Ethylene / propylene / non-conjugated diene interpolymer composition

Abstract

The present disclosure provides a composition. The composition can be formed into a foam composition. In an embodiment, the composition comprises a pure ethylene / propylene / non-conjugated polyene interpolymer. The pure ethylene / propylene / non-conjugated polyene interpolymer comprises more than 6.0 wt% to 15.0 wt% of a non-conjugated polyene. The pure ethylene / propylene / non-conjugated polyene interpolymer has the following properties: (i) a molecular weight (Mw) of 240,000 to 270,000; (ii) a Mooney viscosity (ML (1+4), 125°C) of 85 to 95; (iii) a rheological ratio (RR) of 35 to 65; (iv) Mw / Mn of 2.2 to 3.5; and (v) Mw<1389.6 [g / mole] MV+140,000 g / mol, wherein Mw is a weight average molecular weight, and MV is a Mooney viscosity (ML 1+4, 125°C). MV is the Mooney viscosity (ML 1+4, 125°C), and Mw is the weight average molecular weight, as determined by conventional GPC.

Description

Background Art

[0001] Ethylene-propylene-non-conjugated polyene terpolymers (also known as "EPDM") are widely used in many automotive and industrial applications. For example, EPDM foams are used in automotive sealing applications. However, conventional EPDM foams are limited due to low foam expansion rates and rough foam surface quality.

[0002] The art recognizes a continuing need for new EPDM compositions having higher molecular weight to provide improved foam expansion, extrudate surface smoothness, high physical properties, and shape retention during extrusion. The art further recognizes a need for new foam compositions made from such EPDM compositions. Summary of the invention

[0003] The present disclosure provides an EPDM composition. The EPDM composition exhibits high molecular weight and high Mooney viscosity and is used to improve foaming characteristics and foam physical properties. The present disclosure also provides a foam composition made from the EPDM composition.

[0004] The present disclosure provides a composition. In an embodiment, the composition comprises a pure ethylene / propylene / non-conjugated polyene interpolymer. The pure ethylene / propylene / non-conjugated polyene interpolymer comprises from greater than 6.0 wt% to 15.0 wt% of a non-conjugated polyene. The pure ethylene / propylene / non-conjugated polyene interpolymer has the following properties:

[0005] (i) a molecular weight (Mw) of 240,000 to 270,000;

[0006] (ii) Mooney viscosity (ML(1+4), 125°C) of 85 to 95;

[0007] (iii) rheological ratio (RR) of 35 to 65;

[0008] (iv) Mw / Mn of 2.2 to 3.5; and

[0009] (v) Mw<1389.6 [g / mole] MV+140,000 g / mol, where Mw is the weight average molecular weight and MV is the Mooney viscosity (ML 1+4, 125°C). MV is the Mooney viscosity (ML 1+4, 125°C) and Mw is the weight average molecular weight as determined by conventional GPC.

[0010] The present disclosure provides a foam composition. In an embodiment, the foam composition comprises a pure ethylene / propylene / non-conjugated polyene interpolymer. The pure ethylene / propylene / non-conjugated polyene interpolymer comprises from greater than 6.0 wt% to 15.0 wt% of a non-conjugated polyene. The pure ethylene / propylene / non-conjugated polyene interpolymer has the following properties:

[0011] (i) a molecular weight (Mw) of 240,000 to 270,000;

[0012] (ii) Mooney viscosity (ML(1+4), 125°C) of 85 to 95;

[0013] (iii) rheological ratio (RR) of 35 to 65;

[0014] (iv) Mw / Mn of 2.2 to 3.5; and

[0015] (v) Mw<1389.6 [g / mole] MV+140,000 g / mol, where Mw is the weight average molecular weight and MV is the Mooney viscosity (ML 1+4, 125°C). MV is the Mooney viscosity (ML 1+4, 125°C) and Mw is the weight average molecular weight as determined by conventional GPC.

[0016] definition

[0017] Any reference to the Periodic Table of the Elements is to the Periodic Table as published by CRC Press, Inc., 1990-1991. Reference to a group of elements in the table is made by a new notation for numbering the groups.

[0018] For purposes of U.S. patent practice, the contents of any cited patent, patent application, or publication, particularly with respect to disclosure of definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure) and general knowledge in the art, are incorporated by reference in their entirety (or their equivalent U.S. versions are also so incorporated by reference).

[0019] Numerical ranges disclosed herein include all values ​​from the lower limit to the upper limit, and include the lower limit and the upper limit. For ranges containing exact values ​​(e.g., 1 or 2, or 3 to 5, or 6, or 7), any sub-ranges (e.g., 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.) between any two exact values ​​are included.

[0020] Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are by weight and all test methods are current as of the filing date of this disclosure.

[0021] As used herein, the term "blend" or "polymer blend" is a blend of two or more polymers. The blend may or may not be miscible (phase separated). The blend may or may not be phase separated. The blend may or may not contain one or more domain configurations, as determined by transmission electron spectroscopy, light scattering, x-ray scattering, and other methods known in the art.

[0022] The term "composition" refers to a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0023] The terms "comprises," "including," "having," and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether or not the components, steps, or procedures are specifically disclosed. For the avoidance of any doubt, all compositions claimed by using the term "comprising" may include any additional additives, adjuvants, or compounds, whether in polymeric form or otherwise, unless stated to the contrary. In contrast, the term "consisting essentially of excludes any other components, steps, or procedures (except those that are not essential to operability) from the scope of any subsequent statements. The term "consisting of" excludes any components, steps, or procedures that are not specifically described or listed. Unless otherwise stated, the term "or" refers to the listed members individually and in any combination. The use of the singular includes the use of the plural, and vice versa.

[0024] An "ethylene polymer" is a polymer that contains, in polymerized form, units derived from ethylene as a majority of the weight percentage of the total weight of the polymer. Non-limiting examples of ethylene polymers include low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), ultra low density polyethylene (ULDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), and functionalized polyethylenes, e.g., ethylene vinyl acetate (EVA), ethylene ethyl acrylate (EEA), and the like.

[0025] "Interpolymer" is a polymer prepared by polymerizing at least two different monomers. This general term encompasses copolymers, usually employed to refer to polymers prepared from two different monomers, and polymers prepared from more than two different monomers, for example, terpolymers, tetrapolymers, and the like.

[0026] "Olefin polymers" or "polyolefins" are polymers containing more than 50 weight percent polymerized olefin monomers (based on the total amount of polymerizable monomers) and optionally may contain at least one comonomer. Non-limiting examples of olefin polymers include ethylene polymers and propylene polymers.

[0027] "Polymer" is a compound prepared by polymerizing monomers of the same or different types, which provide multiple and / or repeated "units" or "monomer units" constituting the polymer in a polymerized form. Therefore, the general term polymer covers the term homopolymer, which is usually used to refer to polymers prepared from only one type of monomer, and the term copolymer, which is usually used to refer to polymers prepared from at least two types of monomers. It also covers all forms of copolymers, such as random copolymers, block copolymers, etc. The terms "ethylene / α-olefin polymer" and "propylene / α-olefin polymer" represent copolymers prepared by polymerizing ethylene or propylene and one or more other polymerizable α-olefin monomers, respectively, as described above. It should be noted that although polymers are usually referred to as "made of" one or more specified monomers, "based on" a specified monomer or monomer type, "containing" a specified monomer content, etc., in this context, the term "monomer" should be understood to refer to the polymerized residue of the specified monomer rather than the unpolymerized substance. Generally, the polymers herein are referred to as "units" based on the polymerized form of the corresponding monomers.

[0028] Test Method

[0029] Absolute tan delta slope. The absolute value of tan delta slope is defined by equation (A) below.

[0030]

[0031] For analysis of EPDM compositions 13 C NMR method. The sample was prepared by adding about "2.6 g" of "tetrachloroethane-d2 / o-dichlorobenzene 50 / 50 mixture" with a "0.025 M" content of chromium acetylacetonate (relaxant) to "0.2 g sample" in a 10 mm NMR tube. The sample was dissolved and homogenized by heating the tube and its contents to 150°C. Data were collected using a Bruker 400 MHz spectrometer equipped with a Bruker Dual DUL high temperature CryoProbe. Data were acquired at a sample temperature of 120°C using "160 scans per data file" and a six second pulse repetition delay. Acquisition was performed using a spectral width of 25,000 Hz and a file size of 32K data points.

[0032] NMR spectroscopy analysis of the compositions of the Examples was performed using the following analytical method: The quantification of the monomers present in the EPDM can be calculated using the following equations (1 to 9).

[0033] The calculation of the number of ethylene moles normalized the spectrum range from 55.0-5.0 ppm to 1000 integration units. The contribution under the normalized integration area accounts for only 7 of the ENB carbons. The ENB diene peaks at 111 ppm and 147 ppm were excluded from the calculation due to concerns that the double bonds might react at high temperatures.

[0034] Equation 1

[0035] Equation 2 ENB moles = CH3 (13.6-14.7 ppm)

[0036] Equation 3 P moles = CH3 (19.5-22.0 ppm)

[0037] Equation 4

[0038] Equation 5

[0039] Equation 6

[0040] Equation 7

[0041] Equation 8

[0042] Equation 9

[0043] The percentage of intermediate chain branching area 13 C NMR. "Intermediate chain branching" (or "iCB") is the phenomenon whereby oligomers generated in situ are rapidly incorporated into the polymer backbone. The branches resulting from the incorporation of these oligomers do not increase viscosity at low shear rates, and the resulting polymer therefore exhibits behavior similar to that of linear molecules. The incorporation of the oligomers is efficient, rendering the oligomer content undetectable in the final polymer. It is believed that the combination of the high branch density (estimated by NMR) and the intermediate length (30 to 75 carbon units) exhibited by iCB polymers extends the backbone length required for entanglement in the molten state. This behavior is in fact similar to that of linear molecules.

[0044] The EPDM was performed using tetrachloroethane-d2 with 0.025 M chromium acetylacetonate 13 C NMR spectroscopy was performed to quantify the level of intermediate chain branching, thereby improving the spectral resolution in the 34.6-34.4 ppm region. The sample was prepared by adding approximately "2.6 g" of "tetrachloroethane-d2 with 0.025 M chromium acetylacetonate" to "0.3 g of sample" in a 10 mm NMR tube. The sample was dissolved and homogenized by heating the tube and its contents to 140°C. Data were collected using a Bruker 400 MHz spectrometer equipped with a Bruker Dual DUL high temperature CryoProbe with inverse gated NMR pulses. Data were acquired at a sample temperature of 120°C using "8000 scans per data file" and a 7.3 second pulse repetition delay. The spectral data were referenced to the EEE backbone at 30 ppm.

[0045] As disclosed in WO2018 / 005922, the EPDM polymer with iCB exhibits a methylene peak in the region of 34.4 ppm to 34.6 ppm, which is greater than 0.01% of the total integrated area from 160.0 to 100.0 ppm plus 60.0 to 0.000 ppm (excluding the entire spectrum of tetrachloroethane solvent). 13 C NMR spectral analysis showed no methylene peak in the region of 34.4 ppm to 34.6 ppm. The inventive EPDM interpolymers of the present disclosure have no intermediate chain branching.

[0046] Density was measured according to ASTM D792, Method B. Results were reported in grams per cubic centimeter (g / cc).

[0047] Differential Scanning Calorimetry (DSC). Differential Scanning Calorimetry (DSC) is used to measure the crystallinity in ethylene (PE) samples (including EPDM) and propylene (PP) samples. The sample (0.5g) sample was compression molded into a film at 5000psi, 190°C for two minutes. About 5 to 8mg of the film-forming sample was weighed and placed in a DSC pan. The lid was screwed on the pan to ensure a closed atmosphere. The sample pan was placed in the DSC unit and then heated to a temperature of 180°C for PE (for PP, heated to 230°C) at a rate of about 10°C / min. The sample was kept at this temperature for three minutes. Then, the sample was cooled to -90°C for PE (for PP, cooled to -90°C) at a rate of 10°C / min, and was isothermally kept at the temperature for three minutes. The sample was then heated at a rate of 10°C / min until completely melted (second heating). The heat of fusion (H) determined by the second heating curve was determined by the heat of fusion (H f ) divided by the theoretical heat of fusion of 292 J / g for PE (165 J / g for PP) and multiplying this number by 100 to calculate the percent crystallinity (e.g., Crystallinity % = (H f / 292J / g)x100(for PE)).

[0048] Unless otherwise stated, the melting point (T m ) is determined from the second heating curve, and the crystallization temperature (T c ) is determined by the first cooling curve.

[0049] Dynamic Mechanical Spectroscopy (DMS). Small angle oscillatory shear (melt DMS) was performed using a TA Instruments ARES equipped with a "25 mm parallel plate" under nitrogen purge. For all samples, the time between sample loading and the start of the test was set to five minutes. The experiments were performed at 190°C in a frequency range of 0.1 rad / s to 100 rad / s. The strain amplitude was adjusted from 1% to 3% based on the response of the sample. The stress response was analyzed in terms of amplitude and phase, from which the storage modulus (G'), loss modulus (G"), dynamic viscosity η* and tan δ were calculated. The specimen for the dynamic mechanical spectroscopy was a "25 mm diameter x 3.3 mm thick" compression molded disc formed at 180°C and 10 MPa molding pressure for five minutes, and then quenched between cooled platens (15°C to 20°C) for two minutes. The rheological ratio (V0.1 / V100 at 190°C; also referred to as "RR"), tan δ (0.1 rad / s, 190°C) and tan δ (100 rad / s, 190°C) were recorded.

[0050] FTIR Method for Analysis of EPDM Compositions. Terpolymers containing ethylene, propylene and 5-ethylidene-2-norbornene were analyzed for ethylene content using ASTM D9300 and for ethylidene-norbornene or dicyclopentadiene content using ASTM D6047.

[0051] Gel Permeation Chromatography. The chromatography system consisted of a Polymer Laboratories Model PL-210 or a Polymer Laboratories Model PL-220. The column and transfer chamber were operated at 140°C. The columns were three 10 micron mixed B columns from Polymer Laboratories. The solvent used was 1,2,4 trichlorobenzene. The sample was prepared at a concentration of "0.1 g polymer in 50 ml solvent". The solvent used to prepare the sample contained "200 ppm butylated hydroxytoluene (BHT)". The sample was prepared by gentle stirring at 160°C for four hours. The injection volume was 100 microliters, and the flow rate was 1.0 ml / min.

[0052] Calibration of the GPC column set was performed using 21 "narrow molecular weight distribution polystyrene standards" with molecular weights ranging from 580 g / mol to 8,400,000 g / mol, arranged in six "cocktail" mixtures with at least ten times intervals between individual molecular weights. The standards were purchased from Polymer Laboratories (Shropshire, UK). The polystyrene standards were prepared as follows: for molecular weights equal to or greater than 1,000 kg / mol, they were prepared as "0.025 grams in 50 milliliters of solvent", and for molecular weights less than 1,000 kg / mol, they were prepared as "0.05 grams in 50 milliliters of solvent". The polystyrene standards were gently stirred at 80 degrees Celsius for 30 minutes to dissolve. The narrow standards mixture was run first, and in order to reduce the "highest molecular weight" component to reduce degradation. The polystyrene standard peak molecular weight was converted to polyethylene molecular weight using the following equation: M 聚乙烯 =A×(M 聚苯乙烯 ) B , where M is the molecular weight, A has a value of 0.431 and B equals 1.0 (as described in Williams and Ward, J. Polym. Sc., Polym. Let., 6, 621 (1968)). Polyethylene equivalent molecular weight calculations were performed using Viscotek TriSEC software version 3.0.

[0053] Mooney viscosity. Mooney viscosity (ML 1+4 at 125°C) was measured according to ASTM D1646 with a preheat time of one minute and a spindle operating time of four minutes. The instrument was an Alpha Technologies Mooney Viscometer 2000. The viscosity of each formulated composition was measured using an uncured blanket (see Experimental Section) so that the viscosity of the uncured composition could be checked. The samples were conditioned at room temperature for 24 hours prior to testing.

[0054] Tan δ ratio. The tan δ ratio is defined as tan δ (0.1 rad / s, 190° C.) of the first polymer component produced in the first reactor / tan δ (0.1 rad / s, 190° C.) of the final composition in the second reactor. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] Figure 1A and 1B The prior art EPDM of comparative sample 3 (CS3) according to one embodiment of the present disclosure shows that there is a peak at 34.4 ppm to 34.6 ppm 13 C NMR spectroscopy ( Figure 1A ), the comparison shows that the EPDM of Example 1 of the present invention has no peak at 34.4ppm to 34.6ppm13 C NMR spectroscopy ( Figure 1B ). DETAILED DESCRIPTION

[0056] The present disclosure provides a composition. In an embodiment, the composition comprises a pure ethylene / propylene / non-conjugated polyene interpolymer. The pure ethylene / propylene / non-conjugated polyene interpolymer comprises from greater than 6.0 wt% to 15.0 wt% of a non-conjugated polyene. The pure ethylene / propylene / non-conjugated polyene interpolymer has the following properties:

[0057] (i) a molecular weight (Mw) of 240,000 to 270,000;

[0058] (ii) Mooney viscosity (ML(1+4), 125°C) of 85 to 95;

[0059] (iii) rheological ratio (RR) of 35 to 65;

[0060] (iv) Mw / Mn of 2.2 to 3.5; and

[0061] (v) Mw<1389.6 [g / mole]MV+140,000 g / mol, where Mw is the weight average molecular weight and MV is the Mooney viscosity (ML 1+4, 125° C.).

[0062] MV is the Mooney viscosity (ML 1+4, 125°C), and Mw is the weight average molecular weight, as determined by conventional GPC.

[0063] The ethylene / propylene / non-conjugated polyene interpolymer is pure. A "pure" ethylene / propylene / non-conjugated polyene interpolymer does not contain added oil, is otherwise free of oil, or is otherwise "oil-free." It is therefore understood that the Mooney viscosity values ​​and rheological ratio values ​​are applicable to pure ethylene / propylene / non-conjugated polyene interpolymers that do not contain oil.

[0064] Pure ethylene / propylene / non-conjugated polyene interpolymers include ethylene monomer, propylene comonomer and non-conjugated polyene terpolymer. Although propylene is a copolymer, it should be understood that other α-olefins can be used as comonomers. Non-limiting examples of suitable comonomers other than propylene include C4-C8 α-olefins, such as 1-butene, 1-hexene and 1-octene.

[0065] Non-conjugated polyene is C6-C 15Straight chain, branched or cyclic hydrocarbon diene. Non-limiting examples of suitable straight chain acyclic dienes include 1,4-hexadiene, 1,5-heptadiene. Non-limiting examples of suitable branched acyclic dienes include 5-methyl-1,4-hexadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene, 5,7-dimethyl-1,7-octadiene, 1,9-decadiene and mixed isomers of dihydromyrcene. Non-limiting examples of suitable monocyclic alicyclic dienes include 1,4-cyclohexadiene, 1,5-cyclooctadiene and 1,5-cyclododecadiene. Non-limiting examples of polycyclic alicyclic fused and bridged cyclodienes include tetrahydroindene, methyltetrahydroindene, alkenyl, alkylene, cycloalkenyl and cycloalkylene norbornenes, such as 5-methylene-2-norbornene (MNB), 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene and 5-cyclohexylidene-2-norbornene.

[0066] In an embodiment, the diene is selected from ENB, dicyclopentadiene, 1,4-hexadiene, 7-methyl-1,6-octadiene, dicyclopentadiene and 1,4-hexadiene.

[0067] In an embodiment, the diene is 5-ethylidene-2-norbornene (ENB).

[0068] In an embodiment, the pure ethylene / propylene / non-conjugated polyene interpolymer comprises (i) 50 wt% to 60 wt%, or 52 wt% to 58 wt%, or 53 wt% to 56 wt% ethylene monomer; (ii) 35 wt% to 45 wt%, or 37 wt% to 43 wt%, or 38 wt% to 41 wt% propylene comonomer; (iii) 7 wt% to 10 wt%, or 8 wt% to 9 wt% ENB, and the pure ethylene / propylene / non-conjugated polyene interpolymer has the following properties:

[0069] (i) Mw of 240,000 to 260,000, or 245,000 to 258,000, or 248,000 to 256,000,

[0070] (ii) a Mooney viscosity of 90 to 95 or 92 to 94,

[0071] (iii) a rheological ratio of 35 to 45, or 37 to 43, or 39 to 41;

[0072] (iv) Mw / Mn of 2.8 to 3.2 or 2.9 to 3.1;

[0073] (v) Mw<1389.6 [g / mole]MV+140,000 g / mol, where Mw is the weight average molecular weight and MV is the Mooney viscosity (ML 1+4, 125° C.); and

[0074] (vi) No 34.4ppm to 34.6ppm 13 C NMR peaks.

[0075] The weight percentages are based on the total weight of the pure ethylene / propylene / non-conjugated polyene interpolymer.The pure ethylene / propylene / non-conjugated polyene interpolymer having the aforementioned amounts of ethylene, propylene and ENB and properties (i)-(vi) is referred to hereinafter as Composition 1.

[0076] In an embodiment, Composition 1 comprises (i) 50 wt% to 60 wt%, or 52 wt% to 58 wt%, or 53 wt% to 56 wt% of ethylene monomer; (ii) 35 wt% to 45 wt%, or 37 wt% to 43 wt%, or 38 wt% to 41 wt% of propylene comonomer; (iii) 7 wt% to 10 wt%, or 8 wt% to 9 wt% of ENB, and the pure ethylene / propylene / non-conjugated polyene interpolymer has the following properties:

[0077] (i) Mw of 240,000 to 260,000, or 245,000 to 258,000, or 248,000 to 256,000,

[0078] (ii) a Mooney viscosity of 90 to 95 or 92 to 94,

[0079] (iii) and a rheology ratio of 35 to 45, or 37 to 43, or 39 to 41.

[0080] iv) Mw / Mn is from 2.8, or 2.9 to 3.1, or 3.2;

[0081] (v) Mw<1389.6 [g / mole]MV+140,000 g / mol, where Mw is the weight average molecular weight and MV is the Mooney viscosity (ML 1+4, 125° C.);

[0082] (vi) No 34.4ppm to 34.6ppm 13 C NMR peaks; and

[0083] (vii) The Mw / V0.1 ratio is less than 1.80 (g / mol) or is 1.5 to 1.7 (g / mol).

[0084] In an embodiment, Composition 1 comprises (i) 50 wt% to 60 wt%, or 52 wt% to 58 wt%, or 53 wt% to 56 wt% of ethylene monomer; (ii) 35 wt% to 45 wt%, or 37 wt% to 43 wt%, or 38 wt% to 41 wt% of propylene comonomer; (iii) 7 wt% to 10 wt%, or 8 wt% to 9 wt% of ENB, and the pure ethylene / propylene / non-conjugated polyene interpolymer has the following properties:

[0085] (i) Mw of 240,000 to 260,000, or 245,000 to 258,000, or 248,000 to 256,000,

[0086] (ii) a Mooney viscosity of 90 to 95 or 92 to 94,

[0087] (iii) and a rheology ratio of 35 to 45, or 37 to 43, or 39 to 41.

[0088] iv) Mw / Mn is from 2.8, or 2.9 to 3.1, or 3.2;

[0089] (v) Mw<1389.6 [g / mole]MV+140,000 g / mol, where Mw is the weight average molecular weight and MV is the Mooney viscosity (ML 1+4, 125° C.);

[0090] (vi) No 34.4ppm to 34.6ppm 13 C NMR peak;

[0091] (vii) a Mw / V0.1 ratio of less than 1.80 (g / mol) or from 1.5 to 1.7 (g / mol); and

[0092] (viii) Mn is 80,000 to 90,000.

[0093] In an embodiment, the pure ethylene / propylene / non-conjugated polyene interpolymer of the present invention is produced in two polymerization reactors configured and operated in series, i.e., the output of one reactor is fed to the second reactor. The reactors may be the same or different. In an embodiment, each reactor is the same and each reactor is a loop reactor.

[0094] The reactors may be operated in the same or different modes. In an embodiment, the first reactor is operated in a manner that promotes the formation of a high molecular weight fraction of the desired polymer, while the second reactor (i.e., the reactor that receives the output from the first reactor as feed) is operated in a manner that promotes the formation of a low molecular weight fraction of the desired polymer.

[0095] The temperature difference between the first reactor and the second reactor affects the Mw / Mn of the final product, with the greater the temperature difference, the wider the Mw / Mn. Although the operating temperature of each reactor will depend on many factors, such as the alpha olefin, diene, catalyst, solvent, equipment and equipment design, pressure, flow rate and turbulence, relative amounts of reagents, the nature of the desired product, etc., the typical operating temperature of the first reactor is 65°C to 90°C, and the typical operating temperature of the second reactor is 85°C to 120°C. The residence time of the reactants in each reactor will also depend on these factors, but the typical residence time of the reactants in each reactor is two minutes to 90 minutes.

[0096] Ethylene, alpha-olefin (i.e., propylene) and diene (if any), solvent and optional hydrogen are blended in desired proportions by any convenient means, and the blend is then introduced into a first reactor, i.e., a reactor whose output is used as a feed to another or second reactor. The first catalyst is usually introduced into the first reactor separately from the other reagents. The first reactor and the second reactor are operated on a continuous basis so that when the output of the first reactor is discharged as a feed to the second reactor, additional reagents are added to the first reactor to maintain the reaction mass in a steady state, i.e., relatively constant and proportional concentrations of ethylene, alpha-olefin, diene (if any), solvent, catalyst and molecular weight regulator (if any).

[0097] The first reactor and the second reactor are in fluid communication with each other, usually connected by one or more conduits. These conduits are usually equipped with one or more mixers (to promote uniform mixing of the reaction materials).

[0098] As with the first reactor, ethylene, alpha-olefins, dienes (if any), solvents and optional hydrogen are blended in a desired ratio, and the blend is then introduced into a second reactor, that is, a reactor receiving the output from another or the first reactor as a feed. Similarly, a second catalyst (a catalyst different from the first catalyst introduced into the first reactor) is usually introduced into the second reactor separately from other reagents. The output of the first reactor usually contains 1 weight percent to 30 weight percent solids (that is, polymers), and it can be fed into the second reactor separately from other reagents, or it can be first blended with one or more other reagents before being introduced into the second reactor. The output of the second reactor usually contains 8 weight percent to 30 weight percent solids, wherein the desired polymer product is separated from the solvent and unreacted monomers, and the latter (that is, the solvent and unreacted monomers) are circulated separately or disposed of in a safe and environmentally friendly manner.

[0099] In an embodiment, the pure ethylene / propylene / non-conjugated polyene interpolymer is an in-reactor blend of a first polymer component and a second polymer component. The first polymer component is produced in a first reactor, and the second polymer component is produced in a second reactor. The first polymer component consists of ethylene, propylene and ENB, and has a Mw of 400,000 to 450,000, or 410,000 to 440,000, or 420,000 to 430,000.

[0100] In an embodiment, the first polymer component is composed of ethylene / propylene / ENB, and the ENB content in the first polymer component is less than 80%, or 60% to less than 80% of the total ENB content in the final composition.

[0101] The first catalyst can be introduced into the first reactor and the second catalyst can be introduced into the second reactor. The second catalyst can be the same as or different from the first catalyst. Alternatively, only a single catalyst (the first catalyst) is introduced into the first reactor.

[0102] In the examples, only the first catalyst is introduced into the first reactor. The first catalyst (introduced into the first reactor) is a zirconium-based catalyst. The pure ethylene / propylene / non-conjugated polyene interpolymer contains a residual amount of zirconium.

[0103] In an embodiment, the first catalyst is [[rel-2',2"'-[[(1R,3S)-1,3-methyl-1,3-propanediyl]bis(oxy-κO)]bis[3-[3,6-bis(1,1-dimethylethyl)-9H-carbazole-9-yl]-5'-fluoro-5-(1,1,3,3-tetramethylbutyl)[1,1'-biphenyl]-2-hydroxy-κO]](2-)]dimethylzirconium and is hereinafter referred to as Catalyst A. Catalyst A has structure (A) provided below.

[0104] Structure (A)

[0105]

[0106] In an embodiment, a single catalyst is introduced into the first reactor and the single catalyst is a zirconium-based catalyst (Catalyst A), and the pure ethylene / propylene / non-conjugated polyene interpolymer contains a residual amount of zirconium. As used herein, the term "residual amount" is greater than 0 ppm to 5 ppm.

[0107] In an embodiment, Composition 1 contains 1 ppm to 5 ppm residual zirconium. In further embodiments, the residual amount of zirconium metal does not include titanium.

[0108] In an embodiment, a second catalyst is introduced into the second reactor. The second catalyst is [[[2',2"'-[1,3-propanediylbis(oxy-κO)]bis[3-[3,6-bis(1,1-dimethylethyl)-9H-carbazole-9-yl]-5'-fluoro-5-(1,1,3,3-tetramethylbutyl)[1,1'-biphenyl]-2-hydroxy-κO]](2-)]-dimethylhafnium or OC-6-33)-dimethyl[[2',2"'-[1,3-propanediylbis(oxy-κO)]bis[3-[3,6-bis(1,1-dimethylethyl)-9H-carbazole-9-yl]-5'-fluoro-5-(1,1,3,3-tetramethylbutyl)[1,1'-biphenyl]-2-hydroxy-κO]](2-)]hafnium, and is hereinafter referred to as catalyst B. Catalyst B has the structure (B) provided below.

[0109] Structure (B)

[0110]

[0111] 2. Additives

[0112] The pure ethylene / propylene / non-conjugated polyene interpolymers of the present invention may contain optional other additives. Non-limiting examples of suitable additives include oils, fillers, antioxidants, UV stabilizers, blowing agents, flame retardants, colorants or pigments, and combinations thereof.

[0113] In an embodiment, oil is added to a pure ethylene / propylene / non-conjugated polyene interpolymer such that the ethylene / propylene / non-conjugated polyene interpolymer is no longer oil-free.

[0114] In an embodiment, the pure ethylene / propylene / non-conjugated polyene interpolymer composition includes at least one additive selected from fillers, antioxidants, UV stabilizers, foaming agents, or combinations thereof. Fillers include, but are not limited to, carbon black; aluminum silicate, magnesium silicate, calcium silicate, sodium silicate, potassium silicate, and mixtures thereof; calcium carbonate, magnesium carbonate, and mixtures thereof; silicon oxide, calcium oxide, zinc oxide, iron oxide, titanium oxide, and aluminum oxide; calcium sulfate, barium sulfate, and lead sulfate; aluminum oxide trihydrate; magnesium hydroxide; phenol-formaldehyde, polystyrene, and poly(a-methyl)-styrene resins, natural fibers, synthetic fibers, and the like. In an embodiment, the filler is carbon black.

[0115] In an embodiment, the pure ethylene / propylene / non-conjugated polyene interpolymer comprises an antioxidant. Non-limiting examples of suitable antioxidants include hindered phenols, bisphenols and thiobisphenols; substituted hydroquinones; tri(alkylphenyl)phosphites; dialkylthiodipropionates; phenylnaphthylamines; substituted diphenylamines; dialkyl, alkylaryl and diaryl substituted p-phenylenediamines; monomeric and polymeric dihydroquinolines; 2-(4-hydroxy-3,5-tert-butylaniline)-4,6-bis(octylthio)l,3,5-triazine, hexahydro-l,3,5-tris-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl-s-triazine, 2,4,6-tris(nl,4-dimethylpentylphenylene-diamino)-l,3,5-triazine, tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, nickel dibutyldithiocarbamate, 2-mercaptotolylimidazole and its zinc salt, petroleum wax, and the like.

[0116] 3. Bubbles

[0117] The present disclosure provides a foam composition. In an embodiment, the foam composition comprises a pure ethylene / propylene / non-conjugated polyene interpolymer. The pure ethylene / propylene / non-conjugated polyene interpolymer comprises from greater than 6.0 wt% to 15.0 wt% of a non-conjugated polyene. The pure ethylene / propylene / non-conjugated polyene interpolymer has the following properties:

[0118] (i) a molecular weight (Mw) of 240,000 to 270,000;

[0119] (ii) Mooney viscosity (ML(1+4), 125°C) of 85 to 95;

[0120] (iii) rheological ratio (RR) of 35 to 65;

[0121] (iv) Mw / Mn of 2.2 to 3.5; and

[0122] (v) Mw<1389.6 [g / mole]MV+140,000 g / mol, where Mw is the weight average molecular weight and MV is the Mooney viscosity (ML 1+4, 125° C.).

[0123] In an embodiment, the foam composition comprises Composition 1 as previously disclosed above. Composition 1 has the properties previously disclosed herein.

[0124] 4. Application

[0125] The pure ethylene / propylene / non-conjugated polyene interpolymer composition of the present invention can be further compounded into a rubber formulation (Banbury mixer or extruder) and further cured into a final article (extrusion, injection molding, calendaring).

[0126] The pure ethylene / propylene / non-conjugated polyene interpolymers and / or the final products can be used in automotive hoses, automotive belts, weather strip profiles, building profiles, roof membranes, injection molded products, general rubber products, tires, impact modification, TPE compounds and other traditional and non-traditional rubber elastomer applications.

[0127] By way of example and not limitation, some embodiments of the present disclosure will now be described in detail in the following examples.

[0128] Examples

[0129] 1. Synthesis of Experimental EPDM

[0130] Continuous polymerization

[0131] The polymerization reaction was carried out under steady-state conditions, i.e., constant reactant concentrations and continuous input of solvent, monomer and catalyst and constant withdrawal of unreacted monomer, solvent and polymer. The reactor system was cooled and pressurized to prevent the formation of a gas phase. Monomers: ethylene (CAS 74-85-1); propylene (CAS 115-07-1); 5-ethylidene-2-norbornene, ENB (CAS 16219-75-3).

[0132] The polymer composition was prepared in a solution polymerization process using two reactors, (i) a continuous stirred tank reactor ("first reactor") followed by (ii) a loop reactor (second reactor). Ethylene was introduced into a mixture of ISOPAR E solvent (available from ExxonMobil), propylene was introduced and 5-ethylidene-2-norbornene (ENB) was introduced, each forming a reactor feed stream.

[0133] Catalyst A was fed into the first reactor, and Cocatalyst 1 and Cocatalyst 2 were used to activate Catalyst A in situ.

[0134] Cocatalyst-1 is methyl di(C 14-18 A mixture of trialkylamines (ARMEEN M2HT, available from Akzo-Nobel, Inc.), HCl and Li[B(C6F5)4] was prepared by the reaction of long chain trialkylamines (ARMEEN M2HT, available from Akzo-Nobel, Inc.), HCl and Li[B(C6F5)4], essentially as disclosed in USP 5,919,988 (Example 2). Cocatalyst-1 was from Boulder Scientific and used without further purification.

[0135] Cocatalyst-2 was modified methylaluminoxane (MMAO) from Akzo Nobel and was used without further purification.

[0136] The structure of Catalyst A is provided below.

[0137] Catalyst A: [[rel-2',2"'-[[(1R,3S)-1,3-methyl-1,3-propanediyl]bis(oxy-κO)]bis[3-[3,6-bis(1,1-dimethylethyl)-9H-carbazol-9-yl]-5'-fluoro-5-(1,1,3,3-tetramethylbutyl)[1,1'-biphenyl]-2-hydroxy-κO]](2-)]dimethylzirconium. CAS# 1360629-63-5.

[0138]

[0139] Thus, the outlet of each reactor is a mixture of polymer, solvent, and reduced levels of initial monomer. The output of the first reactor is fed directly into the second reactor (unless otherwise sampled). The molecular weight of the polymer is controlled by adjusting the temperature of each reactor, the monomer conversion, and / or the addition of chain terminators such as hydrogen.

[0140] After polymerization, a small amount of water is introduced into the reactor outlet stream as a catalyst kill and the reactor outlet stream is introduced into a flash vessel wherein the solids concentration is increased by at least 100 percent. A portion of the unreacted monomers, i.e., ENB, ethylene and propylene and unused diluent are then collected and appropriately recycled back to the reactor feed.

[0141] The monomer feed rate and polymerization temperature as well as other conditions are listed in Tables 1 and 2 below.

[0142] Table 1: Reaction conditions for EPDM of the present invention

[0143]

[0144] Table 2: Reaction conditions for EPDM of the present invention

[0145]

[0146] Table 3: Property data of comparative EPDM and EPDM of the present invention

[0147]

[0148] # CS3 is the present invention 1, Table 3, Figure 3, WO2018 / 005922 S CS4 is the present invention 2, Table 4, WO2018 / 005852

[0149] ％ CS5 is EPDM B47, Table 2, WO2014 / 003857 IE—Inventive Example

[0150] IE1 contained 38 wt% of the first polymer component (EPDM produced in Reactor 1) and 62 wt% of the second polymer component (EPDM produced in Reactor 2). The weight percentages are based on the total weight of the final EPDM terpolymer.

[0151] Inventive example (IE1) contains more ENB (8.3 wt%) than CS2 (4.9 wt% ENB), CS3 (5.1 wt% ENB), CS4 (4.3 wt% ENB) and CS5 (4.9 wt% ENB), which facilitates the production of the foam composition.

[0152] like Figure 1B As shown, IE1 has no iCB (no 13 C NMR peak) while CS3 has iCB, such as Figure 1A In the range of 34.4ppm to 34.6ppm 13 C NMR peaks.

[0153] The Mw / Mn of IE1 is 3.04, which is broader than the Mw / Mn of CS1 (2.84), CS2 (2.09), CS3 (2.44), and CS5 (2.7) and narrower than that of CS4 (4.14).

[0154] The Mw of IE1 is less than the Mooney viscosity relationship of 1389.6 [g / mole] MV + 140,000 g / mol.

[0155] IE1 exhibits high Mn (80,000-90,000), medium Mw / Mn (2.8-3.5) and high ENB (6-15 wt%), which yields beneficial features of suitable expansion, suitable extrudate surface smoothness and suitable shape retention during extrusion for foam applications.

[0156] It is particularly intended that the present disclosure is not limited to the embodiments and descriptions contained herein, but encompasses modifications of those embodiments including parts of the embodiments and combinations of elements of different embodiments as appear within the scope of the following claims.

Claims

1. A composition comprising: A pure oil-free ethylene / propylene / non-conjugated polyene interpolymer, the interpolymer comprising greater than or equal to 50 wt% and less than or equal to 60 wt% ethylene monomer, greater than or equal to 35 wt% and less than or equal to 45 wt% propylene comonomer and greater than or equal to 7 wt% and less than or equal to 10 wt% non-conjugated polyene, the interpolymer having the following properties (i) a molecular weight Mw of 245,000 to 258,000; (ii) a Mooney viscosity ML1+4 at 125°C of 85 to 95; (iii) a rheological ratio V0.1 / V100 of 35 to 65, measured by dynamic mechanical spectroscopy DMS at 190° C. in a frequency range of 0.1 rad / s to 100 rad / s; (iv) Mw / Mn of 2.2 to 3.5; and (v) Mw<1389.6 g / mol MV+140,000 g / mol, where Mw is the weight average molecular weight and MV is the Mooney viscosity ML 1+4 at 125°C.

2. The composition of claim 1, wherein the pure ethylene / propylene / non-conjugated polyene interpolymer has a Mw / V0.1 ratio of less than 1.80 g / mol, wherein V0.1 is measured by dynamic mechanical spectroscopy (DMS) at 190°C and at 0.1 rad / s.

3. The composition of claim 1 or 2, wherein the pure ethylene / propylene / non-conjugated polyene interpolymer has no 34.4 ppm to 34.6 ppm 13 C NMR peaks.

4. The composition according to claim 1 or 2, wherein the non-conjugated polyene is 5-ethylidene-2-norbornene termonomer ENB.

5. The composition of claim 4, wherein the pure ethylene / propylene / non-conjugated polyene interpolymer has the following properties (i) a molecular weight Mw of 240,000 to 260,000; (ii) a Mooney viscosity ML1+4 at 125°C of 90 to 95; (iii) a rheological ratio V0.1 / V100 of 35 to 45, measured by dynamic mechanical spectroscopy DMS at 190° C. in a frequency range of 0.1 rad / s to 100 rad / s; (iv) Mw / Mn of 2.8 to 3.2; and (v)Mw<1389.6g / mol MV+140,000g / mol.

6. The composition of claim 1 or 2, wherein the pure ethylene / propylene / non-conjugated polyene interpolymer is an in-reactor blend of: a first polymer component consisting of ethylene / propylene / ENB and having a Mw of 400,000 to 450,000; and The second polymer component consists of ethylene / propylene / ENB.

7. The composition of claim 1 or 2, wherein the pure ethylene / propylene / non-conjugated polyene interpolymer comprises 1 ppm to 5 ppm zirconium.

8. A foam composition comprising: A pure oil-free ethylene / propylene / non-conjugated polyene interpolymer, the interpolymer comprising greater than or equal to 50 wt% and less than or equal to 60 wt% ethylene monomer, greater than or equal to 35 wt% and less than or equal to 45 wt% propylene comonomer and greater than or equal to 7 wt% and less than or equal to 10 wt% non-conjugated polyene, the interpolymer having the following properties (i) a molecular weight Mw of 245,000 to 258,000; (ii) a Mooney viscosity ML1+4 at 125°C of 85 to 95; (iii) a rheological ratio V0.1 / V100 of 35 to 65, measured by dynamic mechanical spectroscopy DMS at 190° C. in a frequency range of 0.1 rad / s to 100 rad / s; (iv) Mw / Mn of 2.2 to 3.5; and (v) Mw<1389.6 g / mol MV+140,000 g / mol, where Mw is the weight average molecular weight and MV is the Mooney viscosity ML 1+4 at 125°C.

9. The composition of claim 1 or 2, wherein the interpolymer comprises greater than or equal to 8 wt% and less than or equal to 9 wt% of a non-conjugated polyene, and The molecular weight Mw of the interpolymer is from 240,000 to 260,000.

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