WO2004113438A1 - Procede pour fabriquer des polymeres olefiniques viscoreduits - Google Patents

Procede pour fabriquer des polymeres olefiniques viscoreduits Download PDF

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WO2004113438A1
WO2004113438A1 PCT/IB2004/002061 IB2004002061W WO2004113438A1 WO 2004113438 A1 WO2004113438 A1 WO 2004113438A1 IB 2004002061 W IB2004002061 W IB 2004002061W WO 2004113438 A1 WO2004113438 A1 WO 2004113438A1
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propylene
olefin
ethylene
weight
copolymer
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PCT/IB2004/002061
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English (en)
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Vu A. Dang
Cheng Q. Song
Ming Wu
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Basell Poliolefine Italia S.R.L.
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Publication of WO2004113438A1 publication Critical patent/WO2004113438A1/fr

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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/30—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by oxidation
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
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    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C08L2666/06—Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof

Definitions

  • the present invention relates to a process for making visbroken olefin polymer compositions with improved rheological properties and reduced molecular weights in a post polymerization treatment. More particularly, the process includes visbreaking of polyolefins in the presence of reactive, peroxide-containing olefin polymer materials.
  • Polyolefins are well known commercial polymers, used for a variety of products such as packaging films and extruded and molded shapes. They are produced by polymerization of olefin monomers over transition metal coordination catalysts, specifically titanium halide containing catalysts or single site catalysts. Most commonly used polyolefins include polypropylene, polyethylene and polybutene.
  • the olefin polymer usually has certain limitations in its use for applications that require improved flow performance and fabricating performance. It is known by those familiar with the manufacture of polyolefm polymers that production of high melt flow polymers in the reactor may be difficult due to chain transfer reaction limitations, and the products thereof may suffer embrittlement.
  • U.S. Pat. No. 4,493,923 discloses a polymer composition that has such improved flow performance as obtained through visbreaking by using organic peroxides.
  • a process for modifying polyolefins is disclosed in U.S. Pat. No. 5,405,917, in which an organic peroxide was mixed with the polymer and then the mixture was fed through an extruder. It is well known that organic peroxides are unstable chemicals which are difficult for transportation, storage or application, hi addition, all the organic peroxides will release toxic by-products upon degradation in a chemical reaction. The most common degradation by-product is t-butyl alcohol. These toxic by-products exclude the use of the final polymer products in many applications, such as, toys, food packaging, medical device, etc.
  • a visbreaking process for making modified polyolefins by using a reactive, peroxide-containing olefin polymer material is disclosed.
  • the present invention relates to a process for making visbroken olefin polymers comprising: a) preparing an olefin polymer mixture comprising:
  • I about 0.5 to about 90.0% by weight of a reactive, peroxide-containing olefin polymer material (A); and ⁇ . about 10.0 to about 99.5% by weight of an olefin polymer material (B) selected from a propylene polymer material and a butene-1 polymer material; wherein the sum of components I + II is equal to 100 wt%; b) extruding or compounding in molten state the olefin polymer mixture, thereby producing a melt mixture; and optionally c) pelletizing the melt mixture after it is cooled.
  • A reactive, peroxide-containing olefin polymer material
  • B olefin polymer material selected from a propylene polymer material and a butene-1 polymer material
  • the present invention relates to a process for making visbroken olefin polymers containing ionomer functionality comprising: (a) preparing an olefin polymer mixture comprising:
  • I about 2.0 to about 90.0% by weight of a reactive, peroxide-containing olefin polymer material (A); LI. up to about 98.0%) by weight of an olefin polymer material (B) selected from a propylene polymer material and a butene-1 polymer material; and m. about 0.1 to about 10%> by weight of a base compound selected from metal oxides, hydroxides, and salts; wherein the sum of components I + II + III is equal to 100 wt%>;
  • Olefin polymer suitable as a starting material for preparing reactive, peroxide- containing olefin polymer materials is a propylene polymer material, an ethylene polymer material, a butene-1 polymer material, or mixtures thereof.
  • the starting material used in the present invention can be selected from:
  • Olefin polymers suitable as the olefin polymer material (B) is a propylene polymer material, a butene-1 polymer material, or mixtures thereof.
  • the propylene polymer material used in the present invention can be selected from:
  • the useful polybutene- 1 homo or copolymers can be isotactic or syndiotactic and have a melt flow rate (MFR) from about 0.1 to 150 dg/min, preferably from about 0.3 to 100, and most preferably from about 0.5 to 75.
  • MFR melt flow rate
  • butene-1 polymer materials their methods of preparation and their properties are known in the art.
  • Suitable polybutene- 1 polymers can be obtained, for example, by using Ziegler-Natta catalysts with butene-1, as described in WO 99/45043, or by metallocene polymerization of butene-1 as described in WO 02/102811, the disclosures of which are incorporated herein by reference.
  • the butene-1 polymer materials contain up to about 15 mole %> of copolymerized ethylene or propylene. More preferably, the butene-1 polymer material is a homopolymer having a crystallinity of at least about 30% by weight measured with wide- angle X-ray diffraction after 7 days, more preferably about 45%> to about 70%, most preferably about 55%> to about 60%o.
  • the olefin polymer material (B) and the starting material for the reactive, peroxide- containing olefin polymer material can be the same or different from each other.
  • the olefin polymer material (B) and the starting material for making the reactive, peroxide-containing olefin polymer material is a propylene polymer material, more preferably a propylene homopolymer having an isotactic index greater than about 80%o.
  • the reactive, peroxide-containing olefin polymer material can be present in an amount from about 0.5 to about 90%) by weight, preferably about 1 to about 30%>, more preferably about 2 to about 20%>. The balance of the composition up to 100%> by weight is the olefin polymer material.
  • the reactive, peroxide-containing olefin materials are prepared by exposing the starting material to high-energy ionizing radiation under a blanket of inert gas, preferably nitrogen.
  • the ionizing radiation should have sufficient energy to penetrate the mass of polymer material being irradiated to the extent desired.
  • the ionizing radiation can be of any kind, but preferably includes electrons and gamma rays. More preferred are electrons beamed from an electron generator having an accelerating potential of 500-4,000 kilovolts. Satisfactory results are obtained at a dose of ionizing radiation of about 0.1 to about 15 megarads ("Mrad"), preferably about 0.5 to about 9.0 Mrad.
  • Mrad megarad
  • rad is usually defined as that quantity of ionizing radiation that results in the absorption of 100 ergs of energy per gram of irradiated material regardless of the source of the radiation using the process described in U.S. Pat. No. 5,047,446.
  • Energy absorption from ionizing radiation is measured by the well-known convention dosimeter, a measuring device in which a strip of polymer film containing a radiation-sensitive dye is the energy absorption sensing means.
  • rad means that quantity of ionizing radiation resulting in the absorption of the equivalent of 100 ergs of energy per gram of the polymer film of a dosimeter placed at the surface of the olefin material being irradiated, whether in the form of a bed or layer of particles, or a film, or a sheet.
  • the first treatment step consists of heating the irradiated polymer in the presence of a first controlled amount of active oxygen greater than 0.004%o by volume but less than 15%> by volume, preferably less than 8% by volume, more preferably less than 5%> by volume, and most preferably from 1.3%o to 3.0%o by volume, to a first temperature of at least 25°C but below the softening point of the polymer, preferably about 25°C to 140°C, more preferably about 40°C to 100°C, and most preferably about 50°C to 90°C. Heating to the desired temperature is accomplished as quickly as possible, preferably in less than 10 minutes.
  • the polymer is then held at the selected temperature, typically for about 5 to 90 minutes, to increase the extent of reaction of the oxygen with the free radicals in the polymer.
  • the holding time which can be determined by one skilled in the art, depends upon the properties of the starting material, the active oxygen concentration used, the irradiation dose, and the temperature. The maximum time is determined by the physical constraints of the fluid bed used to treat the polymer.
  • the irradiated polymer is heated in the presence of a second controlled amount of oxygen greater than 0.004% by volume but less than 15% by volume, preferably less than 8%> by volume, more preferably less than 5%> by volume, and most preferably from 1.3% to 3.0%> by volume to a second temperature of at least 25°C but below the softening point of the polymer.
  • the second temperature is from 80°C to less than the softening point of the polymer, and greater than the temperature of the first treatment step.
  • the polymer is then held at the selected temperature and oxygen concentration conditions for about 10 to 300 minutes, preferably 20 to 180 minutes, most preferably about 30 to 60 minutes, to increase the rate of chain scission and to minimize the recombination of chain fragments so as to form long chain branches, i.e., to minimize the formation of long chain branches.
  • the holding time is determined by the same factors discussed in relation to the first treatment step.
  • the oxidized olefin polymer material is heated under a blanket of inert gas, preferably nitrogen, to a third temperature of at least 80°C but below the softening point of the polymer, and held at that temperature for about 10 to about 120 minutes, preferably about 60 minutes.
  • a more stable product is produced if this step is carried out. It is preferred to use this step if the reactive, peroxide-containing olefin polymer material is going to be stored rather than used immediately, or if the radiation dose that is used is on the high end of the range described above.
  • the polymer is then cooled to a fourth temperature of about below 50°C under a blanket of inert gas, preferably nitrogen, before being discharged from the bed. In this manner, stable intermediates are formed that can be stored at room temperature for long periods of time without further degradation.
  • room temperature or “ambient” temperature means approximately 25°C.
  • active oxygen means oxygen in a form that will react with the irradiated olefin polymer material. It includes molecular oxygen, which is the form of oxygen normally found in air.
  • the active oxygen content requirement of this invention can be achieved by replacing part or all of the air in the environment by an inert gas such as, for example, nitrogen.
  • the preferred method of making the reactive, peroxide-containing olefin polymer material is to carry out the treatment by passing the irradiated polymer through a fluid bed assembly operating at a first temperature in the presence of a first controlled amount oxygen, passing the polymer through a second fluid bed assembly operating at a second temperature in the presence of a second controlled amount of oxygen, and then maintaining the polymer at a third temperature under a blanket of nitrogen, in a third fluid bed assembly.
  • a continuous process using separate fluid beds for the first two steps, and a purged, mixed bed for the third step is preferred.
  • the process can also be carried out in a batch mode in one fluid bed, using a fluidizing gas stream heated to the desired temperature for each treatment step.
  • the fluidized bed method does not require the conversion of the irradiated polymer into the molten state and subsequent re-solidification and comminution into the desired fonn.
  • the fluidizing medium can be, for example, nitrogen or any other gas that is inert with respect to the free radicals present, e.g., argon, krypton, and helium.
  • the concentration of peroxide groups formed on the reactive, peroxide-containing polymer can be controlled easily by varying the radiation dose during the preparation of the reactive, peroxide-containing olefin polymer and the amount of oxygen to which such polymer is exposed after irradiation.
  • the oxygen level in the fluid bed gas stream is controlled by the addition of dried, filtered air at the inlet to the fluid bed. Air must be constantly added to compensate for the oxygen consumed by the formation of peroxides in the polymer.
  • the typical peroxide concentration of the reactive, peroxide-containing olefin polymers is ranging from about 10 to about 100 milli-equivalent of peroxide in one kilogram of the reactive, peroxide-containing olefin polymer (meq/kg).
  • the reactive, peroxide-containing olefin polymer material of the invention contains peroxide linkages that degrade during compounding to form various oxygen-containing polar functional groups, e.g., carboxylic acids, ketones and esters.
  • oxygen-containing polar functional groups e.g., carboxylic acids, ketones and esters.
  • the number average and weight average molecular weight of the reactive, peroxide- containing olefin polymer is usually much lower than that of the corresponding olefin polymer used to prepare the same, due to the chain scission reactions during irradiation and oxidation.
  • Suitable equipment for conducting visbreaking process includes but not limited to single screw extruder, twin screw extruder, Ferrell Continuous Mixer (FCM), B anbury mixer, a kneading machine, and an autoclave, etc.
  • the visbroken olefin polymers can be further melt processed with a base compound to form visbroken olefin polymers containing ionomer functionality.
  • the process comprises: a) mixing about 90 to 99.9 wt% of a visbroken melt mixture or a pelletized mixture with about 0.1 to about 10 wt%» of a base compound of a metal oxide, a hydroxide or a salt, thereby producing a base mixture; b) extruding or compounding in molten state the base mixture, thereby producing a melt base mixture; and optionally c) pelletizing the melt base mixture after it is cooled;
  • visbroken olefin polymers containing ionomer functionality were prepared in the presence of a suitable base compound in the extrusion or compounding process.
  • the base compound is defined as a substance that accepts a proton (Lowry-Bronsted definition) or as a substance that can furnish an electron pair to form a covalent bond (Lewis definition).
  • Suitable base compounds of metal oxides, hydroxides or salts include sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium carbonate monohydrate, sodium dihydrogenphosphate, sodium dihydrogenpyrophosphate, sodium hydrogenphosphate, sodium hydrogenphosphate heptahydrate, sodium pyrophosphate, sodium pyrophosphate decahydrate, sodium triphosphate, potassium hydroxide, potassium carbonate, potassium bicarbonate, potassium carbonate sesquihydrate, potassium hydrogenphosphate, potassium hydrogenphosphate trihydrate, potassium pyrophosphate, lithium hydroxide, lithium carbonate, lithium bicarbonate, lithium hydroxide monohydrate, lithium phosphate, zinc oxide, aluminum hydroxide, etc.
  • the reactive, peroxide-containing olefin polymer material can be present in an amount from about 2.0 to about 80.0 %> by weight, preferably about 4.0 to about 30%>, more preferably about 5.0 to about 20%>, and the base compound can be present in an amount of about 0.1 to about 10% > by weight, preferably from about 0.2 to about 5%>, more preferably about 0.5 to about 1.5%.
  • the balance of the composition up to 100% is the olefin polymer material.
  • the polymer composition of the present invention may also contain conventional additives, for instance, anti-acid stabilizers, such as, calcium stearate, hydrotalcite, zinc stearate, calcium oxide, and sodium stearate.
  • the olefin polymer material, the reactive, peroxide-containing olefin polymer material, and the base when making visbroken olefin polymers containing ionomer functionality can be combined at ambient temperature in conventional operations well known in the art; including but not limited to, drum tumbling, manual mixing, or with low or high speed mixers.
  • the resulting mixture is then extruded or compounded in the molten state to conduct the visbreaking reaction in any conventional manner well known in the art in batch or continuous mode; for example, by using a Banbury mixer, a kneading machine, a single screw extruder, a twin screw extruder or an autoclave equipped with adequate agitation.
  • the melt mixture can then be optionally pelletized according to conventional methods well know in the art.
  • MFR Melt Flow Rate
  • Isotactic Index Defined as the percent of olefin polymer insoluble in xylene.
  • the weight percent of olefin polymer soluble in xylene at room temperature is determined by dissolving 2.5 g of polymer in 250 ml of xylene at room temperature in a vessel equipped with a stirrer, and heating at 135°C with agitation for 20 minutes. The solution is cooled to 25 °C while continuing the agitation, and then left to stand without agitation for 30 minutes so that the solids can settle. The solids are filtered with filter paper, the remaining solution is evaporated by treating it with a nitrogen stream, and the solid residue is vacuum dried at 80°C until a constant weight is reached. These values correspond substantially to the isotactic index determined by extracting with boiling n-heptane, which by definition constitutes the isotactic index of polypropylene.
  • the samples are prepared at a concentration of 70 mg/50 ml of stabilized 1, 2, 4 trichlorobenzene (250 ⁇ g/ml BHT). The samples are then heated to 170 degC for 2.5 hours to solubilize. The samples are then run on a Waters GPCV2000 at 145 degC at a flow rate of 1.0 ml/min. using the same stabilized solvent. Three Polymer Lab columns were used in series (Plgel, 20 ⁇ m mixed ALS, 300 X 7.5 mm). Gas Chromatograph determination of reaction byproduct: ⁇ Weigh accurately 7-8 g polymer sample into a 50 ml serum vial.
  • a polypropylene homopolymer having a MFR of 0.7 dg/min and LI. of 95.6% commercially available from Basell USA h e. was irradiated at 0.5 Mrad under a blanket of nitrogen.
  • the irradiated polymer was then treated with 2.5% by volume of oxygen at 55°C for 60 minutes and then with 2.5% by volume of oxygen at 140°C for an additional 60 minutes. The oxygen was then removed.
  • the polymer was then heated at 140°C under a blanket of nitrogen for 90 minutes, cooled and collected.
  • the MFR of the resultant polymer material was 1300 dg/min.
  • the peroxide concentration was 28 meq/kg of polymer.
  • a reactive, peroxide-containing propylene polymer was prepared from a propylene homopolymer, commercially available from Basell USA Inc., having a MFR of 12.0 dg/min and LI. of 95.0%> according to the procedure of Preparation 1, except that the irradiated polymer was treated with 1.75% by volume of oxygen at 80°C for 60 minutes and then with 1.75%) by volume of oxygen at 140°C for another 60 minutes. The oxygen was then removed. The polymer was then heated at 140°C under a blanket of nitrogen for 60 minutes, cooled and collected. The MFR of the resultant polymer material was 852 dg/min. The peroxide concentration was 38.0 meq/kg of polymer.
  • a reactive, peroxide-containing propylene polymer was prepared from a propylene homopolymer, commercially available from Basell USA Inc., having a MFR of 1.5 dg/min and LI. of 96.0% according to the procedure of Preparation L. except that the irradiated polymer was treated with 2.0% by volume of oxygen at 80°C for 90 minutes and then with 2.0% by volume of oxygen at 140°C for 60 minutes. The oxygen was then removed. The polymer was then heated at 140°C under a blanket of nitrogen for 60 minutes, cooled and collected. The MFR of the resulting polymer material was 709 dg/min. The peroxide concentration was 43.4 meq/kg of polymer. Preparation 4
  • a reactive, peroxide-containing propylene polymer was prepared from a propylene homopolymer, commercially available from Basell USA Inc., having a MFR of 1.5 dg/min and LI. of 96.0% according to the procedure of Preparation 3, except that the irradiated polymer was treated with 2.2%> by volume of oxygen in both treatment steps.
  • the MFR of the resulting material was 890 dg/min.
  • the peroxide concentration was 43.4 meq/kg of polymer.
  • a reactive, peroxide-containing propylene polymer was prepared from a propylene homopolymer, commercially available from Basell USA Inc., having a MFR of 0.48 dg/min and LI. of 95.4%>, according to the procedure of Preparation 1, except that the irradiated polymer was first treated with 3.0%> by volume of oxygen at 80°C for 5 minutes, then with 3.0%) by volume of oxygen at 140°C for 60 min and finally with 5% > by volume of oxygen at 130 °C for 3 hours.
  • the MFR of the resulting polymer material was 17,000 dg/min.
  • the peroxide concentration was 102 meq/kg of polymer.
  • This example shows the characteristics of a blend of a propylene homopolymer, and a reactive, peroxide-containing olefin polymer material.
  • the comparative sample uses organic peroxide, Lupersol 101, commercially available from ELF Atochem in place of the reactive, peroxide-containing olefin polymer as a visbreaking agent.
  • the propylene homopolymer has a MFR of 4.0 and I.I. of 95.5%, commercially available from Basell USA Inc.
  • Irganox B225 antioxidant is a 1:1 blend of Irganox 1010 antioxidant and Irgafos 168 tris(2,4-di-t-butylphenyl) phosphite anitoxidant and is commercially available from Ciba Specialty Chemicals Corporation.
  • the composition of each sample is shown in Table 1. The amounts given for the stabilizers are in parts per hundred parts of the polymer composition.
  • the by-product of t-butanol in the polymer was measured using Gas Chromatograph determination as defined therein.
  • the comparative sample 2 shows a high level of t-butanol residue in the polymer after visbreaking reaction, whereas the samples containing a reactive, peroxide-containing olefin polymer have very low or are absent of t-butanol.
  • the resulting polymer shows a low level of t-butanol, which provides a major advantage due to its purity.
  • This example shows the characteristics of a blend of an olefin copolymer, and a reactive, peroxide-containing polypropylene.
  • the olefin copolymer was a copolymer of ethylene and propylene with ethylene content of 19.5%), having a MFR of 0.65 and LI. of 41.0%, commercially available from Basell USA Inc.
  • This example shows the characteristics of a blend of a propylene homopolymer, and an reactive, peroxide-containing olefin polymer.
  • the propylene homopolymer has a MFR of 3.5 and LI. of 95.0%, commercially available from Basell USA Inc.
  • composition of each sample containing a reactive, peroxide-containing olefin polymer is shown in Table 3.
  • the samples 1-4 in Table 3 show the melt flow increases with the increase of the content of the reactive, peroxide-containing olefin polymer.
  • Table 4 shows the composition of the comparative samples containing a high MFR propylene homopolymer as controls.
  • the comparative samples 2-6 in Table 4 show the melt flow increases with the increase of the high MFR propylene homopolymer (A) due to the dilution effect.
  • the rate increase in MFR is much slower than that of polymer blends disclosed in Table 3. Therefore, the reactive, peroxide-containing olefin polymer provides additional visbreaking for the propylene homopolymer due to its peroxide functionality.
  • This example shows the characteristics of a blend of a propylene copolymer, and a reactive, peroxide-containing olefin polymer.
  • the propylene copolymer has a MFR of 3.8, LI. of 88.6%, and ethylene content of 9.4%), commercially available from Basell USA Inc.
  • Table 6 shows the composition of comparative samples containing a high MFR propylene homopolymer as controls.
  • the comparative samples 2-5 in Table 6 show the melt flow of the polymer blend containing propylene copolymer increases with the addition of the high MFR propylene homopolymer (A) due to the dilution effect. But the rate increase in MFR is much slower that of polymer blends disclosed in Table 5. Therefore, the reactive, peroxide-containing olefin polymer provides additional visbreaking for the propylene copolymer due to its peroxide functionality.
  • This example shows the characteristics of a blend of a propylene copolymer, and a reactive, peroxide-containing olefin polymer.
  • the propylene copolymer has a MFR of 3.8, I.I. of 88.6%, and ethylene content of 9.4%o, commercially available from Basell USA Inc.
  • each sample containing reactive, peroxide-containing olefin polymer is shown in Table 7.
  • the samples 1-2 in Table 7 show the melt flow increases with the increase, of the reactive, peroxide-containing olefin polymer content.
  • This example shows the characteristics of a blend of a propylene copolymer, and a reactive, peroxide-containing olefin polymer.
  • the propylene copolymer has a MFR of 0.5, LI. of 37.5%>, and ethylene content of 21.7%, commercially available from Basell USA Lhc.
  • composition of each sample containing a reactive, peroxide-containing polymer is shown in Table 8.
  • the samples 1-3 in Table 8 show the melt flow increases with the increase of the reactive, peroxide-containing olefin polymer content.
  • This example shows the characteristics of a blend of a propylene copolymer, and a reactive, peroxide-containing olefin polymer, containing ionomer functionality.
  • the propylene copolymer has a MFR of 2.0, LI. of 93.8%>, and ethylene content of 3.4%o, commercially available from Basell USA Inc.
  • Sodium carbonate, potassium carbonate and zinc oxide were obtained from Aldrich Chemical Company, Inc. without further purification.
  • the amounts given for the base are in parts per hundred parts of the polymer composition.
  • each sample containing reactive, peroxide-containing olefin polymer is shown in Table 9.
  • the samples 1-3 in Table 9 show the melt flow characteristics of the visbroken olefin polymers containing ionomer functionality made by using various base compounds. Table 9
  • This example shows the characteristics of a blend of a propylene copolymer, and a reactive, peroxide-containing olefin polymer, containing ionomer functionality.
  • the propylene copolymer has a MFR of 2.0, LI. of 93.8%, and ethylene content of 3.4%o, commercially available from Basell USA Inc.
  • Sodium carbonate, potassium carbonate and zinc oxide were obtained from Aldrich Chemical Company, Inc. without further purification.
  • the amounts given for the base are in parts per hundred parts of the polymer composition.
  • each sample containing a reactive, peroxide-containing olefin polymer is shown in Table 10.
  • the samples 1-3 in Table 10 show the melt flow characteristics of the visbroken olefin polymers containing ionomer functionality made by using various bases. Table 10
  • This example shows the characteristics of a blend of a propylene homopolymer, and a reactive, peroxide-containing olefin polymer, containing ionomer functionality.
  • the propylene homopolymer has a MFR of 0.7, and LI. of 95.6%, commercially available from Basell USA Inc.
  • Sodium carbonate, potassium carbonate and zinc oxide were obtained from Aldrich Chemical Company, Inc. without further purification.
  • the amounts given for the base are in parts per hundred parts of the polymer composition.
  • composition of each sample containing a reactive, peroxide-containing olefin polymer is shown in Table 11.
  • the samples 1-3 in Table 11 show the melt flow characteristics of the visbroken olefin polymers containing ionomer functionality made by using various bases.
  • This example shows the characteristics of a blend of a propylene homopolymer, and a reactive, peroxide-containing olefin polymer.
  • two high melt flow propylene homopolymers were used in the comparative samples.
  • the propylene homopolymer has a MFR of 5.4 and LI. of 95.0%>, commercially available from Basell USA Inc. Two high MFR propylene homopolymers were used to evaluate the dilution effect.
  • the first high MFR homopolymer (A) has a MFR of 695 dg/ml and the second high MFR homopolymer (B) has a MFR of 1051 dg/ml.
  • each sample containing a reactive, peroxide-containing olefin polymer and comparative samples is shown in Table 12.
  • the samples 1-2 in Table 12 show the melt flow increases with the increase of the reactive, peroxide-containing olefin polymer content.
  • the visbreaking process effectively reduced molecular weight of the polymer and at the same time narrowed the molecular weight distribution as compared with the comparative samples 2 and 3, which showed only dilution effect.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

L'invention concerne un procédé pour fabriquer des polymères oléfiniques viscoréduits, avec un faible niveau de sous-produits, au moyen d'un matériau polymère oléfinique réactif contenant du peroxyde. Ce procédé consiste à: a) préparer un mélange polymère oléfinique renfermant: I. environ 0,5 à environ 90,0 % en poids d'un matériau polymère oléfinique réactif contenant du peroxyde (A); et II. environ 10,0 à environ 99,5 % en poids d'un matériau polymère oléfinique (B); b) procéder à l'extrusion ou au compoundage, à l'état fondu, du mélange polymère oléfinique, en vue d'obtenir un mélange fondu; et éventuellement c) pastiller le mélange fondu.
PCT/IB2004/002061 2003-06-20 2004-06-17 Procede pour fabriquer des polymeres olefiniques viscoreduits WO2004113438A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2113541A1 (fr) 2008-04-28 2009-11-04 Borealis AG Composition de polymère en propylène adhésive adaptée à l'extrusion de revêtement de substrats papiers
EP2251375A1 (fr) 2009-05-07 2010-11-17 Borealis AG Composés de polyoléfine thermoplastique dotés d'une plus faible sensibilité au flammage
US8192813B2 (en) 2003-08-12 2012-06-05 Exxonmobil Chemical Patents, Inc. Crosslinked polyethylene articles and processes to produce same
EP3118249A1 (fr) 2015-07-14 2017-01-18 Borealis AG Composite renforcé à l'aide de fibres
US10793753B2 (en) 2016-04-22 2020-10-06 Borealis Ag Visbreaking process

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0980877A2 (fr) * 1996-04-02 2000-02-23 Montell North America Inc. Polypropylène dégradé par irradiation et fibres à partir de celui-ci
US6444722B1 (en) * 2000-11-02 2002-09-03 Basell Poliolefine Italia S.P.A. Making polyolefin graft copolymers with low molecular weight side chains using a polymeric peroxide as an initiator
WO2002096986A2 (fr) * 2001-05-30 2002-12-05 Basell Poliolefine Italia S.P.A. Composition de resine de polypropylene

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0980877A2 (fr) * 1996-04-02 2000-02-23 Montell North America Inc. Polypropylène dégradé par irradiation et fibres à partir de celui-ci
US6444722B1 (en) * 2000-11-02 2002-09-03 Basell Poliolefine Italia S.P.A. Making polyolefin graft copolymers with low molecular weight side chains using a polymeric peroxide as an initiator
WO2002096986A2 (fr) * 2001-05-30 2002-12-05 Basell Poliolefine Italia S.P.A. Composition de resine de polypropylene

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8192813B2 (en) 2003-08-12 2012-06-05 Exxonmobil Chemical Patents, Inc. Crosslinked polyethylene articles and processes to produce same
US8703030B2 (en) 2003-08-12 2014-04-22 Exxonmobil Chemical Patents Inc. Crosslinked polyethylene process
EP2113541A1 (fr) 2008-04-28 2009-11-04 Borealis AG Composition de polymère en propylène adhésive adaptée à l'extrusion de revêtement de substrats papiers
EP2251375A1 (fr) 2009-05-07 2010-11-17 Borealis AG Composés de polyoléfine thermoplastique dotés d'une plus faible sensibilité au flammage
US20120077919A1 (en) * 2009-05-07 2012-03-29 Borealis Ag Thermoplastic polyolefin compounds with decreased flaming sensitivity
US8846805B2 (en) 2009-05-07 2014-09-30 Borealis Ag Thermoplastic polyolefin compounds with decreased flaming sensitivity
EP3118249A1 (fr) 2015-07-14 2017-01-18 Borealis AG Composite renforcé à l'aide de fibres
WO2017009380A1 (fr) 2015-07-14 2017-01-19 Borealis Ag Composite renforcé par des fibres
US10174189B2 (en) 2015-07-14 2019-01-08 Borealis Ag Fiber reinforced composite
US10793753B2 (en) 2016-04-22 2020-10-06 Borealis Ag Visbreaking process

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