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WO2017009193A1 - Composition comprenant un copolymère de propylène hétérophasique - Google Patents

Composition comprenant un copolymère de propylène hétérophasique Download PDF

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Publication number
WO2017009193A1
WO2017009193A1 PCT/EP2016/066192 EP2016066192W WO2017009193A1 WO 2017009193 A1 WO2017009193 A1 WO 2017009193A1 EP 2016066192 W EP2016066192 W EP 2016066192W WO 2017009193 A1 WO2017009193 A1 WO 2017009193A1
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Prior art keywords
composition
propylene
copolymer
polyamide
heterophasic propylene
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PCT/EP2016/066192
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English (en)
Inventor
Said Fellahi
Azzedine KIOUL
Syed Mehmood Ahmed
Abdullah Shamroukh AL-OTAIBI
Original Assignee
Sabic Global Technologies B.V.
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Publication of WO2017009193A1 publication Critical patent/WO2017009193A1/fr

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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
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
    • 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
    • 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
    • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
    • C08L59/04—Copolyoxymethylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/02—Heterophasic composition

Definitions

  • the invention relates to a composition comprising a heterophasic propylene copolymer, to a process for obtaining such composition and to the use of such composition.
  • Heterophasic propylene copolymers also known as impact propylene copolymers or propylene block copolymers, are an important class of polymers due to their attractive combination of mechanical properties, such as impact strength over a wide temperature range and their low cost. These copolymers find a wide range of applications ranging from the consumer industry (for example packaging and housewares), the automotive industry to electrical applications.
  • Nucleating agents are chemical compounds or compositions that enable faster nucleation or a higher crystallization temperature of thermoplastic polymers, resulting in productivity gains during their processing and in improved mechanical and physical properties of articles made from such thermoplastics. These compounds provide nucleation sites for crystal growth during cooling of a thermoplastic molten composition.
  • a nucleating agent such as talc and carboxylate salts, e.g. sodium benzoate.
  • nucleating agents are highly unpredictable technology area. Small changes in a molecular structure of the nucleator can drastically alter the ability of a nucleating agent to nucleate effectively a polymer composition. There are still many unknowns regarding the effect of a nucleating agent on polymer morphology during (re-)crystallization of thermoplastics.
  • WO2014202603 discloses a thermoplastic composition comprising a heterophasic propylene copolymer and a nucleating composition comprising a cyclic dicarboxylate salt compound and talc.
  • the composition of WO2014202603 has good mechanical properties such as flexural modulus and impact strength.
  • composition of WO2014202603 is satisfactory for some cases, there is a demand in the industry for a composition which is more cost efficient. It is an object of the invention to provide a composition in which above-mentioned and/or other problems are solved.
  • propylene-based matrix consists of a propylene homopolymer and/or a propylene- a-olefin copolymer consisting of at least 70 wt% of propylene and at most 30 wt% of a-olefin, based on the total weight of the propylene-based matrix and
  • propylene-based matrix is present in an amount of 60 to 95 wt% based on the total heterophasic propylene copolymer and
  • dispersed ethylene-a-olefin copolymer is present in an amount of 40 to 5 wt% based on the total heterophasic propylene copolymer and
  • component (b) is from 0.005 to 5 wt% based on the total weight of the components (a) and (b) and
  • the heterophasic polypropylene copolymer (a) has a melt temperature TmPP and a crystallization temperature TcPP,
  • the polymer (b) has a melt temperature TmP and a crystallization temperature TcP, wherein the TcP is 5-40 °C higher than TcPP,
  • T m melting temperature
  • T c crystal growth temperature
  • the polymer having TcP which is 5-40 °C higher than TcPP is selected from polyoxymethylene, polyamide and mixtures thereof.
  • the polyoxymethylene has a melt temperature TmPOM and a crystallization temperature TcPOM.
  • the polyamide has a melt temperature TmPA and a crystallization temperature TcPA.
  • TmPOM is higher than TmPP.
  • TmPA is higher than TmPP.
  • TcPOM is 5-40 °C higher than TcPP.
  • TcPA is 5-40 °C higher than TcPP.
  • a polymer having TcP which is 5-40 °C higher than TcPP preferably polyoxymethylene and/or polyamide
  • a polypropylene composition comprising a heterophasic propylene copolymer
  • TcP which is 5-40 °C higher than TcPP
  • a heterophasic propylene copolymer provides an increase in heat distortion temperature, mechanical properties such as stress at yield, stress at break, elastic modulus, flexural strength and flexural modulus, as well as an increase in the degree of crystallinity and the crystallization temperature.
  • the impact strength is maintained at an acceptable level or may even be increased. Strain at yield and strain at break are lowered.
  • a higher crystallization temperature means that the composition will crystallize with less cooling, as compared to a composition with a lower crystallization temperature. This is advantageous in many applications, such as for example injection molding. In a composition with a higher crystallization temperature, the cooling will go faster hence release from the mold can also be done faster. Hence, shorter cycle times for the preparation of articles can be achieved.
  • polystyrene resin preferably polyoxymethylene and/or polyamide
  • TcP is at least 5 °C higher, for example at least 10 °C higher or at least 20 °C higher, and/or at most 40 °C higher, for example at most 30 °C higher.
  • TmP is higher than TmPP, for example at least 1 °C higher, and/or for example at most 20 °C higher, at most 10 °C higher or at most 5 °C higher.
  • TmPOM is at least 1 °C higher, and/or for example at most 20 °C higher, at most 10 °C higher or at most 5 °C higher.
  • TcPOM is at least 5 °C higher, for example at least 10 °C higher or at least 20 °C higher, and/or at most 40 °C higher, for example at most 30 °C higher.
  • TmPA is at least 1 °C higher, and/or for example at most 20 °C higher, at most 10 °C higher or at most 5 °C higher.
  • TcPA is at least 5 °C higher, for example at least 10 °C higher or at least 25 °C higher, and/or at most 40 °C higher.
  • TmPP is from about 140 to 180 °C, for example from about 145 to about 175°C, for example from about 150 to about 170°C, for example from about 155 to about 165°C.
  • TcPOM is from about 120 to about 155°C, for example from about 135 to about 150 °C.
  • TmPA is from about 175 to about 225°C, for example from about 180 to 200 °C.
  • TcP 5-40 °C higher than TcPP preferably polyoxymethylene and/or polyamide
  • the polymer with TcP 5-40 °C higher than TcPP acts as a nucleating agent even without the presence of a further nucleating agent.
  • the polymer having a higher crystallization temperature than polypropylene crystallizes first upon cooling of the melted composition, after which the polypropylene crystallizes around the crystallized polymer.
  • the composition may further comprise a nucleating agent, for example in an amount of about 0.1 parts per million (ppm) or more, of about 1 ppm or more, about 5 ppm or more, or about 10 ppm or more, based on the weight of the total weight of the polymer composition.
  • the nucleating agent typically is present in the polymer composition in an amount of about 10,000 ppm or less, about 5,000 ppm or less, or about 2,000 ppm or less.
  • the composition comprises little or no further nucleating agent.
  • the composition comprises less than 1500ppm (parts per million as weight based on the total composition), for example less than l OOOppm , more preferably less than l OOOppm, for example less than 500ppm, for example less than 300ppm, for example less than l OOppm, for example less than 10ppm, for example less than 1 ppm, for example less than 0.1 ppm, for example less than 0.05ppm, for example less than 0.01 ppm of a nucleating agent, preferably of nucleating agents chosen from the group of benzoic acid salts, substituted benzoic acid salts, dicarboxylate metal salts,
  • the composition comprises less than 1500ppm (parts per million as weight based on the total composition), for example less than l OOOppm , more preferably less than l OOOppm, for example less than 500ppm, for example less than 300ppm, for example less than l OOppm, for example less than 10ppm, for example less than 1 ppm, for example less than 0.1 ppm, for example less than 0.05ppm, for example less than 0.01 ppm of talc or pigments as further nucleating agent.
  • benzoic acid salts suitable for use as the nucleating agent include, but are not limited to sodium benzoate, lithium benzoate, aluminum para-tertiary butyl benzoate, and combinations thereof.
  • nucleating agent any material that effectively accelerates the phase change from liquid polymer to semi-crystalline polymer (evident via faster crystallization rates measured with a differential scanning calorimeter or small crystallites observed with an optical microscope).
  • nucleating agents examples include 2,6-naphthalene dicarboxamides, aliphatic mono- and di- carboxylate salts such as calcium pimelate and calcium suberate; and polyvinylcyclohexane.
  • Mi and M2 are independently selected from the group consisting of: sodium, calcium, strontium, lithium, zinc, magnesium, and monobasic aluminum; wherein Ri , R2, R3, R4, R5, Re, R7, Re, R9, and R10 are independently selected from the group consisting of: hydrogen and C1-C9 alkyls; and further wherein any two adjacently positioned R3-R10 alkyl groups optionally may be combined to form a carbocyclic ring.
  • suitable bicyclic dicarboxylate metal salts include disodium bicyclo[2.2.1]heptane-2,3- dicarboxylate, calcium bicyclo[2.2.1]heptane-2,3-dicarboxylate, and combinations thereof.
  • Di-acetal derivatives which may be used as nucleating agent include, but are not limited to, alditol acetals, such as the sorbitol di-acetals described in U.S. Patent No. 5,049,605. Suitable di-acetal derivatives preferably conform to the formula
  • n typically is a value selected from 0, 1 , or 2.
  • R typically is selected from the group consisting of hydrogen, alkenyl (such as allyl), alkyl, alkoxy, hydroxylalkyl, alkyl-halide, aromatic and substituted aromatic groups.
  • Ri , R2, R3, R4, R5, Re, R7, Re, R9, and R10 typically are independently selected from the group consisting of hydrogen, fluorocarbons, alkenyl, alkyl, alkynyl, alkoxy, carboxy, halides, amino, thioether and aromatic groups.
  • any two adjacent groups selected from Ri , R2, R3, R4, R5, Re, R7, Re, R9, and R10 may be combined to form a cyclic group selected from the group consisting of methylenedioxy, cyclopentyl, cyclohexyl, or other similar cyclic groups.
  • the nucleating agent preferably is 1 ,3:2,4-bis(3,4- dimethylbenzylidene) sorbitol (hereinafter DMDBS), available from Miliiken Chemical under the trade name Millad(R) 3988.
  • Di-, tri-, and tetra-amides suitable for use as the nucleating agent include, but are not limited to: di- and tri-amides containing amide cores comprised of either single and fused 4,5,6,7-membered aromatic or cycloaliphatic rings; di- and tri-amides containing amide cores comprised of di and tri aliphatic carboxylic acids or di and tri aliphatic amines; and tri- and tetra- amides containing amide cores comprised of aliphatic tri- and tetracarboxylic acids and aliphatic or cycloaliphatic amines.
  • the composition according to the invention comprises a nucleating agent in an amount of 10-2000 ppm, preferably 100-1500 ppm, and the nucleating agent is sodium benzoate.
  • a nucleating agent in an amount of 10-2000 ppm, preferably 100-1500 ppm, and the nucleating agent is sodium benzoate.
  • Heterophasic propylene copolymers are generally prepared in one or more reactors, by polymerization of propylene in the presence of a catalyst and subsequent polymerization of a propylene-oolefin mixture.
  • the resulting polymeric materials are heterophasic, but the specific morphology usually depends on the preparation method and monomer ratios used.
  • the heterophasic propylene copolymer is made using Ziegler-Natta catalyst.
  • the heterophasic propylene copolymer may be prepared by the process comprising - polymerizing propylene and optionally a-olefin in the presence of a catalyst system to obtain the propylene-based matrix and
  • the heterophasic propylene copolymer of the composition of the invention consists of a propylene-based matrix and a dispersed ethylene-oolefin copolymer.
  • the propylene- based matrix typically forms the continuous phase in the heterophasic propylene copolymer.
  • the amounts of the propylene-based matrix and the dispersed ethylene-a- olefin copolymer may be determined by 13 C-NMR, as well known in the art.
  • the heterophasic propylene copolymer consists of (i) a propylene-based matrix,
  • propylene-based matrix consists of a propylene homopolymer and/or a propylene-oolefin copolymer consisting of at least 70 wt% of propylene and at most 30 wt% of a-olefin, based on the total weight of the propylene-based matrix and
  • propylene-based matrix is present in an amount of 60 to 95 wt% based on the total heterophasic propylene copolymer and
  • dispersed ethylene-a-olefin copolymer is present in an amount of 40 to 5 wt% based on the total heterophasic propylene copolymer and
  • the propylene-based matrix consists of a propylene homopolymer and/or a propylene- a-olefin copolymer consisting of at least 70 wt% of propylene and up to 30 wt% of a- olefin, for example ethylene, for example consisting of at least 80 wt% of propylene and up to 20 wt% of a-olefin, for example consisting of at least 90 wt% of propylene and up to 10 wt% of a-olefin, based on the total weight of the propylene-based matrix.
  • the ⁇ -olefin in the propylene- a-olefin copolymer is selected from the group of a-olefins having 2 or 4-10 carbon atoms, for example ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexen, 1-heptene or 1-octene, and is preferably ethylene.
  • the propylene-based matrix consists of a propylene homopolymer.
  • the melt flow index (MFI) of the propylene-based matrix (before it is mixed into the composition of the invention), (MFIPP) may be for example at least 0.1 dg/min, at least 0.2 dg/min, at least 0.3 dg/min, at least 0.5 dg/min, at least 1 dg/min, at least 1.5 dg/min, and/or for example at most 50 dg/min, at most 40 dg/min, at most 30 dg/min, at most 25 dg/min, at most 20 dg/min, measured according to ASTM D 1238 (2.16 kg/230°C).
  • the MFIPP is 10-40 dg/min, for example 30-40 dg/min, measured according to ASTM D 1238 (2.16 kg/230°C), for preparing a heterophasic propylene copolymer suitable for injection molding.
  • the propylene-based matrix is present in an amount of 60 to 95wt%, for example 65 to 85 wt%, for example 70 to 85wt%, for example 70 to 80wt%, for example 65 to 75wt% or 75 to 85wt% based on the total heterophasic propylene copolymer.
  • the propylene-based matrix is preferably semi-crystalline, that is it is not 100% amorphous, nor is it 100% crystalline.
  • the propylene-based matrix is at least 40% crystalline, for example at least 50%, for example at least 60% crystalline and/or for example at most 80% crystalline, for example at most 70% crystalline.
  • the propylene-based matrix has a crystallinity of 60 to 70%.
  • the degree of crystallinity of the propylene-based matrix is measured using differential scanning calorimetry (DSC) according to IS01 1357-1 and IS01 1357-3 of 1997, using a scan rate of 10°C/min, a sample of 5mg and the second heating curve using as a theoretical standard for a 100% crystalline material 207.1 J/g.
  • DSC differential scanning calorimetry
  • the MFI of the dispersed ethylene a-olefin copolymer may be for example at least 0.001 dg/min, at least 0.01 dg/min, at least 0.1 dg/min, at least 0.3 dg/min, at least 0.7 dg/min, at least 0.8 dg/min or at least 1 dg/min, and/or for example at most 30 dg/min, at most 20 dg/min, at most 15 dg/min at most 10 dg/min, at most 5 dg/min or at most 1 dg/min.
  • the MFI of the dispersed ethylene a-olefin copolymer is calculated taking into account the MFI of the propylene-based matrix (MFIPP), the MFI of the heterophasic propylene copolymer (MFIheterophasic) and rubber content (RC) according to the following formula: if FISPB 1 ⁇ & ⁇ ⁇ ⁇ MFlfntArapkasie— matt* ffseiefit * isg M PP
  • MFIEPR is 0.1-5 dg/min, 0.5-3 dg/min or 0.8-1 dg/min. This is particularly preferred for preparing a heterophasic propylene copolymer suitable for injection molding.
  • the dispersed ethylene-a-olefin copolymer is present in an amount of 40 to 5 wt%, for example in an amount of at least 8 wt% or at least 10 wt%, and/or at most 35 wt%, at most 30 wt%, at most 25 wt% or at most 20 wt%, based on the total heterophasic propylene copolymer.
  • the sum of the total weight of the propylene-based matrix and the total weight of the dispersed ethylene-a-olefin copolymer is 100 wt%.
  • the amount of ethylene in the ethylene-a-olefin copolymer is preferably in the range of 15-65 wt% based on the ethylene-a-olefin copolymer. More preferably, the amount of ethylene in the ethylene-a-olefin copolymer is 30-62 wt%, more preferably 40-60 wt%.
  • the a-olefin in the ethylene-a-olefin copolymer is preferably chosen from the group of a- olefins having 3 to 8 carbon atoms and any mixtures thereof, preferably the a-olefin in the ethylene-a-olefin copolymer is chosen from the group of a-olefins having 3 to 4 carbon atoms and any mixtures thereof, more preferably the ⁇ -olefin is propylene, in which case the ethylene-a-olefin copolymer is ethylene-propylene copolymer.
  • Suitable a-olefins having 3 to 8 carbon atoms which may be employed as ethylene comonomers to form the ethylene ⁇ -olefin copolymer include but are not limited to propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexen, 1-heptene and 1-octene.
  • the MFI of the heterophasic propylene copolymer may be for example at least 0.1 dg/min, at least 0.2 dg/min, at least 0.3 dg/min, at least 0.5 dg/min, at least 1 dg/min, at least 1.5 dg/min, at least 3 dg/min, at least 5 dg/min or at least 10 dg/min, and/or for example at most 120 dg/min, at most 100 dg/min, at most 80 dg/min, at most 60 dg/min, at most 50 dg/min, at most 40 dg/min, at most 30 dg/min, at most 25 dg/min, at most 20 dg/min, at most 15 dg/min or at most 10 dg/min, measured according to ASTM D 1238 (2.16 kg/230°C).
  • the MFIheterophasic is 5-120 dg
  • the MFIheterophasic is the original MFI value of the heterophasic propylene copolymer.
  • the MFIheterophasic is the value of the heterophasic propylene copolymer after such vis-breaking or shifting.
  • the amount of the heterophasic propylene copolymer in the composition of the invention is at least 80wt%, for example at least 85wt%, for example at least 90wt%, for example at least 95wt%, for example at least 97wt%, for example at least 98wt% based on the total composition.
  • Polyoxymethylene is also known as polyacetal and may be one or more homopolymers, copolymers, or a mixture of these.
  • the polyoxymethylene (or polyacetal) polymers described herein can be branched or linear and generally have a number average molecular weight of at least 10,000, preferably 20,000 to 90,000. The molecular weight may be measured: 1 ) by gel permeation chromatography in m-cresol at 160 degrees centigrade using a DuPont PSM bimodal column kit with nominal pore size of 60 and 1000 angstrom; or 2) by determining the melt flow using ASTM D1238 or ISO 1 133.
  • Polyacetal homopolymers are prepared by polymerizing formaldehyde or formaldehyde equivalents, such as cyclic oligomers of formaldehyde. Preferred are homopolymers having terminal hydroxyl groups that are-capped by a chemical reaction to form ester or other groups. Preferred end groups for homopolymers are acetate and methoxy.
  • Polyacetal copolymers can contain one or more typical co-monomers, which include acetals and cyclic ethers that lead to the incorporation into the polymer chain of ether units with 2 to 12 sequential carbon atoms.
  • these compositions include such a copolymer, the quantity of co-monomer will not be more than 20 weight percent, preferably not more than 15 weight percent, and most preferably about two weight percent.
  • Preferable co-monomers include ethylene oxide, butylene oxide and, more preferably1 ,3-dioxolane.
  • preferable polyoxymethylene copolymers are those for which the quantity of co-monomer is about 2 weight percent and are not completely end-capped, but have some free hydroxy ends from the co-monomer unit or are terminated with ether groups.
  • Preferred end groups for copolymers are hydroxy and methoxy.
  • the polyamide may be homopolymer, copolymer, terpolymer or higher order polymer. Blends of two or more polyamides may be used. Suitable polyamides can be condensation products of dicarboxylic acids or their derivatives and diamines, and/or aminocarboxylic acids, and/or ring-opening polymerization products of lactams.
  • Suitable dicarboxylic acids include, adipic acid, azelaic acid, sebacic acid,
  • dodecanedioic acid isophthalic acid and terephthalic acid.
  • Suitable diamines include tetramethylenediamine, hexamethylenediamine, octamethylenediamine,
  • nonamethylenediamine dodecamethylenediamine, 2- methylpentamethylenediamine, 2- methyloctamethylenediamine, trimethylhexamethylenediamine, bis(p- aminocyclohexyl)methane, m- xylylenediamine, and p-xylylenediamine.
  • a suitable aminocarboxylic acid is 1 1-aminododecanoic acid.
  • Suitable lactams include caprolactam and laurolactam.
  • polyamide 69 polyamide 610; polyamide 612; polyamide 1010; polyamide 1 1 ;
  • polyamide 12 ; semi-aromatic polyamides such as poly(m-xylylene adipamide)
  • polyamide MXD6 poly(dodecamethylene terephthalamide) (polyamide 12T), poly(decamethylene terephthalamide) (polyamide 10T), poly(nonamethylene terephthalamide) (polyamide 9T), the polyamide of hexamethylene terephthalamide and hexamethylene adipamide (polyamide 6T/66); the polyamide of
  • polyamide 6T/DT polyamide of hexamethylene isophthalamide
  • hexamethylene adipamide polyamide 61/66
  • polyamide of hexamethylene terephthalamide, hexamethylene isophthalamide, and hexamethylene adipamide polyamide 6T/6I/66) and copolymers and mixtures of these polymers.
  • suitable aliphatic polyamides include polyamide 66/6 copolymer; polyamide 66/68 copolymer; polyamide 66/610 copolymer; polyamide 66/612 copolymer; polyamide 66/10 copolymer; polyamide 66/12 copolymer; polyamide 6/68 copolymer; polyamide 6/610 copolymer; polyamide 6/612 copolymer; polyamide 6/10 copolymer; polyamide 6/12 copolymer; polyamide 6/66/610 terpolymer; polyamide 6/66/69 terpolymer;
  • polyamide 6 examples include polyamide 6 and polyamide 66.
  • the polyamide may be a glass fiber reinforced polyamide.
  • the glass fibers may be any glass fibers available for the reinforcement of plastic materials.
  • the amount of the glass fiber may e.g. be 1-50 wt%, 5-45 wt%, 10-40 wt% or 30-35 wt% of the total of the glass fiber and the polyamide.
  • the glass fibers include, but are not limited to, chopped strand E-glass fibers.
  • the amount of the polymer having TcP which is 5-40 °C higher than TcPP is from 0.005 to 5 wt% based on the total weight of the
  • heterophasic propylene copolymer and said polymer in the composition.
  • the total amount of POM and polyamide is from 0.005 to 5 wt% based on the total weight of the the heterophasic propylene copolymer, the POM and the polyamide in the composition.
  • the amount of polyamide in the composition is preferably at least 0.01 , for example at least 0.02, for example at least 0.03, for example at least 0.04, for example at least 0.05, for example at least 0.1 , for example at least 0.2, for example at least 0.3, for example at least 0.4, for example at least 0.5, for example at least 0.7, for example at least 1 , for example at least 2 and/or for example at most 3, for example at most 1.5, for example at most 1wt% based on the total weight of the polypropylene and the polyamide in the composition.
  • the amount of polyamide in the composition is from about 0.01 to about 5 wt% based on the total weight of components a) and b) in the composition.
  • the composition comprising no POM is herein understood to mean that the composition comprises less than 1500ppm (parts per million as weight based on components a) and b) of the composition) of POM, for example less than l OOOppm , more preferably less than l OOOppm, for example less than 500ppm, for example less than 300ppm, for example less than l OOppm, for example less than 10ppm, for example less than 1 ppm, for example less than 0.1 ppm, for example less than 0.05ppm, for example less than 0.01 ppm based on components a) and b) of the composition.
  • the amount of the total of POM and polyamide in the composition is preferably at least 0.01 , for example at least 0.02, for example at least 0.03, for example at least 0.04, for example at least 0.05, for example at least 0.1 , for example at least 0.2, for example at least 0.3, for example at least 0.4, for example at least 0.5, for example at least 0.7, for example at least 1 , for example at least 2 and/or for example at most 3, for example at most 1.5, for example at most 1wt% based on the total weight of components a) and b) in the composition.
  • the amount of the total of POM and polyamide in the composition is from about 0.01 to about 5 wt% based on the total weight of components a) and b) in the composition.
  • the weight ratio between POM to polyamide may be chosen at any value.
  • the weight ratio between POM to polyamide may e.g.
  • the weight ratio between POM to polyamide may e.g.
  • polypropylene have been disclosed in US 4,282,076 and EP 0063654. It is also possible to first melt-mix a peroxide with the heterophasic propylene copolymer, which changes the melt flow index of the heterophasic propylene copolymer, and then mix with polymer (b).
  • organic peroxides are well known and include dialkyl peroxides, e.g. dicumyl peroxides, peroxyketals, peroxycarbonates, diacyl peroxides, peroxyesters and peroxydicarbonates. Specific examples of these include benzoyl peroxide,
  • dichlorobenzoyl peroxide dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5- di(peroxybenzoato)-3-hexene, 1 ,4-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butyl peracetate, a,a'-bis(tert-butylperoxy)diisopropylbenzene (Luperco® 802), 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexene, 2,5-dimethyl-2,5-di(tert- butylperoxy)-hexane, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl per- sec-octoate, tert-butyl perpivalate, cumyl perpivalate.
  • the amount of peroxide will typically lie in the range of 0.02 to 0.5 wt% based on the heterophasic propylene copolymer.
  • the composition according to the invention is prepared without using a peroxide.
  • composition of the invention may be prepared by melt-mixing the polymer having TcP which is 5-40 °C higher than TcPP (preferably the POM and/or PA) with the heterophasic propylene copolymer.
  • the invention also relates to a process for the preparation of the composition of the invention comprising the step of
  • TcP which is 5-40 °C higher than TcPP (preferably POM and/or the PA) with the heterophasic propylene copolymer and the optional additives.
  • the polymer having TcP which is 5-40 °C higher than TcPP (preferably the POM and/or the PA) and the heterophasic propylene copolymer and the optional additives may be pre-mixed in a mixer, for example a dry blender (as may be purchased from Henschell).
  • a mixer for example a dry blender (as may be purchased from Henschell).
  • the polymer having TcP which is 5-40 °C higher than TcPP (preferably the POM and/or the PA) and the heterophasic propylene copolymer are preferably pre-mixed or melt-mixed in the form of a powder or granules but, although less preferred may also be melt-mixed in the form of pellets.
  • Suitable conditions for melt-mixing such as temperature, pressure, amount of shear, screw speed and screw design when an extruder is used are known to the skilled person.
  • a conventional extruder such as a twin-screw extruder may be used.
  • the temperature can vary through the different zones of the extruder as required.
  • the temperature may vary from 150°C in the feed zone to 300°C at the die.
  • the temperature in the extruder varies from 165 to 250°C; likewise, the screw speed of the extruder may be varied as needed. Typical screw speeds are in the range from about l OOrpm to about 400rpm.
  • Thin wall packaging produced via thin wall injection molding provides an answer to the desire for a more sustainable way of packaging, since less material and energy are needed for the injection molding. Consequently, thin wall packaging produced via thin wall injection molding reduces the carbon footprint of the packaging.
  • compositions of the invention may have a high heat distortion temperature as well as a low brittleness around freezing temperature, articles produced from said composition can be used at high as well as at lower temperatures.
  • Application areas where use at both higher and lower temperatures are desired are for example food applications, for example microwaveable, freezer-safe and ovenable containers and medical applications, where sterilization is needed prior to the filling of a container, but the medication inside the container needs to be stored at a low temperature (e.g. from 4 to 7°C).
  • a low temperature e.g. from 4 to 7°C.
  • the invention relates to a process comprising the step of injecting the composition of the invention in a mold, preferably a thin wall mold, wherein a thin wall mold is a mold providing a space having a wall thickness in the range from 0.5 to 2 mm.
  • the invention further relates to use of a polymer (b) preferably chosen from the group consisting of polyoxymethylene, polyamide and mixtures thereof for increasing heat distortion temperature, stress at yield, stress at break, elastic modulus, flexural strength, flexural modulus, degree of crystallinity, crystallization temperature and/or impact strength of a composition comprising
  • propylene-based matrix consists of a propylene homopolymer and/or a propylene- a-olefin copolymer consisting of at least 70 wt% of propylene and at most 30 wt% of a-olefin, based on the total weight of the propylene-based matrix and wherein the propylene-based matrix is present in an amount of 60 to 95 wt% based on the total heterophasic propylene copolymer and
  • dispersed ethylene-a-olefin copolymer is present in an amount of 40 to 5 wt% based on the total heterophasic propylene copolymer and
  • heterophasic propylene copolymer (a) has a melt temperature TmPP and a crystallization temperature TcPP,
  • the polymer (b) has a melt temperature TmP and a crystallization temperature TcP,
  • TcP is 5-40 °C higher than TcPP
  • T m and T c and the degree of crystallinity are determined using Differential Scanning Calorimetry according to ASTM D 3418-08 using a scan rate of 10°C/min on a sample of 10mg and using the second heating cycle,
  • the elastic modulus is measured according to ASTM D-638,
  • the flexural modulus is measured according to ASTM D-790A and
  • the impact strength is measured according to ASTM D-256 at 23 °C.
  • the invention relates to the use of the polymer (b) for increasing heat distortion temperature, elastic modulus, flexural strength, flexural modulus, degree of crystallinity and crystallization temperature in the composition comprising the heterophasic propylene copolymer.
  • the product/composition consisting of these components may be advantageous in that it offers a simpler, more economical process for the preparation of the product/composition.
  • a description on a process comprising certain steps also discloses a process consisting of these steps. The process consisting of these steps may be advantageous in that it offers a simpler, more economical process.
  • compositions were injection molded in the Battenfeld Injection molding machine using 2 mm thick plaque mold according the following operating conditions.
  • the heterophasic propylene copolymer composition and polyoxymethylene were cryogenically grinded in powder form prior to injection molding. Table 1
  • composition used for injection molding comprises a heterophasic propylene copolymer composition and various nucleating agents indicated in Table 2.
  • Various properties were measured according to methods indicated in Table 2 and results are also in Table 2.
  • the heterophasic propylene copolymer composition has an MFI of 21 g/10min
  • the type of the nucleating agent in the heterophasic propylene copolymer composition is sodium benzoate and its amount is 900 ppm.
  • the type of the antistatic agent in the heterophasic propylene copolymer composition is glycerol monostearate (GMS 90) and its amount is 3000 ppm.
  • Melt volume flow rate (MVR): 8.0 cm 3 /10min Tm and T c of POM were determined using Differential Scanning Calorimetry according to ASTM D 3418-08 using a scan rate of 10°C/min on a sample of 10mg and using the second heating cycle. MVR was determined by ISO 1 133 using a 2.16 kg weight and at a temperature of 190 °C.
  • the heat distortion temperature (HDT) was determined using ASTM D648-07 at 0.455 MPa on a 3.2 mm sample, wherein the temperature is increased at 2 degrees centigrade /min until the sample deflects 0.25 mm.
  • the Vicat softening point was as determined using ASTM D 1525-09 using a 1 mm 2 needle having a circular cross-section and a load of 10N wherein the temperature is increased at 2 degrees centigrade/min until the needle penetration reaches 1 mm.
  • the melt temperature (T m ) and the crystallization temperature (T c ) of the heterophasic propylene copolymer compositions were determined using Differential Scanning Calorimetry according to ASTM D 3418-08 using a scan rate of 10°C/min on a sample of 10mg and using the second heating cycle.
  • the impact strength was measured according to ASTM D-256 (measured at 23 °C).
  • the stress at yield, strain at yield and the elastic modulus were measured according to D-638.
  • the flexural strength and the flexural modulus were measured according to D-790A.
  • compositions according to the invention have a higher crystallization temperature, the composition will crystallize at a higher temperature and articles can be released from a mould faster. Hence, shorter cycle times for the preparation of articles can be achieved.
  • the impact strength is higher in the compositions according to the invention. It is particularly notable that the addition of POM-2 led to an increase in the impact strength compared to when POM was not added.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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Abstract

L'invention concerne une composition comprenant (a) un copolymère de propylène hétérophasique constitué de 5 (i) une matrice à base de propylène, la matrice à base de propylène étant constituée d'un homopolymère de propylène et/ou d'un copolymère de propylène-alpha-oléfine constitué d'au moins 70 % en poids de propylène et d'au plus 30 % en poids d'alpha-oléfine, sur la base du poids total de la matrice à base de propylène et la matrice à base de propylène étant présente en quantité de 60 à 95 % en poids sur la base du poids total du copolymère de propylène hétérophasique et (ii) un copolymère d'éthylène-alpha-oléfine dispersé, le copolymère d'éthylène-alpha-oléfine dispersé étant présent en quantité de 40 à 5 % en poids sur la base du poids total du copolymère de propylène hétérophasique et la somme de la quantité totale de matrice à base de propylène et de la quantité totale du copolymère d'éthylène-alpha-oléfine dispersé dans le copolymère de propylène hétérophasique étant de 100 % en poids et (b) un polymère choisi de préférence dans le groupe constitué de polyoxyméthylène, de polyamide et des mélanges de ceux-ci, la quantité du composant (b) étant de 0,005 à 5 % en poids sur la base du poids total des composants (a) et (b) et le copolymère de propylène hétérophasique (a) ayant une température de fusion TmPP et une température de cristallisation TcPP, le polymère (b) ayant une température de fusion TmP et une température de cristallisation TcP, TcP étant de 5 à 40 °C supérieure à TcPP, Tm et Tc étant déterminées à l'aide de la calorimétrie à balayage différentiel selon la norme ASTM D 3418-08 à l'aide d'une vitesse de balayage de 10 °C/min sur un échantillon de 10 mg et à l'aide du deuxième cycle de chauffage.
PCT/EP2016/066192 2015-07-13 2016-07-07 Composition comprenant un copolymère de propylène hétérophasique WO2017009193A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3342816A1 (fr) * 2016-12-27 2018-07-04 Hanwha Total Petrochemical Co., Ltd. Résine de polypropylène pour câble électrique et câble électrique la comprenant dans une couche d'isolation
CN110730805A (zh) * 2017-06-30 2020-01-24 北欧化工公司 具有优异表面外观的聚丙烯组合物
US20220348750A1 (en) * 2021-04-27 2022-11-03 Borealis Ag Beta nucleated heterophasic polypropylene composition

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3342816A1 (fr) * 2016-12-27 2018-07-04 Hanwha Total Petrochemical Co., Ltd. Résine de polypropylène pour câble électrique et câble électrique la comprenant dans une couche d'isolation
CN110730805A (zh) * 2017-06-30 2020-01-24 北欧化工公司 具有优异表面外观的聚丙烯组合物
US11332603B2 (en) 2017-06-30 2022-05-17 Borealis Ag Polypropylene composition with excellent surface appearance
CN110730805B (zh) * 2017-06-30 2022-05-31 北欧化工公司 具有优异表面外观的聚丙烯组合物
US20220348750A1 (en) * 2021-04-27 2022-11-03 Borealis Ag Beta nucleated heterophasic polypropylene composition

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