Unimodal polyethylene copolymer and film thereof
阅读说明：本技术 单峰聚乙烯共聚物和其膜 (Unimodal polyethylene copolymer and film thereof ) 是由 刘钵 章翼 A·A·巴夫纳 F·亚历山大 R·N·赖布 于 2019-07-29 设计创作，主要内容包括：一种单峰乙烯-共-1-己烯共聚物,当在190摄氏度下呈熔融形式时,其特征在于由熔融弹性和复数粘度比(剪切稀化)特性的组合限定的独特熔融特性空间。一种吹塑膜,其基本上由所述单峰乙烯-共-1-己烯共聚物组成。一种合成所述单峰乙烯-共-1-己烯共聚物的方法。一种制造所述吹塑膜的方法。一种制品,其包含所述单峰乙烯-共-1-己烯共聚物。(A unimodal ethylene-co-1-hexene copolymer, when in molten form at 190 degrees celsius, characterized by a unique melting property space defined by a combination of melt elasticity and complex viscosity ratio (shear thinning) properties. A blown film consisting essentially of said unimodal ethylene-co-1-hexene copolymer. A process for the synthesis of said monomodal ethylene-co-1-hexene copolymer. A method of making the blown film. An article comprising the monomodal ethylene-co-1-hexene copolymer.)
1. A unimodal ethylene-co-1-hexene copolymer, when in molten form at 190 ℃, characterized by a melt property space defined by a combination of melt elasticity and complex viscosity ratio properties, wherein the combination is according to equation 1 (equation 1):6*SH1000+1,971<G'(G"＝3,000Pa)<6*SH1000+2,138 (equation 1); wherein<Is less than;*is a multiplication; + is addition; g' (G "═ 3,000Pa) is the melt elasticity in pascals (Pa) measured at a loss modulus G" ═ 3000 pascals according to the melt storage modulus test method (described herein); SH1000 is equal to Eta*0.126/Eta*126 complex viscosity ratio of Eta*0.126 is the complex viscosity in pascal-seconds (Pa-s) measured at 0.126 radians per second (rad/s) by dynamic mechanical analysis test method (described herein); and Eta*126 is the complex viscosity in Pa-s measured by dynamic mechanical analysis test method at 126 rad/s.
2. The monomodal ethylene-co-1-hexene copolymer according to claim 1 characterized in that at least one of the characteristics (a) to (g):
(a) a density of 0.935 to 0.945 grams per cubic centimeter (g/cm) as measured according to ASTM D792-13, method B3)；
(b) High load melt index (I) measured according to ASTM D1238-13(190 ℃, 21.6kg)21) From 20.5 to 22.6 grams/10 minutes (g/10 min);
(c) melt flow ratio (MFR5 orI21/I5) Is 22.1 to 24.5, wherein I21Is measured according to ASTM D1238-13(190 ℃, 21.6kg) and I5Is a melt index in grams/10 minutes measured according to ASTM D1238-13(190 ℃, 5.0 kg);
(d) degree of molecular mass dispersionIs 38 to 44, wherein MwAnd MnMeasured according to the GPC test method;
(e) wherein the combination of melt elasticity and complex viscosity ratio (shear thinning) characteristics is defined according to equation 1a (equation 1 a): 6*SH1000+1,975<G'(G"＝3,000Pa)<6*SH1000+2,134 (equation 1 a);
(f) complex viscosity Eta measured by dynamic mechanical analysis test method at 126 rad/sec*126 is 1220 to 1240 pascal-seconds (Pa-s); and
(g) the complex viscosity ratio SH1000 is 43 to 50.0, where SH1000 is 0.126 radians/sec (Eta)*0.126)/Eta*Complex viscosity ratio measured at 126.
3. The unimodal ethylene-co-1-hexene copolymer according to claim 2 further defined by any of the restrictions (i) to (xi): (i) characteristics (a) and (b); (ii) characteristics (a) and (c); (iii) characteristics (a) and (d); (iv) characteristics (a) and (e); (v) characteristics (a) and (f); (vi) characteristics (a) and (g); (vii) characteristics (a), (b) and (c); (viii) characteristics (a), (b), and (d); (ix) characteristics (f) and (g); (x) Any six of characteristics (a) through (g); and (xi) each of the characteristics (a) to (g).
4. The monomodal ethylene-co-1-hexene copolymer according to any of claims 1 to 3 further characterized by any of the characteristics (h) to (i) or a combination of the characteristics (h) and (i): (h) weight average molecular weight (M) measured according to Gel Permeation Chromatography (GPC) test methodw) From 300,000.0 to 400,000.0 grams per mole (g/mol); and (i) number average molecular weight (M) measured according to GPC measurement methodn) From 7,000.0 to 8,000.0 g/mol.
5. A method of synthesizing a monomodal ethylene-co-1-hexene copolymer according to any of claims 1 to 4, consisting essentially of: reacting ethylene and 1-hexene ('C')6") is contacted with a single catalyst system consisting of a unimodal chromium catalyst system in a single fluidized bed gas phase polymerization (FB-GPP) reactor under effective operating conditions comprising a Reactor Bed Temperature (RBT), an average polymer residence time (avgPRT), and an ethylene partial pressure (C2P) and receiving ethylene (C2) Feed, comonomer (1-hexene or "C6") feed, hydrogen (H)2) Feed and optionally oxygen (O)2) A feed, wherein the feed is characterized by H2/C2Gas molar ratio (H)2/C2) Comonomer/ethylene gas molar ratio ("C)6/C2") and O2/C2Gas volume ratio ("[ O ]2/C2]", vol/vol in ppmv); wherein RBT is 101 ℃ to 111 ℃; avgPRT is 1.70 to 3.10 hours, C2P is 1,100 to 1,900 kilopascals (kPa); h2/C2The gas molar ratio is 0.01 to 0.150; c6/C2The gas molar ratio is 0.010 to 0.021; and O is2/C2Gas volume ratio of>0 to 130ppbv (parts per billion volume); whereby said unimodal ethylene-co-1-hexene copolymer is synthesized in said FB-GPP reactor.
6. The process of claim 5, further comprising removing the monomodal ethylene-co-1-hexene copolymer from the FB-GPP reactor to yield a removed monomodal ethylene-co-1-hexene copolymer.
7. An article comprising the monomodal ethylene-co-1-hexene copolymer according to any of claims 1 to 4.
8. A film consisting essentially of the monomodal ethylene-co-1-hexene copolymer according to any one of claims 1 to 4.
9. A process for producing a blown film, the process comprising melting the monomodal ethylene-co-1-hexene copolymer according to any one of claims 1 to 4 so as to obtain a melt thereof, extruding the melt through a die configured for forming gas bubbles so as to produce gas bubbles of the monomodal ethylene-co-1-hexene copolymer, and blowing the gas bubbles with a film blowing machine, thereby producing the blown film.
10. Blown film produced by the process according to claim 9 and consisting essentially of the monomodal ethylene-co-1-hexene copolymer according to any of the claims 1 to 4.
Technical Field
Polyethylene copolymers, films, articles, and related methods.
Background
Patent applications in the field and patents relating to the field include US 2016/0068623 a 1; US 2016/0297907 a 1; WO 2017/132092 a 1; US 6,989,344B 2; US 7,078,467B 1; US 7,157,531B 2; US 7,223,825B 2; US 7,300,988B 2; US 8,227,552B 2 and US 8,497,329B 2.
Bubble instability in blown polyethylene film extrusion can create one or more of the following problems: (a) variations in film dimensions, such as variations in film gauge (thickness) and/or width; (b) loss of film integrity, such as scratches and/or tears in the film; and (c) film misbehavior such as sagging, warping or chattering.
Disclosure of Invention
A unimodal ethylene-co-1-hexene copolymer, when in molten form at 190 degrees celsius (° c), is characterized by a unique melting property space defined by a combination of melt elasticity and complex viscosity ratio (shear thinning) properties ("unimodal ethylene-co-1-hexene copolymer"). Unimodal ethylene-co-1-hexene copolymers are used for the production of films with enhanced bubble stability ("unimodal ethylene-co-1-hexene copolymers"). Enhanced bubble stability means either a reduction in bubble instability or an increase in bubble stability.
A method of synthesizing a unimodal ethylene-co-1-hexene copolymer, said method consisting essentially of: ethylene (monomer) and 1-hexene (comonomer) are polymerized with a single unimodal catalyst system in a single fluidized bed gas phase polymerization (FB-GPP) reactor under effective operating conditions, thereby producing a unimodal ethylene-co-1-hexene copolymer. The transition phrase "consisting essentially of … …" means that the process is free of other catalysts (i.e., free of multimodal or bimodal catalyst systems or two or more separate catalysts), that the polymerization is carried out in a single reactor (i.e., in a FB-GPP reactor), and that the operating conditions are effective to impart a unique combination of melt elasticity and complex viscosity ratio (shear thinning) characteristics to the unimodal ethylene-co-1-hexene copolymer. Otherwise, the process composition and operating conditions are not limited.
A film consisting essentially of said unimodal ethylene-co-1-hexene copolymer ("said film"). The membranes are characterized by enhanced bubble stability. The transition phrase "consisting essentially of … …" means that when the examples are characterized by bubble stability, the film is free of other polyolefin polymers, but the composition thereof is not particularly limited.
A method for producing a blown film, the method comprising melting a monomodal ethylene-co-1-hexene copolymer to obtain a melt thereof, extruding the melt through a die configured for forming gas bubbles to produce a foam of the monomodal ethylene-co-1-hexene copolymer, and blowing (inflating) the gas bubbles with a film blowing machine, thereby producing the blown film. Blown films are characterized by enhanced bubble stability (reduced bubble instability). When the examples are characterized by bubble stability, the blown film is free of other polyolefin polymers, but the composition thereof is not particularly limited.
An article comprising the monomodal ethylene-co-1-hexene copolymer.
Drawings
FIG. 1 (FIG. 1) is a graph of the melt behavior space defined by melt viscosity on the y-axis versus shear thinning on the x-axis.
Detailed Description
The summary and abstract are incorporated herein by reference. Certain embodiments are described below as numbered aspects to facilitate cross-referencing.
Aspect 1. a unimodal ethylene-co-1-hexene copolymer, when in molten form at 190 ℃, characterized by a melting property space defined by a combination of melt elasticity and complex viscosity ratio (shear thinning) properties, wherein said combination is according to equation 1 (equation 1):6*SH1000+1,971<G′(G"＝3,000Pa)<6*SH1000+2,138 (equation 1); wherein<Is less than;*is a multiplication; + is addition; g' (G "═ 3,000Pa) is the melt elasticity in pascals (Pa) measured at a loss modulus G" ═ 3000 pascals according to the melt storage modulus test method (described herein); SH1000 is equal to Eta*0.126/Eta*126 complex viscosity ratio (shear thinning), wherein Eta*0.126 is the complex viscosity in pascal-seconds (Pa-s) measured at 0.126 radians per second (rad/s) by dynamic mechanical analysis test method (described herein); and Eta*126 is the complex viscosity in Pa-s measured by dynamic mechanical analysis test method at 126 rad/s. Eta may be*0.126 is called (eta)*)0.126, Eta*126 is called (eta)*)126, and SH1000 ═ η (η)*)0.126/(η*)126. Dynamic Mechanical Analysis (DMA) is also known as Dynamic Mechanical Spectroscopy (DMS). In some embodiments, the high load melt index (I) of the unimodal ethylene-co-1-hexene copolymer21) Is 15.0 to 25.0 grams/10 minutes (g/10min), alternatively 17 to 23 grams/10 min; melt flow ratio (MFR5 or I)21/I5) Is 18.0 to 25.0, alternatively 20.0 to 23.0; molecular mass dispersity (M)w/Mn)，Is 25.0 to 45.0, alternatively 28.0 to 38.4; and SH1000 is 30.0 to 50.0, alternatively 32.0 to 45.0.
Aspect 2. the monomodal ethylene-co-1-hexene copolymer according to aspect 1, further characterized by at least one of the characteristics (a) to (g): (a) a density of 0.935 to 0.945 grams per cubic centimeter (g/cm) as measured according to ASTM D792-13, method B3) Or alternatively 0.936 to 0.942g/cm3Alternatively 0.938 to 0.940g/cm3Or 0.938.5 to 0.940.4g/cm3. (b) High load melt index (I) measured according to ASTM D1238-13(190 ℃, 21.6kg)21) From 20.5 to 22.6 grams/10 minutes (g/10min), or from 20.85 to 22.54 grams/10 min; (c) melt flow ratio (MFR5 or I)21/I5) Is from 22.1 to 24.5, alternatively from 22.45 to 24.24, wherein I21Measured according to ASTM D1238-13(190 ℃, 21.6kg)Quantitative and I5Is a melt index in grams/10 minutes measured according to ASTM D1238-13(190 ℃, 5.0 kg); (d) molecular mass dispersity (M)w/Mn)Is 38 to 44, or 38.75 to 43.74, wherein MwAnd MnMeasured according to the GPC test method; (e) wherein the combination of melt elasticity and complex viscosity ratio (shear thinning) characteristics is defined according to equation 1a (equation 1 a): 6*SH1000+1,975<G'(G"＝3,000Pa)<6*SH1000+2,134 (equation 1 a); (f) complex viscosity Eta measured by dynamic mechanical analysis test method at 126 rad/sec*126 is 1220 to 1240 pascal-seconds (Pa-s); and (g) a complex viscosity ratio (shear thinning) SH1000 of 43 to 50.0, alternatively 43.85 to 49.24.
Aspect 3. the monomodal ethylene-co-1-hexene copolymer according to aspect 2, further defined by any one of the limitations (i) to (xi): (i) characteristics (a) and (b); (ii) characteristics (a) and (c); (iii) characteristics (a) and (d); (iv) characteristics (a) and (e); (v) characteristics (a) and (f); (vi) characteristics (a) and (g); (vii) characteristics (a), (b) and (c); (viii) characteristics (a), (b), and (d); (ix) characteristics (f) and (g); (x) Any six of characteristics (a) through (g); and (xi) each of the characteristics (a) to (g).
Aspect 4. the monomodal ethylene-co-1-hexene copolymer according to any of aspects 1 to 3, further characterized by any one of characteristics (h) to (i) or a combination of characteristics (h) and (i): (h) weight average molecular weight (M) measured according to Gel Permeation Chromatography (GPC) test methodw) Is 300,000.0 to 400,000.0 grams/mole (g/mol), alternatively 301,000.0 to 350,000.0g/mol, alternatively 301,000.0 to 325,000.0 g/mol; and (i) number average molecular weight (M) measured according to GPC measurement methodn) Is 7,000.0 to 8,000.0g/mol, alternatively 7,100.0 to 7,900.0g/mol, alternatively 7,300 to 7,700 g/mol. Some embodiments combine features (a) and (b) of aspect 2 with feature (h) of aspect 4; or combining the characteristics (a) and (d) of aspect 2 with the characteristic (h) of aspect 4; or combining the characteristics (a), (b) and (d) of aspect 2 with the characteristic (h) of aspect 4.
Aspect 5. a method of synthesizing the monomodal ethylene-co-1-hexene copolymer according to any one of aspects 1 to 4, the method consisting essentially of: contacting ethylene and 1-hexene with a single catalyst system consisting of a unimodal chromium catalyst system in a single fluidized bed gas phase polymerization (FB-GPP) reactor under effective operating conditions comprising Reactor Bed Temperature (RBT), average polymer residence time (avgPRT), and ethylene partial pressure (C2P) and receiving ethylene (C22) Feed, comonomer (1-hexene or "C6") feed, hydrogen (H)2) Feed and optionally oxygen (O)2) A feed, wherein the feed is characterized by H2/C2Gas molar ratio (H)2/C2) Comonomer/ethylene gas molar ratio ("C)6/C2") and O2/C2Gas volume ratio ("[ O ]2/C2]", vol/vol in ppmv); wherein RBT is 101 ℃ to 111 ℃; avgPRT is 1.70 to 3.10 hours, C2P is 1,100 to 1,900 kilopascals (kPa); h2/C2The gas molar ratio is 0.05 to 0.150; c6/C2The gas molar ratio is 0.010 to 0.021; and O is2/C2Gas volume ratio of>0 to 130ppbv (parts per billion volume); thereby synthesizing a unimodal ethylene-co-1-hexene copolymer in the FB-GPP reactor; the method may be characterized by any of the restrictions (i) to (ix): (i) RBT is 104.0 ℃ to 110.0 ℃, alternatively 105.0 ℃ to 109.0 ℃; (ii) C2P is 1,300 to 1,500kPa, or 1,375 to 1,384 kPa; (iii) h2/C2A gas molar ratio of 0.010 to 0.030, alternatively 0.015 to 0.024; (iv) c6/C2A gas molar ratio of 0.0140 to 0.0175, alternatively 0.0145 to 0.0170; (v) o is2/C2A gas volume ratio of 10 to 120ppbv, or 14 to 113 ppbv; (vi) (ii) both (i) and (iii); (vii) (iv) each of (i), (iii), and (iv); (viii) any four of (i) to (v); and (ix) each of (i) to (v). The RBT can be adjusted within the above-mentioned range thereof to adjust the unimodal ethylene-co-1-hexene copolymer produced by said process(Mw/Mn) Within its above range and thus SH1000 is adjusted within its above range. Can combine RBT and H2/C2The gas molar ratio is adjusted within the above range thereof to adjust the melt elasticity of the monomodal ethylene-co-1-hexene copolymer produced by the process. H2/C2Gas molar ratio, C6/C2Gas molar ratio and O2/C2The gas volume ratio is determined by measuring (e.g. metering) the H fed to the FB-GPP reactor2、C2、C6And O2The amount of gas. Reactor bed temperatures RBT and H2/C2The gas molar ratio is suitable for use in a process for the synthesis of a monomodal ethylene-co-1-hexene copolymer, which, when in molten form at 190 ℃, satisfies equation 1 described previously. The transition phrase "consisting essentially of … …" means that the process is free of other catalysts (i.e., free of multimodal or bimodal catalyst systems or two or more separate catalysts), that the polymerization is carried out in a single reactor (i.e., in a FB-GPP reactor), and that the operating conditions are effective to impart a unique combination of melt elasticity and complex viscosity ratio (shear thinning) characteristics to the unimodal ethylene-co-1-hexene copolymer. In addition to this, the composition and the operating conditions of the process are not particularly limited. Described herein are unimodal chromium catalyst systems and their preparation. The unimodal chromium catalyst system may be a reduced chromium oxide catalyst system, which is described herein along with its preparation. The reduced chromium oxide catalyst system may be ACCLAIM available from Union Technologies LLC of Houston, TexTMK-100 advanced chromium catalysts (described herein).
Aspect 6. the process of aspect 5, further comprising removing the monomodal ethylene-co-1-hexene copolymer from the FB-GPP reactor to obtain a removed monomodal ethylene-co-1-hexene copolymer. In some aspects, an inert gas (e.g., N) may be used2) Purging the removed monomodal ethylene-co-1-hexene copolymer to remove hydrocarbons entrained therewith and/or with humidified nitrogenQi (N)2) Stream treatment to deactivate any residual amounts of the reduced chromium oxide catalyst system therein in situ. In some aspects, the removed unimodal ethylene-co-1-hexene copolymer is pelletized to obtain pellets of the removed unimodal ethylene-co-1-hexene copolymer. In some aspects, the removed unimodal ethylene-co-1-hexene copolymer may be combined with one or more film additives suitable for polyethylene films. The combining may comprise melt mixing one or more film additives into the melt of the removed unimodal ethylene-co-1-hexene copolymer. Alternatively, the combining may comprise immersing or injecting one or more film additives into the removed pellets of the unimodal ethylene-co-1-hexene copolymer.
Aspect 7. an article comprising the monomodal ethylene-co-1-hexene copolymer according to any one of aspects 1 to 4.
Aspect 8. a film consisting essentially of the monomodal ethylene-co-1-hexene copolymer according to any one of aspects 1 to 4 ("the film"). The transition phrase "consisting essentially of … …" means that the film is free of other polyolefin polymers, but its composition is not particularly limited. Films may be used in packaging applications to protect a substance that needs to be covered, wherein the film is configured to at least partially cover the substance. Examples of substances that need to be covered are paper, paperboard (e.g., cardboard), food, pharmaceutical compounds, and a stack of cartons (e.g., where the film is shrink wrap for wrapping a tray stacked with cartons). In some aspects, the film is a blown film made as described below.
Aspect 9. a method of producing a blown film, the method comprising melting the monomodal ethylene-co-1-hexene copolymer according to any one of aspects 1 to 4 so as to obtain a melt thereof, extruding the melt through a die configured for forming bubbles so as to produce bubbles of the monomodal ethylene-co-1-hexene copolymer, and blowing (inflating) the bubbles with a film blowing machine, thereby producing a blown film that is restricted in one dimension. The bubbles are confined in one dimension. Blown films can be made or prepared without Internal Bubble Cooling (IBC) by any suitable method, including IBC-free high neck film blowing (high stage film blowing), for example by using a high neck film blowing manufacturing line without (active) IBC equipment. The blown film consists essentially of the monomodal ethylene-co-1-hexene copolymer according to any of aspects 1 to 4 ("blown film"). The transition phrase "consisting essentially of means that the blown film is free of other polyolefin polymers, but the composition thereof is not particularly limited.
Aspect 10. a blown film made by the process according to aspect 9 and consisting essentially of the monomodal ethylene-co-1-hexene copolymer according to any one of aspects 1 to 4 ("blown film"). The transition phrase "consisting essentially of means that the blown film is free of other polyolefin polymers, but the composition thereof is not particularly limited. Blown films are characterized by enhanced (enhanced) bubble stability, i.e., reduced bubble instability. The blown film may optionally contain zero, one or more film additives. Blown films may be characterized by enhanced (enhanced) toughness and/or enhanced bubble stability (reduced bubble instability). Blown films can be used in packaging applications.
Unimodal ethylene-co-1-hexene copolymers can generally be described as medium molecular weight medium density polyethylene (MMW MDPE).
Unimodal ethylene-co-1-hexene copolymers, films and methods of making unimodal ethylene-co-1-hexene copolymers are free of Ziegler-Natta catalysts (Ziegler-Natta catalysts), metallocene catalysts and post-metallocene catalysts. For example, Ti, Hf, Zr metals are not included.
Definition of
As used herein, bubble stability is measured according to the methods described herein.
A material that increases the rate of reaction (e.g., polymerization of ethylene and 1-hexene) and is not therefore completely consumed.
The catalyst system, the catalyst itself, and a companion material such as a modifier compound for reducing the reactivity of the catalyst, a support material on which the catalyst is disposed, a support material in which the catalyst is disposed, or a combination thereof, or a reaction product of a reaction of the catalyst itself and the companion material.
Consisting essentially of … … (structural and/or consenting(s) of), etc..) excludes anything that affects the basic and novel features of what it describes, but otherwise allows for the partially closed representation of anything else. In some aspects, any one, or each "comprising" may be replaced by "consisting essentially of … … (inclusive of) respectively; or respectively replaced by "consisting of … … (constraints of)".
Consisting of … … (containing of constraints of excluded from closed-form expression of anything specifically described by the limitations not modified by it. In some aspects, any one, or each, of the expressions "consisting essentially of … … (of a consistent essentiality of)" may be replaced by the expression "consisting of … … (of a consistent of a) respectively.
Generally, the moisture content is from 0 to less than 5ppm (parts per million) based on total weight parts. The material fed to the one or more reactors during the polymerization reaction is dry.
Amount of reactants and/or reagents added or "fed" to the reactor. In a continuous polymerization operation, each feed may independently be continuous or batch-wise. The amounts or "feed amounts" may be measured, for example, by metering, to control the amounts and relative amounts of the various reactants and reagents in the reactor at any given time.
Film formation: limited to one dimension. The confinement dimension may be referred to as a thickness of the film, and the thickness is substantially uniform therein. The claimed film properties were measured on a single layer film 13(12.7) microns thick.
And (4) inertia. In general, it is not (significantly) reactive or interferes with the polymerization reaction of the present invention. The term "inert" as applied to the purge gas or ethylene feed means molecular oxygen (O) as a total part weight of the purge gas or ethylene feed2) The content is 0 to less than 5 ppm.
Internal bubble cooling or IBC is an aspect of film blowing by actively using auxiliary dedicated IBC equipment (such as the IBC equipment of US 2002/0150648a1 by r.e. cree.).
A metallocene catalyst. Substantially single-or dual-site catalytic molecules based on metal-cyclopentadienyl ligand complexes.
A post metallocene catalyst. Substantially single-or double-site catalytic molecules based on metal-ligand complexes, wherein the ligands are substituted cyclopentadienyl or multidentate molecular anions.
A single peak. When referring to polymers: there is one peak (no shoulder) in the plot of dW/dlog (mw) on the y-axis versus log (mw) on the x-axis to provide a Gel Permeation Chromatography (GPC) chromatogram, where log (mw) and dW/dlog (mw) are as defined herein and measured by the Gel Permeation Chromatography (GPC) test method described herein. When referring to a catalyst or catalyst system: producing a unimodal polymer.
Ziegler-Natta catalysts (Ziegler-Natta catalysts). Enhance the olefin polymerization rate and are typically heterogeneous materials prepared by contacting an inorganic titanium compound, such as a titanium halide, supported on a magnesium chloride support with an activator.
The melt elasticity of a thermoplastic polymer can be considered to be the behavior of a melt of the polymer during a forming process, such as extrusion or film formation. It is one of the determinants of viscoelastic melt behavior, where viscosity decreases as shear rate increases. Undesirable melt elasticity can undesirably cause die swell during extrusion or bubble stability problems during film blowing. As used herein, a measure or indicator of melt elasticity is the value of the storage modulus of fusion (G ') as measured using DMA (dynamic mechanical analysis) on a polymer melt at 190 ℃, by small strain (10%) oscillatory shear at varying frequencies from 0.02 radians/second (rad/s) to about 200rad/s using an ARES-G2Advanced rheological amplification System (ARES-G2Advanced Rheometric Expansion System) with parallel plate geometry from TA Instruments of america (TA Instruments) to obtain the value of G ' (G "-3,000 Pa) of the storage modulus of fusion (G ') in pascals at dynamic frequencies, where the loss modulus (G") equals 3,000 pascals.
Polymerization process
In an illustrative pilot plant process for making a unimodal ethylene-co-1-hexene copolymer, a fluidized bed, a gas phase polymerization reactor ("FB-GPP reactor") having a reaction zone with an inner diameter of 304.8mm (twelve inches) and a straight-sided height of 2.4384 meters (8 feet), and containing a fluidized bed of unimodal ethylene-co-1-hexene copolymer particles. The FB-GPP reactor was configured with a recycle gas line for flowing a recycle gas stream. The FB-GPP reactor was equipped with a gas feed inlet and a polymer product outlet. Gaseous feed streams of ethylene and hydrogen are introduced into the recycle gas line below the FB-GPP reactor bed along with comonomer (e.g., 1-hexene). Control of ethylene (' C)2"), hydrogen gas (" H ")2") and 1-hexene or" C6"to maintain a fixed comonomer to ethylene monomer gas mole ratio (C)x/C2E.g. C6/C2) Equal to the value described (e.g., 0.0050), constant hydrogen to ethylene gas molar ratio ("H2/C2") is equal to the value described (e.g., 0.0020), and constant ethylene (" C2") partial pressure equal to the value described (e.g., 1,000 kPa). The concentration of all gases was measured by an on-line gas chromatograph to understand and maintain the composition in the recycle gas stream. The reacting bed of growing polymer particles is maintained in a fluidized state by continuously flowing the make-up feed and recycle gas through the reaction zone. Superficial gas velocities of 0.49 to 0.67 meters per second (m/sec) (1.6 to 2.2 feet per second (ft/sec)) are used. The FB-GPP reactor is operated at a total pressure of about 2344 to about 2413 kilopascals (kPa) (about 340 to about 350 pounds per square inch gauge (psig)) and at the first reactor bed temperature RBT (e.g., 105 ℃) described. The fluidized bed is maintained at a constant height by withdrawing a portion of the bed at a rate equal to the production rate of the particulate form of the unimodal ethylene-co-1-hexene copolymer, which may be from 10 to 20 kilograms per hour (kg/hr), or from 13 to 18 kilograms per hour. Semi-continuously removing the product monomodal ethylene-co-1-hexene copolymer through a series of valves into a fixed volume chamber, wherein such removed monomodal ethylene-co-1-hexene copolymer is purgedTo remove entrained hydrocarbons and with humidified nitrogen (N)2) The stream is treated to deactivate any traces of residual catalyst.
The polymerization or operating conditions are any variable or combination of variables that may affect the composition or characteristics of the polymerization reaction in the GPP reactor or the unimodal ethylene-co-1-hexene copolymer product made therefrom. Variables may include reactor design and size, catalyst composition and amount; reactant composition and amount; the molar ratio of the two different reactants; feed gas (e.g. H)2And/or O2) Presence or absence of (a), molar ratio of feed gas to reactant(s), interfering material (e.g., H)2O), absence or concentration of Induced Condensing Agent (ICA), average polymer residence time in the reactor, partial pressure of the ingredients, feed rate of the monomers, reactor bed temperature (e.g., fluidized bed temperature), nature or sequence of process steps, transition time period between steps. Variables other than the variable/variables described or changed by the method or use can be held constant.
Comonomer/ethylene gas molar ratio CX/C2Is equal to the comonomer (1-hexene, C) fed to the Gas Phase Polymerization (GPP) reactor6) Divided by the operating conditions of the moles of ethylene fed to the GPP reactor during the polymerization process. For calculating Cx/C2The gas mole ratio of the moles of comonomer and moles of ethylene is measured by gas flow meter or other suitable means.
Ethylene partial pressure in GPP reactor (e.g., C2P). Typically 690 to 2070 kilopascals (kPa, i.e., 100 to 300 psia). 1.000psia 6.8948 kPa.
Hydrogen and ethylene (H)2/C2) The gas molar ratio is the operating condition in the GPP reactor and is equal to the number of moles of molecular hydrogen fed to the GPP reactor divided by the number of moles of ethylene gas fed to the GPP reactor during the polymerization.
Induced Condensing Agent (ICA). An inert liquid for cooling material in one or more polymerization reactors, such as fluidized bed reactors. In thatIn some aspects, the ICA is (C)5-C20) Alkane, or (C)11-C20) Alkane, or (C)5-C10) An alkane. In some aspects, the ICA is (C)5-C10) An alkane. In some aspects, (C)5-C10) The alkane is a pentane, such as n-pentane or isopentane; hexane; heptane; octane; nonane; decane; or a combination of any two or more thereof. In some aspects, the ICA is isopentane (i.e., 2-methylbutane). The polymerization process of the present invention using ICA may be referred to herein as an Induced Condensing Mode Operation (ICMO). The concentration of ICA in the gas phase was measured using gas chromatography by calibrating the peak area percentage to mole percent (mol%) using gas mixture standards of known concentrations of gas phase components. The ICA concentration may be 1 to 10 mol%, or 3 to 8 mol%.
Oxygen (O) relative to ethylene in GPP reactors2) Concentration ("[ O ]2/C2]”，O2Parts by volume per million parts by volume of ethylene (ppmv)). In general [ O ]2/C2]Is 0.0000 to 150 ppbv.
The polymerization process uses a Gas Phase Polymerization (GPP) reactor, such as a stirred bed gas phase polymerization reactor (SB-GPP reactor) or a fluidized bed gas phase polymerization reactor (FB-GPP reactor), to produce a unimodal ethylene-co-1-hexene copolymer. Such reactors and processes are generally well known in the art. For example, GPP reactors/processes may employ induced condensing agents and proceed in condensing mode polymerization, as in US4,453,399; US4,588,790; US4,994,534; US5,352,749; as described in US5,462,999 and US 6,489,408. The GPP reactor/process may be a fluidized bed gas phase polymerization reactor (FB-GPP reactor)/process, such as described in US 3,709,853; US4,003,712; US4,011,382; US4,302,566; US4,543,399; US4,882,400; US5,352,749; US5,541,270; EP-A-0802202; and belgium patent No. 839,380. These SB-GPP and FB-GPP polymerization reactors and processes mechanically agitate or fluidize the polymerization medium inside the reactor by continuous flow of gaseous monomer and diluent, respectively. Other reactors/processes contemplated include series or multistage polymerization processes, as described in US5,627,242; US5,665,818; US5,677,375; EP-A-0794200; EP-B1-0649992; EP-A-0802202; and EP-B-634421.
The polymerization conditions may further include one or more additives such as chain transfer agents, accelerators or scavengers. Chain transfer agents are well known and may be metal alkyls such as diethyl zinc. Promoters are known, as in US4,988,783, and may include chloroform, CFCl3Trichloroethane and difluorotetrachloroethane. The scavenger may be a trialkylaluminium. The gas phase polymerization can be operated without (unintentionally added) scavenger. The polymerization conditions for the gas phase polymerization reactor/process may further comprise an amount (e.g., 0.5 to 200ppm based on all feeds to the reactor) of a static control agent and/or a continuity additive, such as aluminum stearate or polyethyleneimine. Static control agents can be added to the FB-GPP reactor to inhibit the formation or build-up of static charges therein.
Start-up or restart of the GPP reactor can be illustrated with a fluidized bed, GPP reactor. The start-up (cold start) or in transition restart (hot start) of the re-enabled FB-GPP reactor comprises a period of time before reaching the steady state polymerization conditions of step (a). The start-up or restart may include the use of a bed of polymer seeds that are preloaded or loaded into the fluidized bed reactor, respectively. The polymer seed bed may be composed of polyethylene powder, such as a polyethylene homopolymer or a previously manufactured batch of unimodal ethylene-co-1-hexene copolymer.
The start-up or restart of the FB-GPP reactor may also include a gas atmosphere transition comprising purging the air or one or more other unwanted gases of the reactor with a dry (anhydrous) inert purge gas, followed by purging the dry inert purge gas of the FB-GPP reactor with dry ethylene gas. The dry inert purge gas may consist essentially of molecular nitrogen (N)2) Argon, helium, or a mixture of any two or more thereof. When not operating, the FB-GPP reactor contained an air atmosphere prior to start-up (cold start-up). Dry inert purge gas may be used to purge the air of the reactivated FB-GPP reactor during early start-upTo obtain an FB-GPP reactor with an atmosphere consisting of dry inert purge gas. The FB-GPP reactor in transition may contain an atmosphere of unwanted ICA or other unwanted gases or vapors prior to restart (e.g., after a seed bed change). The dry inert purge gas may be used to purge the FB-GPP reactor of unwanted vapors or gases during early restart transitions to give the FB-GPP reactor an atmosphere consisting of the dry inert purge gas. Any dry inert purge gas can itself be purged from the FB-GPP reactor with dry ethylene gas. The dry ethylene gas may further contain molecular hydrogen so that the dry ethylene gas is fed to the fluidized bed reactor in the form of a mixture thereof. Alternatively, the dry molecular hydrogen can be split and introduced after the atmosphere in the fluidized bed reactor is converted to ethylene. The gas atmosphere transition may be performed before, during or after heating the FB-GPP reactor to the reaction temperature of the polymerization conditions.
The start-up or restart of the FB-GPP reactor also includes introducing thereto feeds of reactants and reagents. The reactants include ethylene and alpha-olefins. The reagents fed to the fluidized bed reactor include molecular hydrogen and Induced Condensing Agent (ICA) and chromium-based catalyst systems (e.g., ACCLAIM)TMK-110 or K-120 higher chromium catalysts).
In an embodiment, the process uses a pilot scale fluidized bed gas phase polymerization reactor (pilot reactor) comprising the following reactor vessels: a fluidized bed containing unimodal ethylene-co-1-hexene copolymer powder and a distributor plate disposed above a bottom head (bottom head) and defining a bottom gas inlet and having an amplification zone or cyclonic system at the top of the reactor vessel to reduce the amount of resin fines that may escape from the fluidized bed. The amplification zone defines a gas outlet. The pilot reactor further contained a compression blower of sufficient power to circulate or circulate the ambient gas continuously down from the gas outlet in the amplification zone in the top of the reactor vessel, to and into the bottom gas inlet of the pilot reactor and through the distributor plate and the fluidized bed. The pilot reactor further contained a cooling system to remove the heat of polymerization and maintain the fluidized bed at the targetAt the target temperature. The composition of the gas fed to the pilot reactor, such as ethylene, alpha-olefin, hydrogen and oxygen, was monitored in the recycle loop by an on-line gas chromatograph in order to maintain specific concentrations that define and enable control of the polymer properties. In some embodiments, the gas is cooled, causing the temperature of the gas to drop below its dew point, while the pilot reactor is in Condensing Mode Operation (CMO) or Induced Condensing Mode Operation (ICMO). In CMO, liquid is present in the bottom head downstream of the cooler and below the distributor plate. Chromium-based catalyst systems (e.g. ACCLAIM)TMK-110 or K-120 advanced chromium catalyst) can be fed from a high pressure apparatus to a pilot reactor as a slurry or as a dry powder, wherein the slurry is fed by a syringe pump and the dry powder is fed by a metering disc. Chromium-based catalyst systems typically enter the fluidized bed below its bed height of 1/3. The pilot reactor further included a means of weighing the fluidized bed and an isolation port (product discharge system) for discharging a powder of unimodal ethylene-co-1 hexene copolymer from the reactor vessel in response to increasing fluidized bed weight as the polymerization reaction proceeded.
In some embodiments, the FB-GPP reactor is a commercial scale reactor, such as UNIPOLTMReactor or second generation UNIPOLTMReactors, all of which are available from Enyvit science and technology, Inc., a subsidiary of The Dow Chemical Company, Midland, Michigan, USA, Midland, Mich.
Chromium-based catalyst system
Chromium-based catalyst systems (e.g. ACCLAIM)TMK-110 or K-120 higher chromium catalysts) are unimodal and comprise a reduced chromium oxide catalyst compound and optionally one or more of a modifier, a reductant, an activator, and a support material. The reduced chromium oxide catalyst compound may comprise or may be a reaction product prepared from an activated chromium oxide catalyst compound and a reducing agent, optionally modified by a silyl chromate catalyst compound. The chromium-based catalyst system may be an unsupported catalyst system without a support material. The carrier material is functional (e.g., reactive), composed: (E.g., metal content) and characteristics (e.g., porosity) are different from the activator and chromium-based catalyst compound. Alternatively, the chromium-based catalyst system may further comprise a support material for containing the chromium-based catalyst compound and/or the activator. The chromium-based catalyst compound of the chromium-based catalyst system may be activated by any suitable method, which may or may not employ an activator, under any suitable activation conditions, as described herein.
The chromium oxide catalyst compound comprises CrO3Or can be converted to CrO under catalyst activation conditions3Any of the chromium compounds of (a). Can be converted into CrO3Compounds of (a) are disclosed in, for example, US 2,825,721; US 3,023,203; US 3,622,251 and US4,011,382. Examples are chromium acetyl acetonate, chromium halides, chromium nitrate, chromium acetate, chromium sulfate, ammonium chromate, ammonium dichromate and other soluble chromium-containing salts. Chromium oxide catalyst compounds include Philips-type catalyst compounds, commonly referred to as "inorganic oxide-supported Cr+6"catalyst". Philips-type catalyst compounds may be formed by a process comprising the reaction of Cr+3The compound is impregnated into a silica support, and then the impregnated silica support is calcined under an oxidizing condition of 300 ℃ to 900 ℃, or 400 ℃ to 860 ℃, to obtain a philips-type catalyst compound. Under these conditions, Cr is added+3At least some of which are converted to Cr+6。
The silyl chromate catalyst compound may be a bis (trihydrocarbylsilyl) chromate or a poly (diorganosilyl) chromate. The bis (trihydrocarbylsilyl) chromate may be bis (triethylsilyl) chromate, bis (tributylsilyl) chromate, bis (triisopentylsilyl) chromate, bis (tri-2-ethylhexylsilyl) chromate, bis (tridecylsilyl) chromate, bis (tri (tetradecyl) silyl) chromate, bis (tribenzylsilyl) chromate, bis (triphenylethylsilyl) chromate, bis (triphenylsilyl) chromate, bis (tritolylsilyl) chromate, bis (tristrimethylsilylsilyl) chromate, bis (trinaphthylsilyl) chromate, bis (triethylphenylsilyl) chromate, bis (trimethylnaphthylsilyl) chromate. The poly (diorganosilyl) chromate may be poly diphenyl silyl chromate or poly diethyl silyl chromate. In some embodiments, the silyl chromate compound is bis (triphenylsilyl) chromate, bis (tritolylsilyl) chromate, bis (trixylylsilyl) chromate, or bis (trinaphthylsilyl) chromate; or bis (triphenylsilyl) chromate. See US 3,324,101; US 3,704,287; and as described in US4,100,105.
A supported catalyst compound. The chromium-based catalyst compound (e.g., a chromium oxide catalyst compound, a silyl chromate catalyst compound, and/or a reduced chromium oxide catalyst compound) can independently be unsupported, i.e., free of a support material. Alternatively, a chromium-based catalyst compound (e.g., a chromium oxide catalyst compound, a silyl chromate catalyst compound, or a reduced chromium oxide catalyst compound) may be disposed on the support material. That is, the chromium-based catalyst system may comprise a chromium-based catalyst compound and a support material. Typically, the supported reduced chromium oxide catalyst compound is made in situ by contacting a pre-activated and supported chromium oxide catalyst compound (optionally modified with a silyl chromate catalyst compound) with a reducing agent to give an activated and supported reduced chromium oxide catalyst compound.
A carrier material. The support material may be an inorganic oxide material. The terms "support" and "support material" as used herein are the same and refer to a porous inorganic or organic substance. In some embodiments, the desired support material may be an inorganic oxide comprising a group 2, group 3, group 4, group 5, group 13, or group 14 oxide, or a group 13 or group 14 atom. Examples of inorganic oxide type support materials are silica, alumina, titania, zirconia, thoria, and mixtures of any two or more of such inorganic oxides. Examples of such mixtures are silica-chromium, silica-alumina and silica-titania.
The inorganic oxide support material is porous and has a variable surface area, pore volume, and average particle size. In some embodiments, the surface area is 50 to 1000 square meters per gram (m)2,/g) and an average particle size of 20 to 300 micrometers (μm). Alternatively, the pore volume is 0.5 to 6.0 cubic centimeters per gram (cm)3Per g) and a surface area of 200 to 600m2(ii) in terms of/g. Alternatively, the pore volume is 1.1 to 1.8cm3Per g and a surface area of 245 to 375m2(ii) in terms of/g. Alternatively, the pore volume is 2.4 to 3.7cm3Is/g and has a surface area of 410 to 620m2(ii) in terms of/g. Alternatively, the pore volume is 0.9 to 1.4cm3A surface area of 390 to 590m2(ii) in terms of/g. Each of the above characteristics is measured using conventional techniques known in the art.
The support material may comprise silica, or amorphous silica (other than quartz), or high surface area amorphous silica (e.g. 500 to 1000 m)2In terms of/g). Such silicas are commercially available from a variety of sources, including the Davison Chemical Division (e.g., Davison 952 and Davison 955 products) of graves chemicals corporation (w.r. grace and Company) and PQ corporation (e.g., ES70 products). The silica may be in the form of spherical particles obtained by a spray-drying process. Alternatively, the MS3050 product is silica from PQ corporation that has not been spray dried. As obtained, all of these silicas were uncalcined (i.e., not dehydrated). Silica calcined prior to purchase may also be used as a support material.
Supported chromium compounds (e.g., supported chromium acetates) are commercially available and can be used as examples of chromium-based catalyst systems. Commercial examples include davison 957, davison 957HS and davison 957BG products from davison chemical division, and ES370 products from PQ corporation. The supported chromium compound may be in the form of spherical particles obtained by a spray-drying process. Alternatively, the C35100MS and C35300MS products from PQ corporation were not spray dried. As obtained, all these silicas were not activated. The supported chromium compound activated before purchase may be used as the supported chromium compound.
The support material may be pretreated by heating the support material in air to obtain a calcined support material prior to contacting with the chromium oxide catalyst compound. The pre-treatment comprises heating the support material at a peak temperature of 350 ℃ to 850 ℃, or 400 ℃ to 800 ℃, or 400 ℃ to 700 ℃, or 500 ℃ to 650 ℃, and for a period of 2 to 24 hours, or 4 to 16 hours, or 8 to 12 hours, or 1 to 4 hours, thereby producing a calcined support material. In some aspects, the support material is a calcined support material.
In some embodiments, the supported chromium oxide catalyst system further comprises a silyl chromate compound as a modifier. Thus, the silyl chromate compound may be added to a slurry of an activated (unsupported or supported) chromium oxide catalyst system in a non-polar aprotic solvent to obtain a slurry of a modified activated supported chromium oxide catalyst system. According to the drying method described herein, the solvent may be removed by heating, optionally under reduced pressure.
And (5) activating the catalyst. Any of the foregoing chromium oxide catalyst compounds or silyl chromate catalyst compounds, whether unsupported or supported on an uncalcined or calcined support material, can be independently activated by heating in an oxidizing environment (e.g., substantially dry air or oxygen) at an activation temperature of 300 ℃ or greater, provided that the maximum activation temperature is below the activation temperature at which substantial sintering of the compound and/or support material will occur. Activation yields an activated (unsupported or supported) chromium oxide catalyst compound and/or an activated (unsupported or supported) silyl chromate catalyst compound. For example, to activate a philips-type catalyst, a fluidized bed of supported chromium oxide catalyst compound may be activated by passing a flow of dry air or oxygen therethrough, displacing any water therefrom and displacing at least some of the Cr+3Conversion of compounds to Cr+6A compound is provided. The maximum activation temperature may be 300 ℃ to 900 ℃, or 400 ℃ to 850 ℃, or 500 ℃ to 700 ℃, or 550 ℃ to 650 ℃. The activation period may be from 1 to 48 hours, alternatively from 1 to 36 hours,or 3 to 24 hours, or 4 to 6 hours. All other things being equal, the higher the activation temperature used, the shorter the activation period to achieve a given level of activation and vice versa. The resulting activated (unsupported or supported) chromium oxide catalyst system can be in the form of a powdered, free-flowing particulate solid.
Reducing the chromium oxide catalyst compound. Activated (unsupported or supported) reduced chromium oxide catalyst compounds and systems can be made from activated (unsupported or supported) chromium oxide catalyst systems. In one embodiment, the activated (unsupported or supported) chromium oxide catalyst system has been made from a calcined support material. The activated (unsupported or supported) chromium oxide catalyst system may be unmodified or may be modified with a silyl chromate compound according to the modification methods described previously. The preparation comprises stirring a slurry of an activated (unsupported or supported) chromium oxide catalyst system in a non-polar aprotic solvent under an inert atmosphere, adding a reducing agent to the stirred slurry for a period of time (addition time), and then reacting the resulting reaction mixture under an inert atmosphere for a period of time (reaction time) to produce an activated (unsupported or supported) reduced chromium oxide catalyst compound and system, typically supported on a support material as a slurry in a non-polar aprotic solvent. The inert atmosphere may comprise anhydrous N2Gas, Ar gas, He gas, or a mixture thereof. The inert atmosphere may be at a pressure of 101 to 700 kilopascals (kPa). The temperature of the stirred slurry during the addition step may be 30 ℃ to 80 ℃, or 40 ℃ to 60 ℃. The stirring may be performed at a rate of less than 70 revolutions per minute (rpm), and the addition time may be less than 20 minutes. Alternatively, the stirring rate may be greater than 70rpm and the addition time may be less than 20 minutes. Alternatively, the stirring rate may be greater than 70rpm and the addition time may be greater than 20 minutes. The stirring rate may be 30 to 50rpm, and the addition time may be 20 to 80 minutes. During the allowing step, the temperature of the reaction mixture may be 20 ℃ to 80 ℃, or 20 ℃ to 60 ℃, or 20 ℃ to 40 ℃. The reaction time period may be 0.08 to 2 hours.
The reducing agent may be an organoaluminum compound such as an aluminum alkyl or an aluminum alkyl alkoxide. The alkylaluminum alkoxide can be of the formula R2AlOR, wherein each R is independently unsubstituted (C)1-C12) Alkyl, or unsubstituted (C)1-C10) Alkyl, or unsubstituted (C)2-C8) Alkyl, or unsubstituted (C)2-C4) An alkyl group. Examples of alkylaluminum alkoxides are diethylaluminum methoxide, diethylaluminum ethoxide, diethylaluminum propoxide, dimethylaluminum ethoxide, diisopropylaluminum ethoxide, diisobutylaluminum ethoxide, ethylmethylaluminum ethoxide and mixtures thereof. In one aspect, the reducing agent is diethyl aluminum ethoxide (DEAIE).
The non-polar aprotic solvent can be an alkane or a mixture of alkanes, where each alkane independently has from 5 to 20 carbon atoms, alternatively from 5 to 12 carbon atoms, alternatively from 5 to 10 carbon atoms. Each alkane independently may be acyclic or cyclic. Each acyclic alkane can independently be straight or branched chain. The acyclic alkane can be pentane, 1-methylbutane (isopentane), hexane, 1-methylpentane (isohexane), heptane, 1-methylhexane (isoheptane), octane, nonane, decane, or a mixture of any two or more thereof. The cyclic alkane may be cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, methylcyclopentane, methylcyclohexane, dimethylcyclopentane, or a mixture of any two or more thereof. The non-polar aprotic solvent can be a mixture of at least one acyclic alkane and at least one cyclic alkane.
Thereafter, the slurry of activated (unsupported or supported) reduced chromium oxide catalyst compound and system can be dried to remove the non-polar aprotic solvent. Drying involves heating the slurry, optionally at low pressure, and in an environment that excludes oxidizing contaminants (such as air or oxygen). The drying process converts the activated (unsupported or supported) reduced chromium oxide catalyst compound and system from a viscous slurry to a partially dried slurry or mud and then to a free flowing powder. Helical ribbon stirrers can be used in vertical cylindrical blenders to accommodate varying mixture viscosities and stirring requirements. Drying can be carried out at pressures above, below, or at normal atmospheric pressure, so long as contaminants such as oxygen are strictly excluded from the activated (unsupported or supported) reduced chromium oxide catalyst compounds and systems. The drying temperature may range from 0 ℃ to 100 ℃, alternatively from 40 ℃ to 85 ℃, alternatively from 55 ℃ to 75 ℃. The drying time may be 1 to 48 hours, or 3 to 26 hours, or 5 to 20 hours. All other conditions being equal, the higher the drying temperature and/or the lower the drying pressure, the shorter the drying time and vice versa. After drying, the activated (unsupported or supported) reduced chromium oxide catalyst compound and system can be stored under an inert atmosphere until used.
An activator. Activators, also known as cocatalysts, are compounds that enhance the catalytic performance of the catalyst. The aluminum alkyl may be used as an activator for reducing the chromium oxide catalyst compound. Aluminum alkyls may also be used to improve the performance of activated (unsupported or supported) reduced chromium oxide catalyst compounds and systems. The use of aluminum alkyls allows variable control of side-branching in the polymer product and the desired catalyst yield. The aluminum alkyl may be applied directly to the reduced chromium oxide catalyst compound prior to feeding the reduced chromium oxide catalyst compound to the GPP reactor. Alternatively, the reduced chromium oxide catalyst compound and the aluminum alkyl may be fed separately into the GPP reactor, where the reduced chromium oxide catalyst compound and the aluminum alkyl contact each other in situ, which may shorten or eliminate any catalyst induction time. See US 7,504,467B 2.
During the process or use of the present invention, the chromium-based catalyst system, once activated, may be fed to the GPP reactor in dry powder form, or as a slurry in a non-polar aprotic solvent as described above.
Chromium oxide catalyst compounds and reduced chromium oxide catalyst compounds and methods of making the same, as well as polymer products formed therefrom, are characterized by US 6,989,344; US 2011/0010938 a 1; US 2016/0297907 a1 or WO 2017/132092 a 1.
In some embodiments, the chromium speciesThe catalyst system comprises a reduced chromium oxide catalyst system. In some embodiments, the reduced chromium oxide catalyst system comprises ACCLAIMTMK-100 catalyst system, ACCLAIMTMK-110 catalyst system or ACCLAIMTMK-120 catalyst system. ACCLAIMTMAll catalyst systems are available from Unionverest science and technology, Inc., of Houston, Tex.
ACCLAIMTMThe K-100, K-110 and K-120 catalyst systems can be prepared on a commercial scale as follows. The preparation was slightly different according to the slight difference in the aluminum (DEALE) concentration used in part (B) described herein. Part (a): activating the supported chromium oxide catalyst system in powder form. A fluidized bed heating vessel was charged with a quantity of porous silica support containing about 5 wt% chromium acetate (C35300 MSF grade chromium on silica, manufactured by PQ corporation) having a Cr content of about 1 wt%, a particle size of about 82 micrometers (μm) and a surface area of about 500m2(ii) in terms of/g. The vessel contents were heated at a rate of about 50 ℃/hour under a stream of dry nitrogen up to 200 ℃ and held at that temperature for about 4 hours. The vessel contents were then further heated to 450 ℃ under dry nitrogen at a rate of about 50 ℃ per hour and held at that temperature for about 2 hours. The dry nitrogen stream was replaced with a dry air stream and the vessel contents were heated to 600 ℃ at a rate of about 50 ℃ per hour and maintained at 600 ℃ for about 6 hours to give an activated chromium oxide catalyst. The activated catalyst dry air stream (at ambient temperature) was cooled to about 300 ℃, replaced with a dry nitrogen stream, and further cooled from 300 ℃ to room temperature under a dry nitrogen stream (at ambient temperature). The resulting cooled, activated supported chromium oxide catalyst system was a powder. The powder was stored in a mixing vessel under a dry nitrogen atmosphere until used in part (B).
Partial (B) reduction of the activated chromium oxide catalyst system to obtain ACCLAIMTMK-100, K-110 or K-120 catalyst systems. For pilot plant, the vertical catalyst blender was equipped with a double helical ribbon stirrer and charged under an inert atmosphereAbout 0.86kg of part (a) of the activated supported chromium oxide catalyst in powder form. Dry hexane or isopentane solvent (7.1L solvent/kg powder) was added to fully suspend the powder and form a slurry. The slurry was stirred, warmed to about 45 ℃, and a 25 wt% solution of DEAlE (Akzo Nobel) in isopentane or hexane was added above the surface of the catalyst slurry at a rate such that the addition was completed in a period of about 40 minutes to obtain a selected wt% aluminum loading on the powder, wherein the wt% aluminum loading varied depending on acllaimTMWhether a K-100, K-110 or K-120 catalyst system is prepared. The resultant was further stirred at a controlled rate for about 1 hour on a pilot scale or 2 hours on a commercial scale. The solvent is then substantially removed from the resulting reaction mixture by drying at a selected jacket temperature (jack temperature) for about 16 to 21 hours. During the subsequent drying hours, typically 16 hours for pilot scale, the jacket temperature was chosen to obtain a target material temperature of approximately 61 ℃, 64 ℃,71 ℃ or 81 ℃. As the drying time progresses, a gradually increasing vacuum is applied to the container. Obtaining a powder comprising ACCLAIM in the form of a dry, free-flowing powderTMReduced chromium oxide catalyst systems of the K-100, K-110 or K-120 catalyst systems, which are stored in containers under dry nitrogen pressure until used in the polymerization reaction.
Unimodal ethylene-co-1-hexene copolymer
And (5) diluting the ethylene. Formula H2C＝CH2A compound of (a). A polymerizable monomer.
1-hexene. Formula H2C＝C(H)CH2CH2CH2CH3A compound is provided. A polymerizable comonomer.
Unimodal ethylene-co-1-hexene copolymer. A macromolecule or collection of macromolecules comprised of repeat units, wherein 50.0 to <100 mole percent (mol%), or 70.0 to 99.99 mol%, or 95.0 to 99.9 mol% of such repeat units are derived from ethylene monomer, and >0 to 50.0 mol%, or 0.01 to 30.0 mol%, or 0.1 to 5.0 mol% of the remaining repeat units are comonomer units derived from 1-hexene; or a collection of such macromolecules. The collection of macromolecules is characterized by two distinct peaks (without shoulder peaks) in a plot of dW/dlog (mw) on the y-axis versus log (mw) on the x-axis, resulting in a Gel Permeation Chromatography (GPC) chromatogram in which log (mw) and dW/dlog (mw) are defined below and measured by the Gel Permeation Chromatography (GPC) test method described herein.
Film
The film. The film may be unembossed or embossed. The film thickness can be adjusted to tailor the film for a particular application by combining with or without other films or additives. The film may be a monolayer film. In some aspects, the film has a thickness of 0.0051 to 0.254mm (0.2400 mils to 10 mils), or 0.0102mm to 0.254mm (0.400 mils to 10 mils), or 0.01143mm to 0.254mm (0.450 mils to 10 mils), or 0.01143mm to 0.127mm (0.450 mils to 5.00 mils), or 0.01143mm to 0.0762mm (0.450 mils to 3.00 mils), or 0.0127mm to 0.0635mm (0.500 mils to 2.50 mils).
Embodiments of the blown film may optionally contain zero, one or more film additives. A "film additive" is a compound or material other than a polyolefin polymer that imparts and/or enhances one or more properties of a blown film. Examples of film additives are biocides, antioxidants, catalyst neutralizers (of the chromium-based catalysts), colorants and light stabilizers. The one or more film additives (when present) may be pre-mixed with the unimodal ethylene-co-1-hexene copolymer prior to the melting step in the process for making blown film. Alternatively, one or more film additives (when present) may be added to the melt of the monomodal ethylene-co-1-hexene copolymer during or after the melting step in the process for manufacturing blown film and before the extrusion step. When two or more film additives are used, the one or more film additives may be premixed with the unimodal ethylene-co-1-hexene copolymer prior to the melting step in the process for manufacturing blown film, and the one or more film additives may be added to the melt of the unimodal ethylene-co-1-hexene copolymer during or after the melting step and prior to the extrusion step in the process for manufacturing blown film. In some aspects, the blown film consists essentially of a unimodal ethylene-co-1-hexene copolymer, at least one antioxidant, and at least one catalyst neutralizer (of a chromium-based catalyst). Examples of at least one antioxidant and at least one catalyst neutralizer are described herein.
The film may be manufactured using any extrusion or coextrusion process including blown, tenter and cast film processes. Blown films can be manufactured on blown film line machines configured for the manufacture of polyethylene films. The machine may be configured with a feed hopper in fluid communication with an extruder in heating communication with a heating device capable of heating the polyethylene in the extruder to a temperature of up to 500 ℃ (e.g., 430 ℃), and wherein the extruder is in fluid communication with a die having an inner diameter of 10.2 to 20.3 centimeters (4 to 8 inches) and a fixed die gap (e.g., 1.0 to 1.5 millimeter gap (39 to 59 mils)), a blow-up ratio of 3:1 to 5:1, and a stem Neck Height (NH)/die diameter of 8:1 to 9: 1. Step (a) may be accomplished in a feed hopper.
The film may be unoriented, uniaxially oriented, or biaxially oriented. The film may be oriented in the extrusion direction (machine direction or MD) or in a direction transverse to the extrusion direction (transverse direction or TD). The film may be produced by stretching or pulling the film in the MD to produce an MD oriented film, while or subsequently by stretching or pulling the MD oriented film in the TD to produce a film that is biaxially oriented in the MD and TD.
The film may have one or more improved properties, such as enhanced (lifted) bubble stability, enhanced (lifted) MD and/or TD Elmendorf Tear (Elmendorf Tear) performance, enhanced (lifted) MD tensile strength and/or TD tensile strength, enhanced (lifted) dart drop impact performance, or a combination of any two or more thereof.
The film may be combined with one or more other film layers to make a multilayer film or laminate.
The films are suitable for use in making containers and packages. Examples of such containers are bags, such as ice bags and grocery bags. Examples of such packages are stretch films, meat packages and food packages. The copolymers of the present invention may also be used in various non-film related applications, including vehicle parts.
Unless otherwise specified, the following applies. Or prior to different embodiments. ASTM means the standardization organization, ASTM International (ASTM International, West Conshooken, Pennsylvania, USA) of West Conshoken, Pa. Any comparative examples are for illustrative purposes only and should not be prior art. Absent or absent means completely absent; or not detectable. IUPAC is the International Union of Pure and Applied Chemistry (the IUPAC secretary of Triangle Research Park, North Carolina, USA) of the International Union of Pure and Applied Chemistry. Permission options may be given, not necessarily essential. Operability means being functionally capable or effective. Optional (optionally) means absent (or excluded), or present (or included). The properties (e.g., viscosity: 23 ℃ C. and 101.3kPa) were measured using standard test methods and conditions for measurement. Ranges include endpoints, sub-ranges and whole and/or fractional values subsumed therein, with the exception of integer ranges that do not include fractional values. Room temperature: 23 ℃ plus or minus 1 ℃.
Examples of the invention
Density is measured according to ASTM D792-13 using Standard Test Methods for Density and Specific Gravity (Relative Density) of displaced Plastics (Standard Test Methods for Density and Specific Gravity of Plastics by Displacement), method B (for testing solid Plastics in liquids other than water (e.g., liquid 2-propanol)). Results are reported in grams per cubic centimeter (g/cm)3) Is a unit. In some aspects, the density is from 0.89 to 0.98g/cm3Or 0.92 to 0.97g/cm3Alternatively 0.940 to 0.960g/cm3。
Dynamic Mechanical Analysis (DMA) test method: dynamic mechanical analysis method measured at 190 ℃ and 0.126 radians/second (rad/s) or 126rad/s using the following procedure: small strain (10%) oscillatory shear measurements were performed on polymer melts at 190 ℃ using the ARES-G2advanced rheology expansion System with parallel plate geometry from TA instruments to obtain storage modulus (G ') values, loss modulus (G ') values, complex modulus (G ') values as a function of frequency (ω)*) Value and complex viscosity (. eta.)*) The value is obtained. By calculating for a given frequency value (ω)Complex viscosity (. eta.)*) And calculating the ratio of the two viscosities to obtain the SH1000 value. For example, using frequency values (ω) of 0.126rad/s and 126rad/s, SH1000 ═ Eta is obtained*0.126/Eta*126 (i.e., 3,000 pascals (Pa) loss modulus G ″) constant value*(0.126rad/s)/η*(126 rad/s). SH1000 is defined as two complex viscosities Eta*0.126/Eta*126 (i.e. η)*(0.126rad/s)/η*(126rad/s)。
Gel Permeation Chromatography (GPC) test method: weight average molecular weight test method: mw, number average molecular weight (M) were measured using a chromatogram obtained on a high temperature gel permeation chromatograph (HTGPC, Polymer Laboratories)n) And Mw/Mn. HTGPC was equipped with a transmission line, a differential refractive index Detector (DRI) and three polymer laboratory PLgel 10 μm Mixed-B columns, all contained in an oven maintained at 160 ℃. The method uses a solvent consisting of TCB treated with BHT at a nominal flow rate of 1.0 milliliters per minute (mL/min.) and a nominal injection volume of 300 microliters (μ L). The solvent was prepared by dissolving 6 grams of butylated hydroxytoluene (BHT, antioxidant) in 4 liters (L) of reagent grade 1,2, 4-Trichlorobenzene (TCB) and filtering the resulting solution through a 0.1 micron (μm) Teflon filter to give the solvent. The solvent was degassed with an in-line degasser before entering the HTGPC instrument. The column was calibrated with a series of monodisperse Polystyrene (PS) standards. Separately, a known concentration of test polymer dissolved in a solvent was prepared by heating a known amount of test polymer in a known volume of solvent at 160 ℃ and shaking continuously for 2 hours to give a solution. Target solution concentration c for the test polymer was 0.5 to 2.0 milligrams polymer per milliliter of solution (mg/mL), with lower concentrations c being used for higher molecular weight polymers. Before running each sample, the DRI detector was purged. The flow rate in the apparatus was then increased to 1.0 ml/min and the DRI detector was allowed to stabilize for 8 hours before injecting the first sample. Calculating M using a universal calibration relationship with column calibrationwAnd Mn. MW at each elution volume was calculated using the following equation:wherein the subscript "X" represents the test sample, the subscript "PS" represents the PS standard, aPS＝0.67、KPS0.000175 and aXAnd KXObtained from published literature. For polyethylene, ax/Kx0.695/0.000579. For polypropylene, ax/Kx0.705/0.0002288. At each point in the resulting chromatogram, the DRI signal I from the baseline was subtractedDRICalculating the concentration c: c is KDRIIDRIV (dn/dc), where KDRIFor constants determined by calibrating DRI,/indicates a division, and dn/dc is the refractive index increment of the polymer. For polyethylene, dn/dc is 0.109. The polymer mass recovery is calculated from the ratio of the integrated area at the elution volume of the concentration chromatography chromatogram and the injected mass, which is equal to the predetermined concentration multiplied by the injection loop volume. All molecular weights are reported in grams per mole (g/mol) unless otherwise indicated. About measurement Mw、MnAdditional details of the MWD process are described in US 2006/0173123, pages 24-25 [0334 ]]Segment to [0341 ]]In a section. A plot of dW/dlog (mw) on the y-axis versus log (mw) on the x-axis gives GPC chromatograms, where log (mw) and dW/dlog (mw) are as defined above.
High Load Melt Index (HLMI) I21The test method comprises the following steps: standard Test methods for Melt Flow Rates of Thermoplastics with an Extrusion profilometer (Standard Test Method for Melt Flow Rates of Thermoplastics by Extrusion testing machine) using ASTM D1238-13, conditions of 190 ℃/21.6 kilograms (kg) were used. Results are reported in units of grams eluted per 10 minutes (g/10 min.).
Melt index I5(“I5") test method: ASTM D1238-13 was used, using conditions of 190 ℃/5.0 kg. Results are reported in units of grams eluted per 10 minutes (g/10 min.).
Melt flow ratio MFR5: (` I `)21/I5") test method: by adding a reagent from HLMI I21Value from test method divided by melt index I5Test methodIs calculated.
Method for testing melt storage modulus: small strain (10%) oscillatory shear measurements were performed on the polymer melt at 190 ℃ at varying frequencies from 0.02 radians/second (rad/s) to about 200rad/s using an ARES-G2advanced rheology expansion system with parallel plate geometry from TA instruments, usa, to obtain G '(G "═ 3,000Pa) values of the melt storage modulus (G') in pascals at dynamic frequencies, where the loss modulus (G") equals 3,000 Pa.
Antioxidant 1: pentaerythritol tetrakis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate was obtained as IRGANOX1010 from BASF.
Antioxidant 2: tris (2, 4-di-tert-butylphenyl) phosphite. IRGAFOS 168 from BASF.
Catalyst neutralizer 1: and (3) zinc stearate.
Chromium-based catalyst system: ACCLAIMTMK-110 catalyst system or ACCLAIMTMK-120 catalyst system. Obtained from the Union of Youyvern science and technology, Houston, Tex.
Comonomer (b): 1-hexene. See below, C6/C2Gas molar ratio.
Ethylene (' C)2"): see below, C2Partial pressure of (c).
Molecular hydrogen (' H)2"): see, infra H2/C2Gas molar ratio.
Molecular oxygen (' O)2"): see below O2/C2Gas volume ratio.
Unimodal ethylene-co-1-hexene copolymer: the target density is 0.938 to 0.941g/cm3And a target flow index (I)21) From 17 to 23 g/10min.
Inventive examples 1 to 2(IE1 to IE 2): polymerization procedure: according to the pilot reactor and the previously described process, ACCLAIMTMThe K-120 catalyst and comonomer 1-hexene were run starting with different fractions as described below to give different examples of unimodal ethylene-co-1-hexene copolymers in the form of a granular resin. The operating conditions for the polymerization are reported in Table 1 belowIn (1).
Table 1: operating conditions of IE1 through IE 2.
IE1
IE2
Part numbering
1
5A
Reactor type
S、CM、PP、FB GPP*
S、CM、PP、FB GPP
Reactor purge gas
Anhydrous N2
Anhydrous N2
Bed temperature (. degree. C.)
105.0
109.0
C2Partial pressure (kpa)
1379
1379
H2/C2Molar ratio of
0.020
0.020
C6/C2Molar ratio of
0.0169
0.0146
O2/C2Volume ratio (ppbv)
113
14
Induced condensing agent (mol%)
0.02
0.02
Apparent air velocity (meter/second)
0.60
0.60
Unimodal catalyst system
K-120
K-120
Catalyst loading (Cr, wt%)
0.862
0.862
Catalyst loading (Al, wt%)
1.542
1.542
Starting seed bed ═ granular HDPE resin
Preloaded in the reactor
Preloaded in the reactor
Initial bed weight (kg)
51
46
Copolymer production Rate (kg/hr)
19.1
17.9
Copolymer residence time (hours)
2.70
2.57
Bulk density of copolymer fluid, comparative (kg/m)3)
188
172
Comparison of settled bulk Density of copolymers (kg/m)3)
373
396
*S, CM, PP, FB, GPP: single, continuous mode, pilot plant, fluidized bed gas phase polymerization.
As shown in table 1, the bed temperature of the operating conditions for the preparation of monomodal ethylene-co-1-hexene copolymers from IE1 to IE2 was from 105.0 ℃ to 109.0 ℃; ethylene (C)2) The partial pressure was 1379 kpa; h2/C2The molar ratio is 0.020; c6/C2The molar ratio is 0.0146 to 0.0169; o is2/C2A volume ratio of 14 to 113ppbv (parts per billion volume); and the superficial gas velocity was 0.60m/sec (m/sec). In certain embodiments, the method of synthesizing a unimodal ethylene-co-1-hexene copolymer employs the foregoing operating conditions.
Formulation and granulation procedure: mixing each of the different pelletized resins IE1 through IE2 with 1,300 parts per million by weight, respectivelyAntioxidant 1,1,300 ppm antioxidant 2,1,000 ppm catalyst neutralizer 1 were mixed in a ribbon blender and then compounded into underwater cut pellets using a twin screw extruder LCM 100. The resulting pellets of each resin were subjected to a flow index (I) according to its corresponding test method previously described21) Density and melt storage modulus G' (G ═ 3,000Pa) were tested. The results are reported later. In certain embodiments, the unimodal ethylene-co-1-hexene copolymer further comprises at least one antioxidant selected from antioxidants 1 and 2; at least one catalyst neutralizer selected from the group consisting of catalyst neutralizer 1 and calcium stearate; or a combination thereof. The results are reported in table 2 below.
Table 2: inventive melting characteristics of IE1 to IE 2.
Testing
IE1
IE2
I21(190 ℃, 21.6kg) (g/10min)
20.9
22.5
MFR5(I21/I5)
24.2
22.5
Melt elasticity G' (G ═ 3,000Pa) (Pa)
2416
2267
Eta*126(Pa-s)
1232
1228
Shear thinning SH1000
49.2
43.9
Is equation 1 satisfied?
Is that
Is that
As shown in Table 2, the melt characteristics of the unimodal ethylene-co-1-hexene copolymers from IE1 to IE2 comprise a high load melt index I of from 20.9 to 22.5 g/10min21(190 ℃, 21.6 kg); melt flow ratio MFR5 (I) of 22.5 to 24.221/I5) (ii) a 2267 to 2416Pa (G ″ ═ 3,000 Pa); a complex viscosity at 126 radians/sec of 1228 to 1232 Pa-s; shear-thinning SH1000 of 43.9 to 49.2; and equation 1 is satisfied. In certain embodiments, the unimodal ethylene-co-1-hexene copolymer is characterized by any one, all but one, or each of the foregoing melt characteristics.
The melt property data of the unimodal ethylene-co-1-hexene copolymers in table 2 were analyzed to find that the melt properties depend on what reactor/process operating conditions. The following operating conditions were found to affect the melting characteristics of the monomodal ethylene-co-1-hexene copolymer thus produced: increasing H in said method2/C2The gas molar ratio and reactor bed temperature produce the inventive unimodal ethylene-co-1-hexene copolymer advantageously having reduced shear thinning and reduced melt elasticity G' (G ═ 3,000Pa) (Pa) to meet the combination defined by equation 1, and thus having enhanced (enhanced) bubble stability during film blowing.
The particulate resins of IE 1-IE 2 are characterized by density, molecular weight, Mw/Mn I5、I21. The results are reported in table 3 below.
Table 3: inventive resin characteristics of IE1 to IE 2.
As shown in Table 3, the resin properties of the monomodal ethylene-co-1-hexene copolymers of the invention from IE1 to IE2 comprise a density of 0.939g/cm3(ii) a A number average molecular weight of 7,339 to 7,882 g/mol; the weight average molecular weight is 305,882-321,078 g/mol; molecular mass dispersity Mw/Mn 38.8 to 43.7. In certain embodiments, the unimodal ethylene-co-1-hexene copolymer is characterized by any one, all but one, or each of the foregoing resin properties.
Film formation procedure: pellets of pelletized resin of inventive unimodal ethylene-co-1-hexene copolymer of IE1 to IE2 were separately melted at the melting temperatures described herein and separately blown into films using Alpine 50 millimeter (mm)25:1 length to diameter (L/D) sized barrier single screw extruder, die with an internal diameter of 120mm, die gap of 1.2mm, blow ratio 4:1, stem neck height 8:1, without IBC (internal bubble cooling). The bubble stability of the film was measured according to the following method: (a) bubble rating at a standard output rate of 6.9 kilograms per hour-centimeters (kg/hour-cm, bubble rating STD); (b) wherein the maximum linear velocity is greater than the bubble grade at a standard output rate of 14.2 meters per minute (m/min, bubble grade MLS); and (c) a bubble level at maximum output rate (20% or higher output rate, bubble level MOR). The air bubble rating is scored in the range of 1 to 5 as follows: 1. the film cannot be manufactured. 2. Membranes can be made but the membranes produced have bubble instability. 3. Films can be made, but the films produced have slight bubble instability. 4. A film with bubble stability can be produced. 5. A film with very stable bubbles can be produced. If the STD bubble rating is 4 or 5, the resin passes the bubble stability test and it is characterized as "good". If the STD bubble rating is 3, the resin passes the bubble stability test and it is characterized as "good". If the STD bubble rating is 2, the resin fails the bubble stability test and it is characterized as "medium". If the STD bubble rating is 1, the resin fails the bubble stability test and is characterized as "poor". The film results are reported in table 4 below.
Table 4: inventive film characteristics of inventive IEs 1 to IE 2.
Testing
IE1
IE2
Extruder speed (rpm)
96
97
Load of electric motor (%)
59.6
61.5
Melting temperature (. degree.C.)
199
197
Mold pressing (MPa)
N/r
N/r
Bubble grade STD
4
4
STD bubble quality
Good effect
Good effect
Bubble level MLS
3
3
Bubble rating MOR
2
4
N/r means not recorded. As shown in table 4, the inventive film properties of the blown films of the inventive unimodal ethylene-co-1-hexene copolymer of IE1 to IE2 comprised a bubble rating STD of 4, a bubble rating MLS of 3, a bubble rating MOR of 2 or 4, and good STD bubble quality. In certain embodiments, the unimodal ethylene-co-1-hexene copolymer and blown films thereof are independently characterized by any one, or all but one, or each of the foregoing film grades.
Using ACCLAIMTMK-110 or K-120 catalyst systems comparative unimodal ethylene-co-1-hexene copolymers of comparative examples 1 to 4(CE1 to CE4) were prepared and the target densities were from 0.938 to 0.940g/cm3And a target flow index (I)21) Under process conditions different from those used for the preparation of the unimodal ethylene-co-1-hexene copolymers of IE1 to IE2 of the present invention, from 20 to 23 g/10min. The density of the product resin was 0.939g/cm3The melt elasticity G' (G ″ ═ 3,000Pa) and the complex viscosity ratio (shear thinning) characteristics were 2205Pa and 45.1(CE1), 2136Pa and 43.4(CE2), 2055Pa and 36.1(CE3) or 2095Pa and 43.0(CE 4). The comparative resins were prepared as blown films and the bubble stability was evaluated as previously described in IE 1. The results are shown in table 5 below.
Table 5: comparative film properties of CE1 to CE4 were compared.
Testing
CE1
CE2
CE3
CE4
Extruder speed (rpm)
97
97
97
97
Load of electric motor (%)
N/r
N/r
N/r
N/r
Melting temperature (. degree.C.)
N/r
N/r
N/r
N/r
Mold pressing (MPa)
N/r
N/r
N/r
N/r
Bubble grade STD
2
1
1
1
STD bubble quality
Medium and high grade
Is poor
Is poor
Is poor
Bubble level MLS
N/T
N/T
N/T
N/T
Bubble rating MOR
1
1
4
4
N/r means not recorded. As shown in table 5, comparative film properties for blown films of the comparative unimodal ethylene-co-1-hexene copolymers of CE1 to CE4 comprised a bubble rating, STD, of 2 or 1, a bubble rating, MOR, of 1 or 4, and a moderate or poor STD bubble quality.
Fig. 1 is a graph of the melting property space of inventive examples IE1 to IE2 and comparative examples CE1 to CE 4. The melt characteristic space is defined by the combination of melt elasticity G' (G ″ ═ 3,000Pa) in pascals (Pa) measured at a loss modulus G ″ ═ 3000 pascals according to the melt storage modulus test method (described herein), relative to a value equal toEta*0.126/Eta*SH1000 complex viscosity ratio (shear thinning) of 126, where Eta*0.126 is the complex viscosity in pascal-seconds (Pa-s) measured by dynamic mechanical analysis test method at 0.126 radians per second (rad/s). In fig. 1, the endpoints of equation 1 are shown as dashed lines labeled y ═ 6x + ## # # #, where x is SH1000, y is G' (G "═ 3,000Pa) and # # # # is 1,971 or 2,138. Comparative examples CE1 to CE4 (circles with white centers) are located in the non-inventive melt characteristics space defined below the line defined by y-6 x + 1971. Inventive examples IE1 and IE2 (top two black dots) are located in the inventive melt characteristics space defined by the line defined by y-6 x +1971 (lower dashed line in fig. 1) and the line defined by y-6 x +2138 (upper dashed line in fig. 1).
The claims (modification according to treaty clause 19)
1. A unimodal ethylene-co-1-hexene copolymer, when in molten form at 190 ℃, characterized by a melt property space defined by a combination of melt elasticity and complex viscosity ratio properties, wherein the combination is according to equation 1 (equation 1):6*SH1000+1,971<G'(G"＝3,000Pa)<6*SH1000+2,138 (equation 1); wherein<Is less than;*is a multiplication; + is addition; g' (G "═ 3,000Pa) is the melt elasticity in pascals (Pa) measured at a loss modulus G" ═ 3000 pascals according to the melt storage modulus test method; SH1000 is equal to Eta*0.126/Eta*126 complex viscosity ratio of Eta*0.126 is the complex viscosity in pascal-seconds (Pa-s) measured by dynamic mechanical analysis test method at 0.126 radians/second (rad/s); and Eta*126 is the complex viscosity in Pa-s measured by dynamic mechanical analysis test method at 126 rad/s; wherein the unimodal ethylene-co-1-hexene copolymer has a high load melt index (I) measured according to ASTM D1238-13(190 ℃, 21.6kg)21) Is 15.0 to 25.0 grams/10 minutes (g/10 min).
2. The monomodal ethylene-co-1-hexene copolymer according to claim 1 characterized in that at least one of the characteristics (a) to (g):
(a) measured according to ASTM D792-13, method BHas a density of 0.935 to 0.945 grams per cubic centimeter (g/cm)3)；
(b) High load melt index (I) measured according to ASTM D1238-13(190 ℃, 21.6kg)21) From 20.5 to 22.6 grams/10 minutes (g/10 min);
(c) melt flow ratio (MFR5 or I)21/I5) Is 22.1 to 24.5, wherein I21Is measured according to ASTM D1238-13(190 ℃, 21.6kg) and I5Is a melt index in grams/10 minutes measured according to ASTM D1238-13(190 ℃, 5.0 kg);
(d) degree of molecular mass dispersionIs 38 to 44, wherein MwAnd MnMeasured according to the GPC test method;
(e) wherein the combination of melt elasticity and complex viscosity ratio (shear thinning) characteristics is defined according to equation 1a (equation 1 a): 6*SH1000+1,975<G'(G"＝3,000Pa)<6*SH1000+2,134 (equation 1 a);
(f) complex viscosity Eta measured by dynamic mechanical analysis test method at 126 rad/sec*126 is 1220 to 1240 pascal-seconds (Pa-s); and
(g) the complex viscosity ratio SH1000 is 43 to 50.0, where SH1000 is 0.126 radians/sec (Eta)*0.126)/Eta*Complex viscosity ratio measured at 126.
3. The unimodal ethylene-co-1-hexene copolymer according to claim 2 further defined by any of the restrictions (i) to (xi): (i) characteristics (a) and (b); (ii) characteristics (a) and (c); (iii) characteristics (a) and (d); (iv) characteristics (a) and (e); (v) characteristics (a) and (f); (vi) characteristics (a) and (g); (vii) characteristics (a), (b) and (c); (viii) characteristics (a), (b), and (d); (ix) characteristics (f) and (g); (x) Any six of characteristics (a) through (g); and (xi) each of the characteristics (a) to (g).
4. The monomodal ethylene-co-1-hexene copolymer according to any of claims 1 to 3 further characterized by any of the characteristics (h) to (i) or a combination of the characteristics (h) and (i): (h) weight average molecular weight (M) measured according to Gel Permeation Chromatography (GPC) test methodw) From 300,000.0 to 400,000.0 grams per mole (g/mol); and (i) number average molecular weight (M) measured according to GPC measurement methodn) From 7,000.0 to 8,000.0 g/mol.
5. A method of synthesizing a monomodal ethylene-co-1-hexene copolymer according to any of claims 1 to 4, consisting essentially of: reacting ethylene and 1-hexene ('C')6") is contacted with a single catalyst system consisting of a unimodal chromium catalyst system in a single fluidized bed gas phase polymerization (FB-GPP) reactor under effective operating conditions comprising a Reactor Bed Temperature (RBT), an average polymer residence time (avgPRT), and an ethylene partial pressure (C2P) and receiving ethylene (C2) Feed, comonomer (1-hexene or "C6") feed, hydrogen (H)2) Feed and optionally oxygen (O)2) A feed, wherein the feed is characterized by H2/C2Gas molar ratio (H)2/C2) Comonomer/ethylene gas molar ratio ("C)6/C2") and O2/C2Gas volume ratio ("[ O ]2/C2]", vol/vol in ppmv); wherein the RBT is 104.0 ℃ to 110.0 ℃; avgPRT is 1.70 to 3.10 hours, C2P is 1,100 to 1,900 kilopascals (kPa); h2/C2The gas molar ratio is 0.01 to 0.150; c6/C2The gas molar ratio is 0.010 to 0.021; and O is2/C2Gas volume ratio of>0 to 130ppbv (parts per billion volume); whereby said unimodal ethylene-co-1-hexene copolymer is synthesized in said FB-GPP reactor.
6. The process of claim 5, further comprising removing the monomodal ethylene-co-1-hexene copolymer from the FB-GPP reactor to yield a removed monomodal ethylene-co-1-hexene copolymer.
7. An article comprising the monomodal ethylene-co-1-hexene copolymer according to any of claims 1 to 4.
8. A film consisting essentially of the monomodal ethylene-co-1-hexene copolymer according to any one of claims 1 to 4.
9. A process for producing a blown film, the process comprising melting the monomodal ethylene-co-1-hexene copolymer according to any one of claims 1 to 4 so as to obtain a melt thereof, extruding the melt through a die configured for forming gas bubbles so as to produce gas bubbles of the monomodal ethylene-co-1-hexene copolymer, and blowing the gas bubbles with a film blowing machine, thereby producing the blown film.
10. Blown film produced by the process according to claim 9 and consisting essentially of the monomodal ethylene-co-1-hexene copolymer according to any of the claims 1 to 4.
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