Definitions

• composition containing a non-functionalized polyolefin and a grafted polyolefin, and article manufactured by using such a composition
• the present invention relates to a polymeric composition containing a non-functionalized polyolefin and a grafted polyolefin, and to an article produced using such a composition.
• various substrates have been coated (in particular sheets of paper, metal sheets or plates, textile surfaces or fibers, organic or inorganic fibers, food products), in order to preserve and protect them, substances such as paraffins, mixtures of paraffins and ethylene-vinyl acetate copolymers.
• thermoplastic polymers in particular of vinyl polymers
• thermoplastic polymers in particular of vinyl polymers
• EPR ethylene copolymer elastomer
• metal ions US Pat. No. 4,371,583, in the name of Schulman, Inc.
• the content of recurring units derived from carboxylic acid in the ionomer is very important: in the case of the zinc ionomer Surlyn ® -which is used in Examples of US Patent 4,371,583-, it reaches about 10%. Notwithstanding, just like the previous compositions, the elastomer-ionomer compositions envisaged in US Pat. No. 4,371,583 generally exhibit less good adhesion than desired, are very expensive and show other weaknesses, in particular, insufficient rigidity. It has finally been proposed to replace the unmodified polyolefin with a mixture of the unmodified polyolefin and of a polyolefin on which acid and / or anhydride groups have been grafted.
• US patent 3,856,889 (Eastman Kodak Co.) describes mixtures of unmodified polyethylene and of a polyalphaolefin (in particular of polypropylene) grafted with acid or anhydride groups which have improved adhesion on substrate compared to unmodified polyethylene . Admittedly, this solution could solve the cost problem mentioned above, but the improvement in grip remains generally insufficient.
• Patent application US 2002/0107329 (Ding et al.) Generically describes mixtures comprising a propylene polymer modified with acid or anhydride groups neutralized by a metal salt (grafted or copolymerized) and an ethylene polymer grafted with acid or anhydride groups also neutralized by a metal salt (grafted or copolymerized).
• the above-mentioned mixture may also comprise a polyolefin, in particular an unmodified propylene polymer (section [0030]).
• the above-mentioned mixture may also comprise up to 40 parts by weight of an elastomeric impact resistance modifying agent chosen from copolymers of ethylene and an ⁇ -monolefin [sections 0077 and 0083].
• an elastomeric impact resistance modifying agent chosen from copolymers of ethylene and an ⁇ -monolefin [sections 0077 and 0083].
• the subject of the present invention is a polymer composition containing a non-functionalized polyolefin and a grafted polyolefin which has many advantages, in particular improved adhesion, compared to the compositions containing a non-functionalized polyolefin and a grafted polyolefin of the prior art without present the disadvantages.
• the invention relates to a polymeric composition containing - more than 50% by weight, relative to the total weight of the composition, of a non-functionalized polyolefin (POl), and - more than 0.5% by weight, based on the total weight of the composition, of at least one polyolefin containing carboxyl grafts [polyolefin (POg)], functionalized by grafting using at least one grafting agent chosen from ethylenically unsaturated carboxylic acids, their anhydrides and their metal salts, at least part of the carboxyl grafts of which is neutralized by a metal, optionally by neutralization, concomitant and / or after grafting, of the carboxyl grafts with at least one base metallic, and which has been synthesized from a non-functionalized polyolefin (PO2) of which at least 0.5% and at most 50% by weight of the repeating units are derived from at least one ethylenically unsaturated
• a non-functionalized polyolefin within the meaning of the present invention, is a polyolefin free of functional group, of any nature whatsoever, in any form whatsoever (eg the functional group may be copolymerized or grafted); a non-functionalized polyolefin, within the meaning of the present invention, is in particular free of repeating units derived from an ethylenically unsaturated comonomer having at least one functional group such as ethylenically unsaturated carboxylic acids, their metal salts and their esters, or vinyl esters ; it is also free from functional groups grafted using grafting agents such as ethylenically unsaturated carboxylic acids, their anhydrides, their metal salts and their esters.
• polyolefin is meant a polymer of which more than 50% by weight of the repeating units are derived from at least one olefin.
• Olefin here means a monoolefin.
• the olefin can in particular be branched or linear.
• linear olefins mention may be made of ethylene, propylene, 1 -butene, 1 -pentene, 1 -hexene, 1 -heptene, 1-octene, 1 -nonene and 1-decene.
• the non-functionalized polyolefin (PO1) is preferably a polymer of which more than 50% by weight of the repeating units are derived from the same olefin (Ol).
• the olefin (Ol) is preferably linear.
• the olefin (Ol) preferably contains from 2 to 8 carbon atoms, particularly preferably from 2 to 6 carbon atoms, and very particularly preferably from 2 to 4 carbon atoms. Excellent results have been obtained when (Ol) was propylene.
• the non-functionalized polyolefin (PO1) can in particular be a homopolymer or a copolymer.
• the optional olefin (Ol) comonomers are advantageously chosen from the linear olefins described above, from diolefins comprising from 4 to 18 carbon atoms, such as 4-vinylcyclohexene, dicyclopentadiene, methylene and ethylidene-norbornene, 1,3-butadiene, isoprene and 1,3-pentadiene.
• they are chosen from the above linear olefins.
• the non-functionalized polyolefin (PO1) is derived from the olefin (Ol ). Even more preferably, the non-functionalized polyolefin (PO1) is a homopolymer. Excellent results have been obtained when the nonfunctionalized polyolefin (POl) was a homopolymer of propylene, such as propylene homopolymers ELTEX ® P HL.
• the term “carboxyl grafts” is intended to denote acid and / or anhydride groups grafted to a polymer, here in this case a polyolefin.
• the grafting agent can be a mono- or a monoethylenically unsaturated dicarboxylic acid, or an anhydride or a metal salt derived from mono- or diacid.
• the grafting agent preferably comprises from 3 to 20 carbon atoms.
• the grafting agent is particularly preferably chosen from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, anhydride maleic, itaconic anhydride, crotonic anhydride and citraconic anhydride.
• maleic anhydride is very particularly preferred.
• the amount of carboxyl grafts is advantageously greater than 0.01% by weight, preferably greater than 0.02% by weight, and particularly preferably greater than 0.03% by weight. weight. In addition, this amount is advantageously less than or equal to 2.0% by weight, preferably to 1.5% by weight, and in a particularly preferred manner less than or equal to 1.0% by weight.
• the grafting of carboxyl grafts is advantageously initiated by a radical-generating agent.
• radical-generating agents of t-butylcumyl peroxide, l, 3-di (2-t- butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylpero ⁇ y) hexane, di (t-butyl) peroxide and 2,5-dimethyl-2,5-di (t-butylperoxy) - 3-hexyne.
• 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 (POg) advantageously contains little free grafting agent (ungrafted), typically an amount less than or equal to 500 ppm, preferably less than 400 ppm and particularly preferably 200 ppm.
• the polyolefin (POg) has advantageously been purified into a free grafting agent, preferably by entrainment with acetone, by stripping with hot air, by stripping with steam, by stripping with a gas. inert or by degassing.
• a metal preferably aluminum oxide
• the neutralization of the carboxyl grafts can be obtained in particular (i) using a grafting agent chosen from metal salts of carboxylic acids (such as disodium maleate, sodium acrylate or zinc acetate), or (ii) by the neutralization, concomitant and / or after grafting, of carboxyl grafts (derived, where appropriate, from a grafting agent chosen from carboxylic acids and their anhydrides) with at least one metal base.
• the neutralization of carboxyl grafts is preferably obtained by route (ii).
• the metal base 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 metal base is preferably an organic salt or a mixture of an organic salt and an inorganic salt.
• the metal base is a mixture of an organic salt and an inorganic salt. Excellent results have been obtained using as a metallic base either a mixture of sodium lactate and sodium carbonate or a mixture of zinc acetate and sodium carbonate.
• the metal base is used in an amount preferably greater than 0.5 molar equivalent relative to the number of carboxyl grafts of the polyolefin (POg).
• the neutralizing agent is used in an amount preferably less than 3 eq.mol. relative to the number of carboxyl grafts of the polyolefin (POg).
• the non-functionalized polyolefin (PO2) is preferably a polymer of which more than 50% by weight of the repeating units are derived from the same olefin (O2).
• the olefin (O2) is preferably linear.
• the olefin (O2) preferably contains from 2 to 8 carbon atoms, particularly preferably from 2 to 6 carbon atoms, and very particularly preferably from 2 to 4 carbon atoms. Excellent results have been obtained when the olefin (O2) was propylene.
• the non-functionalized polyolefin (PO2) can in particular be a homopolymer or a copolymer.
• the optional comonomers of the olefin (02) are advantageously chosen from the linear olefins described above, from diolefins comprising from 4 to 18 carbon atoms, such as 4-vinylcyclohexene, dicyclopentadiene, methylene- and ethylidene-norbornene, 1,3-butadiene, isoprene and 1,3- ⁇ entadiene.
• they are chosen from the above linear olefins.
• the optional comonomer of the olefin (O2) is ethylene, provided of course that the olefin (O2) itself differs from ethylene; in the particular case where the olefin (02) is ethylene, it is particularly preferred that the optional comonomer of the olefin (02) is propylene or 1 -butene.
• the non-functionalized polyolefin (PO2) is advantageously other than an elastomer, and preferably other than an agent modifying impact resistance. Excellent results have been obtained when the non-functionalized polyolefin (PO2) was a random copolymer of propylene and ethylene (i.e. a random copolymer composed of repeating units derived from ethylene and propylene ), comprising at least 94% by weight and at most 98% by weight of repeating units derived from propylene.
• At least 1% by weight and in a particularly preferred manner at least 2% by weight of the repeating units of the non-functionalized polyolefin (PO2) are derived from at least one ethylenically unsaturated monomer of chemical nature different from that of the repeating units of non-functionalized polyolefin (POl).
• Preferably at most 20% by weight, particularly preferably at most 10% by weight, and very particularly preferably at most 6% by weight of the repeating units of the non-functionalized polyolefin (PO2) are derived from at least one ethylenically unsaturated monomer of a chemical nature different from that of the recurring units of non-functionalized polyolefin (POl).
• the non-functionalized polyolefins (PO1) and (PO2) each have a melting point.
• the non-functionalized polyolefins (PO1) and (PO2) each have a melting point and their respective melting enthalpies differ by an amount greater than 10 J / g.
• the non-functionalized polyolefins (PO1) and (PO2) each have a melting point and their respective melting enthalpies differ by an amount between 10 and 100 J / g.
• the non-functionalized polyolefins (PO1) and (PO2) each have a melting point and their respective melting enthalpies differ by an amount between 25 and
• the enthalpy of fusion is advantageously determined by differential thermal calorimetry, on the 2nd heating and with a scanning speed of 10 ° C / min during heating and 20 ° C / min during intermediate cooling [the sample is heated from ambient temperature to a temperature above its melting temperature, at the speed of 10 ° C / min ( 1st heating); then it is cooled at a rate of 20 ° C / min to room temperature; finally, it is again heated from room temperature to a temperature above its melting temperature at the rate of 10 ° C / min ( 2nd heating)].
• the non-functionalized polyolefins (PO1) and (PO2) each have a melting point and their respective melting enthalpies differ by an amount between 30 and 60 J / g.
• the weight of the non-functionalized polyolefin (PO1), relative to the total weight of the composition, is advantageously greater than or equal to 80%, preferably greater than or equal to 90% and particularly preferably greater than or equal to 93%.
• the weight of the non-functionalized polyolefin (PO1), based on the total weight of the composition is advantageously less than or equal to 99%, preferably less than or equal to 98% and in a particularly preferred manner less than or equal to 97%.
• the weight of the polyolefin (POg), based on the total weight of the composition is advantageously at most 20%, preferably at most 10% and particularly preferably at most 7%.
• the weight of the polyolefin (POg), based on the total weight of the composition is advantageously at least 1%, preferably at least 2% and particularly preferably at least 3%.
• the composition according to the invention can be prepared by any known process, in particular the solution processes, the processes taking place in a mixer, for example a BR ⁇ BENDER® mixer, and the processes taking place in an extruder, for example a PRISM® extruder. Good results are usually obtained if the compositions according to the invention are prepared by a process taking place in an extruder.
• composition according to the invention may optionally also contain the usual additives for polyolefin compositions, in an amount advantageously up to 40% by weight, preferably up to 10% by weight, and particularly preferably up to 5% by weight, based on the total weight of the composition.
• usual additives mention may be made of antioxidants such as sterically hindered phenols, lubricants, fillers, dyes, nucleating agents, anti-UV agents, antacid agents such as stearate calcium, metal deactivating agents and anti-static agents.
• the composition according to the invention is advantageously free of polymer other than the polyolefins (PO1) and (POg).
• the composition according to the present invention has an overall level of properties markedly improved compared to that of the compositions containing a non-functionalized polyolefin and a grafted polyolefin of the prior art.
• the surface properties are particularly improved.
• the composition according to the present invention has adhesive properties superior to those of the compositions containing a non-functionalized polyolefin and a grafted polyolefin of the prior art.
• the present invention also relates to an article comprising a polymer composition which has many advantages compared to articles comprising a composition containing a non-functionalized polyolefin and a grafted polyolefin of the prior art, without having the disadvantages.
• the invention relates to an article comprising the composition according to the invention, as described above.
• the article according to the invention can be chosen in particular from tubes, films and sheets, fibers and foams made in the composition.
• the article according to the invention can also be in particular a part of a self-propelled vehicle selected from fuel tanks, fuel pipes, bumpers and dashboards.
• the article according to the invention can also be in particular a substrate coated with the composition as described above.
• the substrate can for example be chosen from paper sheets, metal sheets and plates, textile surfaces and fibers, organic fibers and inorganic fibers, and food products.
• the article according to the invention is preferably a substrate coated with the composition as described above.
• the article according to the invention has many advantages. In particular, in the case of the substrate coated with the composition, the adhesion of the composition to the substrate is generally excellent, a significant improvement over that of the articles of the prior art.
• the examples which follow are intended to illustrate the invention without however limiting its scope.
• Example 1 Preparation of a maleic anhydride grafted polyolefin-based random copolymer of propylene (PP), neutralized with sodium lactate (POgl) was used as reactant (a) a resin PRIEX ® 25097, a random copolymer of polypropylene chemically modified by SOLVAY.
• the random copolymer of PP on which SOLVAY carried out the chemical modification is a random copolymer composed of 95 to 98% by weight of repeating units derived from propylene and from 2 to 5% by weight of recurring units derived from ethylene, marketed by BP under the name
• the PRIEX ® 25097 resin had a weight average molecular weight of 50,000 was also used as reagents (b) of the title sodium lactate neutralizing agent (sodium lactate: mixture of D- and L-isomer in ACROS: 256.4 ml of solution at 60% by weight per liter of aqueous solution), at a rate of 5 eq.mol (c) of disodium carbonate at a rate of 2 eq.mol. , in the form of an aqueous solution at 200 g / 1.
• the barrel of this extruder consists of 10 independent zones (Zl to Z10) as well as a convergence and a die.
• the screw speed was 200 rpm.
• the feed rate was 10 kg / h.
• the temperature profile was as follows: Zl (resin supply): 70 ° C; Z2: 170 ° C; Z3 (fusion) and Z4: 200 ° C; Z5 to Z8 (reaction, pressure degassing atmospheric, reaction, degassing under vacuum at a set point of 2 mbar): 240 ° C; Z9: 230 ° C; Z10: 220 ° C; convergence and sector: 220 ° C.
• High pressure injectors were used for the injection into Z4 of sodium lactate, and into Z7 of disodium carbonate.
• a polyolefin grafted with maleic anhydride was thus obtained based on a random copolymer of PP, neutralized with sodium lactate [resin (POgl)], of which the MFI (2.16 kg, 230 ° C.) was 1.6 g / 10 minutes.
• the resin (POgl) had a sodium content of 6.1 g / kg and its melting temperature was 135 ° C.
• Example 2 Preparation of a maleic anhydride grafted polyolefin based on a propylene homopolymer (PP), neutralized with sodium lactate (POG2) was used as reagent (a ') a PRIEX ® 20093 resin, a polypropylene homopolymer chemically modified by SOLVAY.
• the homopolymer of PP on which SOLVAY carried out the chemical modification is marketed by BP under the name ELTEX ® P HL. It has a melting point of 163 ° C and an enthalpy of melting of 111 J / g.
• the chemical modification which was carried out by SOLVAY on the homopolymer of the abovementioned PP consisted in grafting with maleic anhydride in an amount of 0.26% by weight.
• the PRIEX 20093 resin had a weight-average molecular weight of 75,000.
• Reagents (b) and (c) were also used as defined in Example 1 (nature, quantity, packaging).
• Reaction (a ′), (b) and (c) was carried out in the CLEXTRAL model BC 21 extruder, under operating conditions identical in all respects to those used for Example 1.
• a polyolefin grafted with maleic anhydride was thus obtained.
• the resin (POg2) had a sodium content of 3.1 g / kg and its melting temperature was 165 ° C.
• Example 3 preparation of reference compositions (not in accordance with the invention)
• Composition (CRI) composition based on a random copolymer of PP.
• composition (CRI) a composition Eltex P KS ®, marketed by BP in the form of granules stabilized.
• This composition is composed of (i) more than 99.5% by weight, relative to the total weight of the composition, of a random copolymer composed of 95 to 98% by weight of repeating units derived from propylene and from 2 to 5% by weight of repeating units derived from ethylene and (ii) less than 0.5% by weight, based on the total weight of the composition of a sterically hindered phenol stabilizer.
• Composition (CR2) composition based on a PP homopolymer.
• composition (CR2) a composition ELTEX ® P HL, marketed by BP in the form of granules stabilized.
• This composition is composed of (i) more than 99.5% by weight, relative to the total weight of the composition, of a homopolymer of propylene and (ii) less than 0.5% by weight, based on the total weight of the composition of a sterically hindered phenol stabilizer.
• Composition (CR3) composition based on a random copolymer of PP and a random copolymer of PP grafted with maleic anhydride, neutralized with sodium lactate.
• composition (CR3) composed of 95% by weight of the composition (CRI) and 5% by weight of the resin (POgl) synthesized in Example 1.
• CR3 composition composed of 95% by weight of the composition (CRI) and 5% by weight of the resin (POgl) synthesized in Example 1.
• a PRISM ® twin screw co-rotating extruder with a diameter of 15 mm and a length of 24 cm (i.e. a length-to-diameter ratio of 16), the sheath of which consists of 2 independent zones (Zl and Z2) as well of a convergence and a die with a hole.
• composition (CR4) composition based on a PP homopolymer and a PP homopolymer grafted with maleic anhydride, neutralized with sodium lactate.
• a fourth reference composition was prepared, hereinafter composition (CR4), composed of 95% by weight of the composition (CR2) and 5% by weight of the resin (POg2) synthesized in Example 2. To this Indeed, the same equipment and the same operating conditions were used as those used for the preparation of the composition (CR3).
• Example 4 preparation of a composition in accordance with the invention.
• Composition (CI5) composition based on a PP homopolymer and a random copolymer of PP grafted with maleic anhydride. neutralized with sodium lactate.
• a composition was prepared in accordance with the invention, hereinafter composition (CI5), composed of 95% by weight of the composition (CR2) and 5% by weight of the resin (POgl) synthesized in Example 1.
• composition (CI5) composed of 95% by weight of the composition (CR2) and 5% by weight of the resin (POgl) synthesized in Example 1.
• the same equipment and the same operating conditions were used as those used for the preparation of the composition (CR3).
• Example 5 tests to assess cohesion and adhesion on a steel plate treated in a sulfochromic bath. These tests were carried out according to standard NF T 76-104.
• the shear specimens were prepared by pressing, at a temperature of 230 ° C. and under a pressure of 20 bars between two steel plates previously immersed for 10 minutes in a sulfochromic bath.
• the tensile strength (T R ) of the shear specimens was determined in a shear test carried out using an MTS 50LP machine equipped with a 50 kN sensor. The following results were obtained:
• composition (CI5) which was based on a non-functionalized polyolefin (PO1) and an ionomer of a grafted polyolefin formed from a non-functionalized polyolefin (PO2) different from the non-functional polyolefin functionalized (POl), in the sense that said non-functionalized polyolefin (PO2) comprised from 2 to 5% by weight of repeating units derived from ethylene whereas (POl) consisted only of repeating units derived from propylene adhesive properties superior in particular to the composition (CR4), which was based on the non-functionalized polyolefin (PO1) and on an ionomer of a grafted polyolefin formed from the same non-functionalized polyolefin (PO1).

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• 2004
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