SIMPLIFIED BIMODAL PROCESS

Abstract: The present invention is a continuous process for producing a rubber-reinforced polymer composition derived from a vinyl aromatic monomer, using a single reactor to produce a prepolymer composition containing dispersed rubber particles and to mix the prepolymer composition produced with a second prepolymer composition containing dispersed rubber particles.

Description: SIMPLIFIED BIMODAL PROCESS The present invention relates to a process for preparing rubber modified polymers from vinyl aromatic monomers, particularly polymers containing two distinct volume average particle sizes, herein referred to as bimodal compositions. Rubber modified polymers have typically been prepared from vinyl aromatic monomers by polymerizing the vinyl aromatic monomer in the presence of a dissolved rubber. As depicted in Figure 1 , the monomer and dissolved rubber are introduced by a feed line (I) into reactor A, wherein the vinyl aromatic monomer polymerizes forming a discontinuous phase dispersed throughout a continuous phase of dissolved rubber in monomer. As the vinyl aromatic monomer continues to polymerize, the discontinuous polymer phase becomes larger in volume thus forming a continuous phase, while the rubber forms a discontinuous phase dispersed throughout. This phenomenon, referred to as "phase inversion", is, therefore, the conversion of the polymer from a discontinuous phase dispersed in the continuous phase of the rubber/monomer solution, through the point where there is no distinct continuous or discontinuous phase in the polymerization mixture, to a continuous polymer phase having the rubber dispersed throughout. Phase inversion typically occurs in the bottom portion of reactor A. Bimodal compositions are known to have better property balance between gloss and impact strength than monomodal compositions. Polymers having bimodal distributions can currently be produced in several ways including compounding and continuous polymerization processes. Compounding is achieved by producing two separate rubber modified polymers, each having a desired rubber particle size, and blending the two resins to achieve a bimodal product. However, this process requires additional equipment which adds cost and reduces efficiency. Bimodal compositions can also be prepared in a continuous polymerization process such as that disclosed in U.S. Patent No. 5,240,993 which is depicted in Figure 2. This process uses two reactors (A and E), wherein each reactor is used to form a mixture of rubber particles within a partially polymerized continuous phase, wherein one mixture contains large particles while the other mixture contains small particles. The two partially polymerized mixtures are then combined in feed line V and further polymerized in yet another reactor (B). This process configuration allows for variations in the two different rubber particle sizes and the production of highly occluded particles. However, the use of another reactor is required. Other continuous polymerization processes can be used to produce bimodal compositions, including that disclosed in EP-0096447, which can be depicted as in Figure 3. In this process, two feeds (I and III) are added in two different reactors (A and B) within the polymerization process to generate a bimodal rubber particle size distribution. Feed I comprises a vinyl aromatic monomer and rubber while feed III can be the same as feed I, or a partial polymerizate comprising polymerized vinyl aromatic monomer having rubber particles dispersed therethrough. However, if feed III comprises vinyl aromatic monomer and rubber, the particle size produced is difficult to control, thus producing a rubber modified polymer having a broad particle size distribution. If feed III is a partial polymerizate, then an additional reactor would be required for its production. Additionally, this process is limited in its ability to vary the rubber particle size and obtain highly occluded particles. Therefore, it would be desirable to develop a process for producing a rubber modified polymer composition from a vinyl aromatic monomer, particularly a bimodal composition, which produces compositions having controlled particle size and has the ability to obtain highly occluded particles without requiring an additional reactor. One aspect of the present invention is a continuous process for the production of a rubber-reinforced polymer composition comprising: continuously polymerizing a vinyl aromatic monomer containing a dissolved rubber, in a substantially plug flow reactor to produce a first prepolymer composition containing rubber particles, continuously introducing a second prepolymer composition containing rubber particles into the substantially plug flow reactor such that the second prepolymer composition and the first prepolymer composition are mixed thus forming a third prepolymer composition, and further polymerizing the third prepolymer composition, to produce a rubber-reinforced polymer composition. A second aspect of the present invention is a continuous process for the production of a rubber-reinforced polymer composition having a bimodal particle size distribution comprising: continuously polymerizing a vinyl aromatic monomer containing a dissolved rubber, in a substantially plug flow reactor to produce a first prepolymer composition containing rubber particles, continuously introducing a second prepolymer composition containing rubber particles into the substantially plug flow reactor such that the second prepolymer composition and the first prepolymer composition are mixed thus forming a third prepolymer composition, wherein one of the prepolymer compositions contains small rubber particles having a volume average particle size of from 0.05 to 1.5 micrometers, and the other prepolymer composition contains large rubber particles having a volume average particle size ot from 0.7 to 10 micrometers, with the proviso that the volume average particle size of the large rubber particles is at least 1.3 times the volume average particle size of the small rubber particles, and further polymerizing the third prepolymer composition, to produce a rubber- reinforced polymer composition. This process utilizes a single reactor to produce a prepolymer composition having rubber particles of a controlled size and to combine the prepolymer composition with a second prepolymer composition containing rubber particles. This process allows the production of rubber-reinforced polymers, particularly bimodal compositions, having a good balance of gloss, impact strength, controlled particle sizes and highly occluded particles without the use of an additional reactor Fig 1 of the drawings generally represents schematically a conventional process and apparatus for the production of high impact polystyrene (HIPS) or acrylonitπle-butadiene-styrene copolymers (ABS) Fig 2 of the drawings generally illustrates schematically an apparatus and process as disclosed in U.S. Patent No. 5,240,993. Fig. 3 of the drawings generally illustrates schematically an apparatus and process as disclosed in EP-0096447 Fig. 4 of the drawings generally illustrates schematically a preferred embodiment of an apparatus and process in accordance with the present invention. The process of the present invention is a process for producing rubber modified polymers from vinyl aromatic monomers, a representative process of which is depicted in Figure 4 A feed (III) of vinyl aromatic monomer and dissolved rubber is introduced into the top of a substantially plug flow reactor(B) and the vinyl aromatic monomer is polymenzed such that phase inversion occurs and rubber particles are formed in a zone of the reactor The resultant mixture of polymenzed vinyl aromatic monomer, rubber particles and vinyl aromatic monomer is referred to as a first prepolymer composition. Another feed of vinyl aromatic monomer and dissolved rubber (I) is introduced into a separate substantially plug flow reactor (A) and the vinyl aromatic monomer is polymenzed such that phase inversion has occurred before exiting reactor A via line II, thus forming a second prepolymer composition. The second prepolymer composition in line II is introduced into reactor B at a point at which the first prepolymer composition has been formed and the two prepolymer compositions are mixed within reactor B to form a third prepolymer composition. The third prepolymer composition is further polymenzed in reactor B and throughout subsequent reactors if desired. The rubber-reinforced polymers produced by the process of the present invention are derived from one or more vinyl aromatic monomers. Representative vinyl aromatic monomers include styrene, alkyl substituted styrenes such as alpha-alkyl-styrenes, for example, alpha- methylstyrene, alpha-ethylstyrene; πng substituted styrenes, for example, vinyltoluene, particularly p-vinyltoluene, o-ethylstyrene and 2,4-dιmethylstyrene; ring substituted halo-styrenes such as chlorostyrene, and 2,4-dιchloro-styrene, styrene substituted with both halo and alkyl groups, such as 2-chloro-4-methylstyrene, vinyl anthracene; and mixtures thereof. Preferably styrene and/or alpha-methyl-styrene is used as the vinyl aromatic monomer, with styrene being most preferred. Comonomers may also be used in combination with the vinyl aromatic monomer, preferably in an amount of up to 40 percent by weight of the polymeπzable monomer mixture Representative comonomers include unsaturated nitriles, such as acrylonitnle; alkyl acrylates and alkyl methacrylates such as methyl methacrylate or n-butylacrylate; ethylenically unsaturated carboxylic acids, and ethylenically unsaturated carboxyhc acid deπvatives including anhydrides and imides, such as maleic anhydride and N-phenyl maleimide. The rubber may be any rubbery polymer which can be dissolved in the vinyl aromatic monomer. Typically, the rubbery polymer employed in the preparation of the dispersed rubber particles exhibits a second order transition temperature not higher than 0 °C, and preferably not higher than -20 °C. Preferred rubbery polymers include a homopolymer or copolymer of an alkadiene or a ethylene-propylene copolymer optionally containing a non-conjugated diene. More preferably, the rubber is a homopolymer of a 1 ,3-conjugated diene such as butadiene, isoprene, piperylene, and chloroprene, or a copolymer of a conjugated diene with one or more vinyl aromatic monomers such as styrene; alpha, beta-ethylenically unsaturated nitrites such as acrylonitπle; and alpha-olefins such as ethylene or propylene. Most preferred rubbers are homopolymers of 1 ,3-butadιene and block or random copolymers of at least 30, more preferably from 50 to 90, weight percent 1 ,3-butadιene and up to 70, more preferably from 5 to 50, weight percent of a vinyl aromatic compound, preferably styrene. The rubber utilized to produce large rubber particles is preferably a polybutadiene. The rubber utilized to produce small rubber particles is preferably a polybutadiene or a poly(butadιene-styrene)block copolymer The amount of rubber initially dissolved in the vinyl aromatic monomer is dependent on the desired concentration of the rubber in the final rubber-reinforced polymer product, the degree of conversion duπng polymeπzation and the viscosity of the solution. The rubber is typically used in amounts such that the rubber-reinforced polymer product contains from 2 to 20 percent, preferably from 3 to 17 percent, and more preferably from 3 to 15 weight percent rubber, based on the total weight of the vinyl aromatic monomer and rubber components, expressed as rubber or rubber equivalent. The term "rubber" or "rubber equivalent" as used herein is intended to mean, for a rubber homopolymer, such as polybutadiene, simply the amount of rubber, and for a block copolymer, the amount of the copolymer made up from monomer which when homopolymeπzed forms a rubbery polymer, such as for a butadiene- styrene block copolymer, the amount of the butadiene component of the block copolymer. The polymeπzation can be conducted in the presence of an initiator Suitable initiators include any initiator capable of imparting the desired grafting of polymer to the rubber particle under the conditions of polymeπzation and accelerating the polymeπzation of the vinyl aromatic monomer. Representative initiators include peroxide initiators such as peresters, for example, tertiary butyl peroxybenzoate and tertiary butvl peroxyacetate, dibenzoyl peroxide, dilauroyl peroxide, 1.1 -bis tertiarybutyl peroxycyclohexane, 1-3-bιs tertιarybutylperoxy-3,3,5-tπmethyl cyclohexane, and di-cumyl peroxide. Photochemical initiation techniques can be employed if desired. Preferred initiators include dibenzoyl peroxide, tertiarybutylperoxy benzoate, 1 ,1- bistertiarybutylperoxy cyclohexane and tertiarybutylperoxy acetate. Initiators may be employed in a range of concentrations dependent on a variety of factors including the specific initiators employed, the desired levels of polymer grafting and the conditions at which the mass polymerization is conducted Specifically, initiators may be employed in amounts from 0 to 2000, preferably from 100 to 1500, parts by weight per million parts by weight of vinyl aromatic monomer Additionally, a solvent may be used in the process of the present invention Acceptable solvents include normally liquid organic mateπals which form a solution with the rubber, vinyl aromatic monomer and the polymer prepared therefrom. Representative solvents include aromatic and substituted aromatic hydrocarbons such as benzene, ethylbenzene, toluene, or xylene; substituted or unsubstituted, straight or branched chain saturated aliphatics of 5 or more carbon atoms, such as heptane, hexane, or octane; alicyclic or substituted alicyclic hydrocarbons having 5 or 6 carbon atoms, such as cyclohexane. Preferred solvents include substituted aromatics, with ethylbenzene and xylene being most preferred. In general, the solvent is employed in amounts sufficient to improve the processability and heat transfer during polymerization Such amounts will vary depending on the rubber, monomer and solvent employed, the process equipment and the desired degree of polymerization If employed, the solvent is generally employed in an amount of up to 35 weight percent, preferably from 2 to 25 weight percent, based on the total weight of the solution. Other materials may also be present in the process of the present invention, including plasticizers, for example, mineral oil; flow promoters, lubricants, antioxidants, catalysts, mold release agents, or polymerization aids such as chain transfer agents, including alkyl mercaptans, for example, n-dodecyl mercaptan. If employed, a chain transfer agent can be present in an amount of from 0.001 to 0.5 weight percent based on the total weight of the polymerization mixture to which it is added. The polymeπzation is preferably conducted in one or more substantially linear stratified flow or so-called plug-flow type reactors, as described in U.S. Pat No. 2,727,884. Advantageously, the process according to the present invention can be practiced by modifying existing standard mass polymerization process equipment not otherwise capable of the preparation of bimodal rubber reinforced compositions, without the need for an additional reactor. The feed used to form the first prepolymer composition is typically prepared by dissolving the rubber in the vinyl aromatic monomer The feed is then introduced into a reactor and the vinyl aromatic monomer is polymenzed to a conversion of from 2 to 70 percent, preferably from 5 to 65 percent, more preferably from 10 to 55 percent, and most preferably from 10 to 50 percent. The rubber particle becomes grafted with the vinyl aromatic monomer which aids its dispersion and stabilizes the moφhology of the particle Preferably, the polymerization is conducted such that phase inversion has occurred and rubber particles of a desired size have been produced within the first prepolymer composition before it is combined with the second prepolymer composition The second prepolymer composition is typically prepared by a similar process as described for the first prepolymer composition. The vinyl aromatic monomer is typically polymerized to a conversion from 2 to 70 percent, preferably from 5 to 65 percent, more preferably from 10 to 55 percent, and most preferably from 10 to 50 percent Preferably, phase inversion has occurred, thus producing rubber particles of a desired size, before being combined with the first prepolymer composition The rubber and vinyl aromatic monomer are as described previously. The particle size of the rubber particles produced in the first and second prepolymer compositions can be influenced by a number of factors including the rubber used, the amount of grafting, the viscosity and the shear rate. The techniques of mass-polymeπzation and the conditions needed for producing the desired average particle sizes are well known to one skilled in the art. The process of the present invention can be advantageously used to produce both monomodal and bimodal compositions, that is compositions containing one or two distinct volume average particle sizes. In monomodal compositions, both prepolymer compositions would produce particles of approximately the same volume average particle size Typically, these sizes can vary from 0.05 to 10 micrometers, preferably from 0.1 to 8 micrometers, more preferably from 0.5 to 6 micrometers and most preferably from 1 to 5 micrometers. In bimodal compositions, two distinct volume average particle sizes are produced and combined. In particular, the rubber particles of the first and second prepolymer compositions have different volume average particle sizes, wherein one contains small rubber particles having a volume average particle size of from 0.05 to 1.5 micrometers, and the other contains large rubber particles having a volume average particle size of from 0.7 to 10 micrometers, wherein the volume average particle size of the large rubber particles is at least 1.3 times the volume average particle size of the small rubber particles. Preferably, the volume average particle size of the large rubber paticies are at least 1.5 times, more preferably 1.8 times and most preferably 2.0 times the volume average particle size of the small rubber particles. The small or large rubber particles of the bimodal composition may be present in either the first or the second prepolymer compositions, with the stipulation that if the small particles are present in the first prepolymer composition, then the large particles are present in the second prepolymer composition and vice versa. Preferably, the small rubber particles are present in the second prepolymer composition and the large rubber particles are present in the first prepolymer composition. In bimodal compositions, the desired ratio of the small to large particles is dependent upon the properties desired in the final rubber-reinforced polymer. Typically the amount of small particles ranges from 65 to 95, preferably from 75 to 90, and most preferably from 80 to 90 percent of the total amount of rubber particles in the rubber-reinforced polymer For products which require high gloss properties, the amount of small particles is from 85 to 98 percent and the amount of large particles is 2 to 15 percent. Other polymers in which higher impact strength is desirable can have 65 to 75 percent small particles and 25 to 35 percent large particles As used herein, the volume average particle size refers to the diameter of the rubber particles, including all occlusions of vinyl aromatic polymer within the rubber particles. Volume average particle sizes and distπbutions may be measured using conventional techniques such as a Coulter Counter™ or, transmission electron microscopy image analysis. The small rubber particles typically have a core-shell (single, major occlusion), cellular (multiple, minor occlusions) or labyrinth moφhology. The large particles typically have a cellular or similar multiple-occlusion moφhology After phase inversion has occurred the second prepolymer composition is added to the first prepolymer composition and the two compositions are mixed in a desired ratio such that a third prepolymer composition is obtained It is preferable that the conversion of vinyl aromatic monomer within the first and second prepolymer compositions be similar or that the first composition be slightly higher than the second in order to prevent phase remversion. However, it is also within the scope of the present invention for the first composition to be at a lower conversion than the second composition. The third prepolymer mixture is then further polymerized to a desired vinyl aromatic monomer conversion. Typically, the third prepolymer mixture is polymenzed to a conversion of from 50 to 70 percent and can be further reacted to a conversion of 80 to 90 percent. The temperature at which the polymeπzations are conducted will vary according to the specific components, particularly initiator, but will generally vary from 60 to 190°C Crosslinking of the rubber in the resulting product and removal of the unreacted monomers, as well as any solvent, if employed, and other volatile mateπals is advantageously conducted employing conventional techniques, such as introducing the polymeπzation mixture into a devolatilizer, flashing off the monomer and other volatiles at elevated temperature, for example, from 200 to 300°C under vacuum and removing them from the devolatilizer In one embodiment of the present invention, the process is used for the preparation of a HIPS composition compπsing a polymerized vinyl aromatic monomer, with dispersed particles of rubber. The size of the rubber particles are dependent upon the desired gloss and impact properties of the polymer product. For bimodal HIPS compositions the small rubber particles are typically in the range of from 0.1 to 1 micrometer, preferably from 0.1 to 0.9, more preferably from 0.2 to 0.8 and most preferably from 0.2 to 0.7 micrometers, and the large rubber particles are typically from 1 to 6, preferably from 1 to 5.5, more preferably from 1.5 to 5.5 and most preferably from 1.5 to 5 micrometers. Alternatively, the process may be utilized in the preparation of ABS type compositions, in which an alkenyl nitrile, generally acrylonitπle is used as a comonomer. For bimodal ABS compositions the small particles are typically in the range of from 0.2 to 1 , preferably from 0.3 to 1 , more preferably from 0.4 to 0.9 and most preferably from 0.5 to 0.8 micrometers and the large rubber particles are typically from 0 8 to 10, preferably from 0 9 to 8, more preferably from 1 to 7 and most preferably from 1 to 5 micrometers. Due to the excellent balance of gloss and toughness properties, these rubber- reinforced compositions, particularly bimodal compositions, are useful in a wide variety of applications such as consumer electronics, small household appliances, toys and furniture These polymers are also useful in extrusion applications such as in the preparation of a gloss layer using coextrusion techniques for refπgerator liners. The following examples are provided to illustrate the present invention. The examples are not intended to limit the scope of the present invention and they should not be so inteφreted. Amounts are in parts by weight unless otherwise indicated. EXAMPLE 1 Figure 4 is representative of the apparatus used and is referred to in the following examples. Preparation of the First Preoolvmer Composition A feed (III) of the following components is continuously charged at a rate of 1.74 kg/hr into the top of the first zone of a substantially plug flow stirred tube reactor (B), having three temperature control zones, the first being set at 125°C, the second at 140°C, and the third at 148°C, and equipped with a variable speed agitator set at an agitation rate of 50 φm. 3.8 wt.% ppoollyybbuuttaaddiieennee (about 35% 1 ,4 cis, about 55% 1 ,4 trans and about 10% 1.2 vinyl) 88.2 wt.% styrene 5.6 wt.% ethylbenzene 2.4 wt.% mineral oil Additional ethylbenzene is added to the top of the first zone of reactor B at a rate of 80 gm/hr. The mixture is polymenzed such that the prepolymer solution has about a 31 percent conversion at the end of the first zone. Preparation of the Second Prepolymer Composition A feed (I) of the following components is continuously charged at a rate of 8.17 kg/hr into the top of a first zone of a substantially plug flow stirred tube reactor (A), having three temperature control zones, the first zone being set at a temperature of 114°C, the second at 119°C and the third at 123°C, and equipped with a vaπable speed agitator set at an agitation rate of 50 φm. 10.3 wt.% 70/30 butadiene styrene block copolymer rubber 79.05 wt.% styrene 8.2 wt.% ethylbenzene 2.4 wt.% mineral oil 403 ppm, based on the total weight of the composition, of 1 ,1 -di(t-butylperoxy)cyclohexane) is added to the feed at a rate of 26 gm/hr and the mixture is polymerized sequentially in zones 1 , 2 and 3 such that the prepolymer composition exiting reactor A via line II has about a 50 percent conversion. The first and second prepolymer compositions are combined in the second zone of reactor B and polymerization is continued through reactor B and a third reactor, (C) which has three temperature control zones, zone one being set at 153°C, zone two at 157°C and zone three at 162°C, until solids reach approximately 65 to 70 percent. The polymer stream is then devolatilized in D in two stages at 184°C, 850 mm Hg and at 246°C, 21 mm Hg. The product is a bimodal HIPS composition having about 90/10 weight ratio of small to large rubber particles, wherein the large particles have a volume average particle size of about 1.3 micrometers and the small particles have a volume average particle size of about 0.3 micrometers. A bimodal composition is prepared using a single reactor to produce a prepolymer composition having rubber particles of a volume average particle size of about 1.3 micrometers, and to combine the prepolymer composition with a second prepolymer composition containing rubber particles having a volume average particle size of about 0.3 micrometers. EXAMPLE 2 The same procedure of Example 1 is followed except the monomer-rubber feed stream (III) composition consists of 3.8 wt.% polybutadiene (about 35% 1 ,4 cis, about 55% 1 ,4 trans and about 10% 1.2 vinyl) 88.2 wt.% styrene 5.6 wt.% ethylbenzene 2.4 wt.% mineral oil An additional feed of 99.66 wt.% ethylbenzene and 0.34 wt.% n- -dodecylmercaptan is added to the top of the first zone of reactor B at a rate of 80 gm/hr. The product is a bimodal HIPS composition having about 90/10 weight ratio of small to large rubber particles, wherein the large particles have a volume average particle size of about 2.1 micrometers and the small particles have a volume average particle size of about 0.3 micrometers. A bimodal composition is prepared using a single reactor to produce a prepolymer composition having rubber particles of a volume average particle size of about 2.1 micrometers, and to combine the prepolymer composition with a second prepolymer composition containing rubber particles having a volume average particle size of about 0.3 micrometers.

Claims: CLAIMS 1 A continuous process for the production of a rubber-reinforced polymer composition comprising: continuously polymerizing a vinyl aromatic monomer containing a dissolved rubber, in a substantially plug flow reactor to produce a first prepolymer composition containing rubber particles, continuously introducing a second prepolymer composition containing rubber particles into the substantially plug flow reactor such that the second prepolymer composition and the first prepolymer composition are mixed thus forming a third prepolymer composition, and further polymeπzing the third prepolymer composition, to produce a rubber- reinforced polymer composition. 2. A continuous process for the production of a rubber-reinforced polymer composition having a bimodal particle size distnbution comprising continuously polymerizing a vinyl aromatic monomer containing a dissolved rubber, in a substantially plug flow reactor to produce a first prepolymer composition containing rubber particles, continuously introducing a second prepolymer composition containing rubber particles into the substantially plug flow reactor such that the second prepolymer composition and the first prepolymer composition are mixed thus forming a third prepolymer composition, wherein one of the prepolymer compositions contains small rubber particles having a volume average particle size of from 0.05 to 1.5 micrometers, and the other prepolymer composition contains large rubber particles having a volume average particle size of from 0.7 to 10 micrometers, with the proviso that the volume average particle size of the large rubber particles is at least 1.3 times the volume average particle size of the small rubber particles, and further polymeπzing the third prepolymer composition, to produce a rubber- reinforced polymer composition. 3. The process of Claim 1 or 2 wherein the vinyl aromatic monomer is styrene. 4. The process of Claim 1 or 2 wherein the rubber is a homopolymer or copolymer of an aikadiene, an ethylene-propylene copolymer or an ethylene-propylene copolymer containing a non-conjugated diene. 5. The process of Claim 4 wherein the rubber is a homopolymer of an aikadiene. 6. The process of Claim 5 wherein the rubber is a homopolymer of butadiene, isoprene, piperylene, or chloroprene. 7. The process of Claim 1 or 2 wherein the rubber is a copolymer of a conjugated diene and one or more vinyl aromatic monomers. 8. The process of Claim 7 wherein the rubber is a copolymer of butadiene and styrene. 9 The process of Claim 1 or 2 wherein the rubber-reinforced polymer composition is a HIPS composition. 10. The process of Claim 1 or 2 wherein the rubber-reinforced polymer composition is an ABS composition. 11. The process of Claim 2 wherein the small rubber particles are present in the second prepolymer composition and the large rubber particles are present in the first prepolymer composition. 12. The process of Claim 2 wherein the small particles have an average particle size of from 0.05 to 1.5 micrometers and the large particles have an average particle size of from 0.7 to 10 micrometers.

Inventors: BLACK STEVEN M, SCHRADER DAVID, SODERQUIST MARK E, BLACK, STEVEN, M., SCHRADER, DAVID, SODERQUIST, MARK, E.
Applicants: DOW CHEMICAL CO, THE DOW CHEMICAL COMPANY
Application year: 1997
Main classification: C08F279
IPC codes: C08F255, C08F279, C08F291