Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
  • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
  • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated

Definitions

• This invention relates generally to a process for preparing polymers having a low residual monomer content while retaining material properties such as flow, impact and color.
• a rubber latex is made in the first step.
• EPA 762693 discloses the first step of the emulsion process, a semi-batch process for the manufacture of diene rubber latex wherein a chain transfer agent such as t-ddm, is added upfront in the beginning of the reaction with the butadiene monomer and initiator.
• a chain transfer agent such as t-ddm
• acrylonitrile and styrene may be emulsion polymerized with the diene rubber latex to form an acrylonitrile-butadiene-styrene (ABS) graft polymer.
• ABS acrylonitrile-butadiene-styrene
• the polymerization reaction is typically run to completion. However, sometimes even when the polymerization is substantially complete, undesired amounts of acrylonitrile monomer and/or styrene monomer dissolved or occluded in the polymer and in the reaction system water can still remain.
• the normal unit operations of stripping by vacuum or steam stripping the reaction system content do not remove all of this undesirable residual acrylonitrile and/or styrene monomer.
• ABS material e.g., pellets
• additional monomers to aid in conversion has been employed both during the main reaction and at the end of the grafting reaction.
• vinyl carboxylates have been used during the course of the reaction.
• Other patents describe the use of additional monomers at the end of the reaction including butadiene (U.S. Patent No. 4,272,425), acrylonitrile (U.S. Patent No. 4,822,858), n-vinyl mercaptans (German Patent No. DE 3,327,190), and methyl methacrylate (MMA) (U.S. Patent No. 3,991,136 - after polymerizing at least about 90% of monomer formulation).
• Most of the work with additional monomers do include some additional initiators also.
• U.S. Patent No. 4,301,264 describes the use of a secondary initiator late in the reaction.
• graft molecular weight is increased and/or a higher molecular weight matrix styrene acrylonitrile (SAN) is used.
• SAN molecular weight matrix styrene acrylonitrile
• Another approach used is to increase rubber level in the product formulation, which also reduces flow and reduce modulus.
• a semi-batch process for preparing low crosslink density diene rubber substrate includes adding an initial liquid batch to a reaction system, said liquid batch includes water, an emulsifier, and a diene monomer.
• the process further includes adding a liquid feed composition including butadiene, an initiator and a chain transfer agent to the reactor system, at or after the conclusion of the addition of the liquid batch to the reaction system.
• the continuous addition of the chain transfer agent allows for the preparation of a low density cross linked diene rubber substrate.
• a method of optimizing the flow and low temperature impact of ABS graft polymers includes associating the rubber crosslink density of diene substrate used to make ABS graft polymer with the room temperature and low temperature impact strength of the ABS graft polymer made therefrom, and selecting the appropriate crosslink density diene substrate associated with the desired flow and low temperature impact of the ABS graft polymer.
• a method of maintaining the flow-impact balance in an ABS graft polymer product while achieving higher conversion and reduced monomer emissions includes offsetting a crosslink density (%A) increase in the ABS graft polymer (due to increased conversion) by selecting a diene substrate of lower crosslink density (%A) to prepare the ABS graft polymer product.
• %A crosslink density
• an emulsion polymerization process for the preparation of polybutadiene grafted with styrene and acrylonitrile monomers in a reaction system is provided. The resultant product has a low end content of unreacted residual monomers.
• the process includes: a) charging the reaction system with a diene emulsion; b) adding to the reaction system, over a predetermined time, an optional initiator, acrylonitrile and styrene monomers; c) polymerizing the catalyzed reaction mixture of polybutadiene, styrene and acrylonitrile; and d) adding a third monomer and an optional initiator to the reaction mixture after the conversion rate of the monomers is about 98% or higher.
• an emulsion polymerization process for the preparation of ABS graft polymer having a low yellowness index includes maintaining an appropriate ratio of unreacted styrene to acrylonitrile monomers in the reaction system.
• Figure 1 shows the dependence of rubber crosslink density (%A) of an ABS graft polymer on rubber crosslink density (%A) of a substrate.
• Figure 2 shows the dependence of notched Izod impact at room temperature on rubber crosslink density (%A) of the ABS graft polymer.
• Figure 3 shows the dependence of notched Izod impact at low temperature (-20°C) on rubber crosslink density (%A) of the ABS graft polymer.
• Figure 4 is an overlay plot showing the optimum crosslink density of rubber (%A) in a substrate needed for low temperature (-20C) notched Izod impact, while meeting low NAV requirements.
• Figure 5 is a plot of the results of a design of experiments (DOE), showing the correlation of a continuous feed of the chain transfer agent t-DDM feed with the crosslink density of diene rubber substrate.
• ABS polymers can be produced via emulsion or mass (bulk) polymerization processes.
• the emulsion polymerization process is a two-step process, with the first step to prepare a rubber latex, and the second step for the polymerization of styrene and acrylonitrile in the rubber latex solution to form an ABS latex.
• the ABS polymer is recovered through coagulation of the ABS latex by adding a stabilizing agent.
• the slurry is filtered or centrifuged to recover the ABS resin.
• a low-crosslink density rubber latex is achieved.
• Applicants have surprisingly found that the continuous addition of the chain transfer agent during the feed portion of the semi-batch process to make rubber latex allows for the production of low crosslink density rubber latex, as compared to batch charging the chain transfer agent (adding all the chain transfer agent at the beginning of the reaction) in the prior art process.
• the rubber latex is a diene rubber latex.
• Suitable diene monomer feed includes butadiene and isoprene and various comonomers, which may be present to produce copolymers of butadiene with up to 50 percent by weight of comonomers such as styrene, acrylonitrile, methylmethacrylate or C ⁇ -C 6 -alkylacrylate. In another embodiment, up to 35 percent by weight of comonomers is added.
• Comonomers can be present in the rubber at a level of less than 50 percent by weight, preferably less than 40 weight percent and most preferably less than about 25 weight percent based on the total weight of the monomers. Most preferably no comonomer is used due generally to the tendency of comonomer to reduce the efficiency of the reflux cooling.
• Suitable comonomers include vinyl aromatic monomers and vinyl cyanide (unsaturated nitrile) monomers.
• Monovinylidene aromatic monomers (vinyl aromatic monomers) which may be employed include styrene, alpha-methyl styrene, halostyrenes i.e.
• Monovinylidene aromatic monomer i.e. vinyl toluene, vinylxylene, butylstyrene, para- hydroxystyrene or meth-oxystyrene or mixtures thereof.
• the monovinylidene aromatic monomers utilized are generically described by the following formula:
• X is selected from the group consisting of hydrogen, alkyl groups of 1 to 5
• R is selected from the group consisting of hydrogen, alkyl groups of 1 to 5 carbon atoms and halogens such as bromine and chlorine.
• substituted vinyl aromatic compounds include styrene, 4-methyistyrene, 3, 5-diethylstyrene, 4-n-propylstyrene, -methylstyrene, ⁇ -methyl vinyltoluene, ⁇ -chlorostyrene, ⁇ -bromostyrene, dichiorostyrene, dibromostyrene, tetrachiorostyrene mixtures thereof and the like.
• the preferred monovinylidene aromatic monomers used are styrene and/or a- methylstyrene.
• Suitable vinyl cyanide monomers include acrylonitrile and substituted vinyl cyanides such as methacrylonitrile.
• the acrylonitrile and substituted acrylonitrile are described generically by the following formula:
• R 1 may be selected from the same group set out for R as previously defined.
• monomers include acrylonitrile, ethacrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, and ⁇ -bromoacrylonifrile. It should be noted that the monomers listed above are useful in the first step of polymerizing butadiene to make diene rubber latex, and also in the second step of the emulsion polymerization process to make ABS graft polymers.
• Chain-transfer agents are added to the emulsion polymerization systems of the present invention in order to improve final polymer properties.
• Chain-transfer agents generally function as molecular weight modifiers.
• the chain-transfer agent reacts with a growing polymer chain to form a "dead" polymer with the concurrent formation of a new center for polymer growth.
• Typical agents are, for example, organic sulphur compounds, such as Ci -C 15 alkyl mercaptans, n-, i- and t-dodecyl mercaptan being preferred.
• the amount of chain-transfer agent employed will vary based on the particular chain-transfer agent ("CTA"), the monomer or mixture of monomers employed, the initiator employed, the polymerization reaction conditions, etc.
• the CTA is added in the range of about 0.1 to 3 weight part of CTA per 100 weight part of the monomer .
• the amount is about 0.1 to 2 weight part of CTA per 100 weight part of the monomer.
• the amount is about 0.2 to 0.5 weight part.
• chain transfer agents In one embodiment, about 10 - 50% of the chain transfer agents are added to the initial liquid batch composition, with the rest of the chain transfer agents being included with the continuous feed composition. In another embodiment, 100% of the chain transfer agents are added with the continuous feed.
• Stabilizer and/or emulsifier are also added to the emulsion polymerization in such a manner that the final particle size of the finished latex is controlled.
• Emulsifiers are known and are commonly used in emulsion polymerization (D.C. Blackley, Emulsion Polymerization, chapter 7, Applied Science Publishers Ltd., London, 1975).
• Emulsifiers which may be used according to the invention include the so-called anionic emulsifiers, such as higher fatty alcohol sulphates, higher alkyl sulphonates, alkylaryl sulphonates, aryl sulphonates, together with the condensation products thereof with formaldehyde, salts of sulphosuccinic acid esters and sulphated ethylene oxide adducts;
• the so-called non-ionic emulsifiers include the known reaction products of ethylene oxide with fatty alcohols, such as lauryl, myristyl, cetyl, stearyl and oleyl alcohol, with fatty acids, such as lauric, myristic, palmitic, stearic and oleic acid, and the amides thereof, and with alkylphenols, such as isooctyl-, isononyl- and dodecylphenol.
• Emulsifiers are generally used in quantities of 0.1 to 10 wt. %, in particular of 0.2 to 8 wt. %, based on the total quantity of monomers used.
• Free radical initiators well-known in the art are also employed in the emulsion process to enhance the reaction rate.
• the initiator can be introduced with the feed to maximize the heat generation rate early in the process.
• examples of initiators include water soluble initiators, such as, for example, peroxygen compounds, especially inorganic persulfate compounds such as for example ammonium persulfate, potassium persulfate and sodium persulfate; peroxides such as for example hydrogen peroxide; organic hydroperoxides, such as for example cumene hydroperoxide t-butyl hydroperoxide, acetyl peroxide, lauroyl peroxide; peracetic acid and perbenzoic acid; redox initiators wherein a water soluble reducing agent such as a ferrous compound promotes the decomposition of peroxides, persulfates and the like; as well as other free radical producing materials such as 2,2'-azobisisobutyronitrile, 4,4'-azobis(4
• the initiator is a high activity redox initiator such as cumene hydroperoxide or other hydroperoxides in combination with other compounds such as reducing agents, heavy metal salts and complexing agents.
• initiators are added to provide an initial reaction rate of about at least 10 percent of the total diene of the reaction reacted per hour. In another embodiment, between 15 and 20 percent.
• a semi-batch process for the production of a diene-based rubber latex involves: a) providing the reaction system with an initial liquid batch composition comprising water, emulsifier, diene monomer, optionally a chain transfer agent, an initiator and / or co-monomers such as acrylonitrile and styrene, optionally inorganic and organic salts; b) feeding into the vessel a liquid feed composition comprising diene monomer and a chain transfer agent, optionally co-monomers such as acrylonitrile and styrene, and initiator in which the initiator may be dissolved in water; c) providing cooling during the continuous feeding; and d) reacting the diene monomer during and after the continuous feeding.
• the rate of feed is such that the level of unreacted diene monomer is minimized and peak heat generation occurs early in the process.
• the liquid batch composition also contains electrolytes, reducing agents, heavy metal salts and complexing agents.
• the initial liquid batch composition may contain from 10 to 30 weight percent of the total weight of diene monomer used in the process. In one embodiment, from 12 to 28 weight percent thereof. In another embodiment of the invention, from 15 to 25 weight percent thereof. This low level of initial diene monomer allows for greater reaction rate control.
• the feed is to supply the remaining diene monomer and chain transfer agents to the reaction vessel over a period of time and at a controlled rate.
• the continuous feed occurs at a rate of between 5 and 20 volume present per hour based on the total volume of the initial batch liquid composition, and the feeding is completed during the first 2 to 12 hours of the process.
• Mixing is done during the reaction by using a stirrer.
• the continuous feed composition includes diene monomer and 100% of the total amount chain transfer agents to be used in the reaction. In a second embodiment, the continuous feed includes about 80% of the total amount of chain transfer agents used. In one embodiment, the feed is controlled to achieve a final liquid volume of at least 80 volume % in the reactor based on the total volume of the reactor, and a diene monomer conversion of at least 80 wt. % on the total weight of diene used in the process. In another embodiment, the final liquid volume is 84 volume % and the diene monomer conversion is at least 90% based on the total weight of diene used in the process. In another embodiment, the conversion rate of the diene monomer is at least about 93%.
• the initial liquid batch composition in to fill the reactor is about 40% to about 80% of the reactor volume. In one embodiment, from 50 to 70 % thereof. In another embodiment, from 50 to 60 %.
• the volume of the vessel is defined as the internal volume of the vessel available for occupation by the liquid and vapor containing diene reactant.
• the reaction time of a semi-batch process is typically about 5 - 20 hours or so, with the reaction temperature ranging from about 120°F to about 185°F and preferably from about 135°F to about 165°F. In one embodiment, the reaction time of the semi- batch process of the present invention is about 5 to 15 hrs. In a third embodiment, from about 8 to 12 hrs.
• the reactor pressure is typically between 20 -150 psig depending on the reaction temperature. Reaction rate generally peaks during the first two hours of the reaction when the vapor space is greatest in the vessel, thereby allowing for the greatest level of vapor space cooling which is generally more efficient than the liquid space cooling.
• the latex viscosity of the rubber latex is no greater than 200 centipoises (for example, as measured by using Automation Products, Inc. Model #CL-10 DV3 online yiscometer). In another embodiment, it is between 50 and 200 centipoises throughout the reactor.
• the rubber latex produced has a number average particle size diameter of between 600 Angstroms and 1200 Angstroms, and has less than 10% by number of particles having diameters of less than 500 Angstroms.
• the viscosity of the reaction liquid is preferably less than 200 centipoises throughout the reactor.
• the final crosslink density (%A) of the polybutadiene is from about 10 to about 60 and in another embodiment, about 20 to about 50%. In a third embodiment, the final crosslink density (%A) of the polybutadiene is about 24 - 44%.
• the rubber crosslink density is represented as %A, which measurement method can be found in "Pulsed NMR Analysis of Polybutadiene Emulsion Polymerization Reactions: Preliminary Evidence for Changes in Cross-Link Density," Donald H. Ellington, GE Plastics, Bruker Minispec Application Note 36, 1991.
• an initial charge of substrate including water, surfactant and polybutadiene is made to a reaction system and at or after the conclusion of the completion of the initial charge, a pre-soak operation is carried out which include the addition of at least one of styrene, acrylonitrile or a mixture of styrene and acrylonitrile.
• the conversion rate is based on the total conversion rate of the monovinylidene aromatic hydrocarbon monomers and ethylenically unsaturated nitrile monomers.
• the resultant ABS product has a low content of unreacted residual monomers.
• the delayed addition of a third monomer is referred herein as a "post-shot" addition.
• a delay addition of an initiator was made in conjunction with the third monomer.
• the third monomer to be added to the emulsion grafting reaction after the 98% plus monomer conversion point is selected on the basis of being highly reactive with the monomer formulation, including both the monovinylidene aromatic hydrocarbon monomer and the ethylenically unsaturated nitrile monomer.
• the third monomer is a monomer having a low boiling point below 120°C so that it can easily volatilized during the recovery of the polyblend from a latex by coagulation, washing, and drying.
• the third monomers typically include at least one of methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, benzyl acrylate, isopropyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isopropyl methacrylate, isodecyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, acrylamide, methacrylamide, vinylidine chloride, vinylidine bromide, vinyl esters, such as, vinyl acetate, and vinyl propionate, dialkyl maleates or fumarates such as dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
• the third monomer is selected from methyl acrylate and methyl methacrylate,
• a graft polymerization process to make ABS includes charging the reaction system with a substrate such as diene rubber latex, adding a first portion of at least one of a styrene and one of an acrylonitrile to the diene rubber latex, adding to the reaction system, over a predetermined time, a catalyst (or initiator) and a second portion of at least one of acrylonitrile and styrene monomers, and polymerizing the catalyzed reaction mixture of diene rubber latex, styrene and acrylonitrile.
• the graft polymerization process may include an emulsifier, which is a molecule with a hydrophobic end and a hydrophillic end.
• the term "substrate” refers to the rubber latex backbone onto which the styrene and acrylonitrile is grafted. In another embodiment, there is no pre-soak, or there is no addition of the first portion of styrene and / or acrylonitrile before the addition of the initiator.
• the substrate is a polybutadiene emulsion, dispersed in water with an emulsifying agent, such a fatty acid soap or a high molecular weight alkyl or alkaryl sulfate or sulfonate.
• an emulsifying agent such as a fatty acid soap or a high molecular weight alkyl or alkaryl sulfate or sulfonate.
• the substrate may be polybutadiene, styrene-butadiene rubber (SBR), acrylonitile-butadiene rubber (NBR), homopolymers of chloroprene, homopolymers of isoprene, copolymers of butadiene with isoprene, or chloroprene, 2-methyl-l,3-butadiene, 2,3-dimethyl-l,3-butadiene, 1 ,2-propadiene, 1 ,4-pentadiene, 1,5-hexadiene, 1 ,2-pentadiene and ABS.
• the substrate may be homogenized, unhomogenized, direct growth or chemically or colloidally agglomerated.
• the average particle size of the substrate about 150 nanometers to about 500 nanometers. If direct growth substrate is employed, the particle size distribution is about 60 nanometers to about 500 nanometers.
• the catalyst or initiator used in the graft reaction includes peroxides and/or azo compounds which are active in grafting and decompose into radicals.
• peroxy initiators which have the capability to provide free radicals to the reaction may also be used. Examples include cumene hydroperoxide (CHP), sodium persulfate, potassium persulfate, ammonium persulfate, di-isopropylbenzene hydroperoxide, tertbutyl-peroxide, and 2-2'azo-bis-isobutyrylnitrile (AIBN), in combination with other compounds such as reducing agents, heavy metal salts and complexing agents.
• CHP cumene hydroperoxide
• sodium persulfate sodium persulfate
• potassium persulfate potassium persulfate
• ammonium persulfate di-isopropylbenzene hydroperoxide
• tertbutyl-peroxide tertbutyl-peroxide
• AIBN
• the initiator is cumene hydroperoxide in combination with a redox catalyst, such as, Fe(II) with sugar or vanadium with sugar.
• a redox catalyst such as, Fe(II) with sugar or vanadium with sugar.
• Thermal initiators should provide similar results if sufficient polymerization rates can be obtained.
• a single initiator system or multiple initiator additions over intervals of time can be employed.
• the initiator(s) are added at various times including at the beginning of the addition of the third monomer, during the addition of the third monomer, at or after the completion of the addition of the third monomer. If desired, one or more late addition monomers may be employed.
• initiator is added to the reaction system in an amount to provide sufficient initiator for the duration of the polymerization reaction.
• the initiator or catalyst is included within the range of 0.01 to 2 percent by weight of the polymerizable monomer.
• initiator is added in an about of about 0.1 to 0.5 wt. % of the polymerizable monomer.
• initiator is added during the addition of monomer formulation to ensure favoring of the grafting reaction.
• the post-shot addition of the third monomer and/or initiator is delayed until the conversion of styrene and acrylonitrile monomers is greater than about 98% in one embodiment, or greater than 99% in another embodiment, or greater than 99.5% in a further embodiment, based on the original acrylonitrile monomer charged to the reaction polymerization system.
• Emulsifying agents which may be used in the graft polymerization process include a fatty acid soap, an alkaline metal or ammonium soap of a high molecular weight alkyl or alkaryl sulfate or sulfonate, etc., in total amounts of about 0.1 to 8 parts by weight per 100 parts by weight of the monomer formulation.
• the afore-described process may be carried out in a batch, semi-batch, or continuous operation. If in a semi-batch operation, then an initial charge of substrate including water, surfactant and polybutadiene is made to a reaction system and at or after the completion of the initial charge, a pre-soak operation may be carried out which include the addition of at least one of styrene, acrylonitrile or a mixture of styrene and acrylonitrile.
• the temperature of the reaction system varies from about 100°F to about 200°F. In a second embodiment, from about 120°F - 180°F. hi a third embodiment, from about 130°F to about 160°F.
• the ratio of total styrene monomer added to acrylonitrile monomer added is about 1.5 to 1 to about 4 to 1, and in another exemplary embodiment, about 2 to 1 to about 3.5 to 1.
• the ratio of total diene rubber added to the total of styrene monomer and acrylonitrile monomer is about 0.1 to 1 to about 3.0 to 1, and in another exemplary embodiment, about 0.2 to 1 to about 2 to 1.
• the post-shot addition of the third monomer is delayed until the conversion of acrylonitrile is greater than about 99% and the ratio of unreacted styrene to unreacted acrylonitrile monomer is greater than about 4 for a final product that is low in yellowness and residual monomers.
• At least one of acrylonitrile and styrene monomers are added to the reaction system over a time of about 30 minutes to about 200 minutes. In another embodiment, at least one of acrylonitrile and styrene monomers are added to the reaction system over a time of about 45 minutes to about 160 minutes.
• the ratio of the first portion of styrene monomer to the second portion of styrene monomer is about 1 to 3 to about 1 to 5 and the ratio of a first portion of acrylonitrile monomer to the second portion of acrylonitrile monomer is about 1 to 3 to about 1 to 5.
• a first portion of at least one of styrene monomer and acrylonitrile monomer or a mixture thereof is added to the polybutadiene emulsion.
• the reaction mixture after permitting the reaction to proceed for about 40 to 90 minutes after the addition of the initiator, the acrylonitrile monomer, and the styrene monomer is completed, about 0.5 to about 5.0 parts of a third monomer per 100 parts of total polymer and monomer, and/or additional initiator is added to the reaction mixture.
• Applicants have found a method of optimizing the impact of the ABS graft polymer, by optimizing the rubber crosslink density of diene substrate, and selecting the appropriate rubber crosslink density associated with the desired room temperature and / or low temperature impact strength of the ABS graft polymer (thus offsetting the low impact strength associated with the late addition of a third monomer).
• the resultant product has a low content of unreacted residual monomers along with a uniquely improved impact strength.
• a flow-impact balance in an ABS graft polymer product is obtained while achieving higher conversion and reduced monomer emissions, by offsetting the crosslink density (%A) increase in the ABS graft polymer (due to increased conversion) by selecting the diene substrate of lower crosslink density
• the diene substrate has a crosslink density of 20 - 60%A. In a second embodiment, it is 25 - 45%A. In yet another embodiment, an optimum product performance is obtained with a crosslink density of 30 - 45% of the diene substrate.
• the emulsion polymerization reaction of the present invention can be carried out in a batch process, a semi-batch process, or a continuous process.
• Examples 1-13 are baseline runs, showing the preparation of a high rubber ABS graft polymer by grafting polybutadiene with styrene and acrylonitrile in accordance with an embodiment of the present invention.
• Examples 1-13 were prepared according with the following general procedure. An initial charge of a polybutadiene emulsion was added to a three liter reaction vessel and heated to 57.2°C. Next, 12.06 parts by weight of styrene were added to the reaction vessel as a "pre-soak". After a pre-soak of about 20 minutes an addition of 0.375 parts of cumene hydroperoxide initiator was started. The initiator was added to the reaction vessel over a period of 70 minutes.
• Example 14 is a comparative example and was prepared similar to the baseline runs of Examples 1-13 described above, except that there was no addition of styrene to the polybutadiene emulsion prior to the start of the initiator addition. Instead, the entire amount of styrene, 36.15 parts, was feed into the reaction vessel over a period of 60 minutes starting ten minutes after the start of the initiator feed. Upon completion of the reaction, the reaction product was analyzed for residual styrene and acrylonitrile monomers and is shown in Table 1 below. Again, the run was high in NAVs with more than 3500 parts per million (ppm) of styrene. The results are follows:
• Emulsion A is an homogenized emulsion of polybutadiene having an average particle size of 290 to 320 nanometers with a crosslink density of 56%A.
• Emulsion B is an homogenized emulsion of polybutadiene having an average particle size of 290 to 320 nanometers with a crosslink density of 30-36%A.
• Examples 15-31 show the preparation of ABS in accordance with the late addition of a third monomer.
• polybutadiene is grafted with styrene and acrylonitrile in a process that does not include a "pre-soak,” but includes a "post-shot” of a monomer that is reactive with styrene and acrylonitrile.
• the examples were prepared according with the following general procedure. An initial charge of a polybutadiene emulsion B was added to a three liter reaction vessel and heated to 57.2°C. Next, 0.475 parts of CHP initiator was added. The initiator was added to the reaction vessel over a period of 70 minutes (Examples 15-27) or 85 minutes (Examples 28-31).
• the acrylonitrile was added to the reaction vessel over a period of 70 minutes (Examples 15-27) or 90 minutes (Examples 28-31).
• the post-shot of initiator and monomer was a batch addition. See Table 2 for the amounts and the initiators and added monomers for each example.
• the reaction product was analyzed for residual styrene and acrylonitrile monomers. It is desirable to have less than 3500 parts per million (ppm) of styrene and less than 1500 ppm of acrylonitrile in the final product. It is noted that the late addition of the third monomer in accordance to the present invention (Post shot T of 135 and 160 minutes) gives surprisingly lower residual styrene and acrylonitrile compared to the earlier addition of the third monomer as in the prior art (Post shot T of 110 minutes).
• AN acrylonitrile
• PB polybutadiene
• CHP cumene hydroperoxide
• PPS potassium persulfate
• M A methymethacrylate
• Mon, monomer.
• T is time measured in minutes from first initiator feed.
• Example 32 50 parts of styrene and acrylonitrile were added in a 3:1 ratio to an emulsion containing 50 parts of polybutadiene.
• the emulsion polymerization was initiated by means of a CHP redox system using Fe(II) and sugar.
• the monomers were fed into the emulsion over a period of 70 minutes but 12 parts of the styrene are added prior to the pumping of the initiator and the remaining monomers.
• the total solid was about 36% and styrene and acrylonitrile levels were 3800 and 1500 ppm respectively.
• Examples 33-38 of the present invention there was no styrene presoak.
• the reaction was carried otherwise in the same manner of semi-batch emulsion polymerization conditions. There was a delay of 40 or 90 minutes (for post shot time of 110 or 160 minutes) until the addition of the methyl methacrylate monomer (MMA) in conjunction with additional CHP initiator. It was noted that for each case, either with 1 part MMA or 3, 0.15 or 0.25 parts of CHP, total residual monomer was surprisingly less with late addition time as compared to the base run. TABLE 3
• polybutadiene was at 50 parts
• the styrene was at 37 parts
• acrylonitrile at 13 parts.
• Some of the styrene was pre-soak, i.e., added to the polybutadiene prior to the beginning of the polymerization with acrylonitrile.
• EXAMPLE 48 In this example, a design of experiments (DOE) 5 five factors (CHP level initially, styrene/acrylonitrile feed time, CHP level in post-shot, methyl methacrylate level in post-shot, timing of post-shot) was conducted for a total of 19 runs. A statistical analysis of the Yellowness Index (YI) showed that the YI is not impacted by the late addition of the third monomer, as indicated below:
• the statistically significant factor with respect to the YI is from the monomer feed time, i.e., from the maintenance of the appropriate ratio of unreacted styrene to acrylonitrile.
• EXAMPLE 49 In this example, butadiene substrates were made by a batch process using 85/15 weight ratio of butadiene / styrene at different crosslink density levels of %A, and then pressure homogenized. Graft reactions were run on the homogenized substrates at 51.3 parts rubber. Styrene monomers at 34 parts, acrylonitrile at 11.7 parts and MMA at 3 parts were used for grafting. MMA was added 30 minutes after the styrene and acrylonitrile charge was completed. %A's were measured on the ABS graft polymer.
• EXAMPLE 50 The ABS graft polymers in Example 49 were blended with SAN, compounded, and molded into bars for the notched Izod impact measurement at room temperature. The results are as follows.
• Figure 1 and Figure 2 are plots of data indicating the role that the rubber crosslink density of diene rubber has in defining room temperature and low temperature impact of ABS graft polymer.
• Figure 1 it has been discovered that the polybutadiene substrate provides a baseline for the crosslink density of rubber in ABS graft polymer.
• Figure 2 the room temperature notch Izod impact strength is enhanced when substrate crosslink density of the ABS graft polymer is lower.
• the notched Izod impact strength is dependent on the rubber crosslink density of the substrate.
• Figure 3 shows the dependence of notched Izod impact at -20°C on crosslink density (%A) of the rubber in an ABS graft product, containing 70% polybutadiene rubber.
• EXAMPLE 51 (30 runs total). A design of experiments (DOE) of 2-level, four factor, full factorial response surface central composite design (alpha of 1) was carried out according to the factors and settings as shown in table below. Applicant's 30 runs, including 6 repeats of the center point, showed the effect of conversion and rubber crosslink density and to optimize the flow and low temperature impact. Table 5 - DOE Factors and Settings of Graft Reaction
• Parts Parts per hundred parts of ABS graft polymer to be formed
• the styrene to acrylonitrile ratio was maintained at about 3 to 1.
• the amounts varied from reaction to reaction such that the parts of polybutadiene, styrene, acrylonitrile and methyl methacrylate added up to a total of 100 parts.
• the monomer charges were completed in about 45 minutes. When 50 minutes had elapsed after the start of the monomer addition, 3 parts of methyl methacrylate were added over a period of 5 minutes and another aliquot of CHP "post-shot" was started at the same time and was charged over a period of 30 minutes.
• the reaction temperature was gradually raised by 8°F in the first 40 minutes once the monomer charges began, and then raised again to 160°F in the next 20 minutes, where it was held constant for the next 60 minutes.
• ABS graft polymer latex was aged for about 5 hours, and appropriate amount of an anti-oxidant emulsion was added and aged again for another 3 hours.
• the latex was then coagulated with acid, and ABS graft polymer was isolated and dried. Just before coagulation the latex was tested for the content of residual monomers (NAVs).
• NAVs residual monomers
• the dried polymer was blended with styrene- acrylonitrile (SAN) polymer by melt-mixing, molded into test bars and tested for notched Izod impact.
• SAN styrene- acrylonitrile
• Figure 4 is representation of the results of the DOE, showing the optimum crosslink density of rubber (%A) in the polybutadiene substrate needed for low temperature (- 20C) notched Izod impact, while exhibiting low non-aqueous volatile (NAVs).
• an ABS graft polymer can be designed with non-aqueous volatiles (NAVs) in desired levels, by choosing the substrate appropriate crosslink density which meets impact requirements.
• NAVs non-aqueous volatiles
• the initial charge of the reactor for the runs included: 150 parts water, 0.01 part ferrous sulfate FeSO4, 0.0039 EDTA; 0.4 part tetra sodium pyrophosphate or TSPP; "E” parts of t-DDM as indicated in the DOE factors table; "B” parts of butadiene charge level as indicated in table above; and 0.050 parts of sodium formaldehyde sulfoxalate dyhydrate SFS.
• the feeds for the runs were as follows: "C” parts of initial CHP for the 1 st hour; 0.0882 parts of CHP until completion of reaction at a rate of 0.0126 pphm (parts per 100 parts of monomer); Butadiene monomer feed at a rate of 100 - "B” in the table above, spread over a period of 5 hr. reaction time; and "F" parts t-DDM, spread over a period of 5 hr. reaction time.
• the initiation temperature was at "D” with the polish temperature (after the BD feed stops) of 160°F.
• the reaction procedure included first pulling a vacuum on the reactor and then adding the initial charge of water, FeSO 4 , ETDA, TFA soap, TSPP, initial TDDM, and the initial butadiene monomer.
• the reaction mixture was heated to an initiation temperature and then the SFS was added.
• the reaction mixture was then mixed for five minutes and then the CHP feed was started.
• Ten minutes after the start of the CHP feed the butadiene and the t-DDM feeds were started.
• the temperature of the reaction mixture was raised to the polish temperature.
• the CHP feed was continued until a conversion of between 93% to 96% was obtained and then the reaction mixture was cooled to 150°F. Any unreacted butadiene was removed by vacuum and then the resultant latex was homogenized to the desired particle size.
• Table 7 The results are as shown in Table 7.

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