Patent Description:
The majority of polyether alcohols produced on industrial scale are prepared by anionic base-catalysed oxyalkylation as well as by heterogeneous coordination catalysis, for example by oxyalkylation using a double metal cyanide catalyst (DMC). The DMC complex represents a rather recent class of catalysts for the production of polyether polyols and the term "DMC" commonly refers to the catalyst having at least two metal centers and cyanide ligands.

For many years the base-catalysed process (normally a KOH catalyst) for polymerization of propylene oxide and ethylene oxide was the main method for polyether polyol production. However this anionic polymerization has some limitations in the process and in the properties of the final product including high unsaturation of the product, as well as economic aspects based on production cycle time, purification and filtration. Further disadvantages result from the high concentration of unreacted propylene oxide during the polymerization process, during which monols and aldehydes are generated by isomerization of propylene oxide, causing a profound increase of unsaturation and smell.

<CIT> overcame some of the limitations of the base-catalysed process above by synthesizing high molecular weight polyethers with a DMC catalyst that do not promote in an extensive manner the isomerization of propylene oxide. However, the high cost and high concentration of DMC catalysts and the necessity to remove them from the polyol prevented the widespread application of DMC catalysts for several years. <CIT> describes that removal of the DMC catalyst from the finished polyether is not required for most of the applications when the concentration of the DMC catalyst is <NUM> ppm or less. The development of new reactive DMC catalysts together with improvements in the alkoxylation process as applied for example by ARCO Chemical Company in the <NUM> resulted in a low concentration of the DMC catalyst in the final polyol.

DMC-catalyzed alkylene oxide polymerization processes have been mainly conducted in two different ways.

For example <CIT> describes the preparation of polyether polyols by DMC catalysis by charging a reactor with a starter compound having hydroxyl groups and DMC catalyst followed by introducing propylene oxide into the reactor at about <NUM> for polymerization to prepare a polyether polyol. This process is normally referred to as the "conventional DMC process". Disadvantages of the conventional DMC production process of diols include the limitation of the hydroxyl number of the polyether diol product to the ratio of the hydroxyl number of the initiator compound divided by the build ratio and the need for initiator molecules with high molecular weights. In fact, low molecular weight initiator molecules such as glycerin or water cause rapid deactivation of the DMC catalyst. Thus, rather than employing low molecular weight starter molecules directly, oligomeric starters are prepared in a separate process by base-catalyzed alkoxylation of a low molecular weight starter to equivalent weights in the range of <NUM> Da to <NUM> Da or higher as described for example in <CIT>.

The second way of conducting DMC-catalyzed alkylene oxide polymerization processes is commonly referred to as the "continuous addition of starter" (CAOS) process developed by Pazos et al. and published in <CIT> and <CIT>. In this process, which can be conducted as a batch process, a semi-batch process or a continuous process, a starter is continuously added slowly together with a large excess of the alkylene oxide during the alkylene oxide polymerization. The continuously added starter (Sc) can be the same or different from an initial starter (Si) present in the reactor before adding the alkylene oxide. Different from the conventional DMC process, it was now possible to employ even low molecular weight compounds such as water, glycerin or glycols. The low molecular weight compounds could be used as the continuously added starter when an oligomeric initial starter was present in the reactor. Moreover, it was possible to conduct the CAOS process without the initial starter and only adding the low molecular weight molecules as a continuous starter.

One drawback of the CAOS process is the formation of a fraction of low molecular weight material in the final polyether polyol. <CIT> teaches that these low molecular weight polyols, which have molecular weights lower than <NUM>% of the peak molecular weight and constitute <NUM> to <NUM>% of the total mass of the polyether polyol can be reduced by "activating a DMC catalyst complex in the presence of i) an alkoxylated starter having a hydroxyl equivalent weight of <NUM> to <NUM>% of the hydroxyl equivalent weight of the polyether polyol product and ii) up to <NUM> weight-%, based on the weight of the alkoxylated starter, of <NUM>,<NUM>-propylene oxide iii) a low equivalent weight starter is fed continuously to the activated DMC catalyst under polymerization conditions, the feed of low molecular weight starter is continued until <NUM> to <NUM>% of the alkylene oxide feed in step b) has been completed and the feed of low molecular weight starter is then discontinued while continuing the alkylene oxide feed, wherein the total weight of low molecular weight starter added in step b) is <NUM> to <NUM>% of the total weight of alkylene oxide added in step b)". Thus, <CIT> teaches that the equivalent molecular weight of the initial starter must be close (<NUM>-<NUM>%) to the equivalent molecular weight of the final product and that the addition of the continuously added starter should be stopped before the addition of the alkylene oxide is stopped (also referred to as "non-CAOS capping").

<CIT> discloses a for preparing low viscosity polyoxyalkylene polyols (P) that have a narrow molecular weight distribution. This process comprises reacting a H-functional starter substance (Si), a H-functional starter substance (Sx) and a H-functional starter substance (Sc) with one or more alkylene oxides in the presence of a double metal cyanide catalyst. In <CIT>, during the activation process, pure oxide without Sc primer was added to two Si primers, one is a polymer and the other is glycol or glycerin. An important difference for a person skilled in the art is that <CIT> uses Si polyol for activation, which already contains an active catalyst. In a process according to claim <NUM>, catalyst in not activated before the process begin - Sc primer id added from the beginning. <CIT> also does not mentioned that StartOH is larger than PolOH and does not investigate the impact of BR on the amount of water added in the process.

<CIT> discloses a process for the production of a polyether involving establishing oxyalkylation conditions in an oxyalkylation reactor in the presence of from about <NUM> ppm to about <NUM>,<NUM> ppm, based on the final polyether weight, of a double metal cyanide (DMC) catalyst, continuously introducing into the reactor at least one alkylene oxide and a low molecular weight starter. <CIT> discloses that the acidic environment during the activation and polymerization process reduces the sensitivity of the DMC catalyst to deactivation. In the process according to the present invention applying the acidification after the polymerization process is completed, and yet we can start with wet alkylene oxide without having an active Si starter. <CIT> also does not mentioned that StartOH is larger than PolOH and does not investigate the impact of BR on the amount of water added in the process.

Removal or deactivation of the DMC catalyst from the polyether product after the polymerization has finished may be carried out in different ways, including adsorbing to synthetic silicate such as magnesium silicate or aluminum silicate, treatment with an ion exchange resin and activated clay, or a neutralization method. In the crude polyether as synthesized, there are acetals and ketals which are stable in basic environment, but can be transformed into aldehydes and ketones, which can be easier removed under vacuum as described in <CIT>, <CIT>.

<CIT> describes a method of extracting and removing water-soluble compounds from a crude unsaturated-group-containing crude polyether polyol made by DMC catalysis having a molecular weight in the range of <NUM>'<NUM> to <NUM>'<NUM>/mol with <NUM> to <NUM> parts by weight of water relative to <NUM> parts by weight of the crude polyether polyol.

While different low molecular weight compounds can be employed in the CAOS process as continuously added starter, mainly glycols have been used for this purpose, while water has seldomly been used as continuously added starter.

Among the few examples that employ water as the continuously added starter, <CIT> describes an example of a so-called product-to-product CAOS process, in which the molecular weight of the initial starter compound and of the polyether product are substantially the same. However, product-to-product processes are inflexible because they do not allow to prepare polymers with molecular weights that are larger than the molecular weight of the initially added starter.

<CIT> also describes a series of CAOS processes with varying water contents in propylene oxide of <NUM> ppm, <NUM> ppm, <NUM> ppm, and <NUM> ppm but without providing detailed experimental information. <CIT> does not present a clear influence of the water content on the properties of the polyether products that also have rather high polydispersity indices of <NUM> and above.

According to <CIT> and <CIT>, the water content in the continuously added starter does not have to be controlled suggesting that the influence of water as continuously added starter is unclear. Moreover, according to <CIT>, the production of low molecular weight polyol from an initial starter with a hydroxyl number of <NUM> KOH/g to <NUM> mgKOH/mol with low DMC catalyst levels is possible without controlling the water content in the range of <NUM> to <NUM> ppm in the continuously added starter glycerin or other continuously added low molecular weight starters.

As explained above, water in alkylene oxides has infrequently been used as a continuously added starter Sc. In fact, water has not been used systematically as a continuously added starter. This is presumably because glycols are much better soluble in polyether polyols and can be applied at higher concentration than water. However, ethylene glycol, for example, is hazardous to human health. Moreover, it would be desirable to employ a continuously added starter that can be provided with a high purity.

It was therefore an object of the present invention to provide a method for the manufacture of polyethers with low unsaturation and good polydispersity indices, which is improved concerning the use of hazardous substances. It was a further object of the invention to provide a reliable method that is improved concerning the molecular weights of the polyether products that can be obtained, in particular from a given initial starter. It was a further object of the invention to provide a method that can be used with different build ratios, in particular with high build ratios.

Other and further objects, features and advantages of the present invention will become apparent more fully from the following description.

Some or all of these objects are achieved according to the invention by a method for the manufacture of a polyether diol product having a polyether hydroxyl number PolOH of from <NUM> to <NUM> KOH/g by reaction of an initial starter substance Si having two hydroxyl groups (initial starter Si) with one or more alkylene oxides in the presence of water and a double metal cyanide (DMC) catalyst, comprising the steps of.

With the expression "the amount of continuously added water is adjusted such that cH2O substiantially fulfills the equation" is meant that in equation (<NUM>) above, the term [(PolOH - A - B*StartOH)/C] can be from about <NUM>*cH2O to about <NUM>*cH2O. Hence, "cH2O substantially fulfills equation (<NUM>)" means that the value of cH2O can be up to about <NUM>% smaller or up to about <NUM>% larger than the ratio [(PolOH - A - B*StartOH)/C].

According to the invention, it has thus surprisingly been found that by adjusting the total amount of continuously added water as explained above, polyether diol products with low unsaturation and good polydispersity indices, in particular with polydispersity indices of <NUM> and below, can be obtained without the use of hazardous substances as continuously added starter. In particular, it is possible with the method according to the invention to prepare with good build ratios polyether diol products having hydroxyl numbers PolOH from initial starter compounds having hydroxyl numbers StartOH, wherein the ratio StartOH/PolOH is larger than <NUM>, for example from <NUM> to <NUM>. Moreover, the method reliably yields polyether diols, in particular also on an industrial scale.

Hydroxyl numbers given herein are determined according to ASTM D4274-<NUM>, met.

According to the present invention, the method comprises.

The initial starter substance Si having two hydroxyl groups is herein also referred to as initial starter Si. The starter mixture can optionally be stripped under vacuum. The vacuum stripping can occur with or without nitrogen and/or steam. This starter mixture is typically formed in a reactor. The portion of DMC catalyst and initial starter Si is effective to initiate polyoxyalkylation of the starter mixture once an alkylene oxide is introduced into the reactor.

The method of the invention requires two different types of starters: an initially charged starter substance Si having two hydroxyl groups and water that is continuously added. The initially charged starter substance Si is different from water.

Suitable initial starters Si to be used in accordance with the present invention include, for example, a polyether diol product having a hydroxyl number StartOH of from <NUM> to <NUM> KOH/g, advantageously from <NUM> to <NUM> KOH/g, preferably from <NUM> to <NUM> KOH/g, more preferably from <NUM> to <NUM> KOH/g.

Advantageously, StartOH is <NUM>*PolOH or larger, preferably from <NUM>*PolOH to <NUM>*PolOH, more preferably from <NUM>*PolOH to <NUM>*PolOH, most preferred from <NUM>*PolOH to <NUM>*PolOH.

When the initial starter Si of the starter mixture comprises a polyether diol, this polyether diol can be a known residual amount of the product left in the reactor from a prior batch of the same product. This polyether diol may be prepared from the same reactants as the final product prepared by the method of the invention, have the same functionality, molecular weight and hydroxyl number as the final product resulting from the method of the present invention, and thus be essentially the same as the final product prepared by the instantly claimed method. The skilled artisan would, however, recognize that it is not actually the same product as the final product since it was prepared in a different lot or reactor batch. As an example, after completion of the production of a batch of polyether diol product in a reactor by DMC catalysis, <NUM>% of the product is removed from the reactor. The remaining <NUM>% of the polyether diol product can be left in the reactor and used as the initial starter Si of the starter mixture of the present invention. It is also possible that the initial starter Si of the starter mixture can comprise a final polyether diol product that is stored in a finished goods storage vessel from a previous campaign which can be brought back into the reactor as the initial starter Si of the starter mixture.

The initial starter Si of the starter mixture can also comprise a final polyether diol product that has a similar molecular weight as the target product that was made using any alkoxylation catalyst known in the art, examples are basic catalysts (KOH or equivalent) and acid catalysts (Lewis acid or Bronsted acid induced catalysis), and which was refined to remove or neutralize the basic or acidic catalyst. The use of a basic catalyzed and subsequently neutralized polyether diol product is necessary, for example, when using this product as the initial starter Si for the initial or first production of the polyether diol product. Removal or neutralization of the basic catalyst from the final polyether diol product to be used as the initial starter Si is required, as those skilled in art will recognize, because even trace levels of base or alkalinity deactivates and/or inhibits the DMC catalyst present in the starter mixture. In all cases, when a polyether diol is used as the initial starter Si, the polyether diol acts as a reaction medium to provide the minimum starter charge required by the reactor configuration (e.g. cover agitator blade, fill recirculation loop, cover internal heating/cooling coils, etc.).

In one embodiment, the polyether diol which is used as the initial starter Si of the starter mixture has a hydroxyl number StartOH that is larger than the polyether hydroxyl number PolOH of the targeted final polyether diol product.

In another embodiment, where water concentration in the alkylene oxide is high the polyether diol used as the initial starter Si of the starter mixture does not substantially participate in the reaction. The minimization of the molecular weight growth of the initial starter Si of the starter mixture which comprises a polyether diol provides the opportunity to produce a final product with a low viscosity. It may also yield a narrow molecular weight distribution, in particular for higher molecular weight polyols.

In another embodiment, this initial starter Si of the starter mixture may comprise a polyether diol that contains DMC catalyst residuals. In another embodiment, the DMC catalyst residuals were previously exposed to alkylene oxide. In another embodiment, the DMC catalyst residuals of the polyether diol used as the initial starter Si of the starter mixture were previously exposed to alkylene oxide under reaction conditions ("pre-activated" catalyst).

The initial starter Si comprising a polyether diol can contain antioxidants and/or acids known to those skilled in the art. For example, suitable antioxidants for polyoxyalkylene polyols include sterically hindered phenolic compounds such as BHT (i.e. butylated hydroxytoluene), octadecyl <NUM>-(<NUM>,<NUM>-di-tert-butyl-<NUM>-hydroxyphenyl) propionate (i.e. Irganox <NUM>), <NUM>,<NUM>-dihydro-<NUM>,<NUM>,<NUM>,<NUM>-tetramethyl-<NUM>-(<NUM>,<NUM>,<NUM>-trimethyltridecyl)-<NUM>-<NUM>-benzopyran-<NUM>-ol (i.e. Irganox E-<NUM>), etc. Examples of suitable acids include any inorganic protic mineral acid or organic acid which is known to be suitable as described in the art. Phosphoric acid is an example of a suitable acid.

The initial starter Si which may comprise a polyether diol can be vacuum stripped, with or without steam and/or nitrogen, to remove any residual compounds introduced from the reaction or the raw materials including water. Stripping of the initial starter Si can occur either before or after the addition of the DMC catalyst. Vacuum stripping of the initial starter Si can occur with or without steam and/or nitrogen at ambient temperature, reaction temperature, or any value in between.

Optionally, the initial starter Si which may comprise a polyether diol can also be treated by inert gas stripping, in particular nitrogen gas stripping, which can occur at ambient pressure or by applying vacuum at ambient temperature, reaction temperature, or any value in between.

According to the method of the invention, the build ratio BR, defined as the mass of polyether diol product divided by the mass of initial starter Si in the starter mixture, is at least <NUM>. Advantageously, the build ratio is from <NUM> to <NUM>, preferably from <NUM> to <NUM>, more preferably from <NUM> to <NUM>, even more preferably from <NUM> to <NUM>, most preferred from <NUM> to <NUM>. However, the skilled person can conceive build ratios that are higher than <NUM>.

Suitable double metal cyanide catalysts for the present invention include any DMC catalysts known in the art. The well-known DMC catalysts are typically the reaction product of a water-soluble metal salt (e.g. zinc chloride) and a water-soluble metal cyanide salt (e.g. potassium hexacyanocobaltate). The preparation of DMC catalysts is described in various references, including, for example, <CIT>, <CIT>, <CIT>,<CIT>, <CIT> and<CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT> and <CIT>, <CIT>, or <CIT>.

Particular DMC catalysts that are preferred in some embodiments of the present invention are zinc hexacyanocobaltates. In one embodiment, the DMC catalysts are amorphous. The DMC catalyst includes an organic complexing agent. As taught in the preceding references, the complexing agent is needed for an active catalyst. Preferred complexing agents include water-soluble heteroatom-containing organic compounds that can complex with the DMC compound. In one embodiment, the preferred complexing agents are water soluble aliphatic alcohols. Tert-butyl alcohol is a preferred complexing agent for some embodiments. In addition to the organic complexing agent, the DMC catalyst may also include a polyether as is described in <CIT>.

Preferred DMC catalysts for use in accordance with one or more embodiments of the present method are the highly active DMC catalysts such as are described in <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT> and <CIT> and <CIT>, <CIT> or <CIT> or the ARCOL CATALYST <NUM> (DRY) ® catalyst from Covestro. High activity allows for the use of very low concentrations of the catalyst to be used. More specifically, the concentrations of catalyst required is typically low enough to overcome or eliminate any need to remove the catalyst from the finished polyether diol products formed in the method. In particular, the concentration of catalyst in the finished polyether diol product is typically in the range of from <NUM> ppm to <NUM> ppm, or from <NUM> ppm to <NUM> ppm, or from <NUM> ppm to <NUM> ppm.

The DMC catalyst can be added as a dry powder directly to the starter mixture, or dispersed in the initial starter Si and added to the starter mixture. The DMC catalyst added to the starter mixture can be the same as the DMC catalyst residual contained in the polyoxyalkylene polyol used as the initial starter Si of the starter mixture or can be different therefrom. Preferably, the DMC catalyst added to the starter mixture is the same as the DMC catalyst residual contained in the polyoxyalkylene polyol used as the initial starter Si of the starter mixture. The DMC catalyst added to the starter mixture can be un-activated or fresh catalyst, i.e. catalyst that has not previously been exposed to alkylene oxide, catalyst that has been exposed to alkylene oxide under non-reaction conditions (i.e. temperature < <NUM>); or "pre-activated" catalyst, i.e. catalyst that was previously exposed to alkylene oxide under reaction conditions (i.e. temperature ≥ <NUM>). The DMC catalyst residuals in the polyether diol initial starter Si of the starter mixture are considered "pre-activated" catalyst as this catalyst was exposed to alkylene oxides under reaction conditions during the making of the polyether diol initial starter Si of the starter mixture. The "pre-activated" catalyst in the polyether diol initial starter Si of the starter mixture is advantageous to the present invention to allow a rapid activation of the starter mixture when alkylene oxide is added. The combination of "pre-activated" catalyst from the polyether diol initial starter Si of the starter mixture and fresh or "pre-activated" catalyst added to the starter mixture also insures a good reaction (i.e. no rapid pressure increase or temperature fluctuations) when the continuously added water is added. The DMC catalyst added to the starter mixture can be the same as or different from the residual catalyst or "pre-activated" catalyst in the polyether diol initial starter Si of the starter mixture.

The DMC catalyst (which may be fresh catalyst or pre-activated catalyst) is typically added to the starter mixture. It can, however, also be split between the starter mixture and the continuously added starter or continuously added separately. Splitting the DMC catalyst provides a lower initial catalyst concentration in the starter mixture, and a more uniform catalyst concentration during the production of the polyether diol product.

In the method of the present invention, the DMC catalyst present in the starter mixture may be activated in the presence of alkylene oxide. Activation of the DMC catalyst present in the starter mixture may occur by optionally adding an activation amount of an alkylene oxide to the starter mixture provided in step a. The activation step is preferably conducted before steps b and c. The alkylene oxide for the activation of the starter mixture can be added all at once in the activation step to the initial starter Si and DMC catalyst mixture of step a wherein the pressure in the reactor system will increase rapidly, or the alkylene oxide can be slowly added, for example during the initial ramp-up of the alkylene oxide feed in step b wherein the pressure in the reactor system will increase slowly.

The activation of the DMC catalyst present in the starter mixture may be detected for example when the pressure decreases to half of the amount of the peak pressure detected in the case of the rapid addition of the alkylene oxide, or when the pressure begins to decrease and the reactor system begins to cool the reaction (indicating the presence of a reaction) in the case of slow addition of the alkylene oxide.

The amount of alkylene oxide added for activation is from <NUM> to <NUM> wt. %, preferably from <NUM> to <NUM> wt. %, based on the amount of the initial starter Si present in the starter mixture. As used herein, the amount of alkylene oxide necessary to activate the DMC catalyst present in the starter mixture of step a may be referred to as the "initial" or "activation" alkylene oxide. The alkylene oxide in the activation amount preferably has a water content below <NUM> ppm, preferably below <NUM> ppm, more preferably below <NUM> ppm.

According to a preferred embodiment, the method additionally comprises before steps b and c an activation step of adding an activation amount of an alkylene oxide having a water content below <NUM> ppm, preferably below <NUM> ppm, more preferably below <NUM> ppm, to the starter mixture to initiate the double metal cyanide catalyst.

When an activation step is present in the method according to the invention, the activation step advantageously has a duration of from <NUM> to <NUM> minutes, preferably from <NUM> to <NUM> minutes. When present, the activation step is advantageously conducted at a temperature from <NUM> to <NUM>, preferably from <NUM> to <NUM>, more preferably from <NUM> to <NUM>. When an activation step is present, the activation amount of alkylene oxide advantageously amounts to <NUM> wt. % to <NUM> wt. %, preferably <NUM> to <NUM> wt. %, based on the amount of initial starter Si.

The method of the invention additionally comprises the step b of continuously adding an alkylene oxide to the starter mixture after activation with the activation amount of alkylene oxide when an activation step is present or to the starter mixture of step a when an activation step is not present. This continuous addition may comprise starting and increasing the addition of alkylene oxide in a steady manner until the final target feed rate of alkylene oxide is reached. The ramp-up of the alkylene oxide feed(s) may take from <NUM> minutes to <NUM> hours before reaching the final target feed rate(s).

The total time of addition of the continuously added alkylene oxide in the method according to the invention may vary. Advantageously, the total time of addition of the continuously added alkylene oxide is from <NUM> to <NUM> hours, preferably from <NUM> to <NUM> hours, more preferably from <NUM> to <NUM> hours. The alkylene oxide can in particular also be added at an average rate of <NUM> to <NUM> wt. %, preferably <NUM> to <NUM> wt. %, of the total amount of alkylene oxide, per hour.

Different alkylene oxides may be used in the method according to the invention. Advantageously, the alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and mixtures thereof. Preferably, the alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, and mixtures thereof. More preferably, the alkylene oxide is propylene oxide.

In one or more embodiments of the present method, the quantity of the initial starter Si used depends on many factors, including, for example, the reactor dimensions, the identity of the initial starter Si, the hydroxyl number of the initial starter Si and of the target polyether diol product, and other factors such as the minimum quantity of initial starter Si needed to achieve proper mixing based on agitator and/or heat exchanger loop configuration. The amount of continuously added water is within the range of about <NUM> mole % to about <NUM> mole %, or from <NUM> mole % to <NUM> mole %, in particular for a build ratio of <NUM> to <NUM>, based on the total amount of hydroxyl-equivalent moles of initial starter Si and water, which may also be referred to as the total amount of starter substances (St). The total amount of starter substances (St) equals the sum of the amount of continuously added water plus the amount of initially charged initial starter Si. Thus, St = Sc +Si.

The alkylene oxide composition may also be varied during the initial polymerization of the initial starter Si and/or at some point during and/or after the addition of the continuously added water. This provides flexibility for controlling the distribution of alkylene oxides within the polyether diol product and allows some control of the primary versus secondary hydroxyl functionality of the polyether diol product, and thus, the relative reactivity of the final composition. In this way, it is possible to design the product to meet the reactivity and performance requirements of the intended applications such as polyurethane foams, sealants, adhesives and coatings.

The continuously added alkylene oxide and the continuously added water are advantageously added at a <MAT> wherein during addition of the water and the alkylene oxide the ratio R remains substantially constant or is variable, preferably is variable in the range from <NUM> to <NUM> ppm, preferably from <NUM> to <NUM> ppm.

The continuously added water and the continuously added alkylene oxide may be added separately to the starter mixture. The continuously added water and the continuously added alkylene oxide may also be intimately mixed before being added to the starter mixture. Mixing of the water and the alkylene oxide may occur outside or inside of a reaction vessel in which the polyether diol product is manufactured. By mixing the water and the alkylene oxide, a wet alkylene oxide is obtained. The wet alkylene oxide may have a water concentration of from <NUM> ppm to <NUM> ppm, based on the combined masses of the water and the alkylene oxide. The water concentration of the wet alkylene oxide may be varied or may be constant during addition of the wet alkylene oxide. Preferably, the water concentration of the wet alkylene oxide remains substantially constant. The water and the alkylene oxide may be mixed in a separate reactor to obtain the wet alkylene oxide. The water and the alkylene oxide may also be mixed using a static mixer device. For example, the water supply line may be connected to the alkylene oxide supply line via a static mixer device such that after the static mixer device, wet alkylene oxide is supplied to the reaction vessel in which the polyether diol product is manufactured.

According to a preferred embodiment, a monomer mixture comprising an alkylene oxide and water are added continuously to the starter mixture, wherein the water in the monomer mixture is at a concentration in the range from <NUM> to <NUM> ppm, preferably from <NUM> ppm to <NUM> ppm, based on the combined masses of the water and the alkylene oxide. The concentration of the water in the monomer mixture may be varied or may be constant during addition of the monomer mixture. According to an embodiment, the concentration is substantially constant during addition of the monomer mixture. According to another embodiment, the concentration is variable during addition of the monomer mixture, preferably is variable in the range from <NUM> to <NUM> ppm, more preferably from <NUM> to <NUM> ppm.

According to an embodiment, the ratio R or the concentration reduced to <NUM> to <NUM> ppm after <NUM> wt. % or more, preferably <NUM> wt. % or more, more preferably <NUM> wt. % or more of the alkylene oxide have been added. This may also be referred to as "non-CAOS end cap".

In an embodiment of the invention, a solvent may be included to reduce the process viscosity. This solvent may be introduced to the reactor with the starter mixture comprising the initial starter Si and the DMC catalyst. The solvent may or may not be removed from the polyether diol product. The solvent preferably does not have a proton that is active in DMC catalysis such as a proton from a hydroxyl group or a proton from an amine group.

The method according to the invention may be used to manufacture polyether diol products with different hydroxyl numbers. The polyether diol product manufactured with the method according to the invention has a polyether hydroxyl number PolOH of from <NUM> to <NUM> KOH/g. Advantageously, the polyether diol product has a polyether hydroxyl number PolOH from <NUM> to <NUM> KOH/g, preferably from <NUM> to <NUM> KOH/g, more preferably from <NUM> to <NUM> KOH/g, most preferably from <NUM> to <NUM> KOH/g.

The polyether diol product according to the invention has a polydispersity index PDI of <NUM> or less. Advantageously, the polydispersity index PDI is <NUM> and below, preferably <NUM> and below, more preferably from <NUM> to <NUM>.

In accordance with the present invention, the method may be carried out in a stainless steel reaction vessel (e.g. <NUM> Liter or larger) equipped with an electrically heated jacket and an internal coil that can be used for heating or cooling the reaction mixture. Steam, water or a combination of the two may be passed through the cooling coil to control the reaction temperature. Tempered water or a hot oil system may also be used to control the temperature. The reactor system preferably includes a mechanical agitator that may be equipped with a single agitating device such as a gate-type mixer or an anchor type mixer or other such devices known to those skilled in the art. The agitator may also be equipped with one or multiple mixers such as pitched blade impeller, Rushton-type impeller, flat blade, curved blade, tilted blade or other such devices known to those skilled in the art. The various types of blades may be used individually or in combination with one another. It is not necessary for the agitator blade to directly agitate the liquid surface at all times, particularly during the addition of the alkylene oxide. When the agitator directly agitates the liquid surface of the reaction mixture in the production of a polyether diol product with a low hydroxyl number, this can result in the product having a lower polydispersity. The agitator speed may be constant or varied during the batch. The reactor internals may include baffles. The reactor may also be equipped with a recirculation pump loop that withdraws the reaction mixture from the bottom portion of the reactor and pumps the reaction mixture back into the reactor, or example through a dip tube or spray nozzle in the upper part of the reactor or through a dip tube or sparge ring at the bottom part of the reactor. The recirculation loop may include a heat exchanger for temperature control or may include a static mixing device. In one embodiment, the reactor can be a loop reactor equipped with a jet mixer. The loop reactor preferably comprises a heat exchanger for temperature control. The loop reactor may comprise a static mixing device. Loop reactors are described for example in <CIT> and in <CIT>. The reactor and associated metering and monitoring equipment are preferably connected to a digital process control system.

The reactor system preferably includes an alkylene oxide dosing system for one or more alkylene oxide feeds (e.g. propylene and/or ethylene oxide). When more than one alkylene oxide is used, the alkylene oxides may be introduced to the reactor together or separately. They may be mixed and added together, or they may be stored separately and mixed using a static mixing device before being introduced to the reactor. The alkylene oxides may be introduced into the headspace of the reactor through a dip tube or spray nozzle or into the liquid phase in the reactor through a dip tube or sparge ring. The mixing impellers may be optimized to match the location of alkylene oxide addition to provide a high shear / mixing zone near the alkylene oxide injection location. The alkylene oxides may also be introduced to the recirculation line directly orvia a static mixing device. In one embodiment that employs a loop reactor, the alkylene oxides may also be introduced to the recirculation line of the loop reactor.

The reactor system preferably includes a dosing system for the continuously added water. The continuously added water may be introduced into the headspace of the reactor through a dip tube or spray nozzle or into the liquid phase in the reactor through a dip tube or sparge ring. The mixing impellers may be optimized to match the location of the continuously added water addition point to provide a high shear / mixing zone near the continuously added water injection location. The continuously added water can also be introduced to the recirculation line directly or via a static mixing device. The continuously added water may also be premixed with the alkylene oxide yielding wet alkylene oxide and the wet alkylene oxide is then introduced to the reactor directly via a dip tube or sparge ring or via a static mixing device. In one embodiment that employs a loop reactor, the water may also be introduced to the recirculation line of the loop reactor.

The finished polyether diol product of the present invention containing residual DMC catalysts may be vacuum stripped with steam and/or nitrogen to remove any residual compounds introduced from the reaction or the raw materials. Advantageously, the polyether diol product contains the DMC catalyst at a concentration of less than about <NUM> ppm, preferably less than about <NUM> ppm, more preferably less than about <NUM> ppm.

The finished polyether diol product may also be inhibited with antioxidants known to the skilled artisan for polyether polyols. Examples of suitable antioxidants for polyoxyalkylene polyols include sterically hindered phenolic compounds such as BHT (i.e. butylated hydroxytoluene), octadecyl <NUM>-(<NUM>,<NUM>-di-tert-butyl-<NUM>-hydroxyphenyl) propionate (i.e. Irganox <NUM>), <NUM>,<NUM>-dihydro-<NUM>,<NUM>,<NUM>,<NUM>-tetramethyl-<NUM>-(<NUM>,<NUM>,<NUM>-trimethyltridecyl)-<NUM>-<NUM>-benzopyran-<NUM>-ol (i.e. Irganox E-<NUM>), or other equivalent antioxidants or inhibitors.

The finished polyether diol product may also be acidified with an acid. Advantageously, an acid is added to the polyether diol product after all of the alkylene oxide has been added to adjust the pH to a value below <NUM>, preferably to a value of <NUM> to <NUM>, more preferably from <NUM> to <NUM>. The pH value is advantageously determined by preparing a solution by dissolving <NUM> of the polyether diol product in <NUM> of a mixture of isopropanol : water at a weight ratio of <NUM>:<NUM> and determining the pH value using a potentiometric pH meter. The acid may be an organic acid or an inorganic acid which is known to be suitable as described in the art, preferably an inorganic acid, more preferably phosphoric acid. The acid may be added as a solution in a solvent, preferably as an aqueous solution. The acid may be added at a concentration of <NUM> to <NUM> ppm, preferably <NUM> to <NUM> ppm, based on the finished polyether diol.

The finished polyether diol product is preferably inhibited with an antioxidant prior to stripping, with or without steam and/or nitrogen. Additional inhibitor may be added after the stripping, with or without steam and/or nitrogen, and any acid addition, if required, is preferably added after the stripping, with or without steam and/or nitrogen. The final inhibitor and/or acid may be added directly to the stripping vessel, or to the storage vessel, or may be continuously added to the product in the transfer line between the stripping vessel and the storage vessel. Alternatively, the polyether diol product may be stored with only antioxidant and any required acid may be added to the storage vessel prior to shipment or to the shipping container, either directly to the container or added continuously to the transfer line between the storage vessel and the shipping container or prior to the final product use.

A double metal cyanide (DMC) catalyst according to <CIT>, or <CIT>, <CIT> or <CIT> were employed.

The propylene oxide was obtained from PCC Rokita SA and had a purity of <NUM>% and a water content of <NUM> ppm or less.

Hydroxyl numbers were measured according to ASTM D4274-<NUM>, met.

Number average molecular weight Mn and weight average molecular weight Mw were measured by gel permeation chromatography (GPC). GPC was performed according to DIN <NUM>-<NUM>: "Gel permeation chromatography, part <NUM> - tetrahydrofuran as eluent" using an Agilent Technologies <NUM> gel permeation chromatography system. The following data processing device was used: Cirrus GPC offline ver. The following cross-linked polystyrene columns were used: <NUM> x Plgel <NUM> Mixed -E, 300x7,<NUM>, Guard <NUM>, <NUM> x <NUM>,<NUM>. Temperature: <NUM> ° C, detector: RID, Solvent: Tetrohydrofuran, Flow rate <NUM> / min. As standard sample for creating the calibration curve, Polystyrene standards (SPSS) were used. The polydispersity index (PDI) was calculated as PDI=Mw/Mn.

Unsaturation of the polyethers was measured according to ASTM D4671-<NUM> met.

The water content in the propylene oxide was measured according to the method PN-ISO <NUM>, which is a Karl Fischer method, on a compact titrator for coulometric water determination (model: <NUM> Coulometer Metrohm with generator electrode with diaphragm). Catholyte for coulometric Karl Fischer titration (methanol-based) was HYDRANAL™ - Coulomat CG. Anolyte for coulometric Karl Fischer titration (methanol-based), for cells with and without diaphragm was HYDRANAL™ - Coulomat AG. For sampling propylen oxide, Neotecha Sapro system was applied Together with Gas tight syringes (<NUM> series syringes by Hamilton): <NUM>, <NUM>, and <NUM>.

Viscosity was measured according to ASTM D4878-<NUM>, test A.

General synthetic procedure is described below. All syntheses described in the synthesis examples below were carried out in the same fashion, the only process variables were: type of initial starter (Si), with properties listed in Table <NUM>; DMC catalyst concentration; continuously added amount of water (cH2O) and build ratio (BR).

A reactor was fed with the appropriate starter Si (see Table <NUM> and <NUM>) and with DMC catalyst at a concentration ranging between <NUM> and <NUM> ppm, based on the final product (the concentration was adjusted in order to maintain the comparable process kinetics). The resulting mixture (the "starter mixture") was heated under protective gas atmosphere (e.g. nitrogen) with stirring, and finally nitrogen flow was maintained under vacuum in order to reduce the oxygen content below the concentration for safe operation. Then the temperature of the mixture was increased above <NUM> but lower than <NUM> and dry propylene oxide in the amount of up to <NUM> wt% of the amount of Si starter corresponding to <NUM> to <NUM> wt. %, based one the total amount of propylene oxide adde, was continuously added until an accelerated pressure loss was observed in the reactor (activation step). This accelerated pressure loss indicated that the catalyst was activated. After catalyst activation has been observed, the remainder of the <NUM> wt. % of the dry propylene oxide was fed, in such a way that the reaction temperature was kept below <NUM>.

Then the continuous feed of water and propylene oxide in the form of wet propylene oxide were started, with a total water concentration (cH2O) and build ratio (BR) as defined in Table <NUM>, and continued over a duration of <NUM>-<NUM> hours with increasing ramping of the feed rate, where the final feeding rate was higher than the initial feeding rate. During the feeding of the mixture of propylene oxide and water the pressure in the reactor was kept below <NUM> bar by adjusting the feeding rate of propylene oxide, and the pressure was decreased by increasing the feeding time of propylene oxide. Unless written otherwise in Table <NUM>, the concentration of water in propylene oxide was constant during the whole feed process. After addition of all the wet propylene oxide, the resulting mixture was stirred for <NUM> hours above <NUM>. Then the mixture was degassed, optionally under vacuum for at least <NUM> hour. Then, the mixture was cooled below <NUM> to <NUM>. Then at least <NUM> wt% of demineralized water were fed or alternatively between <NUM> and <NUM> ppm of phosphoric acid were fed to deactivate the catalyst and treat possible by-products, and the resulting mixture was then stirred for at least <NUM> hour. Then, water and the volatile constituents were distilled off at a temperature below <NUM>, with stirring, and finally the reactor was purged with nitrogen under vacuum followed by cooling the mixture to <NUM>.

The properties of obtained polyols are given in Table <NUM>.

Explanations to Table <NUM>: PO = propylene oxide; a Si - Si starter as listed in Table <NUM>; b H<NUM>O - total water concentration in PO (cH2O) [ppm], calculated as {<NUM>*(total mass of continuously added water in g)/[(total mass of continuously added water in g) + (total mass of continuously added alkylene oxide in g)]}; c BR-- Build ratio (Mass of the Si initiator to the total mass of the batch); d - water post treatment; e - H<NUM>PO<NUM> post treatment; f - catalyst concentration <NUM> ppm; g-the first <NUM> wt. % of wet PO had a water concentration of 1096ppm, the second <NUM> wt. % had a water concentration of <NUM> ppm; h-- Activated starter containing <NUM> ppm of active DMC catalyst.

Explanations to Table <NUM>: a PolOH - hydroxyl number of the polyether diol product [mg KOH/g]; b StartOH - initiator OH number [mg KOH/g]; c MW - molecular weight calculated as <NUM>*<NUM>/(PolOH); d Visc - Viscosity at <NUM>, see above for details of the measurement [mPas]; e Unsat - Unsaturation [mMol/kg]; f PDI - Polydispersity.

Claim 1:
A method for the manufacture of a polyether diol product having a polyether hydroxyl number PolOH of from <NUM> to <NUM> KOH/g by reaction of an initial starter substance Si having two hydroxyl groups (initial starter Si) with one or more alkylene oxides in the presence of water and a double metal cyanide (DMC) catalyst, comprising the steps of
a. providing a starter mixture, comprising the initial starter Si and the DMC catalyst,
b. continuously adding an alkylene oxide to the starter mixture,
c. continuously adding water to the starter mixture,
wherein
i. steps b and c either start simultaneously or step b starts before step c, preferably steps b and c start simultaneously,
ii. the initial starter Si has a starter hydroxyl number StartOH of from <NUM> to <NUM> KOH/g,
iii. the water is added in such an amount that the concentration of the water, based on the total masses of the water and the alkylene oxide, is from <NUM> ppm to <NUM> ppm,
iv. the build ratio BR, defined as the mass of polyether diol product divided by the mass of initial starter Si in the starter mixture, is at least <NUM>,
v. the polydispersity index PDI of the polyether diol product is <NUM> or less, and PDI is calculated as Mw/Mn, wherein Mw and Mn are determined according to the method outlined in the description
vi. StartOH is <NUM>*PolOH or larger,
vii. StartOH and PolOH are determined by ASTM D4274-<NUM>, met. D,
viii. the amount of the continuously added water is adjusted such that cH2O, calculated as {<NUM>*(total mass of continuously added water in g)/[(total mass of continuously added water in g) + (total mass of continuously added alkylene oxide in g)]} fulfills the equation <MAT> wherein
A is in mg KOH/g and is calculated as
A = <NUM>*BR + <NUM>,
B is calculated as
B = <NUM>*(BR)<NUM> - <NUM>*BR + <NUM>,
C is in mg KOH/g and is calculated as
C = -<NUM>*(BR)<NUM> + <NUM>*BR + <NUM>, and
ix. the ratio of PolOH/StartOH is in the range between <NUM> and <NUM>/BR.