MXPA96005110A - A process to develop a multipolimero with high content of nitrile prepared from deacrilonitrilo and monomeros olefinicam insistura - Google Patents

Abstract

The present invention relates to a process for polymerizing an acrylonitrile monomer and one or more olefinically unsaturated monomers to make an olefinically unsaturated acrylonitrile multipolymer, said process comprising the steps of: heating an initial multimonomer mixture comprising acrylonitrile monomer and one or more olefinically unsaturated monomers, under an inert atmosphere, in the range of about 30 ° C to about 120 ° C, adding an initiator to the initial multimonomer mixture to initiate a polymerization reaction, adding a multimonomer feed mixture comprising monomer of acrylonitrile and olefinically unsaturated monomer (s) to the polymerization mixture wherein the multimonomer feed mixture contains from about 50 wt% to about 95 wt% acrylonitrile monomer and from about 5 wt% to about 50% by weight of monomer (s) or Lefined unsaturated (s) wherein the multimonomer feed mixture has a constant and fixed molar ratio of acrylonitrile monomer to the olefinically unsaturated monomer (s), and wherein the addition ratio of the multimeromer feed mixture is lower or equal to the proportion of polymerization

Description

A PROCESS FOR. DEVELOP A MULTIPOLIMER WITH HIGH CONTENT OF NITRILE PREPARED FROM ACRYLONITRILE AND OLYMPHINICALLY UNSATURATED MONOMERS BACKGROUND OF THE INVENTION RELATED APPLICATION This patent application is a continuation in part of the patent application entitled "A PROCESS FOR MAKING A POLYMER OF ACRYLONITRILE, METHACRYLONITRILE AND OLEFINICALLY UNSATURATED MONOMERS", (? A PROCESS FOR MAKING A POLYMER OF ACRYLONITRIL, METACRYLONITRILE AND OLYMPHINICALLY UNSATURATED MONOMERS "), USSN 08 / 150,515 and filed on November 10, 1993. It is understood that the term" multipolymer "herein includes copolymers, terpolymers, and multipolymers throughout the entire specification Field of the Invention The present invention refers to a homogeneous olefinically unsaturated acrylonitrile multipolymer and to a process for making the same.This multipolymer has molecularly uniform monomer sequences throughout the multipolymer, has a high nitrile polymer content and is melt processable. specifically the invention relates to a monomer-lacking process for producing a multipolymer of olefinically unsaturated acrylonitrile in which the polymerization ratio exceeds or equals the addition ratio of the multimonomers of acrylonitrile monomers and olefinically unsaturated monomer (s). Description of the Prior Art Acrylic polymers are polymers with high nitrile content which are desirable in the production of textile fibers, films, molded objects, packaging applications and the like. Polymers with high nitrile content have excellent physical, thermal and mechanical properties such as barrier properties, chemoresistance, stiffness, heat resistance, UV resistance, resistance to moisture retention and bacteria. However, acrylic polymers and multipolymers having long repeating sequences of acrylonitrile monomer units are known to degrade when heated and processed by commercial methods. Long sequences of nitrile units produce non-processable acrylic polymers with high nitrile content without the use of solvents. The thermoplastic nitrile barrier polymer resins are known in the art and have been described in US Patent Nos. 3, 426, 102 and 3,586,737. These nitrile polymers are known to have desirable barrier and chemoresistance properties. However, these thermoplastic nitrile polymers, although they are melt processable, are difficult to process. U.S. Patent No. 5,106,925 describes a thermoplastic nitrile polymer. However, the process for producing the nitrile polymer is based on the tracking of the polymer conversion and the addition of the reactants in the same amount in which they are separated and converted to polymer. This process must be done by appropriately adjusting the proportions and quantities throughout the polymerization process. It is desirable to produce high nitrile thermoplastic multipolymers by a process in which the nitrile monomer units are uniformly sequenced throughout the chain. It is advantageous to produce an olefinically unsaturated acrylonitrile multipolymer with improved thermoplastic properties and a high nitrile content whose polymers are melt processable in the absence of a solvent. It is an object of the invention to make a nitrile polymer chain uniformly sequential and with short sequences of the nitrile monomer in a process having a fixed monomer feed ratio. Summary of the Invention The present invention provides a novel melt-processable multipolymer comprising from about 50% to about 90% polymerized acrylonitrile and from about 10% to about 50% olefinically unsaturated polymerized monomer in which it is melt processable and contains a relatively uniform distribution of monomers in the multipolymer chain. The present invention provides a new and improved process for producing an olefinically unsaturated acrylonitrile multipolymer with improved thermal stability, excellent machining properties and excellent physical properties. The process comprises polymerizing an acrylonitrile monomer and one or more olefinically unsaturated monomers in which the addition ratio of the acrylonitrile monomer and the olefinically unsaturated monomer (s) is set to be equal to or less than the polymerization ratio to maintain a process Lack of monomer In addition, the weight of the unreacted acrylonitrile monomer and the unreacted olefinically unsaturated monomer (s) is not more than 15% by weight of the polymerization mixture. Moreover, the molar ratio of the acrylonitrile monomer and the olefinically unsaturated monomer (s) is fixed and constant for the multimeromer fed throughout the polymerization process and the multipolymer product ratio is similar to the feed ratio of multimeromer. The present invention provides in particular a process for polymerizing an acrylonitrile monomer and one or more olefinically unsaturated monomers to make an olefinically unsaturated acrylonitrile multipolymer, said process comprising the steps of: heating an initial multimonomer mixture comprising an acrylonitrile monomer and one or more olefinically unsaturated monomers, under an inert admosphere, in the temperature range from about 30 C to about 120 C; adding an initiator to the initial multimonomer mixture to initiate a polymerization reaction; adding a multimonomer feed mixture comprising an acrylonitrile monomer and an olefinically unsaturated monomer (s) to the polymerization mixture wherein the multimonomer feed mixture contains from about 50% by weight to about 95% by weight of acrylonitrile monomer and about 5% by weight to about 50% by weight of olefinically unsaturated monomer (s), wherein the monomer fed mixture has a fixed and constant molar ratio of acrylonitrile monomer to the olefinically unsaturated monomer (s), wherein the The addition ratio of the multimonomer feed mixture is less than or equal to the polymerization ratio resulting from a homogenous olefinically unsaturated acrylonitrile multipolymer product; wherein the olefinically unsaturated acrylonitrile multipolymer produced is from about 50% by weight to about 95% by weight of polymerized acrylonitrile monomer and from about 5% by weight to about 50% by weight of olefinically unsaturated polymerized monomer (s) and wherein said multipolymer is thermally stable and melt processable without the use of solvents. The process of the present invention produces a homogenous homogeneous thermoplastic olefinically unsaturated acrylonitrile multipolymer in which the short sequences of acrylonitrile monomer and the short sequences of olefinically unsaturated monomer (s) are randomly interdispersed throughout the polymerized chain resulting in a thermally stable, melt-processable multipolymer with improved characteristics. The olefinically unsaturated acrylonitrile multipolymer is melt processable in the absence of a solvent or plasticizing agent to produce high nitrile products. Detailed Description of the Invention The present invention relates to a high melt processable homogeneous nitrile multipolymer prepared from the polymerization of an acrylonitrile monomer and one or more olefinically unsaturated monomers and the process for producing the multipolymer. The new and improved process for producing a thermostable, melt processable multipolymer from an acrylonitrile monomer and olefinically unsaturated monomer (s) is carried out by controlling the addition ratio of the acrylonitrile monomer and the olefinically unsaturated monomer (s) in relation to the polymerization rate. The process of the invention is a monomer-lacking process in which the polymerization reaction ratio exceeds or equals the addition rate of the multimonomer feed mixture. The low concentration of the unreacted multimonomers during the polymerization step generates a lack of monomer condition which avoids the long sequences of the acrylonitrile monomer in the multipolymer. The multipolymer contains short sequences of interdispersed olefinically unsaturated polymerized monomer between the short sequences of the polymerized acrylonitrile monomer, for example, AN-AN-X-AN-XX-AN-XX (AN = acrylonitrile unit and X = olefinically unsaturated unit ) allowing the melt processability of the thermoplastic olefinically unsaturated acrylonitrile multipolymer with high nitrile content in the absence of a solvent. The addition ratio of the monomer of acrylonitrile and the olefinically unsaturated monomer (s) is continuous throughout the polymerization reaction. The molar ratio of the mixture of acrylonitrile monomer fed with multimeromer and the olefinically unsaturated monomer (s) is constant and fixed through the whole process. The process produces a homogeneous composition of a thermoplastic multipolymer with a high nitrile content similar to the molar proportion of the incoming multimonomer feed mixture. The multipolymer material prepared in the initial part of the process is substantially similar to the multipolymer material "- * elaborated at the end of the process, meaning that there is no major change in either the composition or the sequence of the multipolymers that result in a homogeneous multipolymer product.20 The thermoplastic multipolymer with high content of nitrile that is produced by the process of the present invention comprises from about 50% to about 95%, preferably about 65% to about 90% and more preferably From about 70% to about 90% of polymerized acrylonitrile monomer and from about 5% to about 50%, preferably about 10% to about 35% and more preferably about 10% to about 30% of olefinically unsaturated polymerized monomer (s) . The olefinically unsaturated monomer employed in the present invention is one or more of any olefinically unsaturated monomer with a C = C double bond polymerizable with an acrylonitrile monomer. The olefinically unsaturated monomer in the multimonomer mixture can be a single polymerizable monomer resulting in a copolymer or a combination of polymerizable monomers resulting in a terpolymer or a multipolymer. The olefinically unsaturated monomer generally includes but is not limited to acrylates, methacrylates, acrylamides and their derivatives, methacrylamides and their derivatives, vinyl esters, vinyl ethers, vinyl amides, vinyl ketones, styrenes, halogen-containing monomers, monomers ionics, monomers containing acid-containing monomers, olefins and the like. Acrylates include but are not limited to alkyls of Ci to Ci2, aryl and cyclic acrylates such as methyl acrylate, ethyl acrylate, phenyl acrylate, butyl acrylate, and isobornyl acrylate, 2-ethylhexyl acrylate and functional derivatives of acrylates such as 2- hydroxyethyl acrylate, 2-chloroethyl acrylate and the like. Preferred acrylates are methyl acrylate and ethyl acrylate. Methacrylates include but are not limited to Ci to C 2 alkyls, cyclic aryl methacrylates such as methyl methacrylate, ethyl methacrylate, phenyl methacrylate, butyl methacrylate, isobornyl methacrylate, 2-ethylhexyl methacrylate and functional derivatives of methacrylates such as methacrylates. -hydroxyethyl methacrylate, 2-chloroethyl methacrylate and the like. The preferred methacrylate is methyl methacrylate. The acrylamides and methacrylamides and each of their N-substituted alkyls and aryl derivatives include but are not limited to acrylamide, methacrylamide, N-methyl acrylamide, N, N-dimethyl acrylamide and the like. Vinyl esters include but are not limited to vinyl acetate, vinyl propionate, vinyl butyrate and the like. The preferred vinyl ester is vinyl acetate. Vinyl ethers include but are not limited to Ci to C% vinyl ethers such as ethyl vinyl ether, butyl vinyl ether and the like. Vinyl amides include but are not limited to vinyl and pyrrolidone and the like. Vinyl ketones include but are not limited to vinyl acetones of C ± a Cs such as ethyl vinyl acetone, butyl vinyl acetone and the like. Styrenes include but are not limited to methyl styrenes, styrene, indene, a styrene of the formula: D wherein each of A, B, C, and D, are independently selected from hydrogen (h) and the alkyl groups from Ci to Cr substituted styrenes, show us multiple substitutes and the like. Halogen-containing monomers include but are not limited to vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene bromide, vinylidene fluoride, halogen-substituted propylene monomers and the like the preferred halogen-containing monomers they are vinyl bromide and vinylidene chloride. The ionic monomers include but are not limited to sodium vinyl sulfanate, sodium styrene sulfonate, sodium methallyl sulfonate, sodium sodium methacrylate acrylate and the like. The ionic monomers are sodium vinyl sulfonate, sodium styrene sulfonate and sodium methallyl sulfonate. Acid-containing monomers include but are not limited to acrylic acid, methacrylic acid, vinyl sulfonic acid, metaconic acid, styrene sulfonic acid and the like. Preferred acid-containing monomers are itaconic acid, styrene sulfonic acid and vinyl sulfonic acid. Base-containing monomers include but are not limited to vinyl pyridine, 2-aminoethyl-N-acrylamide, 3-aminopropyl-N-acrylamide, 2-aminoethyl acrylate, 2-aminoethyl methacrylate and the like. The olefins include but are not limited to isoprene, butadiene, straight and branched chain alpha-olefins from C2 to Ce such as propylene, ethylene, isobutylene, diisobutylene, 1-butene and the like. Preferred olefins are isobutylene, ethylene and propylene. Olefinically unsaturated monomers do not include nitrile monomers such as methacrylonitrile. The olefinically unsaturated acrylonitrile multipolymers do not contain methacrylonitrile. The choice of the olefinically unsaturated monomer or combination of monomers depends on the properties desired to be imparted to the resultant high nitrile multipolymer and its end uses. For example, the polymerization monomers of acrylonitrile and styrene and / or indene result in a multipolymer with high nitrile content and its end products with improved thermistorization temperature and glass transition temperature. Acrylonitrile and isobutylene polymerization monomers improve the flexibility of the high nitrile multipolymer and its final products. The acrylonitrile polymerization monomers and the acrylates and / or methacrylates improve the processability of the high nitrile multipolymer and its final products. Acid-containing polymerization monomers, base-containing monomers and / or monomers containing the hydroxyl group with an acrylonitrile monomer provide useful shading sites that improve the colorability of the resultant high nitrile multipolymer. The acrylonitrile polymerization monomers and a halogen-containing monomer increase the incombustibility of the high nitrile multipolymer and its final products. In the practice of the present invention the polymerization process is carried out as an emulsion, a solution, a suspension or bulk in continuous addition. Preferably, the polymerization process is carried out as an emulsion or a suspension. The present invention can be practiced as a continuous or semi-continuous process. The process of the present invention is not carried out as a batch process whose batch process is defined herein as a process in which all reagents are initially charged to the reaction vessel prior to the initiation of the polymerization. Initially the acrylonitrile monomer and the olefinically unsaturated monomer (s) are contacted in an aqueous medium at about 0.1% by weight to about 15% by weight of the total average of the polymerization reaction. The initial multimonomer mixture contains from about 50% by weight to about 95% by weight of acrylonitrile monomer and from about 5% by weight to about 50% by weight of olefinically unsaturated monomer (s). The aqueous medium contains water and a suitable surfactant such as an emulsifier or a dispersing agent. Surfactants and their uses are known to those skilled in the art. A molecular weight modifier can be added to the initial multimonomer mixture in the range of from about 0 wt% to about 5 wt%, preferably about 0.1% by weight to 4% by weight and more preferably about 0.1% by weight to about 3% by weight of the total multimonomer mixture. The initial multimonomer mixture is placed in a reaction vessel containing an aqueous medium. The reaction vessel with the aqueous medium is purified with an inert gas such as nitrogen, argon and the like. Preferably, but optionally, the purification with inert gas is continued throughout the polymerization reaction. The initial multimonomer mixture is then heated to a temperature in the range of about 30 C to about 120 C, preferably about 40 C to about 100 C and more preferably about 50 C to about 80 C. The polymerization reaction temperature it is maintained throughout the process in the range of about 30 C to about 120 C, preferably about 40 C to about 100 C and more preferably about 50 C to about 80 C. An initiator is added to the initial multimonomer mixture heated to start the polymerization reaction. The initiator is generally added in the range of about 0.01% by weight to about 5% by weight of the total multimonomer mixture. After the polymerization reaction begins, a multimonomer feed of acrylonitrile monomer and olefinically unsaturated monomer (s) is continuously added to the polymerization reaction in the reaction vessel. The combined weight of the unreacted acrylonitrile monomer and the unreacted olefinically unsaturated monomer (s) present in the polymerization mixture, at any time, is not greater than about 15% by weight, preferably not more than about 10% by weight and more preferably not more than about 5% by weight of the polymerization mixture. The limited multimonomer mixture contains from about 50% by weight to about 95% by weight of acrylonitrile monomer and from 5% by weight to about 50% by weight of olefinically unsaturated monomer (s). The molar ratio of the acrylonitrile monomer and the olefinically unsaturated monomer (s) in the monomer feed mixture is fixed and constant throughout the polymerization process resulting in a homogeneous multipolymer. The molar ratio fed from the acrylonitrile monomer to the olefinically unsaturated monomer depends on the composition of the desired olefinically unsaturated acrylonitrile multipolymer. The multipolymer composition is similar to the composition of the multimonomer feed mixture. A molecular weight modifier is optionally added to the polymerization mixture. Preferably, a molecular weight modifier is used in the polymerization mixture. The molecular weight modifier is added continuously or incrementally to the polymerization mixture. Preferably, the molecular weight modifier is continuously added to the polymerization mixture. The molecular weight modifier is preferably added to the polymerization average in the range of from about 0 wt% to about 5 wt%, preferably about 0.1 wt% to about 4 wt% and more preferably about 0.1%. by weight up to about 3% by weight of the total multimonomer mixture. The molecular weight modifier includes but is not limited to mercaptans, halogen-containing alcohols and any other chain transfer agent known to those skilled in the art. Mercaptans are the preferred molecular weight modifiers and include mono-mercaptans, multifunctional mercaptans or combinations thereof. Mercaptans include but are not limited to alkyl mercaptans from C5 to Cis either straight chain, substituted or unsubstituted branched, d-limonene dimercaptan, dipentene, dimercaptan and the like. Preferred mercaptans are C5 to C12 alkyl mercaptans whether straight chain, branched chain, substituted or unsubstituted, for example t-dodecyl mercaptan and n-octyl mercaptan. The molecular weight modifier can be used singly or in combination. The molecular weight modifier can be the same or a different molecular weight modifier than that used with the initial multimonomer mixture. The molecular weight modifier controls the molecular weight of the polymerized unsaturated olefinic acrylonitrile multiplexer chain at the end of the growth chain. The molecular weight modifier useful in the present invention produces an olefinically unsaturated acrylonitrile multipolymer with a molecular weight in the range of about 15,000 molecular weight to about 500,000 molecular weight. The initiator is typically added as a single solution continuously or incrementally to the polymerization mixture as a separate stream. Preferably the initiator is added continuously. The initiator is added in a proportion to maintain the polymerization ratio, the proportion of which can be determined by those skilled in the art. The concentration of the initiator is generally in the range of about 0.01% by weight to about 5% by weight of the total multimonomer mixture. The initiator is any free radical initiator known to those skilled in the art. The initiator includes but is not limited to compounds of azo compounds, peroxides, hydroperoxides, alkyl peroxides, peroxydicarbonates, peroxiesters, dialkyl peroxides, persulfates, perfosphates, and the like. The persulfates are the preferred initiators. The initiator can be used singly or in combination. The initiator can be the same or a different initiator than the one used at the start of the polymerization reaction. The polymerization mixture is stirred continuously or intermittently by any known method such as stirring, shaking and the like. Preferably the polymerization mixture is continuously stirred. The reaction is continued until the polymerization has proceeded to the desired extent, generally from about 40% to about 99% conversion and preferably from about 70% to about 95% conversion. The polymerization reaction is stopped by cooling; adding an inhibitor; such as diethyl hydroxylamine, 4-methoxyphenol and the like, discontinuing the multimonomer feed mixture, and the like. Inhibitors and their uses are known to those skilled in the art. It will be readily apparent to one skilled in the art that the olefinically unsaturated acrylonitrile multipolymer can be further modified by the addition of lubricants, dyes, washing agents, plasticizers, pseudoplasticizers, pigments, detangling agents, stabilizing agents, anti-oxidant static control agents, Reinforcement such as fillers and the like. It is understood that any additive which possesses the ability to function in such a manner can be used since it has no effect of deterioration in the melting characteristics and thermal stability of the high nitrile multipolymer. At the end of the polymerization reaction the olefinically unsaturated acrylonitrile multipolymer is isolated as a solid, mixture or latex. Any known technique can be used to isolate the olefinically unsaturated acrylonitrile multipolymer such as coagulation by disintegration, by spraying the multipolymer solution in a heated chamber and / or vacuum to remove water vapors, distillate, filtration, centrifugation and the like. The unsaturated olefinicalent acrylonitrile multipolymer produced by the process of the present invention is a high nitrile thermoplastic multipolymer containing polymerized acrylonitrile monomer and olefinically unsaturated monomer (s). The multipolymer comprises from about 50% by weight to about 95% by weight of polymerized acrylonitrile and from about 5% by weight to about 50% by weight of olefinically unsaturated polymerized monomer (s). The multipolymer product is homogeneous because the composition and sequence of the multipolymer produced is substantially the same throughout the entire process. The unsaturated olefinic acid acrylonitrile multipolymer is thermally stable, melt processable without the addition of any solvent and homogeneous. The multipolymer of the present invention can be further processed by chemical spinning, molding, extrusion and the like without the use of solvents. The unsaturated olefinic acid acrylonitrile multipolymer possesses excellent physical and mechanical thermal properties, can be easily oriented and is homogeneous with short sequences of polymerized nitrile monomer units. In addition, the unsaturated olefinic acid acrylonitrile multipolymer can be used in numerous applications such as for use as fibers, sheets, films, tubes, pipes, molded articles and the like. SPECIFIC MODALITY The following examples demonstrate the process and advantages of the present invention. Equipment A reactor covered with circulating hot water of 1 or 2 liters was equipped with a reflux condenser, a thermocouple / controller, a stirring blade, whose blade was set at approximately 230 rpm to approximately 250 rpm, an argon purge tube (continuous), a monomer feed mixer pump and an ammonia persulfate initiator feed pump. Components The total polymerization components for the examples were as follows: Example 1 Component Grams (gm) Water 1260.0 Rhofac RE-610 12.6 Acrylonitrile (AN) 342.3 a-Methyl styrene (MS) 77.7 n-Octyl Mercaptan 8.4 Ammonia Persulfate 1.3 Total: 1702.3 Example 2 Component Grams (gm) Water 1320.0 Rhofac RE-610 17.6 Acrylonitrile (AN) 378.4 Methyl Acrylate (MA) 30.8 Methyl Methacrylate (MMA) 30.8 n-Octyl Mercaptan Ammonia Persulfate 2.8 Total: 1789.2 Example 3 Component Grams (gm) Water 1320.0 Rhofac RE-610 17.6 Acrylonitrile (AN) 338.8 Methyl Methacrylate (MMA) 101.2 n-Octyl Mercaptan Ammonium Persulfate 2.8 Total: 1789.2 Example 4 Component Grams (gm) Water 1200.0 Dowfax 8390 (35% active) 45.7 Acrylonitrile (AN) 340.0 Methyl Acrylate (MA) 60.0 n-Dodectil Mercaptan 11.2 Ammonia Persulfate 0.8 Total: 1657.7 Example 5 Component Grams (gm) Water 1200. .0 Rhofax RE-610 12., 0 Acrylonitrile (AN) 344., 0 Styrene (ST) 56. .0 n-Octil Mercaptan 9. .0 Ammonia Persulfate 2. .5 Total: 1623. .5 Example 6 Component Grams (gm) Water 750.0 Dowfax 8390 (35% active) 7.5 Acrylonitrile (AN) 212.5 Vinyl Acetate (VA) 37.5 n-Dodecil Mercaptano 7.0 Ammonia Persulfate 1.6 Total: 1016.1 Example 7 Component Grams (gm) Water 1200. .0 Rhofax RE-610 12. .0 Acrylonitrile 340. .0 Methyl methacrylate (MMA) 30. .0 Vinyl Acetate (VA) 30, .0 n-Octil Mercaptan 8. .0 Ammonia Persulfate 2. .5 Total: 1622. .5 The Rohfac RE-610 is available from Rhone Poulenc Dowfax is available from Dow Chemical Co. Procedure: The reactor was pre-charged with water and the surfactant which has been pre-dissolved at about 50 ° C with stirring at about 230-250 rpm (see Table I). The reactor was heated to about 70 ° C with a continuous argon purge. The initial monomer charge (see Table II) was added to the reactor. The ammonia persulphate initiator was added to the reactor to initiate the polymerization reaction. The mixture fed of multimonómero (see Table III) containing mercaptan is continuously pumped into the reactor at a constant fixed weight ratio, from acrylonitrile monomer ("AN") to the olefinically unsaturated monomer ("X") (see Table IV). Simultaneously, the ammonia persulphate initiator was pumped into the reactor (See Table IV). Both the multimonomer feed mix stream and the initiator stream were fed to the reactor as separate streams. The total polymerization reaction time was about 4 to about 6 hours. After the polymerization reaction was completed the resulting multipolymer emulsion was filtered through a piece of pre-weighed gauze to collect and separate any clot coming from the multipolymer. The clot was packed in gauze and washed with warm tap water. The gauze was dried overnight at about 60 C. After that the dry gauze / clot was weighed. The clot was from about zero to about 3% by weight of multimonomers. The latexes were then coagulated in approximately 1% aqueous aluminum sulfate solution at approximately 75 C to 85 C with continuous agitation. The washing and filtering of the multipolymer slurry was dried for about 3 to about 24 hours in a vacuum filtration funnel The multipolymer was then dried in a fluidized bed dryer at about 55 C for about 3 hours. of olefinically unsaturated acrylonitrile was then analyzed (See Table V and VI) TABLE 1 Water Preload Example Water Rhofac RE-blu (gm) Dowf, ax 8390 1 1160 12.6 0 2 1220 17.6 0 3 1220 17.6 0 4 1100 0 45.7 5 1100 12.0 0 6 677. 5 0 20.0 7 1100 12.0 0 TABLE II INITIAL MONOMER LOAD (gm) Example Mercaptan Monomer Monomer Monomer Acplonitin Initiator Olefinically Olefinically Unsaturated Persulfate Xl Unsaturated X-2 Ammonia (gm) 2. 1 gm n- 21.0 21. WHO 0 0.71 octyl mercaptan 2.2 gm n- 37. í 3.1 MMA 3.1 MA octyl mercaptan 2.2 gm n- 41.8 2.2 MMA 1.45 octyl mercaptan 2.8 gm n- 34.0 6.0 MA 0.42 dodecyl mercaptan 2.24 gm n- 38.0 2 ST 1.32 octyl mersaptane 1.8 gm n- 13.8 11.3 VA 0.53 dodecyl mercaptan 2.0 gm n- 34.0 3.0 MA 3.0 MA 1.33 octil mersaptano TABLE III MULTIMONOMETER FEED MIXTURE Mersaptano * Monomer AN Monomer Xi Monomer X2 Polymeasurement (gm) ( gm) (gm) (gm) Total (hrs) 1 6.3 321.3 56.7 MS 0 6 2 6.6 336.6 29.7 MMA 29.7 MA 6 3 6.6 297 99.0 MMA 0 6 4 8.4 306 54 MA 0 4 5 6.76 306 54 ST 0 6 6 5.3 199 26.2 VA 0 5 7 6.0 306 27.0 VA 27.0 MA 6"n-octyl mercaptan was used in examples 1, 2, 3, 5, and 7. n-dodecyl mercaptan was used in examples 4 and 6.

TABLE IV Aqueous Primer Feeding Mixture Example Water Persulfate (gms) Ammonia (gms) 1 0.63 100 2 1.31 100 3 1.31 100 4 0.38 100 5 1.2 100 6 1.1 61 7 1.31 100 TEST: Molecular Weight: The molecular weight (MW) of a multipolymer was determined by Gel Permeation Chromatography (GPC) in a solvent of dimethyl formamide and calibrated with polystyrene standards. This is a known standard method. The results are presented in Table V. Vitreous State Fusion Temperature: NMR Analysis: Samples were prepared for NMR Analysis using DMS-DC6 as solvent. The compositions were determined using H spectra and the sequence distributions 13 were determined using C spectra. The H spectra were obtained using a Varian Gemini Spectrometer 300 to 300 MHz and / or a Spectrometer Varian VXR-400 at 400 MHz. The C spectra were obtained using a Varmin Gemini Spectrometer 300 at 75.5 MHz and / or a Spectrometer Varies VXR-400 at 100.7 MHz. The numerical data are presented in Table VI.

Brabender Plastiencordonador: The Brabender plastiencordonador, available from C.W. Brabender Instruments Inc., South Hackensack, New Jersey, is a slow shear mixing device that measures the torque (meters-grams, m-g) required to melt-activate a molten polymer. The test determines if a polymer can be melted and processed using standard thermoplastic equipment. The Brabender analyzes were run at approximately 200 C with the reading of torque taken at intervals of approximately 5 minutes to approximately 30 minutes. This method measures the degradation of the polymer as a function of time, temperature and physical abrasion. The numerical data are presented in Table V.

TABLE V Physical Properties of the Polymer Example Tg (° C) Torque Torque Molecular Torque Brabender Brabender Brabender Mw m-gm, 200 ° C m-gm, 200 ° C m-gm, 200 ° C 10 minutes 20 minutes 30 minutes 1 103 50,000 420 420 429 2 81 46,000 653 641 641 3 83 43,000 298 286 298 4 77 62,000 939 996 1115 5 93 43,000 529 (220 ° C) 550 (220 ° C) 732 (220 ° C) 6 90 59,000 900 1329 1836 7 86 48,000 1026 957 992 TABLE VI Chemical Properties of the Polymer by 13 C NMR Composition Example Composition of the Monomer Analysis Rate Polymer Load (%) Monomer (%) 1 AN / MS 81/19 76.4 / 23.6 2 AN / MMA / MA 85 / 7.5 / 7.5 83.2 /11.2/5.6 3 AN / MMA 75/25 68.5 / 31.5 4 AN / MA 85/15 85.7 / 14.3 5 AN / ST 85/15 84.8 / 15.2 6 AN / VA 85/15 84.6 / 15.4 7 AN / MA / VA 85 / 7.5 / 7.5 87.4 / 7.7 / 4.9 Sequence of Monomer Example XXX XXA AXA XAX AAX AAA 1 12.9 43.4 43.7 8.2 48.3 43.5 BBA ABA CCA ACA XAX AAX AAA 2 18.7 81.3 7.9 92.1 2.7 14.8 82.5 XXX XXA AXA XAX AAX AAA 3 0 20.8 79.2 0 31.3 68.7 4 7.5 24.6 67.9 4.0 19.6 76.5 16.0 59.9 24.0 1.5 13.1 85.5 6 * * * 3.1 20.2 76.7 7 * * * 2.9 18.3 78.8 A = acrylonitrile B = methyl methacrylate C = Methyl acrylate X = olefinically unsaturated monomer = Not measurable by 13C NMR Results: A very uniform and homogeneous olefinically unsaturated acrylonitrile multipolymer was produced by the process described herein. The final conversion to multipolymer was about 90% based on the total multimonomers. The average molecular weight of the multipolymer examples was in the range of approximately 43, 000 to approximately 62,000. The Brabender torque data for the examples ranged from about 420 m-gm to about 1026 m-gm at ten minutes and about 429 m-gm to about 1329 m-gm at thirty minutes. This shows that the multipolymers are easily melt processed and thermally stable. The Brabender torque data are shown in Table V.

The NMR data showed that the multipolymer sequence was interdispersed and had a high degree of randomness as shown in Table VI. Furthermore, the analysis of the polymer shows that the proportion of the multipolymer product is similar to the feed proportion of multimeromer. From the description and previous examples of the invention those skilled in the art will perceive improvements, changes and modifications in the invention. Such improvements, changes and modifications within the understanding of the subject are intended to be covered by the appended claims.

Claims (12)

1. NOVELTY OF THE INVENTION Having described the present invention, it is considered as novelty and therefore what is described in the following claims is claimed as property. A process for polymerizing an acrylonitrile monomer and one or more olefinically unsaturated monomers to make an olefinically unsaturated acrylonitrile multipolymer, said process comprising the steps of: heating an initial multimonomer mixture comprising acrylonitrile monomer and one or more olefinically monomers unsaturated, under an inert atmosphere, in the range of about 30 C to about 120 C; adding an initiator to the initial multimonomer mixture to initiate a polymerization reaction; adding a multimonomer feed mixture comprising acrylonitrile monomer and olefinically unsaturated monomer (s) to the polymerization mixture wherein the multimonomer feed mixture contains from about 50 wt% to about 95 wt% acrylonitrile monomer and about 5% by weight to about 50% by weight of olefinically unsaturated monomer (s) wherein the multimonomer feed mixture has a constant and fixed molar ratio of acrylonitrile monomer to the olefinically unsaturated monomer (s) ( s); and wherein the addition ratio of the multimonomer feed mixture is less than or equal to the polymerization ratio; resulting in a homogeneous olefinically unsaturated acrylonitrile multipolymer product; wherein the olefinically unsaturated acylonitrile multipolymer is from about 50% by weight to about 95% by weight of polymerized acrylonitrile monomer and from 5% by weight to about 50% by weight of polymerized olefinically unsaturated monomer; and wherein said multipolymer is thermally stable and melt processable without the use of solvents.
2. 2. The process according to claim 1, characterized in that a molecular weight modifier is added to the initial multimonomer mixture, to the multimonomer feed mixture or to both mixtures in the range from about 0% by weight to about 5% by step of the Total multimonomer mixture and is selected from the group consisting of mercapatans, alcohols, halogen compounds and combinations thereof.
3. The process according to claim 2 characterized in that the mercaptan is selected from the group consisting of t-dodecyl mercaptan, n-octyl mercaptan, d-limonene dimercaptan and combinations thereof.
4. The process according to claim 1 characterized in that the initiator is continuously added as an aliquot to the polymerization reaction in the range of 0.01% by weight to approximately 5% by weight of the total multimonomer mixture and is selected from the group consisting of azo compounds, peroxides, hydroperoxides, alkyl peroxides, peroxydicarbonates, peroxyesters, dialkyl peroxides, persulfates, perfosphates and combinations thereof.
5. The process according to claim 1 characterized in that the combined weight of the unreacted acrylonitrile monomer and the unreacted olefinically unsaturated monomer present in the polymerization mixture, at any time, is not greater than about 15% by weight of the mixture of polymerization and wherein further said process is carried out as an emulsion, a solution, a suspension or in bulk in continuous addition.
6. The process according to claim 1 characterized in that the olefinically unsaturated monomer is selected from the group consisting of acrylates, methacrylates, acrylamides, methacrylamides, acrylamide derivatives, methacrylamide derivatives, vinyl esters, vinyl ethers, vinylamides, vinyl ketones, styrenes, halogen-containing monomers, ionic monomers, acid-containing monomers, base-containing monomers, olefins and combinations thereof.
7. 7. The process according to claim 6, characterized in that the olefinically unsaturated monomer is selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, vinyl acetate, styrene, 5-methyl styrene, indene, vinyl bromidene, vinylidene chloride, sodium vinyl sulfonate, sodium styrene sulfonate, sodium methallyl sulfonate, itaconic acid, styrene sulfonic acid, vinyl sulphonic acid, isobutylene, ethylene, propylene and combinations thereof and wherein in addition the olefinically unsaturated monomer excludes a methacrylonitrile monomer.
8. 8. A melt processable homogeneous multipolymer comprising from about 50% to about 95% polymerized acrylonitrile and From about 5% to about 50% polymerized olefinically unsaturated multipolymer which is melt processable and contains a relatively uniform distribution of monomers in the multipolymer chain.
9. The multipolymer according to claim 8, characterized in that the acrylonitrile and the olefinically unsaturated monomer are randomly interdispersed throughout the polymer chain in short sequences of acrylonitrile monomer and Olefinically unsaturated monomer, resulting in a heat-stable stable melt-processable homogeneous multipolymer which is melt processable in the absence of solvent or plasticizing agent or water.
10. The multipolymer according to claim 8 characterized in that the olefinically unsaturated monomer is selected from the group consisting of acrylates, methacrylates, acrylamides, methacrylamides, acrylamide derivatives, methacrylamide derivatives, vinyl esters, vinyl ethers, vinylamides, vinyl ketones, styrenes, halogen-containing monomers, ionic monomers, acid-containing monomers, base-containing monomers, olefins and combinations thereof.
11. 11. The multipolymer according to claim 8, characterized in that the acrylates are selected from the group consisting of Ci to C12 alkyl, aryl and cyclic acrylates, their functional derivatives and combinations thereof; and wherein the methacrylates are selected from the group consisting of C 1 to C 2 alkylaryl and cyclic acrylates, their functional derivatives and combinations thereof; and wherein the acrylamides and methacrylamides are selected from the group consisting of acrylamide, N-substituted alkyl and aryl derivatives, methacrylamide, N-methyl acrylamide, N, N-dimethyl acrylamide and combinations thereof and wherein the vinyl esters are selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate and combinations thereof; and wherein the vinyl ethers are selected from the group consisting of vinyl ethers of Ci to Ce, vinyl ethyl ether, vinyl butyl ether and combinations thereof; and wherein the vinyl amides are selected from the group consisting of vinyl pyrrolidones and combinations thereof; and wherein the vinyl ketones are selected from the group consisting of vinyl acetones from Ci to Ce, ethyl vinyl acetone, butyl vinyl acetone and combinations thereof; and wherein the styrenes are selected from the group consisting of methyl styrene, styrene, indene, a styrene of the formula wherein each of A, B, C and D are independently selected from hydrogen (H) and the alkyl group from Ci to C4, substituted styrenes, multiply substituted styrenes and combinations thereof; and wherein the halogen-containing monomers are selected from the group consisting of vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene bromide, vinylidene fluoride, halogen-substituted propylene monomers and combinations thereof; and wherein the ionic monomers are selected from the group consisting of sodium vinyl sulfonate, sodium styrene sulfonate, sodium methallyl sulfonate, sodium acrylate, sodium methacrylate and combinations thereof; and wherein the acid-containing monomers are selected from the group consisting of acrylic acid, methacrylic acid, vinyl sulfonic acid, itaconic acid and combinations thereof; and wherein the base-containing monomers are selected from the group consisting of vinyl pyridine, 2-aminoethyl-N-acrylamide, 3-aminopropyl-N-acrylamide, 2-aminoethyl acrylate, 2-amino ethyl methacrylate and combinations thereof; and wherein the olefins are selected from the group consisting of isopropene, butadiene, straight and branched chain alpha-olefins of C2 to Ce, propylene, ethylene, isobutylene, diisobutylene, 1-butene and combinations thereof.
12. 12. The multipolymer according to claim 10 characterized in that the acrylates are selected from the group consisting of methyl acrylate, ethyl acrylate, phenyl acrylate, butyl acrylate, isobornyl acrylate, 2-hydroxy ethyl acrylate, 2-chloroethyl acrylate, 2-ethylhexyl acrylate and combinations thereof; and wherein the methacrylates are selected from the group consisting of methyl methacrylate, ethyl methacrylate, phenyl methacrylate, butyl methacrylate, isobornyl methacrylate, 2-hydroxyethyl methacrylate, 2-chloroethyl methacrylate, 2-ethylhexyl methacrylate and combinations thereof.