WO2023108584A1 - Olefin/silane interpolymer compositions with reduced residual aldehyde and/or ketone content - Google Patents
Olefin/silane interpolymer compositions with reduced residual aldehyde and/or ketone content Download PDFInfo
- Publication number
- WO2023108584A1 WO2023108584A1 PCT/CN2021/138999 CN2021138999W WO2023108584A1 WO 2023108584 A1 WO2023108584 A1 WO 2023108584A1 CN 2021138999 W CN2021138999 W CN 2021138999W WO 2023108584 A1 WO2023108584 A1 WO 2023108584A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composition
- olefin
- propylene
- component
- interpolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/005—Processes for mixing polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
- C08L23/0892—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with monomers containing atoms other than carbon, hydrogen or oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2443/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Derivatives of such polymers
- C08J2443/04—Homopolymers or copolymers of monomers containing silicon
Definitions
- TPO thermoplastic polyolefin
- a car interior application including instrumental panels, door panels and seats.
- 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/m 3 , acetaldehyde less than 0.20 mg/m 3 , and acrolein less than 0.05 mg/m 3 .
- Polyolefin elastomers 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.
- TPO formulations typically have higher aldehyde concentrations then what is required by the proposed law in China.
- Such TPO formulations should also maintain excellent mechanical properties, such as elongation, tensile modulus, tensile strength, and impact strength.
- Cipheral Patent Application CN103788471A 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.
- 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.
- VOC Low-Volatile Organic Compound
- 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.
- 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. Patent 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. Patent 6,258,902.
- Silyl-terminated polyolefins and/or silane functionalized polyolefins are disclosed in the following references: U.S. Patent 6,075,103; U.S. Patent 5,578,690; U.S. Patent 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. Patent 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) .
- a process to form a composition comprising thermally treating at least the following components:
- a process to form a composition comprising thermally treating at least the following component (s) :
- composition does not comprise a peroxide
- composition comprising at least the following components:
- a propylene-based polymer or a propylene-based composition that comprises at least one propylene-based polymer.
- composition comprising at least the following component (s) :
- composition does not comprise a peroxide
- 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.
- a process to form a composition comprising thermally treating at least the components as described above.
- a process to form a composition the process comprising thermally treating at least the component (s) as described above.
- a composition comprising at least the following components a) and b) as described above.
- 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.
- 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.
- the components are mixed during the thermal treatment.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- I2 melt index
- 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.
- 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.
- 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.
- 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.
- MFR melt flow rate
- 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.
- MFR melt flow rate
- 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.
- 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;
- H is hydrogen, and x ⁇ 0;
- E is a hydrocarbyl group or hydrogen
- F is a hydrocarbyl group or hydrogen
- E and F may be the same or different.
- Formula 1 is selected from the following compounds s1) through s16) below:
- 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.
- 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.
- compositions 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.
- 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.
- the silane monomer is selected from Formula 1, as discussed above.
- 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.
- 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
- 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.
- 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.
- 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
- random copolymers also reactor modified, and usually containing 1.5-7.0 wt %ethylene copolymerized with the propylene
- 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.
- 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.
- 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.
- bis-biphenyloxy metal complex 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.
- 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.
- M1 is a metal selected from zirconium (Zr) or hafnium (Hf) or titanium (Ti) , and further Zr of Hf; and wherein the metal is in a formal oxidation state of +2, +3, or +4;
- each X is independently selected from a substituted or unsubstituted (C1-C30) hydro-carbyl, a substituted or unsubstituted (C1-C30) heterohydrocarbyl, or -H; and wherein each X is independently a monodentate ligand or a bidentate ligand;
- n 0, 1, or 2, and optionally when n is 1, X may be a bidentate ligand;
- each of -T 2 -and -T 3 - is independently selected from -O-, -S-, -N (R N ) -, or –P (R P ) -;
- J 4 is a substituted or unsubstituted (C1-C40) hydrocarbylene or a substituted or unsubstituted (C1-C40) heterohydrocarbylene, wherein the substituted or unsubstituted (C1-C40) hydrocarbylene has a portion that comprises a 1-carbon atom to 10-carbon atom linker backbone, linking the groups T 2 and T 3 in Formula D1 (to which J 4 is bonded) ; or the substituted or unsubstituted (C1-C40) heterohydrocarbylene has a portion that comprises a 1-atom to 10-atom linker backbone, linking the groups T 2 and T 3 in Formula D1, wherein each of the 1 to 10 atoms of the 1-atom to 10-atom linker backbone, independently, is a carbon atom or a heteroatom of a heteroatom group, wherein each heteroatom group is independently O, S, S (O) , S (O) 2 , Si (R C ) 2 , Ge (R C
- each R P , R N , and remaining R C in Formula D1 is independently a substituted or unsubstituted (C1-C30) hydrocarbyl, a substituted or unsubstituted (C1-C30) -heterohydro-carbyl, or -H; and wherein the metal complex is overall charge-neutral
- composition 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.
- polymer 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.
- ppm amounts
- interpolymer refers to polymer prepared by the polymeri-zation 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.
- olefin-based polymer 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.
- propylene-based polymer 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.
- propylene/alpha-olefin interpolymer 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.
- propylene/alpha-olefin copolymer 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.
- propylene/ethylene interpolymer 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.
- propylene/ethylene copolymer 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.
- ethylene-based polymer 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.
- ethylene/alpha-olefin interpolymer 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.
- ethylene/alpha-olefin copolymer 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.
- olefin/silane interpolymer 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.
- 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.
- a silane monomer is depicted in Formula 1, as described above.
- ethylene/silane interpolymer 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.
- 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.
- ethylene/alpha-olefin/silane interpolymer 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.
- ethylene/alpha-olefin/silane terpolymer 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.
- 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.
- organic multi-block interpolymer 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.
- 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.
- n represents a hard block or segment
- B represents a soft block or segment.
- 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.
- the A segments and the B segments are randomly distributed along the polymer chain.
- These multi block interpolymers are produced via a chain shuttling process, such as, for example, described in U.S. Patent 7,858,706, which is herein incorporated by reference. See also U.S. Patent 9,243,173; U.S. Patent 7,608,668; U.S. Patent 7,893,166; U.S. Patent 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.
- an olefin such as ethylene or propylene
- ethylene/alpha-olefin multi-block interpolymer 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.
- ethylene/alpha-olefin multi-block copolymer 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.
- 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.
- propylene-based composition refers to a composition comprising a propylene-based polymer.
- total aldehyde content refers to the amount of one or more aldehyde compound (s) , each which can be detected by the “Carbonyl Analysis” described herein.
- 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.
- heteroatom refers to an atom other than hydrogen or carbon (for example, O, S, N or P) .
- heteroatom group refers to a heteroatom or to a chemical group containing one or more heteroatoms.
- 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.
- heterohydrocarbon refers 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.
- substituted hydrocarbon refers to a respective hydrocarbon or hydrocarbyl group, etc., in which one or more hydrogen atoms is/are independently substituted with a heteroatom group.
- substituted heterohydrocarbon refers to a respective heterohydrocarbon or heterohydro-carbyl group, etc., in which one or more hydrogen atoms is/are independently substituted with a heteroatom group.
- substituted or unsubstituted (C 1 –C 30 ) 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.
- substituted or unsubstituted (C 1 –C 30 ) 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.
- thermo treating 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.
- 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 alkenyl group is a hydrocarbon group containing at least one carbon-carbon double bond, and further containing only one carbon-carbon double bond.
- bis-biphenyloxy 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.
- 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.
- 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.
- a process to form a composition comprising thermally treating at least the following components:
- composition does not comprise a peroxide
- alpha-olefin of the ethylene/alpha-olefin/silane interpolymer or terpolymer is a C3-C20 alpha-olefin, or a C3-C10 alpha-olefin, or a C3-C8 alpha-olefin, or one of propylene, 1-butene, 1-hexene or 1-octene, or one of propylene, 1-butene, or 1-octene, or one of 1-butene or 1-octene, or 1-octene.
- the interpolymer of component a comprises, in polymerized form, ⁇ 0.10 wt%, or ⁇ 0.20 wt%, or ⁇ 0.40 wt%, or ⁇ 0.60 wt%, or ⁇ 0.80 wt%, or ⁇ 1.0 wt%, or ⁇ 1.2 wt%, or ⁇ 1.3 wt%, or ⁇ 1.4 wt%, or ⁇ 1.5 wt%, or ⁇ 2.0 wt%, or ⁇ 2.5 wt%, or ⁇ 2.8 wt%, or ⁇ 3.0 wt%, or ⁇ 3.2 wt%, or ⁇ 3.4 wt%of the silane, based on the weight of the interpolymer.
- the interpolymer of component a comprises, in polymerized form, ⁇ 40 wt%, or ⁇ 30 wt%, or ⁇ 20 wt%, or ⁇ 10 wt%, or ⁇ 8.0 wt%, or ⁇ 6.0 wt%, or ⁇ 5.0 wt%, or ⁇ 4.5 wt%, or ⁇ 4.0 wt%of the silane, based on the weight of the interpolymer.
- 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.
- component a has a melt index (I2) ⁇ 0.2 g/10 min, or ⁇ 0.5 g/10 min, or ⁇ 0.6 g/10 min, or ⁇ 0.7 g/10 min, or ⁇ 0.8 g/10 min.
- 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.
- I2 melt index
- composition comprising at least the following components:
- composition comprising at least the following component (s) :
- composition does not comprise a peroxide
- Y The composition of any one of R] -X] above, wherein the olefin/silane interpolymer of component a is an ethylene/silane interpolymer, or an ethylene/alpha-olefin/silane interpolymer, or an ethylene/alpha-olefin/silane terpolymer.
- D2] The composition of any one of R] -C2] above, wherein 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.
- 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/c
- component a has a melt index (I2) ⁇ 0.2 g/10 min, or ⁇ 0.5 g/10 min, or ⁇ 0.6 g/10 min, or ⁇ 0.7 g/10 min, or ⁇ 0.8 g/10 min.
- 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.
- I2 melt index
- component b is the propylene-based polymer, and further selected from the following: a) a polypropylene homopolymer, b) a propylene/ethylene interpolymer or a propylene/ethylene copolymer, or c) a propylene/alpha-olefin interpolymer or a propylene/alpha-olefin copolymer.
- component b is the propylene-based composition
- the propylene-based polymer of the propylene-based composition is selected from the following: a) a polypropylene homopolymer, b) a propylene/ethylene interpolymer or a propylene/ethylene copolymer, or c) a propylene/alpha-olefin interpolymer or a propylene/alpha-olefin copolymer.
- alpha-olefin of the propylene/alpha-olefin interpolymer or copolymer is a C4-C20 alpha-olefin, or a C4-C10 alpha-olefin, or a C4-C8 alpha-olefin, or one of 1-butene, 1-hexene or 1-octene, or one of 1-butene, or 1-octene, or 1-octene.
- 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.
- 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.
- 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.
- MFR melt flow rate
- component b has a melt flow rate (MFR) ⁇ 120 g/10 min, or ⁇ 110 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.
- MFR melt flow rate
- M3 The process of any one of A] , B] , E] -P] or A3] -L3] above, or the composition of any one of Q] -S] , V] -F2] or A3] -L3] above, wherein the ratio of the melt flow rate (MFR) of component b to the melt index (I2) of component a is ⁇ 90, or ⁇ 85, or ⁇ 80, or ⁇ 78, or ⁇ 76, or ⁇ 75.
- MFR melt flow rate
- I2 melt index
- A is a C2-C50 alkenyl group, or a C2-C40 alkenyl group, or a C2-C30 alkenyl group, or a C2-C20 alkenyl group.
- R 1 R 2 C CR 3 -, where each of R 1 , R 2 is independently hydrogen or an alkyl group, and R 3 is hydrogen, and wherein R 1 and R 2 may be the same or different;
- R 1 R 2 C CR 3 - (CR 4 R 5 ) n -, where each of R 1 , R 2 , R 4 , R 5 is independently hydrogen, or an alkyl group, and R 3 is hydrogen, and wherein two or more from R 1 , R 2 , R 4 , R 5 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;
- each of R 1 and R 2 is independently hydrogen or an alkyl group, and wherein R 1 , and R 2 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
- each of R 1 and R 2 is independently hydrogen or an alkyl group, and wherein R 1 , and R 2 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.
- H 2 C CH- (CH 2 ) n -, 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;
- 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
- n is from 1 to 10, or 1 to 8, or 1 to 6, or 1 to 4, or 1 to 2, or 1.
- T3 The process of any one of N3] -S3] above, or the composition of any one of N3] -S3] above, wherein, for Formula 1, C is an alkyl, or a C1-C5 alkyl, or a C1-C4 alkyl, or a C1-C3 alkyl, or a C1-C2 alkyl, or methyl.
- V3 The process of any one of N3] -U3] above, or the composition of any one of N3] -U3] above, wherein, for Formula 1, F is an alkyl, or a C1-C5 alkyl, or a C1-C4 alkyl, or a C1-C3 alkyl, or a C1-C2 alkyl, or methyl.
- silane is derived from a silane monomer selected from the following compounds: allyldimethylsilane, 3-butenyldimethyl-silane, 1- (but-3-en-1-yl) -1, 1, 3, 3-tetramethyl-disiloxane (BuMMH) , 1- (hex-5-en-1-yl) -1, 1, 3, 3-tetramethyldisiloxane (HexMMH) , (2-bicyclo- [2.2.1] hept-5-en-2-yl) ethyl) dimethyl-silane (NorDMS) , 1- (2-bicyclo [2.2.1] hept-5-en-2-yl) ethyl) -1, 1, 3, 3-tetramethyldisiloxane (NorMMH) , or any combination thereof.
- a silane monomer selected from the following compounds: allyldimethylsilane, 3-butenyldimethyl-silane, 1- (but-3-en-1-
- component a has a melting temperature (T m ) ⁇ 56°C, or ⁇ 58°C, or ⁇ 59°C, or ⁇ 60°C, or ⁇ 61°C, or ⁇ 62°C and/or ⁇ 85°C, or ⁇ 80°C, or ⁇ 78°C, or ⁇ 76°C, or ⁇ 74°C, or ⁇ 72°C, or ⁇ 70°C, or ⁇ 68°C, or ⁇ 66°C.
- T m melting temperature
- Mw Mw/Mn
- component a has a number average molecular weight (Mn) ⁇ 10,000, or ⁇ 15,000, or ⁇ 20,000, or ⁇ 25,000, or ⁇ 30,000, or ⁇ 32,000, or ⁇ 35,000, or ⁇ 40,000 g/mol and/or ⁇ 100,000, or ⁇ 90,000, or ⁇ 80,000, or ⁇ 75,000, or ⁇ 70,000, or ⁇ 65,000 g/mol, or ⁇ 60,000 g/mol, or ⁇ 55,000 g/mol.
- Mn number average molecular weight
- component a has a weight average molecular weight (Mw) ⁇ 20,000, or ⁇ 30,000, or ⁇ 40,000, or ⁇ 50,000, or ⁇ 60,000, or ⁇ 70,000, or ⁇ 80,000 g/mol, or ⁇ 90,000 g/mol and/or ⁇ 300,000, or ⁇ 250,000, or ⁇ 200,000, or ⁇ 150,000, or ⁇ 120,000, or ⁇ 110,000 g/mol.
- Mw weight average molecular weight
- component a has an I10/I2 ratio ⁇ 6.0, or ⁇ 7.0, or ⁇ 8.0, or ⁇ 9.0, or ⁇ 10 and/or ⁇ 30, or ⁇ 25, or ⁇ 20, or ⁇ 15, or ⁇ 12.
- component c is selected from inorganic fillers and/or organic fillers, and further from talc, glass fiber, carbon fiber, wood fiber, clay, calcium carbonate, carbon black, magnesium hydroxide whisker, ATH (Aluminium Trihydrate) , TiO2 or any combination thereof, and further from talc, glass fiber, carbon fiber, wood fiber, clay, calcium carbonate, TiO2 or any combination thereof.
- component c comprises two fillers, Filler A and Filler B, and further the weight ratio of Filler A to Filler B is ⁇ 5.0, or ⁇ 10, or ⁇ 15, or ⁇ 18, or ⁇ 20 and/or ⁇ 60, or ⁇ 50, or ⁇ 40, or ⁇ 30, or ⁇ 25.
- component a is present in an amount ⁇ 0.1 wt%, or ⁇ 0.5 wt%, ⁇ 1.0 wt%, or ⁇ 2.0 wt%, or ⁇ 4.0 wt%, or ⁇ 6.0 wt%, ⁇ 8.0 wt%, or ⁇ 9.0 wt%, or ⁇ 10 wt%, and/or ⁇ 70 wt%, or ⁇ 60 wt%, or ⁇ 50 wt%, or ⁇ 45 wt%, or ⁇ 40 wt%, or ⁇ 35 wt%, or ⁇ 30 wt%, based on the weight of the composition.
- component b is present in an amount ⁇ 30 wt%, ⁇ 35 wt%, ⁇ 40 wt%, or ⁇ 45 wt%, or ⁇ 50 wt%, and/or ⁇ 99 wt%, or ⁇ 95 wt%, or ⁇ 90 wt%, or ⁇ 85 wt%, or ⁇ 80 wt%, or ⁇ 75 wt%, or ⁇ 70 wt%, or ⁇ 68 wt%, or ⁇ 65 wt%, based on the weight of the composition.
- N4 The process of any one of G4] -M4] above, or the composition of any one of G4] -M4] above, wherein the sum of component a, component b and component c is present in an amount ⁇ 80 wt%, ⁇ 85 wt%, or ⁇ 90 wt%, or ⁇ 95 wt%, or ⁇ 98 wt%, and/or ⁇ 100 wt%, or ⁇ 99 wt%, based on the weight of the composition.
- composition comprises component d (at least one antioxidant (AO) ) , and further component d is present in an amount ⁇ 0.05 wt%, ⁇ 0.1 wt%, based on the weight of the composition 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.
- component d at least one antioxidant (AO)
- further component d is present in an amount ⁇ 0.05 wt%, ⁇ 0.1 wt%, based on the weight of the composition and/or ⁇ 10 wt%, or ⁇ 5.0 wt%, ⁇ 2.0 wt%, or ⁇ 1.5 wt%, or ⁇ 1.0 w
- R4 The process of any one of A] -P] or A3] -Q4] above, or the composition of any one of Q] -F2] or A3] -Q4] above, wherein the composition has a strain at break ⁇ 30%, or ⁇ 35%, or ⁇ 40%, or ⁇ 50%, or ⁇ 100%, or ⁇ 200%, or ⁇ 300%, or ⁇ 400%, or ⁇ 450%, or ⁇ 460%, or ⁇ 470%, or ⁇ 480%, and/or ⁇ 2000%.
- T4 The process of any one of A] -P] or A3] -S4] above, or the composition of any one of Q] -F2] or A3] -S4] above, wherein the composition has an Notched Izod Impact Strength at 23°C (IZOD RT) ⁇ 10 J/m, or ⁇ 12 J/m, or ⁇ 15 J/m, or ⁇ 20 J/m, or ⁇ 30 J/m, or ⁇ 35 J/m, or ⁇ 40 J/m, or ⁇ 45 J/m, or ⁇ 50 J/m, or ⁇ 55 J/m.
- IZOD RT Notched Izod Impact Strength at 23°C
- thermoplastic polymer different from the olefin/silane interpolymer of component a in one or more features, such as monomer (s) types, monomer (s) amounts, monomer (s) distributions, density, melt index (I2) , Mn, Mw, MWD, or any combination thereof, and further, in one or more features, such as monomer (s) types, monomer (s) amounts, monomer (s) distributions, density, melt index (I2) , or any combination thereof.
- the thermoplastic polymer is selected from an olefin-based polymer, further an ethylene-base polymer or a propylene-based polymer, further an ethylene-based polymer.
- a blend composition comprising the composition of any one of Q] -F2] or A3] -U4] above, and an ethylene/alpha-olefin interpolymer, and further an ethylene/alpha-olefin copolymer; or an ethylene/alpha-olefin multi-block interpolymer, and further an ethylene/alpha-olefin multi-block copolymer.
- a blend composition comprising the composition of any one of Q] -F2] or A3] -V4] above, and a polymer selected from the following: an ethylene/propylene/nonconjugated diene interpolymer, an ethylene/alpha-olefin copolymer, an ethylene/alpha-olefin multi-block copolymer, a polyethylene homopolymer, a styrene/ethylene interpolymer (for example, a SEBS) or any combination thereof.
- a polymer selected from the following: an ethylene/propylene/nonconjugated diene interpolymer, an ethylene/alpha-olefin copolymer, an ethylene/alpha-olefin multi-block copolymer, a polyethylene homopolymer, a styrene/ethylene interpolymer (for example, a SEBS) or any combination thereof.
- thermoplastic polyolefin (TPO) composition formed by the process of any one of A] -P] or A3] -T4] above.
- thermoplastic polyolefin (TPO) composition formed from the composition of any one of Q] -F2] or A3] -T4] above.
- A5 An article comprising at least one component formed from the TPO composition of Y5] or Z5] above.
- D5 The article of any one of A5] -C5] above, wherein the article is thermally treated at a temperature ⁇ 40°C, or ⁇ 50°C, or ⁇ 60°C, or ⁇ 70°C, or ⁇ 80°C, or ⁇ 90°C, or ⁇ 100°C, or ⁇ 110°C, or ⁇ 120°C, or ⁇ 130°C, or ⁇ 140°C, or ⁇ 150°C.
- Polymer composition (200 g, pellets) was placed inside a gas bag (10 L, TEDLAR PVF, Dalian Delin Gas Packaging Co. Ltd. ) along with nitrogen (5L) .
- 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.
- 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/m 3 ) .
- the nitrogen gas in the bag was pumped out, for the carbonyl analysis, using an air pump.
- 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/m 3 .
- 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) .
- 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 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 160° 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) .
- BHT butylated hydroxytoluene
- the solvent source was nitrogen sparged.
- the injection volume used was 200 microliters, and the flow rate was 1.0 milliliters/minute.
- M polyethylene A ⁇ (M polystyrene ) B (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 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.
- Equation 2 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 1/2 height is 1/2 height of the peak maximum; and where RV is the retention 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.
- Equations 4-6 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 TM 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:
- 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.
- Flowrate (effective) Flowrate (nominal) * (RV (FM Calibrated) /RV (FM Sample) ) (EQ7) .
- Processing of the flow marker peak was done via the PolymerChar GPCOne TM 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 I10 to the I2.
- 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 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.
- 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 13 C NMR spectrum was referenced to “74.5 ppm” for the resonance peak of the solvent.
- 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) .
- each sample was dissolved, in 8 mm NMR tubes, in tetrachloroethane-d 2 (with or without 0.001 M Cr (acac) 3 ) .
- the concentration was approximately100 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 1 H NMR spectrum was taken on a BRUKER AVANCE 600 MHz spectrometer, equipped with a 10 mm C/H DUAL cryoprobe.
- a standard, single pulse 1 H NMR experiment was performed. The following acquisition parameters were used: 70 seconds relaxation delay, 90 degree pulse of 17.2 ⁇ s, 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 1 H NMR spectrum was referenced to “5.99 ppm” for the resonance peak of the solvent (residual protonated tetrachloroethane) .
- 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.
- DSC Differential Scanning Calorimetry
- 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) .
- melting point (T m ) and the glass transition temperature (T g ) of each polymer were determined from the second heat curve, and the crystallization temperature (T c ) was determined from the first cooling curve.
- the respective peak temperatures for the T m and the T c are typically recorded.
- Carbon Black (CB) Masterbatch UN2014 available Cabot
- Antioxidant (AO) IRGANOX B225, available from BASF;
- 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 reactor temperature was measured at or near the exit of the reactor.
- the interpolymer was isolated and pelletized.
- 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 ENGAGETM 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.
- 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.
- ⁇ LOQ less than the limit of quantitation of the HPLC.
- Total aldehyde content the sum of formaldehyde, acetaldehyde, acrolein and propionaldehyde.
- compositions were injection molded using a FANUC S-2000I B series injection molding machine with a 28 mm diameter.
- the injection profile temperature was set at 204°C, and the mold temperature was set at 38°C.
- the injection molding speed was 26 mm/s, 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.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
| Resin | Mn (kg/mol) | Mw (kg/mol) | Mw/Mn |
| SiH-POE D | 49 | 108 | 2.2 |
| SiH-POE E | 45 | 100 | 2.2 |
| POE D | 52 | 112 | 2.2 |
| HDMS* | CE-1 | IE-1 | CE-2 | IE-2 | CE-3 | IE-3 | ||
| PP | BX3900 | 64.8 | 64.8 | 48.8 | 48.8 | 48.8 | 48.8 | |
| POE | ENGAGE 8100 | 15 | 30 | |||||
| POE D | 0 (No SiH) | 30 | ||||||
| SiH-POE D | 2 (1.5 wt%) | 30 | ||||||
| SiH-POE E | 5 (3.4 wt%) | 15 | 30 | |||||
| Talc | HPT-ULTRA 5L | 20 | 20 | 20 | 20 | 20 | 20 | |
| AO | B225 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | |
| CB | UN2014 | 1 | 1 | 1 | 1 |
| Barrels | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| ℃ | 140 | 180 | 200 | 200 | 200 | 200 | 200 | 200 | 200 | 180 |
Claims (20)
- A process to form a composition, the process comprising thermally treating at least the following components:a) an olefin/silane interpolymer comprising at least one Si-H group, andb) a propylene-based polymer, or a propylene-based composition that comprises a propylene-based polymer.
- The process of claim 1, wherein the components are mixed during the thermal treatment.
- The process of claim 1, wherein 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 aldehyde content in (SC) ) – (total aldehyde content in (C) ) ] / (total aldehyde content in (SC) ) } x 100;
- The process of claim 3, wherein the composition has a reduced total aldehyde content (%) that is ≥ 40%, as determined from Equation Y.
- The process of any one of claims 1-4, wherein the olefin/silane interpolymer of component a is an ethylene/alpha-olefin/silane interpolymer.
- The process of any one of claims 1-5, wherein component a has a density from 0.855 g/cc to 0.940 g/cc.
- The process of any one of claims 1-6, wherein, 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, or c) a propylene/alpha-olefin interpolymer.
- The process of any one of claims 1-7, wherein component b has a density from 0.870 g/cc to 0.930 g/cc.
- The process of any one of claims 1-8, wherein the composition is thermally treated at a temperature from 140℃ to 250℃.
- A composition comprising at least the following components:a) an olefin/silane interpolymer comprising at least one Si-H group, andb) a propylene-based polymer, or a propylene-based composition that comprises a propylene-based polymer.
- The composition of claim 10, wherein the olefin/silane interpolymer of component a is an ethylene/alpha-olefin/silane interpolymer.
- The composition of claim 10 or claim 11, wherein component a has a density from0.855 g/cc to 0.940 g/cc.
- The composition of any one of claims 10-12, wherein, 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, or c) a propylene/alpha-olefin interpolymer.
- The composition of any one of claims 10-13, wherein component b has a density from 0.870 g/cc to 0.930 g/cc.
- The composition of any one of claims 10-14, wherein 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;H is hydrogen, and x ≥ 0;E is a hydrocarbyl group or hydrogen, F is a hydrocarbyl group or hydrogen, and where E and F may be the same or different.
- The composition of any one of claims 10-16, wherein the composition is thermally treated.
- The composition of claim 17, wherein 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 aldehyde content is determined from the following Equation Y: Reduced Total Aldehyde Content (%) = { [ (total aldehyde content in (SC) ) – (total aldehyde content in (C) ) ] / (total aldehyde content in (SC) ) } x 100.
- The composition of claim 18, wherein the composition has a reduced total aldehyde content (%) that is ≥ 40%, as determined from Equation Y.
- An article comprising at least one component formed from the composition of any one of claims 10-19.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2024535638A JP2024546886A (en) | 2021-12-17 | 2021-12-17 | Olefin/silane interpolymer compositions having reduced residual aldehyde and/or ketone content |
| EP21967719.2A EP4448651A4 (en) | 2021-12-17 | 2021-12-17 | OLEFIN/SILANE INTERPOLYMER COMPOSITIONS WITH REDUCED RESIDUAL ALDEHYDE AND/OR KETONE CONTENT |
| PCT/CN2021/138999 WO2023108584A1 (en) | 2021-12-17 | 2021-12-17 | Olefin/silane interpolymer compositions with reduced residual aldehyde and/or ketone content |
| KR1020247023614A KR20240118869A (en) | 2021-12-17 | 2021-12-17 | Olefin/silane interpolymer compositions with reduced residual aldehyde and/or ketone content |
| US18/719,668 US20250136798A1 (en) | 2021-12-17 | 2021-12-17 | Olefin/silane interpolymer compositions with reduced residual aldehyde and/or ketone content |
| CN202180105367.8A CN118591588A (en) | 2021-12-17 | 2021-12-17 | Olefin/silane interpolymer compositions having reduced residual aldehyde and/or ketone content |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2021/138999 WO2023108584A1 (en) | 2021-12-17 | 2021-12-17 | Olefin/silane interpolymer compositions with reduced residual aldehyde and/or ketone content |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2023108584A1 true WO2023108584A1 (en) | 2023-06-22 |
Family
ID=86775298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2021/138999 Ceased WO2023108584A1 (en) | 2021-12-17 | 2021-12-17 | Olefin/silane interpolymer compositions with reduced residual aldehyde and/or ketone content |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20250136798A1 (en) |
| EP (1) | EP4448651A4 (en) |
| JP (1) | JP2024546886A (en) |
| KR (1) | KR20240118869A (en) |
| CN (1) | CN118591588A (en) |
| WO (1) | WO2023108584A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2025145275A1 (en) * | 2024-01-02 | 2025-07-10 | Dow Global Technologies Llc | Thermoplastic vulcanizates based on olefin/silane polymers |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053071A (en) * | 1989-12-28 | 1991-07-17 | 三井东压化学株式会社 | Polymer and polypropylene resin composition |
| US5578690A (en) * | 1995-04-28 | 1996-11-26 | Northwestern University | Silyl-terminated interpolymer of ethylene and method for preparing silyl-terminated polyolefins |
| WO2001009207A2 (en) * | 1999-07-29 | 2001-02-08 | The Dow Chemical Company | Improved silane functionalized olefin interpolymers and derivatives thereof |
| US20020019469A1 (en) | 1999-04-07 | 2002-02-14 | Hiroshi Mori | Polyacetal resins with reduced formaldehyde odor |
| CN1840576A (en) | 2005-04-01 | 2006-10-04 | 上海金发科技发展有限公司 | High-performance and low-odor automobile instrument panel special polypropylene and preparation method thereof |
| JP2008086436A (en) | 2006-09-29 | 2008-04-17 | Kao Corp | Deodorant filter |
| US7608668B2 (en) | 2004-03-17 | 2009-10-27 | Dow Global Technologies Inc. | Ethylene/α-olefins block interpolymers |
| US7858706B2 (en) | 2004-03-17 | 2010-12-28 | Dow Global Technologies Inc. | Catalyst composition comprising shuttling agent for ethylene multi-block copolymer formation |
| US7947793B2 (en) | 2008-01-30 | 2011-05-24 | Dow Global Technologies Llc | Ethylene/α-olefin block copolymers |
| US20110160368A1 (en) | 2009-12-30 | 2011-06-30 | Bohling James C | Low Odor Styrenic Polymer Dispersions |
| CN103897567A (en) | 2014-03-06 | 2014-07-02 | 华南理工大学 | Wood lacquer for purifying formaldehyde and preparation method thereof |
| WO2015082316A1 (en) | 2013-12-02 | 2015-06-11 | Basf Se | Polyurethanes having reduced aldehyde emission |
| US9243173B2 (en) | 2012-03-30 | 2016-01-26 | Dow Global Technologies Llc | Polyolefin adhesive composition |
| WO2018222460A1 (en) | 2017-05-29 | 2018-12-06 | Dow Global Technologies Llc | Thermoplastic polyolefin compositions useful for aldehyde abatement |
| US10308829B2 (en) | 2013-11-25 | 2019-06-04 | Dow Global Technologies Llc | Moisture-and peroxide-crosslinkable polymeric compositions |
| US20190225786A1 (en) | 2016-08-31 | 2019-07-25 | Dow Global Technologies Llc | Modified polyethylenes |
| US20200197880A1 (en) | 2015-03-31 | 2020-06-25 | Toray Industries, Inc. | Separation membrane |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3137701B2 (en) * | 1990-12-19 | 2001-02-26 | 三井化学株式会社 | Method for producing crosslinked polyolefin molded article |
-
2021
- 2021-12-17 EP EP21967719.2A patent/EP4448651A4/en active Pending
- 2021-12-17 WO PCT/CN2021/138999 patent/WO2023108584A1/en not_active Ceased
- 2021-12-17 JP JP2024535638A patent/JP2024546886A/en active Pending
- 2021-12-17 US US18/719,668 patent/US20250136798A1/en active Pending
- 2021-12-17 CN CN202180105367.8A patent/CN118591588A/en active Pending
- 2021-12-17 KR KR1020247023614A patent/KR20240118869A/en active Pending
Patent Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053071A (en) * | 1989-12-28 | 1991-07-17 | 三井东压化学株式会社 | Polymer and polypropylene resin composition |
| JPH03255112A (en) * | 1989-12-28 | 1991-11-14 | Mitsui Toatsu Chem Inc | New polymer and polypropylene resin composition containing the same |
| US5225507A (en) * | 1989-12-28 | 1993-07-06 | Mitsui Toatsu Chemicals, Inc. | Polymer and polypropylene resin composition |
| US5578690A (en) * | 1995-04-28 | 1996-11-26 | Northwestern University | Silyl-terminated interpolymer of ethylene and method for preparing silyl-terminated polyolefins |
| US20020019469A1 (en) | 1999-04-07 | 2002-02-14 | Hiroshi Mori | Polyacetal resins with reduced formaldehyde odor |
| WO2001009207A2 (en) * | 1999-07-29 | 2001-02-08 | The Dow Chemical Company | Improved silane functionalized olefin interpolymers and derivatives thereof |
| US7893166B2 (en) | 2004-03-17 | 2011-02-22 | Dow Global Technologies, Inc. | Ethylene/alpha-olefins block interpolymers |
| US7608668B2 (en) | 2004-03-17 | 2009-10-27 | Dow Global Technologies Inc. | Ethylene/α-olefins block interpolymers |
| US7858706B2 (en) | 2004-03-17 | 2010-12-28 | Dow Global Technologies Inc. | Catalyst composition comprising shuttling agent for ethylene multi-block copolymer formation |
| CN1840576A (en) | 2005-04-01 | 2006-10-04 | 上海金发科技发展有限公司 | High-performance and low-odor automobile instrument panel special polypropylene and preparation method thereof |
| JP2008086436A (en) | 2006-09-29 | 2008-04-17 | Kao Corp | Deodorant filter |
| US7947793B2 (en) | 2008-01-30 | 2011-05-24 | Dow Global Technologies Llc | Ethylene/α-olefin block copolymers |
| US20110160368A1 (en) | 2009-12-30 | 2011-06-30 | Bohling James C | Low Odor Styrenic Polymer Dispersions |
| US9243173B2 (en) | 2012-03-30 | 2016-01-26 | Dow Global Technologies Llc | Polyolefin adhesive composition |
| US10308829B2 (en) | 2013-11-25 | 2019-06-04 | Dow Global Technologies Llc | Moisture-and peroxide-crosslinkable polymeric compositions |
| WO2015082316A1 (en) | 2013-12-02 | 2015-06-11 | Basf Se | Polyurethanes having reduced aldehyde emission |
| CN103897567A (en) | 2014-03-06 | 2014-07-02 | 华南理工大学 | Wood lacquer for purifying formaldehyde and preparation method thereof |
| US20200197880A1 (en) | 2015-03-31 | 2020-06-25 | Toray Industries, Inc. | Separation membrane |
| US20190225786A1 (en) | 2016-08-31 | 2019-07-25 | Dow Global Technologies Llc | Modified polyethylenes |
| WO2018222460A1 (en) | 2017-05-29 | 2018-12-06 | Dow Global Technologies Llc | Thermoplastic polyolefin compositions useful for aldehyde abatement |
Non-Patent Citations (2)
| Title |
|---|
| MODERN PLASTICS ENCYCLOPEDIA/89, vol. 65, no. 11, October 1988 (1988-10-01), pages 86 - 92 |
| See also references of EP4448651A4 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2025145275A1 (en) * | 2024-01-02 | 2025-07-10 | Dow Global Technologies Llc | Thermoplastic vulcanizates based on olefin/silane polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20240118869A (en) | 2024-08-05 |
| EP4448651A4 (en) | 2025-10-15 |
| EP4448651A1 (en) | 2024-10-23 |
| JP2024546886A (en) | 2024-12-26 |
| CN118591588A (en) | 2024-09-03 |
| US20250136798A1 (en) | 2025-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20100324225A1 (en) | Controlled-Rheology Polypropylene | |
| WO2021258328A1 (en) | Crosslinkable olefin/silane interpolymer compositions | |
| WO2009055486A1 (en) | Polymeric compositions and processes for molding articles | |
| KR20140005219A (en) | Compositions, methods of making the same, and articles prepared from the same | |
| CN104837906A (en) | Automotive compounds with improved odor | |
| EP1647573B1 (en) | Corner molding compositions for automotive sealant systems | |
| EP3371256A1 (en) | Low emission propylene-based polymer resins | |
| WO2020097102A1 (en) | High gloss black tpo replacing paint | |
| WO2023108584A1 (en) | Olefin/silane interpolymer compositions with reduced residual aldehyde and/or ketone content | |
| KR20240125602A (en) | Crosslinking, foam-forming olefin/silane copolymer composition | |
| EP3707205B1 (en) | Thermoplastic vulcanizates and compositions thereof | |
| EP4448636A1 (en) | Crosslinkable olefin/silane interpolymer compositions with reduced peroxide levels | |
| CN112739735B (en) | Crosslinked plastomers as rubber substitutes | |
| US20250051529A1 (en) | Crosslinkable olefin/silane interpolymer compositions | |
| US11261316B2 (en) | Plastic living hinges with block composite polymer | |
| US11345802B2 (en) | Thermoplastic polyolefin compositions useful for aldehyde abatement | |
| WO2025057767A1 (en) | Polypropylene-based resin composition and molded article | |
| WO2025057768A1 (en) | Polypropylene-based resin composition and molded article | |
| JP2023542465A (en) | Polymers of ethylene and monocyclic organosiloxanes | |
| JP2004043770A (en) | Thermoplastic elastomer composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21967719 Country of ref document: EP Kind code of ref document: A1 |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 18719668 Country of ref document: US |
|
| ENP | Entry into the national phase |
Ref document number: 2024535638 Country of ref document: JP Kind code of ref document: A |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 202417046249 Country of ref document: IN |
|
| REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112024012284 Country of ref document: BR |
|
| ENP | Entry into the national phase |
Ref document number: 20247023614 Country of ref document: KR Kind code of ref document: A |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 202180105367.8 Country of ref document: CN |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2021967719 Country of ref document: EP |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| ENP | Entry into the national phase |
Ref document number: 2021967719 Country of ref document: EP Effective date: 20240717 |
|
| ENP | Entry into the national phase |
Ref document number: 112024012284 Country of ref document: BR Kind code of ref document: A2 Effective date: 20240617 |
|
| WWP | Wipo information: published in national office |
Ref document number: 18719668 Country of ref document: US |



















