MXPA98006861A - Process for elaborating polypropylene grafting pools that contain anhydr groups - Google Patents

Abstract

A graft copolymer containing anhydride groups is made by (1) making a graft copolymer comprising a basic structure of a propylene polymer material having a graft polymerized thereto, polymerized monomers selected from the group consisting of (a) ) at least one acrylic substituted with an alkyl group of 1 to 3 carbon atoms and (b) a mixture of at least one of these substituted acrylic acids and a vinyl compound capable of being polymerized therewith, wherein the total amount of the polymerized monomers is from about 20 parts to about 240 parts per hundred parts of the propylene polymer material, and the amount of the substituted acrylic acid is 60 mole percent or more of the polymerized monomers, and (2) the graft copolymer is heated to a temperature of about 170 ° C to about 300 ° C to dehydrate the acid groups of the copolymer of grafting to form the anhydride groups

Description

ßí > - ' "PROCESS FOR ELABORATING COPYRIGHTED POLYPROPYLENE CONTAINERS OF ANHYDRID GROUPS" This invention relates to a process for making polypropylene graft copolymers having anhydride groups in the side chains. Acrylic and methacrylic acids are the simplest unsaturated organic acids. Due to the presence of carbon-to-carbon unsaturated double bonds, these acids react easily with electrophilic, free radical and nucleophilic agents. Polymerization initiated with free radical of the double bonds is the most common reaction. Small amounts of the acids are commonly used as comonomers to vary the properties mechanics of the other polymers. Most acrylic and methacrylic acids are used in the form of their ethyl, methyl and butyl esters. The polymerized acids themselves are brittle solids that can not be molded and therefore their use is very limited. It is also known that these polyacids are easily dehydrated to form polyanhydrides. In general, the vitreous state transition temperature (Tg) of the dehydrated polyacids increases with an increase in the anhydride concentration.

* - Although not of commercial importance, the acrylic and methacrylic anhydrides can be polymerized to form the polyacryl and polymethacrylic anhydrides. The mechanical properties of polymerized polyacids and polymerized polyanhydrides have not been disclosed in the literature. The grafting of the vinyl monomers towards the basic structure of the olefin polymer is disclosed in US Pat. No. 5,140,074, wherein the The graft copolymers are made by contacting an olefin polymer with a free radical polymerization initiator, such as organic peroxide, and a vinyl monomer in a non-oxidizing environment, deactivating the residual free radicals, and decomposing the unreacted initiator. The acrylic and methacrylic acids are described as appropriate vinyl monomers. U.S. Patent No. 5,411,994 discloses a process for making the graft copolymers by irradiating an olefin polymer and then treating it with a monomer of vinyl in liquid form in a non-oxidizing environment, deactivating the free radicals, and removing the unreacted monomer. It has been reported in the literature that the incorporation of ionic residues such as acid methacrylate in polystyrene, raise the Tg - significantly (~ 19 ° C / molar percentage of methacrylic acid). We have found an improvement in the thermal resistance of the polypropylene graft polymerized with styrene and methacrylic acid to form styrene / methacrylic acid copolymer side chains. However, when methacrylic acid is incorporated into the polymer chain at levels up to 40 mole percent, there is a corresponding reduction in the ductility of the product as indicated by resistance in the weld line, elongation, and difficulty in modification. of impact and extrusion. There is no known process for making graft copolymers containing anhydride groups from a propylene polymer material having a graft polymerized thereto, acrylic acids substituted with alkyl groups of 1 to 3 carbon atoms. Therefore, the effect that these anhydride groups would have on the mechanical properties of the graft copolymer product is also unknown. The process of this invention for making graft polymer containing anhydride groups comprises: (1) producing a graft copolymer comprising a basic structure of a propylene polymer material having a graft polymerized thereto, the polymerized monomers which are select from the group consisting of: (a) at least one alkyl-substituted acrylic acid of 1 to 3 carbon atoms, and 5 (b) a mixture of (a) with at least one vinyl monomer capable of copolymerizing therewith, # wherein the total amount of the polymerized monomers is from about 20 parts to about 1040 parts per hundred parts. of the propylene polymer material, and the amount of the substituted acrylic acid is equal to or greater than 60 mole percent of the polymerized monomers, and 15 (2) heating the resulting graft copolymer at a temperature of about 170 ° C to about 300 ° C, to dehydrate the acid groups in the graft copolymer to form anhydride groups. The graft copolymers of this invention exhibit a good ductility balance (elongation at break), impact strength and resistance to the weld line in the finished product, and can be easily modified upon impact with a wide variety of materials. rubber. The graft copolymer compositions - * Reinforced with glass with a good balance of properties, they are also produced. Figure 1 shows the infrared spectra (IR) before and after extrusion for a copolymer of graft comprising a basic structure of the propylene homopolymer to which a copolymer comprising 20 mole percent methyl methacrylate and 80 mole percent methacrylic acid was grafted. The spectra were recorded using the infrared spectrometer of Fourier Nicolet 60SX transformation (FTIR) with an IR plane microscope and a Nicolet 740SX FTIR. Figure 2 shows the infrared spectra before and after extrusion for a graft copolymer comprising a basic structure of the propylene homopolymer to which a copolymer comprising 20 weight percent of 4-t-butyl styrene was grafted and 80 weight percent methacrylic acid. Figure 3 shows the infrared spectra before and after extrusion for a graft copolymer comprising a basic structure such as propylene homopolymer which was grafted to a copolymer comprising 20 weight percent alpha-methylstyrene and 80 weight percent weight of methacrylic acid. Figure 4 shows the infrared spectra 25 before and after the extrusion of a graft copolymer - "comprising a propylene homopolymer basic structure to which poly (methacrylic acid) was grafted in. The first step in the process of this invention is the preparation of a graft copolymer having a basic structure of a propylene polymer material The propylene polymer material which is used as the basic structure of the graft copolymer in the process of this invention, can be: (a) ) a crystalline propylene homopolymer having an isotactic Index greater than 80, preferably from about 85 to about 99, (b) a crystalline propylene random copolymer and an olefin selected from the group consisting of ethylene and alpha-olefins of 4 to 10 carbon atoms, as long as the olefin is ethylene, the maximum polymerized ethylene content is 10 weight percent, preferably of 4 percent, and when the olefin is an alpha-olefin of 4 to 10 carbon atoms, the maximum polymerized content thereof is 20 percent, preferably about 16 percent, by weight, the copolymer having an isotactic index greater than 85; (c) a random crystalline terpolymer of propylene and two olefins which are selected from the group consisting of ethylene and alpha-olefins of 4 to 8 carbon atoms, as long as the alpha-olefin content of 4 to 8 carbon atoms, polymerized maximum is 20 weight percent, preferably about 16 weight percent, and when ethylene is one of the 5 olefins, the maximum polymerized ethylene content is 5 weight percent, preferably about 4 weight percent , the terpolymer having a ^ F isotactic index greater than 85; (d) an olefin polymer composition comprising: (i) from about 10 percent to about 60 percent by weight, preferably from about 15 percent to about 55 percent of a crystalline propylene homopolymer that has an isotactic index greater than 80, preferably from about 85 to about 98, or a crystalline polymer that is selected from the group consisting of (a) propylene and ethylene (b) propylene, ethylene and an alpha-olefin of 4 to 8 carbon atoms, and (c) propylene and an alpha-olefin of 4 to 8 carbon atoms, the copolymer having a propylene content of more than 85 weight percent, preferably from about 90 percent to about 99 weight percent. hundred, and an isotactic index greater than 85; (ii) from about 5 percent to about 25 percent, preferably from about 5 percent to about 20 percent, of an ethylene-propylene copolymer or an alpha-olefin of 4 to 8 carbon atoms that is insoluble in xylene at room temperature, and (iii) from about 30 percent to about 70 percent, preferably 20 percent percent to about 65 percent, of an elastomeric copolymer selected from the group consisting of (a) ethylene and propylene, (b) ethylene, propylene and an alpha-olefin of 4 to 8 carbon atoms, and (c) ethylene and an alpha-olefin of 4 to 8 carbon atoms, the copolymer optionally containing from about 0.5 percent to about 10 percent of a diene, and containing less than 70 percent by weight, preferably about 10 percent by weight. percent to about 60 percent, especially preferably from about 12 percent to about 55 percent ethylene, and being soluble in xylene at room temperature, and having an intrinsic viscosity of approximately 1.5 percent to approximately - 4. 0 deciliters per gram, wherein the total amount of (ii) and (iii) based on the total olefin polymer composition, is from about 50 percent to about 90 percent, the weight ratio of (ii) / ( iii) is less than 0.4, preferably from 0.1 to 0.3, and the composition is prepared by polymerization in at least two * stages and has a flexural modulus of less than 150 MPa; or (e) a thermoplastic olefin comprising: (i) from about 10 percent to about 60 percent, preferably from about 20 percent to about 50 percent, of a 15-crystalline propylene homopolymer having a isotactic index greater than 80, or a crystalline copolymer selected from the group consisting of (a) ethylene and propylene, (b) ethylene, propylene and an alpha-olefin of 4 to 8 carbon atoms, and (c) ethylene and an alpha-olefin of 4 to 8 carbon atoms, the copolymer having a propylene content greater than 85 percent, and an isotactic index greater than 85; (ii) from about 20 percent to about 60 percent, preferably from about 25 percent to about 50 percent - one hundred of an amorphous copolymer selected from the group consisting of (a) of ethylene and propylene, (b) ethylene, propylene, and an alpha-olefin of 4 to 8 carbon atoms, and (c) ethylene and an alpha- olefin of 4 to 8 carbon atoms, optionally containing the copolymer from about 0.5 percent to about 10 percent of a diene, containing less than * 70 percent ethylene and being soluble in xylene at room temperature; and (iii) from about 3 percent to about 40 percent, preferably about 10 percent to about 20 percent, of an ethylene and propylene copolymer, or an alpha-olefin of 4 to 8 carbon atoms which is insoluble in xylene at room temperature, wherein the composition has a flexural modulus greater than 150 but less than 1200 MPa, Preferably from about 200 to about 1100 MPa, particularly preferably from about 200 to about 1000 MPa. The ambient temperature is -25 ° C.

- Alpha-olefins of 4 to 8 carbon atoms useful in the preparation of (d) and (e) include, for example, buten-1; penten-1; hexen-1; 4-methylpenten-1, and octen-1. The diene, when present, is typically butadiene; 1,4-hexadiene; 1, 5-hexadiene, or ethylidene norbornene. The materials (d) and (e) of propylene polymer can be prepared by polymerization in at least two stages, wherein the first stage, propylene; propylene and ethylene; propylene and alpha-olefin, or propylene, ethylene and alpha-olefin are polymerized to form component (i) of (d) or (e), and in the following stages mixtures of ethylene and propylene, ethylene and alpha-olefin, or ethylene, propylene and the alpha-olefin, and optionally a diene, are polymerized to form the components (ii) and (iii) of (d) or (e). The polymerization can be carried out in the liquid phase, the gas phase or the liquid-gas phase using separate reactors, all of which are carried out either by batch polymerization or continuously. For example, it is possible to carry out the polymerization of component (i) using liquid propylene as a diluent, and the polymerization of components (ii) and (iii) in the gas phase, without intermediate steps except as - refers to the partial degassing of propylene. The entire gas phase is the preferred method. The preparation of the propylene polymer material (d) is described in greater detail in U.S. Patent Nos. 5,212,246 and 5,409,992, the preparation of which is incorporated herein by reference. The preparation of the propylene polymer material (e) is described in greater detail in the US Patents * Numbers 5,302,454 and 5,409,992, whose preparation is incorporate the present by reference. The propylene homopolymer is the preferred basic propylene polymer structure material. The monomers that make up the grafted polymers or copolymers that contain anhydride groups in The basic structure of the propylene polymer material is selected from the group consisting of (a) at least one alkyl-substituted acrylic acid of 1 to 3 carbon atoms, and (b) a mixture of (a) with minus one vinyl monomer capable of copolymerizing therewith.

The vinyl monomer may be any monomeric vinyl compound capable of polymerizing by free radicals, wherein the vinyl radical, H 2 C = CR-, wherein R is H or methyl, is attached to a straight or branched aliphatic chain or a aromatic ring Heterocyclic or alicyclic substituted or unsubstituted in - - * a mono- or poly-cyclic compound. Typical substituent groups may be alkyl, hydroxyalkyl, aryl and halo. Usually the vinyl monomer will be a member of one of the following classes: (1) vinyl-substituted heterocyclic or alicyclic aromatic compounds, heterocyclic or alicyclic compounds, including styrene, vinylnaphthalene, vinylpyridine, vinylpyrrolidine, vinylcarbazole and homologs thereof, eg, alpha- and para-methylstyrene, methylchlorostyrene, pt-butylstyrene, -methylvinylpyridine and ethylvinylpyridine; (2) vinyl esters of the saturated aromatic and aliphatic carboxylic acids, including vinyl formate, vinyl acetate, vinyl chloroacetate, vinyl cyanoacetate, vinyl propionate, and vinyl benzoate, and (3) nitriles Unsaturated aliphatics and carboxylic acid derivatives including acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, acrylate esters, such as methyl, ethyl, hydroxyethyl-2-ethylhexyl esters, and butylacrylate, and methacrylate esters such as methyl esters, Ethyl, butyl, benzyl, phenylethyl, phenoxyethyl, epoxypropyl and hydroxypropylmethacrylate. Polymerizable free radical dienes such as butadiene, isoprene and their derivatives can also be used. Multiple monomers of the same or different kinds can used. Styrene is the preferred vinyl monomer.

- During graft polymerization, the monomers are also polymerized to form a certain amount of free or ungrafted polymer or copolymer. Any reference to "polymerized monomers" in this specification is meant to include both grafted and non-grafted polymerized monomers. The polymerized monomers comprise from about 20 parts to about 240 parts per hundred parts of the propylene polymer material, preferably from about 30 to about 95 pph. The morphology of the graft copolymer is such that the propylene polymer material is the continuous or matrix phase and the polymerized monomers, both grafted and ungrafted, are a dispersed phase. The amount of the substituted acrylic acid is equal to or greater than 60 mole percent, preferably greater than 80 mole percent, of the polymerized monomers. When methacrylic acid is used as a monomer, 100 percent of the monomers are more preferably. The graft copolymer can be made according to any of several methods. One of these methods involves forming active graft sites in the propylene polymer material either in the presence of the graft monomers or followed by treatment with the monomers. Grafting sites can occur - by treatment with a peroxide or other chemical compound which is a free radical polymerization initiator, or by irradiation with high energy ionization radiation. Free radicals produced in the polymer as a result of chemical treatment or irradiation form the active graft sites in the polymer and initiate the polymerization of the monomers at these sites. Graft copolymers produced by peroxide-initiated grafting methods are preferred. The preparation of graft copolymers by contacting the propylene polymer with a free radical polymerization initiator such as organic peroxide and a vinyl monomer is described in greater detail in U.S. Patent No. 5,140,074, the preparation of which is incorporated herein by reference. by reference. The preparation of the graft copolymers by irradiating an olefin polymer and then treating with a vinyl monomer is described in greater detail in U.S. Patent No. 5,411,994, the preparation of which is incorporated herein by reference. The second step in the process of this invention is the heating of the graft copolymer produced in the first step, to a temperature of about 170 ° C to about 300 ° C in order to dehydrate the - acid groups in the graft copolymer to form the anhydride groups. The heating may be effected, for example, in a reaction vessel or in an extrusion apparatus such as an apparatus for extruding twin screws. Dehydration and formation of the anhydride groups are indicated by weight loss by thermogravimetric analysis (TGA), moisture analysis and analysis of the functional group by IR (see Figures 1 to 4). The degree of dehydration is directly proportional to the acid content in the graft copolymer. As shown by TGA, the graft copolymers containing the polymethacrylic acid as the polymerized monomer undergo almost complete dehydration to yield side chains containing the groups of anhydride and methacrylic acid groups grafted onto the -átk basic structure of the propylene polymer material. The anhydride groups are predominantly glutaric anhydride groups, but small amounts of succinic anhydride groups may also be present. If the acrylic acid instead of the alkyl-substituted acrylic acid of 1 to 3 carbon atoms is used as the acrylic monomer, the graft copolymer is difficult to extrude, exhibits poor quality and has poor physical properties.

- ^ B - ^ - ' Graft copolymers containing an amount equal to or greater than 60 mole percent of the alkyl-substituted acrylic acid groups of 1 to 3 carbon atoms which are subsequently dehydrated to form the anhydride groups can be extruded to produce products with a good balance of properties such as resistance to Izod crash with notch, elongation at break and resistance in the welding line. The compositions containing the anhydride group containing the graft copolymers of this invention can be modified by shock by the addition of a rubber component which is selected from one or more of the groups consisting of (i) a rubber of copolymer of olefin, (ii) a conjugated diene block polymer by monoalkenyl aromatic hydrocarbon, and (iii) a core hull rubber. Any of these rubber components may have acid or anhydride functionality or may be exempt from these groups functional. The preferred rubber components are (i) or (ii), either alone or in combination. Suitable olefin copolymer rubbers include, for example, saturated olefin copolymer rubbers such as ethylene monomer rubbers. propylene (EPM), ethylene / octen-1 rubbers, and ethylene / - buten-1, and unsaturated olefin copolymer rubbers such as ethylene / propylene / diene monomer rubbers (EPDM). Preferred olefin copolymer rubbers are ethylene / propylene, ethylene / buten-1, and ethylene / octen-1 copolymers. The monoalkenyl aromatic hydrocarbon-conjugated diene block copolymer can be a thermoplastic elastomer of the AB (or diblock) structure, the linear ABA (or triblock) structure, the radial type (AB) n where n = 3- 20 percent, or a combination of these types of structure, wherein each block A is a monoalkenyl aromatic hydrocarbon polymer block, and each block B is an unsaturated rubber block. Different grades of copolymers of this type can be obtained commercially. The qualities differ in structure, molecular weight and intermediate and end blocks, and the ratio of monoalkenyl aromatic hydrocarbon to rubber. The block copolymer can also be hydrogenated. Typical monoalkenyl aromatic hydrocarbon monomers are styrene, linear or branched alkyl styrenics of 1 to 4 carbon atoms, ring-substituted and vinyl toluene. Styrene is preferred. Suitable conjugated dienes include, for example, butadiene and isoprene. The - Preferred block copolymers are hydrogenated styrene / ethylene-butene / styrene triblock copolymers. The weight average molecular weight Mw of the block copolymers will generally be within the range of 45,000 to about 260,000 grams per mole, the average molecular weights within the range of 50,000 to about 125,000 grams per mole being preferred over the They provide mixing compositions that have the best balance of shock resistance and rigidity. Also, even when block copolymers having unsaturated as well as saturated rubber blocks can be used, copolymers having saturated rubber blocks are preferred, also on the basis of the shock / stiffness balance of the compositions containing them. The weight ratio of the monoalkenyl aromatic hydrocarbon to the conjugated diene rubber in the block copolymer is within the range of about 5/95 to about 50/50, preferably about 10/90 to about 40/60. The core hull rubber components comprise small particles of the cross-linked rubber phase surrounded by a compatibilization shell, usually a vitreous polymer or copolymer. The core is typically a diene rubber such as butadiene or - # isoprene or an acrylate. The hull is typically a polymer of two or more monomers selected from styrene, methyl methacrylate and acrylonitrile. Particularly preferred core hull rubbers have an acrylate core. Suitable shock modifiers include, for example, Engage 8100, 8150 and 8200 which are ethylene / octen-1 copolymers, which can be obtained commercially from DuPont Dow Elastomers; EPM 306P the ethylene copolymer random / propylene EPM 306P, which can be obtained commercially from Miles Inc., Polysar Rubber Div .; Kraton G 1652; the styrene / ethylene-butene / styrene triblock copolymer Kraton G 1652, which is commercially available from Shell Chemical Company; the copolymers ethylene / buten-1 Exact, commercially available from Exxon Chemical Company, and the heterophasic polyolefins KS080 and KS350, which are commercially available from Montell USA Inc. The shock modifier, if present, is uses in an amount of from about 2 percent to about 30 percent, preferably from about 5 percent to about 15 percent by weight, based on the total weight of the composition. The composition may also contain a material of propylene polymer molecular weight distribution - - wide (Mw / Mn) (BMW DB). The BMPD PP has an Mw / Mn of from about 5 to about 60, preferably from about 5 to about 40; a melt flow rate of about 0.5 to about 50, preferably about 1 to about 30 grams per 10 minutes, and insoluble xylene at 25 ° C greater than or equal to 94 percent, preferably greater than or equal to 96 percent, and especially preferred greater than, or equal to 98 percent. The propylene polymer material having a broad molecular weight distribution can be a propylene homopolymer or a propylene homopolymer modified to the shock of ethylene / propylene rubber, wherein the propylene homopolymer has a broad molecular weight distribution. The BMWD PP can be prepared by sequential polymerization in at least two stages, in the presence of a Ziegler-Natta catalyst supported on magnesium halide in active form. The polymerization process occurs in separate and consecutive stages and in each stage, the polymerization is carried out in the presence of the polymer and the catalyst coming from the previous stage. The polymerization process can be carried out batchwise or continuously according to techniques - known, by operating in the liquid phase in the presence or absence of an inert diluent or in the gas phase, or in the liquid-gas phase, preferably in the gas phase. The preparation of the BMWD PP is described in greater detail in U.S. Patent No. 5,286,791, the preparation of which is incorporated herein by reference. Other additives such as fillers or fillers and reinforcing agents, e.g. carbon black and glass fibers, as well as inorganic powders such as calcium carbonate, talc and mica; pigments; slip agents; waxes; oils; Antiblock agents, and antioxidants may also be present. When the glass fibers are used as a reinforcing agent, it is used in an amount of from about 2.5 percent to about 40 percent, preferably from about 20 percent to about 40 percent, based on the total weight of the composition . A compatibilizing agent such as polypropylene modified with maleic anhydride is generally used as glass fibers. Polypropylenes modified with various amounts of maleic anhydride can be obtained commercially, for example, from Eastman Chemical Co. and Aristech Chemicals. The compatibilizing agent is used in an amount of from about 0.5 percent to about 5 percent preferably from about 1 percent to about 3.0 percent, based on the total weight of the composition. The test methods used to evaluate the molded specimens were: Izod Shock ASTM D-256A Tensile Strength ASTM D-638-89 Flex Module ASTM D-790-86 Flex Resistance ASTM D-790-86 10 Elongation to Break ASTM D-638-89 Resistance to Welding Line ASTM D-638-89 Retention of Resistance It is determined by dividing the the welding line resistance of the welding line 15 between the tensile strength and multiplying by 100 Elongation to performance ASTM D-638-89 Elongation at break @ 20 welding line ASTM D-638-89 Thermal distortion temperature ASTM D-648 Flow rate by melting, 230 ° C, 3.8 kg ASTM D-1238 - The porosity of the propylene homopolymer using as the polymer of the basic structure in the manufacture of the graft copolymers in the examples is measured as described in the article by N.M. Winslow, and J.J. Shapiro "An Instrument for the Measurement of Pore-Size Distribution by Mercury Penetration", ASTM Bull., TP 49, 39-44 (February 1959), and HM Rootare, "A Review of Mercury Porosimetry", 225-252 (In JS Hirshhom, and KH Roll, Editors, Advanced Experimental Techniques in Powder Metallurgy, Plenum Press, New York, 1970). In this specification, all parts and percentages are by weight unless otherwise stated.

Example 1 This example describes the effect of anhydride formation on the mechanical and thermal properties of the net and impact modified formulations containing a graft copolymer comprising a basic structure of propylene homopolymer to which a styrene / methacrylic acid copolymer was grafted (S / MAA), a copolymer of 4-t-butylstyrene / MAA, a copolymer of alpha-methylstyrene / MAA, or polymethacrylic acid (MAA). The - - Molar ratio of the monomer or weight ratio for each sample is given in Table 1. In this and the following examples, the propylene homopolymer used as the polymer of the basic structure had the following properties: spherical shape, flow rate per fusion (MFR) of 9 grams per 10 minutes, a porosity of 0.45 cubic centimeter per gram and an Mw of 170,000. The monomers were grafted onto the polypropylene backbone at a grafting temperature of 100 ° C using the peroxide-initiated graft polymerization process described above. Ninety-five parts by weight of the monomers were added per 100 parts of the polypropylene. Lupersol PMS 50 percent t-butyl-peroxy-2-ethyl hexanoate in mineral essence, which can be obtained commercially from Elf Atochem, was used as the peroxide initiator. The monomers were fed at 1 ppm / minute. A molar ratio of monomer to initiator of 100 was used. The reaction conditions were maintained at 100 ° C for 30 minutes after completing the addition of the monomer and the peroxide, and the temperature was raised to 140 ° C for 1.5 to 2.0 hours under a nitrogen purge. The percent conversion of monomer to polymer was 98.4 percent to 99.7 percent when a mixture of styrene and methacrylic acid monomers was used, and 96 percent when monomer was used as 100 percent methacrylic acid . The graft copolymer was then mixed with a broad molecular weight distribution polypropylene (BMWD PP) having a polydispersity index of 7.4, an MFR of 1 gram per 10 minutes, and xylene solubles at room temperature of 1.5 percent, which can be obtained commercially from Montell USA Inc. The amount of BMWD PP used for each sample is given in Table 1. adds a sufficient amount of BMWD PP to adjust the effective addition level up to 50 pph of the polymerized monomer (s) per one hundred parts of the polypropylene. The additional polypropylene makes the composition easier to process by reducing the amount of moisture bounce during the dehydration of the acid groups to form the anhydride groups. They were revolved for 'property evaluations, two different formulations with or without Engage 8100, the ethylene / octen-1 copolymer having an MFR of 1.0 gram for 10 minutes as the shock modifier. The samples were stirred in a 34 mm co-rotary intermeshing Leistritz LSM twin screw extruder. Each sample was extruded as granules at a temperature of 230 ° C, a screw speed of 300 revolutions per minute, and a - - yield regime of 11.35 kilograms per hour. A good vacuum and exhaust system or discharge due to gasification experienced in formulations having an acid content greater than 80 mole percent was essential. The stabilizer package used was calcium stearate, Irganox 1010 tetrakis [methylene (3, 5, di-t-butyl-4-hydroxyhydrocinnamate)] methane, an antioxidant, which is commercially available from CIBA Specialty Chemicals Corporation, and the P-stabilizer EPQ, the main component of which is diphosphite tetrakis (2,4-di-tert-butylphenyl) -4-4 '-biphenylene, which can be obtained commercially from CIBA Specialty Chemicals Corporation. The mixed samples were dried at 80 ° C for at least 4 hours before molding to remove surface moisture. Test bars of 25.40 millimeters x 3.18 millimeters were used for all physical property measurements. Thermal deformation temperature (HDT) measurements used bending bars of 6.35 millimeters unless otherwise stated. The test bars were produced on a 140 gram Battenfeld injection molding machine at a temperature of 254 ° C and a mold temperature of 66 ° C. The results of the property evaluations for each formulation are given in Table 1.

- - Table 1 Shows Comp Comp. l (a) 2 (a) 3 (a) 4 (a) 5 (a) 6 (a) 7 (a) S / MAA (molar ratio) 80/20 60/40 40/60 20/80 0/100 4-t-Butylstyrene / MAA (weight ratio) 20/80 a-Methylstyrene / MAA (weight ratio) 20/80 Graft Copolymer (% by weight) 68.2 68.2 68.2 68.2 68.2 68.2 68.2 BWMD PP (% by weight) 31.5 31.5 31.5 31.5 31.5 31.3 31.3 Ca stearate (% by weight) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Antioxidant (by weight) 0.05 0.05 0.05 0.05 0.05 0.4 0.4 Stabilizer P-EPQ (% by weight) 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Shock modifier (% by weight) 0 0 0 0 0 0 0 Resistance to Shock Izod with notch (kilogrammeters per meter) 1.96 2.12 2.45 3.43 3.3 2.67 3.80 - Stress Resistance (kg / cm2) 384.5 426.0 398.6 402.8 400 403 398 Elongation to Performance (%) 3 3.9 3.7 3.8 4.8 4.2 4.4 Elongation at Break (%) 6.6 4.2 7.4 7.7 15 8.2 13 Resistance to the welding line (kg / cm2) 164.5 153.3 131.5 351 398.6 391.5 385.9 Resistance retained (%) 43 36 33 87 99 97.2 97 Bending module at 12.70 mm per min (Kkg / cm2) 25.9 27.6 27.1 27.6 25.2 23.7 23.5 Resistance to bending at 12.70 mm per minute (kg / cm2) 704.4 773.3 729.0 729 740.2 690 673.2 HDT at 4.64 kg / cm2 (6.35 mm bar) (° C) 119 132 137 128 133 129 128 HDT at 18.54 kg / cm2 (6.35 mm bar) (° C) 90.3 103 91.5 89.6 84 77.9 77.6 MFR (230 ° C, 3.8 Kg) 12 8.2 6.2 4.5 5.2 6 5.2 Table 1 (continued) Shows Comp Comp. l (b) 2 (b) 3 (b) 4 (b) 5 (b) 6 (b) 7 (b) S / MAA (molar ratio) 80/20 60/40 40/60 20/80 0/100 4-t-Butylstyrene / MAA (weight ratio) 20/80 a-Methylstyrene / MAA (weight ratio) 20/80 Graft Copolymer (% by weight) 61.38 61.38 61.38 61.38 61.38 61.32 64.92 B MD PP (% by weight) 28.35 28.35 28.35 28.35 28.35 28.23 24.62 Ca stearate (% by weight) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Antioxidant (% by weight) 0.05 0.05 0.05 0.05 0.05 0.4 0.4 Stabilizer P-EPQ (% by weight) 0.15 0.15 0.15 0.15 0.15 Shock Modifier (% by weight) 9.97 9.97 9.97 9.97 9.97 9.95 9.95 Resistance to Izod Shock with notch (kilogrammeters per meter) 4.57 3.10 5.22 8.00 9.14 7.17 9.41 - # Stress Resistance (kg / cm2) 308.6 359.2 319.2 310.7 300.2 308.9 311 Elongation to Performance (%) 3.9 4.4 4.3 4.3 4.1 4.3 4.5 Elongation at 10 Break (%) 23 6.7 47 49 77 44.5 63.6 Resistance to the welding line (kg / cm2) 162.4 154 149 278.39 296.7 287.95 286.61 Retained Resistance () 53 43 47 90 99 93.2 92.4 Bending module 20 to 12.70 mm per min (Kkg / cm2) 20.1 22.2 21.2 22.5 20.9 18.4 18.4 Resistance to Bending at 12.70 mm 25 per minute (kg / cm2) 554 623.40 565.9 556.8 555.4 529.8 522.4 HDT at 4.64 kg / cm2 (6.35 mm bar) (° C) 109 129 127 122.6 125 117 115 HDT at 18.56 kg / cm2 (6.35 mm bar) (° C) 85 91.6 79.2 76.5 67.4 69 67.4 MFR (230oC, ~ ~ 3 ~ .8 Kg) 12 8.8 7.3 4.9 7.4 5 5.2 The data show that the products made from the compositions contain a significant amount of anhydride groups (Samples 3 (a), 4 (a)) , 3 (b), 4 (b), 5 (a), 5 (b), 6 (a), 6 (b), 7 (a) and 7 (b) had a better balance of properties such as resistance to Izod crash with notch, elongation at break, weld line resistance, 'thermal distortion temperatures, compared to Comparison Samples 1 (a), 2 (a), 1 (b) and 2 (b) made with less than 60 mole percent methacrylic acid.

Example 2 This example describes the effect of anhydride formation on the mechanical and thermal properties of net and impact-modified glass-reinforced formulations containing a graft copolymer comprising a basic structure of propylene homopolymer to which a styrene copolymer was grafted. / methacrylic acid (S / MAA) or polymethacrylic acid (MMA). The molar ratio of the styrene / methacrylic acid monomer for each sample is given in Table 2. The graft copolymers and their preparation were the same as those described in Example 1. The graft copolymers were mixed with an amount - - enough of BMWD PP that was used in Example 1 to adjust the level of effective addition to 50 parts of the polymerized monomer (s) per one hundred parts of the polypropylene. Two different formulations, with and without a heterophasic polyolefin as a shock modifier, were stirred for property evaluations. Sufficient heterophasic polyolefin was added so that the effective rubber content of the composition was 15 weight percent. 10 The samples were stirred in an extrusion apparatus of 40 millimeter co-rotating twin interlock bolts Werner & Pfleiderer ZSK. Each sample was extruded as granules at a temperature of 250 ° C, a screw speed of 450 revolutions per minutes, and a performance regime of 90.80 kilograms per hour. The stabilizer package used was 0.1 percent calcium stearate and 0.2 percent Irgánox B-225 which is "an antioxidant, a mixture of 1 part of Irganox 1010 tetrakis stabilizer [methylene (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane and 1 part of Irgafos 168 tris (2,4-di-t-butylphenyl) phosphite, which can be obtained commercially from CIBA Specialty Chemicals Corporation. 3790 glass fibers, of 13 micrometers in diameter and prepared with an agent of - - sizing of aminosilane in an amount of 29.5 weight percent. The glass fibers can be obtained commercially from PPG Industries Inc. A polypropylene grafted with maleic anhydride having a maleic anhydride content of 1.4 percent was added as a compatibilizing agent in an amount of 1.37 weight percent. In Table 2, the shock modifier was a heterophasic polyolefin containing (i) 35 percent of a propylene homopolymer having an isotactic Index, defined as the insoluble fraction of xylene of 97.5, (ii) 6.9 percent of an ethylene-propylene copolymer is crystalline which is insoluble in xylene at room temperature, and (iii) 58.1 percent of a rubber of amorphous ethylene-propylene copolymer which is soluble in xylene at room temperature. The mixed samples were dried and molded into test bars as described in Example 1. The results of the evaluations are owned for each formulation are provided in Table 2.

# Table 2 Shows Comp Com . Ka) 2 (a) 3 (a) 4 (a) 5 (a) S / MAA (molar ratio) SO / 20 60/40 40/60 20/80 0/100 Graft copolymer 10 (% by weight) 47.2 47.2 47.2 47.2 47.2 BMWD PP (% by weight) 21. .63 21. .63 21. .63 21.63 21.63 Glass Fibers (by weight) 29 .5 29 .5 29 .5 29.5 29.5 Compatibilizer (% by weight) 1. .37 1. .37 1., 37 1.37 1.37 Ca stearate (% by weight) 0. 1 0. 1 0. .1 0.1 0.1 Antioxidant (% by weight) 0. 2 0. 2 0. 2 0.2 0.2 Shock Modifier (in weight) Izod shock (kilogrammeter per meter) 4.41 4.49 4.79 7.13 7.7.

Stress Resistance 30 (kg / c 745. 18 593. 33 815. 48 856. 25 1075. 59 - Elongation at Break (%) 1.2 1.3 1.5 2.3 3.1 Welding line resistance (kg / cm2) 270.66 254.49 302.99 323.38 410.55 Elongation at break to weld line 0 (%) 2.3 2.2 2.5 2.8 3.1 # Resistance Withheld (%) 36.3 43 37.2 37.8 38.2 Bending module at 12.70 15 millimeters per minute (Kkg / c 2) 75.22 70.73 73.22 64.51 74.78 Resistance to Bending at 12.70 mm per minute 20 (kg / cm2) 1131.13 1115.66 1226.03 1353.98 1746.25 H.D.T. at 4.64 kg / cm2 (3.18 mm bar) (° C) 156 158 160 160 162 H.D.T. at 25.6 kg / cm2 (3.18 mm bar) (° C) 137 131 146 145 150 MFR (230 ° C, 3.8 kg) 5.2 2.5 1.2 1 1.5 * Table 2 (Continued) Shows Comp Comp. 5 l (b) 2 (b) 3 (b) 4 (b) 5 (b) S / MAA (molar ratio) 80/20 60/40 40/60 20/80 0/100 Ü Graft copolymer 10 (weight%) 37.1 37.1 37.1 37.1 37.1 BMWD PP (. In weight) 9. .26 9. .26 9, .26 9.26 9.26 Glass Fibers (% by weight) 29 .5 29 .5 29 .5 29.5 29.5 Compatibilizer (% by weight) 1., 37 1., 37 1., 37 1.37 1.37 Ca stearate (% by weight) 0. 1 0. 1 0. 1 0.1 0.1 Antioxidant (% by weight) 0. 2 0. 2 0. 2 0.2 0.2 Shock Modifier (% by weight) 22.17 22.17 22.17 22.17 22.17 Izod Shock (kilogrammeter per meter) 5.06 4.61 6.96 13.06 17.95 Stress Resistance 30 (kg / cm2) 504.75 534.28 594.04 717.06 710.03 Elongation at Break (%) 1.2 1.3 1.9 3.3 6.1 Welding line resistance (kg / cm2) 211.60 209.49 228.48 235.51 244.64 Elongation at break to the welding line Resistance withheld (%) 42 39.2 38.4 32.8 34.5 Bending module at 12.70 15 millimeters per minute (Kkg / cm2) 52.09 55.45 51.12 52.35 48.23 Resistance to bending at 12.70 mm per minute 20 (kg / cm2) 745.88 802.12 867.50 1098.79 1141.67 H.D.T. at 4.64 kg / cm2 (3.18 mm bar) (° C) 148.8 155 157 157 157 H.D.T. at 25.6 kg / cm2 (3.18 mm bar) (° C) 129 138 138 137 138 MFR (230 ° C, 3.8 kg) 5.6 2.4 1.2 1.3 2 The data in Table 2 show that the formulations, both with and without a shock modifier, - # were brittle and had low Izod crash resistance with undercut when there was little or no anhydride formation (Comparison Samples 1 (a), 2 (a), 1 (b) and 2 (b)). total shock / stiffness / thermal equilibrium were better in formulations that had a significant anhydride concentration in the net formulation as well as modified to shock. f * Example 3 This example shows the effect on the physical and thermal properties of the different classes of shock modifiers that are mixed with a graft copolymer containing anhydride groups, made from a copolymer of grafting comprising a basic structure of the propylene homopolymer wherein the methacrylic acid was polymerized by grafting. The graft copolymer and its preparation are described in Example 1. The graft copolymer is mixed with the same BMWD PP as described in Example 1. Sufficient BMW DB was added to adjust the level of addition effect to 50 parts of the polymerized monomer per one hundred parts of the polypropylene. The samples that contain the different shock modifiers were revolved for evaluations of - property as described in Example 1. The amount of each shock modifier that was added is shown in Table 3. The stabilizer package used was 0.1 percent calcium stearate and 0.4 percent antioxidant Irganox B-225. The samples were dried and the test bars were produced as described in Example 1. The results of the evaluations of f. property for each formulation are given in Table 3. 10 In Table 3, Engage 8200 is an ethylene / octen-1 copolymer having an MFR of 5.0 grams per 10 minutes (190 ° C, 2.16 kilograms) and obtainable commercially from DuPont-Dow Elastomers. The EPR 306P is a ethylene / propylene alloy copolymer that has a percent ethylene content, and can be obtained commercially from Polysar Rubber Division of Miles, Ineorporated. The ethylene / octen-1 Engage 8150 copolymer contains 25 percent octen-1, has an MFR of 0.5 gram per 10 minutes, and can be obtained commercially from DuPont-Dow Elastomers. Kraton G 1652 is a styrene / ethylene-butene / styrene triblock copolymer containing 29 percent styrene and 71 percent ethylene / butene rubber intermediate block and can be obtained commercially from Shell Chemical Company. Polyolefin The heterophasic is the same as in Example 2.

Table 3 Sample 1 2 3 4 5 Graft copolymer (%) 62.68 62.68 62.68 62.68 62.68 BMWD PP (% by weight) 26.87 26.87 26.87 21.5 28.87 Engage Copolymer 8200 (% by weight) 9.95 15 - __ Copolymer Engage 8150 (% by weight) 9.95 Heterophasic polyolefin 20 (% by weight) 15.32 Kraton G 1652 rubber (% by weight) 9.95 Ca stearate (% by weight) 0.1 0.1 0.1 0.1 0.1 Antioxidant (% by weight) 0.4 0.4 0.4 0.4 0.4 Shock Izod (kilogrammeters per meter) 7.62 6.75 8.62 7.65 7.46 Break mode Complete Complete Complete Complete Complete - - Resistance to Tension (Kkg / cm2) .302 .306 .304 .318 .31.

Elongation to performance () 3.88 4.09 4.1 4.92 4.28 Elongation at break with / extensometer (%) 54.81 60.72 83.14 95.37 90.71 Resistance to Welding Line s * ^^^ (Kkg / cm2) .298 .290 .290 .303 .302 Elongation at 15 Break to weld line (%) 3.86 3.09 3.15 3.93 3.93 Resistance Withheld (%) 98.8 94.9 95 95.3 94.7 Flex Module at 12.70 mm per minute (Kkg / cm2) 18.48 19.28 19.16 18.26 19.13 Flexural strength 25 to 12.70 mm per minute (kg / cm2) .532.544.552.553.605 H.D.T at 4.64 kg / cm2 (6.35 mm bar) (° C) 124 128 128 125 125 H.D.T. at 25.6 kg / cm2 (6.35 mm bar (° C) 66.2 68.9 70 68.1 71.6 MFR (3800 grams at 230 ° C) 5 3.2 3.2"4.46 35 - The data shows that compositions having good physical and thermal properties can be obtained with a wide variety of shock modifiers.

Example 4 This example describes the effect of S L anhydride formation on the mechanical and thermal properties of net and shock modified formulations containing a graft copolymer comprising a basic structure of propylene homopolymer to which a methyl methacrylate / methacrylic acid copolymer was grafted by polymerization. The molar ratio of the monomer for each sample is given in Table 4. 15 Graft copolymers were prepared as described in Example 1. The graft copolymers were mixed with a sufficient amount of BMWD PP used in Example 1 to adjust the level of effective addition to 50 parts of the polymerized monomers per hundred parts of polypropylene. Two different formulations, with and without 9.95 weight percent of the Engage 8150 ethylene / octen-1 copolymer as a shock modifier, were stirred for property evaluations. The samples were stirred as described in in Example 1. The stabilizer package used was 0.1 by - one hundred percent calcium stearate and 0.4 percent the antioxidant Irganox B-225. The mixed samples were dried and molded into test bars as described in Example 1. The results of the property evaluations of each formulation are given in Table 4. Even when dehydration occurs to form the anhydride groups (see Figure 1), the effect of the formation of the anhydride on the properties of the polymer is not evident because the poly (methyl methacrylate) itself is very ductile. In contrast, the styrene and styrene substituted polymers are very brittle and the effect of the formation of the anhydride on the properties of the polymer is more pronounced.

Table 4 Sample l (a) 2 (a) 3 (a) 1 (b) 2 (b) 3 (b) MMA / MAA (molar ratio) (%) 60/40 40/60 20/80 60/40 40/60 20/80 Graft Copolymer (% by weight) 68.16 68.16 68.16 61.32 61.32 61.32 BWMD PP (% by weight) 31.34 31.34 31.34 28.23 28.23 28.23 Modifier of Shock (% by weight) 9.95 9.95 9.95 Calcium stearate (í 0.1 0.1 0.1 0.1 0.1 0.1 Antioxidant (%) 0.4 0.4 0.4 0.4 0.4 0.4 Izod crash with notch (kilogrammeters / meter) 2.99 2.99 2.61 8.76 8.70 9.19 Resistance to 15 Voltage (kg / cm2) 397.97 407.25 412.87 308.83 305.81 309.46 Elongation to Yield (%) 4.1 4.4 4.2 4.1 4.1 Elongation at break with / extensometer (%) 11.7 9.7 49.2 52.6 51.

Resistance in the welding line (kg / cm2) 378.21 392.14 391.50 296.17 288.92 296.10 Elongation at break to welding line (%) 7.2 7. 7.5 7.4 7.3 7.8 Resistance Withheld (%) 95 96.5 94.8 95.9 94.5 95.7 Bending module at 12.70 mm per min (Kkg / cm2) 24.11 24.42 24.51 18.28 90 18.53 Resistance to bending at 12.70 mm per minute (kg / cm2) 693.37 704.41 706.53 522.33 518.39 528.52 HDT at 4.64 kg / cm2 (6.35 mm bar) (° C) 119 121 126 114 117 116 HDT at 25.6 kg / cm2 (6.35 mm bar) (° C) 30.8 82.1 33.5 69.9 70.8 70.9 MFR (3800 grams at 230 ° C) 6.4 4.8 9.2 5. 4.6 Example 5 This example shows the percentage of dehydration achieved for the various methacrylic acid comonomers, ie, methyl methacrylate (MMA), styrene (S), a-methyl styrene and 4-t-butyl styrene, and for different amounts of comonomer. The reaction does not come to completion, therefore, the percentage of dehydration of the acid groups to form the anhydride groups depends on which comonomer is present and the ratio of comonomer to methacrylic acid.

- # The molar ratio or weight ratio of the monomers for each sample is given in Table 5. The graft copolymers were prepared as described in Example 1. The actual weight loss divided by the calculated weight loss due to dehydration = percentage of dehydration achieved. A Karl Fischer Serodyn Aquatest 10 coulometric moisture analyzer was used to determine the actual weight loss. 10 It seems that there is an improvement in the properties at a dehydration of approximately 50 percent. Therefore, in order to achieve more than 50 percent dehydration, a molar ratio of 50/50 for styrene / acrylic acid and a molar ratio should be used. of 60/40 for methyl methacrylate / methacrylic acid, for example. twenty - Table 5 Composition of Loss in Loss in DehydraMonomer Weight Calculated Actual Weight Due to Due to Achieved Dehydration Dehydration (%) (%) (%) MMA / MAA (80/20 molar%) 0.9 0.36 40 L MMA / MAA (60/40% molar) 1.83 1.08 59 MMA / MAA (40/60 molar%) 2.86 2.24 78.3 MMA / MAA (20/80 molar%) 3.89 3.1 79.7 S / MAA (70/30 molar%) 1.34 0.38 28.3 S / MAA (60/40% molar) 1.81 0.86 47.5 S / MAA (50/50 molar%) 2.32 1.19 51.3 S / MAA (40/60% molar) 2.84 NA NA S / MAA (20/80 molar%) 3.78 3.4 86.4 100% MAA 4.98 4.94 99.35 -Methylstyrene / MAA (20/80% molar, 90%) 3.854 3.6 93.4 4-t-Butylstyrene / MAA (20/80% molar, 95%) 3,967 3.3 33.2 - Comparison Example 1 This example shows the effect of using acrylic acid instead of alkyl-substituted acrylic acid of 1 to 3 carbon atoms as one of the polymerizable monomers for making the graft copolymers of a propylene polymer material. * The graft copolymers were prepared as described in Example 1. Two formulations with and without 9.97 weight percent of the Engage 8100 ethylene / octen-1 copolymer as a shock modifier were stirred for property evaluation as described in Example 1. The stabilizer package was the same as in Example 1. The extrusion was treated under the same conditions as in the Example 1. The results of the extrusion attempts -Jfc property measures are shown in Table 6.

Table 6 Sample Com. Ka) Comp. Kb) Comp. 2 (a) AA / MAA (weight ratio) 50/50 50/50 100/0 AA / MMA (weight ratio) 25 Graft Copolymer (% by weight) 68.2 61.4 68.2 - B MD PP (% by weight) 31.5 28.33 _ 31.5 Ca stearate (% by weight) 0.1 0.1 0.1 Antioxidant (% by weight) 0.05 0.05 0.05 P-EPQ Stabilizer (% by weight) 0.15 0.15 0.15 # 'Shock Modifier (% by weight) 9.97 Crisp, Could not Extrude Izod Shock Resistance with notch (kilogrammeters / 20 meter) Resistance to Tension (kg / cm2) Elongation to Profit (%) Elongation at Break (%) 30 Resistance of welding line (kg / cm2) Resistance retained (%) Bending module at 12.70 mm per min (Kkg / cm2) Resistance to 10 Bending at 12.70 mm per minute (kg / cm2) ft Table 6 (continued) Sample Comp. l (b) Comp .3 (A) Comp. 3 (b) AA / MAA (weight ratio) 100/0 AA / MMA (weight ratio) 50/50 50/50 Graft Copolymer (% by weight) 61.4 68.2 61.4 BWMD PP (% by weight) 1 28.33 31.5 by 28.33 Ca stearate (% by weight) 0.1 0., 1 0.1 Antioxidant (% by weight) 0.05 0. 05 0.05 P-EPQ Stabilizer (% by weight) 0.15 0.15 0.15 - ^ Shock Modifier (% by weight) 9.97 9.97 Crisp, Could not Extrude Resistance to Shock Izod with notch 10 (kilogrammeters / meter) 2.1Í 4.35 «Resistance to Tension (kg / cm ^) 428.29 313.24 Elongation to Performance (%) 3.5 Elongation at 20 Break (%) 4.5 15.3 Welding line resistance (kg / cm2) 422.45 308.72 Resistance withheld (%) 98.6 .8.5 Bending module 30 to 12.70 mm per min (Kkg / cm2) 24.77 19.91 Resistance to Bending at 12.70 mm 35 per minute (kg / cm.2) 743.14 557.21 Other particularities, advantages and modalities of the invention disclosed herein will be readily apparent to those skilled in the art after reading the expositions that anteceden In this regard, even though the specific embodiments of the invention have been described in considerable detail, variations and modifications of these embodiments may be made without departing from the spirit and scope of the invention as described and claimed.

Claims (11)

1. A process for producing graft copolymers containing anhydride groups comprising: (1) making a graft copolymer comprising a basic structure of a propylene polymer material having polymerized by grafting thereto monomers selected from the group consists of: (a) at least one alkyl-substituted acrylic acid of 1 to 3 carbon atoms, and (b) a mixture of (a) with at least one vinyl monomer capable of copolymerizing therewith, wherein the total amount of the polymerized monomers is from about 20 parts to about 240 parts per hundred parts of the propylene polymer material and the amount of the substituted acrylic acid is equal to or greater than 60 mole percent of the polymerized monomers, and (2) heating the resulting graft copolymer to a temperature of about 170 ° C to about 300 ° C, to dehydrate the acid groups in the copolymer grafting to end - of forming anhydride groups.

The process of claim 1, wherein the vinyl monomer is selected from the group consisting of: (a) vinyl-substituted aromatic, heterocyclic and alicyclic compounds, (b) vinyl esters of aromatic carboxylic acids, (c) ) vinyl esters of saturated aliphatic carboxylic acids, (d) unsaturated aliphatic nitriles, (e) unsaturated aliphatic amides, and (f) esters of unsaturated aliphatic carboxylic acids.

3. The process of claim 1, wherein the monomer is methacrylic acid.

4. The process of claim 1, wherein the monomers are a mixture of methacrylic acid and styrene.

5. The process of claim 1, wherein the amount of the substituted acrylic acid is greater than 80 mole percent of the polymerized monomers.

The process of claim 1, wherein the propylene polymer material comprising the basic structure of the graft copolymer is selected from the group consisting of: (a) a crystalline propylene homopolymer having a higher isotactic index of 80; (b) a crystalline propylene random copolymer and an olefin selected from the group consisting of ethylene and alpha-olefins of 4 to 10 carbon atoms, with the proviso that when the olefin is ethylene, the maximum polymerized ethylene content is 10 weight percent, and when the olefin is an alpha-olefin of 4 to 10 carbon atoms, the maximum polymerized content thereof is 20 weight percent, the copolymer having an isotactic index greater than 85; (c) a random crystalline terpolymer of propylene and two olefins which are selected from the group consisting of ethylene and alpha-olefins of 4 to 8 carbon atoms, as long as the alpha-olefin content of 4 to 8 carbon atoms, maximum polymerized is 20_ percent by weight, and when ethylene is one of the olefins, the maximum polymerized ethylene content is 5 weight percent, the terpolymer having an isotactic index greater than 85; (d) an olefin polymer composition comprising: F (i) from about 10 percent to about 60 weight percent of a crystalline propylene homopolymer having an isotactic index greater than 80, or a crystalline copolymer selected from the group consisting of (a) propylene and ethylene (b) propylene, ethylene and an alpha-olefin of 4 to 8 carbon atoms, and ff (c) propylene and an alpha-olefin of 4 to 8 carbon atoms, the copolymer having a propylene content of more than 85 percent by weight, and an isotactic index greater than 85; (ii) from about 5 percent to about 25 weight percent of a copolymer, of ethylene and propylene or an alpha-olefin of 4 to 15 8 carbon atoms that is insoluble in xylene at room temperature, and (iii) of about 30 percent to about 70 weight percent of an elastomeric copolymer selected from the group consisting of (a) ethylene and propylene, (b) ethylene, propylene and an alpha-olefin of 4 to 8 carbon atoms; and (c) ethylene and an alphaolefin of 4 to 8 carbon atoms, the copolymer optionally containing from about 0.5 25 percent to about 10 percent in - F diene and containing less than 70 weight percent ethylene and being soluble in xylene at room temperature, and having an intrinsic viscosity of about 1.5 to about 4.0 deciliters per gram, wherein the total amount of (ii) and (iii) based on the total olefin polymer composition, it is * about 50 percent to about 90 percent, the weight ratio of (ii) (iii) is less than 10 0.4, and the composition is prepared by polymerization in at least two stages and has a flexural modulus of less than 150 MPa; and (e) a thermoplastic olefin comprising: (i) from about 10 percent to about 60 percent, of a crystalline propylene homopolymer having an isotactic index greater than 80, or a crystalline propylene copolymer which is selects from the group consisting of (a) ethylene and propylene, (b) ethylene, propylene and an alpha-olefin of 4 to 8 carbon atoms, and (c) ethylene and an alpha-olefin of 4 to 8 carbon atoms, copolymer has a propylene content greater than 85 percent, and an isotactic index greater than 85; 25 - (ii) from approximately 20 percent to approxima- 60 percent, of an amorphous copolymer selected from the group consisting of (a) of ethylene and propylene, (b) ethylene, propylene, and an alpha-olefin of 4 to 8 carbon atoms, and (c) ethylene and an alpha-olefin of 4 to 8 carbon atoms, the copolymer optionally contains from about 0.5 percent to about 10 percent of a diene, and contains less than 70 percent ethylene and is soluble in xylene at room temperature; and (iii) from about 3 percent to about 40 percent of an ethylene and propylene copolymer, or an alpha-olefin of 4 to 8 carbon atoms that is insoluble in xylene at room temperature, wherein the composition has a modulus. of bending greater than 150 but less than 1200 MPa.

The process of claim 6, wherein the propylene polymer material is a propylene homopolymer.

8. A graft copolymer made by the process of claim 1, comprising a basic structure of a propylene polymer material and side chains comprising glutaric anhydride groups and methacrylic acid groups.

9. The graft copolymer of claim 8, wherein the side chains further comprise at least one polymerized vinyl monomer selected from the group consisting of: (a) vinyl-substituted aromatic, heterocyclic and alicyclic compounds, (b) esters of vinyl of aromatic carboxylic acids, (c) vinyl esters of saturated aliphatic carboxylic acids, (d) unsaturated aliphatic nitriles, (e) unsaturated aliphatic amides, and (f) esters of unsaturated aliphatic carboxylic acids.

10. A graft copolymer comprising a basic structure of a propylene polymer material and side chains comprising glutaric anhydride groups and methacrylic acid groups. The graft copolymer of claim 10, wherein the side chains further comprise at least one polymerized vinyl monomer selected from the group consisting of: (a) vinyl-substituted aromatic, heterocyclic and alicyclic compounds, * ( b) vinyl esters of aromatic carboxylic acids, (c) vinyl esters of saturated aliphatic carboxylic acids, unsaturated 5 (d) aliphatic nitriles, (e) unsaturated aliphatic amides, and (f) esters of unsaturated aliphatic carboxylic acids.