MXPA96006467A

MXPA96006467A - Low insaturac polioxylquylene polyethyl polyoles

Info

Publication number: MXPA96006467A
Application number: MXPA/A/1996/006467A
Authority: MX
Inventors: J Reichel Curtis; L Fisback Thomas; M Aviles Gladys
Original assignee: Basf Corporation
Priority date: 1995-12-29
Filing date: 1996-12-16
Publication date: 1997-06-01

Abstract

A method is provided for making a 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, propylene oxide to form a internal block of oxypropylene groups followed by reacting directly or indirectly to the block of oxypropylene groups, one or more second oxide compounds, at least one of which is alkylene oxide of 4 higher carbon atoms in order to form a second block oxyalkylene groups. The amount of propylene oxide that is advantageously added 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, and the amount of one or more of the second Oxide compounds at least one of which is alkylene oxide of 4 or more carbon atoms, must be effective to reduce the unsaturation of the polyether polyol to 0.06 milliequivalent KOH per gram of the polyol or men

Description

POLYOX POLYOLYL POLYOLS OF LOW I SATURATION 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, sealing compounds, adhesives and elastomers are made with a polyoxyalkylene polyether polyol having an internal polyoxypropylene block attached to the core of an initiator molecule, followed by at least one alkylene oxide of 4 carbon atoms or more, in an amount sufficient to reduce the degree of unsaturation of the polyol to 0.06 univative per gram of polyol or eos.

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 sealant compounds, the chain elongation agent may be a triol or a mixture of diols, triols, and / or tetrols, 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 allylic terminal unsaturation begins to develop. The formation of the unsaturation is believed to be a consequence of the isomerization of the propylene oxide in allyl alcohol, which subsequently reacts with the propylene oxide to form polyoxypropylene allyl (2-propenyl) ethers. The point at which the unsaturation to be developed begins and the unsaturation rate can be influenced by variables such as temperature, pressure, catalyst concentration, and type of catalyst used. Beyond certain equivalent weights, it becomes difficult if not impossible to produce a polyoxypropylene polyether polyol having suitable functionality using conventional catalysts. Therefore, 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 inconvenience of polyether polyols having high levels of unsaturation is that the allylic terminal unsaturation reduces the functionality of the polyol and terminates the chain growth, 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 low unsaturation level can be maintained, producing a very low equivalent weight polyol, the elastomers and sealing compounds must be made with high weight equivalent polyols to improve their elasticity. Therefore, it is highly desirable to make a polyether polyol of high equivalent weight, suitable for 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; 4,985,491, each discloses the preparation of polyether polyols using a double metal cyanide (DMC) catalyst to reduce the level of unsaturation to about 0.04 milliequivalent per gram of polyol or less. The disadvantages of using the DMC catalysts to prepare polyols are that these catalysts are quite expensive; and as disclosed in U.S. Patent 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 polyurethane products. 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 oxypropylene groups before polymerizing the ethylene oxide block, because the residual catalyst of DMC would impede 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 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 of the manner in which and which 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 dual metal cyanide and cesium based catalysts for decreasing the unsaturation of the 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, which is made with conventional tertiary amines or 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 which have a low degree of unsaturation which are not limited to a specific initiator, and which can be manufactured in the presence of conventional catalysts or other low cost catalysts. In this regard, we began to investigate the decrease in the degree of unsaturation through methods other than improving processing techniques or devising new catalysts. We went through 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 can be significantly decreased regardless of the kind of catalyst 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 been found to also be used to improve the air flow and charge carrying properties of polyurethane foams, as disclosed in US Patent Number 4,487,854. Reversing the order of addition of ethylene oxide and propylene oxide is also known. For example, a surfactant, detergent and anti-foaming polyether polyols having an internal block of oxypropylene groups followed by a chain of oxyethylene groups is known in accordance with the teachings of U.S. Patent Nos. 2,674,619 and 2, 94B, 757. These polyols also find 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 is added to the initiator molecule such that the oxyalkylene groups are distributed in a random manner in each molecule, are also already known in accordance with 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 a polyether polyether ether having certain weight proportions of ethylene oxide and either butylene oxide and / or propylene oxide to be used as an adhesion improver in panels. of polyurethane foam covered. U.S. Patent No. 2,733,272 recommends using a glycerol polyoxyethylene-polyoxypropylene hexylene polyether as a lubricant, especially in brake fluids.

Heteric 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 a heteric 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 a heteric and a blocked structure. For example, U.S. Patent No. 4,487,854 discloses a polyether polyol having an internal block of oxyethylene groups, followed by a heteric mixture of ethylene oxide, butylene oxide and / or propylene oxide, optionally followed by a block of oxypropylene or oxybutylene groups, as a terminal block. The polyether polyol is said to impart good air flow properties and load carrying properties to 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 in order to bring about the decrease in the degree of unsaturation. In addition, most of these polyether polyols are too hydrophilic to make useful in applications of a sealant composite elastomer and an adhesive.

COMPENDIUM OF THE INVENTION It would be desirable if there were 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 the use of a specific catalyst in order to achieve a reduction in unsaturation. It is also desired to produce a polyether polyol of reduced unsaturation whose degree of unsaturation does not depend on the kind of initiator used, and specifically to produce 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 polyurethane elastomers, sealants and adhesives, which means that a significant portion of the polyether polyols must be hydrophobic. 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 inner block of oxypropylene groups being placed between the core of the initiator and the second block, the second block containing at least some oxyalkylene groups derived from at least one alkylene oxide of 4 carbon atoms or more. This structure allows a polyether polymer having a low degree of unsaturation is produced, the degree of hydrophobicity is adjusted to a wide 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 4 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 alkylene oxide of 4 carbon atoms or higher is 1,2-butylene oxide.

In another embodiment, a method is provided for producing the polyoxyalkylene polyether polyol by reacting in the presence of a catalyst, an initiator compound having at least two reactive sites with an alkylene oxide directly or indirectly in sequence order, 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 second oxide compounds, at least one of which is an alkylene oxide of 4 carbon atoms or higher, in order to form a second block of oxyalkylene groups. Also, the amount of propylene oxide advantageously added is from 25 weight percent to 80 weight percent based on the weight of all the oxyalkylene compounds added to the initiator, and to the 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 carbon atoms or greater, 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 to form a reaction product having at least an equivalent weight of 800, after which one or 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 oxypropylene groups. This second block of oxyalkylene groups may comprise a random mixture of oxyalkylene groups (ie, the heteric block) or may comprise one or more distinct 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 are 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 which must yield primary hydroxyl functionalities such as ethylene oxide. Other modalities and scales of greater preference will be discussed below in detail. The polyether polyols of the invention have at least one of the following advantages and, in the preferred embodiments, simultaneously possess all 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 of the kind of catalyst used to achieve the reduction shown 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 1,500 and are suitable for the preparation of elastomers, sealants and adhesives having high resistance to elongation and an elongation to a 100 percent and 300 percent modulus.

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 4 carbon atoms or more. , 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 weight equivalent polyethers (such as an equivalent weight of at least 1,500) in the presence of conventional catalysts such as sodium and potassium hydroxides. Before discussing the structure and method of preparation of the polyethers of the invention, a view of some of the terms that are used throughout the specification and means for making the calculations will now be 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 that is reacted in the initiator is relatively large, compounds of unifmolecular weight 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 the alkylene oxide added in the manufacturing process. Therefore, a means to calculate the weight percentage of the oxyalkylene groups in the polyoxyalkylene polyether is to add 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 the polyether polymer can also be calculated by adding the total weight of the specific charged 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 conjugated unitary structure necessary to impart both hydrophobic and hydrophilic properties to the polymer. A block of oxyalkylene groups is typically 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 a random order can also be provided. The different oxyalkylene groups are distributed randomly, however, within the parameters of a discrete block rather than through the entire polymer chain. The degree of unsaturation can be determined by reacting the polyether polymer with mercuric acetate and methanol, in a methanolic solution to liberate the methoxy, acetoxymercuric compounds and the acetic acids. Any remaining mercuric acetate is treated with sodium bromide to convert mercuric acetate into 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 sample of the polyether polymer can be weighed into a sample flask and 50 milliliters of the reactive grade mercuric acetate in methanol 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 flask and titrated with methanolic KOH. of concentration from 0.1 nl to a pink endpoint. The degree of unsaturation is calculated and expressed as milliequivalents per gram: (my sample of KOH - mi of blank space of KOH) X N KOH Acidity (A) as weight of sample milliequivalents per gram - l Acidity correction is only made if the acid number of the sample is greater than 0.04 in which case it is divided by 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 number 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 ratio of 50:50 by weight of water to the solution of reactive-grade isopropanol. 25 grams of the polyether polymer are added to a test tube. Then, 50 milliliters of a water / isopropanol solution is added and the test tube is immersed in a water bath. The mixture in the test tube is stirred at 300 revolutions per minute. If the mixture in the test tube is cloudy at room temperature, the water bath is replaced by a dry ice bath of isopropanol 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 that 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 value of Cl approaches, the mixture in the test tube will become turbid. Shortly after turbidity, the mixture will become a nebula or form discrete particles of a separate phase. This is the temperature of Cl. 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, usually less than 400, and preferably greater 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, trimethylolpropane, 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 -hexanediamine, 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 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 can also be 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 polyols 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 more preferably 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 a 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 the tri-functional initiator or major compounds are added. functionality can mix together to reach an initiator that has an average functionality close to 2, such as 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 the di-functional starter compound when a higher degree of crosslinking is desired, such as in the preparation of sealants and adhesives. As mentioned above, 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 to form an internal block of oxypropylene groups, followed by additional direct or indirect addition of one or more second oxides, comprising 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 wherein 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 all added alkylene oxides and the initiator, and z is an integer of 2 or more, which represents the number of reactive sites in the initiator molecule to which the chains of the oxypropylene groups are linked. The internal block of 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 a polymer can be measured by a compatibility index. The oxypropylene group block is internal to the polyoxyalkylene polyether polymer. By an internal block it is meant that the oxypropylene group block 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 directly attached 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 the propylene oxide. The internal block of the oxypropylene groups consists essentially of oxypropylene groups, giving to understand that essentially all 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 elastomers, sealants and adhesives made with these polyethers. Although the alkylene oxides which would impart hydrophilic properties to the polyether polymer may be tolerated in small amounts, they should be avoided to the extent that the hydrophobicity of the polymer is damaged such that the resulting adhesive elastomers and sealing compounds made therefrom show 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 that is 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 a particularly 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 oxypropylene groups is advantageously 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 itself. In the method of the invention, an initiator compound is reacted in sequence order with propylene oxide followed by a reaction with one or more of the second oxides. By the term "sequential order" is meant only that at least one block of oxypropylene groups internal to the polyether polymer must appear, followed by adding one or more second oxides directly to the inner block as defined in present, or indirectly add 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 sites, and to one or more of the second oxides comprising an alkylene oxide of 4 carbon atoms or greater than they are added directly to the inner block of the oxypropylene groups to form a second block of oxyalkylene groups fixed directly and attached to the inner block of 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 a reaction time, temperature and pressures as they are graded to make reacting all the added propylene oxide 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 of oxyethylene groups, the polyether polymer is made to be insufficiently hydrophobic for many of the applications , and causes the mechanical properties of the elastomers and sealing compounds made with the polyether, to degrade. The upper limit of addition of propylene oxide for most modalities, 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. In an especially preferred scale, the relative amount of oxypropylene groups ranges from 60 percent to 75 percent by weight. In the manufacture of the block of oxypropylene groups, 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 employed have an influence on the degree of unsaturation developed for any given polyether polymer, the development of the unsaturation is started by using conventional KOH catalysts when the equivalent weight of the block of the 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 oxypropylene group block is about 1,700 or more, this large amount of terminal allylic unsaturation develops so that the mechanical properties of the elastomers, sealants and adhesives that are made of these polyether polymers are they deteriorate 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, however, 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 the 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 Oxypropylene oxide groups are measured at 0.010 milliequivalent per gram of polyol or more. In this way, the addition of one or more of the second oxides in this embodiment can begin when 0.01 milliequivalent per gram of the polyol unsaturation or more is developed, or in the alternative, when the equivalent weight of the oxypropylene group block is of approximately 1,700 of greater preference of 1,300. After the internal block of the oxypropylene groups is manufactured, at least one or more of the second oxides, one of which is an alkylene oxide of 4 carbon atoms or greater, is added directly or indirectly to the internal block of the oxypropylene groups. The object for the addition of the alkylene oxide of 4 carbon atoms or higher is to continue to make a block of hydrophobic oxyalkylene groups which 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 following a, and attached to the carbon atoms bonded in the epoxide ring and in particular, to the alkyl substituents fixed to alpha-carbon; or the alkylene oxides that do not contain an alpha-carbon. Examples of one or more of these 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; cyclohexylethylene oxide; Eetirene 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 four carbon atoms or higher. In a preferred embodiment of the invention, one or more of the second alkylene oxides, at least, are the 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 internal block of oxypropylene groups to form a second block of oxyalkylene groups. When only a single 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 where R, 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)? (C2H40) y) s] z H where R, w, xyz are as stated above, and is an integer representing the number of oxyethylene groups; s is an integer, preferably 1, representing the number of oxybutylene-oxyethylene mixture 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 oxypropylene groups. The total amount of one of the second alkylene oxides that is 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 in comparison with a polyether polymer made with the same initiator, under the same reaction conditions and catalysts, and manufactured at the same equivalent weight of the final polyether polymer, but using only propylene oxide as the alkylene oxide added to the starter molecule. A particularly advantageous feature of the invention lies in the flexibility of adjusting the degree of unsaturation by adding only a greater amount of one or more of the second oxides as defined herein, instead of changing the catalyst types or reaction conditions, which are quite expensive or delayed. When 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 or no unsaturation has been developed, during the manufacture of the internal block of 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 lies in the manufacture of a polyether polymer having a degree of unsaturation of 0.03 or less, which finds beneficial use in elastomers, without having to resort to unusual reaction conditions or expensive and exotic catalysts, such as 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, wherein 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 the 1,2-butylene oxide to achieve this object is generally at least 5 weight percent, and most preferably at least 10 weight percent, based on the weight of all the oxyalkylene compounds added to the initiator compound and the initiator. Generally, no more than 20 percent by weight are needed to achieve a reduction in unsaturation. It is possible to reduce the degree of unsaturation of the polyether polymer to 0.06 or less by adding only ethylene oxide to the inner block of oxypropylene groups. However, a very large amount of ethylene oxide would have to be added to achieve a polymer of comparable molecular weight so that the polyether polymer would become too hydrophilic. Thus, it is critical to the invention that the hydrophobic alkylene oxides of 4 carbon atoms or greater 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 when the specific weight ratio of the oxide of 1, 2-butylene to ethylene oxide is not limited, the appropriate relative amounts of each can 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 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 h-1 or of 4 carbon atoms are added in the second block, the greater the hydrophobic nature of the second block of the second oxyalkylene group. The total weight of the second block of one or more oxyalkylene groups will generally range from 5 weight percent to 75 weight percent, more preferably from more than 5 weight percent to 50 weight percent, and from especially preferred 10 percent by weight to 30 percent by weight, 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, sealants 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 used in the manufacture of the second block of one or more of the alkylene oxides, ethylene oxide and oxide. of 1, 2-butylene. 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, incorporated herein by reference. The polyether polymer of the invention is preferably a polyether polyol.

The polyether polyol optionally can be terminated with a terminal block consisting essentially of oxyethylene groups containing a primary hydroxyl group on the terminal carbon of the terminal block. The weight of the terminal block of the oxyethylene groups when employed is at least 4 weight percent, preferably 10 weight percent to 25 weight percent, based on the weight of all added oxyalkylene compounds to the initiator compound and the initiator. 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 a 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. While it is possible to inject the terminal block of oxyethylene groups, it is more desirable that there be a primary hydroxyl group attached to the terminal carbon of the terminal block of the oxyethylene groups. The weight percentage of the terminal block of the oxyethylene groups in the polyether polymers used in the manufacture of elastomers should be at least 4 weight percent, more preferably 10 weight percent to 25 weight percent. weight, 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. The methods of anionic polymerization 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. Catalysts, such as alkali metal alkoxides, cesium-based catalysts and double metal cyanide catalysts as described in US Patent Number 3,829,505, incorporated herein by reference, and the hydroxides and alkoxides of lithium 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 may 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 basic salt-forming compounds mentioned above. 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 graduated 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 more 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 according to the invention can be removed by any of the well-known processes 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 ion exchange, 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 content to less than 500 parts per million, preferably less than 100 parts per million, and more 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 higher 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 a pad of inert gas and the feed of alkylene oxides into 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 of more than 7.03 kilograms per square centimeter gauge increases the risk of a reaction that runs. 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 the polymerization can be controlled by dosing consecutively each alkylene oxide until a desired amount has been added. When a block of a random distribution or a statistical distribution of 1,2-butylene oxide and other alkylene oxides is desired in the polyether polymer, the alkylene oxides may be metered into 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 a starter compound, an intermediate pre-fabricated polyether polyether polymer of propylene oxide 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 this addition occurs only in the main reactor, or in two stages by the formation of an intermediate with the subsequent addition or with greater amount of alkylene oxide in the main reactor. The residual water contained in the initiator or the 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 the intermediate compound, must be purified of the reaction mixture. 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 letting the pressure accumulate beyond about 5.62 kilograms per square centimeter gauge and preferably not greater than 6.33 kilograms per square centimeter gauge. The feeding regime of the propylene oxide must be slow enough to avoid terminal allylic unsaturation to the greatest possible extent, but nevertheless it is added quickly enough 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 for essentially all of the propylene oxide to react. Subsequently, the autoclave must be evacuated until any of the unreacted propylene oxides are purged, after which nitrogen is again introduced to pressurize the reactor again. The reactor is then 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 rate of addition may be higher than the reaction temperature and the rate of feed graduated during the addition of 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; are removed by a carbon dioxide finishing process described in Japanese Patent Number 55-092773-A; or treated with an adsorption agent 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 noticeable at equivalent weights of less than 800, the polyether polymers will 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 made from a polyoxyalkylene polyether polymer having in it is provided. from its polymer structure is a core of an initiator compound, an internal block of oxypropylene groups and a second block of oxyalkylene groups, wherein the internal block of oxypropylene groups lies between the core of the initiator and the second block of oxyalkylene groups and moreover, wherein the second block of oxyalkylene groups contains at least one higher alkylene oxide derivative of 4 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 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 and 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 to a single initiator and mixing the resulting polyether polymer with other polyether polymers made using different initiators. The elastomers can be thermosettable or thermoplastic. The elastomers of the invention can be manufactured in the form of extruded films or sheets to any desired thickness. These films and sheets find applications in conveyor s, the transport of sand and a thick suspension of stone, 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 outer material of ski boots, shoe soles, ice hockey boots, automotive applications, such as exterior automotive body parts, bushings, rims, cleaning blades, wheel component gaskets, tubes, membranes and seals. Still additional applications include wheels, vibration dampers, sieves' for sorting materials, rope pulleys, medical and food industries, hammers, gears, pump chambers, rollers, thrusters, door seals and the like. The various applications for sealing compounds described herein are for windshield wipers, thermal brakes, airport runways, roads, joints or building construction, and waterproof membranes for roofs and bridges. The polyurethane elastomers, sealants and 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 molded process wherein the polyurethane-forming ingredients are mixed together and emptied into a heated mold under pressure. Other techniques include conventional hand-mixed techniques and low-pressure or high-pressure machine mixing techniques followed by casting the polyurethane-forming ingredients into molds. In a single operation process, the polyether polymer of the invention, the catalysts and other isocyanate reactive components ("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 a side-A component with any of the remaining B-side components to form a composite sealant elastomer or polyurethane adhesive. In some cases, all of the isocyanate-reactive B-side components are reacted with a stoichiometric excess of organic isocyanate to form a single component sealant or adhesive. These isocyanate-terminated prepolymers typically have a free NCO content of less than 1 weight percent to 15 weight percent. The single-component prepolymers can be cured by water in the form of moisture in the atmosphere or by adding more water. In other cases, only a portion of the polyether polymer or other polyols are reacted with the 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, such as an elastomer, sealant or two component adhesive. The free NCO content of the prepolymers used to make the elastomers, sealants and adhesives of the invention may vary from 0.5 weight percent to 30 weight percent, preferably 1 weight percent to 15 weight percent , 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 an elastomer, the sealant or adhesive, other polyols can be mixed in the polyol composition. For example, the addition of polyester polyols 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 used 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 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 made with amorphous or crystalline DMC catalysts are suitable, as well as the polyether polyols catalyzed by cesium hydroxide. Sealing compounds or single component adhesives are typically cured by air humidity. Sealants or adhesives and two component elastomers are typically cured by chain elongation agents with compounds containing hydrogen reactive to the isocyanate. Chain extenders 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 of an equivalent weight of less than about 250, having a plurality of hydrogen atoms reactive to the isocyanate. Chain elongation agents include water, hydrazine, aliphatic or primary and secondary aromatic diamines, amino alcohols, amino acids, hydroxy acids, glycols or mixtures thereof. A preferred group of alcohol chain lengthening agents includes water, ethylene glycol, 1,3-propanediol, 1,4-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, '-dialkyl-substituted aromatic diamines, which are unsubstituted or substituted in the aromatic radical by alkyl radicals having from 1 to 20, preferably from 1 to 4, carbon atoms in the N-alkyl radical, e.g., N, N '-diethyl-, N, N'-di-sec-pentyl, N, N' -di-sec-hexyl-, N, '-di-sec -decyl- and N, N'-dicyclohexyl-p- and m-phenylenediamine, N, N'-dimethyl-, N, '-diethyl-, N, N'-diisopropyl-, N, N'-di-sec- butyl- and N, N'-dicyclohexyl-4,4'-diaminodiphenylmethane and N, N'-di-sec-butylbenzidine. The amount of the chain-lengthening agent used varies to a certain degree in the desired physical properties of the elastomer or sealant. A higher proportion of the chain-isocyanate elongation agent provides the elastomer or seal compound with higher stiffness and thermal distortion temperature. The lower 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 higher molecular weight isocyanate-reactive components. Catalysts that greatly accelerate the reaction of the compounds containing hydroxyl groups and with the modified or unmodified polyisocyanates can be employed. Examples of suitable compounds are the curing catalysts which also function to shorten the tack time, activate the strength of the untreated product and prevent foam shrinkage. Suitable catalysts for curing 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 as the metal, are represented by the formula RnSn [X-R1-Y] 2 <; wherein R is an alkyl or aryl group of 1 to 8 carbon atoms, R1 is a methylene group of 0 to 18 carbon atoms optionally substituted or branched with an alkyl group of 1 to 4 carbon atoms, and is a hydrogen or a hydroxyl group, preferably hydrogen, X is methylene, a group of -S-, a group of -SR COO-, -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 R ^ is Cg only when X is a methylene group. Specific examples are tin (II) acetate, tin (II) octanoate, tin (II) ethylhexanoate and tin (II) laurate; tin (IV) dialkyl (1 to 8C) salts of organic carboxylic acids having from 1 to 32 carbon atoms, preferably from 1 to 20 carbon atoms, e.g., diethyltin diacetate, diacetate of dibutyltin, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dihexyltin diacetate and dioctyltin diacetate. Other suitable organotin catalysts are organotin alkoxides and tin salts (IV) of mono- or poly-alkyl (1 to 8C) of the inorganic compounds, such as butyltin trichloride, dimethyl- and diethyl- and dibutyl oxide - and dioctyl- and diphenyl-tin, dibutyltin dibuthoxide, di (2-ethylhexyl) tin oxide, dibutyltin dichloride and dioctyltin dioxide. However, tin catalysts with tin-sulfur bonds which are resistant to hydrolysis, such as dialkyl (1-20C) tin dimercaptides, including dimethyl-, dibutyl- and dioctyl-tin dimercaptides, are preferred. Tertiary amines also promote the formation of the urethane linkage and include triethylamine, 3-methoxypropyl dimethylamine, triethylene diamine, tributylamine, dimethylbenzylamine, N-methyl-, N-ethyl- and N-cyclohexylmorpholine, N, N, N ', N' -tetramethylethylenediamine , N, N, N ', N' -tetramethylbutanediamine or -hexanodiamine, of N, N, N'-trimethylisopropyl-propylenediamine, pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether, bis (dimethylaminopropyl) urea, dimethylpiperazine, 1-methyl-4-dimethylaminoethylpiperazine, 1,2-dimethyl imidazole, 1-azabicyclo [3.3.0] octane and preferably 1,4-diazabicyclo [2.2.2] octane, and the alkanolamine compounds, such as triethanolamine, triisopropanolamine, N-methyl- and N-ethyldiethanolamine and dimethylethanolamine. To prevent retention of air bubbles in sealing compounds or elastomers, a batch mixture may be subjected to degassing under reduced pressure once the ingredients are mixed together. In a degassing method, the mixed ingredients formed with the polyurethane can be heated under vacuum to an elevated temperature to react or volatilize the waste water. By heating at an elevated temperature, the waste water reacts with the isocyanate to release the carbon dioxide it attracts from the mixture through the reduced pressure. Alternatively 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 should not be reactive and include tetrahydrofuran, ketone, dimethylformamide, dimethylacetamide, normal methylpyrrolidone, methylethyl ketone, etc. The reduction in the viscosity of the polyurethane-forming ingredients helps their extrusion capacity. For applications of sealing compounds, however, the amount of the solvent must be kept as low as possible to avoid deteriorating its adhesion to the substrates. Other solvents - 5f include xylene, ethyl acetate, toluene and cellosolve acetate. Plasticizers may also be included in the A-side or B-side components to soften the elastomer or sealing compound and lower its brittle temperature. Examples of the plasticizers include dialkyl phthalates, dibutylbenzyl phthalate, tricresyl phosphate, dialkyl adipates and trioctyl phosphate. In addition to solvents or plasticizers, other ingredients such as adhesion promoters, fillers or fillers, and pigments may be added, such as clay, silica, fuming silica, carbon black, talcum, phthalocyanine blue or green, titanium oxide, magnesium carbonate, calcium carbonate and ultraviolet light absorbing agents in amounts ranging from 0 percent to 75 percent by weight, based on the weight of the polyurethane. Other fillers or fillers include dissolved gels, plasticeldas, graded and coated calcium carbonate, urea solids, the reaction product of hydrogenated castor oils with amines, and fibers. The organic polyisocyanates are used to prepare the prepolymer, used in a single operation process or used for further processing of 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'-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. -biphenyl and 3,3 '-dimethyldiphenylmethane-4,4'-diisocyanate, the triisocyanates such as 4,4', 4", 4" -triphenylmethane triisocyanate, and toluene 2,4,6-triisocyanate; and tetraisocyanates such as 4,4'-dimethyldiphenylmethane-2,2'-5,5'-tetraisocyanate and 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-mentioned 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 which is obtained 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. This 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 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 above, 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 approximately 10/1, more preferably from 1.2 / 1 to approximately 2.5 / 1, to manufacture 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 isocyanate-reactive compounds having functionalities greater than 3, mixed with the diols and triols can be used in the manufacture of an isocyanate-terminated prepolymer. Once the isocyanate-terminated prepolymer is manufactured, the sealant or adhesive can be prepared by curing by prepolymer moisture if the free NCO content is low enough, or by reacting the prepolymer with additional polyoxyalkylene polyether polyols of molecular weight. Higher or polyoxyalkylene polyethers terminated with amine, chain elongation agents, catalysts, fillers or fillers, etc. For more specific applications using sealing compounds, the isocyanate-terminated prepolymer is cured by moisture. In another embodiment of the invention, a hydroxyl-terminated prepolymer suitable for the manufacture of sealants and adhesives is provided. In 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 at 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, to react with the additional organic isocyanate in order to make a compound sealant or adhesive. The object for manufacturing a hydroxyl-terminated prepolymer may 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 the sub-stoichiometric amount of the organic isocyanate.

Any or both of diol or triol, can be manufactured in accordance with the method described herein. In yet a further embodiment of the invention, isocyanate-terminated prepolymers suitable for the manufacture of elastomers, and elastomers produced with the polyoxyalkylene polyether polymers of the invention are provided. The elastomers of the invention can be produced 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 and triol are manufactured in accordance with the invention described herein. Preferably, a polyoxyalkylene polyether diol having an internal block of the 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 the 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 be reacted with additional B-side components such as polyether polyols, chain elongation agents, catalysts and other non-reactive ingredients. Alternatively, the isocyanate-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 diol is about 1000 or more, the diol should be manufactured in accordance with the process described herein, in order 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 hardness Shore A can vary from 0 to approximately 95. For most applications, however, the Shore A hardness of sealing compounds and adhesives will vary from 0 to 40, more typically from 0 to 20. In most applications of elastomer, the Shore A hardness will vary from 20 to 95, values of 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 modalities of the invention.

Preparation of Intermediate A 73. 78 kilograms of trimethylolpropane and .735 kilograms of 90 percent KOH were charged into a dry clean autoclave filled with nitrogen. After loading, the agitator was slowly started and advanced at 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 and discharged to approximately 0.25 bar. Subsequently, the contents were heated to 125 ° C, discharged at 0.15 bar, 334.09 kilograms of propylene oxide were added over 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 raw product had been transferred to the filter-scrubber tank, 11.35 kilograms of MAGNESOL (R) is added to the crude polyol, after which the filter-purifying tank was sealed and purged three (3) times under 3.5 bar pressure 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 haze and less than 20 parts per million NaK. The product was then transferred from the filter-scrubber tank through the filter press to an instant scrubber-scrubber tank. The polyol product was purified from 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; and a 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 a low-unsaturation PO- [BO-EO het] -EO polyether triol block using a conventional KOH catalyst. A 552.9 gram (0.75 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 to 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 under pressure of 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 mixed butylene oxide / ethylene oxide pump was charged to the autoclave at 125 ° C. and at a pressure of less than 5.24 kilograms per square centimeter gauge over a period of two (2) hours. The amount of butylene oxide and ethylene oxide that was added was 706.5 grams (9.8 moles) and 464.3 grams (10.55 moles), respectively. The content was reacted for more than one hour at 125 ° C, and subsequently the autoclave was evacuated to 10 millimeters of mercury. Once evacuated, the autoclave was again pressurized to 2.39 kilograms per square centimeter gauge with nitrogen, and 242.2 grams of ethylene oxide were charged to the autoclave under pressure of 6.33 kilograms per square centimeter gauge at 125 ° C through of 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, the contents cooled to 60 ° C and then discharged to a nitrogen-washed container. 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 cloudiness and then it was purified of water at 110 ° C and less than 10 millimeters of mercury for one (1) hour. The treated product was then cooled to 60 ° C and stabilized with a package of a common stabilizer.

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 functionalities of the initiator molecule, and a block of oxybutylene and oxyethylene groups attached to the block of oxypropylene groups, and ended with a block of oxyethylene groups. Based on the weight of all the alkylene oxide fillers and initiator, the polyether polymer had about 75 weight percent oxypropylene groups, 20 weight percent and oxyethylene groups mixed at random and about 5 percent by weight. weight of a terminal block of oxyethylene groups.

EXAMPLE 2 This example illustrates the manufacture of a polyether triol of PO- [BO-EO het] -EO of low unsaturation manufactured 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 noted. The loads of each ingredient were the following: 588.9 grams of Intermediate Polyol A, 79.1 grams of a 50 percent solution of cesium hydroxide and 3610.7 grams of propylene oxide. In the step of the block manufacture of the 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 step of blocking the polyether polymer with oxyethylene groups, 268.8 grams of ethylene oxide were added. In the process for the manufacture of polyol B of polyether 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. Polyol B of resulting polyether polymer 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 added charges of initiator ethylene oxide, the polyether polymer contained about 75 weight percent of an oxypropylene group block, 20 weight percent of a block of oxyethylene groups and oxybutylene groups mixed together. randomly, and about 5 weight percent of a terminal oxyethylene oxide block.

EXAMPLE 3 This example illustrates the manufacture of sealant compounds using PO- [BO-EO het] -EO polyether polymers of low unsaturation, manufactured with a variety of catalysts. Table 1 shows the results 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 presented below. Each of the triols 2 to 14 was terminated with a 5 weight percent block of oxyethylene groups. The amount of butylene oxide and ethylene oxide that was charged to form the randomly distributed block of oxyethylene groups and oxybutylene groups was measured either on a 1: 1 weight basis or a 1: 1 molar basis. , as manifested in the painting. The 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 prior to submerging in the water bath, while "N" indicates no significant retention of the original tensile strength properties . 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 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 glycol propylene adduct 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 cooled at 40 ° C. The toluene diisocyanate, which can be obtained commercially from BASF Corporation as LUPRANETE T80-1, was heated at 40 ° C in a reaction flask under a constant nitrogen spray. One of the polyol blends was added to one (1) equivalent of the heated toluene diisocyanate as rapidly as possible, maintaining the resulting exothermic reaction at or below 60 ° C. Once the polyol mixture was 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 titration. 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 the talc filler or 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 and cured at 70 ° C for four 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 dropped out of the solution with water, and 100 percent and 300 percent are the module's measurements at an elongation of 100 percent and elongation of 300 percent, respectively according to the Method D412 of the American Society for the Testing of Materials.

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 ° C (IN WEIGHT) ZADOR RACIÓN. (BO / EO) 1) 0 KOH 006 PESO 53 (BO / EO) 50 KOH .021 WEIGHT 24 50 KOH .02 MOL 65 KOH 038 WEIGHT 16 ) 65 KOH .037 MOL -2 65 CsOH .027 WEIGHT 13 65 CsOH .022 MOL 3.5 8) 75 KOH .055 WEIGHT 9) 75 KOH .047 MOL 10) 75 CsOH 03 WEIGHT 11) 75 CsOH 028 MOL 12) 95 KOH 100 NONE < 4 13) 95 CsOH 050 NONE < 4 14) 95 DMC 020 NONE < 4 TABLE I (Continued) % OF MODULE TO MODULE AL SHORE TO PROOF OF (BY WEIGHT) 100% 300 °? WATER * (kg / cm2) (kg / cm2) 1) or 3.66 7.17 21 Y (BO / EO) 2) 50 1.76 3.23 11 N 50 2.11 4.29 AND 65 1.48 2.60 10 N 5) 65 2.11 3.87 8 Y 6) 65 2.04 4.08 14 Y 7) 65 1.41 2.60 7 Y 8) 75 2.32 4.36 15 Y 9) 75 3.02 5.83 13 Y ) 75 2.39 4.71 16 Y 11) 75 2.60 4.78 9 Y 12) 95 NO HEALING WITHOUT HEALING 0 WITHOUT HEALING 13) 95 1.27 2.18 6 Y 14) 95 3.80 2.95 12 Y * WATER TEST: TOTAL IMMERSION FOR 30 DAYS AT 70 ° C, THEN MAKE FUNCTIONING TO THE VOLTAGE AND- RETENTION OF > 50 ORIGINAL PROPERTIES N = NO SIGNIFICANT PROPERTIES RETENTION The data generated from the evaluation of Examples 2-11 of the invention demonstrate a reduction in the degree of unsaturation of each triol when compared to conventional triols prepared either with potassium hydroxide and cesium hydroxide as in Examples 12 and 13. Thus, 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 of groups of oxypropylene followed by a block of oxybutylene and oxyethylene groups randomly distributed and blocked with ethylene oxide, had a much lower degree of unsaturation than polyether polyols of similar molecular weight prepared with the same catalyst, using only propylene oxide and a blockage of ethylene oxide. 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 the ethylene oxide blocking 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, blocked with ethylene oxide, cured well and exhibited improved tensile properties. Neither are the triols of the invention prepared with KOH having much lower degrees of unsaturation much lower than polyol 12 of propylene oxide polyether prepared with KOH, but which also had lower degrees of unsaturation than all polyether polyols of propylene oxide made with cesium hydroxide catalyst as shown in Example 13, and were on par with the tensile properties and triols prepared with the double metal cyanide catalysts. For the most part, 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 in accordance with Comparison Example 1 was too hydrophilic, as demonstrated by its high Cl value. In short, we dramatically reduced the degree of unsaturation of the polyols of polyethers suitable for the preparation of sealing compounds and elastomers without employing an exotic and expensive catalyst such as DMC, 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 the catalysts before the addition of an ethylene oxide block such as in the case of the 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 or could be used to prepare a sealing compound or polyurethane elastomer having improved physical properties.

EXAMPLE 4 This example illustrates the way 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 low degree of unsaturation and high equivalent weight was 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 catalyst. of cesium hydroxide 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, at a pressure less than 6.33 kilograms per square centimeter gauge and over 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 clean, dry, separate autoclave. The autoclave was sealed, the stirring was started and the autoclave was purged three times with nitrogen. The autoclave was then heated to room temperature, 2 - of about 105 ° C and evacuated slowly to purify the volatile substances. Once purified, the vacuum was released with nitrogen after 2.510.7 grams of propylene oxide were added over a period of 5 hours, maintaining the pressure at 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 volatiles, after which it was re-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 ethylene oxide at 125 ° C was added simultaneously to the autoclave over a period of two and a half hours and a pressure of less than 5.24 kilograms per square centimeter gauge. The reaction was continued for about four and a half hours after which it was evacuated to collect any remaining volatile compounds. Once the autoclave had been re-pressurized, approximately 1,080.0 grams of ethylene oxide was added at 125 ° C over a period of two hours and a pressure less than 6.33 kilograms per square centimeter gauge. Ethylene oxide is 3 - it reacted at a constant pressure over a period of one hour, after which the autoclave was evacuated for about half an hour to collect any of the volatile compounds. The content of the reaction in the autoclave was cooled to 60 ° C and discharged to a nitrogen-washed container. The resulting polyether polyol was treated with a 3 percent Magnasol (R) absorption agent and 1.5 percent water at a temperature of about 95 ° C for one and a half hours, recycled through the filter press, it was purified and stabilized with conventional stabilizers. The resulting polyether polyol was subjected to analysis demonstrating 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. 4 - EXAMPLE 5 This example will demonstrate the level of unsaturation for a polyether diol of equivalent weight of 2,000, suitable for the manufacture of elastomers, using as a catalyst cesium hydroxide. The same procedure as 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 resulting polyether polymer diol had an internal block of 60 weight percent ethylene groups, a 20 weight percent block of oxybutylene and oxyethylene groups randomly distributed in a molar ratio of 1 to 1, and a block terminal to 20 weight percent of oxyethylene groups. The analysis showed that the polyether diol had an OH number of about 28.6, which corresponds to the calculated equivalent weight of about 1.960, and a compatibility index greater than 70 ° C. Notably, the level of unsaturation for this high molecular weight polyether diol was only 0.019.

EXAMPLE 6 Examples 6 and 7, which manufactured several polyether polyols of equivalent weight of 1,500, using different catalysts and having different structures. An intermediate 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, 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 kilograms per square centimeter gauge with nitrogen, after which 1,902.7 grams of propylene oxide were added at 105 ° C under a pressure of 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 compounds were stripped for 30 minutes and the vacuum was released with nitrogen. The contents were discharged to a container washed with nitrogen. The OH number was approximately 251.6, the Gardner color was approximately 1, and the weight percentage of cesium hydroxide was approximately 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 was used as in Example 4 with the exception that the amount of propylene oxide added was 2.517.2 grams, the amount of ethylene oxide added as the heteric block was 540 grams, the amount of butylene oxide added. it was 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 in a weight ratio of 1 to 1, and a terminal block of 20 percent by 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 low unsaturation equivalent of 1500. 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 of less than 60 ° C and a pressure of 3.51 kilograms per square centimeter gauge. During the addition of approximately 294 moles of propylene oxide to the reactor, and 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 together with 18 grams of KOH in a clean dry autoclave, 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 rest 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 hours, after which the autoclave was evacuated for 30 minutes instead of 10 minutes; the mixed ethylene and butylene oxides were added in 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 minutes , and 1120 grams of ethylene oxide were added as blocking over a period of 1.5 hours and reacted for more than 1 hour. The polyol was stabilized by the same procedure. The resulting polyether polyol had an OH number of 37, an acid number of 0.004, an unsaturation level of 0.02 and a Cl greater than 70 ° C in an isopropyl / water ratio of 50/50. The polyether polymer was a difunctional polyol of equivalent weight of 1,500 with a 60 weight percent internal block of polyoxypropylene, a 20 weight percent block of randomly mixed polyoxyethylene and polyoxybutylene groups, and a 20 percent block 100 percent by weight of polyoxyethylene groups.

Claims

CLAIMS:

1. A method for producing an isocyanate polyoxyalkylene polyether polymer with reactant comprising reacting, in the presence of a catalyst, an initiator having at least two reactive sites with alkylene oxides directly or indirectly with, in sequence order, propylene oxide to form an internal block of oxypropylene groups, followed by directly or indirectly reacting to the internal block oxypropylene groups, one or more kinds of second oxide (s) comprising a higher alkylene oxide of 4 carbon atoms to form a second block of oxyalkylene groups.

The method according to claim 1, wherein the amount of propylene oxide added is from 25 weight percent to 80 weight percent, based on the weight of the total oxyalkylene compounds that are added to the initiator compound or the initiator, and the total amount of one or more of the second oxides reacted in the internal polyoxypropylene block, is effective to reduce the degree of unsaturation of the polyether polymer to 0.06 milliequivalent KOH per gram of polyol or less.

3. The method according to claim 2, wherein one or more of the second oxide compounds added comprises 1,2-butylene oxide.

4. The method according to claim 3, wherein one or more of the second oxide compounds further comprises adding ethylene oxide.

5. The method according to claim 4, wherein the polyether is terminated with a terminal block of oxyethylene groups containing a primary hydroxyl group on the terminal carbon of the block, in an amount of at least 5 percent by weight. weight .

6. The method according to claim 2, wherein the polyether is a polyol having an equivalent weight of 1,500 or more.

The method according to claim 2, wherein a sufficient amount of propylene oxide is added to the initiator in such a way that the equivalent weight of the resulting block of oxypropylene groups is at least about 800 to no more than about 1700.

The method according to claim 7, wherein the equivalent weight of the oxypropylene group block is from about 1000 to about 1300.

9. The method according to claim 2, wherein the addition of one or more than the second oxides begin when 0.01 milliequivalent per gram of polyol unsaturation or more is developed.

The method according to claim 7, wherein the polyether is a polyol having an equivalent weight of 1500 or more.

The method according to claim 10, wherein the initiator comprises a compound having 2 or 3 hydroxyl functionalities.

The method according to claim 11, wherein one or more of the second oxides comprises 1,2-butylene oxide.

The method according to claim 12, wherein one or more of the second oxides consists of 1,2-butylene oxide.

The method according to claim 12, wherein one or more of the second oxides is a mixture comprising 1,2-butylene oxide and ethylene oxide.

15. The method according to claim 14, wherein the weight ratio of 1,2-butylene oxide to ethylene oxide is 0.5: 1 to 4: 1.

16. The method according to claim 14, wherein the amount of 1,2-butylene oxide that is added is at least 5 weight percent.

17. The method according to claim 16, wherein the amount of 1,2-butylene oxide is at least 10 weight percent.

18. The method according to claim 2, wherein the amount of the internal block of oxypropylene groups ranges from 50 weight percent to 80 weight percent, and the amount of the second block of oxyalkylene groups varies from 5 weight. weight percent to 50 weight percent, each based on the weight of all oxyalkylene compounds added to the initiator compound and the initiator.

The method according to claim 2, wherein the amount of the internal block of oxypropylene groups ranges from 60 weight percent to 75 weight percent, and the amount of the second block of oxyalkylene groups varies from 10 weight. 100 percent by weight to 30 percent by weight.

The method according to claim 18, wherein the polyether is terminated with a terminal block of oxyethylene groups containing a primary hydroxyl group on the terminal carbon of the terminal block.

The method according to claim 20, wherein the amount of terminal block of oxyethylene groups ranges from 5 weight percent to 25 weight percent.

22. The method according to claim 20, wherein the terminal block amount of oxyethylene groups ranges from 10 weight percent to 20 weight percent.

23. The method according to claim 2, wherein one or more of the second oxides is a mixture consisting of 1,2-butylene oxide and ethylene oxide.

The method according to claim 2, wherein the weight ratio of 1,2-butylene oxide to ethylene oxide ranges from 0.5: to 4: 1.

25. The method according to claim 23, wherein the polyether is a polyol having an equivalent weight of at least 1500.

26. The method according to claim 25, wherein the initiator is a compound having 2. or 3 hydroxyl functionalities.

27. The method according to claim 2, wherein the degree of unsaturation of the polyether is 0.03 or less.

The method according to claim 2 which comprises reacting a sufficient amount of propylene oxide and alkylene oxide of 4 carbon atoms or more to yield a polyether having a Cl of 25 ° C or less.

29. The method according to claim 28, wherein the polyether has a Cl of 16 ° C or less.

30. The method according to claim 2, wherein the polyether is a polyol having an equivalent weight of 2000 to 4000, a Cl of 25 ° C or less, and wherein the sufficient amount of propylene oxide is added to achieving an equivalent weight of at least 800.

31. The method according to claim 2, wherein the polyether is a polyol manufactured in the presence of 0.2 weight percent to 1.5 weight percent of a catalyst comprising hydroxides or alkali metal alkoxides, and / or alkaline earth metal hydroxides, based on the weight of the polyol.

32. The method according to claim 31, wherein the catalyst is selected from the group consisting of postasium hydroxide, sodium hydroxide and mixtures thereof.

33. The method according to claim 2, wherein the polyether is a polyol made in the presence of cesium hydroxide.

34. The method according to claim 2, wherein the polyol has a degree of unsaturation of 0.03 milliequivalent per gram or less.