Patent Application
20250136798
TPO (thermoplastic polyolefin) is one of the major plastic compounds used for car interior applications, including instrumental panels, door panels and seats. There are increasing governmental and consumer concerns regarding the air quality of a car interior. For example, in Asia, there are proposed regulations aimed at reducing the concentration of aldehydes in a car interior. China has proposed the following concentrations: formaldehyde less than 0.10 mg/m3, acetaldehyde less than 0.20 mg/m3, and acrolein less than 0.05 mg/m3. Polyolefin elastomers (POEs) are used extensively as impact modifiers in TPO formulations. The typical structure of the POE could be, for example, an ethylene/octene copolymer, an ethylene/butene copolymer, or an ethylene/hexene copolymer. However, such TPO formulations typically have higher aldehyde concentrations then what is required by the proposed law in China. Thus, there is a need for TPO formulations that contain lower concentrations of aldehydes. Such TPO formulations should also maintain excellent mechanical properties, such as elongation, tensile modulus, tensile strength, and impact strength.
Chinese Patent Application CN103788471A (English Abstract) discloses a “low-volatile organic compounds” polypropylene resin composition useful for high class, automotive interior parts. The compositions comprises a polypropylene resin, a volatile organic compound (VOC) inhibitor, and an acid-absorbing agent. The VOC inhibitor comprises the following components, by the weight percentage based on the total weight of the VOC inhibitor: 30%-70% of a fully vulcanized powder silicon rubber, 10%-65% of a zeolite powder, and 5%-40% of pseudo-boehmite. The average particle size of rubber particles of the fully vulcanized powder silicon rubber is 0.05-1 [mu] m, and the fully vulcanized powder silicon rubber has a cross-linking structure, and the gel content is 60 wt % or higher.
Chinese Patent Application CN103589072A (English Abstract) discloses a “low-Volatile Organic Compound (VOC)” polypropylene composite material for automobile interior parts. The low-VOC polypropylene composite material is prepared as follows: mixing a polypropylene, a high density polyethylene resin, a filler, a toughening agent, an odor absorbent, an antioxidant, a lubricant and a light stabilizer; pelleting using a double-vacuum, parallel double-screw extruder, and finally drying pellets in an oven. The polypropylene composite material is disclosed as low in VOC content.
European Patent Application EP2284219A1 discloses a polymer composition for use in making products with a thermoplastic process. The polymer composition comprises a functionalized polyolefin modified with unsaturated anhydrides or carboxylic acids and cyclodextrin. The cyclodextrin is covalently bonded to the functionalized polyolefin through a hydroxyl group of the cyclodextrin, whereby a reaction product is formed, and the cyclodextrin is substantially free of a compound in the central pore of the cyclodextrin ring.
International Publication WO2009/103615A1 discloses a fabric conditioning composition of pH less than 7. The composition comprises the following components: a) a quaternary ammonium; b) encapsulated particles comprising an inner shell of a formaldehyde polymer, preferably of the melamine/urea formaldehyde type, and, an outer shell of a non-formaldehyde polymer, preferably of the vinyl acetate and/or methylacrylate type; and c) a formaldehyde scavenger, preferably selected from the group comprising urea, ethylene urea, ethylacetamide, acetoacetamide and mixtures thereof.
U.S. Publication US2009/0227758 discloses a method for reducing the level of aldehyde impurities, the method comprising mixing an oxazolidine-forming amino alcohol with a polyol or polyamine containing one or more aldehyde impurities, and subjecting the resulting mixture to conditions, such that at least a portion of the aldehyde impurities in the polyol or polyamine react with the amino alcohol to reduce the level of aldehyde impurities in the polyol or polyamine. U.S. Publication US2010/0124524 discloses a method for scavenging airborne formaldehyde, which method comprises contacting the airborne formaldehyde with a formaldehyde scavenger of its Formula 1 as described therein.
U.S. Pat. No. 6,624,254 discloses the syntheses of silane functionalized polymers, and polymer conversions through coupling, hydrolysis, hydrolysis and neutralization, condensation, oxidation and hydrosilation (see abstract). See also, U.S. Pat. No. 6,258,902. Silyl-terminated polyolefins and/or silane functionalized polyolefins are disclosed in the following references: U.S. Pat. Nos. 6,075,103; 5,578,690; 5,741,858; H. Makio et al., Silanolytic Chain Transfer in Olefin Polymerization with Supported Single-Site Ziegler-Natta Catalysts, Macromolecules, 2001, 34, 4676-4679; S. B. Amin et al., Alkenylsilane Effects on Organotitanium-Catalyzed Ethylene Polymerization Toward Simultaneous Polyolefin Branch and Functional Group Introduction, J. Am. Chem. Soc., 2006, 128, 4506-4507.
U.S. Pat. No. 10,308,829 discloses polymeric compositions comprising a polyolefin having hydrolyzable silane groups, an organic peroxide, and optionally, a catalyst (see abstract) to catalyze hydrolyzation and condensation. A second step crosslinking was observed in the presence of a silanol condensation catalyst (for example, a sulfonic acid or a blocked sulfonic acid), to further link the hydrolysable silane groups in the polymer chain, to generate enhanced crosslinking efficiency. Hydrolyzable silane groups include alkoxy groups, aryloxy groups, aliphatic acyloxy groups, amino or substituted amino groups, and lower alkyl groups (see, for example, column 4, lines 30-49).
Additional polymer compositions and/or reduced odor compositions are disclosed in the following references: US20020019469, US20190225786, US20110160368, CN1840576A (English Abstract), CN103897567A (English Abstract), JP2008086436A (English Abstract), and WO 2015/082316.
However, there remains a need for new TPO compositions that have reduced aldehyde content, while maintaining excellent mechanical properties. These needs have been met by the following invention.
In a first aspect, a process to form a composition, the process comprising thermally treating at least the following components:
In a second aspect, a process to form a composition, the process comprising thermally treating at least the following component(s):
In a third aspect, a composition comprising at least the following components:
In a fourth aspect, a composition comprising at least the following component(s):
Polymer compositions, especially suited for TPO applications, have been discovered, as discussed above, and which provide excellent mechanical properties and low total aldehyde content. It has been discovered that the olefin/silane interpolymer acts as a toughing agent of the composition and also stabilizes free radicals generated by the propylene-based polymer during thermal treatment. The silane can reduce the amount of aldehydes, ketones and double bonds, and thus reduce odor in the TPO end use application, such as automotive interior parts.
As discussed, in a first aspect, a process to form a composition, the process comprising thermally treating at least the components as described above. In a second aspect, a process to form a composition, the process comprising thermally treating at least the component(s) as described above. In a third aspect, a composition comprising at least the following components a) and b) as described above. In a fourth aspect, a composition comprising at least the following component a) as described above.
Each process may comprise a combination of two or more embodiments, as described herein Each composition may comprise a combination of two or more embodiments, as described herein. Each component a and b may comprise a combination of two or more embodiments, as described herein. The following embodiments apply to the first through fourth aspects of the invention, unless stated otherwise.
As used herein, the term “peroxide,” refers to a reagent added to a polymer or a polymer composition. This term does not refer to peroxide generated, for example, as a by-product or reaction product, by a polymer or a composition. For example, this term does not refer to a residual amount of peroxide generated by thermally treating a polymer composition.
In one embodiment, or a combination of two or more embodiments, each described herein, the components are mixed during the thermal treatment.
In one embodiment, or a combination of two or more embodiments, each described herein, the composition (C) has a reduced total aldehyde content, as compared to a similar composition (SC) that comprises the same components, except that component a is replaced with a similar olefin-based polymer that contains the same monomer types as component a, except the olefin-based polymer does not contain the “at least one Si—H group,” and wherein the similar olefin-based polymer has a density that is within ±0.005 g/cc of the density of component a, and has a melt index (I2) that is within ±0.5 g/10 min of the melt index of component a; and wherein the reduced total aldehyde content is determined from the following Equation Y: Reduced Total Aldehyde Content (%)={[(total aldehydes content in (SC))−(total aldehyde content in (C))]/(total aldehyde content in (SC))}×100.
In one embodiment, or a combination of two or more embodiments, each described herein, the composition has a reduced total aldehyde content (%) that is ≥25%, or ≥30%, or ≥32%, or ≥35%, or ≥38%, or ≥40%, or ≥42%, or ≥45%, or ≥48%, or ≥50%, or ≥55%, or ≥60%, or ≥65%, or ≥70%, or ≥75%, or 78%, or ≥80%, or ≥82%, or ≥85%, or ≥88%, or >90%, or ≥92%, or >95%, or >97%, as determined from Equation Y.
In one embodiment, or a combination of two or more embodiments, each described herein, the total aldehyde content is selected from one or more of formaldehyde, acetaldehyde, acrolein or propionaldehyde, and further two or more of formaldehyde, acetaldehyde, acrolein or propionaldehyde, further three of more of formaldehyde, acetaldehyde, acrolein or propionaldehyde, further all four of formaldehyde, acetaldehyde, acrolein or propionaldehyde.
In one embodiment, or a combination of two or more embodiments, each described herein, the olefin/silane interpolymer of component a is an ethylene/silane interpolymer, and further an ethylene/alpha-olefin/silane interpolymer, and further an ethylene/alpha-olefin/silane terpolymer.
In one embodiment, or a combination of two or more embodiments, each described herein, component a has a density ≥0.855 g/cc, or ≥0.856 g/cc, or ≥0.857 g/cc, or ≥0.858 g/cc, or ≥0.859 g/cc, or ≥0.860 g/cc, or ≥0.861 g/cc, or ≥0.862 g/cc, or ≥0.863 g/cc, or ≥ 0.864 g/cc, or ≥0.865 g/cc, or ≥0.866 g/cc, or ≥0.867 g/cc, or ≥0.868 g/cc, or ≥0.869 g/cc, or ≥0.870 g/cc (1 cc=1 cm3). In one embodiment, or a combination of two or more embodiments, each described herein, component a has a density≤0.940 g/cc, or ≤0.930 g/cc, or ≤0.920 g/cc, or ≤0.910 g/cc, or ≤0.900 g/cc, or ≤0.890 g/cc, or ≤0.888 g/cc, or ≤0.886 g/cc, or ≤0.884 g/cc, or ≤0.882 g/cc, or ≤0.880 g/cc, or ≤0.879 g/cc.
In one embodiment, or a combination of two or more embodiments, each described herein, component a has a melt index (I2)≥0.2 g/10 min≥0.5 g/10 min, or ≥0.6 g/10 min, or ≥0.7 g/10 min, or ≥0.8 g/10 min. In one embodiment, or a combination of two or more embodiments, each described herein, component a has a melt index (I2)≤100 g/10 min, or ≤ 50 g/10 min, or ≤20 g/10 min, or ≤18 g/10 min, or ≤16 g/10 min, or ≤14 g/10 min, or ≤12 g/10 min, or ≤10 g/10 min, or ≤8.0 g/10 min, or ≤6.0 g/10 min, or ≤4.0 g/10 min, or ≤2.0 g/10 min, or ≤1.0 g/10 min.
In one embodiment, or a combination of two or more embodiments, each described herein, for component b, the propylene-based polymer, or the propylene-based polymer of the propylene-based composition, is each selected from the following: a) a polypropylene homopolymer, b) a propylene/ethylene interpolymer and further a propylene/ethylene copolymer, or c) a propylene/alpha-olefin interpolymer and further a propylene/alpha-olefin copolymer.
In one embodiment, or a combination of two or more embodiments, each described herein, component b has a density ≥0.860 g/cc, or ≥0.865 g/cc, or ≥0.870 g/cc, or ≥0.875 g/cc, or ≥0.880 g/cc, or ≥0.885 g/cc, or ≥0.890 g/cc, or ≥0.895 g/cc, or ≥0.898 g/cc. In one embodiment, or a combination of two or more embodiments, each described herein, component b has a density≤0.930 g/cc, or ≤0.925 g/cc, or ≤0.920 g/cc, or ≤0.915 g/cc, or ≤ 0.910 g/cc, or ≤0.905 g/cc, or ≤0.902 g/cc, or ≤0.900 g/cc.
In one embodiment, or a combination of two or more embodiments, each described herein, component b has a melt flow rate (MFR)≥1.0 g/10 min, or ≥5.0 g/10 min, or ≥10 g/10 min, or ≥20 g/10 min, or ≥30 g/10 min, or ≥40 g/10 min, or ≥45 g/10 min, or ≥50 g/10 min, or ≥55 g/10 min. In one embodiment, or a combination of two or more embodiments, each described herein, component b has a melt flow rate (MFR)≤120 g/10 min, or ≤100 g/10 min, or ≤90 g/10 min, or ≤80 g/10 min, or ≤75 g/10 min, or ≤70 g/10 min, or ≤65 g/10 min, or ≤62 g/10 min.
In one embodiment, or a combination of two or more embodiments, each described herein, the ratio of the density of component b to the density of component a is ≥0.80, or >0.85, or ≥0.90, or ≥0.92, or ≥0.94, or ≥0.96, or ≥0.98, or ≥1.00, or ≥1.01, or 1.02. In one embodiment, or a combination of two or more embodiments, each described herein, the ratio of the density of component b to the density of component a is ≤1.20, or ≤1.15, or ≤1.10, or ≤1.08, or ≤1.06, or ≤1.05, or ≤1.04, or ≤1.03.
In one embodiment, or a combination of two or more embodiments, each described herein, the silane of the olefin/silane interpolymer is derived from a silane monomer selected from Formula 1: A-(SiBC—O)x-Si-EFH (Formula 1), where A is an alkenyl group, B is a hydrocarbyl group or hydrogen, C is a hydrocarbyl group or hydrogen, and where B and C may be the same or different;
In one embodiment, or a combination of two or more embodiments, each described herein, Formula 1 is selected from the following compounds s1) through s16) below:
In one embodiment, or a combination of two or more embodiments, each described herein, the composition is thermally treated at a temperature ≥140° C., or ≥150° C., or ≥155° C., or ≥160° C., or ≥165° C., or ≥170° C., or ≥175° C., or ≥180° C., or ≥185° C., or ≥190° C., or ≥ 195° C., or ≥200° C. In one embodiment, or a combination of two or more embodiments, each described herein, the composition is thermally treated at a temperature≤250° C., or ≤240° C., or ≤230° C., or ≤225° C., or ≤220° C., or ≤215° C., or ≤210° C., or ≤205° C.
Also provided is a composition formed by a process of one embodiment, or a combination of two or more embodiments, each described herein, or formed from a composition of one embodiment, or a combination of two or more embodiments, each described herein.
Also provided is an article comprising at least one component formed a composition of one embodiment, or a combination of two or more embodiments, each described herein.
A silane monomer, as used herein, comprises at least one (type) Si—H group. In one embodiment, the silane monomer is selected from Formula 1, as discussed above.
Some examples of silane monomers include hexenylsilane, allylsilane, vinylsilane, octenylsilane, hexenyldimethylsilane, octenyldimethylsilane, vinyldimethylsilane, vinyldiethylsilane, vinyldi (n-butyl) silane, vinylmethyloctadecylsilane, vinyidiphenylsilane, vinyldibenzylsilane, allyldimethylsilane, allyldiethylsilane, allyldi (n-butyl) silane, allylmethyloctadecylsilane, allyldiphenylsilane, bishexenylsilane, and allyidibenzylsilane. Mixtures of the foregoing alkenylsilanes may also be used.
More specific examples of silane monomers include the following: (5-hexenyl-dimethylsilane (HDMS), 7-octenyldimethylsilane (ODMS), allyldimethylsilane (ADMS), 3-butenyldimethylsilane, 1-(but-3-en-1-yl)-1,1,3,3-tetramethyldisiloxane (BuMMH), 1-(hex-5-en-1-yl)-1,1,3,3-tetramethyldisiloxane (HexMMH), (2-bicyclo[2.2.1]hept-5-en-2-yl) ethyl)-dimethylsilane (NorDMS) and 1-(2-bicyclo[2.2.1]hept-5-en-2-yl) ethyl)-1,1,3,3-tetramethyldisiloxane (NorMMH). Mixtures of the foregoing alkenylsilanes may also be used.
Propylene-based polymers include, but are not limited to, polypropylene homopolymer, propylene/ethylene interpolymers and copolymers, and propylene/alpha-olefin interpolymers and copolymers.
A propylene-based composition that comprises a propylene-based polymer includes, but is not limited to, an impact modified composition. Impact modified compositions comprise a matrix polymer, which is typically toughened via blending with an elastomer. In one embodiment, the matrix polymer is a propylene-based polymer. Propylene-based polymers include, but are not limited to, polypropylene homopolymer, propylene/ethylene interpolymers and copolymers, and propylene/alpha-olefin interpolymers and copolymers.
In one embodiment, the propylene-based polymer is in the isotactic form of homopolymer polypropylene, although other forms of polypropylene homopolymer can also be used (e.g., syndiotactic or atactic).
Polypropylene impact copolymers (for example, those wherein a secondary copolymerization step reacting ethylene with the propylene) and random copolymers (also reactor modified, and usually containing 1.5-7.0 wt % ethylene copolymerized with the propylene) can also be used as the propylene-based polymer. A complete discussion of various propylene-based polymers is contained in Modern Plastics Encyclopedia/89, mid October 1988 Issue, Volume 65, Number 11, pp. 86-92, the entire disclosure of which is incorporated herein by reference.
The elastomer composition used to toughen the propylene-based polymer may be any elastomer with sufficient polypropylene compatibility and sufficiently low glass transition temperature to impart impact toughness to the polypropylene. In one embodiment, the elastomer is an ethylene/alpha-olefin interpolymer of copolymer. Suitable alpha-olefins include, but are not limited to, propylene, isobutylene, 1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, and the like. Propylene, 1-butene and 1-octene are especially preferred.
An inventive composition may comprise one or more additives. Additives include, but are not limited to, UV stabilizers, antioxidants, fillers, flame retardants, tackifiers, waxes, compatibilizers, adhesion promoters, plasticizers (for example, oils), antiblocking agents, anti-static agents, release agents, slipping agents, anti-cling additives, colorants, dyes, pigments, and combination thereof.
In one embodiment, or a combination of two or more embodiments, each described herein, the additive is present in an amount ≥0.05 wt %, ≥0.1 wt %, and/or ≤10 wt %, or ≤ 5.0 wt %, ≤2.0 wt %, or ≤1.5 wt %, or ≤1.0 wt %, or ≤0.8 wt %, or ≤0.6 wt %, or ≤0.4 wt %, or ≤0.3 wt %, or ≤0.2 wt %, based on the weight of the composition.
The term “bis-biphenyloxy metal complex,” as used herein, refers to a chemical structure comprising a metal or metal ion that is bonded and/or coordinated to one or more, and preferably two, biphenyloxy ligands. In one embodiment, the chemical structure comprises a metal that is bonded to two, biphenyloxy ligands, via an oxygen atom of each respective biphenyloxy ligand. The metal complex is typically rendered catalytically active by the use of one or more cocatalysts.
For example, see Formula DI below as a nonlimiting example:
Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percents are based on weight, and all test methods are current as of the filing date of this disclosure.
The term “composition,” as used herein, includes a mixture of materials, which comprise the composition, and may include, as well, reaction products and decomposition products formed from the materials of the composition. Any reaction product or decomposition product is typically present in trace or residual amounts.
The term “polymer,” as used herein, refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus includes the term homopolymer (employed to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure), and the term interpolymer as defined hereinafter.
Trace amounts of impurities, such as catalyst residues, can be incorporated into and/or within the polymer. Typically, a polymer is stabilized with very low amounts (“ppm” amounts) of one or more stabilizers.
The term “interpolymer,” as used herein, refers to polymer prepared by the polymerization of at least two different types of monomers. The term interpolymer thus includes the term copolymer (employed to refer to polymers prepared from two different types of monomers) and polymers prepared from more than two different types of monomers.
The term “olefin-based polymer,” as used herein, refers to a polymer that comprises, in polymerized form, at least 50 wt % or a majority weight percent of an olefin, such as ethylene or propylene (based on the weight of the polymer), and optionally may comprise one or more comonomers.
The term “propylene-based polymer,” as used herein, refers to a polymer that comprises, in polymerized form, a majority weight percent of propylene (based on the weight of the polymer), and optionally may comprise one or more comonomers.
The term “propylene/alpha-olefin interpolymer,” as used herein, refers to an interpolymer (and preferably a random interpolymer) that comprises, in polymerized form, a majority weight percent of propylene (based on the weight of the interpolymer), and an alpha-olefin.
The term “propylene/alpha-olefin copolymer,” as used herein, refers to a copolymer (and preferably a random copolymer) that comprises, in polymerized form, a majority weight percent of propylene (based on the weight of the copolymer), and an alpha-olefin, as the only two monomer types.
The term “propylene/ethylene interpolymer,” as used herein, refers to a interpolymer (and preferably a random interpolymer) that comprises, in polymerized form, a majority weight percent of propylene (based on the weight of the interpolymer), and ethylene.
The term “propylene/ethylene copolymer,” as used herein, refers to a copolymer (and preferably a random copolymer) that comprises, in polymerized form, a majority weight percent of propylene (based on the weight of the copolymer), and ethylene, as the only two monomer types.
The term “ethylene-based polymer,” as used herein, refers to a polymer that comprises, in polymerized form, at least 50 wt % or a majority weight percent of ethylene (based on the weight of the polymer), and optionally may comprise one or more comonomers.
The term “ethylene/alpha-olefin interpolymer,” as used herein, refers to a random interpolymer that comprises, in polymerized form, at least 50 wt % or a majority weight percent of ethylene (based on the weight of the interpolymer), and an alpha-olefin.
The term, “ethylene/alpha-olefin copolymer,” as used herein, refers to a random copolymer that comprises, in polymerized form, at least 50 wt % or a majority weight percent of ethylene (based on the weight of the copolymer), and an alpha-olefin, as the only two monomer types.
The term “olefin/silane interpolymer,” as used herein, refers to a random interpolymer that comprises, in polymerized form, at least 50 wt % or a majority weight percent of an olefin (based on the weight of the interpolymer), and a silane monomer. As used herein, the interpolymer comprises at least one Si—H group, and the phrase “at least one Si—H group” refers to a type of “Si-H” group. It is understood in the art that the interpolymer would contain a multiple number of these groups. The olefin/silane interpolymer is formed by the copolymerization (for example, using a bis-biphenyloxy metal complex (or bis-biphenyl-phenoxy metal complex)) of at least the olefin and the silane monomer. An example of a silane monomer is depicted in Formula 1, as described above.
The term “ethylene/silane interpolymer,” as used herein, refers to a random interpolymer that comprises, in polymerized form, at least 50 wt % or a majority weight percent of ethylene (based on the weight of the interpolymer), and a silane monomer. As used herein, the interpolymer comprises at least one Si—H group as discussed above. The ethylene/silane interpolymer is formed by the copolymerization of at least the ethylene and the silane monomer.
The term “ethylene/alpha-olefin/silane interpolymer,” as used herein, refers to a random interpolymer that comprises, in polymerized form, at least 50 wt % or a majority weight percent of ethylene (based on the weight of the interpolymer), an alpha-olefin and a silane monomer. As used herein, these interpolymer comprises at least one Si—H group, as discussed above. The ethylene/silane interpolymer is formed by the copolymerization of at least the ethylene, the alpha-olefin and the silane monomer.
The term “ethylene/alpha-olefin/silane terpolymer,” as used herein, refers to a random terpolymer that comprises, in polymerized form, at least 50 wt % or a majority weight percent of ethylene (based on the weight of the terpolymer), an alpha-olefin and a silane monomer as the only three monomer types. As used herein, the terpolymer comprises at least one Si—H group, as discussed above. The ethylene/silane terpolymer is formed by the copolymerization of the ethylene, the alpha-olefin and the silane monomer, as the only three monomer types.
The term “olefin multi-block interpolymer,” as used herein, refers to an interpolymer that is characterized by multiple blocks or segments of two or more polymerized monomer units, differing in chemical or physical properties. In some embodiments, the multi-block interpolymers can be represented by the following formula: (AB)n, where n is at least 1, preferably an integer greater than 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or higher. Here, “A” represents a hard block or segment, and “B” represents a soft block or segment. Preferably the A segments and the B segments are linked in a substantially linear fashion, as opposed to a substantially branched or substantially star-shaped fashion. Preferably, the A segments and the B segments are randomly distributed along the polymer chain. These multi block interpolymers, in general, are produced via a chain shuttling process, such as, for example, described in U.S. Pat. No. 7,858,706, which is herein incorporated by reference. See also U.S. Pat. Nos. 9,243,173; 7,608,668; 7,893,166; 7,947,793; and U.S. Publication 2020/0197880; all incorporated herein by reference. The interpolymer comprises, in polymerized form, at least 50 wt % or a majority weight percent of an olefin, such as ethylene or propylene (based on the weight of the multi-block interpolymer), and one or more comonomers.
The term “ethylene/alpha-olefin multi-block interpolymer,” as used herein, refers to an interpolymer that is characterized by multiple blocks or segments of two or more polymerized monomer units, differing in chemical or physical properties, as described above for olefin multi-block interpolymer. The ethylene/alpha-olefin multi-block interpolymer comprises, in polymerized form, at least 50 wt % or a majority weight percent of ethylene (based on the weight of the multi-block interpolymer), and an alpha-olefin.
The term “ethylene/alpha-olefin multi-block copolymer,” as used herein, refers to a copolymer that is characterized by multiple blocks or segments of two polymerized monomer units, differing in chemical or physical properties, as described above for olefin multi-block interpolymer. The ethylene/alpha-olefin multi-block copolymer comprises, in polymerized form, at least 50 wt % or a majority weight percent of ethylene (based on the weight of the multi-block copolymer), and an alpha-olefin, as the only two monomer types.
The phrase “a majority weight percent,” as used herein, in reference to a polymer (or interpolymer, or terpolymer or copolymer), refers to the amount of monomer present in the greatest amount in the polymer.
The term “propylene-based composition,” as used herein, refers to a composition comprising a propylene-based polymer.
The phrase “total aldehyde content,” as used herein, refers to the amount of one or more aldehyde compound(s), each which can be detected by the “Carbonyl Analysis” described herein. Typically, the “total aldehyde content” includes the sum of one or more of formaldehyde, acetaldehyde, acrolein and propionaldehyde, and further two or more of formaldehyde, acetaldehyde, acrolein and propionaldehyde, further three of more of formaldehyde, acetaldehyde, acrolein and propionaldehyde, further all four of formaldehyde, acetaldehyde, acrolein and propionaldehyde.
The term “heteroatom,” refers to an atom other than hydrogen or carbon (for example, O, S, N or P). The term “heteroatom group” refers to a heteroatom or to a chemical group containing one or more heteroatoms.
The terms “hydrocarbon,” “hydrocarbyl,” and similar terms, as used herein, refer to a respective compound or chemical group, etc., containing only carbon and hydrogen atoms. A divalent “hydrocarbylene group” is defined in similar manner.
The terms “heterohydrocarbon,” “heterohydrocarbyl,” and similar terms, as used herein, refer to a respective hydrocarbon,” or “hydrocarbyl group, etc., in which at least one carbon atom is substituted with a heteroatom group (for example, O, S, N or P). The monovalent heterohydrocarbyl group may be bonded to the remaining compound of interest via a carbon atom or via a heteroatom. A divalent “heterohydrocarbylene group” is defined in similar manner; and the divalent heterohydrocarbylene group may be bonded to the remaining compound of interest via two carbon atoms, or two heteroatoms, or a carbon atom and a heteroatom.
The terms “substituted hydrocarbon,” “substituted hydrocarbyl group,” and similar terms, as used herein, refer to a respective hydrocarbon or hydrocarbyl group, etc., in which one or more hydrogen atoms is/are independently substituted with a heteroatom group.
The terms “substituted heterohydrocarbon,” “substituted heterohydrocarbyl group,” and similar terms, as used herein, refer to a respective heterohydrocarbon or heterohydrocarbyl group, etc., in which one or more hydrogen atoms is/are independently substituted with a heteroatom group.
The term “substituted or unsubstituted (C1-C30)hydrocarbyl,” and other like terms, as used herein, denoted the range of total carbon atoms (for example, 1 to 30) that a substituted or unsubstituted hydrocarbyl radical may contain.
The term “substituted or unsubstituted (C1-C30)heterohydrocarbyl,” and other like terms, as used herein, denoted the range of total carbon atoms (for example, 1 to 30) that a “substituted or unsubstituted heterohydrocarbyl radical may contain.
The terms “thermally treating,” “thermal treatment,” and similar terms, as used herein, in reference to a composition comprising an olefin/silane interpolymer, refer to the application of heat to the composition. Heat may be applied by electrical means (for example, a heating coil) and/or by radiation and/or by hot oil and/or mechanical shearing. Note, the temperature at which the thermal treatment takes place, refers to the temperature of the composition (for example, the melt temperature of the composition).
The term “alkenyl group,” as used herein, refers to an organic chemical group that contains at least one carbon-carbon double bond (C═C). In a preferred embodiment, the alkenyl group is a hydrocarbon group containing at least one carbon-carbon double bond, and further containing only one carbon-carbon double bond.
The term “bis-biphenyloxy,” as used herein, refers to an organic chemical group that comprises at least one biphenyl structure that is bonded to at least one oxygen atom, and preferably comprises two biphenyl structures, and each structure is independently bonded to at least one oxygen atom.
The phrase “formed in the presence of a bis-biphenyloxy metal complex,” in reference to an olefin/silane interpolymer, refers to the polymerization of the monomer constituents of such interpolymer in the presence of the bis-biphenyloxy metal complex.
The terms “comprising,” “including,” “having,” and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether the same is specifically disclosed. In order to avoid any doubt, all compositions claimed through use of the term “comprising” may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term, “consisting essentially of” excludes from the scope of any succeeding recitation, any other component, step or procedure, excepting those that are not essential to operability. The term “consisting of” excludes any component, step or procedure, not specifically delineated or listed.
where each of R1 and R2 is independently hydrogen or an alkyl group, and wherein R1, and R2 may be the same or different, and n is from 1 to 10, or 1 to 8, or 1 to 6, or 1 to 4, or 1 to 2, or 1; or
where each of R1 and R2 is independently hydrogen or an alkyl group, and wherein R1, and R2 may be the same or different, and n is from 1 to 10, or 1 to 8, or 1 to 6, or 1 to 4, or 1 to 2, or 1.
where n is from 1 to 10, or 1 to 8, or 1 to 6, or 1 to 4, or 1 to 2, or 1; or
where n is from 1 to 10, or 1 to 8, or 1 to 6, or 1 to 4, or 1 to 2, or 1.
Polymer composition (200 g, pellets) was placed inside a gas bag (10 L, TEDLAR PVF, Dalian Delin Gas Packaging Co. Ltd.) along with nitrogen (5 L). The bag and its contents were thermally treated in an oven (Binder FED 115, equilibrated at 65° C.) for two hours, before being analyzed via the carbonyl analysis. Prior to analysis, the gas bag was washed three times with nitrogen, and a “blank gas bag” was also analyzed.
Carbonyl analysis was performed with a 4 liter sample from the bag, and using DNPH HPLC method (LOD: 0.01 mg/m3). The nitrogen gas in the bag was pumped out, for the carbonyl analysis, using an air pump. Then, the carbonyl compounds were extracted, and injected into a high-performance liquid chromatography (HPLC) column, and separated using a gradient elution. The separated compounds were then quantified by UV detection at 360 nm, with a detection limit of 0.01 mg/m3. Carbonyl analysis provided the concentration of aldehydes, such as formaldehyde, acetaldehyde, acrolein, propionaldehyde, and crotonaldehyde, present in the sample.
DNPH cartridges (CNWBOND DNPH-Silica cartridge, 350 mg, Cat. No. SEEQ-144102, Anple Co. Ltd.) were employed to absorb the carbonyls emitted from the gas bag. The sampling speed was 330 mL/min, and the sampling time was 13 minutes (sampling via an air pump). After absorption, the DNPH cartridges are eluted with 1 gram (precisely weighed) of ACN, and the ACN solution was analyzed by HPLC to quantify the carbonyls in the sample.
The standard solution, with six DNPH derivatives (TO11A carbonyl-DNPH mix, Cat. No. 48149-U, 15 ppm for each individual compound, Supelco Co. Ltd.) was diluted with acetonitrile, and the final solution (0.794 ppm wt (standard)/wt (acetonitrile)) was restored in a 2 mL vial for instrument calibration at −4° C. (refrigerator). The “0.794 ppm (wt/wt)” standard solution was injected into the HPLC system as a “one point external standard” for quantification of carbonyls in the sample. The first two peaks were identified as formaldehyde and acetaldehyde according to the standard specification.
The response factor was calculated for each derivative, according to the formula: Response factor
where: Response factor i=Response factor of derivative i, Peak Area i=Peak Area of derivative i in the standard solution, and 0.794=standard concentration of 0.794 ppm. The concentration of the aldehyde-DNPH derivative in the sample solution was calculated based on the formula: Concentration of
where Concentration of i=Concentration of aldehyde-DNPH derivative in the sample solution, Peak Area i=Peak Area of Derivative i in the sample solution, Response factor i=Response factor of derivative i. The HPLC conditions are shown in Table A below:
The Tensile test on dog-bone test specimens was carried out at 23° C., using a tensile machine (Zwick) at a rate of 50 mm/min. Yield strength and elongation at break were monitored by analyzing the generated stress-strain curve. The elongation at break was defined as a ratio of the distance up to the breaking point to the chuck distance (114 mm). Testing was conducted in the ASTM environment: 23° C. and 50% humidity.
The IZOD impact test was conducted as specified in ISO 180 standard, with an impact tester (Ceast 6960.000) at 23° C. (RT) and −30° C. The specimens (dog-bone) were kept at the test temperature for ≥30 minutes prior to testing. Testing was conducted in the ASTM environment: 23° C. and 50% humidity.
The chromatographic system consisted of a PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph, equipped with an internal IR5 infra-red detector (IR5). The autosampler oven compartment was set at 1600 Celsius, and the column compartment was set at 150° Celsius. The columns were four AGILENT “Mixed A” 30 cm, 20-micron linear mixed-bed columns. The chromatographic solvent was 1,2,4-trichloro-benzene, which contained 200 ppm of butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume used was 200 microliters, and the flow rate was 1.0 milliliters/minute.
Calibration of the GPC column set was performed with 21 narrow molecular weight distribution polystyrene standards, with molecular weights ranging from 580 to 8,400,000, and which were arranged in six “cocktail” mixtures, with at least a decade of separation between individual molecular weights. The standards were purchased from Agilent Technologies. The polystyrene standards were prepared at “0.025 grams in 50 milliliters” of solvent, for molecular weights equal to, or greater than, 1,000,000, and at “0.05 grams in 50 milliliters” of solvent, for molecular weights less than 1,000,000. The polystyrene standards were dissolved at 80 degrees Celsius, with gentle agitation, for 30 minutes. The polystyrene standard peak molecular weights were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):
M
polyethylene
=A×(Mpolystyrene) (EQ1),
where M is the molecular weight, A has a value of 0.4315 and B is equal to 1.0.
A fifth order polynomial was used to fit the respective polyethylene-equivalent calibration points. A small adjustment to A (from approximately 0.375 to 0.445) was made to correct for column resolution and band-broadening effects, such that linear homopolymer polyethylene standard is obtained at 120,000 Mw. The total plate count of the GPC column set was performed with decane (prepared at “0.04 g in 50 milliliters” of TCB, and dissolved for 20 minutes with gentle agitation.) The plate count (Equation 2) and symmetry (Equation 3) were measured on a 200 microliter injection according to the following equations:
where RV is the retention volume in milliliters, the peak width is in milliliters, the peak max is the maximum height of the peak, and ½ height is ½ height of the peak maximum; and
volume in milliliters, and the peak width is in milliliters, Peak max is the maximum position of the peak, one tenth height is 1/10 height of the peak maximum, and where rear peak refers to the peak tail at later retention volumes than the peak max, and where front peak refers to the peak front at earlier retention volumes than the peak max. The plate count for the chromatographic system should be greater than 18,000, and symmetry should be between 0.98 and 1.22.
Samples were prepared in a semi-automatic manner with the PolymerChar “Instrument Control” Software, wherein the samples were weight-targeted at 2 mg/ml, and the solvent (contained 200 ppm BHT) was added to a pre nitrogen-sparged, septa-capped vial, via the PolymerChar high temperature autosampler. The samples were dissolved for two hours at 160° Celsius under “low speed” shaking.
The calculations of Mn(GPC), Mw(GPC), and Mz(GPC) were based on GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph according to Equations 4-6, using PolymerChar GPCOne™ software, the baseline-subtracted IR chromatogram at each equally-spaced data collection point (i), and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve for the point (i) from Equation 1. Equations 4-6 are as follows:
In order to monitor the deviations over time, a flowrate marker (decane) was introduced into each sample, via a micropump controlled with the PolymerChar GPC-IR system. This flowrate marker (FM) was used to linearly correct the pump flowrate (Flowrate(nominal)) for each sample, by RV alignment of the respective decane peak within the sample (RV(FM Sample)), to that of the decane peak within the narrow standards calibration (RV(FM Calibrated)). Any changes in the time of the decane marker peak were then assumed to be related to a linear-shift in flowrate (Flowrate(effective)) for the entire run. To facilitate the highest accuracy of a RV measurement of the flow marker peak, a least-squares fitting routine was used to fit the peak of the flow marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation was then used to solve for the true peak position. After calibrating the system, based on a flow marker peak, the effective flowrate (with respect to the narrow standards calibration) was calculated as Equation 7: Flowrate(effective)=Flowrate(nominal)*(RV(FM Calibrated)/RV(FM Sample)) (EQ7). Processing of the flow marker peak was done via the PolymerChar GPCOne™ Software. Acceptable flowrate correction is such that the effective flowrate should be within +/−0.7% of the nominal flowrate.
The melt index I2 (or MI) of an ethylene-based polymer is measured in accordance with ASTM D-1238, condition 190° C./2.16 kg (melt index I10 at 190° C./10.0 kg). The I10/I2 was calculated from the ratio of 110 to the 12. The melt flow rate MFR of a propylene-based polymer is measured in accordance with ASTM D-1238, condition 230° C./2.16 kg.
Melt flow rate (MFR) of a composition (see expt. section) was measured using pellets in accordance with ASTM D-1238, condition 230° C./2.16 kg.
ASTM D4703 was used to make a polymer plaque for density analysis. ASTM D792, Method B, was used to measure the density of each polymer.
For 13C NMR experiments, samples were dissolved, in 10 mm NMR tubes, in tetrachloroethane-d2 (with or without 0.025 M Cr(acac)3). The concentration was approximately 300 mg/2.8 mL. Each tube was then heated in a heating block set at 110° C. The sample tube was repeatedly vortexed and heated to achieve a homogeneous flowing fluid. The 13C NMR spectrum was taken on a BRUKER AVANCE 600 MHz spectrometer, equipped with a 10 mm C/H DUAL cryoprobe. The following acquisition parameters were used: 60 seconds relaxation delay, 90 degree pulse of 12.0 μs, 256 scans. The spectrum was centered at 100 ppm, with a spectral width of 250 ppm. All measurements were taken without sample spinning at 110° C. The 13C NMR spectrum was referenced to “74.5 ppm” for the resonance peak of the solvent. For a sample with Cr, the data was taken with a “7 seconds relaxation delay” and 1024 scans. The “mol % silane (silane monomer)” was calculated based on the integration of SiMe carbon resonances, versus the integration of CH2 carbons associated with ethylene units and CH/CH3 carbons associated with octene units. The “mol % octene (or other alpha-olefin)” was similarly calculated with reference to the CH/CH3 carbons associated with octene (or other alpha-olefin).
For 1H NMR experiments, each sample was dissolved, in 8 mm NMR tubes, in tetrachloroethane-d2 (with or without 0.001 M Cr(acac)3). The concentration was approximately 100 mg/1.8 mL. Each tube was then heated in a heating block set at 110° C. The sample tube was repeatedly vortexed and heated to achieve a homogeneous flowing fluid. The 1H NMR spectrum was taken on a BRUKER AVANCE 600 MHz spectrometer, equipped with a 10 mm C/H DUAL cryoprobe. A standard, single pulse 1H NMR experiment was performed. The following acquisition parameters were used: 70 seconds relaxation delay, 90 degree pulse of 17.2 μs, 32 scans. The spectrum was centered at 1.3 ppm, with a spectral width of 20 ppm. All measurements were taken, without sample spinning, at 110° C. The 1H NMR spectrum was referenced to “5.99 ppm” for the resonance peak of the solvent (residual protonated tetrachloroethane). For a sample with Cr, the data was taken with a “16 seconds relaxation delay” and 128 scans. The “mol % silane (silane monomer)” was calculated based on the integration of SiMe proton resonances, versus the integration of CH2 protons associated with ethylene units and CH3 protons associated with octene units.
Differential Scanning Calorimetry (DSC) is used to measure Tm, Tc, Tg and crystallinity in ethylene-based (PE) polymer samples and propylene-based (PP) polymer samples. Each sample (0.5 g) was compression molded into a film, at 5000 μsi, 190° C., for two minutes. About 5 to 8 mg of film sample was weighed and placed in a DSC pan. The lid was crimped on the pan to ensure a closed atmosphere. Unless otherwise stated, the sample pan was placed in a DSC cell, and then heated, at a rate of 10° C./min, to a temperature of 180° C. for PE (230° C. for PP). The sample was kept at this temperature for three minutes. Then the sample was cooled at a rate of 10° C./min to −90° C. for PE (−60° C. for PP), and kept isothermally at that temperature for three minutes. The sample was next heated at a rate of 10° C./min, until complete melting (second heat). Unless otherwise stated, melting point (Tm) and the glass transition temperature (Tg) of each polymer were determined from the second heat curve, and the crystallization temperature (Tc) was determined from the first cooling curve. The respective peak temperatures for the Tm and the Tc are typically recorded. The percent crystallinity can be calculated by dividing the heat of fusion (Hf), determined from the second heat curve, by a theoretical heat of fusion of 292 J/g for PE (165 J/g for PP), and multiplying this quantity by 100 (for example, % cryst.=(Hf/292 J/g)×100 (for PE)).
YUPLENE BX3900 (PP), a highly crystalline propylene impact copolymer available from SK Company. Density=0.90 g/cm3 (ASTM D792), MFR=60 g/10 min (ASTM D1238, at 230° C./2.16 kg);
ENGAGE 8100 Polyolefin Elastomer available from The Dow Chemical Company: ethylene/1-octene copolymer, density=0.870 g/cm3 (ASTM D792), I2=1.0 g/10 min (ASTM D1238, at 190° C./2.16 kg), Tm=60.0° C., Tg=−52.0° C.;
The interpolymers SiH-POE D, SiH-POE E, and POE D were each prepared in a one gallon, polymerization reactor that was hydraulically full, and operated at steady state conditions. The solvent was ISOPAR-E, supplied by the ExxonMobil Chemical Company. The 5-hexenyldimethylsilane (HDMS) supplied by Gelest, was used as a termonomer, and was purified over AZ-300 alumina supplied by UOP Honeywell, prior to use. HDMS was fed to the reactor as a 22 wt % solution in ISOPAR-E. The reactor temperature was measured at or near the exit of the reactor. The interpolymer was isolated and pelletized. Polymerization conditions are listed in Table 1B-1D, and catalysts and co-catalysts are listed in Table 1A. The polymer properties of each ethylene/octene/silane terpolymer (SiH-POE) and the ethylene/octene copolymer (POE) are shown in Tables 2A and 2B.
Polymer compositions, as shown in Table 3 below, were formed by extrusion. Comparative CE-1, represents a typical formulation for an automotive interior instrumental panel, with 20 wt % talc, and containing 64.8 wt % BX3900 and 15 wt % ENGAGE 8100, and in which ENGAGE™ 8100 acts as the impact modifier. Inventive IE-1 is similar to CE-1, except that it contained SiH POE E, in place of ENGAGE 8100.
Each composition was compounded in a co-rotating twin screw extruder with a diameter of 18 mm and an L/D of 40. A general purposed screw configuration was used, and the profile temperatures were set as shown below in Table 4. The screw rotated at 200 RPM, and a “20 kg/h” output was achieved during compounding. The extruded composition was granulated into small pellets by a side cutter granulator. Pellets were analyzed for carbonyl content after a 48 hour period, at room temperature (23° C.) and ambient atmosphere.
Carbonyl test results of the formulated compositions are listed in Table 5. It can be seen that for aldehydes, like formaldehyde, acetaldehyde and propionaldehyde, there is a significant difference in the aldehyde content between the inventive compositions and the comparative compositions. Overall, the inventive compositions (TPO) had a significantly decrease in carbonyl content as compared with the respective comparative compositions. It is believed that the SiH-POE is able to reduce the aldehyde levels during the extrusion of the composition, since most of the oxygenates, including aldehydes and ketones, are generated during the thermal treatment process.
Each composition (pellets) was injection molded using a FANUC S-2000I B series injection molding machine with a 28 mm diameter. The injection profile temperature was set at 204SC, and the mold temperature was set at 38° C. The injection molding speed was 26 minis, with a screw rotation at 80 RPM. The injection molding condition was fixed for all the compositions. Dog-bone test specimens (10) for each composition were made according to ISO 527. Mechanical and impact properties are shown in Table 6. For each property, the average of 10 test specimens was reported. As seen in Table 6, each inventive composition maintains excellent mechanical properties and impact properties, and has especially good strain at break and room temperature impact strength, each as compared to the respective comparative composition.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2021/138999 | 12/17/2021 | WO |
