BR112020008075B1 - COMPOSITION, ARTICLE AND PROCESS FOR FORMING A COMPOSITION - Google Patents

Abstract

It is a composition comprising an ethylene/CO interpolymer, formed from high pressure free radical polymerization, and wherein the ethylene/CO interpolymer has the following properties: a) a CO content of greater than 0 weight percent to less than or equal to 10 weight percent CO (carbon monoxide), based on the weight of the interpolymer; and b) a melting point, Tm, in °C that meets the following relationship: Tm (°C) = 601.4 * (Density in g/cm3) - 452.5 (°C).

Description

Cross reference to related orders

[0001] This application claims priority from US Provisional Patent Application 62/579,571, filed on October 31, 2017, which is hereby incorporated by reference in its entirety.

Background of the invention

[0002] Companies that perform extrusion coating a variety of polymers, including low-density polyethylene (LDPE), on paper and paperboard, continually face problems getting good "fiber breakage" adhesion, which is the amount of adhesion required to have adhesion between the polymer and the paper greater than the adhesion of the paper fibers to themselves. When polymer is pulled from a paper substrate, if fiber breakage occurs, this adhesion is considered acceptable. If the polymer is pulled from the paper without fibers (no fiber breakage), this is considered unacceptable adhesion. Improved adhesion in the extrusion lamination process, which is used to manufacture multilayer substrates, is also desirable. Ethylene-based polymers used for coatings and films are disclosed in the following references: International Publications Nos. WO2014/105608, WO2011/071843, WO1991/18944, WO2007/110127, WO1997/45465, WO2012/057975, WO2012/084787; US Patent Nos. 9523015, 6407191, 5178960, 3860538, 4714741, 6558809, 4962164, 3676401; GB 1448062; EP 0230143B1; Publications Nos. 2017/0114163, 2017/0107315, 2008/0242809, and Ward et al., Ethylene-Carbon Monoxide Extrudable Adhesive Copolymers for Polyvinylidene Chloride, June 1988 Tappi Journal, pp. 140 to 144; Scott et al., Degradable Polymers, Principles and Applications, Chapter 8: Ethylene-carbon monoxide copolymers, pp. 156 to 168, Chapman and Hall (1995).

[0003] It is known that when running extrusion coating lines at increasingly high speeds with conventional polymers, unacceptable fiber breakage adhesion occurs. This adhesion is related to the oxidation of the molten polymer as it exits the extrusion die and before it comes into contact with the paper (or the time in the air gap). At higher line speeds, the molten polymer curtain has less time to oxidize, which can reduce adhesion. There is a need for new ethylene-based polymers that can be used in high-speed extrusion coating lines and that have good melt strength and adhesion to paper substrates, and that can be used at lower melt temperatures and/or at higher paper substrate line speeds. These needs have been met by the following invention.

Summary of the invention

[0004] A composition comprising an ethylene/CO (carbon monoxide) interpolymer, formed from high pressure free radical polymerization, and wherein the ethylene/CO (carbon monoxide) interpolymer has the following properties: a) a content of CO from "greater than 0" weight percent to less than or equal to 10 weight percent CO (carbon monoxide), based on the weight of the interpolymer; and b) a melting point, Tm, in °C that meets the following relationship: Tm (°C) < 601.4 * (Density in g/cm3) - 452.5 (°C).

Brief description of the drawings

[0005] Figure 1 represents a reactor system used in the invention.

[0006] Figure 2 shows the graph on a logarithmic scale of the melt strength versus the % CO level of the Inventive Examples.

[0007] Figure 3 shows the graph on a linear scale of the melt strength versus the % CO level of the Inventive Examples.

[0008] Figure 4 shows the melting temperature versus density of the Inventive Examples.

Detailed Description

[0009] It has been found that the observed ethylene/CO interpolymers and other copolymers can be used to increase the melt strength and improve the low temperature adhesion of substrates. It was found that ethylene/CO interpolymers and copolymers made with 2 to 3 wt% CO had substantially higher melt strength compared to those made with 1 wt% or less CO. Higher CO levels also result in better adhesion at lower temperatures compared to samples with lower CO levels.

[0010] A composition comprising an ethylene/CO interpolymer, formed from a high pressure free radical polymerization, and wherein the ethylene/CO interpolymer has the following properties: c) a CO content of “higher that 0” percent by weight to less than 10 percent by weight CO (carbon monoxide), based on the weight of the interpolymer; and d) a melting point, Tm, in °C that meets the following relationship: Tm (°C) < 601.4 (°C/(g/cm3)) * (Density in g/cm3) - 452.5 ( °C). In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0011] The composition may comprise a combination of two or more embodiments as described herein.

[0012] The ethylene/CO interpolymer and another copolymer may comprise a combination of two or more embodiments as described herein.

[0013] As used herein, CO content refers to polymerized CO in the polymer.

[0014] In one embodiment, the ethylene/CO interpolymer has a) a CO content of 0.1% by weight to less than 10% by weight, or from 0.2 to less than 10% by weight, or from 0.5% by weight to less than 10% by weight, based on the weight of the interpolymer. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0015] In one embodiment, the ethylene/CO interpolymer has a) a CO content of 1.0% by weight to 9.0% by weight, or from 1.0% by weight to 9.0% by weight or from 1.2 to 8.0% by weight, or from 1.4% by weight to 7.0% by weight %, or from 1.6% by weight to 6.0% by weight, or from 1, 8% by weight to 5.0% by weight, based on the weight of the interpolymer. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0016] In one embodiment, the ethylene/CO interpolymer has a CO content > 1.2% by weight, or > 1.4% by weight, or > 1.6% by weight, or > 1.8% by weight, or >2.0% by weight, or >2.2% by weight, or >2.4% by weight based on the weight of the interpolymer. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the ethylene/CO interpolymer has a CO content of >4.0% by weight, or >3.8% by weight, or >3.6% by weight, or >3.4% by weight. , or > 3.2% by weight based on the weight of the interpolymer. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0017] In one embodiment, the ethylene/CO interpolymer complies with the following ratio: MS (cN) > 2.0 x (% CO by weight) + 2.0. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0018] In one embodiment, the ethylene/CO interpolymer has a melt index (I2) of 0.1 to 100 g/10 min, or 0.5 to 50 g/10 min, or 1.0 to 30 g/10 min. Furthermore, the ethylene/CO interpolymer may have a melt index (I2) of 0.1 to 6 g/10 min, or 0.3 to 3 g/10 min, or 0.3 to 0.7 g/10 min. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0019] In one embodiment, the ethylene/CO interpolymer has a melt index (I2) > 1.5 g/10 min, or > 2.0 g/10 min, or > 2.5 g/10 min, or > 3.0 g/10 min, or > 3.5 g/10 min. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the ethylene/CO interpolymer has a melt index (I 2 ) < 20 g/10 min, or < 15 g/10 min, or < 10 g/10 min, or < 8.0 g/10 min , or < 7.0 g/10 min or < 6.0 g/10 min. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0020] In one embodiment, the ethylene/CO interpolymer has a Tm (°C) > 601.4 (°C/(g/cm3)) * (Density in g/cm3) - 460.0 (°C) . In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0021] In one embodiment, the ethylene/CO interpolymer has a melting temperature (Tm) > 102 °C, or > 103 °C, or > 104 °C, or > 105 °C, or > 106 °C, as determined by DSC (peak temperature). In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the ethylene/CO interpolymer has a melting temperature (Tm) < 114 °C, or < 113 °C, or 112 °C, or < 111 °C, or < 110 °C, or < 109 °C C, as determined by DSC (peak temperature). In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0022] In one embodiment, the propylene-based polymer has a melting temperature, Tm, of 102°C to 114°C, or 103°C to 113°C, or 104°C to 112°C, or 105°C to 111°C, or 106°C to 110°C as measured by DSC (peak temp). In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0023] In one embodiment, the ethylene/CO interpolymer has a crystallization temperature (Tc) > 91 °C, or > 92 °C, or > 93 °C, or > 94 °C, as determined by DSC (temperature peak). In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the ethylene/CO interpolymer has a crystallization temperature (Tc) < 99 °C, or < 98 °C, or < 97 °C, or < 96 °C, as determined by DSC (peak temperature). In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0024] In one embodiment, the ethylene/CO interpolymer has a percent crystallinity > 45, or > 46, or > 47, or > 48, or > 49, as determined by DSC (peak temperature). In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the ethylene/CO interpolymer has a percent crystallinity < 55, or < 54, or < 53, or < 52, or < 51, as determined by DSC (peak temperature). In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0025] In one embodiment, the ethylene-based polymer has a density >0.940 g/cm3, or >0.945 g/cm3, or >0.950 g/cm3, or >0.955 g/cm3 (1 cc = 1 cm3). In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the ethylene/CO interpolymer has a density >0.990 g/cm3, or >0.985 g/cm3, or >0.980 g/cm3, or <0.975 g/cm3, or <0.970 g/cm3. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0026] In one embodiment, the ethylene/CO interpolymer has a density > 0.910 g/cm3, or > 0.912 g/cm3, or > 0.915 g/cm3, or > 0.918 g/cm3, or > 0.920 g/cm3, or > 0.922 g/cm3, or > 0.925 g/cm3, or > 0.928 g/cm3, or > 0.930 g/cm3, or > 0.932 g/cm3, or > 0.935 g/cm3 (1 cc = 1 cm3). In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the ethylene/CO interpolymer has a density < 0.950 g/cm 3 , or < 0.948 g/cm 3 , or < 0.945 g/cm 3 , or < 0.942 g/cm 3 , or < 0.941 g/cm 3 . In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0027] In one embodiment, the ethylene/CO interpolymer has a density of 0.910 to 0.950 g/cm3 (1 cc = 1 cm3), or 0.920 to 0.950 g/cm3, or 0.925 to 0.950 g/cm3, or from 0.930 to 0.945 g/cm3, or from 0.935 to 0.942 g/cm3. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0028] In one embodiment, the ethylene/CO interpolymer has a molecular weight distribution (cc-GPC Mw/Mn) > 8.0, or > 8.5, or > 9.0, or > 9.5, or > 10.0. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the ethylene/CO interpolymer has a molecular weight distribution (cc-GPC Mw/Mn) < 15.0, or < 14.5, or < 14.0, or < 13.5, or < 13 .0, or < 12.5, or < 12.0. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0029] In one embodiment, the ethylene/CO interpolymer has a molecular weight distribution (cc-GPC Mw/Mn) of 8.0 to 14.0, additionally 9.0 to 13.0, additionally 10, 0 to 12.0 as determined by conventional GPC. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0030] In an alternative embodiment, the ethylene/CO interpolymer has a molecular weight distribution (cc-GPC Mw/Mn) of 3 to 12, or 4 to 11, or 4.5 to 11.

[0031] In one embodiment, the ethylene/CO interpolymer has a number average molecular weight (cc-GPC Mn) < 10,000 g/mol, or < 11,000 g/mol, or < 12,000 g/mol, or < 13,000 g /mol. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the ethylene/CO interpolymer has a number average molecular weight (cc-GPC Mn) < 20,000 g/mol, or < 19,000 g/mol, or < 18,000 g/mol, or < 17,000 g/mol, or < 16,000 g/mol or < 15,000 g/mol. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0032] In one embodiment, the ethylene-based polymer has a number average molecular weight (Mn) of 10,000 g/mol to 25,000 g/mol, plus 10,000 g/mol to 20,000 g/mol, plus 11,000 g /mol to 19,000 g/mol, in addition to 11,000 g/mol to 16,000 g/mol, in addition to 12,000 g/mol to 15,000 g/mol, as determined by conventional GPC. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0033] In one embodiment, the ethylene/CO interpolymer has a number average molecular weight (cc-GPC Mw) > 100,000 g/mol, < 130,000 g/mol, or < 135,000 g/mol, or < 140,000 g/mol mol, or < 145,000 g/mol. In one embodiment, the ethylene/CO interpolymer has a number average molecular weight (cc-GPC Mw) < 200,000 g/mol, or < 195,000 g/mol, or < 190,000 g/mol, or < 185,000 g/mol, or < 180,000 g/mol. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0034] In one embodiment, the ethylene/CO interpolymer has a number average molecular weight (MW) of 135,000 g/mol to 190,000 g/mol, plus 140,000 g/mol to 185,000 g/mol, plus 145,000 g /mol to 180,000 g/mol as determined by conventional GPC. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0035] In alternative embodiments, the ethylene/CO interpolymer may have a number average molecular weight (cc-GPC Mw) of 60,000 to 150,000 g/mol, or 65,000 to 150,000 g/mol, or 70,000 to 145,000 g /mol.

[0036] In one embodiment, the ethylene/CO interpolymer has a Tan Delta (0.1 rad/s, 190 °C) > 1.50, > 2.00, > 3.00, or > 3.10, or > 3.20 or > 3.30 or > 3.40. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the ethylene/CO interpolymer has a Tan Delta (0.1 rad/sec, 190 °C) < 6.40, or < 6.20, or < 6.00, or < 5.80, or < 5.60 g/mol. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0037] In one embodiment, the ethylene/CO interpolymer has a viscosity (0.1 rad/s, 190 °C) > 1800 Pa•s, > 2000 Pa*s, or > 2200 Pa*s, or > 2400 Pa*s, or > 2600 Pa^s, or > 2800 Pa^s. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, or a combination of embodiments described herein, the ethylene-based polymer has a viscosity (0.1 rad/sec, 190 °C) < 5000 Pa^s, or < 4800 Pa^s, or < 4600 Pa^s ^s, or < 4,400 Pa^s, or < 4,200 Pa^s, or < 4,000 Pa^s, or < 25,000 Pa^s. In a further embodiment, the ethylene/CO interpolymer has a viscosity (0.1 rad/s, 190°C) of 1800 to 30,000 Pa*s, or 2000 to 25,000 Pa*s. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0038] In one embodiment, the ethylene/CO interpolymer has a viscosity (100 rad/s, 190 °C) > 200 Pa*s, > 220 Pa*s, > 240 Pa*s, > 260 Pa*s, or > 270 Pa^s, or > 280 Pa^s, or > 290 Pa^s, or > 300 Pa^s. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the ethylene-based polymer has a viscosity (100 rad/s, 190 °C) < 370 Pa*s, or < 360 Pa*s, or < 350 Pa*s, or < 340 Pa*s, or < 330 Pa*s, or < 320 Pa^s, or < 800 Pa^s. In a further embodiment, the ethylene/CO interpolymer has a viscosity (100 rad/s, 190°C) of 200 to 1000 Pa^s, or 220 to 800 Pa^s. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0039] In one embodiment, the ethylene/CO interpolymer has a viscosity ratio (V0.1/V100, 190 °C) > 7.0, or > 7.5, or > 8.0, or > 8, 5, or > 9.0, or > 9.5, or > 15, or > 20, or > 30. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the ethylene/CO interpolymer has a viscosity ratio (V0.1/V100, 190 °C) < 15.5, or < 15.0, or < 14.5, or < 14.0, or < 13.5, or < 13.0, or < 12.0, or < 11.0. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0040] In one embodiment, the ethylene/CO interpolymer has a gpcBR < 2.45, or < 2.50, or < 2.55, or < 2.60, or < 2.65, or < 2.70 . In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the ethylene/CO interpolymer has a gpcBR < 3.20, or < 3.15, or < 3.10, or < 3.05, or < 3.00, or < 2.95. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the ethylene-based polymer has a gpcBR of from 2.50 to 3.20, in addition from 2.60 to 3.10, in addition from 2.70 to 3.00. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the ethylene-based polymer has a gpcBR of 1.00 to 3.20, or 1.10 to 3.10, or 1.10 to 3.00.

[0041] In one embodiment, the ethylene/CO interpolymer has an amyl group level (C5) > 0.50 amyl group per 1,000 carbon atoms, or > 0.75 amyl group per 1,000 carbon atoms, or > 1, 00 amyl group per 1000 carbon atoms or > 1.10 amyl group per 1000 carbon atoms or > 1.20 amyl group per 1000 carbon atoms as determined by 13C NMR. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the ethylene/CO interpolymer has an amyl group (C5) level < 5.00 amyl group per 1000 carbon atoms, or < 4.00 amyl group per 1000 carbon atoms, or < 3.00 amyl group per 1000 carbon atoms or < 2.00 amyl group per 1000 carbon atoms as determined by 13C NMR. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0042] In one embodiment, the ethylene/CO interpolymer has a level of vinyl group > 0.030 vinyl group per 1,000 carbon atoms, > 0.035 vinyl group per 1,000 carbon atoms, > 0.050 vinyl group per 1,000 carbon atoms, or > 0.055 vinyl group per 1000 carbon atoms, or > 0.060 vinyl group per 1000 carbon atoms, or > 0.065 vinyl group per 1000 carbon atoms, or > 0.070 vinyl group per 1000 carbon atoms, as determined by 1H NMR. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the ethylene/CO interpolymer has a level of vinyl group < 0.250 vinyl group per 1000 carbon atoms, < 0.200 vinyl group per 1000 carbon atoms, < 0.110 vinyl group per 1000 carbon atoms, or < 0.105 vinyl group per 1000 carbon atoms, or < 0.100 vinyl group per 1000 carbon atoms, or < 0.090 vinyl group per 1000 carbon atoms, or < 0.095 vinyl group per 1000 carbon atoms, as determined by 1H NMR. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0043] In one embodiment, the ethylene/CO interpolymer has a total level of unsaturation > 0.15 unsaturation per 1,000 carbon atoms, > 0.20 unsaturation per 1,000 carbon atoms, or > 0.22 unsaturation per 1,000 atoms of carbon, or > 0.24 unsaturation per 1000 carbon atoms, or > 0.26 unsaturation per 1000 carbon atoms, or > 0.28 unsaturation per 1000 carbon atoms, as determined by 1H NMR. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the ethylene/CO interpolymer has a level of unsaturation < 0.60 unsaturation per 1000 carbon atoms, < 0.55 unsaturation per 1000 carbon atoms, < 0.44 unsaturation per 1000 carbon atoms, or < 0.42 unsaturation per 1000 carbon atoms, or < 0.40 unsaturation per 1000 carbon atoms, or < 0.38 unsaturation per 1000 carbon atoms, or < 0.36 unsaturation per 1000 carbon atoms, as determined by NMR of 1H. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0044] In one embodiment, the ethylene/CO interpolymer comprises >80% by weight, or >85% by weight, of polymerized ethylene, based on the weight of the interpolymer. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the ethylene/CO interpolymer comprises >90% by weight or >95% by weight of polymerized ethylene, based on the weight of the interpolymer. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0045] In one embodiment, the ethylene/CO interpolymer is a low density polyethylene (LDPE) comprising the CO comonomer. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0046] In one embodiment, the ethylene/CO interpolymer is a copolymer, comprising, in polymerized form, ethylene and CO as the only types of monomer. In a further embodiment, the ethylene/CO copolymer comprises a major amount of polymerized ethylene, based on the weight of the copolymer. In another embodiment, the ethylene/CO copolymer comprises >90% by weight, or >95% by weight, or >98% by weight of polymerized ethylene, based on the weight of the copolymer.

[0047] In one embodiment, the ethylene/CO interpolymer is present at > 10% by weight, or > 20% by weight, or > 30% by weight, or > 40% by weight, or > 50% by weight, or > 60% by weight, or > 70% by weight, or > 80% by weight, or > 90% by weight, or > 95% by weight, or > 98% by weight, or > 99% by weight, with based on the weight of the composition. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0048] In one embodiment, the ethylene/CO interpolymer is present in an amount of from 10 to 50% by weight, or from 20 to 40% by weight based on the weight of the composition. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the ethylene/CO interpolymer is present in an amount of from 60 to 90% by weight, or from 65 to 85% by weight based on the weight of the composition. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the ethylene/CO interpolymer is present in an amount of from 1.0 to 10% by weight, or from 1.5 to 5.0% by weight, based on the weight of the composition. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0049] In one embodiment, the composition further comprises a second ethylene-based polymer. In a further embodiment, the second ethylene-based polymer is selected from an LDPE, an ethylene/alpha-olefin copolymer, or a combination thereof.

[0050] In one embodiment, the composition further comprises another ethylene-based polymer that differs in one or more properties, such as density, melt index, comonomer, comonomer content, etc., from the ethylene/CO interpolymer, and another copolymer. Other ethylene-based polymers include, but are not limited to, DOWLEX Polyethylene Resins, TUFLIN Linear Low Density Polyethylene Resins (LLDPE), ELITE and/or ELITE AT Enhanced Polyethylene Resins (all available from the Dow Chemical Company), polyethylenes high density (d > 0.955 g/cm3), medium density polyethylenes (density 0.935 to 0.955 g/cm3), EXCEED polymers and ENABLE polymers (both available from ExxonMobil), LDPE and EVA (ethylene vinyl acetate).

[0051] In one embodiment, the composition further comprises a propylene-based polymer. Suitable propylene-based polymers include polypropylene homopolymers, propylene/α-olefin interpolymers and copolymers, and ethylene/propylene interpolymers and copolymers.

[0052] In one embodiment, the composition further comprises a heterogeneously branched ethylene/α-olefin interpolymer and, preferably, a heterogeneously branched ethylene/α-olefin copolymer. In one embodiment, the heterogeneously branched ethylene/α-olefin interpolymer, and preferably a heterogeneously branched ethylene/α-olefin copolymer, has a density of from 0.89 to 0.94 g/cm3, additionally from 0.90 to 0.93 g/cm3. In a further embodiment, the composition comprises from 1 to 99 percent by weight, additionally from 15 to 85 percent by weight, of the ethylene/CO interpolymer, based on the weight of the composition. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0053] In one embodiment, the composition comprises less than 5 ppm, additionally less than 2 ppm, additionally less than 1 ppm, and additionally less than 0.5 ppm, sulfur, based on the weight of the composition. In one embodiment, the composition does not contain sulfur.

[0054] In one embodiment, the composition comprises from 1.5 to 80% by weight, based on the weight of the composition, of the ethylene/CO interpolymer and further an ethylene/CO copolymer. In a further embodiment, the composition further comprises an LLDPE.

[0055] In one embodiment, the composition comprises from 1.5 to 20% by weight, based on the weight of the composition, of the ethylene/CO interpolymer and further an ethylene/CO copolymer. In a further embodiment, the composition further comprises an LLDPE.

[0056] In one embodiment, the composition comprises from 20 to 80% by weight, or from 30 to 80% by weight, or from 40 to 80%, or from 50 to 80% by weight based on the weight of the composition, of ethylene/CO interpolymer, and additionally, ethylene/CO copolymer. In a further embodiment, the composition further comprises an LLDPE.

[0057] An inventive composition may comprise a combination of two or more embodiments, as described herein. An inventive ethylene/CO interpolymer can comprise a combination of two or more embodiments, as described herein. An inventive ethylene/CO copolymer may comprise a combination of two or more embodiments as described herein.

[0058] Also provided is an article comprising at least one component formed from a composition of one or more embodiments described herein. In a further embodiment, the article is a coated substrate or film.

[0059] In one embodiment, the article is a coating, which is produced by extrusion coating or extrusion lamination. In one embodiment, the article is a coated substrate. In another embodiment, the substrate is a paper product. In one embodiment, the article is a laminated substrate. In another embodiment, the substrate is a paper product. In one embodiment, the article is produced by extrusion coating or extrusion lamination. An inventive article may comprise a combination of two or more embodiments as described herein.

[0060] The invention also provides a coating formed from the composition of one or more embodiments described herein. An inventive coating can comprise a combination of two or more embodiments, as described herein.

[0061] Also provided is a process for forming the composition of one or more embodiments described herein, said process comprising polymerizing ethylene and CO using a high pressure free radical polymerization process to form the ethylene/CO interpolymer CO and wherein the polymerization takes place in a reactor configuration comprising at least one autoclave reactor comprising > 2 reaction zones and at least one tubular reactor comprising > 2 reaction zones, and wherein in the autoclave reactor the polymerizations take place in the presence of at least one “medium temperature free radical initiator” denoted FRmauto, and at least one “low temperature free radical initiator” denoted FRlauto, and wherein the weight ratio (autoratio) of FRmauto to FRlauto is 0, 04 to 1.00 for each reaction zone in the autoclave reactor; It is

[0062] in which in the tubular reactor, the polymerizations occur in the presence of at least one “high temperature free radical initiator” denoted FRhtube, and at least one “medium temperature free radical initiator” denoted FRmtube, and in which the weight ratio (tube ratio) of FRHtube to Frmtube is 0.06 to 0.50 for each reaction zone in the tubular reactor. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0063] In one embodiment, the weight ratio (auto ratio) of FRmauto to FRlauto for each reaction zone in the autoclave reactor, > 0.05 or > 0.06, or > 0.07, or > 0.08, or > 0.09, or > 0.10, or > 0.11, or > 0.12. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the weight ratio (ratio auto) of FRmauto to FRlauto for each reaction zone in the autoclave reactor, < 0.90 or < 0.80 or < 0.70 or < 0.60 or < 0.50, or < 0.40. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0064] In one embodiment, the weight ratio (tube ratio) of the FRhtube to FRmtube for each reaction zone in the tubular reactor, > 0.07, or > 0.08, or > 0.09, or > 0.10, or > 0.11. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the weight ratio (tube ratio) of FRhtube to FRmtube for each reaction zone in the reactor tube, < 0.45, or < 0.40, or < 0.35, or < 0.30, or < 0 .25, or < 0.20. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0065] In one embodiment, for the autoclave reactor, the weight ratio of “the amount of ethylene added to a reaction zone” to “the amount of CO added to the same reaction zone” is > 30, or > 35 , or > 40, or > 45, or > 50, or > 55, or > 60, or > 65. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the weight ratio of "the amount of ethylene added to a reaction zone" to "the amount of CO added to the same reaction zone" is < 400, or < 395, or < 390, or < 385, or < 380 or < 375. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0066] In one embodiment, for the autoclave reactor, the weight ratio of “the amount of ethylene added to a reaction zone” to “the amount of CO added to the same reaction zone” is > 95, or > 100 , or > 105, or > 110. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer. In one embodiment, the weight ratio of "the amount of ethylene added to a reaction zone" to "the amount of CO added to the same reaction zone" is < 205, or < 200, or < 195, or < 190, or < 185 or < 180. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0067] In one embodiment, for the autoclave reactor, the weight ratio of “the amount of ethylene added to a reaction zone” to “the amount of CO added to the same reaction zone” is 388 to 39. In In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0068] In one embodiment, the polymerization temperature in each reaction zone of the autoclave reactor is independently from 190 °C to 270 °C, or from 200 °C to 260 °C, or from 210 °C or 250 °C, or from 220 °C to 240 °C. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0069] In one embodiment, the polymerization temperature of each reaction zone of the autoclave reactor is independently <250 °C, or < 245 °C, or < 240 °C, or < 235 °C. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0070] In one embodiment, the polymerization temperature of each reaction zone of the tubular reactor is, independently, from 260 °C to 300 °C, or from 265 °C to 295 °C, or from 270 °C to 290 ° C, or from 270 °C to 285 °C. In a further embodiment, the ethylene/CO interpolymer is an ethylene/CO copolymer.

[0071] An inventive process may comprise a combination of two or more embodiments, as described herein.

Process

[0072] To produce the ethylene/CO interpolymer or copolymer as described herein, high pressure free radical initiated polymerization is used. Two different types of high pressure free radical initiated polymerization processes are known. In the first type, an agitated autoclave vessel that has one or more reaction zones is used. The autoclave reactor typically has multiple gates for initiator or monomer feeds or both. In the second type, a jacketed tube is used as a reactor, which has one or more reaction zones. Suitably, but not limitingly, reactor lengths can be from 100 to 3,000 meters (m) or from 1,000 to 2,000 m. The initiation of a reaction zone for both reactor types is typically defined by the lateral injection of any initiator for the reaction, ethylene, chain transfer agent (or telomere), comonomer (or comonomers), as well as any combination thereof. . A high pressure process can be carried out in autoclave or tube reactors that have one or more reaction zones, or in a combination of autoclave and tube reactors, each comprising one or more reaction zones.

[0073] A chain transfer agent (CTA) can be used to control the molecular weight. In one embodiment, one or more chain transfer agents (CTAs) are added to an inventive polymerization process. Typical CTAs that may be used include, but are not limited to, propylene, isobutane, n-butane, 1-butene, methyl ethyl ketone, acetone, and propionaldehyde. In one embodiment, the amount of CTA used in the process is from 0.03 to 10 weight percent of the total reaction mixture.

[0074] The ethylene used for the production of the ethylene/CO interpolymer can be purified ethylene, which is obtained by removing polar components from a closed-loop recycle stream or using a reaction system configuration so that only fresh ethylene be used to produce the inventive polymer. It is not typical that only purified ethylene is needed to produce the ethylene-based polymer. In such cases, ethylene from the closed recycle loop can be used.

Additions

[0075] An inventive composition may comprise one or more additives. Additives include, but are not limited to, stabilizers, plasticizers, antistatic agents, pigments, colorants, nucleating agents, fillers, slip agents, fire retardants, processing aids, smoke inhibitors, viscosity control agents, and antiblocking agents. The polymer composition can, for example, comprise less than 10 percent (by combined weight) of one or more additives, based on the weight of the inventive polymer composition.

[0076] In one embodiment, the polymers of this invention are treated with one or more stabilizers, for example, antioxidants, such as IRGANOX 1010, IRGANOX 1076 and IRGAFOS 168 (Ciba Specialty Chemicals; Glattbrugg, Switzerland). In general, polymers are treated with one or more stabilizers prior to extrusion or other melting processes. Processing aids such as plasticizers include, but are not limited to, phthalates such as dioctyl phthalate and diisobutyl phthalate, natural oils such as lanolin and paraffin, naphthenic and aromatic oils obtained from petroleum refining, and liquid resins from petroleum feedstocks. resin or petroleum. Exemplary classes of oils useful as processing aids include white mineral oil such as KAYDOL oil (Chemtura Corp.; Middlebury, Conn.) and SHELLFLEX 371 naphthenic oil (Shell Lubricants; Houston, Tex.). Another suitable oil is TUFFLO oil (Lyondell Lubricants; Houston, Tex).

[0077] Blends and blends of the inventive polymer with other polymers can be carried out. Polymers suitable for blending with the inventive polymer include natural and synthetic polymers. Exemplary blending polymers include propylene-based polymers (e.g., impact modifier polypropylene, isotactic polypropylene, atactic polypropylene, and random ethylene/propylene copolymers), various types of ethylene-based polymers, including high-energy free radical LDPE pressure, LLDPE prepared with Ziegler-Natta catalysts, PE (polyethylene) prepared with single-site catalysts, including multi-reactor PE ("in-reactor" blends of Ziegler-Natta PE and single-site catalyst PE, as products disclosed in document No. USP 6,545,088 (Kolthammer et al.); 6,538,070 (Cardwell et al.); 6,566,446 (Parikh et al.); 5,844,045 (Kolthammer et al.); 5,869,575 (Kolthammer et al.) al.); and 6,448,341 (Kolthammer et al.)); EVE; ethylenic/vinyl alcohol copolymers; polystyrene; impact-modified polystyrene; ABS; styrene/butadiene block copolymers and hydrogenated derivatives thereof (SBS and SEBS); and thermoplastic polyurethanes. Homogeneous polymers such as plastomers and olefinic elastomers, ethylene and propylene based copolymers (e.g. polymers available under the trade names VERSIFY Plastomers & Elastomers (The Dow Chemical Company) and VISTAMAXX (ExxonMobil Chemical Co.) may also be useful as components in blends comprising the inventive polymer).

applications

[0078] The composition comprising the ethylene/CO interpolymer can be used in a variety of extrusion coating applications, such as sugar pouches, cardboard cups for hot and cold drinks, gable boxes, woven substrates, nonwovens, tubes toothpaste, backing pouches, or any other substrate where traditional LDPE or LLDPE polymers (or blends of both) suffer due to poor adhesion. The inventive polymer can also be used in a variety of extrusion laminations where the advantage would be improved adhesion in multi-layer structures such as aseptic beverage cartons, snack packs, ream packs, backing pouches, toothpaste tubes, cheese packs, laminating films or any other extrusion laminating where LDPE or LLDPE (or mixtures of both) would suffer due to poor adhesion.

[0079] The compositions of this invention can be employed in a variety of conventional thermoplastic manufacturing processes to produce useful articles, including monolayer and multilayer films produced by a blown film process (e.g., an air quenched blown film process ), by a molten film or molten sheet process (e.g., quenching an extruded molten polymer using a chilled roller), or by film or sheet extrusion (e.g., such as through a water bath). In addition to films, these articles may also include molded articles, such as blow-molded, injection-molded, or rotomolded articles; coatings; fibers; and woven or non-woven.

[0080] The composition comprising the ethylene/CO interpolymer can be used in a variety of films, including, but not limited to, extrusion coating, food packaging, consumer, industrial, agricultural lamination films (applications or films) , fresh cut produce films, meat films, cheese films, candy films, glare reduction films, sticking reduction films, stretch films, silage films, greenhouse films, fumigation films, lining, stretch covers, heavy duty carrier bags, pet food, sandwich bags, diaper seals and backsheets.

[0081] The composition comprising the ethylene/CO interpolymer can also be used for coating operations of wires and cables, in the extrusion of sheets for vacuum forming operations and in the formation of molded articles, including the use of molding processes by injection, blow molding or rotomolding. Other suitable applications for the inventive polymers include elastic films and fibers; soft touch products such as appliance handles; gaskets and profiles; car interior parts and profiles; foam products (open and closed cell); impact modifiers for other thermoplastic polymers such as high density polyethylene or other olefin polymers; lid liners; and floor.

Definitions

[0082] The phrase “high pressure free radical polymerization process”, as used herein, refers to a free radical initiated polymerization carried out at an elevated pressure of at least 1,000 bar (100 MPa).

[0083] The term "polymer", as used herein, refers to a polymeric compound prepared by polymerizing monomers, whether of the same or different types. The generic term polymer thus encompasses the term homopolymer (used to denote polymers prepared from only one type of monomer, with the understanding that characteristic amounts of impurity may be incorporated into the polymer structure), and the term interpolymer as defined henceforth. Trace amounts of impurities (eg catalyst residues) may be incorporated into and/or within the polymer.

[0084] The term "interpolymer", as used herein, refers to polymers prepared by polymerizing at least two different types of monomers. The generic term interpolymer includes copolymers (used to refer to polymers prepared from two different types of monomers) and polymers prepared from more than two different types of monomers.

[0085] The term "ethylene-based polymer", as used herein, refers to a polymer comprising 50% or a major amount of polymerized ethylene monomer (based on the weight of the polymer) and optionally may contain at least least one comonomer.

[0086] The term "ethylene/α-olefin interpolymer", as used herein, refers to an interpolymer comprising 50% by weight or a major amount of polymerized ethylene monomer (based on the weight of the interpolymer) and at least one α-olefin. The term "ethylene/α-olefin copolymer", as used herein, refers to a copolymer comprising 50% by weight or a major amount of polymerized ethylene monomer (based on the weight of the copolymer) and an α-olefin olefin, as the only two types of monomer.

[0087] The term "ethylene/CO interpolymer", as used herein, refers to an interpolymer comprising 50% by weight or a major amount of polymerized ethylene monomer (based on the weight of the interpolymer) and a monoxide of carbon (CO). The term "ethylene/CO copolymer", as used herein, refers to a copolymer comprising 50% by weight or a major amount of polymerized ethylene monomer (based on the weight of the copolymer), and carbon monoxide ( CO), as the only two types of monomer.

[0088] The term "propylene-based polymer", as used herein, refers to a polymer that comprises a major amount of polymerized propylene monomer (based on the weight of the polymer) and, optionally, may comprise at least a comonomer.

[0089] The term "composition", as used herein, includes a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0090] The terms "blend" or "polymer blend", as used, refer to a mixture of two or more polymers. A mixture may or may not be miscible (not separated by phases at the molecular level). A blend may or may not be phased. A blend may or may not contain one or more domain configurations, as determined from transmission electron spectroscopy, light scattering, X-ray scattering, and other methods known in the art. Blending can be effected by physically mixing the two or more polymers at the macro level (eg melting or compounding blend resins) or at the micro level (eg simultaneous formation within the same reactor).

[0091] The term "reactor system", as used herein, refers to the components (devices) used to polymerize and isolate a polymer. Such components/devices include, but are not limited to, one or more reactors, a Secondary Compressor, a Primary Compressor, and a Booster Compressor. The term "reactor configuration", as used herein, refers to one or more reactors (eg, autoclave and/or tube reactors) and, optionally, one or more reactor preheaters, used to polymerize a polymer. Reactors can be lined.

[0092] The term “reaction zone”, as used herein, refers to the reactor zone in which the polymerization reaction is initiated or restarted by the addition of free radicals and/or by the decomposition of components into free radicals or components that generate free radicals.

[0093] The term "polymerization temperature", in a reaction zone", or similar phrases, as used herein, refers to the highest temperature measured in a reaction zone. In an autoclave reaction zone (usually, noted as maximum zone temperature) and in a tubular reaction zone (usually noted as peak temperature).

[0094] The terms “comprising”, “including”, “having”, and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether specifically disclosed or not. For the avoidance of doubt, all compositions claimed through the use of the term "comprising" may include any additive, adjuvant or additional compound, whether polymeric or not, unless otherwise stated. In contrast, the term "consisting essentially of " excludes from the scope of any subsequent recitation any other component, step or procedure, except those not essential to operability. The term "consist of" excludes any component, step or procedure not specifically listed.

test methods Density

[0095] Samples for density measurements were prepared in accordance with ASTM D 4703-10. Samples were pressed at 190 °C (374 °F) for five minutes at 68 MPa (10,000 psi). The temperature was held at 190 °C (374 °F) for the above five minutes, and then the pressure was increased to 207 MPa (30,000 psi) for three minutes. This was followed by a one minute hold at 21 °C (70 °F) and 207 MPa (30,000 psi). Measurements were made within one hour of sample pressing using ASTM D792-08, Method B.

melt index

[0096] The melt index, or I2, was measured according to ASTM D 1238-10, Condition 190 °C/2.16 kg, Method B, and was reported in grams eluted per 10 minutes.

Nuclear magnetic resonance (13c nmr)

[0097] The samples were prepared by adding approximately “3 g” of a “50/50 mixture of tetrachloroethane-d2/orthodichlorobenzene, containing 0.025 M Cr(AcAc)3,” to a polymer sample of “0.25 to 0, 40 g”, in a 10 mm NMR tube. Oxygen was removed from the sample by placing the open tubes in a nitrogen environment for at least 45 minutes. The samples were then dissolved and homogenized by heating the tube and its contents to 150 °C using a heating block and heat gun. Each dissolved sample was visually inspected to ensure homogeneity. Samples are thoroughly mixed immediately prior to analysis and not allowed to cool before insertion into heated NMR sample holders.

[0098] All data were collected using a Bruker 400 MHz spectrometer. Data were acquired using a six second pulse repetition delay, 90 degree inversion angles and reverse gate decoupling, with a sample temperature of 120 °C. All measurements were made on non-rotating samples in locked mode. Samples were allowed to thermally equilibrate for seven minutes prior to data acquisition. 13 C NMR chemical shifts were internally referenced to the EEE triad at 30.0 ppm. The “C6+” value is a direct measure of the C6+ branches in LDPE, where the long branches are not differentiated from the "chain ends". The "32.2 ppm" peak, representing the third carbon from the end of all chains or branches of six or more carbons, is used to determine the "C6+" value. The units of CO per 1000 C are determined as the integral of the 43 ppm peak divided by 2. In ethylene/CO copolymers, the mole % CO and weight % CO values are the same. % in mole of CO is calculated from: CO units/1000 C= moles of CO per 1000 total carbons; Ethylene moles = (1000 - CO units/1000 C)/2.

Nuclear magnetic resonance (1H NMR) sample preparation

[0099] Samples were prepared by adding approximately 130 mg of sample to “3.25 g of 50/50, by weight, tetrachloroethane-d2/perchlorethylene” with 0.001 M Cr(AcAc)3, in a NORELL 1001- 7 of 10 mm NMR. The sample was purged by bubbling N2 through the solvent using a pipette inserted into the tube for about five minutes to prevent oxidation. Each tube was capped, sealed with TEFLON tape, and then immersed at room temperature overnight to facilitate sample dissolution. Samples were kept in an N2 purge box during storage, before and after preparation, to minimize exposure to O2. The sample was heated and vortexed at 115 °C to ensure homogeneity.

Data acquisition parameters

[0100] 1H NMR was performed on a Bruker AVANCE 400 MHz spectrometer, equipped with a Bruker Dual DUL high temperature CryoProbe and at a sample temperature of 120 °C. Two experiments were performed to obtain spectra, a control spectrum to quantify the total polymer protons and a double pre-saturation experiment, which suppressed the intense peaks of the polymer main chain and allowed high sensitivity spectra for quantification of the end groups. . Control was performed with ZG pulse, 4 sweeps, SWH 10,000 Hz, AQ 1.64s, D1 14s. The double pre-saturation experiment was performed with a modified pulse sequence, TD 32768, 100 sweeps, DS 4, SWH 10,000 Hz, AQ 1.64 s, D1 1s, D13 13s.

Data analysis - 1H NMR calculations

[0101] The residual 1H signal in TCE (tetrachloroethane)-d2 (at 6.0 ppm) was integrated and adjusted to a value of 100 and the integral from 3 to 0.5 ppm was used as the complete polymer signal in the control experiment. For the pre-saturation experiment, the TCE signal was also adjusted to 100, and the corresponding integrals for unsaturation (vinylene at about 5.40 to 5.60 ppm, trisubstituted at about 5.16 to 5.35 ppm , vinyl at about 4.95 to 5.15 ppm and vinylidene at about 4.70 to 4.90 ppm) were obtained.

[0102] In the spectrum of the pre-saturation experiment, the regions for cis- and trans- vinylene, trisubstituted, vinyl and vinylidene were integrated. The total polymer integral from the control experiment was divided by two to obtain a value that represents X thousands of carbons (ie, if the integral polymer = 28,000, this represents 14,000 carbons and X = 14).

[0103] The integrals of unsaturated groups, divided by the corresponding number of protons that contribute to this integral, represent the moles of each type of unsaturation per X thousand carbons. Dividing the moles of each type of unsaturation by X gives the moles of unsaturated groups per 1000 moles of carbons.

melt strength

[0104] The melt strength measurements were conducted on a Gottfert Rheotens 71.97 (Goettfert Inc.; Rock Hill, SC), fixed to a capillary rheometer Gottfert Rheotester 2000. The molten sample (about 25 to 30 grams) was fed with a Goettfert Rheotester 2000 capillary rheometer, equipped with a flat entry angle (180 degrees) 30 mm long, 2.0 mm diameter, and an aspect ratio (length/diameter) of 15. After equilibrating the samples to 190 °C for 10 minutes, the piston was operated at a constant piston speed of 0.265 mm/second. The standard test temperature was 190 °C. The sample was uniaxially stretched into an acceleration grip assembly, located 100 mm below the die, with an acceleration of 2.4 mm/s2. Traction force was recorded as a function of the retraction speed of the pinch rollers. Melting strength was reported as the plateau force (cN) before wire breakage. The following conditions were used in the melt strength measurements: piston speed = 0.265 mm/second; wheel acceleration = 2.4 mm/s2; capillary diameter = 2.0 mm; capillary length = 30 mm; and cylinder diameter = 12 mm.

Dynamic mechanical spectroscopy (DMS)

[0105] The resins were compression molded into circular plates "3 mm thick x 1 inch (2.54 cm) in diameter" at 176.6 °C (350 °F) for five minutes under 10.34 MPa ( 1,500 psi) of air pressure. The sample was then removed from the press and placed on a bench to cool.

[0106] A constant temperature frequency scan was performed using TA Instruments, an “Advanced Rheometric Expansion System (ARES)”, equipped with 25 mm (diameter) parallel plates, under a nitrogen purge. The sample was placed on the plate and allowed to melt for five minutes at 190 °C. The plates were then closed to a “2 mm gap”, the sample trimmed (extra sample extending beyond the circumference of the “25 mm diameter” plate was removed), and then the test was started. The method had an additional five minute delay built in to allow for temperature equilibration. The experiments were performed at 190 °C over a frequency range of 0.1 to 100 rad/s. The strain amplitude was constant at 10%. The n* complex viscosity, tan (δ) or tan delta, viscosity at 0.1 rad/s (V0.1), viscosity at 100 rad/s (V100) and viscosity ratio (V0.1/V100) were calculated from these data.

Triple Detector Gel Permeation Chromatography (TDGPC) - Conventional GPC, Light Scattering GPC, Viscometry GPC, and GPCBR

[0107] For the GPC techniques used in this document (conventional GPC, light scattering GPC and gpcBR), a Triple Detector Gel Permeation Chromatography (3D-GPC or TDGPC) system was used. This system consisted of a Waters model 150C high temperature chromatograph (Milford, Mass) (other suitable high temperature GPC instruments include the Polymer Laboratories (Shropshire, UK), models 210 and 220), equipped with precision detectors (Amherst, Mass.) Model 2040 Two Angle Laser Light Scattering (LS) Detector, a Polymer ChAR (Valencia, Spain) IR4 Infrared Detector, and a Viscotek (Houston, Texas) 150R Viscometer with 4 DP Capillary Solution (DP).

[0108] A GPC with these last two independent detectors and at least one of the previous detectors is sometimes called "3D-GPC" or "TDGPC", while the term "GPC" alone usually refers to conventional GPC. Data collection is performed using Viscotek TriSEC software, Version 3, and a 4-channel Viscotek Data Manager DM400. The system was also equipped with an on-line solvent degassing device from Polymer Laboratories (Shropshire, UK).

[0109] The eluent from the GPC column set flowed through each detector arranged in series, in the following order: LS detector, IR4 detector, then through the DP detector. The systematic approach to the determination of multidetector biases was carried out in a manner consistent with that published by Balke, Mourey, et. al. (Mourey and Balke, Chromatography Polym., Chapter 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym., Chapter 13, (1992)), which optimizes the triple detector log (MW) results and intrinsic viscosity) from the use of a broad polyethylene standard, as described in the Light Scattering (LS) GPC section below, in the paragraph after Equation (5).

[0110] Suitable high temperature GPC columns can be used, such as four 30 cm long Shodex HT803 13 micron columns, four 30 cm Polymer Labs columns of 20 micron mixed pore size packaging (MixA LS , Polymer Labs) or four packaged 30 cm Olexis-LS columns of 13 micron mixed pore size (Polymer Labs). Here, Olexis-LS columns were used. The sample carousel compartment was operated at 140°C and the column compartment was operated at 150°C. Samples were prepared at a concentration of “0.1 gram of polymer in 50 milliliters of solvent”. The chromatographic solvent and sample preparation solvent was 1,2,4-trichlorobenzene (TCB) containing "200 ppm 2,6-di-tert-butyl-4-methylphenol (BHT)". The solvent was sparged with nitrogen. Polymer samples were gently shaken at 160 °C for four hours. The injection volume was 200 microliters. The flow rate through the GPC was set to 1 ml/minute.

conventional GPC

[0111] For conventional GPC, the IR4 detector was used and the set of GPC columns was calibrated by running 21 polystyrene standards of narrow molecular weight distribution. The molecular weight (MW) of the standards ranged from 580 g/mol to 8,400,000 g/mol, and the standards were contained in 6 "cocktail" mixtures. Each masterbatch had at least a decade of separation between individual molecular weights. Master mixes were purchased from Polymer Laboratories. Polystyrene standards were prepared at “0.025 g in 50 ml of solvent” for molecular weights equal to or greater than 1,000,000 g/mol and at “0.05 g in 50 ml of solvent” for molecular weights less than 1,000,000 g/mol. The polystyrene standards were dissolved at 80°C, with gentle agitation, for 30 minutes. Narrow masterbatch mixes were run first and in descending order of highest molecular weight component to minimize degradation. Polystyrene standard peak molecular weights were converted to polyethylene molecular weight using Equation (1) (as described in Williams and Ward, J. Polym. Sci., Polym. Letters, 6, 621 (1968)): where M is the molecular weight of polyethylene or polystyrene (as marked), and B equals 1.0. It is known to those of ordinary skill in the art that A can be in the range of about 0.38 to about 0.44 and is determined at the time of calibration using a wide polyethylene standard as described in the section on GPC dispersion of light (LS) below in the paragraph after Equation (5). The use of this polyethylene calibration method to obtain molecular weight values, such as molecular weight distribution (MWD or Mw/Mn), and related statistics, is defined herein as the modified method of Williams and Ward. The number average molecular weight, weight average molecular weight, and z-average molecular weight are calculated from the equations below.

Light Scattering (LS) GPC

[0112] For the LS GPC, the Precision Detector PDI2040, Model 2040 was used. Depending on the sample, the 15 degree angle or the 90 degree angle of the light scattering detector is used for calculation purposes. Here, the angle of 15° was used.

[0113] Molecular weight data were obtained in a manner consistent with that published by Zimm (Zimm, BH, J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)). The total injected concentration, used in the molecular weight determination, was obtained from the mass detector area and mass detector constant, derived from a suitable linear polyethylene homopolymer, or from one of the weight-average molecular weight polyethylene standards. known. Calculated molecular weights were obtained using a light scattering constant, derived from one or more of the polyethylene standards mentioned below, and a refractory index concentration coefficient of 0.019 g/ml (0.104 dn/dc). In general, the mass detector response and light scattering constant should be determined from a linear standard with a molecular weight that exceeds about 50,000 g/mol. Viscometer calibration can be achieved using the methods described by the manufacturer or, alternatively, using the published values of suitable linear standards such as Standard Reference Materials (SRM) 1475a (available from the National Institute of Standards and Technology (NIST). )). Chromatographic concentrations are considered low enough to eliminate the effects of the 2nd viral addressing coefficient (concentration effects on molecular weight).

[0114] With 3D-GPC, the absolute weight average molecular weight (“Mw, Abs”) is determined using Equation (5) below, using the “peak area” method for greater accuracy and precision. The “LS Area” and the “Conc.” are generated by the chromatograph/detectors combination.

[0115] For each LS profile, the x axis (log MWcc-GPC), where cc refers to the conventional calibration curve is determined as follows. First, polystyrene standards (see above) are used to calibrate the retention volume in “log MWPS”. Then, Equation 1 (Mpolyethylene = A x (Mpolystyrene)B) is used to convert “log MWPS” to “log MWPE”. The “log MWPE” scale serves as the x axis for the LS profiles of the experimental section (log MWPE is equated to log MW (cc-GPC)). The y-axis for each LS profile is the LS detector response normalized by the mass of the injected sample. Initially, molecular weight and intrinsic viscosity for a standard sample of linear polyethylene, such as SRM1475a or equivalent, were determined using conventional calibrations (“cc”) for both molecular weight and intrinsic viscosity as a function of elution volume. .

[0116] In the low molecular weight region of the GPC elution curve, the presence of a significant peak that is known to be caused by the presence of antioxidants or other additives, will cause an underestimation of the number average molecular weight (Mn) of the polymeric sample , to generate an overestimation of the polydispersity of the sample, defined as Mw/Mn, where Mw is the weight average molecular weight. The molecular weight distribution of the true polymeric sample can therefore be calculated from the GPC elution, excluding this extra peak. This process is commonly described as the peak scrubbing feature in data processing procedures in liquid chromatographic analysis. In this process, this additive peak is stripped from the GPC elution curve before the sample molecular weight calculation is performed from the GPC elution curve.

Differential Scanning Calorimetry (DSC)

[0117] Differential Scanning Calorimetry (DSC) was used to measure the melting and crystallization behavior of a polymer over a wide range of temperatures. For example, the TA Instruments Q1000 DSC, equipped with an RCS (Refrigerated Cooling System) and an autosampler, was used to perform this analysis. During the test, a nitrogen purge gas flow of 50 ml/min was used. Each sample was cast into a thin film at about 175 °C; the molten sample was then air-cooled to room temperature (approximately 25 °C). The film sample was formed by pressing a "0.1 to 0.2 gram" sample at 175 °C at 10.34 MPa (1500 psi) and 30 seconds to form a "0.1 to 0.2 gram" film. thousand thick". A 3 to 10 mg, 6 mm diameter specimen was extracted from the cooled polymer, weighed, placed in a lightweight aluminum container (50 mg) and crimped closed. Analysis was then carried out to determine its thermal properties.

[0118] The thermal behavior of the sample was determined by increasing the temperature of the sample up and down to create a heat flux versus temperature profile. First, the sample was quickly heated to 180 °C and kept isothermal for five minutes in order to remove its thermal history. Then, the sample was cooled to -40 °C, at a cooling rate of 10 °C/minute, and kept isothermal at -40 °C for five minutes. The sample was then heated to 150°C (this is the “second heat” ramp) at a heating rate of 10°C/minute. The cooling and second heating curves were recorded. The cooling curve was analyzed by defining baseline endpoints from the onset of crystallization at -20 °C. The heat curve was analyzed by defining the baseline endpoints from -20 °C to the end of the melt. Values determined were peak melting temperature (Tm), peak crystallization temperature (Tc), heat of fusion (Hf) (in Joules per gram), and the calculated % crystallinity for each sample was determined using : % Crystallinity = ((Hf)/(292 J/g)) x 100.

[0119] The heat of fusion (Hr) and the peak melting temperature were recorded from the second heating curve. The peak crystallization temperature is determined from the cooling curve.

Determination of the one-hour half-life of the initiator

[0120] The “one-hour half-life” of the initiator is determined by differential calorimetry-thermal activity monitoring (DSC-TAM) of a dilute solution of the initiator in monochlorobenzene. The kinetic data of the decomposition of hydroperoxides in monochlorobenzene are determined titrimetrically. The half-life can be calculated by the Arrhenius equation: kd = Ae-Ea/RT and t/ = ln(2)/kd, where kd is the constant rate for primer dissociation at s-1; A is the Arrhenius frequency factor at s-1; Ea is the activation energy for primer dissociation in J/mol; R is 8.3142 J/mole K; T is the temperature in K (Kelvin); and t/ is half-life in seconds (s). A high temperature free radical initiator is defined as an initiator that has a "one hour half-life" at a temperature in the range of 130°C to 200°C. A medium temperature free radical initiator is defined as an initiator that has a "one hour half-life" at a temperature in the range of 90°C to 129°C. A low temperature free radical initiator is defined as an initiator that has a "one hour half-life" at a temperature in the range of 30°C to 89°C.

Experimental Preparation of inventive ethylene-based polymers Inventive examples 1 to 15

[0121] The inventive examples were produced in the same process reaction system; therefore, by referring to the same equipment between runs, the physical process and its units were analogous to each other. Figure 1 is a block diagram of the process reaction system used to produce the aforementioned Examples.

[0122] The process reaction system in Figure 1 is a low-density polyethylene production system, partially closed loop, double recycling and high pressure. The process reaction system comprises a new ethylene feed line 1; a "BP" primary/booster compressor, a "Hyper" hypercompressor, a two-zone autoclave followed by a two-zone tube reactor. The autoclave/tube reactor consists of a first reaction zone 1; a first line 2 of peroxide initiator; a second reaction zone 2; a second line of peroxide initiator 3; a third tube reaction zone 3; a third line peroxide 4 initiator; a fourth tube reaction zone 4; a fourth line of peroxide 5 initiator; cooling jackets (using high pressure water) are fitted around the outer shell of the tube portion of the reactor; a high pressure separator "HPS"; a high pressure recycling line 6; an "LPS" low pressure separator; a low pressure recycling line 7; a CTA 8 power line; and a carbon monoxide supply line 9.

[0123] The reactor also comprises 4 reaction zones demarcated by the location of the peroxide injection points. The first reaction zone feed is attached to the autoclave part, where 50% of the total reactor feed is introduced. The first reaction zone starts at the peroxide injection point #1 and ends at the peroxide injection point #2. The second reaction zone starts at the peroxide injection point #2, where the other 50% of the total feed is injected. The second reaction zone ends at the No. 3 peroxide injection point. The third reaction zone begins at the No. 3 peroxide injection point, located near the start of the tube reactor, and ends at the No. 3 peroxide injection point. 4. The fourth reaction zone begins at peroxide injection #4 and ends just before the reactor pressure control valve.

[0124] For the Inventive Examples, a mixture containing t-butyl peroxy-2-ethylhexanoate (TBPO), tert-butyl peroxypivalate (PIV) and an isoparaffinic hydrocarbon solvent (boiling range > 179 °C) was used as a starter mix for the first and second injection points. For injection points #3 and #4, a mixture containing di-t-butyl peroxide (DTBP) and TPO and the isoparaffinic hydrocarbon solvent was used. The composition of each mixture is shown in Table 1.

[0125] For the inventive examples, a combination of propylene and methyl ethyl ketone was used as chain transfer agent (CTA). The CTA mixture was injected into the ethylene stream on the suction side of the primary/booster compressor. The composition of the CTA feed to the process was adjusted for process runs to adjust the melt index of the product.

[0126] Carbon monoxide was used as a comonomer. Carbon monoxide was injected into the ethylene stream on the suction side of the primary/booster compressor. The reactor process conditions used for fabrication are given in Table 2. Carbon monoxide has an inhibiting effect on the peroxides used. For this reason, a 3:1 mixture by weight of PIV to TBPO was used for mixtures going to the #1 and #2 injection points. The higher portion of the lower dissociation peroxide reduces the chances of transfer of TPO for the tube portion of the reactor. Furthermore, high temperature targets above 240 °C are also avoided to reduce the need to use DTBP, which has a higher dissociation temperature, which can lead to transfer to the tube reactor due to CO inhibition. These process conditions reduce the risk of ethylene decomposition during CO use. Processing conditions are shown in Table 2. Table 1: Peroxide compositions for all inventive examples (used for inventive examples 1 to 15) *t1/2 = one hour half-life (see test method above). **Solvent = (iso-paraffinic hydrocarbon solvent (boiling point > 179 °C)). ***% by weight peroxide in peroxide composition Table 2: Process Conditions for Inventive Examples IE1 to IE15 Insignificant or negligible amounts of CO in the recycle stream.

Comparative example 1

[0127] For Comparative Example 1 (CE1), a mixture containing t-butyl peroxy-2-ethylhexanoate (TBPO), tert-butyl peroxypivalate (PIV) and an isoparaffin hydrocarbon solvent (boiling range > 179 °C), was used as a starter mixture for the first and second injection points. For injection points #3 and #4, a mixture containing di-t-butyl peroxide (DTBP) and TPO and the isoparaffinic hydrocarbon solvent was used. Table 3 shows the peroxide initiator and solvent solution flows used.Table 3: Peroxide initiator (PO) flows in “liters per hour” at each injection point

[0128] For Comparative Example 1, a combination of propylene and methyl ethyl ketone was used as the chain transfer agent (CTA). The CTA mixture was injected into the ethylene stream on the suction side of the primary/booster compressor. For Comparative Example 1, carbon monoxide was used as a comonomer. Carbon monoxide was injected into the ethylene stream on the suction side of the primary/booster compressor. The reactor process conditions used to manufacture Comparative Example 1 are shown in Table 4.

[0129] The properties of Examples and Comparative Examples are listed in tables 5-11. Comparative Example 2 (CE2) is Dow LDPE 5004I (melt index 4.15, 0.924 g/cm3 ), available from The Dow Chemical Company. Table 4: Process Conditions

Property characteristics of inventive and comparative polymers (IE1-IE15, CE1, CE2)

[0130] Table 5 contains the melt index (I2), density, melt strength and speed at break of melt strength data. The melt index of IE1-IE15 is in a suitable range for use in cast film or extrusion coating applications. IE1-15 densities are high (0.935 - 0.941 g/cm3), in part due to incorporation of carbon monoxide (CO). The melt strength of these samples is unexpectedly high, especially as the level of CO is increased in the samples, as shown in Figure 2 and Figure 3. The inventive examples are useful in applications such as extrusion coating, especially due to their tighter distribution. molecular weight range (cc-GPC Mw/Mn in Table 6). Table 7 contains the TDGPC-related properties derived from the LS and viscosity detectors, in conjunction with the concentration detector. Table 8 contains the DMS viscosity data, as summarized by the following: the viscosities measured at 0.1, 1, 10 and 100 rad/s; the viscosity ratio or the ratio between the viscosity measured at 0.1 rad/s and the viscosity measured at 100 rad/s, each measured at 190°C; and the tan delta measured at 0.1 rad/s and 190 °C.

[0131] Table 9 contains the CO (carbon monoxide) content and the branches per 1000 C as measured by 13C NMR. These polymers contain amyl branches, or C5 branches, which are not contained in substantially linear polyethylenes, such as AFFINITY polyolefin plastomers, or LLDPE, such as DOWLEX polyethylene resins, both produced by The Dow Chemical Company. IE1-IE15 and Comparative Examples 1-2 contained greater than or equal to 0.5 amyl groups (branches) per 1000 carbon atoms (examples of the invention contain more than 1.0 amyl groups (branches) per 1000 carbon atoms) . The inventive examples also contain CO at a level of 2 to 4% by mol CO or 2 to 4% by weight CO. Table 10 lists the 1H NMR branching results.

[0132] Table 11 contains the DSC results, including melting point (Tm), heat of fusion, percentage of crystallinity and crystallization point. The melting point for the inventive examples is relatively low for their high densities, as shown in Figure 4. Table 5: Melting index (I2, density, melt strength (ms) and melt strength velocity at 190° W. IE1 to IE5: Different sample points from the same polymerization run. IE6 to IE15: Different sample points from the same polymerization run. CE1: Separate polymerization. CE2: commercial product LDPE 5004I. Table 6: TDGPC related properties (conventional calibration). Table 7: Properties relative to TDGPC (derived from the viscosity and LS detectors, in conjunction with the concentration detector). Table 8: Viscosities in PA^S, viscosity ratio and tan delta, all at 190 °C. Table 9: 13C NMR branching results **ND = not detected. ***Based on polymer weight Table 10: 1H nmr branching results Table 11: DSC Results

extrusion coating

[0133] The Inventive (IE) and Comparative (CE) Examples shown in Table 12 were extrusion coated with a Black-Clawson extrusion coating line. The range consists of an 8.9662 cm (3.53 inch) single flight screw, 30:1 length/diameter and 4:1 compression ratio with two Mattock spiral mixing sections near the end of the screw. Resin evaluations used an extrusion speed of 90 RPM, resulting in an output of ~31.5 g/s (250 lbs/hr). Line speeds were run at 8.04 km/h (440 ft/min), resulting in approximately 1 mil coating on a “22.68 kg/ream (50 lb/ream) brown Kraft paper”.

[0134] The test specimens were cut to the dimensions of “60.96 cm (24 inches) by 91.44 cm (36 inches)”. For each test specimen, two “X cuts, approximately 2 inches (5.08 cm) on each line of the X” were made in the transverse direction of the specimen. Each "X-cut" was made approximately 15.24 cm (6 inches) from one edge of the polymer coating on each test specimen. The “X cut” only penetrated the polymer coating. The polymer in one portion of the "X-cut" was partially separated from the paper using a knife. The released polymer was gripped manually by an operator and the test specimen was held down with the operator's other hand. The polymer was slowly pulled from the paper for a distance of approximately 2.54 to 5.08 cm (1 to 2 inches). Slow pull takes approximately 5 to 10 seconds. A “Pass” value was recorded when the adhesion between the polymer layer and the paper surface was stronger than the adhesion of the interfiber matrix of the paper itself (or greater than or equal to 5% of the paper surface stripped with the polymer). . A “Fail” value was recorded when the polymer layer was pulled from the paper surface, with little or no paper fiber (or less than 5% of the paper surface pulled with polymer). The percentage of the paper surface that sloughed off with the polymer was determined by visual inspection of the total area of the polymer coating that was removed from the paper substrate. For each polymer, one test sample was examined and two "X-cuts" were made in each test specimen. Table 12: Fiber Break Adhesion Results (Two "X-cuts" per sample) *The DD-Melt curtain broke from the die - unable to obtain a sample for the fiber break adhesion test.

[0135] Table 12 shows the results of the Kraft paper fiber break adhesion test. The Inventive Examples were shown as “Passed” at temperatures from 310 °C (590 °F) to 326.6 °C (620 °F) in some cases. Comparative Example 2 showed "Failure" at temperatures from 310°C to 321.1°C (590°F to 610°F). Thus, the adhesion of the Inventive Examples is preferred compared to that of Comparative Example 2. The Inventive Examples can also be extrusion coated at high speeds and high temperatures.

Claims (14)

1. Composition, characterized in that it comprises an ethylene/CO interpolymer, formed from a high pressure free radical polymerization, and the ethylene/CO interpolymer having the following properties: a) a CO content of "greater than 0" weight percent less than or equal to 10 weight percent CO (carbon monoxide), based on the weight of the interpolymer; and b) a melting point, Tm, in °C, that meets the following relationship: Tm (°C) < 601.4 * (Density in g/cm3) - 452.5 (°C), and the interpolymer of ethylene/CO complies with the following ratio: MS (cN) > 2.0 (wt% CO) + 2.0. 2. Composition according to claim 1, characterized in that the ethylene/CO interpolymer has a melting index (I2) of 0.1 to 100 g/10 min. 3. Composition according to claim 1, characterized in that the ethylene/CO interpolymer has a Tm (°C) > 601.4 * (density in g/cm3) — 460.0 (°C). 4. Composition according to claim 1, characterized in that the ethylene/CO interpolymer has a melting temperature, Tm, from 105.5 °C to 110.5 °C. 5. Composition according to claim 1, characterized in that the ethylene/CO interpolymer has a density of 0.910 to 0.990 g/cm3. 6. Composition according to claim 1, characterized in that the ethylene/CO interpolymer has an amyl group level greater than or equal to 0.5 amyl group per 1,000 carbon atoms, as determined by 13C NMR. 7. Composition according to claim 1, characterized in that the ethylene/CO interpolymer is an ethylene/CO copolymer. 8. Composition according to claim 1, characterized in that the composition further comprises a second ethylene-based polymer and the second ethylene-based polymer is selected from an LDPE, an ethylene/alpha copolymer -olefin or a combination thereof. 9. Article, characterized in that it comprises at least one component formed from the composition according to claim 1, the article being a coated substrate or a film, and the article being a coating, which is produced by extrusion coating or extrusion lamination. 10. Process for forming a composition, characterized in that said composition comprises an ethylene/CO interpolymer, formed from a high pressure free radical polymerization, and wherein the ethylene/CO interpolymer has the following properties: a ) a CO content of "greater than 0" percent by weight to less than or equal to 10 percent by weight CO (carbon monoxide), based on the weight of the interpolymer; and b) a melting point, Tm, in °C that meets the following relationship: Tm (°C) < 601.4 * (Density in g/cm3) - 452.5 (°C); - said process comprising polymerizing ethylene and CO, using a high pressure free radical polymerization process, to form the ethylene/CO interpolymer, and wherein polymerization occurs in a reactor configuration comprising at least one autoclave reactor comprising > 2 reaction zones, and at least one tubular reactor comprising > 2 reaction zones, and wherein in the autoclave reactor, the polymerizations occur in the presence of at least one "medium temperature free radical initiator" denoted FRmauto and at least one "low temperature free radical initiator" denoted FRlauto and where the weight ratio (autoratio) of FRmauto to FRlauto is from 0.04 to 1.00 for each reaction zone in the autoclave reactor; and provided that in the tubular reactor, the polymerizations occur in the presence of at least one "high temperature free radical initiator" denoted FRhtube, and at least one "medium temperature free radical initiator" denoted FRmtube and where the weight ratio (tube ratio) from FRhtube to FRmtube is 0.06 to 0.50 for each reaction zone in the tube reactor. 11. Process, according to claim 10, characterized in that the polymerization temperature in each reaction zone of the autoclave reactor is, independently, from 190 °C to 270 °C, and being that, for the reactor autoclave, the weight ratio of "the amount of ethylene added to a reaction zone" to "the amount of CO added to the same reaction zone" is 388 to 39. 12. Process according to claim 10, characterized in that the polymerization temperature of each reaction zone of the autoclave reactor is, independently, <250 °C. 13. Process according to claim 10, characterized in that the polymerization temperature of each reaction zone of the tubular reactor is, independently, from 260 °C to 300 °C. 14. Process according to claim 10, characterized in that the ethylene/CO interpolymer is an ethylene/CO copolymer.