Polycarbonate-based polyols

Abstract

A method of making a poly (ether-carbonate) polyol comprises a polymerization stage comprising polymerizing carbon dioxide and at least one alkylene oxide with a starter in the presence of a double metal cyanide polymerization catalyst and a catalyst promoter free of halogen anions and cyanide ions. The catalyst promoter is separated from the double metal cyanide polymerization catalyst.

Description

[0001] This application is a divisional application of Chinese Patent Application No. 201780068199.3 (Filing Date: November 9, 2017, Inventor Name: Polycarbonate-based polyols). TECHNICAL FIELD

[0002] Embodiments relate to polycarbonate-based polyols, methods of making such polycarbonate-based polyols, and polyurethane products made using such polycarbonate-based polyols. BACKGROUND

[0003] Polycarbonate-based polyols and efficient methods of making such polycarbonate-based polyols are of interest in fields including the field of polyurethane-based polymers. For example, polycarbonate-based polyols can be poly(ether-carbonate) polyols produced using one or more alkylene oxides and carbon dioxide, for example, to make the resulting polyols less expensive and more environmentally friendly. U.S. Patent No. 9,080,010 discusses a process for making polyethercarbonate polyols by catalytic copolymerization of carbon dioxide with an alkylene oxide in the presence of one or more H-functional starter substances, by means of a double metal cyanide (DMC) catalyst and in the presence of a metal salt, such as a metal halide or metal carboxylate. However, such processes disclosed therein can be expensive, for example, due to high operating pressures, and require special operating equipment. Thus, improvements are sought. SUMMARY

[0004] Embodiments can be realized by providing a process for making a poly(ether-carbonate) polyol, comprising a polymerization stage including polymerizing carbon dioxide and at least one alkylene oxide with a starter in the presence of a double metal cyanide polymerization catalyst and a catalyst promoter that is free of halide anions and cyanide ions. The catalyst promoter is separate from the double metal cyanide polymerization catalyst. BRIEF DESCRIPTION OF DRAWINGS

[0005] Figure 1 A process flow rate diagram is illustrated and exemplified for an exemplary process for making a poly(ether-carbonate) polyol. DETAILED DESCRIPTION

[0006] Polycarbonate-based polyols may use carbon dioxide and / or carbon dioxide and alkylene oxides (such as propylene oxide, ethylene oxide, butane oxide, and / or combinations thereof). Carbon dioxide may be at least partially in the gas phase (e.g., because the reaction can occur at relatively low pressures), and alkylene oxides may be at least in the liquid phase (may include at least a portion in the gas phase, but less than a certain amount of carbon dioxide). According to exemplary embodiments, polycarbonate-based polyols may be used to prepare polyurethane products using isocyanate components and isocyanate reactive components. For example, polycarbonate-based polyols may be included as the sole polyol in the isocyanate reactive component or as one polyol in a blend of two or more polyols. Exemplary polyurethane products include polyurethane foams, polyurethane elastomers, polyurethane coatings, polyurethane sealants, polyurethane adhesives, and polyurethane composites. According to embodiments, polycarbonate-based polyols are prepared using a bimetallic cyanide (DMC) catalyst and a catalyst promoter in at least two stages (a preliminary stage and a polymerization stage). The preliminary stage can be used for reactor start-up before the polymerization stage and / or for adding components without the presence of polymerization conditions before the start of the polymerization stage.

[0007] The exemplary embodiments enable the use of DMC catalysts as polymerization catalysts for the production of poly(ether-carbonate) polyols without relying on specialized polymerization catalyst structures, such as the bimetallic catalyst complexes discussed in International Publication No. WO 2009 / 130470 or the catalyst formulas discussed in International Publication No. WO 2016 / 012785. For example, in the exemplary embodiments, the DMC catalyst can be used as the sole polymerization catalyst for the production of poly(ether-carbonate) polyols. It is believed that catalyst promoters are not used directly as polymerization catalysts, but rather to enhance the performance of the DMC polymerization catalyst when forming poly(ether-carbonate) polyols.

[0008] The exemplary embodiments avoid the use of specific polymerization systems, including specialized catalysts (having a metal complex comprising a permanent ligand group and at least one ligand as a polymerization initiator) used with specialized chain transfer agents (having multiple sites capable of initiating copolymerization of epoxides and CO2), for example, as discussed in International Publication WO 2010 / 028362. For example, referring to the disclosure in WO 2010 / 028362, the exemplary embodiments avoid the use of structures having a YA-(Y) structure. n A specialized chain transfer agent, wherein: each -Y group is independently a functional group capable of initiating chain growth of an epoxide CO2 copolymer, and each Y group may be the same or different; -A- is a covalent or multivalent moiety; and n is an integer between 1 and 10 (inclusive). However, each Y group may be independently selected from the group consisting of: -OH, -C(O)OH, -C(OR)OH, -C(O ...y )0H、-0C(R y )0H、-NHR y -NHC(O)R y -NHC=NR y ;-NR y C = NH; -NR y C(NR y 2) = NH; -NHC(NR) y 2) = NR y ;-NHC(0)0R y -NHC(O)NR y 2;-C(O)NHR y -C(S)NHR y -OC(O)NHR y -OC(S)NHR y -SH, -C(O)SH, -B(OR) y )OH、-P(O) Ω (R y ) δ (OR y ) c (OX / H、-OP(O) Ω (R y ) δ (OR y ) c (O) ￡ / H、-N(R y )OH、-ON(R y H, =NOH, =NN(R) y H, where R y Each time it appears independently as -H, or an optionally substituted group selected from the group consisting of: C 1-2 oAliphatic, C 1-2 o heteroaliphatic, 3 to 12-membered heterocyclic, and 6 to 12-membered aryl, a and b are each independently 0 or 1, c is 0, 1 or 2, d is 0 or 1, and the sum of a, b and c is 1 or 2, and wherein the acidic hydrogen atom bonded in any of the above functional groups can be replaced by a metal atom or an organic cation.

[0009] Regarding the preparation of poly(ether-carbonate) polyols, DMC catalysts typically strongly promote propylene oxide polymerization and are thus used to produce high-yield poly(propylene oxide) polyols. DMC catalysts can also be used in the presence of other alkyl oxides, such as ethylene oxide and / or butane oxide. Furthermore, it has been found that very low concentrations of DMC catalyst complexes (e.g., less than 25 ppm of DMC catalyst by weight of the product) provide commercially acceptable polymerization rates, particularly when the hydroxyl equivalent of the polyether product is 800 or greater. The ability to perform polymerization using very low catalyst levels can lead to a very significant reduction in catalyst costs. However, one problem with DMC catalysts is that they are sometimes slowly activated, completely inactive, or deactivated in the presence of certain materials. For example, DMC catalysts can be deactivated in the presence of carbon dioxide. Therefore, the stage of introducing carbon dioxide into the polyol can result in low yields, and such poly(ether-carbonate) polyol products can be very difficult to produce on an industrial scale. Polymerization occurs little or no before the catalyst becomes activated or after it has deactivated, thus these long activation and deactivation times have a direct negative impact on the productivity of the process. What is needed is an economical and efficient way to produce these polycarbonate-based polyols.

[0010] The preparation of polyethers using DMC catalysts includes a catalyst activation period. During this period, the DMC catalyst is considered to transform in situ from an inactive form to a highly active form that allows for the rapid polymerization of epoxides as long as it remains active. This catalyst activation period is typically an indeterminate timeframe following the initial introduction of the epoxide (e.g., propylene oxide) into the reactor. Typically, a small amount of epoxide is introduced at the start of the polymerization process, and then the process is allowed to proceed until the catalyst has become activated (as indicated, for example, by a decrease in reactor pressure due to the initial epoxide load being consumed), before continuing the epoxide feed.

[0011] In the polymerization stage, alkyl oxides and carbon dioxide are added continuously or stepwise in a continuous or semi-batch operation. The preliminary stage may be carried out in the presence of an initiator (such as a low molecular weight initiator polyol) including a monohydric alcohol initiator and / or a polyhydric alcohol initiator, and may include heating the catalyst with or without alkyl oxides and / or carbon dioxide. The catalyst may be activated during the preliminary stage or the polymerization stage, for example, when propylene oxide is added to the reactor. For instance, in a semi-batch operation, the catalyst activation stage may be carried out at least during the preliminary stage and before the polymerization stage, and may optionally be performed in the reactor with or without carbon dioxide. In a continuous operation, catalyst activation may be carried out at least simultaneously with polymerization, as new, unactivated catalyst, alkyl oxide, carbon dioxide, and initiator are continuously introduced into the reactor. During the catalyst activation stage, the recognized catalyst (such as a DMC catalyst) is converted in situ from a deactivated form to a highly active form that rapidly polymerizes carbon dioxide and alkyl oxides. According to exemplary embodiments, despite the presence of carbon dioxide, the polymerization reaction can be continued by an activation step in the presence of low molecular weight polyols and epoxides using an unactivated catalyst.

[0012] For example, during semi-batch or continuous operation, the catalyst activation period may be carried out at a first temperature, and at least a portion of the polymerization stage may be performed at a second temperature. The first temperature for catalyst activation may be higher or lower than the second temperature for the polymerization reaction. For example, the catalyst activation period may be carried out during an initial stage, which includes a heating or cooling stage. The first temperature may be equal to or greater than 50°C, equal to or greater than 120°C, and / or equal to or greater than 150°C. The second temperature may be equal to or greater than 50°C. Both the first and second temperatures may be below 165°C. For example, the second temperature may be in the range of 50°C to 165°C (e.g., 65°C to 155°C, 80°C to 150°C, and / or 90°C to 140°C). The difference between the first and second temperatures may be at least 10°C, at least 20°C, at least 30°C, at least 40°C, and / or at least 50°C. Optionally, the first and second temperatures may be the same temperature.

[0013] According to exemplary embodiments, the formation of polycarbonate-based polyols can be observed under mild operating conditions in the presence of a DMC catalyst and a catalyst promoter. Exemplary DMC catalysts include zinc hexacyanocobaltate catalyst complexes. For example, the mild operating conditions imply that the method can be carried out in conventional low-pressure polyol production equipment, eliminating the need for dedicated equipment for high-pressure and / or high-temperature operations. For example, polycarbonate-based polyols with a carbonate content of 0.1 wt% to 25 wt% can be prepared using the method according to exemplary embodiments in a conventional reactor at a high reaction rate with high selectivity.

[0014] For at least one and / or all stages, exemplary pressure operating conditions for forming polycarbonate-based polyols include pressures in the range of 40 psig to 750 psig (e.g., 80 psig to 150 psig and / or 100 psig to 140 psig). Other exemplary pressures include 0.4 MPa to 5.3 MPa (e.g., 0.7 MPa to 1.1 MPa and / or 0.8 MPa to 0.9 MPa). During the catalyst activation stage, the pressure may range from 0 psig to a maximum of 750 psig before the addition of the epoxide. Under continuous operating conditions, the reactor pressure remains constant under controlled pressures of a fixed operating method, typically corresponding to pressures between 20 psig and 150 psig.

[0015] The resulting polycarbonate-based polyols, such as poly(ether-carbonate) polyols, may have a nominal hydroxyl functionality of 2 to 8 (e.g., 2 to 6 and / or 2 to 4). The hydroxyl equivalent of the polycarbonate-based polyols, such as poly(ether-carbonate) polyols, may be 150 to 4000 g / mol equivalent (e.g., 200 to 2000 g / mol equivalent and / or 500 to 1500 g / mol equivalent).

[0016] Method phase

[0017] Polyols can be prepared using batch, semi-batch, and / or continuous methods. For example, semi-batch or continuous initiator addition (i.e., CAOS) methods can be used. For instance, DMC is considered a more efficient catalyst compared to KOH. Using DMC catalysts allows for the addition of low molecular weight initiators to high molecular weight supported polyols, significantly reducing byproduct formation and volatile organic compound (VOC) formation, and providing a reduction in total energy consumption.

[0018] The polymerization stage in the formation of polycarbonate-based polyols can be carried out in the presence of a DMC catalyst and a catalyst promoter, and may exclude any other polyol polymerization catalysts, such as potassium hydroxide. This is industrially advantageous, for example because the use of a DMC catalyst, along with the important advantage of a catalyst promoter, allows catalyst residues to remain in the product (e.g., because it is present at a very low concentration compared to other catalysts such as potassium hydroxide). This avoids the costly steps of neutralizing and removing polymerization catalysts such as potassium hydroxide. The polymerization stage involves continuously exposing the reaction mixture to polymerization conditions in the presence of a DMC catalyst and a catalyst promoter to polymerize most or all of the remaining oxides. In this step, the amount of unreacted oxides can be reduced to, for example, less than 2 wt%, less than 1 wt%, and / or less than 0.5 wt% by total weight of the mixture of one or more co-feeds.

[0019] During the polymerization stage, carbon dioxide and / or alkyl oxidants are fed into the reaction, and optionally a catalyst and / or catalyst promoter may also be added. Carbon dioxide and alkyl oxidants may be fed together or separately. For example, during the polymerization stage, a mixed feed of carbon dioxide and alkyl oxidants may be fed into the reaction intermittently (e.g., at predetermined intervals) or continuously (e.g., over a predetermined amount of time). In another example, carbon dioxide may be fed into the reactor intermittently (e.g., at predetermined intervals) or continuously (e.g., over a predetermined amount of time). Additionally, independently, alkyl oxidants fed separately during the polymerization stage may be added to the reaction intermittently (e.g., at predetermined intervals) or continuously (e.g., over a predetermined amount of time). In an exemplary embodiment, carbon dioxide may be fed into the reactor intermittently (e.g., at predetermined intervals based on reactor pressure), and alkyl oxidants (such as propylene oxide) may be fed continuously into the reactor. Carbon dioxide may be added continuously after the addition of alkyl oxidants has been stopped, or optionally, alkyl oxidants may be added continuously after the addition of carbon dioxide. Subsequently, the resulting reaction forms a poly(ether-carbonate) polyol having a backbone comprising both diethyl ether groups and carbonate groups. The poly(ether-carbonate) polyol may include primary hydroxyl groups and / or secondary hydroxyl groups.

[0020] The polymerization stage may include more than one digestion stage, wherein different or the same feed rates of carbon dioxide and / or epoxides may be used between each digestion stage relative to another digestion stage. In an exemplary embodiment, each digestion stage may begin after the addition of carbon dioxide and / or epoxides has been stopped, such that the reaction mixture is digested during the stage. In an exemplary embodiment, one or more digestion stages may include a continuous feed of epoxides and an intermittent feed of carbon dioxide prior to each digestion stage. For example, the intermittent feed may be varied such that a higher carbon dioxide feed rate may be used before a first continuous digestion stage and a relatively lower feed rate may be used before subsequent digestion stages, or a lower carbon dioxide feed rate may be used for the first continuous digestion stage and a relatively higher feed rate may be used during subsequent digestion stages.

[0021] Carbon dioxide and / or alkyl oxidants (either individually or as a co-feed mixture) may be added continuously or intermittently under polymerization conditions during the polymerization phase to control the internal pressure of the reactor and to keep the level of unreacted oxides in the reaction vessel at a reasonable level. For example, carbon dioxide may be fed on demand during the polymerization phase by introducing the actual amount of carbon dioxide consumed to create a constant reactor pressure during this phase. Each intermittent addition of carbon dioxide may correspond to the start of the digestion phase, such that the digestion phase begins when the carbon dioxide feed is stopped. In such exemplary embodiments, alkyl oxidants may be fed into the reactor at a continuous feed rate, such that a decrease in reactor pressure is attributable to the consumption of carbon dioxide.

[0022] The epoxide added to the process can be a single epoxide, a mixture of epoxides, or a single oxide or mixture of oxides fed during a portion of the semi-batch process followed by different single oxides or mixtures of different oxides fed during different stages of the process. In this way, any combination of single or multiple epoxides can be added to the semi-batch process.

[0023] For example, a co-feed mixture of carbon dioxide and epoxide comprises 0.5 wt% to 43.0 wt% carbon dioxide and 57.0 wt% to 99.5 wt% epoxide (based on the total weight of the co-feed mixture or, as otherwise described, on the total weight of carbon dioxide and epoxide used to form the polyol), which is polymerized in the presence of a catalyst, a catalyst promoter, and an initiator. In exemplary embodiments, the amount of carbon dioxide incorporated into the poly(ether-carbonate) polyol may be 1 wt% to 30 wt%, 1 wt% to 25 wt%, 1 wt% to 20 wt%, 1 wt% to 15 wt%, 2 wt% to 15 wt%, 3 wt% to 15 wt%, 3 wt% to 12 wt%, etc., with the remainder being epoxide.

[0024] In exemplary embodiments, the alkylene oxide contains 86 wt% to 100 wt% 1,2-propylene oxide, 0 to 12 wt% ethylene oxide, and 0 to 2 wt% other copolymerizable monomers. For example, the amount of carbon dioxide relative to the alkylene oxide may vary and / or the alkylene oxide used may vary. During the polymerization stage, the corresponding co-feed mixture is introduced into the reaction under polymerization conditions, and the co-feed mixture is fed continuously or intermittently and / or at an increasing rate, decreasing rate, or constant rate for a period of time. In exemplary embodiments, the co-feed mixture comprises a majority of the alkylene oxide (e.g., at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 75 wt%, at least 79 wt%, etc.), with the remainder being carbon dioxide. For example, the molar ratio of carbon dioxide to alkylene oxide in the co-feed mixture may be from 1:1 to less than 1:200 (e.g., 1:1 to 1:100, 1:8 to 1:17, 1.0:1.3 to 1.0:9.0, etc.).

[0025] According to an exemplary embodiment using a semi-batch polymerization method, after a preliminary stage, at least carbon dioxide and alkylene oxide are charged into the reaction vessel in the presence of a DMC catalyst, a catalyst promoter, and an initiator, and then heated to a second temperature (i.e., the polymerization temperature) until the desired molecular weight is obtained. One manner to perform batch polymerization is to combine the DMC catalyst, catalyst promoter, and initiator (optionally in the presence of a polyether with a hydroxyl equivalent higher than that of the polymerized product) at a first temperature during the preliminary stage. Carbon dioxide and / or alkylene oxide are then added, and the resulting mixture is subjected to polymerization conditions. Additional DMC catalyst and / or catalyst promoter may be added during the addition of carbon dioxide and / or alkylene oxide.

[0026] In an exemplary semi-batch process, the DMC catalyst, catalyst promoter, and initiator are combined before, after, or during the polymerization stage. A portion of the carbon dioxide and alkylene oxide is introduced into the reaction vessel (e.g., independently, continuously or batchily) and the contents of the vessel are heated (if necessary) to the polymerization temperature. When the DMC catalyst has become activated (typically indicated by a drop in internal reactor pressure), more carbon dioxide and / or alkylene oxide can be fed into the reactor under polymerization conditions. The feeding of carbon dioxide and / or alkylene oxide continues until a sufficient amount has been consumed to reach the target product molecular weight. Additional DMC catalyst and / or catalyst promoter may be added during the addition of carbon dioxide and / or alkylene oxide. In the semi-batch process, the full amount of initiator used may be added at the beginning of the method or optionally during the polymerization stage. After the feeding is complete, the remaining carbon dioxide may be vented. Optionally, the reaction mixture may be boiled at the polymerization temperature in an attempt to consume at least some of the remaining alkylene oxide and / or carbon dioxide. For example, batch and semi-batch methods are suitable for producing poly(ether-carbonate) polyols with a hydroxyl equivalent of up to 1000 from initiators with a hydroxyl equivalent of 30 to 150. Batch and semi-batch methods can also be used to prepare polyethers with higher hydroxyl equivalents. The poly(ether-carbonate) polyols can be diols or triols.

[0027] In exemplary continuous polymerization methods, carbon dioxide and / or alkylene oxides may be continuously added during the polymerization phase, and the product may be continuously removed. For example, the alkylene oxide feed may be continuous, while the carbon dioxide feed may be intermittent. Generally, the continuous process is carried out by establishing a steady-state concentration of the polymerization product in a continuous reactor, such as a loop reactor, tubular or plug flow reactor, or continuous stirred tank reactor, within the operable capacity of the polymerization equipment, including the DMC catalyst, catalyst promoter, initiator, carbon dioxide, and alkylene oxide, under polymerization conditions. The "polymerization product" is a mixture of polyethers and / or poly(ether-carbonates) with a molecular weight greater than that of the initiator and at most the molecular weight of the desired product. Additional DMC catalyst, catalyst promoter, initiator, carbon dioxide, and / or alkylene oxide may be continuously added to the reactor, e.g., as a single stream, as a separate component, or in various sub-combinations. The product stream is continuously withdrawn from the reactor. The rates of one or more additional streams and the product stream are selected to maintain steady-state conditions in the reactor (within the equipment capacity) and to produce a product with the desired molecular weight. The product stream drawn from the continuous reactor can be boiled for a period of time to reduce the consumption of unreacted epoxides in the stream to a low level. For example, the continuous process is particularly suitable for producing poly(ether-carbonate) products with a hydroxyl equivalent of 150 to 5000 (e.g., 350 to 2500 and / or 500 to 2000). The poly(ether-carbonate) product can be a diol or a triol.

[0028] During continuous process startup, a mixture formed by optionally combining the DMC catalyst, catalyst promoter, and initial polymerization initiator in the presence of carbon dioxide may undergo a preliminary heating step as previously described before contact with the epoxide (e.g., during the initial stage). In the continuous process, the initial polymerization initiator may have a lower molecular weight, a higher molecular weight, or the same molecular weight as the final product. The initiator may optionally be compositionally identical to the intended final product.

[0029] Polymerization reactions can be carried out in any type of vessel suitable for the pressures and temperatures encountered. In continuous or semi-continuous processes, the vessel should have one or more inlets through which carbon dioxide and alkyl oxides and additional initiator compounds are introduced during the reaction. In continuous processes, the reactor vessel may contain at least one outlet through which a portion of the polymerization reaction mixture is extracted. Tubular reactors, loop reactors, and continuous stirred tank reactors (CTSRs) with multiple points for injecting starting materials are all suitable vessel types for continuous or semi-batch operation. The reactor should be equipped with means for supplying or removing heat, thus maintaining the temperature of the reaction mixture within the desired range. Suitable means include different types of hot fluid jackets, different types of internal or external heaters, etc. A cooking step performed on the continuously extracted product is conveniently carried out in a reactor that reduces and / or prevents significant backmixing. Plug flow operation in a tubular or tubular reactor is an exemplary mode for performing such a cooking step.

[0030] The product obtained by any of the above methods may contain up to 0.5 wt% unreacted carbon dioxide and / or epoxides, small amounts of its initiator and low molecular weight alkoxylates, and small amounts of other organic impurities and water. Volatile impurities should be flash-distilled or stripped from the resulting product. The product typically contains catalyst residues and catalyst promoter residues. Typically, these residues are left in the product, but can be removed if necessary. Moisture and volatiles can be removed by stripping polyols.

[0031] A method for producing poly(ether-carbonate) polyols involves polymerizing carbon dioxide and at least one alkylene oxide with an initiator in the presence of a DMC catalyst and a catalyst promoter. For example, the method includes a stage in which a DMC catalyst, a catalyst promoter, an initiator, and optionally a relatively small amount of alkylene oxide (to activate the DMC catalyst) are combined to form a starting reaction mixture. The starting reaction mixture is then heated or cooled to polymerization conditions, and carbon dioxide and a large amount of alkylene oxide (as required by the polymerization reaction) are added to the starting reaction mixture. Additional amounts of the DMC catalyst complex, catalyst promoter, and / or initiator may be added to the reactor during the feeding of carbon dioxide and at least one alkylene oxide.

[0032] Carbon dioxide and / or alkylene oxide may be added continuously or intermittently. In exemplary embodiments, the addition of carbon dioxide and optionally alkylene oxide may be based on the pressure in the reactor. For example, the amount of carbon dioxide added may be sufficient to raise the pressure in the reactor to a first predetermined pressure greater than 60 psig (e.g., greater than 0.41 MPa) and less than 200 psig (e.g., 1.38 MPa). Other exemplary pressures include greater than 100 psig, less than 150 psig, less than 125 psig, etc. Once the first predetermined pressure is reached, the carbon dioxide feed may be stopped to allow subsequent digestion stages. Once the reaction pressure reaches a second predetermined pressure below the first predetermined pressure, additional carbon dioxide may be added to perform additional digestion stages and / or the polymerization stage (e.g., after one or more digestion stages) may be allowed to be completed by stopping the addition of any additional materials (if present). The second predetermined pressure may be less than the first predetermined pressure, such as 5 psig (e.g., 0.03 MPa), 10 psig (e.g., 0.07 MPa), 15 psig (e.g., 0.10 MPa), 20 psig (e.g., 0.14 MPa), 25 psig (e.g., 0.17 MPa), 30 psig (e.g., 0.20 MPa), etc.

[0033] An exemplary method for producing poly(ether-carbonate) polyols includes (a) establishing steady-state concentrations of (i) a DMC catalyst, (ii) a catalyst promoter, (iii) an initiator, (iv) carbon dioxide, (v) an alkylene oxide, and (vi) the polymerization product in a continuous reactor under polymerization conditions; and (b) continuously adding an additional initiator, alkylene oxide, DMC catalyst, and catalyst promoter to the continuous reactor under polymerization conditions and continuously extracting a product stream containing poly(ether-carbonate) polyols from the continuous reactor. An exemplary semi-batch process may include adding the initiator, DMC catalyst, and catalyst promoter to the reactor, adding an initial charge of alkylene oxide to the reactor to activate the catalyst, and then co-feeding carbon dioxide and alkylene oxide to the reactor under polymerization conditions. Optionally, carbon dioxide may be added to the reactor in any proportion prior to the initial charge of alkylene oxide used to activate the catalyst.

[0034] A method for producing poly(ether-carbonate) polyols may include combining a DMC catalyst and a catalyst promoter with an epoxide and at least one initiator compound to form a starting reaction mixture, and then heating the starting reaction mixture to polymerization conditions until the bimetallic cyanide catalyst complex becomes activated, and then feeding additional epoxide and carbon dioxide into the starting reaction mixture under polymerization conditions. In an exemplary embodiment, the preliminary stage may include adding carbon dioxide and subsequently venting the added carbon dioxide to prepare a reactor for the polymerization stage.

[0035] During the initial stage, the initial heating step can be performed by heating the DMC catalyst and catalyst promoter to a temperature of 80°C to 220°C for 10 minutes or longer at atmospheric or sub-atmospheric pressure before adding carbon dioxide and epoxide.

[0036] Initiator

[0037] Initiators may include monohydric alcohol initiators and / or polyhydric alcohol initiators (such as low molecular weight initiator polyether polyols). It is possible to perform polymerization in the presence of an initiator comprising a mixture of monohydric alcohol initiators and low molecular weight initiator polyols. The result of such polymerization may be a poly(ether-carbonate) mixture containing monohydric and polyhydric alcohols.

[0038] The hydroxyl equivalent of a monohydric alcohol initiator can be from 30 to 1000. The hydroxyl equivalent of a polyhydric alcohol initiator can be 3,000 g / mol or less (e.g., 1,500 g / mol or less).

[0039] For example, the monohydric alcohol initiator may have at least one aliphatic carbon-carbon double bond, and the carbon dioxide and alkylene oxide are polymerized onto the initiator during one or more digestion stages. The carbon-carbon double bond may be, for example, vinyl (CH2=CH-), allyl (CH2=CH-CH2-), or propenyl (CH3-CH=CH2-) unsaturated. The unsaturated monohydric alcohol may contain, for example, up to 30 carbon atoms, up to 20 carbon atoms, or up to 12 carbon atoms. Examples of unsaturated alcohols include vinyl alcohol, 1-propen-3-ol, 1-buten-4-ol, 1-hexen-6-ol, 1-hepten-7-ol, 1-octen-8-ol, 1-nonen-9-ol, 1-decen-10-ol, 1-undecen-11-ol, 1-dodecen-12-ol, allyl alcohol, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, etc., and alkoxylated forms of any of the above substances with a molecular weight of up to 1000 (e.g., up to 500). Any two or more of the above may be used.

[0040] Exemplary polyol initiators include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerol, trimethylolpropane, pentaerythritol, sucrose, sorbitol, and alkoxylated compounds of any combination thereof with a hydroxyl equivalent of up to 1000.

[0041] Low molecular weight polyol initiators comprise two or more hydroxyl groups, and exemplary initiators include polyols alkoxylated with ethylene oxide, propylene oxide, and / or butane oxide in any relative proportion. At least one other reactive ethylene oxide may also be used alone or in combination with other standard ethylene oxides listed above, such as styrene oxide, epichlorohydrin, epioctane, and allyl glycidyl ether.

[0042] A characteristic of the polymerization reaction used to form poly(ether-carbonate) polyols is the "build ratio," which is defined as the ratio of the number-average molecular weight of the polyether product to that of the initiator. This build ratio can be as high as 160. Exemplary examples include a range from 2 to about 65 (e.g., 2 to 50, 2 to 15, 7 to 11, etc.). For example, during the polymerization stage, the initiator can account for 0.5 wt% to 90.0 wt% of the weight of the poly(ether-carbonate) polyol forming mixture.

[0043] catalyst

[0044] The polymerization catalyst is a bimetallic cyanide catalyst complex, also referred to herein as a DMC catalyst. Exemplary DMC catalysts include, for example, those described in U.S. Patent Nos. 3,278,457, 3,278,458, 3,278,459, 3,404,109, 3,427,256, 3,427,334, 3,427,335, and 5,470,813.

[0045] An exemplary DMC catalyst can be represented by Equation 1:

[0046] M b [M 1 (CN) r (X) t ] c [M 2 (X)6] d ·nM 3 x A y Formula 1

[0047] Among them M and M 3 Each is a metal; M 1 For transition metals different from M, each X represents a transition metal other than cyanide ions that is different from M. 1 Ion-coordinated groups; M 2 For transition metals; A represents an anion; b, c, and d are numbers reflecting electrostatically neutral complexes; r is 4 to 6; t is 0 to 2; x and y are the numbers that make the metal salt M 3 x A y The integer representing the charge balance, where n is zero or a positive integer. The foregoing formula does not reflect the presence of neutral complexing agents (such as tert-butanol) typically found in DMC catalyst complexes. In exemplary embodiments, r is 4 or 6, and t is 0. In some cases, r + t will equal six.

[0048] For example, M and M 3 Metal ions that can be independently selected from the following group: Zn 2+ Fe 2+ Co+2+ Ni 2+ Mo 4+ Mo 6+ Al +3+ V 4+ V 5+ 、Sr 2+ W 4+ W 6+ Mn 2+ Sn 2+ Sn 4+ Pb 2+ Cu 2+ La 3+ and Cr 3+ M 1 and M 2 Each can be selected from the following groups: Fe 3+ Fe 2+ Co 3+ Co 2+ Cr 2+ Cr 3+ Mn 2+ Mn 3+ Ir 3+ Ni 2+ ,Rh 3+ Ru 2+ V 4+ V 5+ Ni 2+ Pd 2+ and Pt 2+ In the above, those in the positive trioxide state can be used as M. 1 and M 2 Metals (e.g., Co) +3 and Fe + Suitable anions A include, but are not limited to, halide ions such as chloride, bromide, and iodide ions, nitrate, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, perchlorate, isothiocyanate, alkyl sulfonates such as methanesulfonate, aryl sulfonates such as p-toluenesulfonate, trifluoromethanesulfonate (trifluoromethanesulfonate), and C. 1-4 Carboxylate ions.

[0049] An exemplary type of DMC catalyst is zinc hexacyanocobaltate complexed with tert-butanol.

[0050] According to exemplary embodiments, the DMC catalyst, when carried out in the presence of carbon dioxide and / or when the concentration of hydroxyl groups is high during the digestion / polymerization process, is rapidly activated and provides a good polymerization rate without premature deactivation. Manufacturing methods using the DMC catalyst are suitable for producing such polycarbonate polyols, such as poly(ether-carbonate polyols) with a hydroxyl equivalent of 150 to 5,000 or greater. Furthermore, the method provides a way to polymerize carbon dioxide and / or alkyl esters to low-equivalent initiators, such as propylene glycol, glycerol, trimethylolpropane, sorbitol, sucrose, low molecular weight alkoxylates of these initiators, or combinations thereof.

[0051] Accelerator

[0052] Catalyst deactivation (such as with DMC catalysts) can occur in the presence of high concentrations of hydroxyl groups. For example, alkoxylation of an initiator may not be readily achieved directly from a low molecular weight monohydric or polyhydric alcohol initiator to the final polyol, because high concentrations of hydroxyl groups and initiator compounds can severely inhibit initial catalyst activation during the early stages of polymerization. Therefore, it is proposed to produce polycarbonate-based polyols comprising the polymerization of carbon dioxide and at least one epoxide in the presence of a DMC catalyst (such as a polymerization catalyst) and a catalyst promoter. The catalyst promoter is separate from the DMC catalyst, for example, not a ligand on the catalyst and can be added separately to the reaction mixture. In exemplary embodiments, the catalyst promoter may be free of halide anions. The catalyst promoter may be free of cyanide ions. In exemplary embodiments, the catalyst promoter may be free of any organic phenols, such as phenols that do not additionally include magnesium, Group 3-15 metals, or lanthanides. In exemplary embodiments, the catalyst promoter may be free of zinc ions, such that the catalyst promoter comprises Group 3-15 metals other than zinc.

[0053] For example, the catalyst promoter is magnesium, a Group 3-15 metal, or a lanthanide compound, wherein the magnesium, Group 3-15 metal, or lanthanide metal is bonded to at least one alkoxide, aryloxy group, carboxylate group, acyl group, pyrophosphate group, phosphate group, thiophosphate group, dithiophosphate group, phosphate ester, thiophosphate ester, amide, silicon oxide, hydride, carbamate, or hydrocarbon anion, and the magnesium, Group 3-15 metal, or lanthanide metal compound does not contain a halide anion. Exemplary promoters are discussed in U.S. Patent No. 9,040,657. In exemplary embodiments, the use of Group 3-15 metals or lanthanides bonded to carboxylate groups can be avoided.

[0054] When using a catalyst promoter, an exemplary method for producing polycarbonate-based polyols includes, before and / or during at least one of one or more digestion / polymerization stages, following (1) forming a catalyst mixture by combining (a) a DMC catalyst and (b) a catalyst promoter, said catalyst promoter being a magnesium, Group 3-15 metal, or lanthanide compound, wherein the magnesium, Group 3-15 metal, or lanthanide compound is bonded to at least one alkoxide, aryloxy group, carboxyl group, acyl group, pyrophosphate group, phosphate group, thiophosphate group, dithiophosphate group, phosphate ester, thiophosphate ester, amide, silicon oxide, hydride, carbamate, or hydrocarbon anion, and wherein the magnesium, Group 3-15 metal, or lanthanide compound is free of halide anions; (2) combining the catalyst mixture with a feed comprising carbon dioxide and / or epoxide; and (3) polymerizing the carbon dioxide and / or epoxide.

[0055] An exemplary method for producing polycarbonate-based polyols, such as poly(ether-carbonate) polyols, includes polymerizing both carbon dioxide and an epoxide in the presence of a DMC catalyst and magnesium, a Group 3-15 metal, or a lanthanide compound, wherein the magnesium, Group 3-15 metal, or lanthanide metal is bonded to at least one alkoxide, aryloxy group, carboxyl group, acyl group, pyrophosphate group, phosphate group, thiophosphate group, dithiophosphate group, phosphate ester, thiophosphate ester, amide, silicon oxide, hydride, carbamate, or hydrocarbon anion, and wherein the magnesium, Group 3-15 metal, or lanthanide metal compound is free of halide anions.

[0056] In exemplary embodiments, it is believed that the presence of catalyst promoters, such as magnesium, Group 3-15 metals, or lanthanide compounds (sometimes referred to herein as "MG3-15LA compounds"), significantly reduces the time required to activate the DMC catalyst compared to using the DMC catalyst alone (e.g., in the absence of the MG3-15LA compound). Once the DMC catalyst is activated, a faster polymerization rate is observed compared to using the DMC catalyst alone (e.g., in the absence of the MG3-15LA compound). Furthermore, certain promoter metals appear to provide particularly rapid polymerization rates.

[0057] The catalyst promoter, such as the MG3-15LA compound, is an added component that is not present during the preparation of the DMC catalyst (i.e., the precipitation step). The MG3-15LA compound contains magnesium, a Group 3-15 metal, or a lanthanide ion bonded to at least one alkoxide, aryloxy group, carboxyl group, acyl group, pyrophosphate group, phosphate group, thiophosphate group, dithiophosphate group, phosphate ester, thiophosphate ester, amide, silicon oxide, hydride, carbamate, or hydrocarbon anion. The catalyst promoter does not contain halide anions. The catalyst promoter does not contain cyanide ions.

[0058] The alkoxide anion signifies having a form - The substance OR, wherein R is an alkyl or substituted alkyl group, and after removal of the hydroxyl hydrogen, is the conjugate base of an alcohol compound having the form HO-R. These alcohols typically have pKa values ​​in the range of 13 to 25 or greater. The alkoxide ion may contain 1 to 20 (e.g., 1 to 6 and / or 2 to 6) carbon atoms. The alkyl or substituted alkyl group may be straight-chain, branched, and / or cyclic. Examples of suitable substituents include, for example, additional hydroxyl groups (which may be in alkoxide form), ether groups, carbonyl groups, ester groups, carbamate groups, carbonate groups, silyl groups, aromatic groups (such as phenyl and alkyl-substituted phenyl groups), and halogens. Examples of such alkoxide ions include methanol salts, ethanol salts, isopropoxide salts, n-propoxide salts, n-butoxide salts, sec-butoxide salts, tert-butoxide salts, benzyloxy groups, etc. In other embodiments, the R group may contain one or more hydroxyl groups and / or may contain one or more ether bonds. Alkoxide ions can correspond to residues of initiator compounds (those described below) present in the polymerization (after the removal of one or more hydroxyl hydrogens). Alkoxide ions can be alkoxides formed by removing one or more hydroxyl hydrogens from polyether monools or polyether polyols.

[0059] The term aryloxy anion refers to a substance having the form -O-Ar, where Ar is an aromatic or substituted group, and after the removal of the hydroxyl hydrogen, it corresponds to a phenolic compound having the form HO-Ar. The pKa of these phenolic compounds can be, for example, 9 to 12. Examples of such aryloxy anions include phenolates and cyclically substituted phenolates, where the cyclic substituents include, for example, alkyl, CF3, cyano, CH3, COCH3, halogen, hydroxyl, alkyl, alkoxy, etc. One or more cyclic substituents (if present) may be in one or more ortho, para, and / or meta positions relative to the phenolic group. Phenocyanate anions also include conjugate bases of polyphenolic compounds (such as bisphenol A, bisphenol F, and various other bisphenols), 1,1,1-tris(hydroxyphenyl)ethane, and fused-ring aromatic compounds (such as 1-naphthol).

[0060] The term "carboxylate anion" refers to a carboxylate anion having 1 to 24 (e.g., 2 to 18 and / or 2 to 12) carbon atoms. It can be aliphatic or aromatic. Aliphatic carboxylic acids may contain substituents such as hydroxyl groups (which may be in alkoxide form), ether groups, carbonyl groups, ester groups, carbamate groups, carbonate groups, silyl groups, aromatic groups (such as phenyl and alkyl-substituted phenyl), halogens, etc. Examples of aliphatic carboxylate anions include formate, acetate, propionate, butyrate, 2-ethylhexanoate, octanoate, decanoate, laurate, and other alkylates, as well as halogen-substituted alkylates (such as 2,2,2-trifluoroacetate, 2-fluoroacetate, 2,2-difluoroacetate, 2-chloroacetate, 2,2,2-trichloroacetate), etc. Aromatic carboxylate ions include benzoate, alkyl-substituted benzoate, halo-substituted benzoate, 4-cyanobenzoate, 4-trifluoromethylbenzoate, salicylate, 3,5-di-tert-butylsalicylate, basic salicylate, etc. In some embodiments, such carboxylate ions may be the conjugate base of a carboxylic acid with a pKa of 1 to 6 (e.g., 3 to 5).

[0061] Acyl anions refer to compounds containing carbonyl groups, including, for example, aldehydes, ketones, carbonates, esters, or conjugate bases of similar compounds in the form of enols. Among these are β-diketone compounds, such as acetylacetonate, butylacetylacetonate, etc.

[0062] Phosphate anions include those with the formula - OP(O)(OR 1 Those of )2, wherein R is an alkyl, substituted alkyl, phenyl, or substituted phenyl. Thiophosphates have corresponding structures in which one or more of the oxygen atoms are replaced by sulfur.

[0063] The term amide anion refers to an ion in which the nitrogen atom carries a negative charge. Amide ions are typically expressed in the form of... - N(R 2 )2, where R 2 The group can be independently hydrogen, alkyl, aryl, trialkylsilyl, triarylsilyl, etc. The alkyl group can be straight-chain, branched, or cyclic. Any of these groups may contain substituents, such as ethers or hydroxyl groups. Two Rs 2 The groups can together form a ring structure, which can be unsaturated and / or contain one or more heteroatoms (other than amide nitrogen) in the ring.

[0064] Hydrocarbon anions include aliphatic, cycloaliphatic, and / or aromatic anions, with a negative charge on a carbon atom. Hydrocarbon anions are conjugate bases of hydrocarbons, typically with pKa values ​​exceeding 30. Hydrocarbon anions may also contain inert substituents. For example, phenyl and substituted phenyl groups can be used in aromatic hydrocarbon anions. Aliphatic hydrocarbon anions can be alkyl groups (e.g., containing 1 to 12 and / or 2 to 8 carbon atoms). Methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, cyclopentadienyl, and tert-butyl anions can be useful.

[0065] In exemplary embodiments, the anion is a conjugate base of a compound with a pKa of at least 1.5 (e.g., at least 2.5 and / or at least 3.0). For example, a shorter activation time can be observed when the anion corresponds to a conjugate base of a compound with a pKa of at least 9 (e.g., at least 12 and / or at least 13). The anion can be a conjugate base of a compound having any higher pKa, such as up to 60 or higher. Anion corresponding to a conjugate base of a compound with a pKa of less than 9 (e.g., less than 5) can result in a longer activation time. Exemplary anions that can be used are alkoxides, aryloxy groups, amides, acetylacetonates, and hydrocarbon anions that are conjugate bases of compounds with a pKa of at least 9 (e.g., at least 12, at least 13, and / or up to 60).

[0066] Groups 3-15 metals are metals belonging to any of Groups III through 15 (inclusive) of the 2010 IUPAC periodic table. These metals may include, for example, scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, aluminum mercury, gallium, indium, tellurium, germanium, tin, lead, antimony, bismuth, and lanthanides including those with atomic numbers 58 (cerium) to 71 (lutetium) (inclusive). Exemplary metals that may be used include those in Groups 3, 4, 5, 12, 13, and 14. Scandium, yttrium, hafnium, titanium, zirconium, niobium, vanadium, zinc, aluminum, gallium, indium, and tin are available in the exemplary embodiments because these metals tend to provide rapid polymerization rates and / or allow for the presence of very small amounts of DMC catalyst. For example, aluminum, zinc, hafnium, gallium, indium, tin, titanium, and / or zirconium can be used.

[0067] An exemplary promoter is one corresponding to formula M 4 A 1 z and M 4 (O)A 1 z Compounds of any one of them, where M 4 It is magnesium, Group 3-15 or lanthanide metal, and each A 1Independently, it is an anion as previously described, and z is a number of at least one, reflecting an electrostatically neutral compound, the condition being any two or more A atoms. 1 Groups can combine to form polyvalent groups. Each A 1 = Independently an alkoxide, aryloxy anion, amide anion, or hydrocarbon anion, which is a conjugate base with a pKa of at least 9 (e.g., at least 12 and / or at least 13). Any A 1 It can be an alkoxide anion, which is the conjugate base of the following substances: initiator compound or polyether monool or polyether polyol, including polyether monool or polyether polyol products obtained from alkoxylation reaction, or polyethers with molecular weights between those of the initiator compound and the alkoxylation reaction product.

[0068] Accelerator compounds may not contain anions of conjugate bases of inorganic acids, such as sulfate, sulfite, persulfate, nitrate, nitrite, chlorate, perchlorate, hypochlorite, carbonate, chromate, etc.; sulfonate anions, such as trifluoromethylsulfonate and methanesulfonate; and hydroxide ions.

[0069] Examples of accelerators include:

[0070] a) Alkyl magnesium, such as diethylmagnesium, dibutylmagnesium, butylethylmagnesium, diphenylmethylmagnesium, etc.; magnesium alkoxides, such as magnesium methoxide, magnesium ethanol, magnesium isopropoxide, magnesium tert-butoxide, magnesium sec-butoxide, etc.; magnesium aryl oxides, such as magnesium phenolate and magnesium phenolate in which one or more phenolic groups are substituted by alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy, etc.; magnesium carboxylic acids, such as magnesium formate, magnesium acetate, magnesium propionate, magnesium 2-ethylhexanoate, magnesium benzoate, magnesium benzoate in which one or more benzoate groups are substituted by alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy, etc.; magnesium salicylate, magnesium 3,5-di-tert-butylsalicylate; magnesium amides, such as magnesium dimethylamide, magnesium diethylamide, magnesium diphenylamide, magnesium bis(trimethylsilyl)amide, etc.; magnesium acetylacetonate and magnesium tert-butylacetylacetonate.

[0071] b) Scandium alkoxides, such as scandium methanol, scandium ethanol, scandium isopropoxide, scandium tert-butoxide, scandium sec-butoxide, etc.; scandium aryl oxides, such as scandium phenolate and scandium phenolate in which one or more phenolic groups are substituted by alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy, etc.; scandium carboxylic acids, such as scandium formate, scandium acetate, scandium propionate, scandium 2-ethylhexanoate, scandium benzoate, scandium benzoate in which one or more benzoate groups are substituted by alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy, etc.; scandium salicylate; scandium acetylated pyruvate and scandium tert-butylacetylated pyruvate.

[0072] c) Yttrium alkoxides, such as yttrium methanol, yttrium ethanol, yttrium isopropoxide, yttrium tert-butoxide, yttrium sec-butoxide, etc.; yttrium aryl oxides, such as yttrium phenolate, and yttrium phenolate in which one or more phenolic groups are substituted by alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy, etc. rings; yttrium carboxylic acids, such as yttrium formate, yttrium acetate, yttrium propionate, yttrium 2-ethylhexanoate, yttrium benzoate, etc. Yttrium benzoate, yttrium salicylate, and 3,5-di-tert-butylsalicylate are substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy, or other rings; yttrium amides, such as dimethylamide yttrium, diethylamide yttrium, diphenylamide yttrium, and bis(trimethylsilyl)amide yttrium; yttrium acetylacetonate and tert-butylacetylacetonate.

[0073] d) Alkyl hafnium, such as tetraethyl hafnium, tetrabutyl hafnium, tetraphenylmethyl hafnium, etc.; hafnium alkoxides, such as tetramethanol hafnium, tetraethanol hafnium, tetraisopropanol hafnium, tetratert-butanol hafnium, tetrasec-butanol hafnium, etc.; hafnium aryl oxides, such as phenol hafnium and phenol hafnium in which one or more phenolic groups are substituted by alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy, etc.; hafnium carboxylates, such as hafnium formate, hafnium acetate, hafnium propionate, hafnium 2-ethylhexanoate, benzoyl hafnium, etc. Hafnium benzoate, hafnium benzoate in which one or more benzoate groups are substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy, or other rings, hafnium salicylate, hafnium 3,5-di-tert-butylsalicylate; amide hafnium, such as tetra(dimethylamide)hafnium, tetra(diethylamide)hafnium, tetra(diphenylamide)hafnium, tetra((bis(trimethylsilyl)amide)amide)hafnium; acetylacetonate hafnium and tert-butylacetylacetonate hafnium.

[0074] e) Alkyl titanium, such as tetraethyl titanium, tetraphenylmethyl titanium, etc.; titanium alkoxides, such as tetramethylethanol titanium, tetraethanol titanium, tetraisopropoxide titanium, tetratert-butoxide titanium, tetrasec-butoxide titanium, etc.; titanium aryl oxides, such as phenolic titanium and phenolic titanium in which one or more phenolic groups are cyclically substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxy, alkoxy, etc.; carboxylic acid titanium, such as titanium formate, titanium acetate, titanium propionate, titanium 2-ethylhexanoate, titanium benzoate, titanium benzoate in which one or more benzoate groups are cyclically substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxy, alkoxy, etc., titanium benzoate, titanium salicylate, titanium 3,5-di-tert-butylsalicylate; amide titanium, such as tetra(dimethylamide)titanium, tetra(diethylamide)titanium, tetra(diphenylamide)titanium, tetra((bis(trimethylsilyl)amide)amide)titanium; acetylated pyruvate titanium and tert-butylacetylated pyruvate titanium.

[0075] f) Alkyl zirconium, such as tetraethyl zirconium, tetrabutyl zirconium, tetraphenylmethyl zirconium, etc.; zirconium alkoxides, such as tetramethyl zirconium, tetraethanol zirconium, tetraisopropoxide zirconium, tetratert-butoxide zirconium, tetrasec-butoxide zirconium, etc.; zirconium aryl oxides, such as zirconium phenolate and zirconium phenolate in which one or more phenolic groups are cyclically substituted by alkyl, CF3, cyano, COCH3, halogen, hydroxy, alkoxy, etc.; zirconium carboxylate, such as zirconium formate, zirconium acetate, zirconium propionate, zirconium 2-ethylhexanoate, zirconium benzoate, zirconium benzoate in which one or more benzoate groups are cyclically substituted by alkyl, CF3, cyano, COCH3, halogen, hydroxy, alkoxy, etc., zirconium benzoate, zirconium salicylate, 3,5-di-tert-butyl salicylate; zirconium amide, such as tetra(dimethylamide)zirconium, tetra(diethylamide)zirconium, tetra(diphenylamide)zirconium, tetra((bis(trimethylsilyl)amide)zirconium); zirconium acetylacetonate and tert-butylacetylacetonate.

[0076] g) Vanadium alkoxides, such as vanadium methanol, vanadium ethanol, vanadium isopropoxide, vanadium tert-butoxide, vanadium sec-butoxide, etc.; Vanadium oxytris(alkoxides), such as vanadium oxytris(methanol), vanadium oxytris(ethanol), vanadium oxytris(isopropanol), vanadium oxytris(tert-butanol), vanadium oxytris(sec-butanol), etc.; Vanadium aryl oxides, such as vanadium phenolate and vanadium phenolate in which one or more phenolic groups are substituted by alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy, etc.; Vanadium carboxylic acids, such as vanadium formate, vanadium acetate, vanadium propionate, vanadium 2-ethylhexanoate, vanadium benzoate, vanadium benzoate in which one or more benzoate groups are substituted by alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy, etc., vanadium benzoate, vanadium salicylate, vanadium 3,5-di-tert-butylsalicylate; Vanadium tri(acetylpyruvate) and Vanadium tri(tert-butylacetylpyruvate); Vanadium oxybis(acetylpyruvate).

[0077] h) Alkyl zinc, such as dimethyl zinc, diethyl zinc, dibutyl zinc, diphenylmethyl zinc, etc.; alkyl zinc alkoxides, such as isopropoxide ethyl zinc; zinc alkoxides, such as zinc methoxide, zinc ethanol, zinc isopropoxide, zinc tert-butoxide, zinc sec-butoxide, etc.; zinc aryl oxides, such as zinc phenolate and zinc phenolate in which one or more phenolic groups are cyclically substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy, etc.; zinc carboxylic acids, such as zinc formate, zinc acetate, zinc propionate, zinc 2-ethylhexanoate, zinc benzoate, zinc benzoate in which one or more benzoate groups are cyclically substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy, etc., zinc benzoate, zinc salicylate, zinc 3,5-di-tert-butylsalicylate; zinc amides, such as zinc dimethylamide, zinc diethylamide, zinc diphenylamide, zinc (bis(trimethylsilyl)amide); zinc acetylacetonate and zinc tert-butylacetylacetonate.

[0078] i) Trialkylaluminum compounds, such as trimethylaluminum, triethylaluminum, tributylaluminum, triphenylmethylaluminum, etc.; aluminum alkoxides, such as aluminum triethanolamine, aluminum triethanolamine, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum tri-tert-butoxide, aluminum trisec-butoxide, etc.; aluminum aryl oxides, such as aluminum phenolate and aluminum phenolate in which one or more phenolic groups are substituted by alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy, etc.; aluminum carboxylate, such as aluminum formate, aluminum acetate, aluminum propionate, aluminum 2-ethylhexanoate, aluminum benzoate, etc., where one or more benzoate groups are substituted by alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy, etc. Aluminum benzoate, aluminum salicylate, and aluminum 3,5-di-tert-butylsalicylate are cyclically substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, or alkoxy groups; aluminum amides, such as tris(dimethylamide)aluminum, tris(diethylamide)aluminum, tris(di(trimethylsilyl)amide)aluminum, etc.; aluminum acetylacetonate; aluminum tert-butylacetylacetonate; and alkyl aluminum oxides and alkoxides, such as diethylaluminum ethanol, dimethylaluminum ethanol, diethylaluminum isopropanol, dimethylaluminum isopropanol, methylaluminoxane, tetraethylaluminoxane, etc. In exemplary embodiments, aluminum carboxylate, such as aluminum formate, aluminum acetate, aluminum propionate, aluminum 2-ethylhexanoate, aluminum benzoate, and aluminum benzoate in which one or more benzoate groups are substituted with alkyl rings, may be avoided.

[0079] j) Trialkyl gallium compounds, such as trimethyl gallium, triethyl gallium, tributyl gallium, triphenylmethyl gallium, etc.; gallium alkoxides, such as trimethylol gallium, triethanol gallium, triisopropoxide gallium, tritert-butoxide gallium, trisec-butoxide gallium, etc.; gallium aryl oxides, such as phenolic gallium and phenolic gallium in which one or more phenolic groups are substituted by alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy, etc.; gallium carboxylate, such as gallium formate, gallium acetate, gallium propionate, gallium 2-ethylhexanoate, gallium benzoate, and one or more benzoate groups. Gallium benzoate, gallium salicylate, and 3,5-di-tert-butylsalicylate are substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy, or other rings; gallium amides, such as tris(dimethylamide)gallium, tris(diethylamide)gallium, tris(diphenylamide)gallium, and tris(di(trimethylsilyl)amide)gallium; gallium acetylated pyruvate; gallium tert-butylacetylated pyruvate; and alkyl gallium alkoxides, such as diethyl gallium ethanol, dimethyl gallium ethanol, diethyl gallium isopropoxide, and dimethyl gallium isopropoxide.

[0080] k) Trialkylindium compounds, such as trimethylindium; indium alkoxides, such as indium methoxide, indium ethanol, indium isopropoxide, indium tert-butoxide, indium sec-butoxide, etc.; indium aryl oxides, such as indium phenolate and indium phenolate in which one or more phenolic groups are substituted by alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy, etc.; indium carboxylate, such as indium formate, indium acetate, indium propionate, indium 2-ethylhexanoate, indium benzoate, indium benzoate in which one or more benzoate groups are substituted by alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy, etc., indium benzoate, indium salicylate, indium 3,5-di-tert-butylsalicylate; indium acetylacetonate; and indium tert-butylacetylacetonate; and

[0081] l) Stannous phosphate; stannous pyrophosphate, stannous alkoxides, such as stannous methanol, stannous ethanol, stannous isopropoxide, stannous tert-butoxide, stannous sec-butoxide, etc.; stannous aryl oxides, such as stannous phenolate and stannous phenolate in which one or more phenolic groups are cyclically substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy, etc.; stannous carboxylic acids, such as stannous formate, stannous acetate, stannous propionate, stannous 2-ethylhexanoate, stannous benzoate, stannous benzoate in which one or more benzoate groups are cyclically substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy, etc., stannous salicylate, stannous 3,5-di-tert-butylsalicylate; stannous acetylacetonate; and tert-butylacetylacetonate.

[0082] In addition to the above, other suitable MG3-15LA compounds include magnesium, Group 3-15 or lanthanide metal alkoxides, wherein one or more of the alkoxide groups are conjugate bases after removing one or more hydroxyl hydrogen atoms from: (1) an initiator compound as described below, (2) a polyether monool or polyether polyol product of polymerization, or (3) a polyether with a molecular weight between that of the initiator and the polymerized polyether monool or polyether polyol product.

[0083] polyurethane products

[0084] Polycarbonate-based polyols, such as poly(ether-carbonate) polyols, are suitable for preparing a variety of polyurethane products, such as block foams, molded foams, flexible foams, viscoelastic foams, flame-modified foams, rigid foams, elastomers, adhesives, sealants, and / or coatings. Polyurethane products are suitable for a wide range of packaging applications, comfort applications (such as mattresses – including mattress covers, pillows, furniture, cushions, etc.), shock absorption applications (such as cushioning pads, sports and medical equipment, helmet padding, etc.), thermal insulation applications, conductivity for antistatic packaging of electronic products, and sound insulation and / or shock absorption applications (such as earplugs, automotive panels, etc.).

[0085] Polyurethane products can be prepared as reaction products to form polyurethane formulations comprising an isocyanate component and an isocyanate reactive component. The isocyanate component may include one or more polyisocyanates, one or more isocyanate-terminated prepolymers, and / or combinations thereof. The poly(ether-carbonate) polyol may be the only polyol included in the isocyanate reactive component or one of two or more polyols (e.g., to adjust the solids content to a desired level or to provide specific properties to the polyurethane). The isocyanate reactive component and / or the isocyanate component may further include at least one additive. Exemplary additives include catalysts, surfactants, blowing agents, and other additives known to those skilled in the art for use in polyurethanes.

[0086] Regarding the isocyanate component, exemplary isocyanates include aromatic, cycloaliphatic, and aliphatic isocyanates and isocyanate-terminated prepolymers derived from at least one selected from the group consisting of aromatic, cycloaliphatic, and aliphatic isocyanates. The amount of isocyanate component used to prepare polyurethane products is generally expressed according to the isocyanate index. The isocyanate index is defined as the molar stoichiometric excess of the isocyanate portion in the reaction mixture relative to the number of moles of isocyanate reactive units (active hydrogen that can be used to react with the isocyanate moiety), multiplied by 100. An isocyanate index of 100 means no stoichiometric excess such that there is 1.0 mole of isocyanate group for every 1.0 mole of isocyanate reactive group, multiplied by 100. In examples, the isocyanate index can range from about 70 to 400.

[0087] Regarding the isocyanate reactive component, polycarbonate-based polyols may be blended with one or more additional polyols. For example, the polycarbonate-based polyol may contain 5 wt% to 90 wt% of the isocyanate reactive component (e.g., 5 wt% to 80 wt%, 10 wt% to 70 wt%, 10 wt% to 60 wt%, 15 wt% to 50 wt%, 15 wt% to 40 wt%, 15 wt% to 30 wt%, 15 wt% to 25 wt%, etc.). The additional polyol may be a polyether polyol with a nominal hydroxyl functionality of 2 to 8 and a number-average molecular weight of 1,000 g / mol to 20,000 g / mol.

[0088] Various additives can be added to the reaction mixture used to form the polyurethane product to adjust the properties of the resulting product, such as additives known to those skilled in the art. Additives can be added as part of the isocyanate component and / or the isocyanate reactive component. Exemplary additives include catalysts, adhesion promoters, surfactants, dehumidifiers, cell openers, antioxidants, curing agents, pH neutralizers, UV stabilizers, antistatic agents, plasticizers, compatibilizers, fillers, reinforcing agents, flame retardants, pigments / dyes, release agents, and / or crosslinking agents.

[0089] If the polyurethane product is a foam, the product can be formed using a single-step method, such as a block method (e.g., as a free-expanding foam), a molding method (e.g., in a box foaming process), or any other method known in the art. In a block method, the components are mixed and poured into a tank or other area, where the formulation reacts, expands freely in at least one direction, and cures. Block methods can be operated continuously on a commercial scale. In a molding method, the components are mixed and poured into a mold / box (heated or unheated), where the formulation reacts, expands without a mold in at least one direction, and cures.

[0090] Polyurethane foam can be prepared under initial environmental conditions (i.e., room temperature in the range of 20°C to 25°C and standard atmospheric pressure of approximately 1 atm). For example, polyurethane foam may include solid functional additives (e.g., polymers with melting points above 100°C) added via modified copolymer polyols without applying heat or pressure to the isocyanate reactive components. Foaming can also be performed at pressures below atmospheric conditions to reduce foam density and soften the foam. Foaming can be performed at pressures above atmospheric conditions to increase foam density and thus increase foam load-bearing capacity, as measured by indentation force deformation (IFD). In molding processes, polyurethane foam can be prepared at initial mold temperatures above environmental conditions (e.g., 50°C and above). The mold can be overfilled, i.e., filled with additional foaming material, to increase foam density.

[0091] The following examples are provided to illustrate the invention, but are not intended to limit its scope. Unless otherwise stated, all parts and percentages are by weight. Unless otherwise specified, all molecular weight values ​​are number average molecular weights.

[0092] Examples

[0093] The following provides approximate properties, characteristics, parameters, etc., for various working examples, comparative examples, and the materials used in the working and comparative examples.

[0094] Preparation of polycarbonate-based polyols

[0095] The following materials are mainly used:

[0096] DMC zinc hexacyanocobaltate catalyst complex (available at Bayer Material Science in exemplary grade).

[0097] The propoxylated polyol initiated by glycerol has a number average molecular weight of 700 g / mol and a nominal hydroxyl functionality of 3 (available from The Dow Chemical Company).

[0098] The propoxylated polyol initiated by the initiator glycerol has a number average molecular weight of 450 g / mol and a nominal hydroxyl functionality of 3 (available from Dow Chemical Company).

[0099] The propoxylated polyol initiated by the initiator 3-propylene glycol has a number average molecular weight of 400 g / mol and a nominal hydroxyl functionality of 2 (available from Dow Chemical Company).

[0100] Accelerator 1, aluminum triisopropoxide (Al(O-iPr)3), is available from Acros Organics.

[0101] Accelerator 2, aluminum trisec-butoxide (Al(OBu)3), is available from Gelest, Inc.

[0102] Accelerator 3, hafnium tert-butoxide (IV)(Hf(OBu)4), is available from Gelest.

[0103] Accelerator 4, magnesium di-tert-butoxide (Mg(OBu)2), is available from Sigma Aldrich.

[0104] Accelerator 5, gallium ethanol (III) (Ga(OEt)3), is available from Gelest.

[0105] Accelerator 6, indium ethoxide (III) (In(OEt)3), is available from Alfa Aesar.

[0106] Accelerator 7, titanium ethoxide (IV)(Ti(OEt)4), is available from Gelest.

[0107] The following section discusses various examples:

[0108] Examples 1 to 3 - Accelerator vs. No Accelerator

[0109] For each of Examples 1 to 3, during the initial stage, the reactor was heated to 130°C and continuously purged with nitrogen for 1.5 hours to dry the reactor contents. This was done after the addition of DMC, initiator 1, and promoter 1 (if used), but before the addition of any propylene oxide. The reactor was then heated to 150°C and an initial charge of 18.4 mL of propylene oxide was added for catalyst activation. The pressure in the reactor was increased to an initial pressure of 11.7 psig and decreased to less than 2 psig during catalyst activation. The reactor was then cooled to 100°C and fed with carbon dioxide to 70 psig and then vented. This method of feeding and venting carbon dioxide was repeated twice more. During the polymerization stage, the pressure was increased to 105 psig by co-feeding propylene oxide and carbon dioxide into the reactor in the molar ratios provided in Table 1. The co-feeding was then stopped, and for the first digestion stage, the pressure in the reactor was decreased to 95 psig. Before the second digestion stage, propylene oxide and carbon dioxide were added again at the same molar ratio and continued until the reactor pressure rose to 105 psig again. Then, again, the co-feed was stopped, and for the second digestion stage, the pressure in the reactor was reduced to 95 psig. The time required for the reactor pressure to drop from 105 psig to 95 psig for each reactant addition cycle (which indicates catalytic activity) is shown in Table 1 below. No further reactants were added after the reactor pressure had dropped to 95 psig for the second time. Following the pressure distribution in the reactor, and once stable (i.e., no further changes), the reactor was cooled and the reactor pressure was released. The reactor contents were purged with nitrogen for 30 minutes with stirring to remove unreacted propylene oxide, carbon dioxide, and volatile organic compounds. The products were analyzed by GPC and NMR.

[0110] Example 1: A sample of 0.05 g of DMC was dissolved in 99.6 g of initiator 1 and then dried in a 1 L capacity reactor according to the general procedure outlined above. The reactor was then heated to 150 °C and an initial charge of 18.4 mL of propylene oxide was added for catalyst activation. The pressure in the reactor was initially increased to 11.7 psig and then reduced to less than 2 psig during catalyst activation. The reactor was then cooled to 100 °C and fed with carbon dioxide to 70 psig and then evacuated. This method of feeding and evacuating carbon dioxide was repeated twice more. Next, during the subsequent polymerization stage, a total of 2.7 g of propylene oxide and 2 g of carbon dioxide were added over a 3-hour period under polymerization conditions.

[0111] Example 2: A sample of 0.05 g of DMC was dissolved in 99.6 g of initiator 1 and then dried in a 1 L capacity reactor according to the general procedure outlined above. The reactor was then heated to 150 °C and an initial charge of 18.4 mL of propylene oxide was added for catalyst activation. The pressure in the reactor was initially increased to 11.7 psig and then reduced to less than 2 psig during catalyst activation. The reactor was then cooled to 100 °C and fed with carbon dioxide to 70 psig and then evacuated. This method of feeding and evacuating carbon dioxide was repeated twice more. Next, during the subsequent polymerization stage, a total of 61.5 g of propylene oxide and 10.1 g of carbon dioxide were added over a 2.5-hour period under polymerization conditions.

[0112] Example 3: A sample of 0.05 g DMC and 0.5 g Accelerator 1 was dissolved in 99.6 g Initiator 1 and then dried in a 1 L capacity reactor according to the general procedure outlined above. The reactor was then heated to 150 °C and an initial charge of 18.4 mL propylene oxide was added for catalyst activation. The pressure in the reactor was initially increased to 11.7 psig and then reduced to less than 2 psig during catalyst activation. The reactor was then cooled to 100 °C and fed with carbon dioxide to 70 psig and then evacuated. This method of feeding and evacuating carbon dioxide was repeated twice more. Next, during the subsequent polymerization stage, a total of 75.9 g propylene oxide and 12.5 g carbon dioxide were added over a 2.5-hour period under polymerization conditions.

[0113] Table 1

[0114]

[0115] Referring to the above, the use of a promoter appears to improve the method when using a DMC catalyst compared to the case where no promoter is present. For example, regarding Example 3, the activity increased by approximately 6-fold and carbon dioxide incorporation increased by approximately 34-fold compared to Example 2. Specifically, Example 3 resulted in a polyol yield of 99.6%.

[0116] Examples 4 to 6 - Amounts of different accelerators

[0117] During the initial stage, DMC catalyst and promoter 1 were dissolved in 144 g of initiator 1 in predetermined amounts as shown in Table 2, and then dried in a 1 L capacity reactor by heating to 130 °C and continuously purging with nitrogen for 2 hours. The reactor was then heated to 150 °C and an initial charge of 21.6 g of propylene oxide was added for catalyst activation. The pressure in the reactor was increased to an initial pressure of approximately 10 psig and decreased to less than 2 psig during catalyst activation. The reactor was then cooled to the reaction temperature (T) provided in Table 2 and fed with carbon dioxide to 70 psig, and then evacuated. This method of feeding and evacuating carbon dioxide was repeated twice more.

[0118] The pressure was then increased or decreased to the reaction pressure (P) provided in Table 2, which initiated the polymerization phase. During the polymerization phase, propylene oxide was fed at a rate of 1 mL / min until the amount (oxides) listed in Table 2 was reached. During the oxide feed, when the pressure dropped below the target pressure of 2.5 psi, the pressure in the reactor was maintained at the pressure shown in Table 2 by feeding CO2 on demand, and the CO2 feed was stopped when the reactor reached a pressure above the target pressure of 2.5 psi. After stopping the propylene oxide feed, the pressure was maintained by feeding carbon dioxide and digestion until the pressure in the reactor no longer changed. The reactor was then cooled to room temperature and the reactor pressure was released. The reactor contents were purged with nitrogen for 30 minutes to remove unreacted propylene oxide and carbon dioxide. The products were analyzed by GPC and NMR.

[0119] Table 2

[0120]

[0121] Referring to Table 2, Examples 4 to 6 demonstrate that the combination of DMC catalyst and accelerator enables carbon dioxide to be incorporated into the polyether polyol at levels of 0.3 wt% to 10.4 wt%, as defined herein, under mild temperature and pressure conditions by first activating the catalyst combination under nitrogen and then adding carbon dioxide at low pressure. The accelerator and DMC catalyst can be present in a weight ratio of 1:1 to 20:1 (e.g., 2:1 to 15:1, 3:1 to 12:1, 4:1 to 10:1, etc.).

[0122] Examples 7 to 12 - Different Temperatures and Pressures

[0123] During the initial stage, DMC catalyst (0.027 g) and promoter 2, as shown in Table 3, were mixed in a flask under dry conditions with 140 g of initiator 1 and sonicated for 45 minutes. The contents of the flask were added to a 1 L capacity reactor and stirring was continued for the entire duration of the method. The reactor was then heated to 130 °C and continuously purged with nitrogen for 2 hours. After closing the reactor outlet and stopping the nitrogen flow, the temperature in the reactor was increased to 140 °C while the feed carbon dioxide pressure was increased to 70 psig and then vented. This method of feeding and venting carbon dioxide was repeated twice more.

[0124] The reactor was then fed carbon dioxide to 60 psig, and an initial charge of 15.6 g of propylene oxide was added for catalyst activation. The pressure in the reactor was initially increased by approximately 10–20 psig, and decreased back to approximately 60–65 psig upon catalyst activation. The reactor was then brought to the temperature (T) and pressure (P) defined in Table 3, which initiated the polymerization phase. During the polymerization phase, propylene oxide was fed at a rate of 1 mL / min and stopped when 259 g of propylene oxide had been fed. During the oxide feed, the pressure in the reactor was maintained as shown in Table 3 by feeding carbon dioxide on demand when the pressure dropped below the target pressure of 2.5 psi, and the carbon dioxide feed was stopped when the reactor reached a pressure above the target pressure of 2.5 psi. After stopping the propylene oxide feed, the pressure was maintained by feeding carbon dioxide and digestion until the pressure in the reactor no longer changed. The reactor was then cooled to room temperature and the reactor pressure was released. The reactor contents were purged with nitrogen for 30 minutes with stirring to remove unreacted propylene oxide and carbon dioxide. Products were analyzed by GPC and NMR.

[0125] Table 3

[0126]

[0127] Referring to Table 3, Example 7 is a comparative example of the same method operated in Example 8, but without the addition of a accelerator. Compared to the same method run with the accelerator added, Example 7 requires significantly longer digestion and total batch times.

[0128] Specifically, Examples 7 to 12 demonstrate that the method according to the exemplary embodiments can be successfully initiated and operated by first activating the DMC catalyst with propylene oxide such as an oxide in the presence of a promoter under carbon dioxide, and then continuing to add the oxide and carbon dioxide under mild temperature and pressure conditions. This method makes it possible to eliminate the separate catalyst activation step performed under a nitrogen atmosphere. Furthermore, the method allows for immediate activation of the DMC catalyst under mild carbon dioxide pressure followed by continuous addition of oxide and carbon dioxide until the process is complete (e.g., a semi-batch process). Therefore, valuable reactor time is saved.

[0129] Examples 13 to 17 - Different Accelerators

[0130] During the initial stage, under dry conditions, 0.028 g of DMC catalyst and promoter (according to the type and amount in Table 4) were mixed with 144 g of initiator 1 in a bottle and sonicated for 45 minutes. The contents of the bottle were added to a 1 L capacity reactor and stirring was continued for the entire duration of the method. The reactor was then heated to 130 °C and continuously purged with nitrogen for 2 hours. After closing the reactor outlet and stopping the nitrogen flow, the temperature in the reactor was increased to 140 °C while the feed carbon dioxide pressure was increased to 70 psig and then vented. This method of feeding and venting carbon dioxide was repeated twice more.

[0131] The reactor was then fed carbon dioxide to 60 psig, and an initial charge of 16.0 g of propylene oxide was added for catalyst activation. The pressure in the reactor was initially increased by approximately 10–20 psig, and during catalyst activation, the pressure dropped back to approximately 60–65 psig. The reactor was then fed carbon dioxide to 110 °C and 100 psig. During the polymerization phase, propylene oxide was fed at a rate of 1 mL / min and stopped when 266.8 g of propylene oxide had been fed. During oxide feeding, when the pressure dropped below the target pressure of 2.5 psi, the pressure in the reactor was maintained as defined above by feeding carbon dioxide on demand, and the carbon dioxide feed was stopped when the reactor reached a pressure above the target pressure of 2.5 psi. After stopping the propylene oxide feed, the pressure was maintained by feeding carbon dioxide and digestion until the pressure in the reactor no longer changed. The reactor was then cooled to room temperature and the reactor pressure was released. The reactor contents were purged with nitrogen for 30 minutes with stirring to remove unreacted propylene oxide and carbon dioxide. The products were analyzed by GPC and NMR.

[0132] Table 4

[0133]

[0134] Referring to Table 4, methods according to exemplary embodiments are shown when using different types of accelerators.

[0135] Example 18 - Different Oxides

[0136] During the initial stage, DMC catalyst (0.454 g) and promoter 2 (2.538 g) were mixed with 908 g of initiator 2 in a bottle under dry conditions and sonicated for 45 minutes. The contents of the bottle were added to a 6 L capacity reactor and stirring was continued for the entire duration of the method. The reactor was then heated to 130 °C and continuously purged with nitrogen for 2 hours. After closing the reactor outlet and stopping the nitrogen flow, the temperature in the reactor was increased to 140 °C while the feed carbon dioxide pressure was increased to 70 psig and then vented. This method of feeding and venting carbon dioxide was repeated twice more.

[0137] Then, the reactor is fed with carbon dioxide to 60 psig, and an initial charge of 100.8 g of propylene oxide is added to the reactor for catalyst activation. The pressure in the reactor is initially increased by about 10-20 psig and then reduced back to 60-65 psig during catalyst activation. The reactor is then fed with carbon dioxide to 105 °C and 90 psig. During the polymerization phase, propylene oxide is fed at 12 mL / min, and ethylene oxide at 1.62 g / min until a total of 4162 g of propylene oxide and 672 g of ethylene oxide are fed. During oxide feeding, when the pressure drops below the target pressure of 2.5 psi, the pressure in the reactor is maintained by feeding carbon dioxide as needed, as shown in Table 3, and the carbon dioxide feed is stopped when the reactor reaches a pressure above the target pressure of 2.5 psi. After stopping the propylene oxide and ethylene oxide feeds, the pressure is maintained by feeding carbon dioxide and digestion until the pressure in the reactor no longer changes. The reactor was then cooled to room temperature and the pressure was released. The reactor contents were purged with nitrogen for 30 minutes with stirring to remove unreacted propylene oxide, ethylene oxide, and carbon dioxide. The number-average molecular weight of the resulting polyol product was 2837 g / mol, as determined by GPC, and it contained 5.2 wt% CO2, with a polyol selectivity of 96.7%.

[0138] Example 18 shows that a polyol containing ethylene oxide, propylene oxide and carbon dioxide can be prepared into a carbon dioxide composition with a target weight percentage, and when compared with a similar polyether polyol prepared without any carbon dioxide, the resulting polyol produces a flexible polyurethane foam of good quality.

[0139] Further testing was conducted on the polyols of Example 18 for exemplary polyurethane formulations. Specifically, Example 18 used the formulations in Table 5 with TDI (which can be voranated). TM Commercially available from Dow Chemical Company, a formulation was used to prepare flexible polyurethane foam. The foam formulation was compared with similar polyether polyols of similar hydroxyl equivalent and ethylene oxide content (wt%), but excluding carbon dioxide as a co-reactant. The polyol used in the comparative example was VORANOL. TM 8136 was prepared using a commercially available polyol prepared using a DMC catalyst from Dow Chemical Company.

[0140] To prepare the foam examples for Examples 19 to 21 in Table 5, a 38cm × 38cm × 24cm wooden box was used for box foaming, lined with a plastic film for easy demolding. A high-shear pin mixer was used to mix the materials. Except... 29 and VORANATE TM Mix all components except T-80 TDI at 2400 rpm for 15 seconds. Then add... 29, where the mixture is further mixed at 2400 rpm for 15 seconds. Next, TDI is added, where the mixture is further mixed at a high speed of 3000 rpm for 3 seconds. The resulting mixture is then poured into a container. The foam is allowed to cure overnight before cutting and testing. Referring to Table 5, Examples 19 and 20 were prepared using commercially available polyols. According to the exemplary examples, Example 21 was prepared using the polyol used in Example 18.

[0141] Table 5

[0142]

[0143] The foam properties of Examples 19 and 20 are shown in Table 6 below.

[0144] Table 6

[0145]

[0146] As shown in Table 6, the physical properties of the flexible polyurethane foam prepared from the polyol of Example 18 are very similar to those of the flexible polyurethane foam prepared from the CO2-free polyol.

[0147] Examples 22-23 - Polyols with different molecular weights and functionalities

[0148] During the initial stage, DMC catalyst (0.0461 g) and promoter 2 (0.258 g) were mixed with 135 g of initiator 3 in a bottle under dry conditions and sonicated for 45 minutes. The contents of the bottle were added to a 1 L capacity reactor and stirring was continued for the entire duration of the method. The reactor was then heated to 130 °C and continuously purged with nitrogen for 2 hours. After closing the reactor outlet and stopping the nitrogen flow, the temperature in the reactor was increased to 140 °C while the feed carbon dioxide pressure was increased to 70 psig and then vented. This method of feeding and venting carbon dioxide was repeated twice more.

[0149] The reactor was then fed carbon dioxide to 60 psig, and an initial charge of 15 g of propylene oxide was added for catalyst activation. The pressure in the reactor was initially increased by approximately 10–20 psig, and during catalyst activation, the pressure dropped back to approximately 60–65 psig. The reactor was then fed carbon dioxide to 110 °C and 100 psig. During the polymerization phase, propylene oxide was fed at a rate of 1.5 mL / min and stopped when 538.7 g of propylene oxide had been fed. During oxide feeding, when the pressure dropped below the target pressure of 2.5 psi, the pressure in the reactor was maintained as defined above by feeding carbon dioxide on demand, and the carbon dioxide feed was stopped when the reactor reached a pressure above the target pressure of 2.5 psi. After stopping the propylene oxide feed, the pressure was maintained by feeding carbon dioxide and digestion until the pressure in the reactor no longer changed. The reactor was then cooled to room temperature and the reactor pressure was released. The reactor contents were purged with nitrogen for 30 minutes with stirring to remove unreacted propylene oxide and carbon dioxide. The products were analyzed by GPC and NMR. The results are shown in Table 7 below.

[0150] Table 7

[0151]

[0152] Examples 22 and 23 further illustrate that polyols of different molecular weights, functionalities, and carbon dioxide contents can be prepared according to the exemplary examples.

[0153] Examples 24 and 25 - Preparation of polyols under high pressure

[0154] According to exemplary embodiments, poly(ether-carbonate) polyols can be prepared under low pressure, which is desirable for industrial-scale operations. However, the embodiments also include the preparation of such polyols under high pressure.

[0155] During the initial stage, the amounts of DMC catalyst, promoter 2, and initiator 1 were mixed in a bottle under dry conditions in the amounts shown in Table 7 and sonicated for 1 hour. The contents of the bottle were added to a 1.8 L capacity reactor and stirring was continued for the entire duration of the method. The reactor was then heated to 130 °C and continuously purged with nitrogen for 3 hours. After the reactor outlet was closed and the nitrogen flow was stopped, the temperature in the reactor was increased to 140 °C while the feed carbon dioxide pressure was increased to 70 psig and then vented. This method of feeding and venting carbon dioxide was repeated twice more.

[0156] The reactor is then fed carbon dioxide to 70 psig, and an initial charge of propylene oxide, in the amounts shown in Table 8, is added to the reactor for catalyst activation. The pressure in the reactor is initially increased by approximately 10–20 psig (0.0689–0.138 MPa), and drops back to 70–75 psig upon catalyst activation. The reactor is then fed carbon dioxide to 110 °C and the pressure defined in Table 8. Once the target reactor pressure is reached, propylene oxide is fed at the flow rate shown in Table 8, and the feeding is stopped when the total amount of propylene oxide shown in Table 8 has been fed. During oxide feeding, the pressure in the reactor is maintained as defined above by feeding carbon dioxide on demand when the pressure drops below the target pressure of 2.5 psi, and the carbon dioxide feed is stopped when the reactor reaches a pressure above the target pressure of 2.5 psi. After stopping the propylene oxide feed, the pressure is maintained by continuing to regulate the carbon dioxide pressure until the addition of carbon dioxide is stopped. The reactor is then cooled to 80 °C and the reactor pressure is released. The reactor contents were purged with nitrogen for 30 minutes with stirring to remove unreacted propylene and carbon dioxide. The product was then cooled to room temperature and analyzed by GPC and NMR.

[0157] Table 8

[0158]

[0159]

[0160] The characteristics of Examples 24 and 25 are shown in Table 9 below.

[0161] Table 9

[0162]

[0163] Examples 24 and 25 illustrate that the embodiments are operable under high pressure, but similar polyols can be prepared under low-pressure operating conditions (such as those used in Example 10) with similar carbon dioxide incorporation levels.

[0164] Example 26 - Continuous Method for Preparing Polyols

[0165] Example 26 illustrates that the method of the embodiment is operable in a continuous polyol production method, and that polyols with different carbon dioxide contents can be prepared by manipulating the method conditions.

[0166] Example 26 was prepared in a 500 mL pressure reactor equipped with a recirculation loop, a mechanical stirrer, and an outlet. The outlet was fitted with a heated plug flow section with a 75 mL conduit. Under the control of a process control computer, the reactor pressure was controlled by a control valve at the outlet of the plug flow section, maintaining the reactor pressure at a specified pressure setpoint. The reactor effluent flowed through a pressure control valve and into a sample collection bottle where the reaction products were collected. The reactor was also equipped with a heated external recirculation loop. The reactor contents were circulated around the recirculation loop by means of a Micropump gear pump. The recirculation loop was equipped with an NIR flow cell attached to an ABB NIR analyzer. The NIR analyzer monitored the hydroxyl content and unreacted ethylene oxide concentration in the reaction mixture. The recirculation loop was further equipped with injection points for propylene oxide, ethylene oxide, carbon dioxide, glycerol (as an initiator), and two separate injection points for the catalyst. The oxides, carbon dioxide, and glycerol were dispensed from the storage tank into the recirculation loop via a Bronkhorst mass flow controller under the control of the process control computer.

[0167] The DMC catalyst was prepared as a 2% by weight suspension in propylene glycol. Accelerator 2 was prepared as a 10% solution in dipropoxy-n-butanol (DPnB). These components were each dispensed into the recirculation loop at independent rates using a Valco Instruments M50 dispenser pump to provide the desired steady-state concentrations of DMC catalyst and aluminum in the reaction mixture.

[0168] The feed ratios of all components are controlled to produce polyols with target number-average molecular weights, carbon dioxide (wt%), ethylene oxide (wt%), and propylene oxide (wt%). The addition rate is controlled to produce a specific residence time in the reactor. Residence time is defined as the amount of time required to completely and precisely displace all the reactor contents once by feeding sufficient components by weight into the reactor.

[0169] 375 g of polyether carbonate polyol from Example No. 18 was placed into the reactor. The polyol had a number-average molecular weight of 2837 g / mol, contained 5.9 wt% CO2 (as defined provided), and also contained 3% propylene carbonate. The polyol contained 50 ppm of DMC catalyst and 5 ppm of aluminum. The mixture was stirred and purged with nitrogen while being heated to 130°C. The reactor was maintained at 130°C for 90 minutes with constant stirring and nitrogen purging to dry the reactor contents.

[0170] After the drying stage, nitrogen purging was stopped and the reactor outlet was closed. The reactor pressure regulator was set to a control pressure of 60 psig. The reactor contents were recirculated through the NIR flow tank and back into the reactor until the reactor temperature reached equilibrium at 130°C. DMC catalyst slurry (2% in MPG) was added at 11.3 μL / min, and promoter 2 (10% w / w in DPnB) was added at 12.6 μL / min. Propylene oxide was added at a rate of 1 g / min for 12 min, then 2 g / min for 12 min, and then ethylene oxide was added at a rate of 0.35 g / min, followed by glycerol at 0.065 g / min, with the propylene oxide addition rate increasing to 2.67 g / min. These streams produced a polyether polyol product with a hydroxyl equivalent of 1128 g / mol and a hydroxyl functionality of 2.74, containing 11.1 wt% EO.

[0171] When the pressure in the reactor rises to 60 psig, open the pressure control valve at the reactor outlet to allow the product to flow out of the reactor and into a collection bottle. The pressure control valve maintains the reactor pressure for the remainder of the reactor operation.

[0172] The addition of oxides was continued until 320 g of propylene oxide, 39 g of ethylene oxide, and 28 g of glycerol were added to the reactor. At this point, the propylene oxide addition rate was reduced to 2.63 g / min, and carbon dioxide was started at a rate of 0.04 g / min. All other streams were maintained as previously described. The reactor temperature was slowly reduced from 130°C to 110°C over 1 hour and then maintained at that temperature. For the low-pressure method, the reactor pressure was reduced to 46 psig.

[0173] These flow rates and operating conditions produce a polyol with a hydroxyl equivalent of approximately 1128 g / mol, containing 11.1% by weight EO and 1% by weight CO2, in a continuous process with a 3-hour residence time, a steady-state concentration of 75 ppm DMC catalyst, and a steady-state concentration of 46 ppm aluminum. The process is operated under steady-state conditions where the total unreacted oxide concentration is equal to 2.0% by weight or less.

[0174] All components were added simultaneously and maintained for a total of 70 hours, corresponding to a residence time greater than 23 times in the reactor. Analysis of the resulting product revealed a hydroxyl equivalent of 1026 mg KOH / g as measured by %OH titration, a number-average molecular weight of 2950 g / mol, and a polydispersity of 1.16 as determined by GPC. The polyol contained 1.2 wt% carbon dioxide and 0.39 wt% cyclic propylene carbonate, as determined by FTIR analysis.

[0175] The addition rate of propylene oxide was then reduced to 2.61 g / min, and the addition rate of carbon dioxide was increased to 0.062 g / min. The addition rate of DMC catalyst slurry was increased to 14 μL / min, and the addition rate of promoter 2 solution was increased to 15.6 μL / min. The reactor pressure was increased to 50 psig. The method stabilized and continued to operate for 16 hours at a total concentration of unreacted oxides of 2.0 wt% or less, corresponding to a residence time in the reactor greater than 5 times. Analysis of the resulting products revealed an OH percentage of 1.63% as measured by %OH titration, a number-average molecular weight of 3139, and a polydispersity of 1.16 as determined by GPC. The polyol contained 1.5 wt% CO2 and 0.39 wt% cyclic propylene carbonate, as determined by FTIR analysis.

[0176] The polyurethane flexible foam was prepared from the polyol according to the formulation in Example 26 of Table 10. The foam was again prepared using VORANOL as described in Example 26. TM Comparison of foams prepared with the same formulation using 8136 polyol substitution. The formulations and properties of the two foams are shown in Table 10 below.

[0177] Table 10

[0178]

[0179] The foam properties of Examples 27 to 26 are shown in Table 11 below.

[0180] Table 11

[0181]

[0182] As shown in Table 11, polyols prepared using CO2 as a co-reactant in a continuous alkoxylation process are used to prepare flexible polyurethane foams, which have properties very similar to those of polyurethane foams prepared from similar polyols prepared in a continuous process but without using CO2 as a co-reactant.

[0183] This disclosure relates to the following implementation plan:

[0184] 1. A method for manufacturing poly(ether-carbonate) polyols, comprising:

[0185] The polymerization stage includes polymerizing carbon dioxide and at least one epoxide with an initiator in the presence of a bimetallic cyanide polymerization catalyst and a catalyst promoter that does not contain halogen anions and cyanide ions, wherein the catalyst promoter is separate from the bimetallic cyanide polymerization catalyst.

[0186] 2. The method according to claim 1, wherein the catalyst promoter is magnesium, a Group 3-15 metal, or a lanthanide compound, wherein the magnesium, Group 3-15 metal, or lanthanide metal is bonded to at least one alkoxide, aryloxy group, carboxyl group, acyl group, pyrophosphate group, phosphate group, thiophosphate group, dithiophosphate group, phosphate ester, thiophosphate ester, amide, silicon oxide, hydride, carbamate, or hydrocarbon anion, and wherein the magnesium, Group 3-15 metal, or lanthanide metal compound does not contain a halide anion.

[0187] 3. The method according to any one of claims 1 to 2, wherein the initiator comprises at least one selected from monohydric alcohol initiators and polyhydric alcohol initiators.

[0188] 4. The method according to any one of claims 1 to 3, wherein the carbon dioxide is added intermittently or continuously to the reactor during the polymerization stage in the presence of the bimetallic cyanide catalyst complex and the catalyst promoter, and each of the at least one epoxide is added intermittently or continuously to the reactor during the polymerization stage.

[0189] 5. The method according to any one of claims 1 to 4, further comprising a preliminary stage prior to the polymerization stage, wherein the bimetallic cyanide catalyst complex, the catalyst promoter, and the initiator form an initial reaction mixture.

[0190] 6. The method according to any one of claims 1 to 5, wherein the carbon dioxide and the at least one epoxide are polymerized with the initiator to form the poly(ether-carbonate) polyol.

[0191] 7. The method according to any one of items 1 to 6, wherein the poly(ether-carbonate) polyol is manufactured in batch or semi-batch manner.

[0192] 8. The method according to any one of items 1 to 6, wherein the poly(ether-carbonate) polyol is manufactured by a continuous process.

Claims

1. A method for manufacturing poly(ether-carbonate) polyols, comprising: The polymerization stage includes polymerizing carbon dioxide and at least one epoxide with an initiator in the presence of a bimetallic cyanide polymerization catalyst and a catalyst promoter free of halide anions and cyanide ions, wherein the catalyst promoter is separate from the bimetallic cyanide polymerization catalyst, and wherein the catalyst promoter is selected from: a) Alkyl magnesium; magnesium alkoxides; magnesium aryl oxides; magnesium amides; magnesium acetylacetate and magnesium tert-butylacetylacetate; b) Scandium alkoxides; scandium aryl oxides; scandium carboxylate; scandium acetylacetonate and scandium tert-butylacetylacetonate; c) Yttrium alkoxides; yttrium aryl oxides; yttrium carboxylate; yttrium amide; yttrium acetylacetonate and yttrium tert-butylacetylacetonate; d) Alkyl hafnium; hafnium alkoxides; hafnium aryl oxides; hafnium carboxylates; amide hafnium; hafnium acetylacetonate and hafnium tert-butylacetylacetonate; e) Alkyl titanium; titanium alkoxides; titanium aryl oxides; titanium carboxylate; titanium amide; titanium acetylated pyruvate and titanium tert-butylacetylated pyruvate; f) Alkyl zirconium; zirconium alkoxides; zirconium aryl oxides; zirconium carboxylate; zirconium amide; zirconium acetylated pyruvate and zirconium tert-butyl acetylated pyruvate; g) Vanadium alkoxides; Vanadium oxytris(alkoxides); Vanadium aryl oxides; Vanadium carboxylic acids; Vanadium tris(acetylpyruvate) and Vanadium tris(tert-butylacetylpyruvate); Vanadium oxybis(acetylpyruvate); h) Alkyl zinc; alkyl zinc alkoxides; zinc alkoxides; zinc aryl oxides; zinc carboxylate; zinc amide; zinc acetylacetonate and zinc tert-butylacetylacetonate. i) Trialkylaluminum compounds; aluminum alkoxides; aluminum aryl oxides; aluminum amides; aluminum tert-butylacetylpyruvate; and alkylaluminum oxides and alkoxides; j) Trialkyl gallium compounds; gallium alkoxides; gallium aryl oxides; gallium carboxylate; gallium amide; and alkyl gallium alkoxides; k) Trialkylindium compounds; indium alkoxides; indium aryl oxides; indium carboxylate; indium acetylacetonate; and indium tert-butylacetylacetonate; and l) Stannous phosphate; stannous pyrophosphate, stannous alkoxide; stannous aryl oxide; stannous carboxylate; stannous acetylacetonate; and tert-butylacetylacetonate.

2. The method according to claim 1, wherein the catalyst promoter is selected from: a) magnesium alkoxide; b) scandium alkoxide; c) yttrium alkoxide; d) hafnium alkoxide; e) titanium alkoxide; f) zirconium alkoxide; g) vanadium alkoxide; h) zinc alkoxide; i) aluminum alkoxide; j) gallium alkoxide; and k) indium alkoxide.

3. The method according to claim 1 or 2, wherein the method further comprises a preliminary stage prior to the polymerization stage, wherein a bimetallic cyanide catalyst complex, a catalyst promoter free of halogen anions and cyanide ions, and an initiator form an initial reaction mixture, followed by the introduction of a portion of carbon dioxide and at least one epoxide into the reactor, and the contents of the reactor being heated to the polymerization temperature.

4. The method according to any one of claims 1 to 2, wherein the initiator comprises at least one selected from monohydric alcohol initiators and polyhydric alcohol initiators; and / or For at least one and / or all of the stages, the pressure operating conditions for forming polycarbonate-based polyols include pressures in the range of 40 psig to 150 psig and / or in the range of 100 psig to 140 psig.

5. The method according to any one of claims 1 to 3, wherein the carbon dioxide is added intermittently or continuously to the reactor during the polymerization stage in the presence of the bimetallic cyanide catalyst complex and the catalyst promoter, and each of the at least one epoxide is added intermittently or continuously to the reactor during the polymerization stage.

6. The method according to any one of claims 1 to 4, wherein the method enables the elimination of a separate catalyst activation step performed under a nitrogen atmosphere.

7. The method according to any one of claims 1 to 5, wherein, The carbon dioxide and at least one epoxide are polymerized using the initiator to form the poly(ether-carbonate) polyol.

8. The method according to any one of claims 1 to 6, wherein the poly(ether-carbonate) polyol is manufactured in batch or semi-batch manner.

9. The method according to any one of claims 1 to 6, wherein the poly(ether-carbonate) polyol is manufactured by a continuous process; and / or Under continuous operating conditions, the pressure is kept constant by a fixed operating method where the reactor pressure is between 20 psig and 150 psig.

10. The method according to claim 1 or 2, wherein the catalyst promoter is selected from: aluminum triisopropoxide (Al(O-iPr)3), aluminum trisec-butoxide (Al(OBu)3), hafnium tert-butoxide (IV) (Hf(OBu)4), magnesium di-tert-butoxide (Mg(OBu)2), gallium ethoxide (III) (Ga(OEt)3), indium ethoxide (III) (In(OEt)3), and titanium ethoxide (IV) (Ti(OEt)4); and / or The amount of carbon dioxide added is sufficient to increase the pressure in the reactor to greater than 60 psig and less than 200 psig, or greater than 100 psig and less than 150 psig, or less than 125 psig.

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