypropylene groups one or more second oxides as defined herein, through other alkylene oxides. In a preferred embodiment of the invention, the oxypropylene groups are attached to the initiator compound through their reactive alkylene oxide sides, and one or more of the second oxides comprising an alkylene oxide of 4 carbon atoms or greater is they add directly to the inner block of the oxypropylene groups to form a second block of directly bound oxyalkylene groups and attached to the inner block of the oxypropylene groups. The block of oxypropylene groups is from 25 weight percent to 80 weight percent based on the weight of all the oxyalkylene compounds added to the initiator compound and the initiator. This percentage by weight can be determined experimentally by gas chromatography or on a calculated basis of the actual weight of the propylene oxide groups added in the manufacture of the polyether polymer, assuming that the reaction time, the temperature and the pressures have been determined. graduated to react all the propylene oxides added in a reaction vessel for the manufacture of the polyether. The amount of propylene oxide is at least 25 weight percent. By adding the propylene oxide in amounts of less than 25 weight percent or a polyether polymer containing less than 25 weight percent oxyethylene groups, renders the polyether polymer insufficiently hydrophobic for many applications, and causes the properties Mechanical elastomers and sealing compounds made with the polyether are degraded. The upper limit of the propylene oxide addition for most of the embodiments, or the upper limit of oxypropylene groups in the polyether polymer structure is 80 weight percent. At amounts greater than 80 weight percent, a significant amount of terminal allylic unsaturation develops in the manufacture of polyether polymers of higher equivalent weight. Within a more favorable scale, the relative amount of oxypropylene groups ranges from 60 percent to 75 percent by weight. In the construction of the block of the oxypropylene groups, the terminal allylic unsaturation develops as the equivalent weight of the block of oxypropylene groups grows; and the degree of unsaturation becomes more pronounced as the equivalent weight increases. Even though the reaction conditions and types of catalysts used influence the degree of unsaturation that develops for any given polyether polymer, it begins to be observed that the unsaturation is developed using conventional KOH catalysts when the equivalent weight of the block of groups of oxypropylene is about 800 or more, with more pronounced effects when the equivalent weight of the oxypropylene groups is about 1,000 or more. When the equivalent weight of the block of the oxypropylene groups is about 1,700 or more, this large amount of terminal allylic hydration which develops the mechanical properties of the elastomers, sealants and adhesives made with the polyether polymers, deteriorates significantly. Therefore, in one embodiment of the invention, a sufficient amount of propylene oxide is added to form a block of oxypropylene groups in such a way that the equivalent weight of the block is at least about 800 and not more than about 1,700, more preferably, from about 1,000 to about 1,300. The object of adding only a limited number of propylene oxide compounds is to avoid a significant accumulation of terminal unsaturation. In some embodiments, e.g., when cesium hydroxide catalysts are used, it is not necessary to discontinue the addition of propylene oxide until a degree of terminal unsaturation develops beyond a certain point. Therefore, instead of discontinuing the addition of propylene oxide within a minimum equivalent weight of about 800 or more to a maximum of about 1,700, the addition of propylene oxide may cease when the degree of unsaturation of the growing block of The oxypropylene oxide groups are measured at 0.010 milliequivalent per gram of polyol or more. Therefore, the addition of one or more second oxides in this mode can begin when 0.01 milliequivalent per gram of polyol unsaturation or more is developed, or in the alternative when the equivalent weight of the oxypropylene group block is about 1,700, more preferably from about 1,700 to about 1,300. After the internal block of oxypropylene groups is manufactured, one or more of the second oxides, at least one of which is an alkylene oxide of four carbon atoms or greater, is added directly or indirectly to the internal block of the oxypropylene groups. The object for the addition of an alkylene oxide of four carbon atoms or higher is to continue to build a block of hydrophobic oxyalkylene groups that are resistant to the formation of terminal allylic unsaturation. Alkylene oxide compounds resistant to this class of isomerization are those compounds having substituents that can donate electron density to the alpha-carbon adjacent to, and attached to the carbon atoms attached to the epoxide ring and in particular the substituents of alkyl fixed to alpha-carbon; or the alkylene oxides that do not contain alpha-carbon. Examples of one or more of the second alkylene oxide compounds are ethylene oxide; 1, 2-butylene oxide; 1,2-hexene oxide; 1, 2-tert-butylethylene oxide; cyclohexene oxide; 1,2-octene oxide; cyclohexyethylene oxide; styrene oxide; phenylglycidyl ether; allylglycidyl ether; 1,2-decene oxide; 1, 2-octadecene oxide; epichlorohydrin; epibromohydrin; epiyodohydrin; perfluoropropylene oxide; cyclopentene oxide and 1,2-pentene oxide among others. When ethylene oxide is used, it must be mixed with an alkylene oxide of 4 carbon atoms or more. In a preferred embodiment of the invention, one or more of the second alkylene oxides are, at least, 1,2-butylene oxide compounds. In another preferred embodiment of the invention, one or more of the second alkylene oxides are constituted of a mixture of 1,2-butylene oxide and ethylene oxide. One or more of the second alkylene oxides preferably are reacted directly with the inner block of the oxypropylene groups to form a second block of oxyalkylene groups. When only one alkylene oxide, such as 1,2-butylene oxide is used as one or more of the second alkylene oxide compounds, the second block of oxyalkylene groups will be a block of oxybutylene groups. This structure can be represented by the following block formula: R [(C3H60) w- (C4H80) x] zH wherein R, w and z are as defined above and x is an integer representing the number of oxybutylene groups. In the case where a mixture of alkylene oxides, such as ethylene oxide and 1,2-butylene oxide, is used, the second block will be constituted by a mixture of oxyethylene and oxybutylene groups in a random distribution. This structure can be represented by the following block formula: R [(C3H60) w - ((C4H80) x (C2H40) y) s] z H wherein R, w, x and z are as stated in the foregoing, and is an integer representing the number of oxyethylene groups; s is an integer, preferably 1, representing the number of oxybutylene and oxyethylene blending blocks, and each block s is a random mixture of oxybutylene and oxyethylene groups, the block sa being fixed through a bond with the block of the oxypropylene groups. The total amount of one or more of the second alkylene oxides that are added in the manufacture of the polyether polyol and the amount of the second block resulting from oxyalkylene groups is effective to reduce the degree of unsaturation of the polyether polyol to 0.06 milliequivalent per gram of polyol or less. By the term "reduce" is meant a reduction in unsaturation compared to a polyether polymer made with the same initiator, under the same reaction conditions and catalysts, and produced at the same equivalent weight of the final polyether polymer, but using only propylene oxide as the alkylene oxide added to the initiator molecule. A particularly advantageous feature of the invention lies in the flexibility of adjusting the degree of unsaturation only by adding a greater amount of one or more of the second oxides as defined herein instead of changing the types of catalyst or reaction conditions, which is quite expensive or delayed. Where the end use of the polyether polymer is in applications that benefit from the degrees of unsaturation much lower than 0.06, one or more of the second alkylene oxides may be added initially when little has been developed in case of any unsaturation having developed during the manufacture of the internal block of the oxypropylene groups. Also, a greater or lesser amount of one or more of the second alkylene oxide compounds can be added to adjust the degree of unsaturation. One of the embodiments of the invention is in the manufacture of a polyether polymer having an unsaturation degree of 0..03 or less, which finds beneficial use in elastomers, without having to resort to unusual reaction conditions or exotic catalysts. and expensive, such as double metal cyanide catalysts. In a particularly preferred embodiment of the invention, the 1,2-butylene oxide is reacted towards the inner block of the oxypropylene groups, in amounts sufficient to reduce the degree of unsaturation of the resulting polyether polymer to 0.06 milliequivalent per gram of polyol or less, where the end use of polyether polymers is in the manufacture of sealants and adhesives and up to 0.03 or less where the end use of the polyether polymer is in the manufacture of elastomers. The amount of 1,2-butylene oxide to achieve this object is generally at least 5 weight percent, more preferably at least 10 weight percent, based on the weight of all the compounds of oxyalkylene added to the initiator compound and the initiator. Usually, no more than 20 weight percent is needed to achieve a reduction in unsaturation. It is possible to reduce the degree of unsaturation of the polyether polymers to 0.06 or less by adding only ethylene oxide to the inner block of the oxypropylene groups. However, a much greater amount of ethylene oxide would have to be added to achieve a polymer of comparable molecular weight whose polyether polymer would also become hydrophilic. It is therefore critical to the invention that the hydrophobic alkylene oxides of 4 carbon atoms or higher are added in significant amounts in the second block of alkylene oxides, in order to maintain the desired hydrophobic characteristics. When a mixture of ethylene oxide and 1,2-butylene oxide is employed, the relative amounts of each alkylene oxide will depend on the desired degree of hydrophobicity as measured by the compatibility index. Even though the specific weight ratio of the 1,2-butylene oxide to ethylene oxide is not limited, the appropriate relative amounts may vary from 0.5: 1 to 4: 1. Preferred amounts of 1,2-butylene oxide to ethylene oxide vary from about 1: 1 to 2: 1, particularly when an improved hydrophobicity of the resulting elastomer, sealant or adhesive is desirable. The more ethylene oxide is added, the more hydrophilic the nature of the second block of one or more of the alkylene oxide groups will be. The more alkylene oxides of 4 carbon atoms or higher are added in the second block, the more hydrophobic the nature of the second block of the second of the oxyalkylene groups will be. The total weight of the second block of one or more of the second blocks of oxyalkylene will generally vary from 5 weight percent to 75 weight percent, more preferably from more than 5 weight percent to 50 weight percent, and especially preferably from 10 weight percent to 30 weight percent, based on the weight of all the oxyalkylene compounds added to the initiator compound and the initiator.

The polyether polymers of the invention are terminated with two or more isocyanate reactive hydrogens. The reactive hydrogens may be in the form of primary or secondary hydroxyl groups, or primary or secondary amine groups. In the manufacture of elastomers, sealing agents and adhesives, it is often desirable to introduce isocyanate reactive groups that are more reactive than secondary hydroxyl groups. The primary hydroxyl groups can be introduced into the polyether by reacting the growing polyether polymer with ethylene oxide. Therefore, in one embodiment of the invention, the polyether polymer can be terminated with a terminal block of oxyethylene groups. Alternatively, in another embodiment, the polyether polymer of the invention can be determined with a mixture of primary and secondary terminal hydroxyl groups when a mixture of ethylene oxide and 1,2-butylene oxide is used in the manufacture of the second block. of one or more of the second alkylene oxides. The primary and secondary amine groups can be introduced into the polyether polymer by a reductive amination process as described in U.S. Patent Number 3,654,370, which is incorporated herein by reference.

The polyether polymer of the invention is preferably a polyether polyol. The polyether polyol can optionally be terminated with a terminal block consisting essentially of oxyethylene groups containing a primary hydroxyl group at the terminal carbon atom of the terminal block. The weight of the terminal block of the oxyethylene groups when employed is at least 4 percent by weight, preferably 10 percent by weight to 25 percent by weight, based on the weight of all the oxyalkylene compounds added to the initiator and the initiator compound. In the manufacture of sealing compounds and adhesives, the polyether polymers used will usually have either a terminal block of low equivalent weight of oxyethylene groups or no terminal block of oxyethylene groups. Sufficient reactivity can be provided by the primary hydroxyl functionality through a mixture of ethylene oxide and the alkylene oxides of 4 carbon atoms or higher, used in the manufacture of the second block. The Cl of the polyether polymer for use in these applications is advantageously 25 ° C or less. In the manufacture of elastomers, however, it is often desirable to improve the reactivity of the polyether polyols. This is achieved by terminating the polyether polymer with a terminal block of oxyethylene groups. Although it is possible to admix the terminal block of the oxyethylene groups, it is more desirable that there be a primary hydroxyl group attached to the terminal carbon atom of the terminal block of the oxyethylene groups. The weight percentage of the terminal block of the oxyethylene groups in polyether polymers used in the manufacture of elastomers should be at least 4 weight percent, more preferably 10 weight percent to 25 weight percent , based on the weight of all the oxyalkylene groups in the polyether polymer and the initiator. The method for polymerizing the polyether polymers of the invention is not limited and can occur in one of three different ways: anionic, cationic and coordinated mechanisms. Anionic polymerization methods are generally known in the art. Typically, an initiator molecule is reacted with the alkylene oxide in the presence of a basic catalyst, such as an alkoxide or an alkali metal hydroxide. The reaction can be carried out under superatmospheric pressure and an aprotic solvent such as DMSO or THF, or in bulk. A particularity of the invention lies in the ability to manufacture a polyether polymer having a low degree of unsaturation and a high equivalent weight without taking into account the type of catalyst used. For example, low degrees of unsaturation can be obtained in polyether polymers of high equivalent weight using conventional catalysts such as potassium and sodium hydroxide. The type of catalyst used is not limited by the invention. The catalysts, such as the alkali metal alkoxides, cesium-based catalysts and double metal cyanide catalysts as described in US Patent Number 3,829,505, which is incorporated herein by reference as well as the lithium hydroxides and alkoxides and rubidium, can be used of course. Cationium-containing catalysts include cesium oxide, cesium acetate, cesium carbonate, cesium alkoxides of the lower alkanols of 1 to 8 carbon atoms, and cesium hydroxide. Other useful catalysts include oxides, hydroxides, hydrated hydroxides and salts of barium or strontium monohydroxide. Suitable alkali metal compounds include compounds containing sodium, potassium, lithium, rubidium and cesium. These compounds can be in the form of alkali metal, oxides, hydroxides, carbonates, salts of organic acids, bicarbonates, natural minerals, silicates, etc. and mixtures thereof. Suitable alkaline earth metal compounds and mixtures thereof include compounds containing calcium, strontium, magnesium, beryllium, copper, zinc, titanium, zirconium, lead, arsenic, antimony, bismuth, molybdenum, tungsten, manganese, iron, nickel , cobalt and barium. Suitable ammonium compounds include but are not limited to compounds containing an ammonium radical such as ammonia, amino compounds, e.g., urea, alkyl ureas, dicyanodiamide, melamine, guanidine, aminoguanidine, amines, e.g. , aliphatic amines, aromatic amines; organic ammonium salts; e.g., ammonium carbonate, quaternary ammonium hydroxide, ammonium silicate and mixtures thereof. The ammonium compounds can be mixed with the above-mentioned basic salt-forming compounds. Other typical anions may include the fluorine halide ions, chlorine, bromine, iodine or nitrates, benzoates, acetates, sulfonates, and the like. The reaction conditions can be graded to those typically employed in the manufacture of polyoxyalkylene polyether polyols. Generally, from 0.005 percent to about 5 percent, preferably from 0.005 to 2.0 percent, and especially preferably from 0.005 percent to 0.5 percent by weight of the catalyst relative to the polyether polymer is used. Any remaining catalyst in the polyether polymers produced in accordance with the invention can be removed by any of the well-known processes that are described in the art, such as by acid neutralization, adsorption, water washing, or ion exchange. Examples of acids used in the neutralization technique include organic acids, solids and liquids, such as acetic acid and 2-ethylhexanoic acid. For the exchange of ions, phosphoric acid or sulfuric acid can be used. The extraction or adsorption techniques employ activated clay or synthetic magnesium silicates. It is desirable to remove the cationic metal contents to less than 500 parts per million, preferably less than 100 parts per million, and especially preferably from 0.1 to 5 parts per million. As for the other processing conditions, the temperature at which the polymerization of the polyether polymers occurs can vary from 80 ° C to 160 ° C, preferably from 100 ° C to 140 ° C. At temperatures above 160 ° C, the product may discolor; and the product tends to develop a high degree of unsaturation. The reaction can be carried out in a columnar reactor, a tube reactor, or batchwise in an autoclave. In the batch process, the reaction is carried out in a closed vessel under pressure which can be regulated by an inert gas pad and the alkylene oxide feed to the reaction chamber. In general, the operating pressures produced by the addition of alkylene oxide vary from .703 to 5.62 kilograms per square centimeter gauge. The generation of a pressure greater than 7.03 kilograms per square centimeter gauge increases the risk of a fugitive reaction. The alkylene oxides can be fed into the reaction vessel either as a gas or a liquid. The contents of the reaction vessel are stirred vigorously to maintain a good catalyst dispersion and uniform reaction regimes throughout the mass. The course of polymerization can be controlled by consecutively regulating each alkylene oxide until a desired amount has been added. When the block of a random distribution or a statistic of the 1,2-butylene oxide and the other alkylene oxides are desired in the polyether polymer, the alkylene oxides may be supplied in a regulated manner to the reaction vessel as mixtures. The stirring of the reactor content at the reaction temperature is continued until the pressure decreases to a low value. The final reaction product can then be cooled, neutralized as desired, and removed. The polyether polymers of the invention can be prepared in a batch process according to the following description. It should be understood that this is only one method for preparing the polyether polymers of the invention, and that other methods would include preparing the polyether polymers in a continuous reactor or a tubular reactor. In a batch reaction, the initiator charge and the catalyst solution are weighed and added to an autoclave, which is subsequently sealed and purged with nitrogen. Instead of weighing and adding an initiator compound, a pre-prepared low molecular weight polyether polymer added to the initiator compound can be added to the autoclave. The scope of the invention, however, includes the addition of propylene oxide to an initiator, whether the addition occurs only in the main reactor or in two stages by the formation of an intermediate with the subsequent addition or greater amount of oxide of alkylene in the main reactor. The residual water contained in the initiator or intermediate polyether polymer of low molecular weight, and the water formed by the reaction of the hydroxide anion in the catalyst and the hydrogen atom in the initiator or intermediate, must be purified from the mixture of reaction. The debugging should occur at approximately the boiling temperature of the water, and at a reduced pressure. Subsequently, the autoclave can be re-pressurized with nitrogen and slowly heated to an appropriate reaction temperature for the addition of the propylene oxide. Typically, this reaction temperature will vary from about 100 ° C to 120 ° C. The propylene oxide is then slowly added over a period of time without allowing the pressure to accumulate beyond about 5.62 kilograms per square centimeter gauge and preferably to not more than 6.33 kilograms per square centimeter gauge. The feed regime of propylene oxide must be sufficiently slow to avoid terminal allylic unsaturation to the greatest possible extent, but nevertheless it is added in a sufficiently rapid manner to bring the production time to optimum. The time can vary from one hour to ten hours depending on the size of the. reaction vessel and the total amount of propylene oxide added. The propylene oxide can be added continuously or stepwise, and in a linear regime or at an exponentially decreased or increased rate. The content of the autoclave continues to be heated for a period of time sufficient to react essentially all of the propylene oxide. Subsequently, the autoclave must be evacuated to purge any unreacted propylene oxide, after which the nitrogen is reintroduced to pressurize the reactor again. The reactor can then be heated to the same temperature or higher temperature than that used for the addition of propylene oxide when 1,2-butylene oxide and / or 1,2-butylene oxide mixtures are added. and other alkylene oxides which do not tend to form terminal allylic unsaturation. Since the alkylene oxides added in this step do not form allylic unsaturation, the reaction temperature and the reaction rate may be higher than the reaction temperature and the rate of graded feed during the addition of the propylene oxide. Again, in this step, the added alkylene oxides are reacted over a period of time, the autoclave is evacuated to purge any of the unreacted alkylene oxides and is re-pressurized with nitrogen and heated during the addition of pure ethylene oxide if it is desired to produce a polyether polymer having an oxyethylene block. Once all of the alkylene oxides have been added and reacted, the autoclave is cooled and evacuated and the contents are subsequently discharged to a container washed with inert gas.

The residual catalysts and the polyols can be neutralized by an organic acid such as phosphoric acid, sulfuric acid, acetic acid, solid organic acids; they are removed by a carbon dioxide finishing process which is described in Japanese Patent Number 55-092773-A; or treated with an adsorber such as magnesium silicate or an activated clay. Any residual water remaining after the removal of the catalyst must be purified from the polyether polymer under an inert gas. Subsequently, the polyether polymer can be cooled and stabilized with conventional well-known polyether polyol stabilizers. Once it is stabilized, the polyether polymer can be exposed to atmospheric oxygen. The invention also relates to new elastomers, sealants and adhesives. The polyether polymers of the invention can be used in a wide variety of applications, and the equivalent weight of the polyether polymer will vary depending on the application. Since the terminal allylic unsaturation is not very perceptible at equivalent weights of less than 800, the polyether polymers usually have equivalent weights of 1,000 or more. Depending on the specific application, the equivalent weight of the polyether polymer can include weights of 1,300 or more or 2,000 or more.

The nominal hydroxyl numbers of the polyether polymers are not limited. For most applications, however, nominal hydroxyl numbers will vary from 15 to 57, preferably from 15 to 38. In one embodiment of the invention, an elastomer produced with a polyoxyalkylene polyether polymer having within it is provided. of its polymeric structure a nucleus of an initiator compound, an internal block oxypropylene groups and a second block of oxyalkylene groups, wherein the internal block of oxypropylene groups is between the core of the initiator and the second block of oxyalkylene groups and in addition , wherein the second block of oxyalkylene groups contains at least one alkylene oxide derivative of four higher carbon atoms, and the amount of the inner block of oxypropylene groups is at least an equivalent weight of 800 based on the weight of all the oxyalkylene groups in the polyether. The polyether polymer is preferably a polyether polyol. The initiator compounds used in the manufacture of this polyether polymer for use in elastomers are difunctional compounds or a mixture of difunctional or higher functional compounds such that the mixture would have an average functionality of less than 2.3. It is especially preferred that the average functionality of the initiator compounds be 2.1 or less, and more preferably 2.0. The functionalities can be graduated by polymerizing the alkylene oxides in a mixture of initiators, or by polymerizing the alkylene oxides in a single initiator and mixing the resulting polyether polymer with other polyether polymers produced using different initiators. The elastomers can be thermosettable or thermoplastic. The elastomers of the invention can be produced in the form of films or sheets extruded to any desired thickness. These films and sheets find applications in conveyor belts, in the transpoorte of sand and a stone suspension, applications where low permeability is required, abrasion resistant coatings, textile lamination, protective coatings and linings for hoses, such as hoses for fire. Other applications include using elastomers for the external material of ski boots, shoe soles, ice hockey boots, automotive applications, such as exterior automotive body parts, bushings, rims, cleaning paddles, wheel component gaskets, tubes , membranes and seals. Still additional applications include wheels, vibration dampers, sieves for classifying materials, cable pulley, medical and food industries, hammers, gears, pump chambers, rollers, propellers, door seals and the like. Various sealants for sealing materials described herein are for windshield wipers, thermal brakes, airport runways, roads, joints or building construction, and waterproof membranes for roofs and bridges. The elastomers, sealants and polyurethane adhesives of the invention can be prepared by the prepolymer technique or in a single operation process. The elastomers of the invention can be prepared by a reaction injection molding technique or in a molding process wherein the ingredients forming the polyurethane are mixed together and emptied into a heated mold under pressure. Other techniques include conventional hand mixing techniques and machine mixing techniques with high pressure or low pressure shock followed by emptying the ingredients forming the polyurethane into molds. In a single-step process, the polyether polymer of the invention, the catalysts and other isocyanate reactive components (the "B-side" components) are reacted simultaneously with an organic isocyanate ("A-side" components). Once the B-side components are mixed together, the urethane reaction begins and the ingredients are emptied or injected into molds. In a prepolymer technique, all or a portion of the polyether polymer and / or the other isocyanate-reactive polyols are reacted with a stoichiometric excess of the organic isocyanate to form an isocyanate-terminated prepolymer. The prepolymer is then reacted as an A-side component with any of the remaining components on the B side to form a polyurethane eiastomer, sealants or adhesives. In some cases all of the isocyanate-reactive B-side components are reacted with a stoichiometric excess of the organic isocyanate to form a single component adhesive or sealant. These isocyanate-terminated prepolymers typically have a low NCO content of from 1 weight percent to 15 weight percent. The single-component prepolymers can be cured with water in a form of moisture in the atmosphere or by the addition of water. In other cases, only a portion of the polyether polymer or other polyols are reacted with a stequimetric excess of the organic isocyanate to form an isocyanate-terminated prepolymer which is subsequently reacted with the rest of the B-side components, including polyols, as an elastomer, sealing compounds or two component adhesives. The free NCO content of the prepolymers used to produce the elastomers, sealants and adhesives of the invention may vary from 0.5 weight percent to 30 weight percent, preferably from 1 weight percent to 15 weight percent. weight and more preferably from 1 weight percent to 10 weight percent. Other ingredients in the composition of the B-side polyol in addition to the polyether polymer of the invention, may include other polyols, chain elongation agents or curing agents, catalysts, fillers or fillers, pigments, ultraviolet light stabilizers and the like . In addition to using the polyoxyalkylene polyether polymer having a low degree of unsaturation in the polyol composition for the manufacture of the elastomer, the adhesive sealant compound, other polyols can be mixed in the polyol composition. For example, the addition of polyol is polyester can be added to improve the mechanical properties of an adhesive. Polyester polyols tend to improve the tensile strength and modulus of the urethane polymer which are important considerations in the adhesive field. For sealing compounds, however, it is preferred to use polyether polyols which are hydrolytically stable and which are processed well due to their lower viscosities. Other polyols that can be cooled in addition to the polyoxyalkylene polyether polymers of the invention are the hydroxyl-terminated hydrocarbons, such as polybutadiene polyols, where a high degree of hydrophobicity is desired. Castor oil and other natural oils can also be used. In addition, polycaprolactones can be used to increase the tensile strengths of sealing compounds. Other polyether polyols may be added and it is preferred that these polyether polyols have a low degree of unsaturation to optimize the mechanical properties of the product. For example, those polyether polyols produced with amorphous or crystalline DMC catalysts are suitable as well as the polyether polyols catalyzed by cesium hydroxide. Sealing compounds or one-component adhesives are typically cured by air humidity. Adhesive sealant compounds and two component elastomers are typically cured by chain elongation agents with compounds containing hydrogen reactive to the isocyanate. Chain-lengthening agents can be employed and are typically employed in the preparation of elastomers, sealants and polyurethane adhesives. The term "chain elongation agent" is used to mean a compound of relatively low equivalent weight, usually less than about an equivalent weight of 250, having a plurality of hydrogen atoms reactive to the isocyanate. Chain elongation agents include water, hydrazine, aliphatic or primary and secondary aromatic diamines, aminoalcohols, amino acids, hydroxy acids, glycols or mixtures thereof. A preferred group of alcohol chain elongation agents include water, ethylene glycol, 1,3-propanediol, 1-butanediol, 1,10-decanediol, o-, m-, p-dihydroxycyclohexane, diethylene glycol, 1,6-hexanediol , glycerin, trimethylolpropane, 1,2,4- 1,3,5-trihydroxycyclohexane and bis (2-hydroxyethyl) hydroquinone. Examples of secondary aromatic diamines are N, N'-dialkyl-substituted aromatic diamines, which are unsubstituted or which are substituted on the aromatic radical by alkyl radicals having from 1 to 20, preferably from 1 to 4 carbon atoms. carbon in the N-alkyl radical, e.g., N, N '-diethyl-, N, N'-di-sec-pentyl, N, N' -di-sec-hexyl-, N, N '- di-sec-decyl- and N, N'-dicyclohexyl-p- and m-phenylenediamine, N, N '-dimethyl-, N, N' -diethyl-, N, N'-diisopropyl-, N, N1 -di -sec-butyl- and N, N '-dicyclohexyl-4,' -diaminodiphenylmethane and N, N'-di-sec-butylbenzidine. The amount of the chain-lengthening agent used varies to some degree in the desired physical properties of the elastomer or sealing compound. A higher proportion of the chain elongation agent and the isocyanate gives the elastomer or sealing compound greater rigidity and higher temperature of thermal distortion. The smaller amounts of the chain elongation agent and the isocyanate provide a more flexible elastomer or sealant compound. Typically, from about 2 to 70, preferably from about 10 to 40, parts of the chain elongation agent are used per 100 parts of the polyether polymer and any of the other isocyanate-reactive components of higher weight molecules. Catalysts which greatly accelerate the reaction of the compounds containing the hydroxyl groups and with the modified or unmodified polyisocyanates can be used. Examples of suitable compounds are curing catalysts that also function to shorten tack time, promote untreated strength and prevent foam shrinkage. The appropriate curing catalysts are organometallic catalysts, preferably organotin catalysts even when it is possible to use metals, for example, lead, titanium, copper, mercury, cobalt, nickel, iron, vanadium, antimony and manganese. Suitable organometallic catalysts exemplified herein by tin, the metal, are represented by the formula RnSn [X-Rl-Y] 2. wherein R is an alkyl or aryl group of one to eight carbon atoms, R1 is a group methylene of 0 to 18 carbon atoms substituted or branched with an alkyl group of 1 to 4 carbon atoms, Y is a hydrogen or a hydroxyl group, preferably hydrogen, X is methylene, a group of -S-, a group of -SR2COO-, -SOOC-, -O3S-, or a group of -OOC-, wherein R2 is an alkyl of 1 to 4 carbon atoms, n is 0 or 2 with the proviso that R1 is Cn only when X is a methylene group. The specific examples are tin acetate (II), tin (II) octanoate, tin ethylhexanoate (II) and tin laurate (II); and the dialkyl (1-8C), tin (IV) salts, of the organic carboxylic acids having from 1 to 32 carbon atoms, preferably from 1 to 20 carbon atoms, e.g., diethyltin diacetate. , dibutyltin diacetate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dihexyltin diacetate and dioctyltin diacetate. Other suitable organotin catalysts are organotin alkoxides and salts of mono- or poly-alkyltin (1-8C) (IV) of inorganic compounds such as butyltin trichloride, dimethyl- and diethyl- oxide and dibutyltin compounds and dioctyl- and diphenyl-tin, dibutyltin dibuthoxide, di (2-ethylhexyl) tin oxide, dibutyltin dichloride and dioctyltin dioxide. Preferred, however, tin catalysts with tin-sulfur bonds which are resistant to hydrolysis, such as dimercapturos dialkyl (1-20C) tin dimercapturos including dimethyl-, dibutyl- and dioctyl tin. Tertiary amines also promote or activate the formation of urethane linkage and include triethylamine, 3-methoxypropyldimethylamine, triethylenediamine, tributylamine, dimethylbenzylamine, N-methyl-, N-ethyl- and N-cyclohexylmorpholine, N, N, N ', N " -tetrametiletilentiamina, N, N, N ', N'-tetrametilbutanodiamina or -hexanodia ina, propylenediamine, N, N, N' -trimetilisopropilo, pentamethyldiethylenetriamine, tetrametildiaminoetilo ether, bis (dimethylaminopropyl) rea, dimethylpiperazine, 1-methyl-4- dimethylaminoethylpiperazine, 1, 2-dimethylimidazole, 1-azabicyclo [3.3.0] octane and preferably 1.4-diazabicyclo [2.2.2] octane, and alkanolamine compounds such as triethanolamine, triisopropanolamine, N-methyl- and N-ethyldiethanolamine and dimethylethanolamine To avoid retention of air bubbles in the elastomer sealing compounds, a batch mixture can be subjected to degassing under reduced pressure once the ingredients have been mixed together. As a result of roasting, the ingredients formed by the mixed polyurethane can be heated under vacuum to an elevated temperature to react or volatilize the residual water. By heating at an elevated temperature, the waste water reacts with the isocya to release the carbon dioxide that is attracted from the mixture by the reduced pressure. Altervely or in addition to the degassing process, the polyurethane-forming ingredients can be diluted with solvents to reduce the viscosity of the polyurethane-forming mixture. These solvents must be non-reactive and include tetrahydrofuran, ketone, dimethylformamide, dimethylacetamide, normal methylpyrrolidone, methylethyl ketone, etc. The reduction in viscosity of the ingredients that make up the polyurethane help its extrusion capacity. For applications of the sealing compound, however, the amount of the solvent must be kept as low as possible to avoid deteriorating its adhesion to the substrates. Other solvents include xylene, ethyl acetate, toluene and cellosolve acetate. Plasticizers can also be included in the A- or B-side components to soften the elastomer or sealing compound and lower its brittleness temperature. Examples of plasticizers include dialkyl phthalates, dibutylbenzyl phthalate, tricresyl phosphate, dialkyl adipates and trioctylphosphate. Besides solvents or plasticizers, other ingredients such as adhesion promoters, fillers or fillers and pigments, for example, clay, silica, fumed silica, carbon black, talc, blue or phthalocyanine green, titanium oxide, carbo of magnesium, calcium carbo and ultraviolet ray absorbing agents can be added in amounts ranging from 0 percent to 75 percent by weight, based on the weight of the polyurethane. Other filling or loading materials include loose gels, plasticeldas, calcium carbonate graded and coated, urea solids, the reaction product of hydrogenated castor oils with amines, and fibers. The organic polyisocyanates are used to prepare the prepolymer, are used in a single operation process or are used for further processing of the hydroxyl terminated prepolymers. The organic polyisocyanates include all the essentially known aliphatic, cycloaliphatic, araliphatic and preferably multivalent aromatic isocyanates. Representative of these types are diisocyanates such as m-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotoluene diisocyanate (and isomers), naphthalene-1,5-diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, 4,4'-diphenylmethane diisocyanate, diisocyanate mixtures of 4,4'- and 2,4'-diphenylmethane, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4-diisocyanate, 4'-biphenyl and 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, triisocyanates such as 4,4 ', 4' ', 4"-triphenylmethane triisocyanate, and toluene 2,4,6-triisocyanate; and the tetraisocyanates such as 4, '-dimethyldiphenylmethane-2,2'-5,5'-tetraisocyanate and the polymeric polyisocyanates such as polymethylene-polyphenylene polyisocyanate, and mixtures thereof. Especially useful due to their availability and properties are the 4,4'-diphenylmethane diisocyanate, polymethylene-polyphenylene polyisocyanate, or mixtures thereof for rigid foams, or a mixture of the above with toluene diisocyanates for semi-rigid foams. The crude polyisocyanates can also be used in the compositions of the present invention, such as crude toluene diisocyanate obtained by the phosgenation of a mixture of toluene diamines or crude diphenylmethane isocyanate by the phosgenation of crude diphenylmethane diamine. Preferred or crude isocyanates are disclosed in U.S. Patent No. 3,215,652. In one embodiment of the invention, an isocyanate-terminated prepolymer suitable for the preparation of sealants and adhesives is provided. The isocyanate-terminated prepolymer can be prepared by reacting a stoichiometric excess of the organic isocyanate with a mixture of a polyoxyalkylene polyether triol and a polyoxyalkylene polyether diol. Any or both of the triol and the diol are the polyoxyalkylene polyether polymers described herein, that is, they contain an internal block of oxypropylene groups and a second block of oxyalkylene groups derived from an alkylene oxide of 4 carbon atoms. upper carbon, preferably butylene oxides or mixture of butylene oxide and ethylene oxide. In a preferred embodiment, it is the triol of the polyoxyalkylene polyether which is the polyether polymer described according to the invention. The equivalent ratio of NCO / OH groups should be graduated from 1.01 / 1 to about 10/1, more preferably from 1.2 / 1 to about 2.5 / 1, to produce the isocyanate-terminated prepolymers of this embodiment. Also, in this embodiment, the equivalent weight of the polyoxyalkylene polyether diol should vary from about 250 to about 7000, and that of the polyoxyalkylene polyether triol ranges from 1300 or more, preferably from 1600 or more. Of course, other compounds reactive to the lysocyanate having functionalities greater than 3 in mixture with the diols and triols can be used in the manufacture of an isocyanate-terminated prepolymer. Once the isocyanate-terminated prepolymer is produced, the sealing material or adhesive can be prepared by curing the prepolymer with moisture if the free NCO content is low enough, or by reacting the prepolymer with weight polyoxyalkylene polyether polyols. further molecular moieties, or polyoxyalkylene polyethers terminated with amine, chain elongation agents, catalysts, fillers or fillers, etc. For most specific applications employing sealant compounds, the isocyanate-terminated prepolymer is cured with moisture. In another embodiment of the invention, a hydroxyl-terminated prepolymer suitable for the manufacture of sealants and adhesives is provided. This embodiment, a stoichiometric deficiency of the organic isocyanate is reacted with a polyoxyalkylene polyether polymer of the invention and optionally other polyols or other isocyanate-reactive compounds, at equivalent ratios of NCO-OH of 0.99: 1 or less, and still a 0.90: 1 or less, or 0.85: 1 or less. The hydroxyl-terminated prepolymer can then be mixed with the other B-side ingredients such as other polyols, chain-lengthening agents, catalysts, surfactants or fillers or fillers, for reaction with additional organic isocyanate to produce a sealant or adhesive. The purpose of producing a hydroxyl-terminated prepolymer can be to adjust the viscosity of the B-side components, if a thicker composition is desired for a given application. As in the above-described embodiment, the B-side components may comprise a mixture of triols and diols which are reacted with a sub-stoichiometric amount of the organic isocyanate. Either one or both of the diol or triol can be manufactured in accordance with the method described herein. In still a further embodiment of the invention, isocyanate-terminated prepolymers suitable for the manufacture of elastomers, and elastomers made with the polyoxyalkylene polyether polymers of the invention are provided. The elastomers of the invention can be manufactured by a single operation technique or a prepolymer technique. In the prepolymer technique, a prepolymer having a free NCO content of 1 weight percent to 30 weight percent, usually 1 weight percent to 10 weight percent may be provided. The prepolymer can be made by reacting a stoichiometric excess of the organic isocyanate with a polyoxyalkylene polyether diol, or a mixture of a polyether diol and a polyether triol having an average functionality of less than 2.3. One or both of the polyether diol or triol are made in accordance with the invention described herein. Preferably, a polyoxyalkylene polyether diol having an internal block of oxypropylene groups and a second block of alkylene oxides of 4 carbon atoms or more such as oxybutylene or a mixture of oxybutylene and oxyethylene groups is reacted with a Stoichiometric excess of organic isocyanate at an equivalent NCO-OH ratio of 1.01: 1 to 10: 1. The polyoxyalkylene polyether diol is preferably terminated with oxyethylene groups to increase its reactivity with the organic isocyanate. The isocyanate-terminated prepolymer can then be reacted with additional B-side components such as polyether polyols, chain elongation agents, catalysts and other non-reactive ingredients. Alternatively, the isocinato-terminated prepolymer can be cured by moisture in the presence of a catalyst to accelerate the cure rate. The polyether diols used in the manufacture of elastomers have equivalent weights ranging from 250 to about 7000. When the equivalent weight of the polyether polyol is about 1000? more, the diol should be manufactured according to the procedure described herein, to reduce the terminal allylic unsaturation. The Shore A hardness of the sealants, adhesives and elastomers made in accordance with the invention can be varied widely depending on the final application. The Shore A hardness can vary from 0 to about 95. For most applications, however, the Shore A hardness for sealants and adhesives will vary from 0 to 40, more typically from 0 to 20. In most of the elastomer applications, Shore A hardness will vary from 20 to 95, with values from 50 to 90 being quite common. In some elastomeric applications, the elastomer will have a Shore D hardness of 55 to 75. The following examples illustrate some of the embodiments of the invention.

Preparation of Intermediate A 77.78 kilograms of trimethylolpropane and .735 kilograms of 90 percent KOH were charged in a clean dry autoclave filled with nitrogen. After loading, the agitator was started slowly and advanced to 150 revolutions per minute, and the autoclave was heated to a temperature of 65 ° to 70 ° C. The reactor was sealed, purged three times with nitrogen, discharged to approximately 0.25 bar. Subsequently, the contents were heated to 125 ° C, discharged to 0.15 bar, 334.09 kilograms of propylene oxide were added over approximately a period of 8 hours to less than 6.2 bar. The content was further reacted for 3 hours, after which a vacuum was applied and the pressure was reduced to 13mb at 125 ° C. The vacuum was then released to about 1 bar with nitrogen, cooled to about 90 ° C, and the contents moved to a filter-scrubber tank. Once the crude product had been transferred to the filter-drainer tank, 11.35 kilograms of MAGNESOL (R) was added to the crude polyol, after which the filter-purifying tank was sealed and purged three times (3) under pressure of 3.5 bar with nitrogen. The final purge was discharged to a bar. The crude product was treated in the filter-scrubber tank at 90 ° C to 95 ° C for one (1) hour. Subsequently, the treated product was recycled through the filter press until it achieved clarity free of turbidity and less than 20 parts per million NaK. The product was then transferred from the filter-scrubber tank through the filter press to the flashing tank. The polyol product was stripped from the water at 105 ° C and less than 13 mb for 60 minutes until the water content was less than 0.05 percent after vacuum stripping. Subsequently, the vacuum was released with nitrogen gas; the stabilizer was added to the filtered purified product. The intermediate product was subsequently cooled. This intermediate product is designated as intermediate A.

EXAMPLE 1 - Polyol A This Example describes the preparation of the low unsaturation block of the polyether triol PO- [BO-EO het] -EO using a conventional KOH catalyst. A 552.9 grams (0.85 mole) of intermediate A and 30.6 grams (0.25 mole) of a 45 percent KOH solution were charged to a clean dry autoclave. The autoclave was sealed, and the agitator was started. The autoclave was purged three (3) times with nitrogen and subsequently heated to 105 ° C while slowly evacuating to a pressure of less than 10 millimeters of mercury. The content was batch-cleaned for two (2) hours. Subsequently, the vacuum was released at 0 kilogram per square centimeter gauge with nitrogen; and the autoclave was then heated to 110 ° C. Propylene oxide was then added at 110 ° C and at a pressure less than 6.33 kilograms per square centimeter gauge over a period of seven hours. The content was reacted for an additional four (4) hours at 110 ° C. Subsequently, the reactor was evacuated to 10 millimeters of mercury and again heated to 125 ° C and pressurized to .703 kilogram per square centimeter gauge. A butylene oxide / ethylene oxide pump was charged to the autoclave at 125 ° C. and less than 5.24 kilograms per square centimeter gauge over a period of two (2) hours. The amount of butylene oxide and ethylene oxide added was 706.5 grams (9.8 moles) and 464.3 grams (10.55 moles), respectively. The content was reacted for an additional hour at 125 ° C, and subsequently the auclave was evacuated to 10 millimeters of mercury. Once it had been evacuated, the autoclave was again pressurized to 2.35 kilograms per square centimeter gauge with nitrogen, and 242.2 grams of ethylene oxide were charged into the autoclave under pressure of 6.33 kilograms per square centimeter gauge and temperature 125 ° C through a period of one hour. The content was reacted for about an additional hour at constant pressure. Finally, the autoclave was evacuated to 10 millimeters of mercury for thirty minutes, and the content was cooled to 60 ° C and then discharged to a container washed with nitrogen. The polyether polyol was treated with 3 percent MAGNESOL (R) and 1.5 percent water at 95 ° C for one and a half hours. The product was recycled through the filter press until it was free of turbidity and then it was purified of water at 110 ° C and less than 10 millimeters of mercury during one hour). The treated product was then cooled to 60 ° C and stabilized with a common stabilizer package.

Chemical analysis of the polyether product revealed that the polyol had a hydroxyl number of 27.5 and a degree of unsaturation of 0.055. The compatibility index was 6 ° C. The structure of the final polyether polyol corresponded to a core of a trimethylolpropane initiator molecule covalently linked to a block of oxypropylene groups through the hydroxyl functional groups of the initiator molecule, and a block of mixed oxybutylene and oxyethylene groups attached to the block of the oxypropylene groups, and was terminated with a block of oxyethylene groups. Based on the weight of all the alkylene oxide fillers and the initiator, the polyether polymer had about 75 weight percent oxypropylene groups, 20 weight percent of a block of oxybutylene groups and oxyethylene groups mixed together. randomly, and about 5 weight percent of a terminal block of the oxyethylene group.

EXAMPLE 2 This example illustrates the manufacture of a low unsaturation polyether triol of PO- [BO-EO het] -EO which is made using cesium hydroxide as a catalyst.

The same procedure that was used in the manufacture of Polyol A in Example 1 above was used to make the Polyol of this example, Polyol B, with the following exceptions. The fillers for each ingredient were the following: 588.9 grams of Intermediate Polyol A, 79.1 grams of a 50 percent cesium hydroxide solution and 3610.7 grams of propylene oxide. In the step of manufacturing the block of oxybutylene and oxyethylene groups mixed at random, the charges were 699.9 grams of butylene oxide and 431.2 grams of ethylene oxide. In the blocking step of the polyether polymer with the oxyethylene group, 268.8 grams of ethylene oxide were added. In the process for manufacturing the polyether polyol B polymer, the following manufacturing steps differed in the following manner from Example 1: The propylene oxide in this case was reacted for 4.5 hours at 110 ° C instead of 4 hours . The mixed oxides of butylene oxide and ethylene oxide were reacted for two (2) hours instead of one (1) hour. The resulting polyether B polymer polyol had a hydroxyl number of 27, a degree of unsaturation of 0.03 and a compatibility index of about 5 ° C. Based on the weight of the alkylene oxide and the initiator, the added fillers of the polyether polymer contained about 75 percent by weight of an oxypropylene group block, 20 percent by weight of a block of oxyethylene groups and oxybutylene groups. randomly mixed, and about 5 weight percent of a terminal oxyethylene block.

EXAMPLE 3 This example illustrates the manufacture of sealing agents employing low-unsaturation PO- [BO-EO het] -E0 polyether polymers, manufactured with a variety of catalysts. Table 1 shows the result obtained from an evaluation of 14 different polyether triols used in the preparation of sealing compounds. Examples 1 and 12 to 14 are comparison examples. Each of the polyols 2 to 11 were prepared according to the procedures of Examples 1 or 2. Those polyether polymer triols using potassium hydroxide as the catalyst were prepared according to Example 1, while those triols prepared with cesium hydroxide as a catalyst, were prepared according to Example 2. The charges of propylene oxide, butylene oxide and ethylene oxide were adjusted to correspond to the percentage by weight of the oxypropylene groups indicated in the table below. is presented below. Each of the triols 2 to 14 was terminated with a 5 percent by weight block of the oxyethylene groups. The amount of butylene oxide and ethylene oxide charged to form a block of the oxyethylene groups and oxybutylene groups randomly distributed, was measured either on a 1: 1 weight basis, or a 1: 1 molar base, as shown in the table. A water test was carried out by immersing the sealing compound for thirty (30) days at 70 ° C in a water bath. The sealing compound was then removed from the water and its tensile properties were measured according to the D412 method of the American Society for the Testing of Materials. A "Y" indicates the retention of more than 50 percent of the original tensile strength of the sealant compound before being submerged in the water bath, while "N" indicates that there was no significant retention of the water resistance properties. original tension. The polyols of comparison examples 12 to 14 were prepared using the listed catalysts, and each had average molecular weights of about 6200, with a terminal blockage of the oxyethylene groups in an amount of about 5 weight percent. The following procedure was used to prepare the sealing compounds. A prepolymer was prepared by reacting an organic isocyanate with a mixture of polyols. The polyol mixture consisted of 0.249 equivalent of Polyol C and 0.249 equivalent of each of Polyols 1 to 14 in separate batches. Polyol C is a propylene oxide adduct of propylene glycol having a hydroxyl number of about 56. Each of the polyol blends was degassed and then dried under reduced pressure at 95 ° C for two (2) hours and then it was cooled to 40 ° C. Toluene diisocyanate, which can be obtained commercially from BASF Corporation as LUPRANETE T80-1, was heated at 40 ° C in a reaction flask under constant nitrogen sparge. One of the polyol blends was added to one (1) equivalent of a toluene diisocyanate heated rapidly as possible, maintaining the resulting exothermic reaction at or below 60 ° C. Once the polyol mixture had been completely added, the mixture was heated to 80 ° C and maintained at that temperature for 1.5 hours. The percentage of free NCO was then measured by evaluation. This procedure was repeated for each batch of polyol.

Each prepolymer was mixed with Polyol D at a ratio of 1: 1 equivalents based on the NCO percentage of the prepolymer, 25 weight percent of a filler or talc filler, 3 drops of a silicone surfactant DC-200 , and 0.5 weight percent of a dibutyltin dilaurate catalyst. Polyol D was an adduct of propylene oxide of propylene glycol having an OH number of about 107. These ingredients were mixed, degassed under reduced pressure and then emptied into a 6.35 millimeter mold, cured at 70 ° C for four hours. hours. The resulting plates were post-cured for two weeks at room temperature, 50 percent relative humidity before being tested. The results of the evaluations are described in the table below. The Cl is a temperature at which the triol drops out of the solution with water, and 100 percent and 300 percent are the measurements of modulus at an elongation of 100 percent and an elongation of 300 percent, respectively. with Method D412 of the American Society for the Testing of Materials. The data generated from the evaluation of Examples 2-11 of the invention demonstrates a reduction in the degree of unsaturation of each triol when compared to conventional triols prepared with either potassium hydroxide and cesium hydroxide as in Examples 12 and 13 Therefore, even though each triol had a molecular weight of approximately 6,200, those triols prepared with an internal block of 25 percent to 80 percent oxypropylene groups followed by a block of randomly distributed oxybutylene and oxyethylene groups. inactivated with ethylene oxide, it had a much lower degree of unsaturation than polyether polyols of similar molecular weight prepared with the same catalyst using only propylene oxide and an ethylene oxide block. When used in the manufacture of a sealing compound, the triol of Example 12 prepared with potassium hydroxide and all of the propylene oxide with a lock of ethylene oxide was not able to be cured. In contrast, the triols prepared with the potassium hydroxide catalyst and a second block comprising at least oxybutylene groups, was blocked with ethylene oxide, cured well and exhibited improved tensile properties. Nor did the triols of the invention prepared with KOH have much lower degrees of unsaturation than polyol 12 of propylene oxide polyether prepared with KOH, but also had lower degrees of unsaturation than all polyether polyols of propylene oxide made with catalysts of sodium hydroxide which are shown in Example 13, and were on par with the properties to the tension and the triols prepared with the double metal cyanide catalysts. For the most part, the sealing compounds prepared using the triols of the invention retained their physical properties under the water immersion test. The triols of the invention were also sufficiently hydrophobic as demonstrated by the low temperatures at which the triols fell out of the solution with water. In contrast, the polyether polyol prepared with only butylene oxide and ethylene oxide according to Comparison Example 1 was too hydrophilic as shown by its high Cl value.

TABLE 1 TRIOLS OF PO / BO / EO OF MOLECULAR WEIGHT OF 6,200, EVALUATED IN CONSTRUCTION SEALANT COMPOUNDS % OF PO CATALI- INSATU PESO / MOLAR Cl (IN WEIGHT) ZADOR RACIÓN. (BO / EO) 1) 0 KOH .006 WEIGHT 53 (BO / EO) 50 KOH 021 WEIGHT 24 3) 50 KOH .02 MOL 4) 65 KOH .038 WEIGHT 16 ) 65 KOH .037 MOL -2 6) 65 CsOH .027 PESO 13 7) 65 CsOH .022 MOL 3.5 8) 75 KOH .055 PESO 6 9) 75 KOH .047 MOL 3 ) 75 CsOH .03 WEIGHT 5 11) 75 CsOH .028 MOL 5 12) 95 KOH .100 NONE < 4 13) 95 CsOH .050 NONE < 4 14) 95 DMC .020 NONE < 4 TABLE I (Continued) % OF PO MODULO TO THE SHORE MODULE TO PROOF OF (BY WEIGHT) 100% 300% WATER * (kg / cm2) (kg / cm2) 1) 0 3.66 7.17 21 (BO / EO) 2) 50 1.7? 3.23 11 N 3) 50 2.1Í 4.29 AND 4) 65 1.48 2.60 10 N ) 65 2.11 3.87 6) 65 2.04 4.08 14 Y 7) 65 1.41 2.60 8) 75 2.32 4.36 15 9) 75 3.02 5.83 13 and 10) 75 2.39 4.71 16 Y 11) 75 2.60 4.78 12) 95 WITHOUT CURE WITHOUT CURE OR WITHOUT CURE 13) 95 1.27 2.11 AND 14) 95 3.80 2.95 12 * WATER TEST: TOTAL IMMERSION FOR 30 DAYS AT 70 ° C AND THEN THE TENSION AND = RETENTION OF > 50% OF THE ORIGINAL PROPERTIES N = NO SIGNIFICANT RETENTION OF THE PROPERTIES In summary, we dramatically reduced the degree of unsaturation of the polyether polyols suitable for the preparation of sealing agents and elastomers without employing any exotic and expensive catalyst, while simultaneously improving the hydrophobicity and tensile strength characteristics of the polyether polyol and the resulting sealing compound. The polyether polyols of the invention also advantageously provide tremendously broad processing and formulation windows, while retaining improved degrees of unsaturation and mechanical properties. For example, the ratio of butylene oxide and ethylene oxide in the block, as well as the total amount of butylene oxide can be varied widely to obtain the desired degree of hydrophobicity. The process also does not depend on removing catalysts before the addition of an inactivation of ethylene oxide in the case of DMC catalysts. It could not be visualized that a polyether polyol of high equivalent weight using potassium hydroxide as a catalyst could be manufactured with low degrees of unsaturation nor could it be used to prepare a sealing compound or polyurethane elastomer having improved physical properties.

EXAMPLE 4 This example illustrates the manner in which the polyether diol having a low degree of unsaturation was manufactured. Diols are frequently used in the manufacture of elastomers. To improve their reactivity, the diols frequently have a high percentage by weight of an oxyethylene block. Accordingly, this example illustrates the manner in which a polyether diol having a 1 - low degree of unsaturation and a high equivalent weight could be manufactured. An intermediate B was manufactured by charging 1,397.7 grams of dipropylene glycol and 732.5 grams of a 50 percent solution of a cesium hydroxide catalyst in a clean dry autoclose. The autoclave was sealed, the stirring was started and purged three times with nitrogen. The autoclave was heated to about 105 ° C and evacuated to less than 10 millimeters of mercury to purify the water for about an hour. The vacuum was released at zero kilogram per square centimeter with nitrogen, after which 3,102.3 grams of propylene oxide were added at 105 ° C and less than 6.33 kilograms per square centimeter gauge and through a period of four and a half hours. After the addition of propylene oxide was complete, the reaction was continued for another hour at the same temperature. The autoclave was then evacuated, the volatile substances were purified and the reaction mixture was cooled to 60 ° C. The contents were discharged to a container washed with nitrogen. 781.6 grams of intermediate B was added to a separate, clean, dry autoclave. The autoclave was sealed, stirring was started and the autoclave was purged three times with nitrogen. The autoclave was then heated to a temperature of approximately 105 ° C and evacuated slowly to purify. the volatile materials. Once it was cleaned, the vacuum was released with nitrogen after which 2.510.7 grams of propylene oxide was added over a period of 5 hours, maintaining the pressure to less than 6.33 kilograms per square centimeter gauge. Once the addition was complete, the reaction continued for another three hour period. Subsequently, the autoclave was evacuated to collect any of the unreacted propylene oxide volatile materials, after which it was again pressurized to zero kilogram per square centimeter gauge with nitrogen. The reactor was then heated to a temperature of about 125 ° C. A mixture of 670.7 grams of butylene oxide and 409.3 grams of Leno eti oxide were simultaneously added to the autoclave at 125 ° C over a period of two and a half hours under pressure of less than 5.24 kilograms per square centimeter gauge. The reaction was continued for about four half hours after which it was evacuated to collect any remaining volatile materials. Once the autoclave was re-pressurized, approximately 1,080.0 grams of ethylene oxide was added at 125 ° C over a period of two hours and at a pressure less than 6.33 kilograms per square centimeter gauge. The ethylene oxide was reacted to a constant pressure through a 3 - one hour period, after which the autoclave was evacuated for about half an hour to collect any of the volatile materials. The content of the reaction in the autoclave was cooled to 60 ° C and discharged to a container washed with nitrogen. The resulting polyether polyol was treated with a 3 percent Magnasol® absorption agent and 1.5 percent water at a temperature of about 95 ° C for one and a half hours, made to be recycled through the filter press , it was purified and stabilized with conventional stabilizers. The resulting polyether polyol was subjected to analysis which showed that the polyether polymer was manufactured from an internal block of 60 weight percent oxypropylene groups, a 20 weight percent block of oxybutylene and oxyethylene groups randomly distributed in a molar ratio of 1 to 1, and a terminal block to 20 weight percent of oxyethylene groups. The resulting polyether polymer had an equivalent weight of about 1,500, an OH number of about 37.3, and a compatibility index of greater than 70 ° C. Notably, the level of unsaturation was only 0.014.

EXAMPLE 5 This example will demonstrate the level of unsaturation for a polyether diol of an equivalent weight of about 2,000, suitable for the manufacture of elastomers using cesium hydroxide as a catalyst. The same procedure used in Example 4 above was used here. The only difference in the loads were 590.8 grams of intermediate B and 2,688.9 grams of propylene oxide. The diol of the resulting polyether polymer had an internal block of 60 weight percent oxybutylene groups, a 20 weight percent block of oxybutylene and oxyethylene groups randomly distributed in a metal ratio of 1 to 1, and a terminal block at 20 percent by weight of oxyethylene groups. The analysis showed that the polyether diol had an OH number of about 28.6, which corresponds to a calculated equivalent weight of about 1,960, and a compatibility index greater than 70 ° C. Notably, the level of unsaturation for this high-weight polyether diol was only 0.019.

EXAMPLE 6 In Examples 6 and 7, different polyether polyols of equivalent weight of 1,500 were made using different catalysts and having different structures. An intermium C was manufactured by charging 847.8 grams of dipropylene glycol and 102.5 grams of a 50 percent solution of a cesium hydroxide catalyst in a clean dry autoclave. The autoclave was sealed, stirring started and purged three times with nitrogen. The autoclave was heated to approximately 105 ° C and evacuated to less than 10 millimeters of mercury to purify the water for about one hour. The vacuum was released to zero kilograms per square centimeter gauge with nitrogen, after which 1,902.7 grams of propylene oxide were added at 105 ° C to less than 6.33 kilograms per square centimeter gauge and over a period of four hours. After the addition of propylene oxide was complete, the reaction was continued for another hour at the same temperature. The autoclave was then evacuated, the volatile materials were stripped for 30 minutes and the vacuum was released with nitrogen. The contents were discharged to a container that was flushed with nitrogen. The OH number was about 251.6, and the Gardner color was about 1, and the weight percentage of cesium hydroxide was about 1.8. In a separate dry clean autoclave, 747.7 grams of Intermediate C and 71.0 grams of a 50 percent cesium hydroxide solution were added. The same procedure as in Example 4 was used with the exception that the amount of propylene oxide was 2.517.2 grams, the amount of ethylene oxide added as the heteric block was 540 grams, the amount of butylene oxide added was of 540 grams and the amount of ethylene oxide added as the terminal block was 1, 080.0 grams. The resulting polyether polyol 6 was subjected to analysis which showed that the polyether polymer was manufactured from an internal block of 60 weight percent oxypropylene groups, a 20 weight percent block of oxybutylene and oxyethylene groups distributed at randomly at a weight ratio of 1 to, and a terminal block of 20 percent to the weight of oxyethylene groups. The resulting polyether polymer had an equivalent weight of about 1500, an OH number of about 37, and a compatibility index of greater than 70 ° C. Notably, the level of unsaturation was only 0.014.

EXAMPLE 7 This polyether polyol was prepared with a normal KOH catalyst as a polyol of equivalent weight of 1500 of low unsaturation. Intermediate D was prepared by adding about 35 moles of propylene glycol to a reactor filled with nitrogen, dried and heated to 49 ° C. A 45 percent solution of KOH was added, mixed at a temperature below 60 ° C and 3.51 kilograms per square centimeter gauge. During the addition of approximately 294 moles of propylene oxide to the reactor, the heat increased to 125.5 ° C and was maintained during the reaction. Upon completion of the reaction, the contents were cooled to 66 ° C and discharged to storage. 700.3 grams of Intermediate D were charged with 18 grams of KOH in a clean dry auclave, sealed and shaken. After purging, the autoclave was heated to 105 ° C and depressurized to less than 10 millimeters of mercury to purify the water. The same procedure was used for the remainder of the reaction as used in Example 4 with the following additional modifications: 2,686.2 grams of propylene oxide were added over a period of 6 hours and reacted for 3 more hours, then of which the autoclave was evacuated for 30 minutes instead of 10 minutes; The mixed oxides of ethylene and butylene were added as a weight ratio of 1: 1 of 560: 560 grams over a period of 1.5 hours and reacted for a further 3 hours after which the autoclave was depressurized for 10 hours. 8 - minutes, and 1120 grams of ethylene oxide were added as blocking over a period of 1.5 hours and reacted for 1 hour more. The polyol was stabilized by the same procedure. The resulting polyether polyol had an OH number of 37, an acid number of 0.004, a level of unsaturation of 0.02 and a Cl of more than 70 ° C in a ratio of 50/50 isopropyl / water. The polyether polymer was a difunctional polyol of equivalent weight of 1,500 with 60 weight percent of an internal block of polyoxypropylene, a block of 20 weight percent of polyoxyethylene and polyoxybutylene groups blended at random, and a block of 20 per cent. weight percent polyoxyethylene.

Claims

CLAIMS:

1. A polyoxyalkylene polyether polymer comprising within its structure the core of an initiator compound, an internal block of oxypropylene groups, and a second block of oxyalkylene groups, wherein the internal oxypropylene block lies between the core and the second block, the second block comprises oxyalkylene groups derived from an alkylene oxide of 4 higher carbon atoms, and the amount of the internal block of oxypropylene groups is from 25 percent to 80 percent by weight based on the weight of the groups of oxyalkylene and the initiator in the polyether polymer, and the amount of the second block is effective to reduce the degree of unsaturation of the polyether to 0.06 milliequivalents of KOH per gram of polyol or less.

2. The polyether according to claim 1, wherein the polyether is a polyol.

3. The polyether according to claim 2, wherein the amount of the internal block is from 50 percent to 80 percent by weight, and the second block comprises a random mixture of oxyethylene groups and oxybutylene groups.

The polyether according to claim 3, wherein the internal block of oxypropylene groups is bonded to and lies between the core of an initiator and the second block, the core of an initiator is derived from an initiator having two or three groups hydroxyl functional groups, and the equivalent weight of the polyol is at least 1500.

5. The polyether according to claim 4, wherein the weight ratio of oxybutylene groups to oxyethylene groups is from 0.5: 1 to 4: 1. .

6. The polyether according to claim 4, wherein the amount of oxybutylene groups is at least 5 weight percent.

The polyether according to claim 6, wherein the amount of oxybutylene groups is at least 10 weight percent.

The polyether according to claim 1, wherein the polyether ends with a terminal block of oxyethylene groups containing a primary hydroxyl group on the terminal carbon of the terminal block.

9. The polyether according to claim 8, wherein the amount of the terminal is from 4 weight percent to 35 weight percent.

The polyether according to claim 9, wherein the amount of the terminal block is from 10 weight percent to 20 weight percent. . gi ¬ l.

The polyether according to claim 1, wherein the polyether is a polyol having a degree of unsaturation of 0.03 milliequivalent per gram of polyol or less, and an equivalent weight of at least 1,500.

12. The polyether according to claim 11, wherein the polyol has a Cl of 25 ° C or less.

The polyether according to claim 1, wherein the polyether is a polyol having a Cl of 25 ° C or less, and an equivalent weight of at least 1500.

The polyether according to claim 13, which has a Cl of 16 ° C or less.

15. The polyether according to claim 13, which has a degree of unsaturation of 0.03 milliequivalent per gram or less.

The polyether according to claim 1, having an equivalent weight of at least 1500, terminated with a terminal block of oxyethylene groups with a primary hydroxyl group attached to the terminal carbon of the terminal block and having a degree of unsaturation of 0.03 or less.

17. The polyether according to claim 1, wherein the polyether is a polyol, and the second block comprises oxybutylene groups.

18. The polyether according to claim 17, wherein the second block consists of oxybutylene groups.

19. A polyoxyalkylene polyether polymer comprising within its structure the core of an initiator compound, an internal block of oxypropylene groups, and a second block of oxyalkylene groups, wherein the internal oxypropylene block lies between the core and the second block, the second block comprises oxyalkylene groups and derivatives of an alkylene oxide of 4 higher carbon atoms, and the amount of the internal block of oxypropylene groups is at least of an equivalent weight of 800 based on the weight of the groups of oxyalkylene in the polyether polymer, and the amount of the second block is effective to reduce the degree of unsaturation of the polyether to 0.06 milliequivalent KOH per gram of polyol or less.

20. A polyoxyalkylene polyether polymer comprising within its structure the core of an initiator compound, an internal block of oxypropylene groups and a second block of oxyalkylene groups, wherein the internal oxypropylene block lies between the core and the second block, and the second block comprises oxyethylene groups and oxyalkylene groups derived from an alkylene oxide of 4 higher carbon atoms, and the amount of the internal block of oxypropylene groups is from 25 weight percent to 80 weight percent. weight, based on the weight of all the oxyalkylene groups and the initiator in the polyether polymer, and the amount of the second block is effective to reduce the degree of unsaturation of the polyether to 0.06 milliequivalent of KOH per gram of polyol or less. SUMMARY OF THE INVENTION An isocyanate-reactive polyoxyalkylene polyether polymer having a structure is now provided in the following manner: the core of an initiator compound, an internal block of oxypropylene groups, and a second block of oxyalkylene groups; the internal block of oxypropylene groups lies between the core of the initiator and the second block, the second block contains at least some oxyalkylene groups derived from at least one alkylene oxide of 4 carbon atoms or more. This structure allows a polyether polymer to be produced which has a low degree of unsaturation, adjust the degree of hydrophobicity to a broad scale of values and can simply be manufactured without relying on the use of exotic catalysts. The amount of the internal block of oxypropylene groups is advantageously from 25 weight percent to 80 weight percent based on the weight of the oxyalkylene groups and the initiator compound. The amount of the second block containing an alkylene oxide of 4 higher carbon atoms must be effective to reduce the unsaturation of the polyether polyol to 0.06 milliequivalent KOH per gram of polyol or less.