Melt dispersion process for making polymer polyols

Abstract

A preformed thermoplastic polymer is dispersed in a polyol by a mechanical dispersion process. A stabilizer is present to stabilize the dispersed polymer particles. A poor solvent is also present. The poor solvent has been shown to result in smaller particle sizes and improved dispersion stability.

Description

[Technical Field]

[0001] The present invention relates to a method for making a dispersion of polymer particles in a polyol.

[0002] So-called "polymer polyols" are well-known materials. Polymer polyols have a continuous liquid phase composed of one or more compounds with multiple hydroxyl groups. Solid particles of another polymer are dispersed in the polyol phase. Common dispersed phase particles are styrene polymers and copolymers (such as styrene-acrylonitrile polymers), polyurea polymers, and polyurethane-urea polymers, among others.

[0003] Historically, polymer polyols have been primarily produced by polymerizing a dispersed phase polymer directly within a continuous polyol phase. However, this process has certain drawbacks that may be overcome using a mechanical dispersion process, such as that described in U.S. Pat. No. 6,613,827. In a mechanical dispersion process, the discontinuous phase polymer is separately formed and then dispersed in the polyol. The dispersion step can be carried out by heat-softening the formed polymer and then mixing the heat-softened polymer with the polyol under shear. The shear action breaks down the heat-softened polymer into small droplets that become dispersed in the polyol phase. Upon cooling, a dispersion of polymer particles is formed.

[0004] A drawback of the mechanical dispersion process is that it has proven difficult to achieve the desired combination of high solids (i.e., a high content of dispersed polymer particles) and low viscosity. For the same solids concentration, polymer polyols produced using the mechanical dispersion process tend to have much higher viscosities than polymer polyols made using in-situ polymerization methods. This problem is particularly pronounced for high-solids products containing more than 35% by weight of dispersed solids.

[0005] It would therefore be desirable to provide a more efficient mechanical dispersion method for making polymer polyols, especially one that can achieve low product viscosities even at high solids contents.

[0006] The present invention is such a method for making a polymer polyol. The method comprises: (a) forming a heated and pressurized mixture of i) one or more 250 to 6000 hydroxyl equivalent alcohols selected from the group consisting of polyethers, polyesters, and natural oil polyols having an oxyalkylene content of 80% by weight or greater, each of which nominally has 1 to 8 hydroxyl groups per molecule, and each of which is liquid at 25°C and 101.3 kPa atmospheric pressure and has a boiling point of 150°C or greater at 101.3 kPa atmospheric pressure; ii) a thermoplastic polymer that is insoluble in component i) and has a Vicat softening temperature of greater than 60°C up to 300°C; iii) a dispersion stabilizer; and iv) an antisolvent, wherein the heated and pressurized mixture is at a temperature above the Vicat softening temperature of the thermoplastic polymer and under a pressure sufficient to maintain the antisolvent and component i) as liquids; (b) shearing the heated and pressurized mixture to form a dispersion of droplets of heat-softened thermoplastic polymer in a liquid phase comprising one or more alcohols having a hydroxyl equivalent weight of 250 to 6000; (c) cooling the dispersion of droplets below the Vicat softening temperature of the thermoplastic polymer to solidify the thermoplastic polymer droplets and form particles of the thermoplastic polymer to form the polymer polyol.

[0007] The presence of an anti-solvent has been found to result in a reduction in the dispersed particle size and a reduction in viscosity in the product after the anti-solvent is removed. Viscosity reduction is observed even at high solids contents of 35% by weight or more. Thus, the present invention provides a simple and inexpensive method for achieving the goal of high solids and low product viscosity. Additionally, the anti-solvent is easy to remove from the product.

[0008] Component i) is one or more alcohols, each having a hydroxyl equivalent weight of 250 to 6000 and nominally 1 to 8 hydroxyl groups per molecule. Each such alcohol is selected from polyethers, polyesters, and natural oil polyols having an oxyalkylene content of 80% or greater. Each alcohol in component i) is liquid at room temperature and at an atmospheric pressure of 101.3 kPa and has a boiling point of 150°C or greater at 101.3 kPa.

[0009] Suitable polyethers are prepared by alkoxylating an initiator compound having one or more active hydrogen atoms. The nominal number of hydroxyl groups per molecule corresponds to the average number of active hydrogen atoms in the initiator or initiators used to prepare the polyether. The active hydrogens are generally present as hydroxyl groups, primary amino groups, secondary amino groups, or thiol groups. Primary amino groups contain two active hydrogen atoms. The initiator is preferably one or more hydroxyl-containing compounds.

[0010] The polyethers of component i) contain at least 80 wt. %, preferably at least 90 wt. % oxyalkylene units. The weight of the oxyalkylene units can be determined by proton NMR or calculated from the weight of the starting materials polymerized to produce each polyether. In some embodiments, the total weight of each polyether is made up of oxyalkylene units and residues of one or more initiators after removal of active hydrogen atoms.

[0011] The polyether of component i) may have a hydroxyl equivalent weight of 350 or greater, 450 or greater, 750 or greater, or 1000 or greater in some embodiments, and in particular embodiments, up to 4000, up to 3000, up to 2500, up to 2200, or up to 2000.

[0012] Examples of polyethers of component i) include, for example, polymers of propylene oxide, ethylene oxide, 1,2-butylene oxide, and tetramethylene oxide, as well as block and / or random copolymers thereof. Of particular interest are random and / or block copolymers of propylene oxide and ethylene oxide containing 1 to 50 weight percent oxyethylene units. In some embodiments, such copolymers may contain 5 weight percent or more, or 7 weight percent or more, of oxyethylene units, and in some embodiments, up to 35 weight percent, up to 25 weight percent, or up to 20 weight percent oxyethylene units. In some embodiments, the copolymer is an ethylene oxide-capped poly(propylene oxide) or an ethylene oxide-capped random copolymer of propylene oxide and ethylene oxide, in either case having the oxyethylene content described above.

[0013] The polyether may contain low levels of terminal unsaturation (e.g., less than 0.02 meq / g or less than 0.01 meq / g). Examples of such low-unsaturation polyethers include those made using so-called double metal cyanide (DMC) catalysts, as described in, for example, 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, 5,470,813, and 5,627,120.

[0014] Alternatively, some or all of the polyether may contain terminal unsaturation. Such terminal unsaturation may include propenyl and / or allylic unsaturation produced in side reactions during polyether production. Some or all of the terminal unsaturation may be produced by capping the polyether with one or more ethylenically unsaturated capping groups. Ethylenically unsaturated isocyanates, ethylenically unsaturated siloxanes, ethylenically unsaturated carboxylic acids, and ethylenically unsaturated epoxides are suitable capping agents. Specific capping agents include isocyanatoethyl methacrylate, isopropenyl dimethyl benzyl isocyanate (especially m-isopropenyl-α,α-dimethyl benzyl isocyanate), and vinyl trimethoxysilane.

[0015] Natural oil polyols useful as all or part of component i) include hydroxyl-functional triglycerides, such as oils and fats produced in biological processes by plants and / or animals. Castor oil is an example of such a triglyceride. Hydroxyl-functional triglycerides also include various oils and fats that have typically been modified by oxidation or hydrolysis of one or more carbon-carbon double bonds to introduce hydroxyl groups. Examples of the latter type of hydroxyl-functional triglyceride include so-called "blown" soybean oil that has been oxidized or hydrolyzed to introduce hydroxyl groups, as described in U.S. Patent Application Publication Nos. 2002 / 0121328, 2002 / 0119321, and 2002 / 0090488.

[0016] Component ii) is a thermoplastic polymer that is insoluble in component i) and is characterized by having a Vicat softening temperature of above 60° C. up to 300° C. The thermoplastic polymer may be semi-crystalline, in which case it preferably also has a crystalline melting temperature in the range of above 60° C. up to 300° C. Alternatively, the thermoplastic polymer may be amorphous, in which case it exhibits the above softening temperature but does not exhibit a crystalline melting point.

[0017] Vicat softening temperature is conveniently determined according to ASTM D1525-17e1 under a load of 10 Newtons and a heating rate of 120°K / hr. In some embodiments, the thermoplastic polymer has a Vicat softening temperature of 75°C or more, or 85°C or more, and 275°C or less, 250°C or less, 225°C or less, 200°C or less, 175°C or less, or 150°C or less.

[0018] The thermoplastic polymer is insoluble in component i). For purposes of the present invention, a thermoplastic polymer is considered insoluble in component i) if it is soluble at 2% or less (i.e., 2 grams of thermoplastic polymer in 100 grams of component i). More preferably, the solubility is 1% or less, and even more preferably, 0.5% or less.

[0019] Solubility in component i) is conveniently determined by forming a mixture containing equal parts by weight of components i) and ii) (in the absence of stabilizers), heating the mixture with stirring to a temperature above the Vicat softening temperature of component ii) for 1 hour to break up the thermoplastic polymer into droplets dispersed in component i), and then cooling the mixture to room temperature. Insolubility is manifested by the settling of particles in the cooled mixture when inspected with the naked eye. Solubility can be determined from the weight of the settled particles.

[0020] The combined content of hydroxyl groups, thiol groups, primary amino groups, and secondary amino groups in the thermoplastic polymer of component ii) is preferably 0.25% by weight or less, preferably 0.05% by weight or less, and may be devoid of these groups. The thermoplastic polymer of component ii) is preferably non-reactive with isocyanate groups.

[0021] Examples of thermoplastic polymers of component ii) include poly(vinyl aromatic) polymers such as polystyrene; copolymers of one or more vinyl aromatic monomers with one or more other monomers, such as styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-butyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-vinyl acetate copolymer, or acrylonitrile-butadiene-styrene copolymer; polymers of conjugated dienes such as butadiene polymers and copolymers; polyolefins such as polyethylene, ethylene-higher alkene copolymers, and polypropylene; polyesters, polylactic acid, polycarbonate, thermoplastic polyurethanes, and polyamides. Polystyrene and styrene-acrylonitrile copolymers are preferred.

[0022] The molecular weight of the thermoplastic polymer is not particularly critical, but it is necessary that the polymer have the desired softening temperature and that the softened polymer have a viscosity at a temperature suitable for making the polymer polyol such that the polymer can be dispersed into droplets of 100 micrometers or less in diameter as measured by optical diffraction. The thermoplastic polymer preferably has a melt flow index of 1 to 20 decigrams per minute when measured according to ASTM D-1238 at 200°C under an applied load of 5 kg.

[0023] Component iii) Dispersion Stabilizer. The stabilizer is one or more materials, distinct from components i), ii), and iv), that function to inhibit or eliminate settling of the dispersed thermoplastic polymer from the liquid component i) phase in the process and product. In some embodiments, such stabilizers have a molecular structure that includes at least one portion that is compatible with the liquid component i) phase and at least one portion that is compatible with the thermoplastic polymer.

[0024] Suitable stabilizers include, for example: a) imide-containing reaction products of maleic anhydride functionalized polyethylene waxes and monoamine polyols, as described, for example, in U.S. Pat. No. 6,613,827; b) reaction products of ethylene-acrylic acid copolymers with monoamine polyols, as described, for example, in U.S. Pat. No. 6,613,827; c) polyester-polyether block copolymers, polyamide-polyether block copolymers, polystyrene-polyether block copolymers, and polyethylene-polyether block copolymers, such as those described in U.S. Pat. No. 8,344,061; and d) (1) a polyether polyol having polymerizable carbon-carbon unsaturation and (2) a copolymer of styrene or a mixture of styrene and one or more other ethylenically unsaturated monomers copolymerizable with styrene, each having a molecular weight of 150 or less. The polyether polyol may be a branched polyol having a number average molecular weight of 4000 to 2000 (by GPC against polyether standards) and having 0.2 to 1.2 polymerizable ethylenically unsaturated groups per molecule and 3 to 8 hydroxyl groups per molecule. Such copolymers are described, for example, in U.S. Pat. Nos. 8,822,581, 9,994,701, U.S. Patent Application Publication Nos. 2017-0044297, and 2017-0051097. They may have a linear, branched, comb, star, or other structure.

[0025] In some embodiments, the stabilizer comprises a copolymer of (1) 10 to 70% by weight of a branched polyol having a number average molecular weight of 4000 to 20,000, at least one polymerizable ethylenically unsaturated group per molecule, and about 3 to about 8 hydroxyl groups per molecule, and (2) 30 to 90% by weight of styrene or a mixture of styrene and one or more other low molecular weight monomers. The copolymer is preferably a copolymer of 10 to 40% by weight of (1) and 60 to 90% by weight of (2). More preferably, it is a copolymer of 15 to 35% by weight of (1) and 65 to 85% by weight of (2). The "low molecular weight" monomer has a molecular weight of 150 g / mol or less. The copolymer described in this paragraph preferably has a number average molecular weight of about 20,000 g / mol to about 300,000 g / mol, as measured by GPC against polystyrene standards. Such copolymers and methods for making them are described, for example, in US Pat. Nos. 8,822,581 and 9,994,701.

[0026] The dispersion stabilizer may be provided as a mixture of the stabilizer in one or more carriers. The carrier may comprise up to about 80%, preferably about 20-80%, and more preferably about 50-80% of the combined weight of the carrier and stabilizer. The carrier material may, in some embodiments, comprise one or more polyethers as described with respect to component i). When such polyethers are present as carriers, their weight is considered to be part of the weight of component i). Such polyether carriers may, for example, comprise unreacted portions of the starting polyethers used in making the dispersion stabilizer.

[0027] The support material may also comprise an anti-solvent as described for component d), in which case that portion of the support material is included in the weight of component d).

[0028] The carrier material may also be a monool or polyol different from component i) and component iv). Such a monool or polyol may have, for example, a hydroxyl equivalent weight of 75 to 249 or more and 1 to 8 or more hydroxyl groups per molecule. Such a monool or polyol carrier is preferably liquid at 25°C and an atmospheric pressure of 101.3 kPa and has a boiling point of 150°C or higher at 101.3 kPa.

[0029] The anti-solvent is liquid at 25°C and atmospheric pressure of 101.3 kPa. The anti-solvent has a boiling point of less than 150°C, preferably 60-125°C or 75-120°C, at atmospheric pressure of 101.3 kPa. The thermoplastic polymer is soluble in the anti-solvent to the extent that there are no more than 2 parts by weight of thermoplastic polymer per 100 parts by weight of anti-solvent. In some embodiments, the anti-solvent has a formula molecular weight of 125 or less or 75 or less.

[0030] In some embodiments, the antisolvent is water and / or one or more organic compounds soluble in water at a concentration of 5 parts by weight or more, preferably 25 parts by weight or more, per 100 parts by weight of water. The organic antisolvent may be, for example, a C1-C4 alcohol, such as ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, and isobutanol. Other useful organic antisolvents include acetone, methyl ethyl ketone, acetonitrile, 1,4-dioxane, pyridine, and tetrahydrofuran. 2-Propanol is a preferred antisolvent. Water is most preferred.

[0031] The polymer polyol is produced in a process that includes forming a heated and pressurized mixture of components i), ii), iii), and iv). The temperature of the mixture is higher than the Vicat softening temperature of the thermoplastic polymer. The temperature of the mixture can be, for example, 100°C or higher, 125°C or higher, 150°C or higher, or 175°C or higher, and 250°C or lower, or 225°C or lower, but must be higher than the Vicat softening temperature. The pressure is sufficient to maintain component i) and the antisolvent (component iv)) as liquids at the temperature used. The pressure can be, for example, 0.25 MPa or higher, 0.5 MPa or higher, 1 MPa or higher, and 50 MPa or lower, 25 MPa or lower, 10 MPa or lower, or 5 MPa or lower.

[0032] The hot-pressurized mixture in some embodiments contains components i) through iv) in the following weight percentages, in all cases these weight percentages are based on the total weight of components i) through iv).

[0033] a) at least 35%, at least 45%, or at least 50% by weight, and at most 90%, at most 80%, at most 70%, or at most 60% by weight of component i); b) at least 5 wt.%, at least 10 wt.%, at least 25 wt.%, and at most 50 wt.%, at most 40 wt.%, or at most 35 wt.% of component ii); c) at least 0.5 wt.%, at least 1 wt.%, at least 1.5 wt.%, or at least 2 wt.%, and at most 10 wt.%, at most 7.5 wt.%, or at most 5 wt.% of component iii), and d) 0.5% by weight or more, 1% by weight or more, 2% by weight or more, or 2.5% by weight or more, and 20% by weight or less, 10% by weight or less, or 7.5% by weight or less of component iv).

[0034] The heated and pressurized mixture is subjected to shear to form a dispersion of droplets of the heat-softened thermoplastic polymer in a liquid phase containing component i). The temperature and pressure conditions for this step are similar to those described above, i.e., a temperature above the Vicat softening temperature of the thermoplastic resin and sufficient pressure to maintain components i) and iv) as liquids. Shearing is continued until the droplets reach the desired size. Generally, it is preferred to produce droplets having a volume average particle size of 100 μm or less, particularly 50 μm or less, 25 μm or less, or 15 μm or less, as measured by laser diffraction. The volume average particle size may be 100 nm or more, 500 nm or more, 1 μm or more, or 2.5 μm or more.

[0035] Once the droplets have been formed and sheared to the desired size, the dispersion of droplets is cooled below the Vicat softening temperature of the thermoplastic polymer. During this step, the dispersion is preferably agitated to minimize coalescence of the dispersed droplets. Upon cooling, the droplets solidify to form particles, thus producing the polymer polyol.

[0036] Suitable apparatus and methods for producing polymer polyols are described, for example, in U.S. Patent No. 6,613,827. The apparatus can be any device or series of devices capable of forming a heated and pressurized mixture, shearing it into droplets in the presence of polyol, and maintaining the dispersed droplets under agitation or shear until they can cool and solidify.

[0037] Examples of suitable equipment include high-shear batch mixers such as Brabender mixers or Parr reactors, rotor-stators, or preferably extruders. Two or more of these devices can be used in combination, such as tandem extruders or extruders coupled with rotor-stators. By "extruder" is meant a device having an elongated barrel, an outlet at or near one end of the barrel, mixing elements within the elongated barrel, and a means for extruding liquid or molten material essentially as a plug flow through the mixing elements and into and out of the outlet. Most typically, extruders have one or more longitudinally rotating screws disposed within the barrel. While the screw or screws are typically designed to perform both extrusion and mixing functions, it is also possible for the screw or screws to perform only one or the other of these functions, with some other device performing the other function. However, the most preferred device is a single-screw or twin-screw extruder, in which one or more screws contain mixing elements.

[0038] A twin-screw extruder equipped with a back-pressure regulator is a particularly preferred device. The back-pressure regulator includes one or more conduits with a variable cross-section. The back-pressure regulator operates by adjusting the cross-sectional area of ​​the one or more conduits so that a predetermined pressure is maintained upstream of the back-pressure regulator. Many devices of this type are commercially available, such as those sold under the trade name GO Regulator by Fluid Control Systems, Inc. (Spartanburg, South Carolina). A preferred back-pressure regulator can be adjusted to provide a predetermined back-pressure and may have a high-pressure relief mechanism that allows it to release excess pressure if a predetermined maximum pressure is exceeded.

[0039] The process can be carried out in a batch, continuous or semi-continuous mode.

[0040] In a batch process, the ingredients are conveniently mixed in a suitable vessel and heated under pressure and shear to heat-soften the thermoplastic polymer droplets and shear the droplets to an appropriate size, followed by cooling to solidify the particles.

[0041] In some embodiments of a continuous or semi-continuous process, the thermoplastic resin may be combined with one or more of the other ingredients and heat softened in the presence of such other ingredients, or the thermoplastic polymer may be heat softened before being combined with the other ingredients.

[0042] In a preferred process, the thermoplastic polymer is heat-softened and mixed with a stabilizer or a mixture of a dispersion stabilizer and a small amount of (component i), and then the resulting mixture is added simultaneously or in any order to the remainder of component i) and the anti-solvent.

[0043] In certain processes, the thermoplastic polymer is introduced into the mixing section of an extruder. The thermoplastic polymer may be fed into the extruder as a solid material from a hopper or similar device and then heat-softened in the mixing section of the extruder or in another section upstream of the mixing section. Alternatively, the thermoplastic polymer may be fed into the extruder as a heat-softened material. In the latter case, the heat-softened polymer may be fed into the extruder through an inlet, hopper, or similar feeding device capable of handling viscous fluids. In certain embodiments, the thermoplastic polymer is heat-softened in a first extruder, and the heat-softened polymer is fed into the barrel of a second extruder, where it is used to form a polymer polyol.

[0044] In a preferred process, the extruder includes at least one injection port within or upstream of the first mixing section, through which components i), iii), and iv) are introduced into the extruder. Components i), iii), and iv) may be introduced in any order or subcombination, but it is preferred that the dispersion stabilizer (optionally combined with a minor portion of component i) be introduced simultaneously with or before the major portion of component i), i.e., at the same or upstream location(s) as the major portion of component i). The antisolvent is preferably introduced simultaneously with the dispersion stabilizer or after the dispersion stabilizer and before the major portion of component i) is introduced. Components i), iii), and iv) are then mixed with the heat-softened polymer in the mixing section of the extruder. The mixing section of the extruder preferably includes a gear mixer or other mixing element.

[0045] In many cases, it is advantageous to use the highest possible temperature in the first mixing section, consistent with the thermal stability of the various materials, to reduce the viscosity of the heat-softened thermoplastic polymer. Temperature conditions that result in significant material degradation should be avoided. Of course, the required temperature in any case will depend on the specific starting materials used. It is usually preferable to avoid using temperatures that are more than 80°C above the crystalline melting point (for semi-crystalline polymers) or glass transition temperature of the thermoplastic polymer, whichever is higher. Pressure conditions throughout the process are sufficient to maintain component i) and the anti-solvent (component iv) as liquids.

[0046] It is preferred that the stabilizer (and any optional component i) that may be present in the stabilizer) be preheated to a temperature at or near the desired temperature in the first mixing section before being introduced therein, which helps to reduce localized cold spots and helps to prevent localized solidification of the molten thermoplastic polymer.

[0047] In a preferred process, the resulting mixture of polystyrene polymer, component i), dispersion stabilizer, and antisolvent is then conveyed to the downstream section of the extruder, where the mixture is subjected to shear conditions to break up the heat-softened thermoplastic polymer into droplets that are dispersed in component i). By "conveyed" in this context, it is simply meant that the mixture is moved downstream within the extruder toward the zone where the second mixing step occurs. This is typically accomplished by the normal action of the extruder's screw or screws, which move the material forward through the extruder in a plug flow fashion.

[0048] The temperature and pressure conditions in the downstream section are generally the same as those described for the first mixing section. The temperature and pressure need not be the same as those in the previous section of the extruder, but they can be.

[0049] After dispersing the heat-softened thermoplastic polymer in component i), the resulting polymer polyol is cooled sufficiently to solidify the dispersed polystyrene polymer droplets and form particles. To prevent agglomeration and / or equipment fouling, the polymer polyol should be stirred until the particles solidify. The resulting particle size will be very similar to the droplet size before cooling, but may differ slightly due to thermal expansion or contraction, or, in the case of crystalline or semi-crystalline polymers, phase changes. The cooling step can be performed within the extruder or after the polymer polyol has exited the extruder. If the polymer polyol is cooled within the extruder, it is preferable to cool the polymer polyol before it reaches any of the restricted flow zones determined by the backpressure regulator. This can reduce or prevent fouling of equipment in that zone and prevent or reduce the occurrence of particle agglomeration in that zone. Alternatively, cooling can be performed after the polymer polyol has exited the extruder, such as by passing it through a parallel-flow or counter-flow heat exchanger. It is also possible to cool the polymer polyol in a mixing vessel operating at low temperature to quench the discharge from the extruder.

[0050] The polymer polyol thus produced may be treated to remove volatile materials (such as anti-solvent) and other impurities. Some or all of the anti-solvent may be released (flashed) upon release of pressure from the equipment or as the product exits the extruder. If the stabilizer contains unremoved solvent, the solvent can be removed from the polymer polyol product at this stage. Volatile materials can be removed by heating and / or reducing the pressure of the polymer polyol using a suitable device such as a rotary evaporator or wiped-film evaporator. Temperatures high enough to melt or soften the dispersed polystyrene polymer particles should be avoided.

[0051] The polymer polyol can be devolatilized in a vacuum zone of the extruder either before or after the cooling step.

[0052] The anti-solvent is preferably removed to a concentration of 0.1% by weight or less, based on the total weight of the polymer polyol.

[0053] The proportions of components i), ii), and iii) in the polymer polyol product generally correspond to the proportions of these components used in the manufacturing process. Specifically, the polymer polyol may contain 5% by weight or more, 10% by weight or more, 25% by weight or more, and 50% by weight or less, 40% by weight or less, or 35% by weight or less of the thermoplastic polymer. In some embodiments, the polymer polyol may contain 30% by weight or more to 50% by weight or less of one or more polymerized vinyl monomers derived from components ii) and iii). In certain embodiments, the polymer polyol contains 30 to 50% by weight of polymerized styrene or polymerized styrene and acrylonitrile. The amount of polymerized vinyl monomers, such as styrene and / or acrylonitrile, in the polymer polyol product can be measured using NMR techniques.

[0054] Polymer polyols are useful for making a wide variety of polyurethane and / or polyurea products. Polyurethane and / or polyurea products will most often be elastomeric materials that can be noncellular, microcellular, or foamed. Polyurethanes are typically prepared by reacting a polymer polyol with a polyisocyanate. The polymer polyol product may be mixed with one or more additional polyols, including those listed above, to adjust the solids content to a desired level or to provide specific properties to the polyurethane. The reaction with the polyisocyanate is carried out in the presence of a blowing agent or gas if a cellular product is desired. The reaction can be carried out in a closed mold, although in some applications, such as slabstock foam, the reaction mixture is generally allowed to expand somewhat freely to form a low-density foam material. Generally, the polymer polyols of the present invention can be used in the same manner as conventional polymer polyol materials, using the same general types of processes used with such materials.

[0055] Suitable polyisocyanates include aromatic, alicyclic, and aliphatic isocyanates. Exemplary polyisocyanates include m-phenylene diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, hexamethylene-1,6-diisocyanate, tetramethylene-1,4-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotolylene diisocyanate, naphthylene-1,5-diisocyanate, 1,3- and / or 1,4-bis(isocyanatomethyl)cyclohexane (including cis and / or trans isomers), methoxyphenyl-2,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, and the like. anate, hydrogenated diphenylmethane-4,4'-diisocyanate, hydrogenated diphenylmethane-2,4'-diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4',4''-triphenylmethane triisocyanate, polymethylene polyphenylisocyanate (PMDI), toluene-2,4,6-triisocyanate, and 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate. Preferably, the polyisocyanate is diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, PMDI, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, or a mixture thereof. Diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, and mixtures thereof, collectively referred to as MDI, can all be used. Toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, and mixtures thereof, collectively referred to as TDI, can all be used.

[0056] The amount of polyisocyanate used in making polyurethanes is generally expressed in terms of the isocyanate index, i.e., 100 times the ratio of NCO groups to isocyanate-reactive groups in the reaction mixture (including those provided by water, when used as a blowing agent). In conventional slabstock foam production, the isocyanate index typically ranges from about 95 to 140, particularly from about 105 to 115. In molded and high-resilience slabstock foams, the isocyanate index typically ranges from about 50 to about 150, particularly from about 85 to about 110.

[0057] A catalyst is often used to promote the polyurethane-forming reaction. The selection of a particular catalyst package can vary somewhat depending on the particular application, the particular polymer polyol or dispersion used, and other ingredients in the formulation. The catalyst may catalyze the "gelling" reaction between one or more polyols and the polyisocyanate, and / or, in many polyurethane foam formulations, the water / polyisocyanate (blowing) reaction, which produces urea bonds and free carbon dioxide to expand the foam. In making water-blown foams, it is typical to use a mixture of at least one catalyst that favors the blowing reaction and at least one other catalyst that favors the gelling reaction.

[0058] A wide variety of materials are known to catalyze the polyurethane-forming reaction, including tertiary amines, tertiary phosphines, various metal chelates, acid metal salts, strong bases, various metal alcoholates and phenolates, and metal salts of organic acids. The most important catalysts are tertiary amine catalysts and tin catalysts. Examples of tertiary amine catalysts include trimethylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, N,N-dimethylbenzylamine, N,N-dimethylethanolamine, N,N,N',N'-tetramethyl-1,4-butanediamine, N,N-dimethylpiperazine, 1,4-diazobicyclo-2,2,2-octane, bis(dimethylaminoethyl)ether, triethylenediamine, and dimethylalkylamines in which the alkyl group contains 4 to 18 carbon atoms. Mixtures of these tertiary amine catalysts are often used.

[0059] Examples of tin catalysts include stannic chloride, stannous chloride, stannous octoate, stannous oleate, dimethyltin dilaurate, dibutyltin dilaurate, and tin catalysts of the formula SnR n (OR) 4-n where R is alkyl or aryl and n is 0-2, and other organotin compounds. When used, tin catalysts are generally used in conjunction with one or more tertiary amine catalysts. Tin catalysts tend to be strong gelling catalysts and are therefore preferably used in small amounts, especially in high resilience foam formulations. Commercially available tin catalysts of interest include Dabco™ T-9 and T-95 catalysts (stannous octoate compositions, both available from Air Products and Chemicals).

[0060] Catalysts are typically used in small amounts, for example, each catalyst is used at about 0.0015 to about 5 weight percent of the high equivalent weight polyol.

[0061] To form a foam, the reaction between the polyisocyanate and the polyol component is carried out in the presence of a blowing agent. Suitable blowing agents include physical blowing agents, such as various low-boiling chlorofluorocarbons, fluorocarbons, and hydrocarbons. Fluorocarbons and hydrocarbons, which have low or no global warming and ozone depletion potential, are preferred among physical blowing agents. Chemical blowing agents that decompose or react under the conditions of the polyurethane-forming reaction are also useful. Water is by far the most preferred chemical blowing agent, reacting with isocyanate groups to liberate carbon dioxide and form urea bonds. Water is preferably used as the sole blowing agent, typically in an amount of about 1 to about 7 parts by weight, and more preferably about 2.5 to about 5 parts by weight, per 100 parts by weight of high equivalent weight polyol. Water may also be used in combination with physical blowing agents, particularly fluorocarbon or hydrocarbon blowing agents. Additionally, gases such as carbon dioxide, air, nitrogen, or argon may be used as blowing agents in the frothing process. Carbon dioxide may also be used as a liquid or supercritical fluid.

[0062] Foam stabilizing surfactants are also used when polyurethane foam is prepared.A wide variety of silicone surfactants, such as those commonly used in the preparation of polyurethane foam, can be used to prepare foam using the polymer polyol or dispersion of the present invention.Examples of such silicone surfactants are commercially available under the trade names Tegostab (Evonkic Industries), Niax (Momentive Performance Materials), and Dabco (Evonik Industries).

[0063] In addition to the aforementioned components, the polyurethane formulation may contain various other optional ingredients such as cell openers; fillers such as calcium carbonate; pigments and / or colorants such as titanium dioxide, iron oxide, chromium oxide, azo / diazo dyes, phthalocyanines, dioxazines, or carbon black; reinforcing agents such as fiberglass, carbon fiber, adhesive glass, mica, talc, and the like; biocides; preservatives; antioxidants; flame retardants, and the like.

[0064] Generally, polyurethane foams are prepared by mixing a polyisocyanate and a polymer polyol in the presence of a blowing agent, a surfactant, one or more catalysts, and other optional ingredients, under conditions such that the polyisocyanate and polyol react to form a polyurethane and / or polyurea polymer, while the blowing agent produces a gas that expands the reaction mixture. Foams can be formed by the so-called prepolymer method (e.g., as described in U.S. Pat. No. 4,390,645), in which a stoichiometric excess of polyisocyanate is first reacted with one or more high equivalent weight polyols to form a prepolymer, which is then reacted in a second step with a chain extender and / or water to form the desired foam. Foaming methods (e.g., as described in U.S. Pat. Nos. 3,755,212, 3,849,156, and 3,821,130) are also suitable. The so-called one-shot process (such as that described in U.S. Pat. No. 2,866,744) is preferred. In such one-shot processes, the polyisocyanate and all polyisocyanate-reactive components are simultaneously combined to cause reaction. Three widely used one-shot processes suitable for use in the present invention include the slabstock foam process, the high resilience slabstock foam process, and the molded foam process.

[0065] The following examples are presented to illustrate the invention but are not intended to limit its scope. All parts and percentages are by weight unless otherwise indicated.

[0066] Examples 1-2 and Comparative Experiments A and B A. Macromer Formation Potassium hydroxide is added to a sorbitol-initiated poly(propylene oxide) starter polyol having a weight average molecular weight of about 700. Sufficient potassium hydroxide is added to provide about 2100 ppm of KOH in the final product. An 88 / 12 mixture of propylene oxide and ethylene oxide is added and polymerized at a temperature of 105°C to produce a hexafunctional polyol in which propylene oxide and ethylene oxide are randomly polymerized. The final ratio of propylene oxide to ethylene oxide is about 88.5:11.5 by weight. The final hydroxyl number is about 28, corresponding to a hydroxyl equivalent weight of 2003 and a number average molecular weight of about 12,000. The oxyalkylene content, calculated from the starting materials, is about 98.4%. After completion and the addition of 250 ppm of antioxidant, 500 parts of this copolymer are heated with stirring to 55°C and 0.55 moles of TMI (per mole of copolymer) are added. 0.05% tin catalyst is then added, and the mixture is stirred at 55°C for 120 minutes. The product of this reaction (Macromer Mixture A) is a mixture containing approximately 55% by weight of macromer, corresponding to the reaction product of TMI and polyether, and approximately 45% by weight of uncapped polyether. The macromer molecules contain one to two polymerizable carbon-carbon double bonds per molecule and four to five hydroxyl groups per molecule.

[0067] B. Preparation of Stabilizer Mixture 120 parts of Macromer Mixture A are placed in a reactor equipped with a pump inlet and agitator. The headspace is purged and backfilled with nitrogen several times. The reactor is sealed, and the reactor and its contents are heated to 120°C. With stirring and while maintaining the reaction temperature at 120°C, a mixture of 160 parts by weight of styrene, 0.96 parts by weight of a free radical initiator, and 519 parts of Polyol A (a polyol with a molecular weight of 4600 and a hydroxyl number of 36, made by adding propylene oxide to glycerin and then adding 20.3% ethylene oxide based on the total weight of the polyol) is added over a period of 2 hours. After the addition of this mixture, stirring is continued while the temperature is increased to 150°C over a period of 3 hours, after which the temperature is held for 1 hour before cooling to 40°C. The resulting stabilizer mixture contains about 28% by weight of the copolymer of styrene and the macromer formed in Step A (dispersion stabilizer) and 72% by weight of polyether polyol (Polyol A plus the amount of uncapped polyether from Step A). ​​The stabilizer mixture contains about 20% polymerized styrene.

[0068] C. Preparation of Polymer Polyols Comparative Sample A: 28 parts of the stabilizer mixture from Step B, 35 parts of polystyrene having a Vicat softening temperature of approximately 103°C and a number average molecular weight of 40,000 g / mole, and 37 parts of Polyol A are charged to a Parr reactor equipped with a Cowles blade. The reactor is closed and pressurized to 400 psig (2.75 MPa). The reactor contents are heated to 220°C, held at that temperature for 20 minutes, and then cooled to room temperature with constant stirring. The Cowles blade is rotated at 60 rpm until the temperature reaches 180°C, at 500 rpm until the temperature reaches 220°C, at 1000 rpm until the temperature returns to 180°C, at 500 rpm until the temperature returns to 100°C, and then at 60 rpm. These high stirring speeds are sufficient to shear the mixture and form a dispersion of polystyrene particles in Polyol A.

[0069] The resulting polymer polyol contains 35 wt. % polystyrene, approximately 7.84 wt. % dispersion stabilizer, and the remainder polyether polyol (Polyol A + uncapped polyether from Step A above). The dispersed polystyrene particles have a volume average particle size of 13.6 μm (as measured with a Beckman Coulter Micro Liquid Module laser diffraction particle sizer after diluting the sample with isopropanol). The polymer polyol has a Brookfield viscosity of 6180 mPa×s (20 rpm, #4 spindle, 25° C.).

[0070] Example 1: Comparative Sample A is repeated by adding 5 parts of water to a Parr reactor, then closing the reactor and heating its contents. Pressure conditions are sufficient to maintain the water in liquid form throughout the process. Water is removed from the product by rotary evaporation until the water content is reduced to less than 0.05 wt. % based on the total weight of the product. The particles dispersed in the resulting polymer polyol have a volume average particle size of 5.8 μm. The polymer polyol has a Brookfield viscosity of 3480 mPa×s. The addition of water to the mechanical dispersion process results in a reduction in both particle size and product viscosity.

[0071] Comparative Sample B: The polystyrene described in the previous example is fed at a rate of 35 parts per hour into the inlet end of a twin-screw extruder with an L / D ratio of 60 and multiple heating zones. The temperature in the heating zones increases from 30°C to 200°C. The screw speed is 1000 rpm. The screw is equipped with a gear mixer element to facilitate mixing of the high-viscosity heat-softened polystyrene into the much lower-viscosity polyol A. In the downstream section where the polystyrene becomes heat-softened, the stabilizer mixture from Step B is added at 28 parts per hour and polyol A at 35 parts per hour through separate inlets. The pressure in the extruder is maintained at 650 psig (4.5 MPa). The heat-softened polystyrene is sheared into small droplets that become dispersed in polyol A, which forms the continuous phase. The resulting dispersion is collected from the outlet end of the extruder and cooled to room temperature in a stirred vessel. The dispersion contains 35 wt. % polystyrene, about 7.84 wt. % dispersion stabilizer, and the remainder polyether polyol (Polyol A + uncapped polyether from Step A above). The dispersed particles have a volume average particle size of 4.0 μm (as measured with a Beckman Coulter Micro Liquid Module particle sizer after diluting the sample with isopropanol). The Brookfield viscosity of the dispersion is 7400 mPa×s.

[0072] This continuous extrusion process produces a smaller particle size product than the batch process of Comparative Sample A, but at the expense of a significantly higher product viscosity.

[0073] Example 2: Comparative Sample B is repeated with the addition of 5 parts / hour of water. The water is injected through the same inlet as the stabilizer mixture from Step B. The pressure conditions in the extruder are sufficient to maintain the water in liquid form. After the extruded product is cooled to room temperature, the water is removed using a rotary evaporator until the product contains less than 0.05% by weight of water. The resulting polymer polyol has a volume average particle size of 3.4 μm (as measured with a Beckman Coulter Micro Liquid Module particle sizer after diluting the sample with isopropanol) and a Brookfield viscosity of 6400 mPa×s.

[0074] Compared to Comparative Sample B, the addition of water results in a significant reduction in particle size and product viscosity. It should be noted that the present invention includes the following aspects. [Aspect 1] 1. A method for making a polymer polyol, comprising: (a)i) one or more alcohols of 250 to 6000 hydroxyl equivalents selected from the group consisting of polyethers, polyesters, and natural oil polyols having an oxyalkylene content of 80% by weight or more, each of said 250 to 6000 hydroxyl equivalent alcohols having nominally 1 to 8 hydroxyl groups per molecule, each of said 250 to 6000 hydroxyl equivalent alcohols being liquid at 25°C and an atmospheric pressure of 101.3 kPa and being soluble in water at a temperature of 150°C or higher at an atmospheric pressure of 101.3 kPa; forming a heated and pressurized mixture of one or more alcohols having a boiling point above 250 to 6000 hydroxyl equivalents, ii) a thermoplastic polymer that is insoluble in component i) and has a Vicat softening temperature above 60°C up to 300°C, iii) a dispersion stabilizer, and iv) an anti-solvent, wherein the heated and pressurized mixture is at a temperature above the Vicat softening temperature of the thermoplastic polymer and under sufficient pressure to maintain the anti-solvent and component i) as liquids; (b) shearing the heated and pressurized mixture to form a dispersion of droplets of the heat-softened thermoplastic polymer in a liquid phase comprising the one or more alcohols having a hydroxyl equivalent weight of 250 to 6000; (c) cooling the dispersion of droplets below the Vicat softening temperature of the thermoplastic polymer to solidify the droplets of the thermoplastic polymer and form particles of the thermoplastic polymer to form the polymer polyol. [Aspect 2] 2. The method of claim 1, wherein the mixture formed in step (a) comprises 30-75 wt. % of i), 20-55 wt. % of ii), 0.5-5 wt. % of iii), and 2-10 wt. % of iv), wherein the weight percentages are based on the combined weight of i), ii), iii), and iv). [Aspect 3] (d) simultaneously with and / or after step (c), removing the anti-solvent from the polymer polyol until the polymer polyol contains less than 0.5 wt.% anti-solvent. [Aspect 4] Aspect 4. The method of aspect 3, wherein after step (d), the polymer polyol contains 35 to 55 weight percent dispersed particles of the thermoplastic polymer. [Aspect 5] Aspect 5. The method of any one of aspects 1-4, wherein the stabilizer comprises: (1) 10 to 40 weight percent of a branched polyol having a molecular weight of 4000 to 20,000 and having at least one polymerizable ethylenically unsaturated group per molecule and from about 3 to about 8 hydroxyl groups per molecule; and (2) 60 to 90 weight percent of a copolymer of styrene or a mixture of styrene with one or more other low molecular weight monomers. [Aspect 6] Aspect 6. The method of any one of aspects 1 to 5, wherein the anti-solvent comprises water. [Aspect 7] Aspect 7. The method of any one of aspects 1 to 6, wherein component i) is one or more polyether polyols. [Aspect 8] Aspect 8. The method of any one of aspects 1 to 7, wherein component ii) is polystyrene or a styrene-acrylonitrile copolymer. [Aspect 9] A polymer polyol made according to any one of embodiments 1-8.

Claims

1. 1. A method for making a polymer polyol, comprising: (a) i) one or more 250 to 6000 hydroxyl equivalent alcohols selected from the group consisting of polyethers, polyesters, and natural oil polyols having an oxyalkylene content of 80% by weight or greater, wherein each of said 250 to 6000 hydroxyl equivalent alcohols nominally has 1 to 8 hydroxyl groups per molecule, and each of said 250 to 6000 hydroxyl equivalent alcohols is a liquid at 25°C and 101.3 kPa atmospheric pressure and has a melting point of 150°C or greater at 101.3 kPa atmospheric pressure; forming a heated and pressurized mixture of one or more alcohols of 250 to 6000 hydroxyl equivalents having a boiling point above 100°C, ii) a thermoplastic polymer which is insoluble in component i) and has a Vicat softening temperature above 60°C up to 300°C, iii) a dispersion stabilizer, and iv) an anti-solvent, wherein the heated and pressurized mixture is at a temperature above the Vicat softening temperature of the thermoplastic polymer and under sufficient pressure to maintain the anti-solvent and component i) as liquids; (b) shearing the heated and pressurized mixture to form a dispersion of droplets of the heat-softened thermoplastic polymer in a liquid phase comprising the one or more alcohols having a hydroxyl equivalent weight of 250 to 6000; (c) cooling the dispersion of droplets below the Vicat softening temperature of the thermoplastic polymer to solidify the droplets of the thermoplastic polymer and form particles of the thermoplastic polymer to form the polymer polyol; Including, 1. The method of claim 1, wherein the mixture formed in step (a) comprises 30 to 75 weight percent of i), 20 to 55 weight percent of ii), 0.5 to 5 weight percent of iii), and 2 to 10 weight percent of iv), said weight percentages being based on the combined weight of i), ii), iii), and iv).

2. 2. The method of claim 1, further comprising the step of: (d) simultaneously with and / or after step (c), removing the anti-solvent from the polymer polyol until the content of the anti-solvent in the polymer polyol is less than 0.5 wt.%.

3. A method for making a polymer polyol, comprising: (a) i) one or more 250 to 6000 hydroxyl equivalent alcohols selected from the group consisting of polyethers, polyesters, and natural oil polyols having an oxyalkylene content of 80% by weight or greater, wherein each of said 250 to 6000 hydroxyl equivalent alcohols nominally has 1 to 8 hydroxyl groups per molecule, and each of said 250 to 6000 hydroxyl equivalent alcohols is a liquid at 25°C and 101.3 kPa atmospheric pressure and has a melting point of 150°C or greater at 101.3 kPa atmospheric pressure; forming a heated and pressurized mixture of one or more alcohols of 250 to 6000 hydroxyl equivalents having a boiling point above 100°C, ii) a thermoplastic polymer which is insoluble in component i) and has a Vicat softening temperature above 60°C up to 300°C, iii) a dispersion stabilizer, and iv) an anti-solvent, wherein the heated and pressurized mixture is at a temperature above the Vicat softening temperature of the thermoplastic polymer and under sufficient pressure to maintain the anti-solvent and component i) as liquids; (b) shearing the heated and pressurized mixture to form a dispersion of droplets of the heat-softened thermoplastic polymer in a liquid phase comprising the one or more alcohols having a hydroxyl equivalent weight of 250 to 6000; (c) cooling the dispersion of droplets below the Vicat softening temperature of the thermoplastic polymer to solidify the droplets of the thermoplastic polymer and form particles of the thermoplastic polymer to form the polymer polyol; Including, (d) simultaneously with and / or after step (c), removing the anti-solvent from the polymer polyol until the content of the anti-solvent in the polymer polyol is less than 0.5 wt. %, A method wherein after step (d), said polymer polyol contains 35 to 55 weight percent dispersed particles of said thermoplastic polymer.

4. A method for making a polymer polyol, comprising: (a) i) one or more 250 to 6000 hydroxyl equivalent alcohols selected from the group consisting of polyethers, polyesters, and natural oil polyols having an oxyalkylene content of 80% by weight or greater, wherein each of said 250 to 6000 hydroxyl equivalent alcohols nominally has 1 to 8 hydroxyl groups per molecule, and each of said 250 to 6000 hydroxyl equivalent alcohols is a liquid at 25°C and 101.3 kPa atmospheric pressure and has a melting point of 150°C or greater at 101.3 kPa atmospheric pressure; forming a heated and pressurized mixture of one or more alcohols of 250 to 6000 hydroxyl equivalents having a boiling point above 100°C, ii) a thermoplastic polymer which is insoluble in component i) and has a Vicat softening temperature above 60°C up to 300°C, iii) a dispersion stabilizer, and iv) an anti-solvent, wherein the heated and pressurized mixture is at a temperature above the Vicat softening temperature of the thermoplastic polymer and under sufficient pressure to maintain the anti-solvent and component i) as liquids; (b) shearing the heated and pressurized mixture to form a dispersion of droplets of the heat-softened thermoplastic polymer in a liquid phase comprising the one or more alcohols having a hydroxyl equivalent weight of 250 to 6000; (c) cooling the dispersion of droplets below the Vicat softening temperature of the thermoplastic polymer to solidify the droplets of the thermoplastic polymer and form particles of the thermoplastic polymer to form the polymer polyol; Including, The dispersion stabilizer comprises: (1) 10 to 40% by weight of a branched polyol having a molecular weight of 4000 to 20,000 and having at least one polymerizable ethylenically unsaturated group per molecule and 3 to 8 hydroxyl groups per molecule; and (2) 60 to 90% by weight of a copolymer of styrene or a mixture of styrene and one or more other low molecular weight monomers.

5. The method of any one of claims 1 to 4, wherein the anti-solvent comprises water.

6. The method of any one of claims 1 to 5, wherein component i) is one or more polyether polyols.

7. The method of any one of claims 1 to 6, wherein component ii) is polystyrene or a styrene-acrylonitrile copolymer.