Patent Application
20240309189
In general, the present disclosure relates to the field of chemistry. More specifically, the present disclosure relates to polymer chemistry. In particular, the present disclosure relates to a filled polyolefin composition.
In some instances, filled polypropylene compounds based on heterophasic polyolefin compositions are used in the automotive industry, thereby obtaining injection molded parts, having aesthetical interior applications.
In some instances, glass fibers reinforced heterophasic polyolefin compositions provide a good balance of stiffness and impact, soft touch haptic, and good scratch resistance.
Beside a good balance of mechanical properties and a soft touch haptic, some applications in the automotive industry rely on good temperature resistance, such as under the hood applications or exterior trims.
In a general embodiment, the present disclosure provides a filled polymer composition made from or containing:
(a) 20-50% by weight of an heterophasic polypropylene made from or containing:
wherein the heterophasic polypropylene (a) has an amount of fraction soluble in xylene at 25° C. XS(a) equal to or higher than 65% by weight, and the amounts of (A), (B), and XS(a) are based on the total weight of (A)+(B);
(c) 5-35% by weight of a propylene polymer, having a melt flow rate MFR(c), measured according to ISO 1133 (230° C., 2.16 kg), from 0.5 to 20 g/10 min. and a tensile modulus, measured according to ISO 527-1,-2, equal to or higher than 1000 MPa, and is selected from the group consisting of propylene homopolymers and propylene copolymers with an alpha-olefin of formula CH2═CHR, wherein R is H or a linear or branched C2-C8 alkyl, wherein the copolymer is made from or containing up to and including 5% by weight of units deriving from the alpha-olefin, based on the weight of (c);
(d) 5-35% by weight of glass fibers; and
(e) 0-5% by weight of a compatibilizer,
wherein the amounts of (a), (b), (c), (d), and (e) are based on the total weight of (a)+(b)+(c)+(d)+(e), the total weight being 100.
While multiple embodiments are disclosed, still other embodiments will become apparent to those skilled in the art from the following detailed description. As will be apparent, certain embodiments, as disclosed herein, are capable of modifications in various aspects, without departing from the spirit and scope of the claims as presented herein. Accordingly, the following detailed description is to be regarded as illustrative in nature and not restrictive.
In the present disclosure, the percentages are expressed by weight, unless otherwise specified.
In the present disclosures, when the term “comprising” is referred to a polymer or to a polymer composition, mixture or blend, the term should be construed to mean “comprising or consisting essentially of”.
In the present disclosure, the term “consisting essentially of” means that, in addition to the specified components, the polymer, the polyolefin composition, the polyolefin mixture, or the polyolefin blend may be further made from or containing other components, provided that the characteristics of the polymer or of the composition, mixture or blend are not materially affected by the presence of the other components. In some embodiments, the other components are catalyst residues, antistatic agents, melt stabilizers, light stabilizers, antioxidants, and antiacids.
In some embodiments, the filled polyolefin composition is made from or containing:
(a) 20-50% by weight, alternatively 25-45% by weight, of an heterophasic polypropylene made from or containing:
(A) 10-40% by weight of a copolymer of propylene with hexene-1 made from or containing from 1% to 6% by weight of units deriving from hexene-1, based on the weight of (A), and having a melt flow rate MFR(A), measured according to ISO 1133 (230° C., 2.16 kg), equal to or greater than 20 g/10 min; and
(B) 60-90% by weight of a copolymer of propylene with an alpha-olefin of formula CH2═CHR, and optionally a diene, wherein R is H or a linear or branched C2-C8 alkyl, made from or containing 20-35% by weight of monomer units deriving from the alpha-olefin, based on the weight of (B),
wherein the heterophasic polypropylene (a) has an amount of fraction soluble in xylene at 25° C. XS(a) equal to or higher than 65% by weight, and the amounts of (A), (B), and XS(a) are based on the total weight of (A)+(B);
(b) 10-25% by weight, alternatively 15-20% by weight, of a propylene polymer having a melt flow rate MFR(b), measured according to ISO 1133 (230° C., 2.16 kg), equal to or higher than 800 g/10 min., and is selected from the group consisting of propylene homopolymers and propylene copolymers with an alpha-olefin of formula CH2═CHR, wherein R is H or a linear or branched C2-C8 alkyl, wherein the copolymer is made from or containing up to and including 5% by weight of units deriving from the alpha-olefin, based on the weight of (b),;
(c) 5-35% by weight, alternatively 8-30% by weight, of a propylene polymer, having a melt flow rate MFR(c), measured according to ISO 1133 (230° C., 2.16 kg), from 0.5 to 20 g/10 min. and a tensile modulus, measured according to ISO 527-1,-2, equal to or higher than 1000 MPa, and is selected from the group consisting of propylene homopolymers and propylene copolymers with an alpha-olefin of formula CH2-CHR, wherein R is H or a linear or branched C2-C8 alkyl, wherein the copolymer is made from or containing up to and including 5% by weight of units deriving from the alpha-olefin, based on the weight of (c);
(d) 5-35% by weight of glass fibers;
(e) 0-5% by weight, alternatively 0.1-3% by weight, of a compatibilizer; and
(f) 0-15% by weight, alternatively 0.1-15% by weight, alternatively 0.5-10% by weight, of an additive selected from the group consisting of fillers, pigments, nucleating agents, extension oils, flame retardants, UV resistants, UV stabilizers, lubricants, antiblocking agents, waxes, and combinations thereof,
wherein the amounts of (a), (b), (c), (d), (e), and (f) are based on the total weight of (a)+(b)+(c)+(d)+(e)+(f), the total weight being 100. In some embodiments, the flame retardants are aluminum trihydrate. In some embodiments, the UV resistants are titanium dioxide. In some embodiments, the lubricants are oleamide.
In some embodiments, the polyolefin composition is made from or containing the individual components in any combination.
In some embodiments, the heterophasic polypropylene (a) is made from or containing a propylene copolymer (A) made from or containing 2.0-5.0% by weight, alternatively 2.8-4.8% by weight, alternatively 3.0-4.0% by weight of units deriving from hexene-1, based on the weight of component (A).
In some embodiments, the propylene copolymer (A) is made from or containing hexene-1 as the comonomer.
In some embodiments, the propylene copolymer (A) is made from or containing units deriving from hexene-1 and 0.1-3.0% by weight of a further alpha-olefin selected from the group consisting of ethylene, butene-1, 4-methyl-1-pentene, octene-1, and combinations thereof, based on the weight of component (A).
In some embodiments, the propylene copolymer (A) has a melt flow rate MFR(A), measured according to ISO 1133 (230° C., 2.16 kg), ranging from 20 to 120 g/10 min, alternatively from 25 to 100 g/10 min.
In some embodiments, the propylene copolymer (A) has an amount of fraction soluble in xylene at 25° C. XS(A) lower than 12.0% by weight, alternatively lower than 9.0% by weight, based on the weight of component (A). In some embodiments, XS(A) is in the range 5.0-12.0% by weight, alternatively 5.0-9.0% by weight, alternatively 6.0-8.0% by weight, based on the weight of component (A).
In some embodiments, the propylene copolymer (B) has an amount of fraction soluble in xylene at 25° C. XS(B) equal to or greater than 80% by weight, alternatively equal to or greater than 85% by weight, alternatively equal to or greater than 90% by weight, based on the total weight of the propylene copolymer (B).
In some embodiments, the upper limit of the amount of the fraction of propylene copolymer (B) soluble in xylene at 25° C. XS(B) is 97% by weight for each lower limit, based on the total weight of component (B).
In some embodiments, propylene copolymer (B) is made from or containing a first copolymer (B1) and a second copolymer (B2), wherein (B1) and (B2) are independently selected from copolymers of propylene with an alpha-olefin of formula CH2═CHR, and optionally a diene, wherein R is H or a linear or branched C2-C8 alkyl, provided that the total amount of units deriving from the alpha-olefin in the propylene copolymer (B) is 20-35% by weight, based on the total weight of component (B).
In some embodiments, component (B) is made from or containing:
(B1) 30-60% by weight, alternatively 40-55% by weight, of a first copolymer of propylene with an alpha-olefin of formula CH2═CHR, and optionally a diene, wherein R is H or a linear or branched C2-C8 alkyl, made from or containing 20-40% by weight, alternatively 25-35% by weight, of the alpha-olefin and has a fraction soluble in xylene at 25° C. XS(B1) equal to or greater than 80% by weight, alternatively equal to or greater than 85% by weight, alternatively equal to or greater than 90% by weight, the amount of alpha-olefin and of XS(B1) being based on the weight of component (B1); and
(B2) 40-70% by weight, alternatively 45-60% by weight, of a second copolymer of propylene with an alpha-olefin of formula CH2═CHR, and optionally a diene, wherein R is H or a linear or branched C2-C8 alkyl, made from or containing 25-45% by weight, alternatively 30-43% by weight, of alpha-olefin and has a fraction soluble in xylene at 25° C. XS(B2) equal to or greater than 80% by weight, alternatively equal to or greater than 85% by weight, alternatively equal to or greater than 90% by weight, the amount of alpha-olefin and of XS(B2) being based on the weight of component (B2),
wherein the amounts of (B1) and (B2) are based on the total weight of (B1)+(B2).
In some embodiments, the upper limit of XS(B1) or of XS(B2) is 97% by weight for each lower limit, XS(B1) and XS(B2) being based on the weight of component (B1) and (B2), respectively.
In some embodiments, the heterophasic polypropylene (a) has an amount of fraction soluble in xylene at 25° C. XS(a) equal to or greater than 70% by weight, alternatively ranging from 71 to 90% by weight, alternatively from 72 to 80% by weight, based on the total weight of (A)+(B).
In some embodiments, the heterophasic polypropylene (a) has a melt flow rate MFR(a), measured according to ISO 1133 (230°° C., 2.16 kg), ranging from 5 to 50 g/10 min., alternatively from 10 to 30 g/10 min., alternatively from 12 to 25 g/10.min.
In some embodiments, the melt flow rate MFR(a) of the heterophasic polypropylene (a), measured according to ISO 1133 (230° C., 2.16 kg), ranges from 5 to 50 g/10 min., alternatively from 10 to 30 g/10 min., alternatively from 12 to 25 g/10.min. and is obtained by visbreaking the heterophasic polypropylene obtained from the polymerization reaction.
In some embodiments, the visbreaking is carried out by mixing the molten polyolefin with an organic peroxide.
In some embodiments, the intrinsic viscosity of the fraction soluble in xylene at 25° C. of the heterophasic polypropylene (a) XSIV(a) is equal to or lower than 1.5 dl/g.
In some embodiments, the heterophasic polypropylene (a) is made from or containing 15-35% by weight, alternatively 20-30% by weight, of component (A) and 65-85% by weight, alternatively 70-80% by weight, of component (B), wherein the amounts of (A) and (B) are based on the total weight of (A)+(B).
In some embodiments, the heterophasic polypropylene (a) is made from or containing:
(A) 10-40% by weight, alternatively 15-35% by weight, alternatively 20-30% by weight, of a copolymer of propylene with hexene-1 made from or containing 1.0-6.0% by weight, alternatively 2.0-5.0% by weight, alternatively 2.8-4.8% by weight, alternatively 3.0-4.0% by weight, of units deriving from hexene-1, based on the weight of copolymer (A), and having a melt flow rate MFR(A), measured according to ISO 1133 (230° C., 2.16 kg), equal to or greater than 20 g/10 min., alternatively ranging from 20 to 120 g/10 min, alternatively from 25 to 100 g/10 min; and
(B) 60-90% by weight, alternatively 65-85% by weight, alternatively 70-80% by weight, of a copolymer of propylene with ethylene made from or containing 20-35% by weight of ethylene, based on the total weight of the component (B),
wherein the heterophasic polypropylene (a):
wherein the amounts of (A), (B), and XS(a) are based on the total weight of (A)+(B).
In some embodiments, the alpha-olefin of component (B) is selected from the group consisting of ethylene, butene-1, hexene-1, 4-methy-pentene-1, octene-1, and combinations thereof. In some embodiments, the alpha-olefin of component (B) is ethylene.
In some embodiments, propylene copolymer (B) is made from or containing recurring units derived from a diene. In some embodiments, the diene is selected from the group consisting of butadiene, 1,4-hexadiene, 1,5-hexadiene, ethylidene-1-norbonene, and combinations thereof.
In some embodiments, the total amount of recurring units deriving from a diene ranges from 1% to 10% by weight, based on the weight of component (B).
In some embodiments, heterophasic polypropylene (a) has a property selected from the following mechanical properties:
In some embodiments, the Shore A value is in the range 70-90. In some embodiments, the Shore D value is in the range 23-30. In some embodiments, the heterophasic polypropylene (a) has flexural modulus, Shore A, and Shore D values in the ranges indicated above.
In some embodiments, the heterophasic polypropylene (a) is prepared by a sequential polymerization process, including at least two polymerization stages, wherein the second and each subsequent polymerization stage is carried out in the presence of the polymer produced and the catalyst, which was present in the immediately preceding polymerization stage.
In some embodiments, the polymerization processes are carried out in the presence of a catalyst selected from the group consisting of metallocene compounds, highly stereospecific Ziegler-Natta catalyst systems, and combinations thereof.
In some embodiments, the polymerization processes are carried out in the presence of a highly stereospecific Ziegler-Natta catalyst system made from or containing:
(1) a solid catalyst component made from or containing a magnesium halide support on which a Ti compound having at least a Ti-halogen bond is present, and a stereoregulating internal donor;
(2) optionally, an Al-containing cocatalyst; and
(3) optionally, a further electron-donor compound (external donor). In some embodiments, the stereospecific Ziegler-Natta catalyst system is further made from or containing the Al-containing cocatalyst. In some embodiments, the stereospecific Ziegler-Natta catalyst system is further made from or containing the electron-donor compound (external donor).
In some embodiments, the solid catalyst component (1) is made from or containing a titanium compound of formula Ti(OR)nXy_n, wherein n is between 0 and y; y is the valence of titanium; X is halogen; and R is a hydrocarbon group having 1-10 carbon atoms or a —COR group. In some embodiments, titanium compounds having a Ti-halogen bond is selected from the group consisting of titanium tetrahalides and titanium halogenalcoholates. In some embodiments, the titanium compounds are selected from the group consisting of TiCl3, TiCl4, Ti(OBu)4, Ti(OBu)Cl3, Ti(OBu)2Cl2, and Ti(OBu)3Cl. In some embodiments, the titanium compound is TiCl4.
In some embodiments, the solid catalyst component (1) is made from or containing a titanium compound in an amount providing from 0.5 to 10% by weight of Ti with respect to the total weight of the solid catalyst component (1).
In some embodiments, the solid catalyst component (1) is made from or containing a stereoregulating internal electron donor compound selected from mono or bidentate organic Lewis bases. In some embodiments, the solid catalyst component (1) is made from or containing a stereoregulating internal electron donor compound selected from the group consisting of esters, ketones, amines, amides, carbamates, carbonates, ethers, nitriles, alkoxysilanes, and combinations thereof.
In some embodiments, the electron donors are selected from the group consisting of aliphatic or aromatic mono-or dicarboxylic acid esters and diethers.
In some embodiments, the alkyl and aryl esters of optionally substituted aromatic polycarboxylic acids are selected from the group consisting of esters of phthalic acids. In some embodiments, the esters of phthalic acids are as described in European Patent Application Nos. EP45977A2 and EP395083A2.
In some embodiments, the internal electron donor is selected from the group consisting of mono-or di-substituted phthalates, wherein the substituents are independently selected from the group consisting of linear or branched C1-10 alkyl, C3-8 cycloalkyl, and aryl radicals.
In some embodiments, the internal electron donor is selected from the group consisting of di-isobutyl phthalate, di-n-butyl phthalate, di-n-octyl phthalate, diphenyl phthalate, benzylbutyl phthalate, and combinations thereof.
In some embodiments, the internal electron donor is di-isobutyl phthalate.
In some embodiments, the esters of aliphatic acids are selected from the group consisting of malonic acids, glutaric acids, and succinic acids. In some embodiments, the esters of malonic acids are as described in Patent Cooperation Treaty Publication Nos. WO98/056830, WO98/056833, and WO98/056834. In some embodiments, the esters of glutaric acids are as described in Patent Cooperation Treaty Publication No. WO00/55215. In some embodiments, the esters of succinic acids are as described in Patent Cooperation Treaty Publication No. WO00/63261.
In some embodiments, the diesters are derived from esterification of aliphatic or aromatic diols. In some embodiments, the diesters are as described in Patent Cooperation Treaty Publication No. WO2010/078494 and U.S. Pat. No. 7,388,061.
In some embodiments, the internal electron donor is selected from 1,3-diethers of formula
wherein RI and RII are independently selected from C1-18 alkyl, C3-18 cycloalkyl, and C7-18 aryl radicals, RIII and RI are independently selected from C1-4 alkyl radicals; or the carbon atom in position 2 of the 1,3-diether belongs to a cyclic or polycyclic structure made up of from 5 to 7 carbon atoms, or of 5-n or 6-n′ carbon atoms, and respectively n nitrogen atoms and n′ heteroatoms selected from the group consisting of N, O, S, and Si, where n is 1 or 2 and n′is 1, 2, or 3, wherein the structure containing two or three unsaturations (cyclopolyenic structures), and optionally being condensed with other cyclic structures, or substituted with one or more substituents selected from the group consisting of linear or branched alkyl radicals; cycloalkyl, aryl, aralkyl, alkaryl radicals, and halogens, or being condensed with other cyclic structures and substituted with one or more of the above mentioned substituents, wherein one or more of the alkyl, cycloalkyl, aryl, aralkyl, or alkaryl radicals and the condensed cyclic structures optionally contain one or more heteroatom(s) as substitutes for carbon or hydrogen atoms. In some embodiments, the substituents are bonded to the condensed cyclic structures. In some embodiments, the ethers are as described in European Patent Application Nos. EP361493 and EP728769 or Patent Cooperation Treaty Publication No. WO02/100904.
In some embodiments, 1,3-diethers are used and the external electron donor (3) is absent.
In some embodiments, mixtures of internal donors are used. In some embodiments, the mixtures are between aliphatic or aromatic mono or dicarboxylic acid esters and 1,3-diethers as described in Patent Cooperation Treaty Publication Nos. WO07/57160 and WO2011/061134.
In some embodiments, the magnesium halide support is magnesium dihalide.
In some embodiments, the amount of internal electron donor which remains fixed on the solid catalyst component (1) is 5 to 20% by moles, with respect to the magnesium dihalide.
In some embodiments, preparation of the solid catalyst components involves a reaction of Mg dihalide precursors with titanium chlorides to form the Mg dihalide support. In some embodiments, the reaction is carried out in the presence of the stereoregulating internal donor.
In some embodiments, the magnesium dihalide precursor is a Lewis adduct of formula MgCl2·nR1OH, wherein n is a number between 0.1 and 6, and R1 is a hydrocarbon radical having 1-18 carbon atoms. In some embodiments, n ranges from 1 to 5, alternatively from 1.5 to 4.5.
In some embodiments, the adduct is prepared by mixing alcohol and magnesium chloride, operating under stirring conditions at the melting temperature of the adduct (100-130° C.).
Then, the adduct is mixed with an inert hydrocarbon immiscible with the adduct, thereby creating an emulsion which is quickly quenched causing the solidification of the adduct in the form of spherical particles.
In some embodiments, the adduct is directly reacted with the Ti compound or subjected to thermal controlled dealcoholation (80-130° C.), thereby obtaining an adduct wherein the number of moles of alcohol is lower than 3, alternatively between 0.1 and 2.5.
In some embodiments, this controlled dealcoholation step is carried out to increase the morphological stability of the catalyst during polymerization or to increase the catalyst porosity as described in European Patent Application No. EP395083A2.
In some embodiments, the reaction with the Ti compound is carried out by suspending the optionally dealcoholated adduct in cold TiCl4. In some embodiment, cold TiCl4 is at 0° C. In some embodiments, the mixture is heated up to 80-130° C. and kept at this temperature for 0,5-2 hours. In some embodiments, the treatment with TiCl4 is carried out one or more times. In some embodiments, the stereoregulating internal donor is added during the treatment with TiCl4. In some embodiments, the treatment with the internal donor is repeated one or more times.
In some embodiments, the preparation of catalyst components is as described in U.S. Pat. No. 4,399,054, U.S. Pat. No. 4,469,648, Patent Cooperation Treaty Publication No. WO98/44009A1, or European Patent Application No. EP395083A2.
In some embodiments, catalyst component (1) is in the form of spherical particles, having an average diameter ranging from 10 to 350 μm, a surface area ranging from 20 to 250 m2/g, alternatively from 80 to 200 m2/g, and a porosity greater that 0.2 ml/g, alternatively of from 0.25 to 0.5 ml/g, wherein the surface area and the porosity are measured by BET.
In some embodiments, the catalyst system is made from or containing an Al-containing cocatalyst (2). In some embodiments, the Al-containing cocatalyst (2) is selected from Al-trialkyls, alternatively the group consisting of Al-triethyl, Al-triisobutyl, and Al-tri-n-butyl.
In some embodiments, the Al/Ti weight ratio in the catalyst system is from 1 to 1000, alternatively from 20 to 800.
In some embodiments, the catalyst system is further made from or containing electron donor compound (3) (external electron donor). In some embodiments, the external electron donor is selected from the group consisting of silicon compounds, ethers, esters, amines, heterocyclic compounds, and ketones. In some embodiments, the heterocyclic compound is 2,2,6,6-tetramethylpiperidine.
In some embodiments, the external donor is selected from the group consisting of silicon compounds of formula (R2)a(R3)bSi(OR4)c, where a and b are integers from 0 to 2, c is an integer from 1 to 4, and the sum (a+b+c) is 4; R2, R3, and R4 are alkyl, cycloalkyl or aryl radicals with 1-18 carbon atoms, optionally containing heteroatoms. In some embodiments, a is 1, b is 1, c is 2, at least one of R2 and R3 is selected from branched alkyl, cycloalkyl or aryl groups with 3-10 carbon atoms, optionally containing heteroatoms, and R4 is a C1-C10 alkyl group. In some embodiments, R4 is a methyl group.
In some embodiments, the silicon compounds are selected from the group consisting of methylcyclohexyldimethoxysilane (C-donor), diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane (D-donor), diisopropyldimethoxysilane, (2-ethylpiperidinyl)t-butyldimethoxysilane, (2-ethylpiperidinyl)thexyldimethoxysilane, (3,3,3-trifluoro-n-propyl)(2-ethylpiperidinyl)dimethoxysilane, methyl(3,3,3-trifluoro-n-propyl)dimethoxysilane, and combinations thereof.
In some embodiments, the silicon compounds are wherein a is 0, c is 3, R3 is a branched alkyl or cycloalkyl group, optionally containing heteroatoms, and R4 is methyl. In some embodiments, the silicon compounds are selected from the group consisting of cyclohexyltrimethoxysilane, t-butyltrimethoxysilane, and hexyltrimethoxysilane.
In some embodiments, the catalyst system is made from or containing di-isobutyl phthalate as internal electron donor and dicyclopentyl dimethoxy silane (D-donor) as external electron donor.
In some embodiments, the catalyst system is pre-contacted with small quantities of olefin (prepolymerization), maintaining the catalyst in suspension in a hydrocarbon solvent and polymerizing at temperatures from 25° to 60° C., thereby producing a quantity of polymer from about 0.5 to about 3 times the weight of the catalyst system.
In some embodiments, the prepolymerization is carried out in liquid monomer, thereby producing a quantity of polymer 1000 times the weight of the catalyst system.
In some embodiments, sequential polymerization processes for preparing the heterophasic polypropylene (a) are as described in European Patent No. EP472946 and Patent Cooperation Treaty Publication No. WO03/011962, which content is incorporated in this patent application.
In some embodiments, components (A) and (B) are produced in any of the polymerization stages.
In some embodiments, the process to prepare the heterophasic polypropylene (a) includes at least two polymerization stages carried out in the presence of a highly stereospecific Ziegler-Natta catalyst system, wherein:
(I) in the first copolymerization stage, monomers are polymerized to form the propylene copolymer (A); and
(II) in the second copolymerization stage, the relevant monomers are polymerized to form the propylene copolymer (B), thereby obtaining polymer granules.
In some embodiments, the second copolymerization stage (II) includes a first copolymerization stage (IIa) and a second copolymerization stage (IIb), wherein the appropriate comonomers are polymerized to form the propylene copolymer (B1) in first copolymerization stage (IIa), and the appropriate comonomers are polymerized to form the propylene copolymer (B2) in the second copolymerization stage (IIb).
In some embodiments, the polymerization is continuous or batch. In some embodiments, the polymerization is carried out according to cascade techniques, operating either in mixed liquid phase/gas phase or totally in gas phase.
In some embodiments, the liquid-phase polymerization is in slurry, solution, or bulk (liquid monomer). In some embodiments, the liquid-phase polymerization is carried out in various types of reactors. In some embodiments, the reactors are continuous stirred tank reactors, loop reactors, or plug-flow reactors.
In some embodiments, the gas-phase polymerization stages are carried out in gas-phase reactors. In some embodiments, the gas-phase reactors are fluidized or stirred, fixed bed reactors.
In some embodiments, the copolymerization stage (I) is carried out in liquid phase, using liquid propylene as diluent. In some embodiments, the copolymerization stage (II), or the copolymerization stages (IIa) and (IIb), are carried out in the gas phase.
In some embodiments, the copolymerization stage (I) is carried out in the gas phase.
In some embodiments, the reaction temperatures of the polymerization stages (I) and (II) are independently selected in the range from 40° to 90° C.
In some embodiments, the polymerization pressure of the copolymerization stage (I) carried out in liquid phase is from 3.3 to 4.3 MPa.
In some embodiments, the polymerization pressure of the copolymerization stages (I) and (II) carried out in gas-phase is independently selected in the range from 0.5 to 3.0 MPa.
In some embodiments, the residence time of each polymerization stage depends upon the ratio of component (A) to component (B). In some embodiments, the residence time in each polymerization stage ranges from 15 minutes to 8 hours.
In some embodiments and in a sequential polymerization process, the amounts of components (A) and (B) in the heterophasic polypropylene (a) correspond to the split between the polymerization reactors.
In some embodiments, the molecular weight of the propylene copolymers obtained in each polymerization stage is regulated using chain transfer agents. In some embodiments, the chain transfer agent is hydrogen or ZnEt2
In some embodiments, the process to prepare the heterophasic polypropylene (a) further includes a step (III) of melt mixing the polymer granules with an organic peroxide or an additive (C) selected from the group consisting of antistatic agents, anti-oxidants, anti-acids, melt stabilizers, and combinations thereof.
In some embodiments, step (III) includes melt mixing the polymer granules with up to and including 1.0% by weight, alternatively from 0.01% to 0.8% by weight, alternatively from 0.01% to 0.5% by weight, of the additive (C) or with up to and including 0.2% by weight, alternatively up to and including 0.1% by weight, of the organic peroxide, wherein:
-the additive (C) is selected from the group consisting of antistatic agents, anti-oxidants, anti-acids, melt stabilizers and combinations thereof; and
-the amounts of the additive and of the organic peroxide are based on the total weight of the polymer further made from or containing the additives, the peroxide, or both.
In some embodiments, the heterophasic polypropylene (a) is made from or containing up to and including 1.0% by weight, alternatively from 0.01% to 0.8% by weight, alternatively from 0.01% to 0.5% by weight, of the additive (C) selected from the group consisting of antistatic agents, anti-oxidants, anti-acids, melt stabilizers and combinations thereof, and up to and including 0.2% by weight, alternatively up to and including 0.1% by weight, of an organic peroxide, wherein the amounts of the additive and of the organic peroxide are based on the total weight of the polymer composition made from or containing the additives, the organic peroxide, or both.
In some embodiments, the heterophasic polypropylene (a) consists of components (A), (B), additive (C), and the organic peroxide.
In some embodiments, propylene polymer (b) is selected from propylene homopolymers and propylene copolymers containing up to and including 5% by weight of an alpha-olefin. In some embodiments, the alpha-olefin is selected from the group consisting of ethylene, butene-1, hexene-1, and combination thereof, wherein the amount of the alpha-olefin is based on the weight of the copolymer (b). In some embodiments, the alpha-olefin is ethylene. In some embodiments, the propylene polymer (b) is a homopolymer.
In some embodiments, the propylene polymer (b) has a melt flow rate MFR(b), measured according to ISO 1133 (230°° C., 2.16 kg), ranging from 800 to 2500 g/10 min, alternatively from 1000 to 2500 g/10 min., alternatively from 1500 to 2300 g/10 min. In some embodiments, the melt flow rate value of the polypropylene (b) is the melt flow rate of the polymer exiting the reactor, the polymer being not peroxide degraded. In some embodiments, the propylene polymer (b) is a homopolymer, having the above-mentioned melt flow rate.
In some embodiments, the propylene polymer (b) is a propylene homopolymer, having a
MFR(b) as described above and a molecular weight distribution Mw/Mn of up to and including 5.5, alternatively of up to and including 5.0. In some embodiments, the molecular weight distribution is equal to or greater than 3.5, alternatively equal to or greater than 4.0, for each upper limit.
In some embodiments, propylene polymer (b) is produced by a polymerization process carried out in the presence of a catalyst selected from the group consisting of metallocene compounds, highly stereospecific Ziegler-Natta catalyst systems, and combinations thereof. In some embodiments, propylene polymer (b) is produced by a polymerization process carried out in the presence of a metallocene compound as catalyst.
In some embodiments, the polymerization process is continuous or batch. In some embodiments, the polymerization is carried out in liquid or in gas phase.
In some embodiments, propylene polymer (c) is a propylene homopolymer or a propylene copolymer made from or containing up to and including 5% by weight, alternatively 0.1-5% by weight, of an alpha-olefin, based on the weight of (c). In some embodiments, the alpha-olefin is selected from the group consisting of ethylene, butene-1, hexene-1, and combinations thereof. In some embodiments, the alpha-olefin is ethylene. In some embodiments, the propylene polymer (c) is a homopolymer.
In some embodiments, the xylene soluble fraction at 25° C. of the propylene polymer (c) XS(c) is equal to or lower than 4% by weight.
In some embodiments, the propylene polymer (c) has a property selected from the following properties:
-a tensile modulus, measured according to the method ISO 527-1,-2, on 4 mm-thick injection molded plaques obtained according to the method ISO 1873-2 equal to or greater than 1200 MPa, alternatively equal to or greater than 1400 MPa. In some embodiments, the upper value of the tensile modulus is 2000 MPa, for each lower limit.
In some embodiments, the propylene polymer (c) is a propylene homopolymer having the properties listed above.
In some embodiments, the weight ratio of propylene polymer (b) to propylene polymer (c) in the filled polyolefin composition ranges from 3/1 to 1/2.
In some embodiments, propylene polymer (c) is produced by a polymerization process carried out in the presence of a catalyst selected from the group consisting of metallocene compounds, highly stereospecific Ziegler-Natta catalyst systems, and combinations thereof. In some embodiments, propylene polymer (c) is produced by a polymerization process carried out in the presence of a Ziegler-Natta catalyst system of the type described above in connection with preparation of heterophasic polypropylene (a).
In some embodiments, the polymerization process is continuous or batch. In some embodiments, the polymerization is carried out in liquid or in gas phase. In some embodiments, the polymerization is carried out in loop reactors, fluidized bed reactors, or a multizone circulating reactor.
In some embodiments, the filled polyolefin composition is made from or containing glass fibers (d). In some embodiments, the glass fibers have a diameter of up to and including 50 μm, alternatively ranging from 5 μm to 20 μm, alternatively from 8 μm to 15 μm, and a length equal to or lower than 10 mm, alternatively ranging from 0.1 mm to 10 mm, alternatively from 1 mm to 8 mm, alternatively from 2 mm to 6 mm.
In some embodiments, the glass fibers are e-glass fibers. In some embodiments, the glass fibers are sized fibers, that is, coated with a coupling agent, thereby increasing the compatibility of the fibers with the polymer into which the fibers are dispersed.
In some embodiments, compatibilizer (e) is present in the filled polyolefin composition. In some embodiments, compatibilizer (e) is a modified olefin polymer functionalized with polar compounds.
In some embodiments, the functionalized polar compounds are selected from the group consisting of acid anhydrides, carboxylic acids, carboxylic acid derivatives, primary and secondary amines, hydroxyl compounds, oxazoline, epoxides, ionic compounds, and combinations thereof. In some embodiments, the functionalized polar compounds are selected from the group consisting of unsaturated cyclic anhydrides, related aliphatic diesters, and diacid derivatives.
In some embodiments, compatibilizer (e) is a polyolefin functionalized with a compound selected from the group consisting of maleic anhydride, C1-C10 linear or branched dialkyl maleates, C1-C10 linear or branched dialkyl fumarates, itaconic anhydride, C1-C10 linear or branched itaconic acid, dialkyl esters, maleic acid, fumaric acid, itaconic acid, and mixtures thereof. In some embodiments, the polyolefin is selected from the group consisting of polyethylenes, polypropylenes, and mixtures thereof.
In some embodiments, compatibilizer (e) is a polyethylene or a polypropylene grafted with maleic anhydride (MAH-g-PP or MAH-g-PE).
In some embodiments, compatibilizer (e) is produced by functionalization processes carried out in solution, in the solid state or in the molten state. In some embodiments, compatibilizer (e) is produced by functionalization processes carried out in the molten state. In some embodiments, compatibilizer (e) is produced by reactive extrusion of the polymer in the presence of the grafting compound and of a free radical initiator. In some embodiments, functionalization of polypropylene or polyethylene with maleic anhydride is as described in European Patent Application No. EP0572028A1.
In some embodiments, the modified polyolefins are selected from products commercially available under the trademark Amplify™ TY from The Dow Chemical Company, the trademark Exxelor™ from ExxonMobil Chemical Company, the trademark Scona® TPPP from Byk (Altana Group), the trademark Bondyram from Polyram Group, the trademark Polybond® from Chemtura, and combinations thereof.
In some embodiments, the filled polyolefin composition is further made from or containing 0.5 to 20% by weight, alternatively from 3 to 20% by weight, alternatively from 5 to 15% by weight, of a polymer (g) selected from the group consisting of:
In some embodiments, the styrene block copolymer is selected from the group consisting of polystyrene-polybutadiene-polystyrene (SBS), polystyrene-poly(ethylene-butylene)-polystyrene (SEBS), polystyrene-poly(ethylene-propylene)-polystyrene (SEPS), polystyrene-polyisoprene-polystyrene (SIS), polystyrene-poly(isoprene-butadiene)-polystyrene (SIBS), and mixtures thereof. In some embodiments, the styrene block copolymer is a polystyrene-poly(ethylene-butylene)-polystyrene (SEBS).
In some embodiments, styrene or alpha-methylstyrene block copolymers are prepared by ionic polymerization of the relevant monomers. In some embodiments, styrene or alpha-methylstyrene block copolymers are commercially available under the tradename of Kraton™ from Kraton Polymers.
In some embodiments, the ethylene copolymer has at least 20% by weight, alternatively from 20% to 50% by weight, of units deriving from the alpha-olefin, based on the weight of the polyolefin (e). In some embodiments, the alpha-olefin is selected from the group consisting of butene-1, hexene-1, octene-1, and combinations thereof.
In some embodiments, the ethylene copolymers are commercially available under the tradename of Engage from The Dow Chemical Company. In some embodiments, the ethylene copolymers have the tradename Engage™ 8100 or Engage™ 8150. In some embodiments, the ethylene copolymers are prepared using solution polymerization processes carried out in the presence of a metallocene-based catalyst system.
In some embodiments, the filled polyolefin composition is prepared by metering components (a), (b), (c), (d), and optionally (e), (f), and (g), to an extruder, operated at a temperature in the range from 180° to 280° C. In some embodiments, the extruder is a twin screw extruder.
In some embodiments, the filled polyolefin composition has a melt flow rate MFR(tot), measured according to ISO 1133 (230° C., 2.16 kg), equal to or greater than 10 g/10 min., alternatively ranging from 10 to 50 g/10 min., alternatively from 12 to 30 g/10 min.
In some embodiments, the filled polyolefin composition has a property selected from the following properties measured on injection molded test specimens:
In some embodiments the HDT A is in the range 90°-110° C. In some embodiments, the Vicat A softening temperature is equal to or lower than 150° C. for each lower limit. The Heat Deflection Temperature A and the Vicat A softening temperature are determined on injection molded multipurpose bars obtained according to EN ISO 20753 (Type A1).
In some embodiments, the filled polyolefin composition has the properties listed above.
In some embodiments, the present disclosure provides a process for producing a molded article, including the steps of:
(I) melt blending the filled polyolefin composition, thereby forming a molten filled polyolefin composition; and
(II) pushing the molten filled polyolefin composition into the cavity of a mold and solidifying the molten filled polyolefin composition inside the cavity.
In some embodiments, the process is carried out using an injection molding apparatus.
In some embodiments, the present disclosure provides an article made from or containing the filled polyolefin composition. In some embodiments, the article is an injection-molded article. In some embodiments, the injection molded article is selected from the group consisting of vehicle interior trims, vehicle exterior trims, and under the hood articles.
The features describing the subject matter are not inextricably linked to each other. In some embodiments, a level of a feature does not involve the same level of the remaining features of the same or different components. In some embodiments, a range of features of components from (a) to (g) is combined independently from the level of other components.
The following examples are illustrative and not intended to limit the scope of the disclosure in any manner whatsoever.
The following methods are used to determine the properties indicated in the description, claims, and examples.
Melt Flow Rate: Determined according to the method ISO 1133 (230° C., 2.16 kg).
Solubility in xylene at 25° C.: 2.5 g of polymer sample and 250 ml of xylene were introduced into a glass flask equipped with a refrigerator and a magnetic stirrer. The temperature was raised in 30 minutes, up to 135° C. The resulting clear solution was kept under reflux and stirred for further 30 minutes. The solution was cooled in two stages. In the first stage, the temperature was lowered to 100° C. in air for 10 to 15 minutes, under stirring. In the second stage, the flask was transferred to a thermostatically-controlled water bath at 25° C. for 30 minutes. The temperature was lowered to 25° C., without stirring during the first 20 minutes, and maintained at 25° C., with stirring for the last 10 minutes. The formed solid was filtered on quick filtering paper (Whatman filtering paper grade 4 or 541). 100 ml of the filtered solution (S1) was poured into a pre-weighed aluminum container, which was heated to 140° C. on a heating plate under nitrogen flow, thereby removing the solvent by evaporation. The container was then kept in an oven at 80°° C. under vacuum until constant weight was reached. The amount of polymer soluble in xylene at 25° C. was then calculated. XS(tot) and XSA values were experimentally determined. The fraction of component (B) soluble in xylene at 25° C. (XSB) was calculated from the formula:
XS=W(A)×(XSA)+W(B)×(XSB)
wherein W(A) and W(B) are the relative amounts of components (A) and (B), respectively, and W(A)+W(B)=1.
Intrinsic viscosity of the xylene soluble fraction: to calculate the value of the intrinsic viscosity IV, the flow time of a polymer solution was compared with the flow time of the solvent tetrahydronaphthalene (THN). A glass capillary viscometer of Ubbelohde type was used. The oven temperature was adjusted to 135° C. Before starting the measurement of the solvent flow time t0, the temperature was stable (135°+0.2° C.). Sample meniscus detection for the viscometer was performed by a photoelectric device.
Sample preparation: 100 ml of the filtered solution (S1) were poured into a beaker and 200 ml of acetone were added under vigorous stirring. Precipitation of insoluble fraction was completed as evidenced by a clear solid-solution separation. The suspension was filtered on a weighed metallic screen (200 mesh). The beaker was rinsed. The precipitate was washed with acetone, thereby removing the o-xylene. The precipitate was dried in a vacuum oven at 70° C. until a constant weight was reached. 0.05 g of precipitate were dissolved in 50 ml of tetrahydronaphthalene (THN) at a temperature of 135° C. The efflux time/of the sample solution was measured and converted into a value of intrinsic viscosity [η] using Huggins' equation (Huggins, M. L., J. Am. Chem. Soc. 1942, 64, 11, 2716-2718) and the following data:
Comonomer content: determined by IR using Fourier Transform Infrared Spectrometer (FTIR). The spectrum of a pressed film of the polymer was recorded in absorbance vs. wavenumbers (cm−1). The following measurements were used to calculate ethylene and hexene-1 content:
The method was calibrated by using polymer standards based on 13C NMR analyses. Sample preparation: Using a hydraulic press, a thick sheet was obtained by pressing about 1 g of sample between two aluminum foils. Pressing temperature was 180±10° C. (356° F.), and about 10 kg/cm2 pressure was applied for about one minute (minimum two pressing operations for each specimen). A small portion was cut from the sheet to mold a film. The film thickness was between 0.02-0.05 cm.
HDT A: measured according to the method ISO 75/A (1.8 MPa).
Flexural modulus: Determined according to the method ISO 178:2019.
Strength and Elongation: Determined according to the method ISO 527-1,-2.
Vicat A softening temperature: Determined according to the method ISO 306 (A/50N).
Charpy impact strength test at 23° C.: measured according to ISO 179/1 eA 2010.
Preparation of compression molded plaques: obtained according to ISO 8986-2:2009.
Shore A and D on compression molded plaques: Determined according to the method ISO 868 (15 sec).
Thermal shrinkage: a plaque of 195×100×2.5 mm was molded in an injection molding machine Krauss Maffei KM250/1000C2 (250 tons of claiming force) under the following injection molding conditions:
wherein
195 and L are, respectively, the initial and measured dimensions of the plaque along the flow direction, in mm; and
100 and T are, respectively, the initial and measured dimensions of the plaque crosswise the flow direction, in mm.
Scratch resistance: measured according to the test specification WV PV 3952 (2021-03) on sample, cut out of a DIN A5 dimension grained with K85 type grain injection molded, using a loading weight of 10N .
The component (a) of the filled polyolefin composition was prepared by a polymerization process carried out in two gas phase reactors, connected in series and equipped with devices to transfer the product from the first reactor to the second reactor. A Ziegler-Natta catalyst system was used, and made from or containing :
The solid catalyst component was contacted with TEAL and DCPMS in a pre-contacting vessel, with a weight ratio of TEAL to the solid catalyst component of 4-5. The weight ratio TEAL/DCPMS was 10.
The catalyst system was then subjected to pre-polymerization by suspending the catalyst system in liquid propylene at 20° C. for about 30-32 minutes before introducing the catalyst system into the first polymerization reactor.
Propylene copolymer (A) was produced in the first gas phase reactor by feeding in a continuous and constant flow, the pre-polymerized catalyst system, hydrogen (used as molecular weight regulator), propylene, and hexene-1, in gaseous phase.
The propylene copolymer (A), coming from the first reactor, was discharged in a continuous flow and, after having been purged of unreacted monomers, was introduced, in a continuous flow, into the second gas phase reactor, together with quantitatively constant flows of propylene, ethylene, and hydrogen, in the gas state. In the second reactor, the propylene copolymer (B) was produced.
The polymerization conditions, molar ratio of the reactants, and composition of the copolymer obtained are shown in Table 1.
The polymer particles exiting the second reactor were subjected to a steam treatment, thereby removing the unreacted monomers and volatile compounds, and then dried.
The heterophasic polypropylene (a) was prepared by mixing the polymer particles exiting the degassing section of the reactor with the additives (C) and an organic peroxide in the amounts indicated in Table 2, in a twin screw extruder Berstorff ZE 25 (length/diameter ratio of screws: 34) and extruded under nitrogen atmosphere in the following conditions:
Irganox® 1010 was 2,2-bis[3-[,5-bis(1, 1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]-1,3-propanediyl-3,5-bis(1,1-dimethylethyl)-4- hydroxybenzene-propanoate; Irgafos® 168 was tris(2,4-di-tert.-butylphenyl)phosphite; Peroxan HX 2,5-dimethyl-2,5-di-(tert-butylperoxy)-hexane was commercially available from Pergan.
The properties of the heterophasic polypropylene (a) are reported in Table 3.
HECO2 (comparative): an heterophasic propylene polymer made from or containing:
The heterophasic propylene polymer (HECO2) had a MFR, measured according to the method ISO 1133 (230° C., 2.16 kg), of 2.7 g/10 min., a flexural modulus, measured according to the method ISO 178:2019, of 40 MPa, a xylene soluble fraction at 25° C. of 72.6 wt. % having an intrinsic viscosity of 1.94 dl/g, a Shore A value of 77, and a Shore D value of 20, measured on compression molded plaques according to the method ISO 868 (15 sec).
Metocene MF650Y: a propylene homopolymer having a MFR (ISO 1133-1, 230° C./2.16 Kg) of 1800 g/10 min., commercially available from LyondellBasell;
Moplen HP501L: a propylene homopolymer having a MFR (ISO 1133-1, 230° C./2.16 Kg) of 6 g/10 min., a xylene soluble fraction of 3% by weight, and a tensile modulus of 1500 MPa (ISO 527-1,-2), commercially available from LyondellBasell;
ECS 03 T497: E-glass fibers (chopped strands) having a filament diameter of 13.0 um and a strand length of 3.0 mm, commercially available from Nippon Electric Glass Co., Ltd .;
Chop Vantage® HP3270: chopped strands glass fibers silane-sized, having a fiber diameter of 10 um and a 4.5 mm length, commercially available from Nippon Electric Glass;
Exxelor PO 1020: a propylene homopolymer grafted with maleic anhydride, having an MA grafting level in the range of 0.5-1.0 wt. %, commercially available from ExxonMobil;
BK MB: a polypropylene masterbatch made from or containing 40 wt. % of carbon black (ASTM D1603) and Moplen EP548S (commercially available from LyondellBasell) as carrier;
Premix: a mixture of additive made from or containing organic oxides, antioxidants, pigments, and 15.8 wt. % (with respect to the premix) of Moplen HF501N (commercially available from LyondellBasell) as carrier for the additives.
The filled polyolefin compositions, having the composition indicated in Table 4, were prepared by mixing the components in a 40 mm Werner & Pfleiderer extruder (L/D of 48), operated under the following extruding conditions:
The compositions were tested for physical and mechanical properties on multipurpose bars obtained by injection molding according to the method EN ISO 20753 (Type A1). The test results are reported in Table 4.
The filled polyolefin compositions, having the composition indicated in Table 5, were prepared by mixing the components in a 40 mm Werner & Pfleiderer extruder (L/D of 48) extruder under the same extruding conditions used for example E1.
The compositions were tested for physical and mechanical properties on multipurpose bars obtained by injection molding according to the method 20753 (Type A1). The test results are reported in Table 5.
| Number | Date | Country | Kind |
|---|---|---|---|
| 21185064.9 | Jul 2021 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/067470 | 6/27/2022 | WO |
