OLEFIN/SILANE INTERPOLYMER COMPOSITIONS WITH REDUCED RESIDUAL ALDEHYDE AND/OR KETONE CONTENT
20250136798 ยท 2025-05-01
Inventors
- Andong Liu (Shanghai, CN)
- Yabin Sun (Shanghai, CN)
- Wenxin Zhang (Shanghai, CN)
- Colin Li Pi Shan (Pearland, TX)
- Gaoxiang WU (Houston, TX, US)
Cpc classification
International classification
Abstract
A process to form a composition, and related composition, the process comprising thermally treating at least the following components: a) an olefin/silane interpolymer comprising at least one SiH group, and b) a propylene-based polymer, or a propylene-based composition that comprises a propylene-based polymer. A process to form a composition, the process comprising thermally treating at least the following component(s): a) an olefin/silane interpolymer comprising at least one SiH group, and wherein the olefin/silane interpolymer is formed in the presence of a bis-biphenyloxy metal complex; and wherein the composition does not comprise a peroxide.
Claims
1. 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 SiH group, and b) a propylene-based polymer, or a propylene-based composition that comprises a propylene-based polymer.
2. The process of claim 1, wherein the components are mixed during the thermal treatment.
3. 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 SiH 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;
4. The process of claim 3, wherein the composition has a reduced total aldehyde content (%) that is 40%, as determined from Equation Y.
5. The process of claim 1, wherein the olefin/silane interpolymer of component a is an ethylene/alpha-olefin/silane interpolymer.
6. The process of claim 1, wherein component a has a density from 0.855 g/cc to 0.940 g/cc.
7. The process of claim 1, 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.
8. The process of claim 1, wherein component b has a density from 0.870 g/cc to 0.930 g/cc.
9. The process of claim 1, wherein the composition is thermally treated at a temperature from 140 C. to 250 C.
10. A composition comprising at least the following components: a) an olefin/silane interpolymer comprising at least one SiH group, and b) a propylene-based polymer, or a propylene-based composition that comprises a propylene-based polymer.
11. The composition of claim 10, wherein the olefin/silane interpolymer of component a is an ethylene/alpha-olefin/silane interpolymer.
12. The composition of claim 10, wherein component a has a density from 0.855 g/cc to 0.940 g/cc.
13. The composition of claim 10, 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.
14. The composition of claim 10, wherein component b has a density from 0.870 g/cc to 0.930 g/cc.
15. The composition of claim 10, 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 x0; 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.
16. The composition of claim 15, wherein Formula 1 is selected from the following compounds s1) through s16) below: ##STR00011## ##STR00012##
17. The composition of claim 10, wherein the composition is thermally treated.
18. 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 SiH 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.
19. The composition of claim 18, wherein the composition has a reduced total aldehyde content (%) that is 40%, as determined from Equation Y.
20. An article comprising at least one component formed from the composition of claim 10.
Description
DETAILED DESCRIPTION OF THE INVENTION
[0022] 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.
[0023] 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.
[0024] 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.
[0025] 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.
[0026] In one embodiment, or a combination of two or more embodiments, each described herein, the components are mixed during the thermal treatment.
[0027] 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 SiH 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.
[0028] 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.
[0029] 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.
[0030] 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.
[0031] 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 cm.sup.3). In one embodiment, or a combination of two or more embodiments, each described herein, component a has a density0.940 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.
[0032] 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 min0.5 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.
[0033] 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.
[0034] 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 density0.930 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.
[0035] 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.
[0036] 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.
[0037] 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-(SiBCO)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; [0038] H is hydrogen, and x0; [0039] 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.
[0040] 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:
##STR00001## ##STR00002##
[0041] 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 temperature250 C., or 240 C., or 230 C., or 225 C., or 220 C., or 215 C., or 210 C., or 205 C.
[0042] 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.
[0043] 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.
Silane Monomer
[0044] A silane monomer, as used herein, comprises at least one (type) SiH group. In one embodiment, the silane monomer is selected from Formula 1, as discussed above.
[0045] 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.
[0046] 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 and Propylene-Based Compositions Comprising the Same
[0047] Propylene-based polymers include, but are not limited to, polypropylene homopolymer, propylene/ethylene interpolymers and copolymers, and propylene/alpha-olefin interpolymers and copolymers.
[0048] 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.
[0049] 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).
[0050] 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.
[0051] 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.
Additives
[0052] 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.
[0053] 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.
Bis-Biphenyloxy Metal Complex
[0054] 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.
[0055] For example, see Formula DI below as a nonlimiting example:
##STR00003## [0056] wherein 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; [0057] 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; [0058] n is 0, 1, or 2, and optionally when n is 1, X may be a bidentate ligand; [0059] each of -T.sup.2- and -T.sup.3- is independently selected from O, S, N(R.sup.N), or P(R.sup.P); [0060] R.sup.6 and R.sup.21 are each independently selected from the group consisting of H, a substituted or unsubstituted (C1-C40)hydrocarbyl, a substituted or unsubstituted (C1-C40)heterohydrocarbyl, Si(R.sup.C).sub.3, Ge(R.sup.C).sub.3, P(R.sup.P).sub.2, N(R.sup.N).sub.2, OR.sup.C, SR.sup.C, NO.sub.2, CN, CF.sub.3, R.sup.CS(O), R.sup.CS(O).sub.2, (R.sup.C).sub.2CN, R.sup.CC(O)O, R.sup.COC(O), R.sup.CC(O)N(R), (R.sup.c).sub.2NC(O), halogen, radicals having formula (I), radicals having formula (II), and radicals having formula (III):
##STR00004## [0061] where each of R.sup.22-R.sup.26, R.sup.27-R.sup.34, and R.sup.35-R.sup.43 is independently selected from a substituted or unsubstituted (C1-C40)hydrocarbyl, a substituted or unsubstituted (C1-C40)heterohydrocarbyl, Si(R.sup.C).sub.3, Ge(R.sup.C).sub.3, P(R.sup.P).sub.2, N(R.sup.N).sub.2, NCHR.sup.C, OR.sup.C, SR.sup.C, NO.sub.2, CN, CF.sub.3, R.sup.CS(O), R.sup.CS(O).sub.2, (R.sup.C).sub.2CN, R.sup.CC(O)O, R.sup.COC(O), R.sup.CC(O)N(R.sup.N), (R.sup.C).sub.2NC(O), halogen, or H; [0062] each of R.sup.7-R.sup.20 is independently selected from a substituted or unsubstituted (C1-C40)hydrocarbyl, a substituted or unsubstituted (C1-C40)heterohydrocarbyl, Si(R.sup.C).sub.3, Ge(R.sup.C).sub.3, P(R.sup.P).sub.2, N(R.sup.N).sub.2, NCHR.sup.C, OR.sup.C, SR.sup.C, NO.sub.2, CN, CF.sub.3, R.sup.CS(O), R.sup.CS(O).sub.2, (R.sup.C).sub.2CN, R.sup.CC(O)O, R.sup.COC(O), R.sup.CC(O)N(R.sup.N), (R.sup.C).sub.2NC(O), halogen, or H; [0063] J.sup.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.sup.2 and T.sup.3 in Formula D1 (to which J.sup.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.sup.2 and T.sup.3 in Formula D1, wherein each of the I 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).sub.2, Si(R.sup.C).sub.2, Ge(R.sup.C).sub.2, P(R.sup.C), or N(R.sup.C), wherein each R.sup.C is independently a substituted or unsubstituted (C1-C30)hydrocarbyl or a substituted or unsubstituted (C1-C30)heterohydrocarbyl; and [0064] wherein each R.sup.P, R.sup.N, and remaining R.sup.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
Definitions
[0065] 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.
[0066] 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.
[0067] 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.
[0068] 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.
[0069] 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.
[0070] 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.
[0071] 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.
[0072] 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.
[0073] 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.
[0074] 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.
[0075] 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.
[0076] 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.
[0077] 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.
[0078] 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.
[0079] 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 SiH group, and the phrase at least one SiH 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.
[0080] 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 SiH group as discussed above. The ethylene/silane interpolymer is formed by the copolymerization of at least the ethylene and the silane monomer.
[0081] 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 SiH 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.
[0082] 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 SiH 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.
[0083] 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.
[0084] 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.
[0085] 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.
[0086] 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.
[0087] The term propylene-based composition, as used herein, refers to a composition comprising a propylene-based polymer.
[0088] 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.
[0089] 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.
[0090] 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.
[0091] 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.
[0092] 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.
[0093] 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.
[0094] The term substituted or unsubstituted (C.sub.1-C.sub.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.
[0095] The term substituted or unsubstituted (C.sub.1-C.sub.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.
[0096] 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).
[0097] The term alkenyl group, as used herein, refers to an organic chemical group that contains at least one carbon-carbon double bond (CC). 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.
[0098] 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.
[0099] 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.
[0100] 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.
Listing of Some Processes and Compositions
[0101] A] A process to form a composition, the process comprising thermally treating at least the following components: [0102] a) an olefin/silane interpolymer comprising at least one SiH group, and [0103] b) a propylene-based polymer, or a propylene-based composition that comprises a propylene-based polymer. [0104] B] The process of A] above, wherein the components are mixed during the thermal treatment. [0105] C] A process to form a composition, the process comprising thermally treating at least the following component(s): [0106] a) an olefin/silane interpolymer comprising at least one SiH group, and wherein the olefin/silane interpolymer is formed in the presence of a bis-biphenyloxy metal complex; and [0107] wherein the composition does not comprise a peroxide. [0108] D] The process of C] above, wherein the component(s) are mixed during the thermal treatment. [0109] E] The process of any one of A]-D](A]through D]) above, 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 SiH 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))}100. [0110] F] The process of E] above, wherein 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. [0111] G] The process of E] or F] above, wherein the total aldehyde content is selected from one or more of formaldehyde, acetaldehyde, acrolein and propionaldehyde, or two or more of formaldehyde, acetaldehyde, acrolein and propionaldehyde, or three of more of formaldehyde, acetaldehyde, acrolein and propionaldehyde, or all four of formaldehyde, acetaldehyde, acrolein and propionaldehyde. [0112] H] The process of any one of A]-G] above, wherein the composition has a reduced total aldehyde content (%), and the total aldehyde content is selected from one or more of formaldehyde, acetaldehyde, acrolein or propionaldehyde, or two or more of formaldehyde, acetaldehyde, acrolein and propionaldehyde, or three of more of formaldehyde, acetaldehyde, acrolein and propionaldehyde, or all four of formaldehyde, acetaldehyde, acrolein and propionaldehyde. [0113] I] The process of any one of A]-H] 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. [0114] J] The process of I] above, wherein the 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. [0115] K] The process of any one of A]-J] above, wherein 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. [0116] L] The process of any one of A]-K] above, wherein 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. [0117] M] The process of any one of A]-L] above, wherein 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 cm.sup.3). [0118] N] The process of any one of A]-M] 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. [0119] O] The process of any one of A]-N] above, wherein 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. [0120] P] The process of any one of A]-O] above, wherein 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. [0121] Q] A composition formed by the process of any one of A]-P] above. [0122] R] A composition comprising at least the following components: [0123] a) an olefin/silane interpolymer comprising at least one SiH group, and [0124] b) a propylene-based polymer, or a propylene-based composition that comprises as propylene-based polymer. [0125] S] The composition of R] above, wherein the composition is formed by thermally treating the components, and further by mixing the components during the thermal treatment. [0126] T] A composition comprising at least the following component(s): [0127] a) an olefin/silane interpolymer comprising at least one SiH group, and wherein the olefin/silane interpolymer is formed in the presence of a bis-biphenyloxy metal complex; and [0128] wherein the composition does not comprise a peroxide. [0129] U] The composition of T] above, wherein the composition is formed by thermally treating the component(s), and further by mixing the component(s) during the thermal treatment. [0130] V] The composition of any one of R]-U] above, 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 SiH 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))}100. [0131] W] The composition of V] above, wherein 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. [0132] X] The composition of V] or W] above, wherein the total aldehyde content is selected from one or more of formaldehyde, acetaldehyde, acrolein and propionaldehyde, or two or more of formaldehyde, acetaldehyde, acrolein and propionaldehyde, or three of more of formaldehyde, acetaldehyde, acrolein and propionaldehyde, or all four of formaldehyde, acetaldehyde, acrolein and propionaldehyde. [0133] 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. [0134] Z] The composition of Y] above, wherein the alpha-olefin of the ethylene/alphaolefin/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. [0135] A2] The composition of any one of R]-Z] above, wherein 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 % of the silane, based on the weight of the interpolymer. [0136] B2] The composition of any one of R]-A2] above, wherein 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. [0137] C2] The composition of any one of R]-B2] above, wherein 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 cm.sup.3). [0138] 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. [0139] E2] The composition of any one of R]-D2] above, wherein 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. [0140] F2] The composition of any one of R]-E2] above, wherein 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. [0141] A3] The process of any one of A], B] or E]-P] above, or the composition of any one of Q]-S] or V]-F2] above, 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 a propylene/ethylene copolymer, or c) a propylene/alpha-olefin interpolymer or a propylene/alpha-olefin copolymer. [0142] B3] The process of any one of A], B], E]-P] or A3] above, or the composition of any one of Q]-S], V]-F2] or A3] above, wherein 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/alphaolefin interpolymer or a propylene/alpha-olefin copolymer. [0143] C3] The process of any one of A], B], E]-P] or A3] above, or the composition of any one of Q]-S], V]-F2] or A3] above, wherein component b is the propylene-based composition, and wherein 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. [0144] D3] The process of any one of A3]-C3] above, or the composition of any one of A3]-C3] above, wherein the 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. [0145] E3] The process of any one of A]-P] or A3]-D3] above, or the composition of any one of Q]-F2] or A3]-D3] above, wherein 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., and/or 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. [0146] F3] The process of any one of A], B], E]-P] or A3]-E3] above, or the composition of any one of Q]-S], V]-F2] or A3]-E3] above, wherein 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 2 0.885 g/cc, or 2 0.890 g/cc, or 0.895 g/cc, or 0.898 g/cc. [0147] G3] The process of any one of A], B], E]-P] or A3]-F3] above, or the composition of any one of Q]-S], V]-F2] or A3]-F3] above, wherein 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. [0148] H3] The process of any one of A], B], E]-P] or A3]-G3] above, or the composition of any one of Q]-S], V]-F2] or A3]-G3] above, wherein 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. [0149] I3] The process of any one of A], B], E]-P] or A3]-H3] above, or the composition of any one of Q]-S], V]-F2] or A3]-H3] above, wherein 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. [0150] J3] The process of any one of A], B], E]-P] or A3]-13] above, or the composition of any one of Q]-S], V]-F2] or A3]-I3] above, wherein 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. [0151] K3] The process of any one of A], B], E]-P] or A3]-J3] above, or the composition of any one of Q]-S], V]-F2] or A3]-J3] above, wherein 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. [0152] L3] The process of any one of A], B], E]-P] or A3]-K3] above, or the composition of any one of Q]-S], V]-F2] or A3]-K3] above, wherein the ratio of the melt flow rate (MFR) of component b to the melt index (I2) of component a is 2.0, or 2.5, or 3.0, or 3.2, or 3.4, or 3.6, or 3.7. [0153] 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. [0154] N3] The process of any one of A]-P] or A3]-M3] above, or the composition of any one of Q]-F2] or A3]-M3] above, wherein the silane is derived from a silane monomer selected from Formula 1, as described above. [0155] O3] The process of N3] above, or the composition of N3] above, wherein, for Formula 1, x is from 0 to 10, or from 0 to 8, or from 0 to 6, or from 0 to 4, or from 0 to 2, or 0 or 1, or 0. [0156] P3] The process of N3] or 03] above, or the composition of N3] or 03] above, wherein, for Formula 1, 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. [0157] Q3] The process of any one of N3]-P3] above, or the composition of any one of N3]-P3] above, wherein, for Formula 1, A is selected from the following structures i)-iv): [0158] i) R.sup.1R.sup.2CCR.sup.3, where each of R.sup.1, R.sup.2 is independently hydrogen or an alkyl group, and R.sup.3 is hydrogen, and wherein R.sup.1 and R.sup.2 may be the same or different; [0159] ii) R.sup.1R.sup.2CCR.sup.3(CR.sup.4R.sup.5).sub.n, where each of R.sup.1, R.sup.2, R.sup.4, R.sup.5 is independently hydrogen, or an alkyl group, and R.sup.3 is hydrogen, and wherein two or more from R.sup.1, R.sup.2, R.sup.4, R.sup.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;
##STR00005##
where each of R.sup.1 and R.sup.2 is independently hydrogen or an alkyl group, and wherein R.sup.1, and R.sup.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
##STR00006##
where each of R.sup.1 and R.sup.2 is independently hydrogen or an alkyl group, and wherein R.sup.1, and R.sup.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. [0160] R3] The process of any one of N3]-Q3] above, or the composition of any one of N3]-Q3] above, wherein, for Formula 1, A is selected from the following structures i)-iv): [0161] i) H.sub.2CCH; [0162] ii) H.sub.2CCH(CH.sub.2).sub.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;
##STR00007##
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
##STR00008##
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. [0163] S3] The process of any one of N3]-R3] above, or the composition of any one of N3]-R3] above, wherein, for Formula 1, B 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. [0164] 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. [0165] U3] The process of any one of N3]-T3] above, or the composition of any one of N3]-T3] above, wherein, for Formula 1, E 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. [0166] 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. [0167] W3] The process of any one of N3]-V3] above, or the composition of any one of N3]-V3] above, wherein Formula 1 is selected from compounds s1) through s16), as described above. [0168] X3] The process of any one of N3]-W3] above, or the composition of any one of N3]-W3] above, wherein Formula 1 is selected from structures s1) to s8), as described above. [0169] Y3] The process of any one of N3]-W3] above, or the composition of any one of N3]-W3] above, wherein Formula 1 is selected from structures s9) to s16), as described above. [0170] Z3] The process of any one of N3]-Y3] above, or the composition of any one of N3]-Y3] above, wherein the 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. [0171] A4] The process of any one of A]-P] or A3]-Z3] above, or the composition of any one of Q]-F2] or A3]-Z3] above, wherein component a has a melting temperature (T.sub.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. [0172] B4] The process of any one of A]-P] or A3]-A4] above, or the composition of any one of Q]-F2] or A3]-A4] above, wherein component a has a molecular weight distribution (MWD=Mw/Mn)1.5, or 1.6, or 1.7, or 1.8, or 1.9 and/or 5.0, or 4.5, or 4.0, or 3.5, or 3.0, or 2.8, or 2.7, or 2.6, or 2.5, or 2.4, or 2.3. [0173] C4] The process of any one of A]-P] or A3]-B4] above, or the composition of any one of Q]-F2] or A3]-B4] above, wherein 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. [0174] D4] The process of any one of A]-P] or A3]-C4] above, or the composition of any one of Q]-F2] or A3]-C4] above, wherein 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. [0175] E4] The process of any one of A]-P] or A3]-D4] above, or the composition of any one of Q]-D4] above, wherein component a has an I10/I2 ratio 6.0, or 7.0, or 8.0, or 9.0, or and/or 30, or 25, or 20, or 15, or 12. [0176] F4] The process of any one of A], B], E]-P] or A3]-E4] above, or the composition of any one of Q]-S], V]-F2] or A3]-E4] above, wherein the weight ratio of component b to component a1.0, or >1.1, or 1.2, or 1.3, or 1.4, or 1.5 or 1.6. Further, the ratio is 20, or 15, or 10, or 5.0. [0177] G4] The process of any one of A]-P] or A3]-F4] above, or the composition of any one of Q]-F2] or A3]-F4] above, wherein the composition comprises component c, at least one filler. [0178] H4] The process of G4] above, or composition of G4] above, wherein 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. [0179] I4] The process of G4] or H4] above, or composition of G4] or H4] above, wherein 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. [0180] J4] The process of any one of A]-P] or A3]-14] above, or the composition of any one of Q]-F2] or A3]-14] above, wherein 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. [0181] K4] The process of any one of A], B], E]-P] or A3]-J4] above, or the composition of any one of Q]-S], V]-F2] or A3]-J4] above, wherein 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. [0182] L4] The process of any one of G4]-K4] above, or composition of any one of G4]-K4] above, wherein component c is present in an amount 0.1 wt %, or 0.5 wt %, 1.0 wt %, or 2.0 wt %, or 5.0 wt %, or 10 wt %, 12 wt %, or 14 wt %, or 16 wt %, or 18 wt %, or 20 wt %, and/or 80 wt %, or 70 wt %, or 60 wt %, or 50 wt %, or 45 wt %, or <40 wt %, or 35 wt %, or 30 wt %, or 25 wt %, based on the weight of the composition. [0183] M4] The process of any one of A], B], E]-P] or A3]-L4] above, or the composition of any one of Q]-S], V]-F2] or A3]-L4] above, wherein the sum of component a and component b is present in an amount 40 wt %, 45 wt %, or 50 wt %, or 52 wt %, or 54 wt %, or 56 wt %, or 58 wt %, or 60 wt %, or 62 wt %, or 64 wt % and/or 90 wt %, or 88 wt %, or 85 wt %, or 82 wt %, or 80 wt %, based on the weight of the composition. [0184] 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. 04] The process of any one of A]-P] or A3]-N4] above, or the composition of any one of Q]-F2] or A3]-N4] above, wherein the 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 %, <.sup.20.0 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. [0185] P4] The process of any one of A]-P] or A3]-04] above, or the composition of any one of Q]-F2] or A3]-04] above, wherein the composition has a gel content 2.0 wt %, or 1.0 wt %, or 0.5 wt %, or 0.2 wt %, or 0.1 wt %, based on the weight of the composition. The gel content is determined by adding and sealing 0.5 g (W.sub.s) of the sample composition in a metal mesh (mesh number is 120) and weight (W.sub.t1) the packed sample (mesh and sample). The packed sample is put into a 250 ml glass bottle containing 100 ml xylene for 24 hours. Then, the packed sample is transferred into 500 ml flask equipped with condenser and containing 350 ml xylene. After reflux for 5 hours, the packed sample is removed from the xylene, and put into a vacuum oven and heated at 120 C. for 2 hours under vacuum condition. The packed sample is removed from the oven and weighed (W). The gel content is calculated by the equation, Gel content=(W.sub.t2W.sub.t1)/W.sub.s*100%. [0186] Q4] The process of any one of A]-P] or A3]-P4] above, or the composition of any one of Q]-F2] or A3]-P4] above, wherein the composition has a melt flow rate (MFR) 1.0, or >2 0.0, or 3.0, or 4.0, or 4.5, or 4.8, or 5.0, and/or 100, or 50, or 20, or 10, or 8.0, or 7.5, or 7.0, or 6.5, or 6.0. [0187] 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 >.sup.300%, or 400%, or 450%, or 460%, or >470%, or 480%, and/or 2000%. [0188] S4] The process of any one of A]-P] or A3]-R4] above, or the composition of any one of Q]-F2] or A3]-R4] above, wherein the composition has a stress at break 5 MPa, 10 MPa, or 12 MPa, or 14 MPa, or 15 MPa, 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. [0189] U4] A blend composition comprising the composition of any one of Q]-F2] or A3]-T4] above, and a 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. In a further embodiment, 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. [0190] V4] 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. [0191] W41 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. [0192] X4] The blend composition of V4] or W4] above, wherein the alpha-olefin of the ethylene/alpha-olefin interpolymer, and further copolymer, or the ethylene/alpha-olefin multiblock interpolymer, and further copolymer, is each, independently, 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. [0193] Y4] A thermoplastic polyolefin (TPO) composition formed by the process of any one of A]-P] or A3]-T4] above. [0194] Z4] A thermoplastic polyolefin (TPO) composition formed from the composition of any one of Q]-F2] or A3]-T4] above. [0195] A5] An article comprising at least one component formed from the TPO composition of Y5] or Z5] above. [0196] B5] An article comprising at least one component formed from the composition of any one of Q]-F2] or A3]-T4] above. [0197] C5] An article comprising at least one component formed from the blend composition of any one of U4]-X4] above. [0198] 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. [0199] E5] The article of any one of any one of A5]-D5] above, wherein the article is thermally treated at a temperature 200 C., or 190 C., or 180 C., or 170 C., or 160 C. [0200] F51 The article of any one of A5]-E5] above, wherein the article is an automobile. [0201] G5] The article of any one of any one of A5]-E5] above, wherein the article is an instrument panel (IP), a door panel, a pillar, an airbag cover, an IP panel soft skin, a noise/vibration/harshness heavy layer or flooring (for example, NVH), a bumper facia, a trim, a fender, or a pedal. [0202] H5] The article of any one of any one of A5]-E5] above, wherein the article is a solar cell module, a cable, a footwear component, an automotive part, a window profile, a tire, a tube, or a roofing membrane.
Test Methods
Carbonyl Analysis2,4-Dinitrophenylhydrzine High Pressure Liquid Chromatography (DNPH HPLC)
[0203] 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.
[0204] Carbonyl analysis was performed with a 4 liter sample from the bag, and using DNPH HPLC method (LOD: 0.01 mg/m.sup.3). 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/m.sup.3. Carbonyl analysis provided the concentration of aldehydes, such as formaldehyde, acetaldehyde, acrolein, propionaldehyde, and crotonaldehyde, present in the sample.
[0205] 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.
[0206] 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.
[0207] 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:
TABLE-US-00001 TABLE A HPLC Conditions Instrument: AGILENT 1200 HPLC Column: Supelco Ascentis Express C18, 15 cm*4.6 mm, 2.7 um Mobile Phase: Solvent A: 0.1 wt % H.sub.3PO.sub.4 in Acetonitrile (ACN) Solvent B: 0.1 wt % H.sub.3PO.sub.4 in DI water Column Oven: 15 C. Detection: DAD detector at 360 nm Flow Rate Gradient: Time (mn) A* B* (ml/min) 0 45 55 1 7 45 55 1 14 50 50 1 20 85 15 1 25 100 0 1 Equilibration Time: 5 min Injection Volume: 10 uL *Volume ratio of A and B.
Tensile
[0208] 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.
Notched Izod Impact Strength
[0209] 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.
Gel Permeation Chromatography
[0210] 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.
[0211] 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.sub.polyethylene=A(M.sub.polystyrene)(EQ1),
where M is the molecular weight, A has a value of 0.4315 and B is equal to 1.0.
[0212] 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 height is 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.
[0213] 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.
[0214] The calculations of Mn.sub.(GPC), Mw.sub.(GPC), and Mz.sub.(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:
[0215] 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.
Melt Index or Melt Flow Rate of Polymer
[0216] 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 of Composition
[0217] 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.
Density of Polymer
[0218] 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.
NMR Characterization of Terpolymers
[0219] For .sup.13C NMR experiments, samples were dissolved, in 10 mm NMR tubes, in tetrachloroethane-d.sub.2 (with or without 0.025 M Cr(acac).sub.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 .sup.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 s, 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 .sup.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).
[0220] For .sup.1H NMR experiments, each sample was dissolved, in 8 mm NMR tubes, in tetrachloroethane-d.sub.2 (with or without 0.001 M Cr(acac).sub.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 .sup.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 .sup.1H 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 .sup.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)
[0221] Differential Scanning Calorimetry (DSC) is used to measure T.sub.m, T.sub.c, T.sub.g 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 si, 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 (T.sub.m) and the glass transition temperature (T.sub.g) of each polymer were determined from the second heat curve, and the crystallization temperature (T.sub.c) was determined from the first cooling curve. The respective peak temperatures for the T.sub.m and the T.sub.c 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)).
Experimental
Polymers and Additives
[0222] YUPLENE BX3900 (PP), a highly crystalline propylene impact copolymer available from SK Company. Density=0.90 g/cm.sup.3 (ASTM D792), MFR=60 g/10 min (ASTM D1238, at 230 C./2.16 kg);
[0223] ENGAGE 8100 Polyolefin Elastomer available from The Dow Chemical Company: ethylene/1-octene copolymer, density=0.870 g/cm.sup.3 (ASTM D792), I2=1.0 g/10 min (ASTM D1238, at 190 C./2.16 kg), Tm=60.0 C., Tg=52.0 C.; [0224] Talc: TALC HTP-ULTRA 5 L, available from AIHAI-IMI; [0225] Carbon Black (CB) Masterbatch: UN2014 available Cabot; [0226] Antioxidant (AO): IRGANOX B225, available from BASF; [0227] SiH POE D: an ethylene/octene/silane terpolymer, density=0.873 g/cc, 12=0.8 g/10 min, 1.5 wt % of HDMS; [0228] SiH POE E: an ethylene/octene/silane terpolymer, density=0.870 g/cc, 12=0.8 g/10 min, 3.4 wt % of HDMS; [0229] POE D: an ethylene/octene copolymer, density=0.871 g/cc, 12=1.2 g/10 min.
Polymer Syntheses and Properties
[0230] 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.
TABLE-US-00002 TABLE 1A Catalysts and Co-catalysts Description Catalyst (CAT) PE CAT 2 (WO2012/027448)
TABLE-US-00003 TABLE 1B Polymerization Conditions to Produce Noted SiH-POEs and POE-D Reactor Reactor ethylene Temp., Pressure, Solvent, Ethylene, Octene, HDMS, Hydrogen, conversion, C. psig lb/hr lb/hr lb/hr lb/h sccm % SiH- 170 729 38 3.8 5.0 1.4 192 83 POE D SiH- 168 726 36 3.8 5.0 2.9 193 82 POE E POE D 170 728 39 3.8 5.4 0 162 83
TABLE-US-00004 TABLE 1C Catalyst Feed Flows and Efficiency Catalyst Overall Catalyst Catalyst Solution Efficiency, (g Solution Metal interpolymer/g Catalyst Flow, lb/hr Conc., ppm* total catalyst metal) SiH- PE CAT 2 0.33 3.96 3,911,000 POE D SiH- PE CAT 2 0.57 3.96 2,385,000 POE E POE PE CAT 2 0.33 3.96 3,939,000 D *The ppm amount based on the weight of the respective catalyst feed solution.
TABLE-US-00005 TABLE 1D Cocatalyst Feed Flows CoCAT 1 CoCAT 1 CoCAT 2 CoCAT 2 Solution Flow, Solution Solution Solution lb/hr Conc., ppm* Flow, lb/hr Conc. ppm Al ** SiH- 0.34 31.25 0.30 32.2 POE D SiH- 0.58 31.25 0.53 32.2 POE E POE 0.33 31.25 0.31 32.2 D *The ppm amount based on the weight of the co-catalyst feed solution. **The ppm amount of Al based on the weight of the co-catalyst feed solution.
TABLE-US-00006 TABLE 2A Polymer Properties Resin Description Silane Information MI Octene Silane Silane Density (dg/ (mol T.sub.m Silane mol wt Resin (g/cc) min) %) (C.sup.0) Type %* %** SiH-POE D 0.873 0.8 11.0 64.5 HDMS 0.4 1.5 SiH-POE E 0.87 0.8 11.0 61.9 HDMS 0.9 3.4 POE D 0.87 1.2 12.0 61.9 *Mol % silane based on total moles of monomers in polymer, and determined by 1H NMR. **Wt % silane calculated from the mol %, and based on the weight of the interpolymer. HDMS = 5-Hexenyldimethylsilane.
TABLE-US-00007 TABLE 2B Polymer Properties (Conventional GPC) Mn Mw Resin (kg/mol) (kg/mol) Mw/Mn SiH-POE D 49 108 2.2 SiH-POE E 45 100 2.2 POE D 52 112 2.2
Study 1Carbonyl Analysis
Preparation of Polymer Compositions
[0231] 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.
TABLE-US-00008 TABLE 3 Polymer Compositions (wt %) 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 *Loading in POE (wt % in terpolymer as determined by 1H NMR).
[0232] 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.
TABLE-US-00009 TABLE 4 Extrusion Temperatures Barrels 1 2 3 4 5 6 7 8 9 10 C. 140 180 200 200 200 200 200 200 200 180
[0233] 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.
TABLE-US-00010 TABLE 5 Carbonyl Test Results CE-1 IE-1 CE-2 IE-2 CE-3 IE-3 Formaldehyde (ug/m.sup.3) 67 20 29 16 104 103 Acetaldehyde (ug/m.sup.3) 1866 38 4454 2666 2036 1148 Acrolein (ug/m.sup.3) <LOQ <LOQ 3 4 28 20 Propionaldehyde 405 7 160 104 652 261 (ug/m.sup.3) Total Aldehyde 2338 65 4646 2790 2820 1532 Content (ug/m.sup.3) Reduced Total 97.2 39.9 45.7 Aldehyde Content (%)* Note, <LOQ = less than the limit of quantitation of the HPLC.*Reduced Total Aldehyde Content (%) = {[(total aldehyde content in CE-1) (total aldehyde content in IE-1)]/(total aldehyde content in CE-1)} 100. Total aldehyde content = the sum of formaldehyde, acetaldehyde, acrolein and propionaldehyde. Note, IE-1 compared against CE-1, IE-2 compared against CE-2, and IE-3 compared against CE-3.
Study 2Mechanical Properties
[0234] 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.
TABLE-US-00011 TABLE 6 Mechanical and Impact Properties Unit CE-1 IE-1 CE-2 IE-2 CE-3 IE-3 E.sub.t(Tensile MPa 2098 2025 1316 1115 1294 1135 modulus), MPa STD. 20 36 38 17 21 55 s.sub.B(Stress at break), MPa 14.2 15.1 14.9 14.9 15.6 15.1 STD. 1.2 0.5 0.1 0.2 0.2 0.3 e.sub.B(Strain at break) % 33 35 474 544 475 485 STD. 7 14 5 19 10 10 MFR g/10 min 10.3 8.2 6.3 5.1 5.3 5.5 IZOD (RT) J/m 9.7 12.3 57.2 58.9 57.6 58.2 STD. 0.6 0.5 0.9 0.4 1 0.9 IZOD (30 C.) J/m 3.6 3.7 20.9 19.7 20.4 20 STD 0.3 0.1 2.5 1 1.7 1.8