阅读说明：本技术 乙烯/丙烯/非共轭二烯互聚物组合物 (Ethylene/propylene/non-conjugated diene interpolymer compositions ) 是由 X·吴 韩涛 C·里皮善 于 2019-04-30 设计创作，主要内容包括：本公开提供了一种组合物。在实施例中,所述组合物包含纯乙烯/丙烯/非共轭多烯互聚物。所述纯乙烯/丙烯/非共轭多烯互聚物包含大于0wt％到6.0wt％的非共轭多烯。所述纯乙烯/丙烯/非共轭多烯互聚物具有以下性质：(i)分子量(Mw)为240,000到270,000；(ii)门尼粘度(ML(1+4),125℃)为80到85；(iii)流变比(RR)为35到65；(iv)Mw/Mn为2.2到3.5；(v)tanδ比率为0.6到0.9；以及(vi)绝对tanδ斜率为5.0到小于10.0。(The present disclosure provides a composition. In an embodiment, the composition comprises a pure ethylene/propylene/nonconjugated polyene interpolymer. The pure ethylene/propylene/nonconjugated polyene interpolymer comprises from greater than 0 wt% to 6.0 wt% of a nonconjugated polyene. The pure ethylene/propylene/nonconjugated polyene interpolymer has the following properties: (i) a molecular weight (Mw) of 240,000 to 270,000; (ii) mooney viscosity (ML (1+4), 125 ℃) of 80 to 85; (iii) a Rheology Ratio (RR) of 35 to 65; (iv) Mw/Mn is from 2.2 to 3.5; (v) a tan delta ratio of 0.6 to 0.9; and (vi) an absolute tan delta slope of from 5.0 to less than 10.0.)

1. A composition, comprising:

a pure ethylene/propylene/nonconjugated polyene interpolymer comprising from greater than 0 wt% to 6.0 wt% of a nonconjugated polyene, the interpolymer having the following properties

(i) A molecular weight (Mw) of 240,000 to 270,000;

(ii) mooney viscosity (ML (1+4), 125 ℃) of 80 to 85;

(iii) a rheology ratio of 35 to 65;

(iv) Mw/Mn is from 2.2 to 3.5;

(v) a tan delta ratio of 0.6 to 0.9; and

(vi) the absolute tan delta slope is from 5.0 to less than 10.0.

2. The composition of claim 1, wherein the pure ethylene/propylene/nonconjugated polyene interpolymer has a Mw/V0.1 ratio of less than 1.80 (g/mol).

3. The composition of any one of claims 1-2, wherein the neat ethylene/propylene/nonconjugated polyene interpolymer does not have from 34.4ppm to 34.6ppm of¹³C NMR peaks.

4. The composition of any one of claims 1-3, wherein the neat ethylene/propylene/nonconjugated polyene interpolymer comprises

From 45 wt% to 55 wt% of ethylene monomer;

40 to 50 wt% of a propylene comonomer; and

3 to 6 wt% of a 5-ethylidene-2-norbornene terpolymer (ENB).

5. The composition of claim 4, wherein the neat ethylene/propylene/nonconjugated polyene interpolymer has the following properties

(i) A molecular weight (Mw) of 240,000 to 260,000;

(ii) mooney viscosity (ML (1+4, 125 ℃) of 80 to 85;

(iii) a rheology ratio of 35 to 45;

(iv) Mw/Mn is from 3.0 to 3.5;

(v) a tan delta ratio of 0.6 to 0.9;

(vii) no 13C NMR peak at 34.4ppm to 34.6 ppm; and

(viii) the Mw/V0.1 ratio is 1.5 to 1.7.

6. The composition of claim 5, wherein the pure ethylene/propylene/nonconjugated polyene interpolymer has a Mw/Mn from 3.2 to 3.5.

7. The composition of claim 6, wherein the pure ethylene/propylene/nonconjugated polyene interpolymer has a tan delta ratio from 0.7 to 0.9.

8. The composition of any one of claims 1-7, wherein the neat ethylene/propylene/nonconjugated polyene interpolymer comprises an in-reactor blend of:

a first polymer component having a Mw of 375,000 to 400,000; and

a second polymer component.

9. The composition of claim 8, wherein the neat ethylene/propylene/nonconjugated polyene interpolymer comprises

30 to 40 wt% of the first polymer component; and

70 to 60 wt% of the second polymer component.

10. The composition of any one of claims 1-9, wherein the pure ethylene/propylene/nonconjugated polyene interpolymer comprises 1ppm of 5ppm hafnium and 1ppm to 5ppm zirconium.

Background

Ethylene-propylene-nonconjugated polyene terpolymers (also known as "EPDM") are widely used in many automotive and industrial applications. For example, EPDM is used in automotive and industrial hose products due to its thermal and oxidative stability and its chemical resistance to polar organic and aqueous inorganic fluids. In automotive applications, higher "under hood" temperatures (due to lower hood profiles), reduced air flow in the engine area, and turbochargers drive the need for more heat resistant materials for items such as coolant hoses, exhaust hoses, brake hoses, and air ducts. However, conventional EPDM automotive hoses are still limited due to poor long-term heat aging performance.

It is known that the heat aging performance increases with increasing chain branching in EPDM. However, as chain branching increases, the processability of EPDM decreases. The art recognizes that there is a continuing need for EPDM compositions that have a balance of chain branching and processability.

Disclosure of Invention

The present disclosure provides an EPDM having a higher molecular weight for better filler absorption and improved processability. The present disclosure relates to EPDM compositions having increased molecular weight and improved processability as indicated by an increase in rheology ratio. The EPDM compositions of the present invention are prepared by polymerizing in two or more separate reactors with two or more catalysts having different reactivities, and the resulting interpolymers are intimately combined.

The present disclosure provides a composition. In an embodiment, the composition comprises a pure ethylene/propylene/nonconjugated polyene interpolymer. The pure ethylene/propylene/nonconjugated polyene interpolymer comprises from greater than 0 wt% to 6.0 wt% of a nonconjugated polyene. The pure ethylene/propylene/nonconjugated polyene interpolymer has the following properties:

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

(ii) mooney viscosity (ML (1+4), 125 ℃) of 80 to 85;

(iii) a Rheology Ratio (RR) of 35 to 65;

(iv) Mw/Mn is from 2.2 to 3.5;

(v) a tan delta ratio of 0.6 to 0.9; and

(vi) the absolute tan delta slope is from 5.0 to less than 10.0.

Definition of

Any reference to the periodic Table of elements is to the periodic Table of elements as published by CRC Press, Inc., 1990-1991. A family of elements in the table is referred to by a new notation for numbering the families.

For purposes of united states patent practice, the contents of any referenced patent, patent application, or publication, particularly with respect to the disclosure of each definition (to the extent not inconsistent with any definitions specifically provided in this disclosure) and the general knowledge in the art, are incorporated by reference in their entirety (or equivalent us versions thereof are so incorporated by reference).

The numerical ranges disclosed herein include all values from the lower value to the upper value, and include both the lower value and the upper value. For ranges containing an exact value (e.g., 1 or 2, or 3 to 5, or 6, or 7), any subrange between any two exact values is included (e.g., 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).

Unless stated to the contrary, implied by 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.

As used herein, the term "blend" or "polymer blend" is a blend of two or more polymers. This blend may or may not be miscible (phase separated). The blend may or may not be phase separated. This 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.

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.

The terms "comprising," "including," "having," and derivatives thereof, are not intended to exclude the presence of any additional component, step or procedure, whether or not the component, step or procedure is specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all compositions claimed through use of the term "comprising" may contain any additional additive, adjuvant or compound, whether polymeric or otherwise. Rather, the term "consisting essentially of … …" excludes any other components, steps, or procedures (other than those that are not essential to operability) from the scope of any subsequently stated content. The term "consisting of … …" excludes any component, step, or procedure not specifically recited or listed. Unless stated otherwise, the term "or" means the listed members individually as well as in any combination. The use of the singular encompasses the use of the plural and vice versa.

An "ethylene-based polymer" is a polymer that contains a majority weight percent, based on the total weight of the polymer, of units derived from ethylene, in polymerized form. Non-limiting examples of ethylene-based 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.

An "interpolymer" is a polymer prepared by polymerizing at least two different monomers. This generic term encompasses copolymers, which are generally used to refer to polymers prepared from two different monomers, as well as polymers prepared from more than two different monomers, such as terpolymers, tetrapolymers, and the like.

An "olefin-based polymer" or "polyolefin" is a polymer containing more than 50% by weight polymerized olefin monomers (based on the total amount of polymerizable monomers) and optionally may contain at least one comonomer. Non-limiting examples of olefinic polymers include ethylene-based polymers and propylene-based polymers.

A "polymer" is a compound prepared by polymerizing monomers of the same or different types that, in polymerized form, provide multiple and/or repeating "units" or "monomer units" that make up the polymer. Thus, the generic term polymer encompasses the term homopolymer, which is commonly used to refer to polymers prepared from only one type of monomer, and the term copolymer, which is commonly used to refer to polymers prepared from at least two types of monomers. It also encompasses all forms of copolymers such as random copolymers, block copolymers, and the like. The terms "ethylene/α -olefin polymer" and "propylene/α -olefin polymer" refer to copolymers prepared by polymerizing ethylene or propylene, respectively, and one or more additional polymerizable α -olefin monomers, as described above. It should be noted that although polymers are generally referred to as being "made from", "based on", "containing" a specified monomer or monomer type, or "containing" a specified monomer content, and the like, in the present context, the term "monomer" should be understood to refer to the polymerized residue of the specified monomer rather than to unpolymerized species. Generally, polymers herein are referred to as being based on "units" in polymerized form as the corresponding monomers.

Test method

Absolute tan delta slope. the absolute value of the tan δ slope is defined by the following equation (a).

For EPDM Neon analysis¹³C NMR method. The samples were prepared by adding about "2.6 g" of a "tetrachloroethane-d 2/o-dichlorobenzene 50/50 mixture" having a chromium acetyl acetonate (relaxant) content of "0.025M" to a "0.2 g sample" in a 10mm NMR tube. The sample was dissolved and homogenized by heating the tube and its contents to 150 ℃. Data were collected using a Bruker 400MHz spectrometer equipped with a Bruker Dual DUL high temperature CryoProbe. Data were acquired at a sample temperature of 120 ℃ using a "160 scans per data file", six second pulse repetition delay. The acquisition was performed using a spectral width of 25,000Hz and a file size of 32K data points.

NMR spectroscopic analysis of the compositions of the examples was performed using the following analytical methods. The quantification of the monomers present in the EPDM can be calculated using the following equations (1 to 9).

Ethylene mole calculations normalize the spectral range from 55.0 to 5.0ppm to 1000 integral units. The contribution under the normalized integration area accounts for only 7 of the ENB carbons. 111ppm and 147ppm ENB diene peaks were excluded from the calculation due to concerns about the possibility of double bonds reacting at high temperatures.

Equation 1

Equation 2 moles ENB CH3(13.6-14.7ppm)

Equation 3P mole CH3(19.5-22.0ppm)

Equation 4

Equation 5

Equation 6

Equation 7

Equation 8

Equation 9

Percent branching area of intermediate chains¹³C NMR. "intermediate chain branching" (or "iCB") is a phenomenon in which oligomers, generated in situ, are rapidly incorporated into the polymer backbone. The branching resulting from the incorporation of these oligomers does not increase viscosity at low shear rates and therefore the resulting polymers exhibit similar behavior to linear molecules. The incorporation of the oligomer is efficient, so that the oligomer content cannot be detected in the final polymer. It is believed that the combination of iCB polymer exhibiting high branch density (as estimated by NMR) and its intermediate length (30 to 75 carbon units) extends the backbone length required for entanglement in the molten state. This behavior is actually similar to that of linear molecules.

EPDM Synthesis Using tetrachloroethane-d 2 with 0.025M chromium acetylacetonate¹³C NMR spectroscopic analysis to quantify the level of intermediate chain branching, thereby improvingSpectral resolution in the region of 34.6-34.4 ppm. Samples were prepared by adding about "2.6 g" "tetrachloroethane-d 2 with 0.025M chromium acetylacetonate" to a "0.3 g sample" in a 10mm NMR tube. The sample was dissolved and homogenized by heating the tube and its contents to 140 ℃. Data were collected using a Bruker 400MHz spectrometer equipped with a Bruker Dual DUL high temperature CryoProbe with back-gated NMR pulses. Data were acquired at a sample temperature of 120 ℃ using a "8000 scans per data file", 7.3 second pulse repetition delay. The spectroscopic data refer to the EEE framework at 30 ppm.

As disclosed in WO2018/005922, EPDM polymers with iCB exhibit a methylene peak in the region of 34.4ppm to 34.6ppm, which is greater than 0.01% (excluding the entire spectrum of tetrachloroethane solvent) of the total integrated area of 160.0 to 100.0ppm plus 60.0 to 0.000 ppm. Process for preparing EPDM of the present invention¹³C NMR spectral analysis showed no methylene peak in the region of 34.4ppm to 34.6 ppm. The EPDM interpolymers of the present disclosure are free of intermediate chain branching.

Density is measured according to ASTM D792, method B. The results are recorded in grams per cubic centimeter (g/cc).

Differential Scanning Calorimetry (DSC). Differential Scanning Calorimetry (DSC) was used to measure crystallinity in ethylene (PE) samples (including EPDM) and propylene (PP) samples. Samples (0.5g) were compression molded into films at 5000psi, 190 ℃ for two minutes. About 5 to 8mg of the film forming sample was weighed and placed in a DSC pan. The lid was screwed down on the pan to ensure a closed atmosphere. The sample pan was placed in a DSC unit and then heated at a rate of about 10 ℃/minute to a temperature of 180 ℃ for PE (for PP, to 230 ℃). The sample was held at this temperature for three minutes. The sample was then cooled to-90 ℃ for PE (for PP, to-90 ℃) at a rate of 10 ℃/min and held isothermally at that temperature for three minutes. The sample was then heated at a rate of 10 deg.C/min until completely melted (second heating). By heat of fusion (H) determined by the second heating curve_f) Percent crystallinity (e.g., crystallization) was calculated by dividing by 292J/g theoretical heat of fusion for PE (165J/g for PP) and multiplying this number by 100Degree%_f/292J/g) x 100 (for PE)).

Unless otherwise stated, the melting point (T) of each polymer_m) Is determined by the second heating curve and the crystallization temperature (T)_c) Is determined by the first cooling curve.

Dynamic Mechanical Spectroscopy (DMS). Under a nitrogen purge, small angle oscillatory shear (melt DMS) was performed using a TA instrument ARES equipped with a "25 mm parallel plate". The time between sample loading and the start of the test was set to five minutes for all samples. The experiments were carried out at 190 ℃ in a frequency range of 0.1rad/s to 100 rad/s. The strain amplitude was adjusted to 1% to 3% based on the response of the sample. The stress response is analyzed in terms of amplitude and phase, from which the storage modulus (G'), loss modulus (G "), dynamic viscosity η, and tan δ are calculated. The samples of the dynamic mechanical spectra were "25 mm diameter x 3.3mm thick" compression molded discs that were formed at 180 ℃ and 10MPa molding pressure for five minutes and then quenched between cooled platens (15 ℃ to 20 ℃) for two minutes. The rheology ratios (V0.1/V100 at 190 ℃ C.; also known as "RR"), tan delta (0.1rad/s, 190 ℃ C.) and tan delta (100rad/s, 190 ℃ C.) were recorded.

FTIR method for EPDM composition analysis. The ethylene content of the terpolymer containing ethylene, propylene and 5-ethylidene-2-norbornene was analyzed using ASTM D9300 and the ethylidene-norbornene or dicyclopentadiene content thereof was analyzed using ASTM D6047.

Gel permeation chromatography. The chromatographic system consisted of Polymer Laboratories model PL-210 or Polvmer Laboratories model PL-220. The column and transfer chamber were operated at 140 ℃. The columns were three Polymer Laboratories 10 micron Mixed B columns. The solvent used was 1, 2, 4 trichlorobenzene. Samples were prepared at a concentration of "0.1 grams of polymer in 50 milliliters of solvent". The solvent used to prepare the samples contained "200 ppm Butylated Hydroxytoluene (BHT)". The samples were prepared by gently stirring for four hours at 160 ℃. The injection volume was 100 microliters and the flow rate was 1.0 milliliters/minute.

Calibration of the GPC column set was performed with 21 "narrow molecular weight distribution polystyrene standards" having molecular weights ranging from 580 g/mole to 8,400In the range of 000 g/mole, arranged as a mixture of six "mixed liquor" and with at least ten times the separation between the individual molecular weights. Standards were purchased from Polymer Laboratories (shoplipshire, uk). The polystyrene standards were prepared as follows: for molecular weights equal to or greater than 1,000kg/mol, are prepared in "0.025 grams in 50 milliliters of solvent" and for molecular weights less than 1,000kg/mol, are prepared in "0.05 grams in 50 milliliters of solvent". Polystyrene standards were gently stirred at 80 degrees celsius for 30 minutes to dissolve. Narrow standard mixtures were run first and to reduce the "highest molecular weight" components to reduce degradation. The polystyrene standard peak molecular weight was converted to polyethylene molecular weight using the following equation: m_Polyethylene＝A×(M_Polystyrene)^BWhere M is molecular weight, a has a value of 0.431 and B equals 1.0 (as described in Williams and Ward, journal of polymer science polymers, journal of polymer science, 6, 621 (1968)). Polyethylene equivalent molecular weight calculations were performed using Viscotek TriSEC software version 3.0.

Mooney viscosity. The mooney viscosity (ML 1+4 at 125 ℃) was measured according to ASTM D1646 with a preheating time of one minute and a rotor operating time of four minutes. The apparatus is 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.

Tan delta ratio. the tan delta ratio is defined as the tan delta of the first polymer component produced in the first reactor (0.1rad/s, 190 ℃) per tan delta of the final composition in the second reactor (0.1rad/s, 190 ℃).

Drawings

FIGS. 1A and 1B are graphs showing that prior art EPDM for comparative sample 3(CS3) has a peak at 34.4ppm to 34.6ppm according to one embodiment of the present disclosure¹³C NMR spectrum (FIG. 1A), comparison shows that EPDM of inventive example 1 is peak-free at 34.4ppm to 34.6ppm¹³C NMR spectrum (FIG. 1B).

Detailed Description

The present disclosure provides a composition. In an embodiment, the composition comprises a pure ethylene/propylene/nonconjugated polyene interpolymer. The pure ethylene/propylene/nonconjugated polyene interpolymer comprises from greater than 0 wt% to 6.0 wt% of a nonconjugated polyene. The pure ethylene/propylene/nonconjugated polyene interpolymer has the following properties:

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

(ii) mooney viscosity (ML (1+4), 125 ℃) of 80 to 85;

(iii) a Rheology Ratio (RR) of 35 to 65;

(iv) Mw/Mn is from 2.2 to 3.5;

(v) a tan delta ratio of 0.6 to 0.9; and

(vi) the absolute tan delta slope is from 5.0 to less than 10.0.

The ethylene/propylene/nonconjugated polyene interpolymer was neat. A "pure" ethylene/propylene/nonconjugated polyene interpolymer has no added oil, is otherwise free of oil, or is otherwise "oil-free". It can thus be appreciated that Mooney viscosity values and rheological ratios apply to pure ethylene/propylene/nonconjugated polyene interpolymers that are free of oil.

A pure ethylene/propylene/nonconjugated polyene interpolymer comprises an ethylene monomer, a propylene comonomer, and a nonconjugated polyene terpolymer. Although propylene is a copolymer, it is understood that other alpha-olefins may be used as comonomers. Non-limiting examples of suitable comonomers other than propylene include C₄-C₈Alpha-olefins, such as 1-butene, 1-hexene and 1-octene.

The nonconjugated polyene being C₆-C₁₅A linear, branched or cyclic hydrocarbon diene. Non-limiting examples of suitable linear 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, 7-octadiene, 5, 7-dimethyl-1, 7-octadiene, 1, 9-decadiene, and mixed isomers of dihydromyrcene. Non-limiting examples of suitable monocyclic cycloaliphatic dienes include 1, 4-cyclohexadiene, 1, 5Cyclooctadiene and 1, 5-cyclododecadiene. Non-limiting examples of polycyclic alicyclic fused and bridged cyclic dienes include tetrahydroindene, methyltetrahydroindene, alkenyl, alkylene, cycloalkenyl, and cycloalkylidene 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.

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

In the examples, the diene is 5-ethylidene-2-norbornene (ENB).

In an embodiment, a neat ethylene/propylene/nonconjugated polyene interpolymer comprises from 45 wt% to 55 wt%, or from 47 wt% to 53 wt%, or from 49 wt% to 51 wt% ethylene monomer, from 40 wt% to 50 wt%, or from 43 wt% to 49 wt%, or from 45 wt% to 47 wt% propylene comonomer, (iii) from 1 wt% to 6 wt%, or from 2 wt% to 5 wt%, or from 3 wt% to 4 wt%, or from 4 wt% to 5 wt% ENB; an ethylene/propylene/nonconjugated polyene interpolymer having the following properties:

(i) a molecular weight (Mw) of 240,000 to 260,000, or 245,000 to 258,000 or 248,000 to 256,000;

(ii) a Mooney viscosity of 80 to 85 or 82 to 84;

(iii) a rheology ratio of 35 to 45, or 37 to 43 or 39 to 41;

(iv) Mw/Mn is from 2.2 to 3.5;

(v) a tan delta ratio of 0.6 to 0.9;

(vi) an absolute tan delta slope of 5.0 to less than 10.0; and

(vii) not containing 34.4ppm to 34.6ppm¹³C NMR peaks.

The weight percentages are based on the total weight of the pure ethylene/propylene/nonconjugated polyene interpolymer. The pure ethylene/propylene/nonconjugated polyene interpolymer having the foregoing amounts of ethylene, propylene, and ENB and properties (i) - (vii) is hereinafter referred to as composition 1.

In an embodiment, composition 1 comprises 47 to 53 or 49 to 51 wt% ethylene monomer, 43 to 49 or 45 to 47 wt% propylene comonomer, (iii)2 to 5, or 3 to 4 or 4 to 5 wt% ENB; an ethylene/propylene/nonconjugated polyene interpolymer having the following properties:

(i) mw from 240,000 to 260,000, or 245,000 to 258,000 or 248,000 to 256,000;

(ii) a mooney viscosity of 80 to 105, or 82 to 100 or 85 to 95;

(iii) a rheology ratio of 35 to 65, or 37 to 60 or 39 to 55;

(iv) Mw/Mn is from 3.0 to 3.5;

(v) a tan delta ratio of 0.65 to 0.9; or 0.7 to 0.85;

(vi) an absolute tan delta slope of 6.0 to less than 12.0 or 7.0 to less than 11.0;

(vii) not containing 34.4ppm to 34.6ppm¹³C NMR peaks; and

(viii) the Mw/V0.1 ratio is less than 1.8 or from 1.5 to 1.7.

Composition 1 is a high-mooney EPDM that exhibits a balance between improved physical properties of high molecular weight linear polymers and improved processability of low molecular weight highly branched polymers, absent intermediate branching.

In an embodiment, the pure ethylene/propylene/nonconjugated 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 identical and each reactor is a loop reactor.

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 a feed) is operated in a manner that promotes the formation of a low molecular weight fraction of the desired polymer.

The temperature difference between the first reactor and the second reactor affects the Mw/Mn of the final product, the larger the temperature difference, the wider the Mw/Mn. While the operating temperature of each reactor will depend on many factors, for example, the alpha-olefin, diene, catalyst, solvent, equipment and equipment design, pressure, flow rates and turbulence, relative amounts of reagents, properties of the desired product, etc., typical operating temperatures for the first reactor are from 65 ℃ to 90 ℃ and for the second reactor from 85 ℃ to 120 ℃. The residence time of the reactants in each reactor will also depend on these factors, but typical residence times for the reactants in each reactor are from two minutes to 90 minutes.

Ethylene, alpha-olefin (i.e., propylene) and diene (if any), solvent and optionally hydrogen are blended in the desired proportions by any convenient means, and the blend is then introduced into the first reactor, i.e., the reactor whose output is used as a feed to the other or second reactor. The first catalyst is typically introduced into the first reactor separately from the other reagents. The first and second reactors are operated on a continuous basis such that as the output of the first reactor is discharged as the 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).

The first and second reactors are in fluid communication with each other, typically connected by one or more conduits. These conduits are typically equipped with one or more mixers (to promote uniform blending of the reaction materials).

As with the first reactor, ethylene, alpha-olefin, diene (if any), solvent, and optionally hydrogen are blended in the desired proportions and the blend is then introduced into the second reactor, i.e., the reactor that receives the output from the other or first reactor as a feed. Likewise, a second catalyst (a different catalyst than the first catalyst introduced into the first reactor) is typically introduced into the second reactor separately from the other reagents. The output of the first reactor typically contains 1 to 30 weight percent solids (i.e., polymer) and it may be fed separately to the second reactor with the other reagents, or it may be first blended with one or more of the other reagents prior to introduction into the second reactor. The output of the second reactor typically contains 8 to 30 weight percent solids, with the desired polymer product separated from the solvent and unreacted monomers, and the latter (i.e., solvent and unreacted monomers) recycled separately or disposed of in a safe and environmentally friendly manner.

In an embodiment, the neat ethylene/propylene/nonconjugated 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 has a Mw of 375,000 or 380,000 to 390,000 or 400,000. In further embodiments, the Mw of the first polymer component is 375,000 to 400,000 or 380,000 to 390,000.

In an embodiment, a first catalyst is introduced into a first reactor and a second catalyst is introduced into a second reactor. The second catalyst is different from the first catalyst. The first catalyst (introduced into the first reactor) is a zirconium-based catalyst and the second catalyst (introduced into the second reactor) is a hafnium-based catalyst, and the pure ethylene/propylene/nonconjugated polyene interpolymer of the present invention contains a residual amount of hafnium and a residual amount of zirconium. As used herein, the term "residual amount" is greater than 0ppm to 5 ppm.

In the examples, the first catalyst was [ [ rel-2 ', 2 "- [ [ (1R, 3S) -1, 3-methyl-1, 3-propanediyl ] bis (oxy- κ O) ] 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- κ O ] ] (2-) ] dimethyl zirconium, and is referred to hereinafter as catalyst a. Catalyst a has the structure (a) provided below.

Structure (A)

The chemical formula is as follows: c₈₇H₁₀₈F₂N₂O₄Zr

Molecular weight: 1375.02

In the examples, the second catalyst is [ [ [ [ [2 ', 2 "- [1, 3-propanediylbis (oxy-kO) ] 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-kO ] ] (2-) ] -dimethylhafnium or OC-6-33) -dimethyl [ [2 ', 2" - [1, 3-propanediylbis (oxy- κ O) ] 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- κ O ] ] (2-) ] hafnium, and is referred to hereinafter as catalyst B. Catalyst B has the structure (B) provided below.

Structure (B)

The chemical formula is as follows: c₈₅H₁₀₄F₂HfN₂O₄

Molecular weight: 1434.23

In the examples, composition 1 contained 1ppm to 5ppm residual zirconium and 1ppm to 5ppm residual hafnium. In further embodiments, the residual amount of each of the hafnium metal and the zirconium metal excludes titanium.

2. Additive agent

The pure ethylene/propylene/nonconjugated polyene interpolymer of the present invention may comprise 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.

In the examples, oil was added to a pure ethylene/propylene/nonconjugated polyene interpolymer such that the ethylene/propylene/nonconjugated polyene interpolymer was no longer free of oil.

In an embodiment, the neat ethylene/propylene/nonconjugated polyene interpolymer composition comprises at least one additive selected from the group consisting of a filler, an antioxidant, a UV stabilizer, a blowing agent, or a combination 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; alumina 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.

In an embodiment, the neat ethylene/propylene/nonconjugated polyene interpolymer comprises an antioxidant. Non-limiting examples of suitable antioxidants include hindered phenols, bisphenols and thiobisphenols; a substituted hydroquinone; a tri (alkylphenyl) phosphite; a dialkylthiodipropionate; a naphthylamine; a substituted diphenylamine; dialkyl, alkylaryl and diaryl substituted p-phenylenediamine; monomeric and polymeric dihydroquinolines; 2- (4-hydroxy-3, 5-t-butylaniline) -4, 6-bis (octylthio) 1, 3, 5-triazine, hexahydro-1, 3, 5-tris- (3, 5-di-t-butyl-4-hydroxyphenyl) propionyl-s-triazine, 2, 4, 6-tris (n-1, 4-dimethylpentylphenylidene-diamino) -1, 3, 5-triazine, tris- (3, 5-di-t-butyl-4-hydroxybenzyl) isocyanurate, nickel dibutyldithiocarbamate, 2-mercaptotolylimidazole and zinc salts thereof, petroleum waxes, and the like.

3. Applications of

The neat ethylene/propylene/nonconjugated polyene interpolymer composition of the present invention can be further compounded into a rubber formulation (Banbury) internal mixer or extruder) and further cured into a final article (extrusion, injection molding, calendering).

The pure ethylene/propylene/nonconjugated polyene interpolymer and/or the final article can be used in automotive hoses, automotive belts, weatherstrip profiles, construction profiles, roofing membranes, injection molded articles, general purpose rubber articles, tires, impact modification, TPE compounds, and other conventional and nonconventional rubber elastomer applications.

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

Examples of the invention

1. Synthesis of Experimental EPDM

Continuous polymerization

The polymerization reaction is carried out under steady state conditions, i.e., constant reactant concentration 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. Monomer (b): ethylene (CAS 74-85-1); propylene (CAS 115-07-1); 5-ethylidene-2-norbornene, ENB (CAS 16219-75-3).

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.

Separately feeding catalyst a to the first reactor and catalyst B to the second reactor; catalyst a and catalyst B were activated in situ using cocatalyst 1 and cocatalyst 2.

Cocatalyst-1 was a mixture of methyl di (C14-18 alkyl) ammonium salts of tetrakis (pentafluorophenyl) borate prepared by the reaction of a long chain trialkylamine (ARMEEN M2HT, available from Akzo-Nobel, Inc.), HCl and Li [ B (C6F5)4], substantially as disclosed in USP 5,919,988 (example 2). Cocatalyst-1 was obtained from Border Scientific and used without further purification.

Cocatalyst-2 was a Modified Methylaluminoxane (MMAO) from Akzo Nobel and was used without further purification

The structures of catalyst a and catalyst B are provided below.

Catalyst A: [ [ rel-2 ', 2 "- [ [ (1R, 3S) -1, 3-methyl-1, 3-propanediyl ] bis (oxy- κ O) ] 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- κ O ] ] (2-) ] dimethylzirconium. CAS # 1360629-63-5.

The chemical formula is as follows: c₈₇H₁₀₈F₂N₂O₄Zr

Molecular weight: 1375.02

Catalyst B: [ [ [2 ', 2 ' - [1, 3-propanediylbis (oxy-kO) ] 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-kO ] ] (2-) ] -dimethylhafnium or OC-6-33) -dimethyl [ [2 ', 2 ' - [1, 3-propanediylbis (oxy-kO) ] 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- κ O ] ] (2-) ] hafnium. CAS # 1360650-53-8.

The chemical formula is as follows: c₈₅H₁₀₄F₂HfN₂O₄

Molecular weight: 1434.23

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

After polymerization, a small amount of water is introduced as a catalyst kill into the reactor outlet stream and the reactor outlet stream is introduced into a flash vessel where 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.

The monomer feed rates and polymerization temperatures and other conditions are listed in tables 1 and 2 below.

Table 1: reaction conditions for the EPDM of the present invention

Table 2: reaction conditions for the EPDM of the present invention

Table 3: comparing EPDM and EPDM of the present invention

^#CS3 is invention 1, Table 3, FIG. 3, WO2018/005922^SCS4 is invention 2, Table 4, WO2018/005852^％CS5 is EPDM B47, Table 2, WO2014/003857 IE-inventive examples

IE1 contained 38.6% by weight of the first polymer component (EPDM produced in reactor 1) and 61.40% by weight of the second polymer component (EPDM produced in reactor 2). The weight percentages are based on the total weight of the final EPDM terpolymer.

As shown in FIG. 1B, IE1 did not have iCB (did not have at 34.4ppm to 34.6 ppm)¹³C NMR peak) and CS3 has iCB, as in FIG. 1A at 34.4ppm to 34.6ppm¹³As indicated by the C NMR peaks.

IE1 had a Mw/Mn of 3.0 to 3.5(3.4), an absolute tan δ slope of 9.5, and a tan δ ratio of 0.6 to 0.9(0.84), and was free of iCB. The combination of these properties indicates that IE1 has a balance of processability and branching (no iCB). The tan delta ratio of 0.6 to 0.9 indicates that the tan delta of the final EPDM terpolymer is lower than the tan delta value of the EPDM terpolymer in the first reactor. the tan delta ratio is the result of a unique dual catalyst/dual reactor configuration. The first catalyst (catalyst a) in the first reactor produced high molecular weight (375,000 to 400,000) linear EPDM terpolymers and the second catalyst (catalyst B) in the second reactor produced branched EPDM terpolymers.

It is specifically intended that the present disclosure not be limited to the embodiments and illustrations contained herein, but include modified forms of those embodiments including portions of the embodiments and combinations of elements of different embodiments as come within the scope of the following claims.