MXPA00009657A - Molded and slab polyurethane foam prepared from double metal cyanide complex-catalyzed polyoxyalkylene polyols and polyols suitable for the preparation thereof - Google Patents

Abstract

Copolymer DMC-catalyzed polyoxypropylene polyols which exhibit processing latitude similar to base-catalyzed copolymer analogs and base-catalyzed homopolyoxypropylene analogs may be prepared by oxyalkylation with a mixture of propylene oxide and ethylene oxide such that a finite ethylene oxide content is maintained in the oxyalkylation reactor for the most substantial part of the oxyalkylation, the polyoxypropylene polyol having randomly distributed oxyethylene moieties which constitute 1.5 weight percent or more of the polyol product.

Description

PREPARED FOAM OF MOLDED POLYURETHANE AND PLATES FROM POLYOLYL OXYLENE POLYOLS CATALYZED WITH COMPLEX OF DOUBLE METAL CYANIDE AND ADEQUATE POLYOLES FOR THE PREPARATION OF THE SAME > TECHNOLOGICAL FIELD The present invention pertains to molded polyurethane foam and plates from polyether polyols catalyzed by double metal cyanide complex showing increased latitude of processing. The present invention further pertains to polyoxyalkylene polyols prepared by a polymerization of alkylene oxide mixtures catalyzed by double metal cyanide (DMC) complex to form polyoxypropylene polyether polyols having properties that increase the latitude of processing suitable for use. in preparing molded foam and in polyurethane plates.

DESCRIPTION OF THE RELATED TECHNIQUE The polyurethane polymers are prepared by reacting a diisocyanate or polyisocyanate with a polyfunctional isocyanate-reactive compound, in particular hydroxyl-functional polyester polyols. There are numerous Ref: 122987 classes of polyurethane polymers recognized in the art, for example casting elastomers, polyurethane RIM, microcellular elastomers and molded and plated oliurethane foam. Each of these polyurethane varieties presents unique problems in formulation and processing. • Two of the highest volume polyurethane categories are molded foam and polyurethane plates. In the molded foam, the reactive ingredients are supplied to a closed mold and foamed, while in the plate foam, the reactive ingredients are supplied on a moving conveyor, or optionally in a discontinuous open mold, and allowed to ascend freely. The resulting foam board, often 2-6 feet (6-8 feet) wide and high, can be sliced into thinner cuts for use as seat collars, carpet bottoms and other applications. The molded foam can be used for contoured foam parts, for example, seat cushions for automotive seats. In the past, polyoxypropylene polyether polyols useful for plating and molding applications have been prepared by oxypropilation catalyzed by a base of suitably hydroic initiators such as propylene glycol, glycerin, sorbitol, etc., which produces the diols, respective polyoxypropylene triols and exoles. As has been well documented, a rearrangement of propylene oxide to allyl alcohol occurs during oxy-propylation catalyzed by a base. Unsaturated and monofunctional allyl alcohol has an oxyalkylatable hydroxyl group and its continuous generation and oxypropylation produces an increasingly large amount of unsaturated polyoxypropylene monools having a broad molecular weight distribution. As a result, the actual functionality of the polyether polyols produced from the "nominal" or "theoretical" functionality decreases significantly. In addition, the generation of onoi is carried out at a relatively low practical limit in the molecular weight obtainable. For example, a base-catalyzed diol of 4000 Da (Dalton) molecular weight (2000 Da of equivalent weight) can have a measured unsaturation of 0.05 meq / g and therefore will contain 30 mole percent of unsaturated polyoxypropylene monoi species . The resulting actual functionality will be only 1.7 instead of the "nominal" functionality of 2 expected for a polyoxypropylene diol. This problem becomes increasingly larger as the molecular weight increases, and the preparation of polyoxypropylene polyols having equivalent weights greater than about 2200-2300 Da is not practical using conventional base catalysts. Over the years many attempts have been made to reduce the monoi content of the polyoxypropylene polyols. The use of lower temperatures and pressures results in some improvement, as illustrated in European published application EP 0 677 543 Al. However, the content of monoi is only decreased to a range of 10-15 mole percent, and the reaction rate decreases to such an extent that the costs are reduced. they increase suddenly due to the reaction time, increased. The use of alternative catalysts such as calcium naphthenate, optionally together with tertiary amine cocatalysts, results in polyols having unsaturation levels of c.a. 0.02 to 0.04 meq / g, which correspond again to 10-20 mole percent of unsaturated monools. It has been found that double metal cyanide catalysts such as zinc hexacyanocobaltate complexes are catalysts for oxypropylation in the 1960s. However, its high cost, coupled with modest activity and the difficulty of removing significant amounts of waste from Catalyst of the polyether product prevent its commercialization. The unsaturation of polyoxypropylene polyols produced by these catalysts is found to be low, however, at c.a. 0.018 meq / g. The improvements in catalytic activity and the catalytic removal methods led to a brief marketing of polyols catalyzed by DMC in the 1980s. However, the economic benefits were marginal at best and the expected improvements did not materialize due to the low content of monoi and unsaturation. Recently, as indicated by the US patents. 5,470,813, 5,482,908 and 5,545,601, researchers at ARCO Chemical Company, have produced DMC catalysts with exceptional activity, which have also resulted in a decrease in unsaturation to unprecedented levels in the range of 0.002 to 0.007 meq / g. It has been found that the polyoxypropylene polyols prepared in this manner react in a quantitatively different manner from the "low" unsaturation polyols above in certain applications, mainly cast elastomers and microcellular foams. Despite their perceived advantages, the replacement of such polyols by their base-catalyzed analogues in molded foam and plate formulations often leads to catastrophic failure. In molded foams, for example, the foam stiffness increases to such an extent that the necessary crushing of the foams after molding proves to be difficult to carry out, if not impossible. Both in the molded foams and in the foams in plate, collapse of foam frequently occurs, which returns to taze unacceptable foams for the production. These phenomena occur even when the high actual functionality of such polyols is deliberately lowered by adding polyols with lower functionality to obtain a real functionality similar to that of the base-catalyzed polyols. The polyoxypropylene polyols catalyzed by DMC have an exceptionally narrow molecular weight distribution, as can be seen from the gel permeation chromatograms of the polyol samples. The molecular weight distribution is often much narrower than that of the base-catalyzed analog polyols, particularly in the upper equivalent weight range. Polydisperities of less than 1.5 are generally obtained, and polydispersities in the range of 1.05 to 1.15 are common. In view of the low levels of unsaturation and low polydispersity, it is surprising that the polyols catalyzed by DMC have not been proven to be "inclusion" substitutions for base-catalyzed polyolees in polyurethane foam applications. Because oxypropylation with modern DMC catalysts is highly efficient, it would be highly desirable to provide DMC-catalyzed polyoxypropylene polyols which can directly replace conventional polyols in plate and cast polyurethane foam applications. A comparison of gel permeation chromatograms of polyols catalyzed by bases and catalyzed by DMC describes differences which until now have not been recognized as a result that depend on the functioning of the polyol. For example, as shown in curve A of figure 1, a catalyst polyol per base shows a significant "front" portion of the low molecular weight oligomers and polyoxypropylene monools before the major molecular weight peak. Turning to the peak, the percentage by weight of the species with the highest molecular weight decreases rapidly. In curve B of FIG. 1, a similar chromatogram of a DMC catalyzed polyol shows a narrowly centered peak with very little "front" portion of low molecular weight, but with a small portion of higher molecular weight species, which it can be called a "high molecular weight tail". Due to the low concentration of the high molecular weight tail portion, generally less than 2-3 weight percent of the total, the polydispersity remains low. Both curves have been idealized for illustration purposes.

BRIEF DESCRIPTION OF THE INVENTION It has now surprisingly been found that DMC-catalyzed polyoxypropylene polyols can be obtained which mimic the performance of base-catalyzed analogs if, during oxypropylation, small but effective amounts of ethylene oxide or other suitable alkylene oxide are copolymerized as defined. here, for the bulk of the oxypropylation, resulting in a random copolymer polyol, preferably a polyoxypropylene / random polyoxyethylene copolymer polyol. It has been found that such polyols are suitable for use in both molded and plated foam applications, and exhibit a latitude of processing similar to their base catalyzed analogs.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates hypothetical molecular weight distribution curves for a conventional base catalyzed polyol (curve A) and a polyol catalyzed by DMC (curve B).

DETAILED DESCRIPTION OF THE INVENTION Intense research has shown that higher molecular weight species are inevitably obtained during DMC-catalyzed oxypropylation, despite their low concentration, and are primarily responsible for the abnormal behavior of DMC-catalyzed polyols in molded foam and plate applications, of urethane. It is conjectured that these high molecular weight species exert a surfactant-like effect which alters the solubility and thus the stepwise removal of the growing polyurethane polymers during the isocyanatopolyol reaction. So far, they have not *. found completely effective methods to avoid the introduction of high molecular weight components during polyoxypropilation using DMC catalysts. The present inventors have conjectured that a processing capacity different from conventional polyols and polyols catalyzed by DMC can receive in the differences shown by these polyols with respect to their content of lower and higher molecular weight species. Since the complex step removal of the hard and soft segments which occurs during the polyurethane polymerization is known to be affected by the molecular weight of the polyol, this stepwise removal is an aspect which is identified as a possible cause of differences in processing capacity. Surprisingly it has been discovered that the preparation of polyoxypropylene polyols from mixtures containing a minimum effective amount of copolymerizable monomers, preferably ethylene oxide, through the bulk of the oxyalkylation catalyzed by DMC, produces polyols which are useful in the same manner as their base-catalyzed polyoxypropylene counterparts in molded foam and plate applications, while maintaining a substantially equal molecular weight distribution compared to the homopolymer polyoxypropylene polyols catalyzed by DMC. It is hypothesized that the incorporation of ethylene oxide alters the compatibility of the high molecular weight fractions of the subject polyols during polyurethane polymerization, so that the stepwise removal of the hard and soft segments also changes. It is very surprising that the foam collapse in the DMC catalyzed polyol-based foam formulations (destabilization) is experienced, while at the same time a stiffness (excessive stabilization) in molded foam is experienced. The inventors have surprisingly found that the incorporation of the random internal ethylene oxide discussed previously into DMC-catalyzed poly-oxypropylene polyols cures both the excessive stiffness of the molded foam as well as a foam-plate collapse. The most surprising thing is that these very different processing difficulties can be solved with the same solution. Although foam stiffness and excessive foam collapse can be avoided by the preparation of polyoxypropylene polyolems catalyzed by DMC, as defined herein, the amount of the high molecular weight tail does not appear to be significantly altered, and therefore the unexpected and meritorious effects shown by the copolymerized product must be the result of some other cause. It is considered that the high molecular weight species generated are also copolymers, and that the presence of a greater quantity of hydrophilic oxyethylene portions, or of stereochemically different portions such as butylene oxides, etc. in these fractions alters the compatibility of these Species with the hard and soft segments of the growing polymer chains during polyurethane polymerization. The mechanism for this change is not known. It can result, for example, from a change in the hydrophilic / lipophilic balance (HLB) of the high molecular weight fractions, which can create a polyurethane polyether equivalent hard and soft segments, or that can alter the crystallinity or stereoregularity, which in any case, can be defined as a change in the "surfactance" of the high molecular weight tail, since the effects are considered to be related to the surface. It has been found that the minimum amount of ethylene oxide or other copolymerizable monomer, copolymerized with propylene oxide, should be about 1.5 weight percent relative to the total monomer feed. For example, amounts of 1% by weight or less of ethylene oxide show substantially the same properties as the homopolyproxylated polyols catalyzed by DMC. Monomers other than ethylene oxide can be used to obtain the meritorious effects of the present invention and include those copolymerizable monomers, with propylene oxide or copolymerizable with mixtures of propylene oxide and ethylene oxide under DMC catalyst. Such monomers include, but are not limited to, substituted olefin oxides, for example unsubstituted, or unsubstituted C5 to C20, especially C4 to C12, such as 1,2-butylene olefin oxide, 2-oxide, 3-butylene (the α-olefins being preferred); oxetane, methyloxetane such as 3-methyloxetane, caprolactone, maleic anhydride, phthalic anhydride, halogenated propylene and butylene oxide and α-olefin oxide. The effective amounts of such monomers in the preparation of polyols which are suitable for use in plate foam can be easily determined by synthesis of a target polyol and evaluation of its operation in a supercritical foam test, as described in the following. In general, the amounts used will be similar to the amounts of ethylene oxide used, on a mol to mol basis. However, the copolymerizable monomers which cause greater alteration of the polyol structure of the high molecular weight fractions can be used in smaller amounts. Mixtures of such monomers are also useful, particularly together with ethylene oxide. In the present, such monomers are referred to as stabilizing modifiers as comonomers. Although ethylene oxide is used in the discussions that follow, these discussions also apply to stabilizing modifying comonomers, unless indicated otherwise. The maximum amount of ethylene oxide which can be used successfully depends on the end use contemplated. As the amount of ethylene oxide increases, the polyol becomes increasingly hydrophilic and the primary hydroxyl content increases. When there is a content of amounts exceeding 10 weight percent of ethylene oxide in the outermost portion of the polyol, the resulting polyols are significantly less processable in free-climbing foam machines. Higher levels of primary hydroxyl content are possible when polyethols capped with ethylene oxide (EO) are subsequently prepared or when a high EO / PO ratio is to be used in the final stage of polymerization, for example, to increase deliberately the primary hydroxyl content for use in molded foam of a filler and foam in plates with high resilience. In such cases, larger quantities of internal oxyethylene portions may be used, for example up to 15-20 weight percent of the total feed. However, when low primary hydroxyl content, and imitations of polyoxypropylene homopolymer are contemplated, the total oxyethylene content should be less than 10 weight percent, more preferably less than 9 weight percent and still less than 10 weight percent. more preferably less than 8 weight percent and much more preferably in the range of about 2 weight percent to about 7 weight percent. When a copolymerizable monomer other than ethylene oxide is used together with ethylene oxide, the polyol may contain ethylene oxide amounts substantially greater than 8-10%. Thus, the polyols of the present invention are substantially polyoxypropylene polyols containing a minimum amount of about 1.5 weight percent oxyethylene or other portions of stabilizing modifier comonomer, these polyols are produced in such a way that not more than 5% of the Total oxypropylation is carried out with propylene oxide alone. These polyols can be referred to as "dispersed EO polyols", as oxyethylene portions, and the preferred comonomers are "dispersed" or randomly distributed through the portion of the polyol prepared by oxyalkylation catalyzed by DMC. The polyolees of the present invention further include capped dispersed EO polyols which have been capped with an alkylene oxide or a mixture of alkylene oxides in the presence of an effective capped catalyst, or a catalyst other than DMC in the case of shotcretes. polyoxypropylene. Dispersed EO polyols and capped dispersed EO polyols also include such polyols prepared, as described below, by further oxyalkylation, in the presence of a DMC catalyst, a polyoxypropylene oligomer prepared by oxyalkylation using a catalyst other than DMC. Surprisingly, the most important thing is not the total oxyethylene content. Rather, it is important that the most substantial part of the polyoxyalkylation be carried out in the presence of DMC catalyst in the presence of ethylene oxide. Although the feeding of ethylene oxide to the polyoxyalkylation reactor can occasionally be interrupted, the ethylene oxide will still be present in smaller amounts but decreasing more and more during such an interruption. By the term "the most substantial part" in this respect is meant that the ethylene oxide will be absent, that is, it will have a concentration in the polyoxyalkylation reactor of 0% by weight for no more than 5% of the total oxyalkylation period when the propylene oxide is fed to the reactor during the DMC catalysis, preferably not more than 3% of this period, and in particular not more than 1% of this period. Therefore, at least 95% of the polyoxyalkylene portion of the resulting polyol will contain randomly distributed oxyethylene portions with a minimum total oxyethylene content which is about 1.5 weight percent. Therefore, any "top" of homopolyxypropylene will also constitute less than 5% by weight of the copolymer, preferably less than 3%, and more preferably 1% or less. The ethylene oxide content of the feed can be cycled from 0 to higher values during oxyalkylation. Such cycling to zero, for brief intervals, even if repeated, does not alter the objective of the invention, since the content of ethylene oxide in the reactor will remain finite despite the fact that the ethylene oxide feed is zero over a period of time. brief. In determining the scope of the claims, this is the principle of the invention which should be emphasized, that is, the minimization of oxyalkylation periods with substantially all propylene oxide; instead, it is preferred that the oxyalkylation mixture comprises at least 1% by weight of ethylene oxide at all times. The oxyalkylation periods discussed above reflect only the oxyalkylation portion that is carried out in the presence of DMC catalysts, and preferably also includes the activation period (induction period), wherein the DMC catalyst is activated. Generally, the DMC catalyst shows an initial induction period wherein the oxyalkylation rate is small or zero. This is most evident in batch-type processes, where after addition of the catalyst to the initiators, alkylene oxide is added to pressurize the reactor and pressure is monitored. The induction period is then considered when the propylene oxide pressure decreases. This pressure drop is often rather rapid and the activated catalyst then shows a high oxyalkylation rate. The ethylene oxide or other modifying copolymer is preferably also present during the induction period. However, the induction period is not taken into consideration when determining the portion of cycloalkylation catalyzed by DMC during which the presence of ethylene oxide is required. Sometimes it is necessary to produce topped polyoxyalkylene polyols. With the base-catalyzed polyols, the finishing is generally carried out by suspending the feed of propylene oxide or mixtures of propylene oxide / ethylene oxide and continuing only with ethylene oxide. This process generates polyols with a polyoxyethylene cap, which results in a high primary hydroxyl content which increases the reactivity of the polyol. For some base-catalyzed copolymer polyols, a "run-on" with all propylene oxide can be used to produce polyols with a high secondary hydroxyl content, that is, a primary hydroxyl content of less than about 3 mole percent. With DMC-catalyzed polyols, the finishing can be carried out to produce polyols with a lower or higher primary hydroxyl content, but the ethylene oxide cap usually can not be carried out using DMC catalysts. Although these latter catalysts can be used to prepare a polyoxypropylene cap, this cap should be less than 5% by weight, and preferably is absent, when the cap is prepared using DMC catalysts. When more than 5% by weight of polyoxypropylene coating catalyzed by DMC is used, the polyols are not suitable in the mold or plate form formulations, which causes the foam to collapse. If the primary hydroxyl content of the polyols catalyzed by DMC is desired to decrease, the capped with propylene oxide can be carried out with a catalyst other than DMC, for example, a traditional basic catalyst such as potassium hydroxide or a catalyst such as calcium naphthenate. However, in general, an increase in the primary hydroxyl content may be desired. In such cases, a polyoxyethylene cap can be prepared by oxyethylation in the presence of a catalyst which is effective in finishing, but which does not generate large amounts of polyoxyethylene or substantially homopolymeric polymers. To date, catalysts other than DMC must be used for this purpose. Heretofore, oximelation catalyzed by DMC has not been practical, since oxyalkylation with ethylene oxide alone or with mixtures of alkylene oxides containing more than about 70% by weight of ethylene oxide generally results in the formation of significant amounts of ethylene oxide. poorly defined polymers which are considered to be polyoxyethylene glycols substantially homopolymeric or nearly homopolymeric, as previously indicated. By the term, "effective capped catalyst" is meant a catalyst which efficiently quenches the DMC catalyzed polyol without production of significant amounts of polyoxyethylene glycols or other polyoxyethylene polymers. With respect to propylene oxide, an "effective capped" catalyst is one which allows oxyalkylation with propylene oxide without the generation of a high molecular weight glue. Basic catalysts such as NaOH, KOH, barium and strontium hydroxides and oxides, as well as amine catalysts are suitable as "effective top-off" catalysts, for example. Most surprising is that even polyoles with high polyoxyethylene closures still show processability difficulties unless the base polyol contains random internal oxyethylene portions. To top off a polyol catalyzed by DMC with either propylene oxide or ethylene oxide, the DMC catalyst must first be removed, destroyed or inactivated. This is most conveniently accomplished by adding ammonia, an organic amine, or preferably an alkali metal hydroxide. When the latter, for example KOH, is added in excess, the catalytic activity of the DMC catalysts is destroyed, and the excess KOH serves as a conventional base catalyst for finishing. A "capped polyol" is a term that is used herein and includes the polyols-catalyzed by DMC which are further oxyalkylated in the presence of a catalyst other than DMC or an "effective capped" catalyst. This term does not include random copolymers of PO / EO catalyzed by DMC which subsequently react with all the propylene oxide in the presence of a DMC catalyst; such polyols must satisfy the limitation described above that the total finish does not include more than 5% of only the polyoxypropylation, more preferably not more than 1%. Although the dispersed EO polyols, described hitherto, are suitable for plaque foam and for some molded foam formulations, many of the latter can conveniently utilize a higher oxyethylene content, i.e., a random internal oxyethylene content in the range from 12 weight percent to about 35 weight percent, preferably 15 to 35 weight percent, excluding any top made by oxyalkylation with a higher amount of ethylene oxide. The capped polyols containing the internal blocks previously described and then the polyoxyethylene capped with mixtures containing a 70 percent excess of ethylene oxide, and more preferably an excess of 80-90 weight percent of ethylene oxide in presence of a catalyst other than DMC, are highly useful. The syntheses of dispersed EO polyols and dispersed and capped EO polyols can be carried out using the catalysts and by methods generally set forth in US Pat. 5,470,813, 5,482,908, 5,545,601 and 5,689,012 and copending application Serial No. 08 / 597,781, incorporated herein by reference. In general, any DMC catalyst can be used as the oxyalkylation catalyst, including those described in US Pat. above and in the patent applications and patents of the US. adding 5,100,997, 5,158,922, and 4,472,560. The activation of the DMC catalysts is carried out by the addition of propylene oxide, as described, preferably with minor amounts of ethylene oxide or other copolymerizable monomer which modifies the stabilization. In conventional batch processing, the DMC catalyst is introduced into the reactor together with the desired amount of initiator, which is generally an oligomer having an equivalent weight in the range of 200 to 700 Da. One or more initiators used can have an average functionality of at least 1.5, preferably 2 to 8 oxyalkylatable hydrogen atoms. Significant amounts of monomeric initiators such as propylene glycol and glycerin tend to retard catalyst activation and may impede activation altogether, or may deactivate the catalyst as the reaction proceeds. An oligomeric initiator can be prepared by oxy-propylation catalyzed by base or by catalysis by DMC. In the latter case, the entirety except the induction period must be carried out in the presence of about 1.5 weight percent or more of ethylene oxide. The induction period during which the catalyst is activated preferably also includes ethylene oxide. The reactor is heated, for example at 110 ° C and propylene oxide, or a mixture of propylene oxide containing a lower amount of ethylene oxide is added to pressurize the reactor, generally at about 69 kPa (10 psig) . A rapid decrease in pressure indicates that the induction period has ended, and that the catalyst is active. Then a mixed feed of propylene oxide and ethylene oxide is added until the desired molecular weight is obtained. The PO / EO ratio can be changed during the reaction, if desired. In the conventional continuous process, a previously activated initiator / catalyst mixture is continuously fed into a continuous reactor such as a continuously stirred tank reactor (CSTR) or a tubular reactor. The same catalyst / initiator constraints described in the batch process apply. A coalition of propylene oxide and ethylene oxide is introduced into the reactor, and the product is continuously stirred. In the process of continuous addition of initiator, it can be carried out either a batch operation or a continuous operation. In the batch process, the catalyst and the DMC catalyst are activated as in a conventional batch process. However, a smaller molar amount of oligomeric initiator is used in relation to the moles of product. The initiator molar deficiency is supplied gradually, preferably in the PO / EO feed, as a low molecular weight initiator, such as propylene glycol, dipropylene glycol, glycerin, etc. In the continuous addition of the initiator process, the initial continuous activation is performed as in the conventional batch process, or as in the conventional continuous process using a preactivated initiator. However, after activation, the continuous addition of monomeric initiator accompanies the PO / EO feed. The product separation is continuous. Preferably, a reactor separation stream is used to activate additional DMC catalyst. In this way, after the initial line output, products can be obtained which are completely composed of random PO / EO, with EO dispersed through the molecule. The initiator molecules useful for preparing dispersed EO polyols depend on the nature of the process. In batch processes, oligomeric primers are preferred. These include homopolymeric and heteropolimeric PO / EO polyols prepared as base catalysts, which preferably have equivalent weights in the range of 200 Da to 700 Da, or PO / EO copolymer polyols catalyzed by DMC which have been prepared using propylene oxide and ethylene oxide co-effected for the most substantial part of the oxyalkylation other than the induction period. It should be noted that the molecular weights and the equivalent weights in Da (Dalton units) are the average molecular number and the equivalent weights, unless otherwise indicated. In the continuous addition of the initiating process, both batch and continuous, the initiator must be the same as previously described; it can be a lower molecular weight oligomer; a monomeric initiator molecule such as, in a non-limiting sense, propylene glycol, dipropylene glycol, glycerin, sorbitol or mixtures of such monomeric initiators; or may comprise a mixture of monomeric and oligomeric initiators, optionally together with a recycle stream from the process itself, this recycle stream contains target weight polyols, or preferably polyols which are oligomeric in relation to the target weight. Unlike batch processes, in the continuous addition of the initiator processes, the initiator feeder may be constituted of a smaller portion, ie less than 20 mole percent of total starter molecules, and preferably less than 10 mole percent , of oligomeric initiators catalyzed by DMC which are oligomeric polyoxypropylene homopolymer polyols. In addition, details regarding the preparation of dispersed EO polyol can be taken as reference to the actual examples presented herein. The polyols of the present invention have functionalities, molecular weights and hydroxyl numbers suitable for use in molded and plated foam. The nominal functionalities generally vary from 2 to 8. In general, the average functionality of the polyol combinations ranges from about 2.5 to 4.0. The equivalent weights of the polyol generally range from a little less than 1000 Da to approximately 5000 Da when the unsaturation of the polyol is less than 0.02 meq / g. The unsaturation is preferably 0.015 meq / g or less, and more preferably in the range of 0.002 to about 0.008 meq / g. Hydroxyl numbers may vary from 10 to about 60, hydroxyl numbers being further preferred in the range of 24 to 56. Of course, the combinations may contain polyols with both lower and higher functionalities, equivalent weight and hydroxyl number. Any combination preferably should not contain more than 20 weight percent undispersed EO polyols, for example, homopolymer polyoxypropylene polyols catalyzed by DMC or polyoxypropylene / polyoxyethylene copolymer polyols catalyzed by DMC having more than 5 weight percent of the block of all internal oxypropylene or 5 percent by weight of polyoxypropylene cap catalyzed by DMC. The operation of the dispersed EO polyols and the dispersed capped EO polyols intended for foam formulations in plate can be determined by testing these polyols in the "eupercritic foam test" (SCFT), a test specifically designed to amplify the differences in the behavior of polyol. It has been found that the polyols that pass the test work well in commercial applications, without foam collapse. In contrast, when testing polyols with conventional formulations, cabinet tests often do not indicate any difference between polyols, whereas in commercial production, such differences are readily apparent.

In the SCFT a foam prepared from a given polyol is reported as "settled" if the surface of the foam appears convex after purging, and is reported as collapsed if the surface of the foam is concave after purging. The amount of collapse can be reported in a relatively quantitative manner by calculating the percentage change in a cross-sectional area taken through the foam. The formulation of the foam is as follows: polyol, 100 parts; water, 6.5 parts; methylene chloride, 15 parts; amine type catalyst NiaxMR A-l 0.10 parts, - tin catalyst T-9, 0.34 parts; silicone surfactant L-550, 0.5 parts. The foam is reacted with a mixture of 80/20 diisocyanate of 2,4- and 2,6-toluene at a rate of 110. The foam can conveniently be poured into a standard cake box of 28.3 dm3 (1 cubic foot) ) or a standard ice cream container of 3.78 liters (1 gallon). In this conventionally prepared formulation, ie, the base-catalyzed polyols cause the foam to settle to about 15% ± 3%, while the polyols prepared from DMC catalysts have homopolyioxypropylene blocks exceeding 5 weight percent of the total polyol weight which causes the foam to collapse by approximately 35-70%. The polyolees of the present invention without homopolyioxypropylene blocks behave in a manner substantially similar to polyolees catalyzed by KOH.

Having generally described this invention, further understanding can be obtained with reference to certain specific examples which are provided herein for purposes of illustration only and are not intended to be limiting unless otherwise specified.

Examples 1 to 5 and Comparative Examples Cl to C3 These examples illustrate the significant and surprising differences between homopolyroxypropylene polyols catalyzed by DMC, catalyzed by bases and the dispersed EO polyols. The base-catalyzed polyol is ARCOLMR 5603, with a hydroxyl number 56, of a homopolymer polyoxypropylene polyol initiated by glycerin, the preparation of which is conventionally catalyzed using KOH. The relatively low equivalent weight results in a c.a. 8.2 mole percent, and a real functionality of 2.83. The DMC-catalyzed polyols are prepared from initiators containing glycerin and propylene glycol in order to obtain real functionalities close to the actual functionality of the base catalyzed control, so as to make the polyol processing comparisons as accurate as possible. The batchwise and continuous addition of process initiators are used to prepare the polyols catalyzed by DMC, the latter process being indicated in Table 1, as "continuous". The polyols are used in the SCFT previously described and compared to the control in terms of percent sedimentation. Since the SCFT is sensitive to environmental conditions, the control foams are carried out on the same day. The data is summarized in Table 1 ..

TABLE 1 or ro 1 The examples preceded by a "C", for example "Cl", are comparative examples. 2 Controls catalyzed by KOH repeatedly provide a sediment of 15 ± 3%. 3 NA = not available. 4 # of OH rated. i The above Examples and the Comparative Examples illustrate both the importance of preparing polyoxyalkylene polyols containing dispersed EO as well as the criticality of the minimum amount necessary to produce a polyol suitable for the production of foam without collapse. In Comparative Example Cl, the KOH-catalyzed polyol works well in the SCFT, with a sediment of 13%. It has been found that polyols that show a maximum of 15-20% sedimentation work without defects in full-scale tests. Lae foams that show sedimentation greater than 35% almost always experience collapse. Foams with a SCFT with sedimentation higher than 25% are not suitable for low density foam, but may be suitable for certain higher density applications. Comparative Examples C2 and C3 are polyols catalyzed by DMC in batches and continuous prepared analogously to the polyol of Comparative Example Cl, ie, from all the propylene oxide. These foams exhibit considerable sedimentation, 32% and 36%, some three times greater than the catalyst polyol by control KOH. In the comparative examples C4 and C5, the polyols in batches catalyzed by DMC, very small amounts of ethylene oxide, 0.5% and 1.0% in peeo, are co-fed with propylene oxide, which generates random copolymers. However, the foams prepared from these polyols also show severe sedimentation, even higher, at 43% and 40%, respectively, compared to all the propylene oxide, the polyols catalyzed by DMC of Comparative Examples C2 and C3. However, in Example 1, the catalyzed batch polyol >; by DMC it contains 1.75 weight percent of copolymerized ethylene oxide which generates foams with a degree of sedimentation virtually the same as the control catalyzed with KOH. An excellent similar performance is obtained with 2.4 to 6.4 weight percent in the polyols catalyzed by DMC in Examples 2 to 5.

Comparative examples C6 and C7 'Additional foam tests of polyolees catalyzed with KOH and catalyzed with DMC are carried out. The polyol with KOH in this case (Comparative Example C6) is a polyol of polyoxypropylene / polyoxyethylene copolymer capped in polyoxypropylene, with hydroxyl number 56. The commercial polyol is prepared to oxyalkylate glycerin with a mixture of propylene oxide containing sufficient oxide of ethylene to provide an oxyethylene content of 8.5 weight percent, using KOH as a basic catalyst. The PO / EO co-fired is then finalized and replaced only with a PO feed to top off the polyol with a polyoxypropylene block to reduce the primary hydroxyl content to less than 3%. Attempts to produce a DMC catalyzed analog (Comparative Example C7) suitable for use in producing polyurethane foam failed.

Table 2 1 Estimated at 2.80 ± 0.08.

The results presented in Table 2 indicate that although polyoxypropylene / polyoxyethylene random copolymer polyols capped with propylene oxide, catalyzed with KOH work well in the foaming tests, their DMC-catalyzed analogs show very high degrees of sedimentation. The preparation of a 6.5 weight percent homopolyoxypropylene cap requires oxypropylation without copolymerization with ethylene oxide for an excessive period, ie, more than 5% by weight of the total oxyalkylation.

Comparative examples C8 to CIO Molded foams are prepared from formulations containing 75 parts of polyol base, 25 parts of ARCOLMR E849 polyol, 1.5 parts of diethanolamine, 0.1 parts of NIAXMR Al catalyst, 0.3 parts of NIAX A-33 catalyst and 1.0 part of silicone surfactant DC5043, which reacts with TDI with an index of 100, with 4.25 parts of water as blowing agents. The collapse of ventilation is measured from a similar formulation but with 20% solids. These polyols are used as the base polyol. In Comparative Example C8, the base polyol is a polyoxypropylene triol with hydroxyl number 28, conventionally base catalyzed, with a 15% oxyethylene cap to provide a high primary hydroxyl content. In Comparative Example C9, the base polyol is a polyoxypropylene triol catalyzed by DMC with a hydroxyl number 28 capped with ethylene oxide using KOH catalyst. The polyol does not contain internal oxyethylene portions. The results of foam tests molded in one process are presented below in Table 3.

TABLE 3 The above results illustrate that the EO-capped polyols show frothing problems compared to their unfinished analogues. The base catalyzed polyol shows typical foaming characteristics. However, the DMC catalyzed polyol (Comparative Example C9) shows a collapse of total ventilation. The force to crush the DMC catalyzed polyol is very low, usually a desirable characteristic. However, this low value is due to the exceptionally large cells, with cell sizes in the order of 4-6 mm, much larger than the relatively thin cell KOH catalyzed polyol derived foam.

Example 6? And CIO comparisons? Cll A series of free-climbing foams are prepared using the polyol ARCOLMR E785, a polyol topped with EO hydroxyl 28, as the control (Comparative example CIO). They are tested against this control wherein a DMC-catalyzed analog of hydroxyl numbers 25 does not contain internal EO but a similar EO spout (Comparative Example Cll) and a polyol with hydroxyl number 28 of the present invention, containing 5% of Internal random EO and an EO 15% spike catalyzed by KOH (Example 6). The results are presented in Table 4. The foam densities are 46.4 ± 0.64 kg / m3 (2.90 ± 0.04 pounds / ft3).

TABLE 4 As can be seen from the above, the capped polyol, catalyzed by DMC has no internal EO (dispersed EO) produced as a thick cell foam with considerable collapse, low air flow (excessive foam stiffness), low resilience and low tensile strength, compared to catalyzed control with a base. By including 5 percent by weight of random EO within the polyol before finishing, the height of the foam is maintained substantially with only a minor shrinkage and identical resilience with fine cells. The tensile strength and the air flow are only moderately lower compared to the control catalyzed by KOH. By the terms "improved latitude of processing" and "which increase latitude of processing" and similar terms, it is meant that the polyol in question shows an operation in the supercritical foam test superior to that shown by a homopolyroxypropylene analogue catalyzed by DMC with a percent sedimentation less than 35%, preferably less than 25%, and more preferably having the same degree or a lesser degree of sedimentation with respect to a polyol catalyzed by comparative base, or showing a crushing capacity or freedom of collapse by improved ventilation, in the case of molded foam. More preferably, such polyoletes also show porosity of foam, measured by air flow, in about the same order as the foam catalyzed by comparative KOH. By the term "system" is meant a production formulation of reactive polyurethane.

By the term "intrinsic unsaturation" is meant the unsaturation produced during oxyalkylation, excluding any unsaturation added deliberately by copolymerizing unsaturated copolymerizable monomers or by reacting a polyol with an unsaturated copolymerizable monomer reactive with it, the latter being termed "unsaturation" induced. "The polyols of the present invention can be used to prepare polymer polyols which do not contribute to foam collapse or excessive foam stabilization.Such polymer polyols are prepared by the in situ polymerization of one or more vinyl monomers in a polyol base which is a polyol of the present invention Vinyl polymerization in itself is a well known process and can be used, for example by carrying out stabilizers or precursors of stabilizers.The preferred vinyl monomers are styrene , acrylonitrile, methacrylate of methyl, vinylidene chloride and the like. The solid contents as prepared preferably range from 30 weight percent to 50 weight percent or greater. By the terms "major" and "minor" if they are used here, they mean 50%, or more, and less than 50%, respectively, unless otherwise indicated. The terms "initiator" are used interchangeably herein and have the same meaning, unless otherwise specified. By the terms "a" or "an" in the claims herein, one or more is meant, unless the language indicates otherwise. Any mode described or claimed herein, may be used for the exclusion of any modality or feature not described, or > not claimed, with the proviso that the characteristics necessary for the invention are present. The necessary features of the invention include carrying out the oxypropylation in the presence of ethylene oxide or a stabilizing modifying monomer for minimally 95% of the oxyalkylation catalyzed by DMC; a minimum of oxyethylene or stabilizing modifying monomer content of 1.5% by weight relative to the weight of the polyol excluding any added cap in the presence of an effective capped catalyst with respect to the polyethylene caps and a catalyst other than DMC with respect to to the polyoxypropylene finials; and at most 5% by weight of a polyoxypropylene cap prepared in the presence of a DMC catalyst.

The molecular weights and equivalent weights herein are average molecular number and equivalent weights, in units Daltons (Da), unless otherwise indicated. Having now completely declassified the invention, it will be apparent to one of ordinary skill in the art that many changes and modifications may be made thereto without departing from the spirit or scope of the invention as set forth herein. It is "stated that in relation to this date, the best method known by the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects or products to which it refers.

Claims (60)

1. Having described the invention as above, the content of the following claims is claimed as property: 1. A polyol catalyzed by DMC (double metal cyanide complex), characterized in that it comprises oxypropylene units and comonomer units randomly copolymerized therewith, polyol which can be prepared by oxyalkylation of one or more initiators with an oxyalkylation mixture comprising propylene oxide and a comonomer copolymerizable therewith such that: at least 95% by weight of the polymerized oxypropylene units are randomly copolymerized with the comonomer units; and the copolymerized comonomer content yields at least 1.5% by weight.
2. 2. A capped DMC catalyzed polyol, according to claim 1, characterized in that it comprises: a) a preparable copolymer internal block as defined in claim 1; and b) at least one external block that is selected from the group consisting of: i) a polyoxyalkylene block comprising oxyethylene portions, oxypropylene portions or a mixture thereof, and optionally including an additional copolymerized comonomer, with the condition that when the block comprises only portions of oxypropylene, or a mixture of portions of oxypropylene and oxyethylene only where the oxyethylene content is less than 1.5% by weight, the block is prepared in the presence of a catalyst other than a catalyst of DMC; and ii) substantially all of the polyoxypropylene block comprising not more than 5% by weight of the capped DMC catalyzed polyol prepared in the presence of a DMC catalyst.
3. 3. A polyol catalyzed by DMC, topped with polyoxyalkylene, according to claim 2, characterized in that the polyoxyalkylene top is prepared by oxyalkylating additionally the polyol catalyzed by DMC with alkylene oxide in the presence of a catalyst different from a DMC catalyst. .
4. 4. The polyol according to any of the preceding claims, characterized in that the comonomer comprises ethylene oxide ..
5. 5. The polyol according to any of the preceding claims, characterized in that the comonomer comprises a substituted or unsubstituted C4 to C20 alkylene oxide; oxetane; methyl oxetane; a copolymerizable internal carboxylic ester or an internal carboxylic anhydride; or a mixture of them.
6. 6. The polyol according to any of the preceding claims, characterized in that there are at least two different comonomers copolymerized with the oxypropylene units.
7. 7. The polyol according to any of the preceding claims, characterized in that the polyol has a different weight from 500 Da, such as 800 Da to 5000 Da.
8. 8. The polyol according to any of the preceding claims 2 to 7, characterized in that the comonomer content copolymerized in the internal block ee of 1.5 to 20% by weight, preferably 2 to 15% by weight, for example 2 to 10% in weigh.
9. 9. The polyol according to any of the preceding claims, characterized in that the content of copolymerized comonomer is 1.5 to 3.5% by weight, for example 1.5 to 10% by weight, preferably 2 to 8% by weight, for example 2 to 7% by weight.
10. 10. The polyol according to any of the preceding claims 1 to 9, characterized in that the content of copolymerized comonomer is from 12 to 35% by weight, preferably from 15 to 30% by weight.
11. 11. The polyol according to any of the preceding claims, characterized in that it causes a sedimentation of less than 35% in the supercritical foam test (SCFT).
12. 12. The polyol according to any of the preceding claims, characterized in that the unsaturation is 0.015 meq / g, such as 0.010 meq / g or less.
13. 13. The capped polyol, according to claim 2 or 3, or any subsequent claim when dependent thereon, characterized in that a catalyst other than the DMC catalyst is selected from the group consisting of alkali metal hydroxide; alkaline earth metal oxide or hydroxide; metal naphthenate; ammonia; or a primary, secondary or tertiary amine.
14. 14. The capped polyol, according to claim 3, or any subsequent claim, when dependent thereon, characterized in that the further oxyethylation is carried out with an oxyalkylation mixture comprising at least 50% by weight, suitably % by weight, and which preferably consists entirely of ethylene oxide.
15. 15. The polyol according to any of the preceding claims, characterized in that it contains a polymer polyol prepared by the polymerization in itself of one or more vinyl monomers in the polyol.
16. 16. The polyol according to any of the preceding claims, characterized in that the initiator has an average functionality of 1.5 to 8.
17. 17. A process for the preparation of a DMC catalyzed polyol according to any of the preceding claims, characterized in that the process comprises: a) supplying a mixture-of activated DMC catalyst / initiator to the reactor, -b) polyoxyalkylating the initiator with an oxyalkylation mixture containing propylene oxide and a comonomer polymerizable therewith such that the concentration of the comonomer during oxyalkylation is greater than 0 by at least 95% of the total oxyalkylation; c) recovering the polyol in which the content of copolymerized comonomer is at least 1.5% by weight.
18. 18. The process according to claim 17, characterized in that the concentration of comoriomer, for example ethylene oxide, in the oxyalkylation mixture is maintained at a level of at least 0.5% by weight during oxyalkylation.
19. 19. The process according to claim 17 or 18, characterized in that it is a continuous process in which additional initiator molecules are added continuously or in increasing amounts to the reactor.
20. 20. The process according to claim 19, characterized in that the additional initiator molecules have an equivalent weight of 100 Da or less.
21. 21. The process according to claim 19 or 20, characterized in that the additional initiator molecules have the same functionality as the initiator molecules in the DCM catalyst / initiator mixture.
22. 22. A process for the preparation of a polyurethane foam in plates or molded by the reaction of a diisocyanate or polyisocyanate with a polyester polyol in the presence of customary blowing agents, catalysts, chain extenders, crosslinkers, surfactants, additives and auxiliaries, process which is characterized in that it comprises: selecting as at least a portion of the polyol component a polyoxypropylene polyol catalyzed by DMC increasing the latitude of processing, according to any of the claims 1 to 16, or that is prepared by the process according to any of claims 17 to 21; and reacting the polyol with a diisocyanate or polyisocyanate to produce plate foam or polyurethane molding.
23. 23. An improved process for the preparation of a foamed or molded polyurethane foam by the reaction of a diisocyanate or polyisocyanate with a polyether polyol in the presence of customary blowing agents, catalysts, chain extenders, crosslinkers, surfactants, additives and auxiliaries , the improvement is characterized in that it comprises: selecting, as at least a portion of the polyol component, a dispersed EO-polyoxypropylene polyol, catalyzed by DMC, which increases the latitude of processing having a nominal functionality of 2 or greater, a content of random oxyethylene of about 1.5 or less than 10% by weight, wherein not more than 5% by weight of the total DMC catalyzed oxyalkylation period used in preparing the dispersed EO polyoxypropylene polyol is carried out in the absence of ethylene oxide.
24. 24. The process according to claim 23, characterized in that the dispersed EO polyoxypropylene polyol has an oxyethylene content in the range of 2 weight percent to 8 weight percent.
25. 25. The process according to claim 23, characterized in that the dispersed EO polyoxypropylene polyol shows a sedimentation of less than about 25% in the supercritical foam test.
26. 26. A process for the preparation of a polyoxypropylene polyol catalyzed by DMC having an increased processing latitude, when used in molded foam systems and polyurethane plate, the process is characterized in that it comprises: a) supplying a catalyst / initiator mixture of DMC activated to a reactor; b) polyoxyalkylating the initiator with a mixture of alkylene oxide containing propylene oxide and ethylene oxide so that the polyol contains about 1.5 weight percent to less than 10 weight percent random oxyethylene portions, and the concentration of ethylene oxide during the oxyalkylation catalyzed by DMC is greater than zero for a minimum of 95% of the total oxyalkylation; c) recovering a dispersed EO polyoxypropylene polyol.
27. 27. The process according to claim 26, characterized in that the dispersed EO polyoxypropylene polyol shows a sedimentation of less than about 35%.
28. 28. The process according to claim 26, characterized in that the concentration of oxide of. Ethylene in the alkylene oxide feed is maintained at a level of 0.5 percent by weight or higher during oxyalkylation.
29. 29. The process according to claim 26, characterized in that the dispersed EO polyol is topped polyoxypropylene, the top of polyoxypropylene constitutes no more than 5 weight percent of the polyoxyalkylene polyol EO dispersed when the top of the polyol EO dispersed with propylene oxide is carried out in the presence of a DMC catalyst.
30. 30. The process according to claim 26, characterized in that the weight percent of oxyethylene portions is from about 2 weight percent to 8 weight percent.
31. 31. The process according to claim 30, characterized in that the weight percent of the oxyethylene portions is between 2 weight percent and 7 weight percent.
32. 32. The process according to claim 26, characterized in that the process is a continuous process in which the additional initiator molecules are added continuously or in increments to the reactor.
33. 33. The process according to claim 32, characterized in that the additional initiator molecules have an equivalent weight of 100 Da or less.
34. 34. The process according to claim 32, characterized in that the additional initiator molecules have the same functionality as the initiator molecules in the DMC catalyst / initiator mixture.
35. 35. A DMC-catalyzed polyoxypropylene polyol which exhibits a broad processing latitude in molded foam and polyurethane plate block formulations, the polyol prepared by oxyalkylation of a starter molecule or mixtures thereof having two or more hydrogen atoms oxyalkylatable, the oxyalkylation is carried out with a mixture of propylene oxide and ethylene oxide so that the concentration of ethylene oxide is from about 0 to not more than about 5% of the oxyalkylation catalyzed by total DMC, the polyol having a content of oxyethylene from 1.5 percent by weight to less than 10 percent by weight.
36. 36. The polyol according to claim 35, characterized in that the polyol has an oxyethylene content of between about 2 weight percent and about 8 weight percent.
37. 37. The polyol according to claim 36, characterized in that it shows a percent sedimentation of about 35 percent or less.
38. 38. The polyol according to claim 35, characterized in that the polyol has an unsaturation of 0.010 meq / g or less.
39. 39. A capped, DMC-catalyzed polyoxypropylene polyol, which shows a broad processing latitude in molded foam formulations and polyurethane plate concentration, the polyol is characterized in that it comprises: a) a first copolymer internal block prepared by oxyalkylating a more initiator molecules having doe or more oxyalkylated hydrogen atoms with a mixture of propylene oxide and ethylene oxide so that the ethylene oxide content is greater than zero for at least 95% of the oxyalkylation, the oxyethylene content of the first internal block varies from 1.5 weight percent to about 20 weight percent; and b) at least one second external block that is selected from the group consisting of: i) a polyoxyalkylene block comprising oxyethylene portions, oxypropylene portions, or mixtures thereof *, optionally including substituted or unsubstituted alkylene oxides substituted C4-CX2 or oxetane, with the proviso that when using propylene oxide or mixtures of only propylene oxide and ethylene oxide containing less than 1.5 weight percent ethylene oxide, the polymerization of the polyoxyalkylene is carried out in the presence of a catalyst different from a DMC catalyst; and ii) substantially all of the polyoxypropylene block polymerized in the presence of a DMC catalyst, the polyoxypropylene block ii) constitutes at most 5 weight percent of the capped DMC catalyzed polyol.
40. 40. The capped polyol according to claim 39, characterized in that the external polyoxyalkylene block is a polyoxyethylene block prepared by polymerizing ethylene oxide on the first internal block in the presence of an effective capped catalyst.
41. 41. The capped polyol according to claim 39, characterized in that the first internal block contains from 2 weight percent to about 15 weight percent oxyethylene portions.
42. 42. The capped polyol according to claim 39, characterized in that the first internal block c contains from 2 weight percent to about 10 weight percent oxyethylene portions.
43. 43. The capped polyol according to claim 39, characterized in that the catalyst used during the preparation of the external block comprises one or more of an alkali metal hydroxide, an alkaline earth metal oxide or hydroxide, a metal naphthenate, ammonia or an amine organic
44. 44. The capped DMC catalyzed polyoxypropylene polyol according to claim 39, characterized in that it shows a sedimentation in percent less than about 35 percent in the supercritical foam test.
45. 45. A DMC-catalyzed polyoxypropylene polyol suitable for producing molded high resilience molded foam with extended processing latitude, the polyol comprises DMC catalyzed oxyalkylation of one or more starter molecules having an average functionality of 1.5 or greater with a mixture of oxyalkylation comprising propylene oxide and ethylene oxide so that the content of ethylene oxide and the oxyalkylation mixture is greater than zero for a minimum of 95 percent of the oxyalkylation catalyzed by total DMC, and wherein the polyol has a total oxyethylene content in the range of at least 12 weight percent to about 35 weight percent, and an equivalent weight from about 800 Da to about 5000 Da.
46. 46. The polyol according to claim 45, characterized in that the total oxyethylene content is from about 15 weight percent to about 35 weight percent.
47. 47. The polymer according to claim 45, characterized in that the oxyalkylation mixture comprises a minimum of 1 weight percent of aldehyde oxide at all times.
48. 48. The polyol according to claim 45, characterized in that it further comprises a finishing portion prepared by oxyalkylating further in the presence of a catalyst other than DMC.
49. 49. The polyol according to claim 47, characterized in that the additional oxyalkylation is carried out with a mixture containing about 50 weight percent or more of ethylene oxide.
50. 50. The polyol according to claim 48, characterized in that the additional oxyalkylation is carried out with a mixture containing a minimum of 70 weight percent ethylene oxide.
51. 51. The polyol according to claim 48, characterized in that the additional oxyalkylation is carried out with ethylene oxide.
52. 52. A DMC-catalyzed polyoxypropylene polyol having a good processing latitude when used in plated or molded polyurethane foam system, the polyol comprises a DMC catalyzed oxyalkylation product prepared by oxyalkylating an initiator molecule with an oxyalkylation mixture which contains propylene oxide and an effective amount of a stabilizing modifier comonomer, the polyol has an intrinsic unsaturation of less than about 0.015 meq / g, an average functionality of from about 1.5 to about 8, and an equivalent weight of from about 800 Da to about 5000 Da /
53. 53. The polyoxypropylene polyol catalyzed by DMC, according to claim 52, characterized in that it shows a percent sedimentation of less than 35 percent in the supercritical foam test.
54. 54. The polyol according to claim 52, characterized in that the stabilizing modifying comonomer is selected from the group consisting of 1,2-butylene oxide, 2,3-butylene oxide, oxetane, methyloxetane, caprolactone, maleic anhydride, anhydride. phthalic, α-olefin oxide .. of C5-C20 and halogenated alkylene oxides.
55. 55. The polyol according to claim 51, characterized in that it further comprises ethylene oxide or a thermonomer in an amount from about 1.5 weight percent to about 35 weight percent.
56. 56. The polyol according to claim 52, characterized in that at least one of ethylene oxide or the stabilizing modifying comonomer is present for at least 95 percent of the oxyalkylation.
57. 57. A polymer polyol containing DMC catalyzed base polyol which does not contribute to the stabilization of excessive foaming or foam collapse in foamed or molded polyurethane foam, the polymer polyol is prepared by the in situ polymerization of one or more vinyl monomers in a base polyol comprising a DMC catalyzed oxyalkylation product prepared to oxyalkylating an initiator molecule having an average functionality of from about 1.5 to about 8 with a mixture of propylene oxide containing an effective modifier amount of stabilization of ethylene oxide, a stabilizing modifying comonomer, or a mixture of ethylene oxide and a stabilizing modifying comonomer, the stabilizing modifying amount is present for at least 95 percent of the oxyalkylation, the base polyol has a intrinsic unsaturation of less than about 0.015 meq / g, and an equivalent weight of approximately 800 Da to approximately 5000 Da.
58. 58. The polymer polyol according to claim 57, characterized in that the base polyol has an oxyethylene oxide content from about 1.5 percent by weight to about 35 percent by weight.
59. 59. DMC-catalyzed polyether polyol, characterized in that it has a wide processing latitude, the polyol comprises a polyoxypropylene-catalyzed polyoxypropilation product capped with polyoxyethylene obtained by oxypropilling one or more starter molecules having from about 2 to about 8 oxyalkylated hydrogen atoms, with a mixture of propylene oxide containing on average 1.5 weight percent or more of ethylene oxide so that no more than 5 weight percent of the polyoxypropilation product catalyzed by DMC is prepared while the ethylene oxide content in the mixture of propylene oxide is about zero, the polyoxyethylene cap is prepared by further oxyethylating the polyoxypropilation product catalyzed by DMC with ethylene oxide in >; presence of a polyoxyalkylation catalyst other than DMC, up to an equivalent weight of about 500 Da to about 5000 Da and a primary hydroxyl content greater than 40 mole percent.
60. 60. The use of a DMC catalyzed polyol, characterized in that it comprises oxypropylene units and comonomer units randomly copolymerized therewith in the preparation of foamed or molded polyurethane foam.