Patent Publication Number: US-2019177450-A1

Title: Functionalized bimodal impact modifiers

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application is a divisional application claiming priority from U.S. application Ser. No. 13/061,231, filed Feb. 28, 2011, which is a national stage application under 35 U.S.C. § 371 of PCT/US2009/053694, filed Aug. 13, 2009, which claims benefit to U.S. Provisional Application No. 61/092,906, filed on Aug. 29, 2008, all of which are hereby incorporated by reference. 
    
    
     FIELD OF THE INVENTION 
     The invention relates to functionalized bimodal butadiene-methylmethacrylate impact modifiers. The impact modifiers are especially useful in blends of engineering resins, particularly where the blend contains both functional and non-functional resins. Polycarbonate (PC)/polyethylene terephthalate (PET) blends using the functionalized bimodal butadiene-methylmethacrylate impact modifiers of the invention have excellent low temperature impact performance. 
     BACKGROUND OF THE INVENTION 
     Synthetic resins are widely used as engineering plastics in a variety of end-uses, such as building materials and automobile parts. The engineering resins have good physical and chemical resistance, and are low cost. A disadvantage of many engineering resins is that they have poor impact strength. Poor impact strength of these materials may be overcome by blending impact modifiers with the resins. 
     Impact modifiers generally consist of low-Tg, elastomeric polymers. Unfortunately the low-Tg polymer particles are typically difficult to handle. They are tacky and tend to stick together (blockiness), forming clumps or agglomerates during processing and storage. The agglomerates may be difficult to separate and disperse into the engineering polymer matrix, leading to a less than optimal modification of the plastic. 
     Core shell impact modifiers typically have rigid high T g  polymers in their outmost shell at levels sufficient to cover the elastomeric components. Such impact modifiers have good anti-blocking properties and are easy to handle. They can also be spray-dried or coagulated. 
     Hydroxy alkyl (meth)acrylate monomers have been incorporated into the shell of a core-shell modifier to improve compatiblization of the shell with the matrix polymer. The use of hydroxy-functional monomers in the shell has been described in U.S. Pat. Nos. 5,321,056 and 5,409,967. 
     JP 54-48850 describes the use of polymers made from hydroxyl-functional monomers for use as impact modifiers. 
     U.S. Pat. No. 6,130,290 describes a core-shell particle having a two-part shell. The outer shell contains a hydroxy alkyl (meth)acrylate copolymer, while the inner shell does not. 
     U.S. Pat. No. 7,195,820 describes a core-shell polymer impact modifier with hydrophilic monomer units in the shell. The purpose of the hydrophilic shell monomers units was to resist migration of the shell polymer into the core—thus reducing the amount of polymer shell needed for complete coverage of the core. These core-shell impact modifiers were considered useful in many different polymer matrixes. 
     Polymer matrixes consisting of blends of functional polymers with non-functional materials present a unique challenge for impact modification. Conventional core-shell impact modifiers with non-functional shells tend to migrate toward the non-functional parts of the blend. This decreases the effectiveness of the impact modifier on the functional polymer. 
     In “Functional MBS Impact Modifiers for PC/PBT Alloy” by William T. W. Tseng, and J. S. Lee, Journal of Applied Polymer Science, Vol. 76, 1280-1282 (2000) the use of a functionalized MBS in a PC/PBT is explored. A PC/PET blend was not described. The reference focuses on a grow-out process and does not describe micro-agglormeration. 
     U.S. patent application 61/042,848 describes an impact modifier having a core-shell impact modifier having a functionalized shell useful in polycarbonate/polyethylene terephthalate alloys. These mono-modal core/shell impact modifiers are made by a grow-out technology. 
     Surprisingly it was found that functionalized bi-modal core-shell impact modifiers provide even more impact modification at the same functionalization and loading as the mono-modal functionalized impact modifiers. While not being bound to any particular theory, it is believed the mono-modal impact modifiers have a poorer dispersion associated with smaller particles. Dart drop impact was dramatically improved with particles containing no styrene. 
     SUMMARY OF THE INVENTION 
     The invention relates to a functionalized impact modifier having an elastomeric core and a functionalized outer shell, in which the functionalized impact modifier particles have a bimodal particle size distribution. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a plot showing the bimodal nature of the microagglomerated impact modifier of the present invention, compared to the unimodal distribution from a typical grow-out process. 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The invention relates to functionalized bimodal butadiene-methylmethacrylate impact modifiers. The bi-modal impact modifiers are formed by the graft polymerization of a high Tg functional polymer over a micro-agglomerated elastomeric rubber particle. 
     By “polymers” and “resins”, as used herein, is meant homopolymers and copolymers—with copolymers including polymers formed from two or more different monomers, such as terpolymers, etc. The copolymer may be random, block, graft, or tapered, and may have any architecture, such as branched, star, or comb polymers. 
     An elastomeric seed polymer is prepared by polymerization of one or more low Tg monomers. The polymerization can occur by any known means, including but not limited to solution polymerization, suspension polymerization, emulsion polymerization and reverse emulsion polymerization. The polymerization can be a bulk polymerization or a staged polymerization. In a preferred embodiment, a bulk emulsion polymerization is used. 
     By “elastomeric” and “elastomer”, as used herein, is meant any polymer or copolymer having a glass transition temperature (Tg) of less than 25° C. Preferably the elastomeric polymer has a Tg of from −120 to 0° C. Most preferably the elastomeric polymer has a Tg of from −90 to −10° C. 
     The elastomeric polymer seed is composed of one or more monomers. Examples of elastomeric polymers that could used as the seed polymer include, but are not limited to, polybutadiene, butadiene-styrene copolymers, methacrylate-butadiene-styrene terpolymers, polyisoprene, C 2 -C 18  acrylic polymers, acrylonitrile copolymers, siloxanes or silicon containing elastomers. In a preferred embodiment, the elastomer is polybutadiene. Small amounts of crosslinking monomer may optionally be added, though a pure polybutadiene will exhibit a slight level of crosslinking due to the nature of butadiene during polymerization. 
     The elastomeric seed polymers useful in the invention have an average particle size of 50 to 100 nanometers, and preferably from 75 to 90 nanometers. 
     The polymers are agglomerated in the presence of an acid-containing polymer. The acid-containing polymer is a copolymer containing from 3-30 weight percent of acid monomers, and preferably from 5 to 25 percent acid monomer. Especially useful acid monomers are carboxylic acid such as acrylic acid and methacrylic acid. Acid anhydrides may also be used, though the acids are preferred. The acid monomer is copolymerized with one or more other ethylenically unsaturated monomers. Useful monomers include, but are not limited to butyl acrylate, methacrylic acid, acrylic acid, methyl acrylate, ethyl acrylate, butyl methacrylate, and styrene. In a preferred embodiment the acid monomer is polymerized with (meth)acrylic monomers. 
     In one embodiment, a C 1-4  alkyl acrylate is used as the co-monomer in a bulk emulsion polymerization to form an acid-containing copolymer latex. The average size particle size of the acid-containing copolymer is generally in the range of 0.01 to 7 microns, and preferably from 0.05 to 1.0 microns. 
     The elastomeric seed latex is agglomerated by heating the elastomeric seed to a temperature of 50-90° C. and slowly adding from 0.5 to 5 weight percent of the acid-containing copolymer latex with stirring. The agglomerated rubber particles have an average particle size of from 0.08 to 0.5 microns, and have a bimodal distribution. 
     The agglomerated latex particles are then graft polymerized to form one or more hard polymer shells. Ideally the shell covers the unagglomerated particles, and most of the agglomerated particles. By hard polymer it is meant a polymer having a Tg of greater than 25° C., preferably in the range of from 40 to 150° C., and most preferably in the range of from 60 to 140° C. The outermost shell layer contains from 0.5 to 40, preferably 0.5 to 30 weight percent, and more preferably 1 to 20 weight percent, of functional units, either as a blend of functional and non-functional polymers, or as least one copolymer formed from at least one non-functional monomer and at least one functional monomer. 
     By “functional shell polymer”, as used herein, means either a blend of functional and non-functional polymers, or at least one copolymer containing one or more different functional groups, either in the copolymer backbone, as pendant groups, or both. The functionalized copolymer may be formed in several different ways, as known in the art. These include copolymerization (random or block) of one or more functional monomers with non-functional monomers, grafting, and post-polymerization functionalization of a polymer, or a mixture thereof. 
     Non-functional ethylenically unsaturated monomers useful in forming the shell polymer include, but are not limited to, styrene, (meth)acrylonitrile, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, divinyl benzene, acrylonitrile, and mixtures thereof. In one embodiment, a first shell of primarily styrene is first formed, and then a second shell containing acrylic monomers (primarily MMA) and the functionalized monomer is polymerized on top of the styrene shell. In a preferred embodiment, there is no styrene monomer in the shell polymers. 
     Functional monomers useful as comonomers to add functionality to the copolymer include, but are not limited to, those containing acid, anhydride, hydroxy, epoxy, and amine groups. Examples of useful functional comonomers include, but are not limited to: N,N-dimethylaminoethyl(meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, (meth)acrylamide, N,N-dimethylacrylamide, N-methylolacrylamide, N-methylaminopropyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N-ethylamino propyl(meth)acrylamide, N,N-diethylaminopropyl (meth)acrylamide, N-methylacrylamide or N-t-butylacrylamide or N-ethyl (meth)acrylamide or chlorides of these compounds, 2-hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl(meth)acrylate, ethyl alpha-hydroxymethacrylate, and 2,3-dihydroxypropyl(meth)acrylate, maleic anhydride, maleic acid, substituted maleic anhydride, mono-ester of maleic anhydride, itaconic anhydride, itaconic acid, substituted itaconic anhydride, glutaric anhydride, monoester of itaconic acid, fumaric acid, fumaric anhydride, fumaric acid, substituted fumaric anhydride, monoester of fumaric acid, crotonic acid and its derivatives, acrylic acid, and methacrylic acid; cyanoalkoxyalkyl (meth)acrylates such as omega-cyanoethoxyethyl acrylate, or omega-cyanoethoxyethyl methacrylate; vinyl monomers containing an aromatic ring and an hydroxyl group, such as vinylphenol, para-vinylbenzyl alcohol, meta-vinylphenethyl alcohol, vinyl pyrrolidone, and vinyl imidazole; and other functional monomers, allyl cellosolve, allyl carbinol, methylvinyl carbinol, allyl alcohol, methyllyl alcohol, glycidyl methacrylate, 3,4-epoxybutyl acrylate, acrylonitrile, methacrylonitrile, beta-cyanoethyl methacrylate, beta-cyanoethyl acrylate, Examples of polymerizable surfactants or macromonomers with hydrophilic moieties useful in the present invention include, but are not limited to sodium 1-allyloxy-2-hydroxypropane sulfonate, phosphate methacrylate monomer, poly(ethylene glycol) methylether methacrylate, 1-methacrylamido, 2-imidazolidinone ethane. A preferred functionality is glycidyl(meth)acrylate or maleic anhydride. 
     The shell of the invention makes up less than 50 weight percent of the core-shell polymer, preferably less than 30 weight percent and most preferably from 5 to 25 weight percent of the core-shell polymer. 
     The final bimodal copolymer is a blend of particles having the smaller particle size distribution of from 30 to less than 200 nanometers, preferably 50 to 150 nanometers. The larger particle size distribution has an average particle size of from 200 to 1,000 nanometers, and preferably from 200 to 600 nanometers, and more preferably from 250-500 nm. The smaller particle size mode comprises 5 to 40 weight percent of the blend, and preferably from 10 to 35 weight percent, while the particles in the larger mode make up 95 to 60 weight percent, and preferably 90 to 65 weight percent of the particles. The smaller particles are present at from 5 to 40 weight percent and preferably from 10 to 35 weight percent, and the larger particles at from 60 to 95 weight percent, and preferably 65 to 90 weight percent, based on the total weight of functionalized impact modifiers. 
     The functionalized bimodal impact modifier of the invention is especially useful in a polymer matrix that is a blend of a functional polymer or resin, and at least one other non-functional component. The good impact performance is especially in providing low temperature impact performance. The key to achieving this excellent low temperature impact performance is the ability to disperse the impact modifiers in the more brittle, polyester phase. While not being bound by any particular theory, it is believed that this localized dispersion is achieved due to the functionalized groups attached to the shell of the impact modifier. Functional groups can react with the hydroxyl groups on the esters in a PC/PET blend to anchor the modifier in the polyester domain. 
     The functional polymer in the matrix is a polymer than can interact with the functional shell on the impact modifier, to form an attraction that helps associate the impact modifier with the functional polymer. Examples of functional polymers useful in the present invention include, but are not limited to polyethylene terephthlate (PET); polybutylene terephthlate (PBT); glycol modified polyethylene terephthlate (PETG); thermosetting polyester; thermoplastic polyesters; thermoplastic co-polyesters; polyetheresteramides; polyamides such as nylon 11, 12, 6, and 6,6; and natural polymers such as carbohydrates, cellulose, and biopolymers such as polylactic acid and polyhydroxy butyrate. 
     The non-functional components could be polymeric, non-polymeric, or a mixture thereof. Engineering resins useful as non-functional resins include, but are not limited to, alkyl (meth)acrylate polymers and copolymers, acrylonitrile/butadiene/styrene terpolymers (ABS), acrylonitrile/styrene/acrylate copolymers, polycarbonates, methacrylate/butadiene/styrene copolymers, polystyrene, acrylonitrile/acrylate copolymers, acrylonitrile/methyl methacrylate copolymers, polyolefins, poly(vinyl chloride), a homopolymer of a vinylidene halide, and alloys thereof. 
     The non-functional components could also be non-polymeric, including fillers such as pigments and glass beads. 
     The blend of nonfunctional to functional polymers is such that the nonfunctional polymer is present at from 20-80 wt percent, preferably from 40-75 weight percent and more preferably at from 50-75 weight percent, while said functional polymer is present at from 20-80 weight percent, preferably from 25 to 60 weight percent and more preferably at from 50 to 75 weight percent, based on the weight of the functional and non-functional polymers (not including the MBS impact modifier or other additives). 
     The functional core-shell impact modifier of the invention is blended into the polymeric composition at a level of from 0.5 to 70 percent by weight, and preferably 2 to 55 percent by weight, based on the weight of the polymers. The impact modified may be blended into the plastic by standard means such as melt extrusion, compaction, roll mill, and other such means as known in the art. 
     In addition to the polymers and the impact modifier, one or more other additives may also be added at usual levels. Typical additives include, but are not limited to, processing aids, anti-oxidants, stabilizers, pigments, dyes, plasticizers, antioxidants, or lubricants. 
     The impact modified thermoplastic composition according to the invention can be prepared by any method which makes it possible to produce a homogeneous mixture containing a thermoplastic polymer, the impact additive according to the invention and optionally other additives. It is possible, for example, to dry-mix the ingredients constituting the resin composition, then to extrude the resulting mixture and to reduce the extrudate to pellets. When the thermoplastic polymer is obtained by emulsion polymerization, it may be convenient to mix the emulsion containing the core-shell additive according to the invention with the emulsion of the thermoplastic polymer and to treat the resulting emulsion in order to separate therefrom the solid product which it contains, as described above with respect to the separation of the core-shell polymer. 
     The impact modifier of the invention provides excellent impact modification in an instrumented dart drop test, run at 2.2 m/s at −25 C. It was found that the functionalized microagglomerated impact modifiers of the invention performed at least twice as well as functionalized grow-out impact modifiers for same level of loading and functionality. 
     Some specific examples of the compositions of the invention are listed below. Those in the art would be able to recognize other examples of the invention, based on the specification and examples listed:
         The bimodal functionalized polymer and a blend of polycarbonate (20 to 80 wt %) and PET or polybutylene terephthalate (PBT) (20-80 wt % based on weight of total polymer solids).   The bimodal functionalized polymer and a blend of a natural or biopolymer (such as polylactic acid) and a methyl(meth)acrylate homopolymer or copolymer.       

     The following examples are intended to illustrate further various aspects of the present invention, but are not intended to limit the scope of the invention in any aspect. 
     EXAMPLES 
     Example 1 
     Step 1: Preparation of Base Rubber Latex (A) 
     To a 1-gallon high-pressure reactor was charged: water, beef tallow fatty acid potassium salts, potassium rosinate, 1,3-butadiene, t-dodecyl mercaptan, and diisopropylbenzene hydroperoxide as an initial kettle charge, as outlined below. The solution was heated, with agitation, to 43° C. at which time a redox-based catalyst solution (sodium tetrapyrophosphate, ferrous sulfate, and dextrose) was charged, effectively initiating the polymerization. Then the solution was further heated to 56° C. and held at this temperature for a period of six hours, yielding a rubber latex (A) of conversion of 98% with average particle size of 0.085 μm. 
     
       
         
           
               
             
               
                   
               
               
                 Synthesis of base rubber latex (A) 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Water 
                 100 
                 parts 
               
               
                   
                 Beef tallow fatty acids, potassium salts 
                 4 
                 parts 
               
               
                   
                 Potassium rosinate 
                 2 
                 parts 
               
               
                   
                 1,3-Butadiene 
                 46 
                 parts 
               
               
                   
                 t-Dodecyl mercaptan 
                 0.18 
                 parts 
               
               
                   
                 Diisopropyl benzene hydroperoxide 
                 0.13 
                 parts 
               
               
                   
                 Sodium tetrapyrophosphate 
                 0.09 
                 parts 
               
               
                   
                 Ferrous sulfate 
                 0.002 
                 parts 
               
               
                   
                 Dextrose 
                 0.11 
                 parts 
               
               
                   
                   
               
            
           
         
       
     
     Step 2: Preparation of Acid-Group Containing Copolymer Latex (B) 
     To a 5 L reactor was charged: water, beef tallow fatty acid, potassium salts, and sodium dioctylsulfosuccinate as an initial charge, as outlined below. The solution was heated under nitrogen, with agitation, to 60° C. at which time a redox-based catalyst solution (sodium formaldehyde sulfoxylate, ferrous sulfate, and disodium ethylenediaminetetraacetate) was charged. Then the monomer mixtures (n-butyl acrylate and methacrylic acid) and the initiator (t-butyl hydroperoxide) were charged over three hours. The polymerization was finished one hour after the monomer charge. The resulting latex (B) had a conversion of 99% with average particle size of 0.10 μm. 
                             Synthesis of acid-group containing latex (B)                                                    Water   200   parts           n-Butyl acrylate   85   parts           Methacrylic acid   15   parts           Beef tallow fatty acids, potassium salts   2.3   parts           Sodium dioctylsulfosuccinate   1.2   parts           t-Butyl hydroperoxide   0.3   parts           Sodium formaldehyde sulfoxylate   0.4   parts           Ferrous sulfate   0.003   parts           Disodium ethylenediaminetetraacetate   0.01   parts                        
Step 3: Preparation of Agglomerated Rubber Latex (C) with Enlarged Particle Size
 
     100 parts (based on solids) of base rubber latex (A) was charged to a 5 L reactor. The rubber latex was heated, with agitation, to 65° C. at which time 1.4 parts (based on solids) of the acid-group containing latex (B) was added slowly to the reactor. After 30 min under agitation, an agglomerated rubber latex (C) was obtained with an enlarged average particle size of 0.30 μm. 
     Step 4: Graft Polymerization onto the Agglomerated Rubber Latex 
     Immediately following the formation of agglomerated rubber latex (73 parts based on solids), 0.15 parts of sodium formaldehyde sulfoxylate was added at 65° C. The solution was heated up to 70° C. Then 23 parts of methyl methacrylate, 2 parts of glycidyl methacrylate, and 0.1 parts of t-butyl hydroperoxide were slowly added to the reactor during 90 min. After the end of addition of monomers, the reaction was kept on hold for one hour. Anti-oxidant package was then added to the reactor and the reaction was allowed to cool to room temperature. [Anti-oxidant emulsion was made by heating a mixture of Triethyleneglycol-bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propionate), Dilauryl Thiodipropionate, and Oleic acid followed by addition of a solution of potassium hydroxide in de-ionized water] 
     The resulting final latex was isolated by dilute sulfuric acid coagulation, washed, and dried to obtain white powders.