Definitions

• the present invention relates to new uses of unmodified polypropylenes and grafted polypropylenes, and more generally of unmodified polyolefins and grafted polyolefins. Since their existence, unmodified polypropylenes, and more generally unmodified polyolefins, have been appreciated for their advantageous properties combined with their low cost. Thus, to date, they are used, in preference to any other plastic, in particular for tubes, films, sheets, hollow bodies and various parts of self-propelled vehicles such as fuel tanks. However, it has often happened that the level of mechanical properties reached by unmodified polypropylenes, and more generally by unmodified polyolefins, did not reach the level required for the intended applications.
• the mechanical properties in question relate in particular to the mechanical behavior at low speed (elastic modulus in tension, elongation at break, etc.), the mechanical behavior at high speed (resilience and / or maximum force on the test of the falling weight instrumented,. ..), the operating temperature range (softening temperature in the Nicat test, ...) and the evolution of the mechanical behavior of the material over time (creep test, ).
• Properties such as adhesion to a support (which depends critically on the chemical nature of the support) or dispersibility in a dispersion liquid are not mechanical properties within the meaning of the present invention.
• patent application GB 1 335 791 in the name of EASTMAN KODAK describes mixtures of unmodified polyproylene and polypropylene grafted with maleic anhydride, which have a level of tensile strength intermediate between that of non-polypropylene modified and that of grafted polypropylene (see Tables 3 and 6) or, at best, equivalent to that of unmodified polypropylene (as illustrated in Table 1).
• the mechanical properties requirements could not be met, that is to say that the grafted polyproylenes (and, more generally, the grafted polyolefins) behaved less well, for the mechanical properties in question, than their non-homologous counterparts.
• a first aspect of the present invention therefore relates to the use of at least one unmodified polyolefin [polyolefin (PI)] as an additive to a polyolefin composition (C2) comprising at least one polyolefin modified by grafting with acid and / or anhydride groups, optionally neutralized in whole or in part by at least one neutralizing agent [polyolefin (P2)], to improve the level of at least one mechanical property of the polyolefin composition (C2), up to a level improved both compared to that of the mechanical property of the polyolefin composition (C2) as compared to that of the mechanical property of a polyolefin composition (Cl) obtained by replacing weight for weight in the polyolefin composition (C2) all of the modified polyolefin (P2 ) with unmodified polyolefin (PI).
• PI unmodified polyolefin
• the weight ratio q w2 of the polyolefin (P2) and of the polyolefin composition (C2) [(P2): (C2)], before the addition of the polyolefin (PI), is advantageously greater than 0.50, preferably greater than 0.90, particularly preferably greater than 0.99 and very particularly preferably greater than 0.995; it can then either be composed of the polyolefin (P2), or be composed of the polyolefin (P2) and of less than 0.5% of the usual ingredients of the polyolefin compositions such as thermal stabilizing agents and antioxidant agents.
• a second aspect of the present invention relates to the use of at least one polyolefin modified by grafting with acid and / or anhydride groups, optionally neutralized in whole or in part by at least one neutralizing agent [polyolefin (P2)] as as an additive to a polyolefin composition (Cl) comprising at least one unmodified polyolefin (polyolefin (PI)), to improve the level of at least one mechanical property of the polyolefin composition (Cl), up to an improved level as compared to that of the mechanical property of the polyolefinic composition (Cl) as compared to that of the mechanical property of a polyolefinic composition (C2) obtained by replacing weight for weight in the polyolefinic composition (Cl) all of the unmodified polyolefin (PI) by modified polyolefin (P2).
• P2 neutralizing agent
• the weight ratio q w ⁇ of the polyolefin (PI) and of the polyolefin composition (Cl) [(PI): (Cl)], before the addition of the polyolefin (P2), is advantageously greater than 0.50, of preferably greater than 0.90, particularly preferably greater than 0.99 and most preferably greater than 0.995; it can then either be composed of the polyolefin (PI) or be composed of the polyolefin (PI) and less than 0.5% of the usual ingredients of the polyolefin compositions such as thermal stabilizers and antioxidants.
• polyolefin is intended to denote a polymer of which more than 50% by weight of the repeating units are derived from at least one alkene.
• alkenes examples include linear olefins containing from 2 to 12 carbon atoms such as ethylene, propylene, 1-butene, 1- pentene, 1-hexene, 1- heptene, 1-octene, 1-nonene, 1-dececene, 1- undecene and 1-dodecene.
• the polyolefins considered in the various aspects of the invention can be selected in particular from the homopolymers of the above-mentioned olefins and from the copolymers of these olefins, in particular copolymers of propylene with one or more comonomers, as well as from mixtures of such polymers.
• the comonomers can be chosen in particular from the linear olefins described above, from styrene monomers such as styrene and alpha-methylstyrene and from alkadienes; the polyolefins considered in the various aspects of the invention are however preferably free of repeating units derived from an alkadiene.
• the weight content of units formed from the comonomers in the polyolefins is advantageously less than 30% and preferably less than 10% by weight. It is understood that by "polyolefin” is understood as well to denote the polymers as described above taken alone as their mixtures.
• the acid and / or anhydride groups which are grafted onto the polyolefin (P2) are advantageously derived from at least one grafting monomer chosen from unsaturated mono- or dicarboxylic acids and their derivatives and unsaturated anhydrides of mono- or dicarboxylic acid and their derivatives.
• These grafting monomers preferably comprise from 3 to 20 carbon atoms.
• Maleic anhydride is most particularly preferred.
• the amount of grafted acid and / or anhydride groups is advantageously greater than 0.01% by weight relative to the weight of the polyolefin (P2), preferably 0.02% by weight or, better still, 0.03% by weight. weight. In addition, this amount is advantageously less than or equal to 2.0% by weight, preferably 1.5% and better still, 1.0% by weight.
• the grafting of the acid and / or anhydride groups is advantageously initiated by a radical-generating agent.
• 2.5- dimethyl-2,5-di-t-butylperoxyhexane (DHBP) has made it possible to synthesize grafted polyolefins which have given good results concerning the various aspects of the present invention.
• the polyolefin (P2) advantageously contains little free (non-grafted) grafting monomer, typically an amount less than or equal to 500 ppm, preferably less than 400 ppm and particularly preferably 200 ppm.
• the polyolefin (P2) has advantageously been purified into a free grafting monomer, preferably by entrainment with acetone, by stripping with hot air, by stripping with steam, by stripping with a gas. inert or by degassing.
• a neutralizing agent is usually used for this purpose.
• the neutralizing agent can be an inorganic salt, an organic salt or a mixture of an organic salt and an inorganic salt.
• the inorganic salt is preferably a hydoxide, a carbonate, a bicarbonate, a phosphate or a monohydrogenphosphate of an alkali metal. Sodium carbonate is particularly preferred.
• the organic salt is preferably a carboxylate or a mono- or polyhydroxycarboxylate of a metal, which can in particular be an alkali metal, an alkaline earth metal, a metal of the Illa family. from the periodic table of elements or a transition metal.
• the organic salt is a carboxylate of a transition metal or a mono- or polyhydroxycarboxylate of an alkali metal.
• the organic salt is chosen from sodium lactate and zinc acetate.
• the neutralizing agent is preferably an organic salt or a mixture of an organic salt and an inorganic salt.
• the neutralizing agent is a mixture of an organic salt and an inorganic salt. Excellent results have been obtained using as a neutralizing agent either a mixture of sodium lactate and sodium carbonate or a mixture of zinc acetate and sodium carbonate.
• the neutralizing agent is used in an amount preferably greater than 0.5 molar equivalent relative to the number of acid and / or anhydride groups of the polyolefin (P2).
• the neutralizing agent is used in an amount preferably less than 3 mol-eq. relative to the number of acid and / or anhydride groups of the polyolefin (P2).
• the polyolefin (PI) can in particular be a polyethylene.
• the definitions and preferences for polyethylenes detailed below relate to both the unmodified polyolefin [polyolefin (PI)] and the modified polyolefin [polyolefin (P2)] considered in the various aspects of the invention whenever (PI) and / or (P2) is a polyethylene.
• polyethylene is intended to denote a polymer of which more than 50% by weight of the repeating units are derived from ethylene.
• the polyethylenes considered in the various aspects of the invention can be selected in particular from homopolymers of ethylene and from copolymers of ethylene with one or more comonomers, as well as from mixtures of such polymers.
• the comonomers can be chosen in particular from the linear olefins described above, in particular propylene, from styrenic monomers such as styrene and alpha-methylstyrene and from alkadienes; the polyethylenes are preferably free of repeating units derived from an alkadiene.
• the content by weight of units formed from the comonomers in the polyethylenes is advantageously less than 30% and preferably less than 10% by weight.
• polyethylene is understood as well to denote the polyethylenes as described above taken alone as their mixtures.
• the polyolefin (PI) is preferably a polyalphaolefin. Unless otherwise specified, the definitions and preferences relating to polyalphaolefins detailed below relate to both the unmodified polyolefin [polyolefin (PI)] and the modified polyolefin [polyolefin (P2)] considered in the various aspects of the invention whenever (PI) and / or (P2) is a polyalphaolefin.
• polyalphaolefin is meant a polymer of which more than 50% by weight of the repeating units are derived from an ⁇ -olefin.
• ⁇ -olefin is intended to denote an alkene comprising at least 3 carbon atoms.
• the ⁇ -olefin preferably comprises at most 12 carbon atoms. In addition, it is preferably linear.
• the polyalphaolephins considered in the various aspects of the invention can be selected from the homopolymers of an ⁇ -olefin and from the copolymers of an ⁇ -olefin with one or more comonomers, as well as from mixtures of such polymers.
• Comonomers can be chosen in particular from the linear olefins described above, in particular ethylene, from styrene monomers such as styrene and alpha-methylstyrene and from alkadienes; the polyalphaolefins are preferably free of repeating units derived from an alkadiene.
• the weight content of units formed from the comonomers in the polyalphaolefins is advantageously less than 30% and preferably less than 10% by weight. It is understood that by “polyalphaolefin” is meant both to denote the polyalphaolefins as described above taken alone and their mixtures.
• the polyolefin (PI) is a polypropylene.
• polypropylene refers to both the unmodified polyolefin [polyolefin (PI)] and the modified polyolefin [polyolefin (P2)] considered in the various aspects of the invention whenever (PI) and / or (P2) is a polypropylene.
• polypropylene is intended to denote a polymer of which more than 50% by weight of the repeating units are derived from propylene.
• the polypropylenes considered in the various aspects of the invention can be selected from homopolymers of propylene and from copolymers of propylene with one or more comonomers, as well as from blends of such polymers.
• the comonomers can be chosen in particular from the linear olefins described above, in particular ethylene, from styrenic monomers such as styrene and alpha-methylstyrene and from alkadienes; the polypropylenes are preferably free of repeating units derived from an alkadiene.
• the content by weight of units formed from the comonomers in the polyethylenes is advantageously less than 30% and preferably less than 10% by weight. It is understood that by "polypropylene” is meant both to designate the polypropylenes as described above taken alone and their mixtures.
• the polyolefin (P2) can in particular be a polyethylene.
• the polyolefin (P2) is preferably a polyalphaolefin.
• the polyolefin (P2) is particularly preferably a polypropylene.
• the mechanical property concerns at least the mechanical behavior at low speed.
• the mechanical property comprises the elastic modulus in tension. Improving the level of the elastic modulus in traction means increasing it.
• the mechanical property includes the elongation at break. Improving the level of elongation at break means increasing it.
• the mechanical property concerns at least the operating temperature range.
• the mechanical property preferably includes the softening temperature in the Nicat 10 ⁇ test. Improving the softening temperature level in the Nicat 10 ⁇ test means increasing it.
• the mechanical property concerns at least the mechanical behavior at high speed.
• the mechanical property preferably comprises the resilience and / or the maximum force when testing the instrumented falling weight; particularly preferably, it comprises both. Improving the level of resilience means increasing it; improving the level of maximum strength also means increasing it.
• the mechanical property concerns at least the evolution of the mechanical behavior of the material over time.
• the mechanical property preferably comprises the elastic modulus in tension after 100 h under a stress of 10 MPa. Improving the level of the elastic modulus in tension after 100 h under a stress of 10 MPa means increasing it.
• a first particularly advantageous embodiment of the invention [mode (I)] involves a homopolymer of propylene as polyolefin (PI).
• PI polyolefin
• the term “propylene homopolymer” is intended to denote a polymer in which all the recurring units are derived from propylene.
• the polyolefin (P2) is preferably a homopolymer of propylene.
• the acid and / or anhydride groups of the propylene homopolymer polyolefin (P2) can be non-neutralized [mode (1.1)].
• mode (1.1) it is preferred that the mechanical property concerns at least the mechanical behavior at low speed.
• the mechanical property comprises elongation at break.
• mode (1.1) it is also preferred that the mechanical property concerns at least the operating temperature range.
• the mechanical property comprises the softening temperature in the Nicat 10 ⁇ test.
• the mechanical property concerns at least the evolution of the mechanical behavior over time.
• the mechanical property comprises the elastic modulus in tension after 100 h under a stress of 10 MPa.
• the acid and / or anhydride groups of the propylene homopolymer polyolefin (P2) can be neutralized in whole or in part [mode (1.2)].
• mode (1.2) it is preferred that the mechanical property concerns at least the mechanical behavior at low speed.
• the mechanical property comprises elongation at break.
• mode (1.2) it is also preferred that the mechanical property concerns at least the operating temperature range.
• the mechanical property comprises the softening temperature in the Nicat 10 ⁇ test.
• the mechanical property concerns at least the mechanical behavior at high speed.
• the mechanical property comprises the resilience and / or the maximum force when testing the instrumented falling weight. Most preferably, it includes both.
• a second particularly interesting embodiment of the invention involves a random copolymer of propylene as polyolefin (PI).
• the term “propylene random copolymer” is intended to denote a copolymer of which more than 90% by weight of the recurring units are derived from propylene.
• the repeating units not derived from propylene are advantageously repeating units derived from ethylene.
• the polyolefin (P2) is preferably a random copolymer of propylene.
• the acid and / or anhydride groups of the polyolefin (P2) random copolymer of propylene can be non-neutralized (mode II.1).
• the mechanical property concerns at least the mechanical behavior at low speed.
• the mechanical property comprises the elastic module in tension.
• the acid and / or anhydride groups of the polyolefin (P2) random copolymer of propylene can be neutralized in whole or in part [mode (II.2)].
• the mechanical property concerns at least the mechanical behavior at high speed.
• the mechanical property comprises the resilience and / or the maximum force when testing the falling weight instrumented. Very particularly preferably, the mechanical property comprises both.
• the weight ratio r w of the polyolefin (PI) and of the polyolefin (P2) [(P1) :( P2)] can be easily adjusted by a person skilled in the art for the use considered, and this for the all aspects of the invention.
• [(P1) :( P2)] is preferably greater than 1, particularly preferably greater than 4, very particularly preferably greater than 8. In the latter case, it has been verified that, depending on the use considered, it was sometimes preferable for r w to be less than 16, sometimes for it to be greater than or equal to 16.
• a third aspect of the present invention relates to a process for the preparation of an improved polyolefin composition, compared to a pre-existing polyolefin composition (C2) comprising at least one polyolefin modified by grafting with acid and / or anhydride groups optionally neutralized in whole or in part with at least one neutralizing agent [polyolefin (P2)], said method being implemented with the aim of improving the level of at least one mechanical property of the pre-existing polyolefin composition (C2), up to a level improved as compared to that of the mechanical property of the pre-existing polyolefin composition (C2) as compared to that of the mechanical property of a polyolefin composition (Cl) obtained by replacing weight for weight in the pre-existing polyolefin composition (C2) all of the modified polyolefin (P
• a fourth aspect of the present invention relates to a process for the preparation of an improved polyolefin composition, compared to a pre-existing polyolefin composition (Cl) comprising at least one unmodified polyolefin (polyolefin (PI)), said process being carried out works with the aim of improving the level of at least one mechanical property of the pre-existing polyolefinic composition (Cl), up to a level improved both compared to that of the mechanical property of the pre-existing polyolefinic composition ( Cl) that compared to that of the mechanical property of a polyolefin composition (C2) obtained by replacing weight for weight in the pre-existing polyolefin composition (Cl) all of the unmodified polyolefin (PI) by at least one polyolefin modified by grafting with acid and / or anhydride groups optionally neutralized in whole or in part with at least one neutralizing agent [polyo lefin (P2)], and said process comprising adding the modified polyolef
• the polyolefin (PI) is preferably a polyalphaolefin, particularly preferably a polypropylene, in particular a homopolymer of propylene or a random copolymer of propylene.
• the polyolefin (P2) is preferably a polyalphaolefin, particularly preferably a polypropylene, in particular a homopolymer of propylene or a random copolymer of propylene.
• a final aspect of the present invention relates to a semi-finished or finished article comprising at least one improved polyolefin composition prepared by the methods detailed above.
• a first preferred choice for the article according to the invention is that made from tubes, films, sheets, fibers, foams and blown hollow bodies made of the composition or of the modified polyolefin. Examples of blown hollow bodies include bottles.
• the tubes are advantageously intended for the petroleum industry, the building industry or the automobile industry.
• the films may in particular be food films which can be sealed in a fatty medium or films which can be printed with aqueous inks.
• a second preferred choice for the article according to the invention is that of a part of a self-propelled vehicle selected from fuel tanks, fuel pipes, bumpers and dashboards.
• the article according to the invention has many advantages. In particular, it has a high level of mechanical properties. When the article according to the invention is a film, this film usually has in particular a high tear resistance.
• Example 1 preparation of mixtures composed of a homopolymer of maleic anhydride grafted propylene homopolymer and an unmodified propylene l)
• Description resins ELTEX ® P HL001P and PRIEX ® 20015 The ELTEX ® P HL001P resin is a homopolymer of propylene unmodified, marketed by BP North America. The sample used had an MFI i 6 kg , 230 ° c of 2.5 g / 10 min, a melting temperature of 161 ° C and a density of 900 kg / m 3 .
• PRIEX ® 20015 resin is a homopolymer of propylene chemically modified by SOLNAY.
• the homopolymer resin of propylene on which SOLNAY performs the chemical modification is ELTEX ® P HL001P resin.
• the chemical modification which is carried out by SOLVAY on the above-mentioned propylene homopolymer consists of grafting with maleic anhydride in an amount of 0.05% by weight, followed by a purification in free maleic anhydride.
• the PRIEX ® 20015 resin sample which was used had an MFI ⁇ 6kg; 23 o ° c of 15g / 10min.
• the screw speed was 200 rpm, the flow rate 2 kg / h and the following temperature profile: Zl (resin supply): 230 ° C; Z2: 230 ° C; convergence and sector: 230 ° C.
• Zl resin supply
• Z2 230 ° C
• convergence and sector 230 ° C.
• Two mixtures of ELTEX ® P HL001P resin and PRIEX ® 20015 resin were made, namely the "5% PRIEX® 20015" and "10% PRIEX ® 20015" mixtures which were respectively composed of 5% and 10% PRIEX resin ® 20015, 100% completed with ELTEX ® P HL001P resin.
• the results obtained showed a synergy relating to the evolution of the mechanical behavior over time between the ELTEX ® P HL001P and PRIEX ® 20015 resins in the 5% and 10% PRIEX ® 20015 mixtures.
• the 5% and 10% PRIEX mixtures ® 20015 indeed had an elastic modulus in tension after 100 h and under a stress of 10 or 12.5 MPa greater than each of their component taken individually.
• Example 2 Preparation of mixtures consisting of a homopolymer of propylene ionomer and an unmodified propylene homopolymer 1) Synthesis of resin (1 ION) were used: - ® 20015 PRIEX the resin described in Example 1; solutions of NaLac (sodium lactate: mixture of D- and L- isomer from ARCOS: 256.4 ml of solution at 60% by weight per liter of aqueous solution) and of Na 2 CO at 200 g / l, respective quantities of 5 and 2 mol eq.
• NaLac sodium lactate: mixture of D- and L- isomer from ARCOS: 256.4 ml of solution at 60% by weight per liter of aqueous solution
• Na 2 CO at 200 g / l
• the sheath consists of 10 independent zones (Zl to Z10) as well as a convergence and a die; - a screw speed of 200 rpm, a flow rate of 10 kg / h and the following temperature profile: Zl (resin supply): 70 ° C; Z2: 170 ° C; Z3 (fusion) and Z4 (NaLac injection): 200 ° C; Z5 to Z8 (reaction, degassing at atmospheric pressure, reaction, degassing under vacuum at a set point of 2 mbar): 240 ° C; Z9: 230 ° C; Z10: 220 ° C; convergence and sector: 220 ° C.
• the resin (ION 1) thus obtained had an MFI (2.16 kg, 230 ° C) of lg / 10 min, an Na content of 0.88 g / kg and a melting temperature of 167 ° C. 2
• Preparation of mixtures of resins (ION 1 and ELTEX ® HL001P We used: - the resin (ION 1) described above; - the ELTEX ® P HL001P resin described in Example 1. The protocol used for obtaining mixtures of these two resins was the same as that described in Example 1.
• Example 3 preparation of mixtures composed of a random copolymer of maleic anhydride grafted propylene and a random copolymer of the unmodified propylene 1) Description resins ELTEX ® P KS001 P and PRIEX ® 25015 The ELTEX P KS001 resin ® P is a unmodified propylene random copolymer, marketed by BP North America Corporation.
• PRIEX ® 25015 resin is a random propylene copolymer chemically modified by SOLVAY.
• the propylene random copolymer resin on which SOLVAY performs the chemical modification is the ELTEX P KS001 ® resin P.
• the chemical modification that is performed by SOLVAY consists of grafting with maleic anhydride in an amount of 0.05% by weight, followed by purification with free maleic anhydride.
• the PRIEX ® 25015 resin sample that was used had an MFI 2 .i 6 kg, 23 o ° c of 15g / 10min.
• Example 4 Preparation of a mixture composed of a random copolymer of propylene ionomer and of a random copolymer of unmodified propylene 1) Synthesis of the resin Random copolymer of propylene (ION 2) We used: - a sample of resin PRIEX ® 25050; PRIEX ® 25050 resin is a random copolymer of propylene chemically modified by SOLVAY; the random propylene copolymer on which SOLVAY performs the chemical modification is the resin ELTEX ® P KS001 P described above; the chemical modification which is carried out by SOLVAY consists of a grafting with maleic anhydride in an amount of 0.1% by weight, followed by a purification in free maleic anhydride.
• the PRIEX ® 25050 resin sample which was used had an MFI 2 . ⁇ 6 g ⁇ 230 ° c of 50g / 10min. solutions of NaLac (sodium lactate: mixture of D- and L-isomer from ARCOS: 256.4 ml of solution at 60% by weight per liter of aqueous solution) and of Na 2 CO at 200 g / 1, in quantities respectively of 5 and 2 mol eq. (molar equivalents relative to the number of carboxylic acid functions of the resin) for NaLac.
• the protocol used for the synthesis of the resin (ION 2) was the same as that described in Example 2.
• the resin (ION 2) obtained had an MFI (2.16 kg, 230 ° C) of 1.4 g / 10 min, an Na content of 1.5 g / kg and a melting temperature of 137 ° C. 2)
• Preparation of a mixture of the resin (IO 2) and resin ELTEX ® P KS OOIP were used: The resin (ION 2) described above, the ELTEX ® P KSOOIP resin described above..
• the protocol used for obtaining the mixture of these two resins was the same as that described in Example 1.
• the “10% (ION 2)” mixture obtained contained 10% resin (ION 2), completed to 100% with ELTEX ® P resin KS 001 P. 3)
• Mechanical properties of the mixture obtained compared to the starting resins impact resistance [test of the falling weight instrumented (ITP)]
• the protocol used for this test was the same as that described in Example 2.
• Table IX Table IX below were obtained: Table IX
• the results showed a synergy relating to the mechanical behavior at high speed between the ELTEX ® KSOOIP resins and (ION 2) in the 10% mixture (ION 2).
• the 10% mixture (ION 2) had indeed a displacement and an energy at the maximum force, as well as a resilience superior to each of their component taken individually.

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