WO2015071807A1 - Enhanced escr bimodal rotomolding resin - Google Patents
Enhanced escr bimodal rotomolding resin Download PDFInfo
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- WO2015071807A1 WO2015071807A1 PCT/IB2014/065855 IB2014065855W WO2015071807A1 WO 2015071807 A1 WO2015071807 A1 WO 2015071807A1 IB 2014065855 W IB2014065855 W IB 2014065855W WO 2015071807 A1 WO2015071807 A1 WO 2015071807A1
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/04—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould
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- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
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- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/18—Bulk density
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2308/00—Chemical blending or stepwise polymerisation process with the same catalyst
Definitions
- the present invention relates to polyethylene for use in rotomolding articles.
- the polymers have exceptional environmental stress crack resistance in view of its high flow properties and stiffness which are useful in a number of custom applications including larger parts.
- the resin needs to be: capable of production at commercially acceptable rates of production; suitable for use in the rotomolding process (e.g. for example having a suitable sintering temperature and a suitable cooling rate to be removed from the mold) and finally must have suitable properties for the end use application.
- suitable for use in the rotomolding process e.g. for example having a suitable sintering temperature and a suitable cooling rate to be removed from the mold
- One important property sought is environmental stress crack resistance.
- the resin should not develop cracks due to exposure to chemicals, sunlight, etc. in applications such as tank sprayers for agricultural use, cisterns, and smaller rotomolded parts.
- United States Patent 8,486,323 issued July 16, 2013 in the name of Davis, assigned to Dow Global technologies Inc., teaches polymer blends used in rotational molded articles and having a high impact resistance.
- the blends have a residual unsaturation of less than 0.06 per 1000 carbon atoms.
- the blends of the present invention have a residual unsaturation of greater than 0.06 per 1000 carbon atoms.
- the present invention seeks to provide a high density polyethylene resin having exceptional environmental stress crack resistance (ESCR) and good flow properties.
- ESCR environmental stress crack resistance
- Flow properties are important for rotomolding resins as the resin must soften and flow in the mold. If the flow properties are too low the resin does not sinter together in a reasonable amount of time and the product cannot be made in an economical manner.
- the present invention provides a bimodal polyethylene composition having a density from 0.937 to 0.942 g/cm 3 , a melt index determined according to ASTM D 1238 (2.16 kg 190°C - l 2 ) from 4.0 to 7.0 g/10min, and l 2 i determined according to ASTM D 1238 (21 .6 kg 190°C - l 2 i ) from 160 to 200 g/10 min, an l 2 i/l 2 from 30 to 40, a bent strip ESCR as determined by ASTM D 1693 in 100% octoxynol -9 for conditions A and B of greater than 1000 hours and a terminal vinyl unsaturation greater than 0.06, preferably greater than 0.08 per 1000 carbon atoms; a primary structure parameter (PSP2) of from 4 to 7, preferably 5 to 6, and an overall Mw/Mn from 2.7 to 3.5 comprising from 2 to 6 weight % of one or more C 4- s alpha olefin
- 100,000 to 180,000 preferably from 1 10,000 to 165,000, most preferably from 120,000 to 150,000 g/mol and a polydipsersity of less than 3;
- the present invention provides a bimodal polyethylene composition as above having a primary structure parameter (PSP2) from 4 to 7.
- PSP2 primary structure parameter
- the present invention provides a bimodal polyethylene composition as above wherein component (i) is present in an amount from 20 to 35 weight %.
- the present invention provides a bimodal polyethylene composition as above, wherein component (i) consists of from 1 to 25 weight % of one or more of one or more C 4- s alpha olefin comonomers and the balance ethylene.
- the present invention provides a bimodal polyethylene composition as above wherein component (i) has a weight average molecular weight (Mw) from 120,000 to 1 50,000 g/mol and a polydipsersity less than 3.
- Mw weight average molecular weight
- the present invention provides a bimodal polyethylene composition as above wherein component (ii) is present in an amount from 65 to 80 weight %.
- the present invention provides a bimodal polyethylene composition as above having wherein component (ii) has a weight average molecular weight (Mw) from 20,000 to 50,000 and a polydispersity less than 3.
- component (ii) has a weight average molecular weight (Mw) from 20,000 to 50,000 and a polydispersity less than 3.
- the present invention provides a bimodal polyethylene composition as above wherein the difference in densities between components (i) and (ii) is less than 0.030, preferably less than 0.027 g/cm 3 .
- the present invention provides a process to make a bimodal polyethylene composition as above, comprising feeding ethylene and one or more C 4-8 comonomers to two sequential solution phase reactors, in the presence of a single site catalyst comprising a phosphinimine ligand together with one or more activators.
- the present invention provides a rotomolded part consisting essentially of the above bimodal polyethylene composition.
- Figure 1 is a plot of the molecular weight distribution obtained by gel permeation chromatograph (GPC), and the short chain branching distribution determined from GPC-FTIR of a resin of example 1 .
- GPC gel permeation chromatograph
- Figure 2 is a plot of A plot of the calculated w, ⁇ PSP2, values against log M for the resin of example 1 .
- Figure 3 is a plot of the molecular weight distribution obtained by GPC of the polymer of example 1 and the computer model predictions of the molecular weight distributions of the first and second ethylene polymers that are comprised in the polymer of example 1 .
- Figure 4 is a plot of the molecular weight distribution obtained by gel permeation chromatograph (GPC), and the short chain branching distribution determined from GPC-FTIR of a resin of example 1 .
- the plot also includes the computer model predictions of the polymer molecular weight distribution as well as the short chain branching distribution.
- Figure 5 is a plot of the mean failure energy from ARM impact testing carried out at -40°C on specimens taken from rotomolded parts of the resin of example 1 .
- Figure 6 is a plot of the bent strip ESCR condition A 100 against the flexural secant modulus 1 % in MPa for the resin of example 1 .
- any numerical range recited herein is intended to include all sub-ranges subsumed therein.
- a range of "1 to 10" is intended to include all sub-ranges between and including the recited minimum value of 1 and the recited maximum value of 10; that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10. Because the disclosed numerical ranges are continuous, they include every value between the minimum and maximum values. Unless expressly indicated otherwise, the various numerical ranges specified in this application are approximations.
- compositional ranges expressed herein are limited in total to and do not exceed 100 percent (volume percent or weight percent) in practice. Where multiple components can be present in a composition, the sum of the maximum amounts of each component can exceed 100 percent, with the understanding that, and as those skilled in the art readily understand, that the amounts of the components actually used will conform to the maximum of 100 percent.
- the polymers of the present invention are bimodal polyethylene and can be deconvolved into two distinct components. Typically, this is demonstrated by the presence of a "shoulder" at the right side of a gel permeation chromatography (GPC) curve ( Figure 1 ). In the present case there is a small shoulder to the right side of the GPC curve as shown in Figure 2 indicating a small amount of a higher molecular weight low density component.
- GPC gel permeation chromatography
- the overall polyethylene composition comprises from 0.1 to 8.0, typically from 2.0 to 6.0 weight % of one or more C 6 -s alpha olefins and the balance ethylene.
- the comonomer is 1 -octene but it could also be 1 -hexene.
- the higher molecular weight component is present in an amount from 20 to 45 weight % of the entire composition, preferably from 20 to 35 weight %, most preferably from 25 to 30 weight %, based on the weight of the entire composition.
- the lower molecular weight component is present in corresponding amounts from 80 to 55 weight %, of the entire composition, preferably from 80 to 65 weight %, most preferably from 65 to 75 weight % based on the weight of the entire composition.
- the higher molecular weight component has a weight average molecular weight (Mw) greater than 100,000, typically from 1 10,000 to 165,000, preferably from 120,000 to 150,000, as determined using gel permeation chromatography (GPC).
- Mw weight average molecular weight
- the higher molecular weight component has a polydispersity (Mw/Mn: weight average molecular weight / number average molecular weight)) less than 3 (e.g. between 2 and 3) typically less than 2.7.
- the higher molecular weight component has a lower density than the lower molecular weight component.
- the density of the higher molecular weight component in the polymer may range from 0.920 to 0.930 g/cm 3 , typically from 0.922 to 0.926 g/cm 3 , preferably from 0.922 to 0.925 g/cm 3 .
- the density of the component, or that of any other component or the total composition, is a function of the degree of comonomer incorporation.
- the higher molecular weight component has a degree of short chain branching per 1000 carbon atoms from 3 to 13, typically from 4 to 10, preferably from 4 to 8.
- the higher molecular weight component does not have any long chain branching.
- the lower molecular weight component has a weight average molecular weight (Mw) less than 100,000, typically from 15,000 to 70,000, preferably from 20,000 to 50,000, desirably from 20,000 to 40,000 g/mol, as determined using gel permeation chromatography (GPC).
- Mw weight average molecular weight
- the lower molecular weight component has a polydispersity (Mw/Mn) less than 3 (e.g. from 2 to 3) typically less than 2.8.
- the lower molecular weight component has a higher density than the higher molecular weight component.
- the density of the lower molecular weight component in the polymer is greater than 0.945 g/cm 3 , typically from 0.945 to 0.955 g/cm 3 , preferably from 0.947 to 0.952 g/cm 3 .
- the lower molecular weight (higher density component) has a degree of short chain branching of less than 5 per 1000 carbon atoms, typically from 0.5 to 4, preferably from 1 to 3 short chain branches per 1000 carbon atoms.
- the lower molecular weight component does not have any long chain branching.
- the difference in density of the higher molecular weight component and the lower molecular weight components is less than 0.030 g/cm 3 , preferably less than 0.027 g/cm 3 .
- the catalysts used to produce the polymers of the present invention do not produce long chain branching.
- the overall properties of the polyethylene composition include the following: density from 0.935 to 0.942 g/cm 3 ;
- PSP2 primary structure parameter
- composition comprises from 2 to 8, preferably from 2 to 5 weight % of one or more C 4- s comonomers.
- the overall polymer incorporates the following molecular features:
- Short chain branch frequency /1000 carbon atoms by FTIR between 1 and 8, preferably between 3 and 6;
- Comonomer content (wt. %) by FTIR from 0.1 to 8.0, preferably from 2.0 to 5.0;
- Mn Number average molecular weight (Mn) by GPC from 1 1 ,000 to 35,000, preferably from 20,000 to 25,000;
- Weight average molecular weight Mw) by GPC from 55,000 to 82,000, preferably from 60,000 to 70,000;
- Z average molecular weight (Mz) by GPC from 140,000 to 200,000, preferably from 160,000 to 180,000;
- An index (Mz/Mw) from 2.0 to 2.9, preferably from 2.30 to 2.60;
- the PSP2 calculation can be generally described as a multistep process.
- the first step involves estimating the homopolymer (or low comonomer polymer) density of a sample from the sample's molecular weight distribution as described by Equation 1 .
- the first step takes into account the effects of molecular weight on sample density.
- Density values at molecular weights less than 720 g/mol are equal to 1 .006 g/cm 3 according to this method.
- the difference between the measured bulk density of copolymer and the calculated homopolymer density is divided by the overall short chain branching (SCB) level (as measured by size exclusion chromatography-Fourier transform infrared spectroscopy or by C13-NMR) and subsequently applied to the SCB level in each MW slice.
- SCB short chain branching
- the original observed bulk density of the copolymer (down to 0.852 g/cm 3 ) is obtained through summation of the MW slices as described above.
- Equation 3 assigned values of 20°C and 142.5°C are given for density values of 0.852 g/cm 3 and 1 .01 g/cm 3 , respectively.
- Equation 4 is a form of the well accepted Gibbs Thompson equation.
- the thickness of the amorphous layer (l a ) is calculated using the equations 5a and 5b:
- the fourth step calculates the tie molecule probability (P) for each molecular weight and respective
- PSP2 values are calculated from Equations 6a and 6b by treating this value essentially as a weighing factor (P,) for each slice of the MWD, where P, was arbitrarily multiplied x 100 and subsequently defined as PSP2,. As in all of the aforementioned calculations, this value at each slice is multiplied by the respective weight fraction (w,) of the MWD profile in order to obtain a value for the bulk polymer.
- FIG. 2 A plot of the calculated w, ⁇ PSP2, values against log M for the inventive example 1 is shown in Figure 2, which can also be insightful when attempting understand and predict structure property relationships.
- the area underneath the resulting w, ⁇ PSP2, vs. log M curve defines PSP2 for the whole polymer sample.
- the polymer may be made using a solution polymerization technique.
- the monomers are typically dissolved in an inert hydrocarbon solvent, typically a C5-12 hydrocarbon, which may be unsubstituted or substituted by a Ci -4 alkyl group, such as pentane, methyl pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane and hydrogenated naphtha.
- an inert hydrocarbon solvent typically a C5-12 hydrocarbon, which may be unsubstituted or substituted by a Ci -4 alkyl group, such as pentane, methyl pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane and hydrogenated naphtha.
- An example of a suitable solvent that is commercially available is "Isopar E" (Cs-12 aliphatic solvent, Exx
- Catalyst and activators are also dissolved in the solvent or suspended in a diluent miscible with the solvent at reaction conditions.
- the catalyst is a compound of the formula: (Pl)m (L)n - M - (Y)p
- M is selected from the group consisting of Ti, Zr and Hf;
- PI is a phosphinimine ligand of the formula:
- each R 21 is independently selected from the group consisting of a hydrogen atom; a halogen atom; hydrocarbyl radicals, typically Ci -10 , which are unsubstituted by or further substituted by a halogen atom; C-i-s alkoxy radicals; Ce- ⁇ aryl or aryloxy radicals; amido radicals; silyl radicals of the formula:
- each R 22 is independently selected from the group consisting of hydrogen, a Ci-s alkyl or alkoxy radical and Ce- ⁇ aryl or aryloxy radicals; and a germanyl radical of the formula:
- R 22 is as defined above;
- L is a monoanionic cyclopentadienyl-type ligand independently selected from the group consisting of cyclopentadienyl-type ligands
- Y is independently selected from the group consisting of activatable ligands
- m is 1 or 2
- n is 0 or 1
- p is an integer and the sum of m+n+p equals the valence state of M.
- each R 21 is a hydrocarbyl radical, preferably a Ci -6 hydrocarbyl radical, most preferably a Ci -4 hydrocarbyl radical.
- cyclopentadienyl refers to a 5-member carbon ring having delocalized bonding within the ring and typically being bound to the active catalyst site, generally a group 4 metal (M) through ⁇ 5 - bonds.
- M group 4 metal
- the cyclopentadienyl ligand may be
- Ci -10 hydrocarbyl radicals which are unsubstituted or further substituted by one or more substituents selected from the group consisting of a halogen atom and a Ci -4 alkyl radical; a halogen atom; a C-i-s alkoxy radical; a Ce- ⁇ aryl or aryloxy radical; an amido radical which is unsubstituted or substituted by up to two Ci -8 alkyl radicals; a phosphido radical which is unsubstituted or substituted by up to two Ci-8 alkyl radicals; silyl radicals of the formula -Si-(R) 3 wherein each R is independently selected from the group consisting of hydrogen, a C-i -s alkyl or alkoxy radical, Ce- ⁇ aryl or aryloxy radicals; and germanyl radicals of the formula Ge-(R)3 wherein R
- the cyclopentadienyl-type ligand is selected from the group consisting of a cyclopentadienyl radical, an indenyl radical and a fluorenyl radical which radicals are unsubstituted or up to fully substituted by one or more substituents selected from the group consisting of a fluorine atom, a chlorine atom; Ci -4 alkyl radicals; and a phenyl or benzyl radical which is unsubstituted or substituted by one or more fluorine atoms.
- Activatable ligands Y may be selected from the group consisting of a halogen atom, Ci - 4 alkyl radicals, C 6 -2o aryl radicals, C7-12 arylalkyl radicals, C 6 -io phenoxy radicals, amido radicals which may be substituted by up to two Ci -4 alkyl radicals and Ci- 4 alkoxy radicals.
- Y is selected from the group consisting of a chlorine atom, a methyl radical, an ethyl radical and a benzyl radical.
- Suitable phosphinimine catalysts are Group 4 organometallic complexes which contain one phosphinimine ligand (as described above) and one cyclopentadienyl-type (L) ligand and two activatable ligands. The catalysts are not bridged.
- the activators for the catalyst are typically selected from the group consisting of aluminoxanes and ionic activators.
- Suitable alumoxane may be of the formula: (R 4 ) 2 AIO(R 4 AIO) m AI(R 4 ) 2 wherein each R 4 is independently selected from the group consisting of C1 -20 hydrocarbyl radicals and m is from 0 to 50, preferably R 4 is a Ci -4 alkyl radical and m is from 5 to 30.
- Methylalumoxane (or "MAO") in which each R is methyl is the preferred alumoxane.
- Alumoxanes are well known as cocatalysts, particularly for metallocene-type catalysts. Alumoxanes are also readily available articles of commerce.
- alumoxane cocatalyst generally requires a molar ratio of aluminum to the transition metal in the catalyst from 20:1 to 1000:1 . Preferred ratios are from 50:1 to 250:1 .
- Commercially available MAO typically contains free aluminum alkyl (e.g.
- TMA trimethylaluminum
- ionic activators initially cause the abstraction of one or more of the activatable ligands in a manner which ionizes the catalyst into a cation, then provides a bulky, labile, non-coordinating anion which stabilizes the catalyst in a cationic form.
- the bulky, non-coordinating anion permits olefin polymerization to proceed at the cationic catalyst center (presumably because the non-coordinating anion is sufficiently labile to be displaced by monomer which coordinates to the catalyst.
- Preferred ionic activators are boron-containing ionic activators described in (i) (iii) below:
- each R 7 is independently selected from the group consisting of phenyl radicals which are unsubstituted or substituted with from 3 to 5 substituents selected from the group consisting of a fluorine atom, a Ci -4 alkyl or alkoxy radical which is unsubstituted or substituted by a fluorine atom; and a silyl radical of the formula ⁇ Si--(R 9 )3; wherein each R 9 is independently selected from the group consisting of a hydrogen atom and a Ci -4 alkyl radical; and
- R 7 is a pentafluorophenyl radical
- R 5 is a triphenylmethyl cation
- Z is a nitrogen atom
- R 8 is a Ci -4 alkyl radical or R 8 taken together with the nitrogen atom forms an anilinium radical which is substituted by two Ci- 4 alkyl radicals.
- the "ionic activator” may abstract one or more activatable ligands so as to ionize the catalyst center into a cation but not to covalently bond with the catalyst and to provide sufficient distance between the catalyst and the ionizing activator to permit a polymerizable olefin to enter the resulting active site.
- ionic activators include: triethylammonium tetra(phenyl)boron ;
- tripropylammonium tetra(phenyl)boron tripropylammonium tetra(phenyl)boron ; tri(n-butyl)ammonium tetra(phenyl)boron ;
- tributylammonium tetra(pentafluorophenyl)boron tripropylammonium tetra(o,p- dimethylphenyl)boron
- tributylammonium tetra(m,m-dimethylphenyl)boron tripropylammonium tetra(o,p- dimethylphenyl)boron
- tributylammonium tetra(m,m-dimethylphenyl)boron tributylammonium tetra(m,m-dimethylphenyl)boron ;
- tributylammonium tetra(p-trifluoromethylphenyl)boron ; tributylammonium
- tetra(pentafluorophenyl)boron tri(n-butyl)ammonium tetra(o-tolyl)boron; N,N- dimethylanilinium tetra(phenyl)boron ; ⁇ , ⁇ -diethylanilinium tetra(phenyl)boron; N,N- diethylanilinium tetra(phenyl)n-butylboron, N,N-2,4,6-pentamethylanilinium
- phenyltrispentafluorophenyl borate benzene (diazonium) phenyltrispentafluorophenyl borate; tropillium tetrakis (2,3,5,6-tetrafluorophenyl) borate; triphenylmethylium tetrakis (2,3,5,6-tetrafluorophenyl) borate; benzene (diazonium) tetrakis (3,4,5-trifluorophenyl) borate; tropillium tetrakis (3,4,5-trifluorophenyl) borate; benzene (diazonium) tetrakis (3,4,5-trifluorophenyl) borate; tropillium tetrakis (1 ,2,2-trifluoroethenyl) borate;
- ionic activators include: N,N- dimethylaniliniumtetrakispentafluorophenyl borate ; triphenylmethylium
- the ionic activator may be use at about molar equivalents of boron to group IV metal in the catalyst. Suitable molar ratios of group IV metal from the catalyst to boron may range from 1 :1 to 3:1 , preferably from 1 :1 to 1 :2.
- the ionic activator may be used in combination with an alkylating activator (which may also serve as a scavenger).
- the ionic activator may be selected from the group consisting of (R 3 ) p MgX 2 -p wherein X is a halide and each R 3 is independently selected from the group consisting of CMO alkyl radicals and p is 1 or 2; R 3 Li wherein in R 3 is as defined above, (R 3 ) q ZnX 2 - q wherein R 3 is as defined above, X is halogen and q is 1 or 2; (R 3 ) S AIX 3 - S wherein R 3 is as defined above, X is halogen and s is an integer from 1 to 3.
- R 3 is a Ci -4 alkyl radical, and X is chlorine.
- Commercially available compounds include triethyl aluminum
- TEAL diethyl aluminum chloride
- DEC diethyl aluminum chloride
- BuEtMg or BuMgEt butyl ethyl magnesium
- the phosphinimine catalyst is activated with a combination of ionic activators (e.g. boron compounds) and alkylating agent
- ionic activators e.g. boron compounds
- the molar ratio of group IV metal from the catalyst : metalloid (boron) from the ionic activator :metal from the alkylating agent may range from 1 :1 :1 to 1 :3:10, preferably from 1 :1 .3 : 5 to 1 :1 .5:3.
- the temperature of the reactor(s) in a high temperature solution process is from about 80°C to about 300°C, preferably from about 120°C to 250°C.
- the upper temperature limit will be influenced by considerations that are well known to those skilled in the art, such as a desire to maximize operating temperature (so as to reduce solution viscosity), while still maintaining good polymer properties (as increased polymerization temperatures generally reduce the molecular weight of the polymer). In general, the upper polymerization temperature will preferably be between 200 and 300°C.
- the most preferred reaction process is a "medium pressure process", meaning that the pressure in the reactor(s) is preferably less than about 6,000 psi (about 42,000 kiloPascals or kPa). Preferred pressures are from 10,000 to 40,000 kPa (1450-5800 psi), most preferably from about 14,000-22,000kPa (2,000 psi to 3,000 psi).
- the pressure in the reactor system should be high enough to maintain the polymerization solution as a single phase solution and to provide the necessary upstream pressure to feed the polymer solution from the reactor system through a heat exchanger system and to a devolatilization system.
- Other systems permit the solvent to separate into a polymer rich and polymer lean stream to facilitate polymer separation.
- the solution polymerization process may be conducted in a stirred "reactor system” comprising one or more stirred tank reactors or in one or more loop reactors or in a mixed loop and stirred tank reactor system.
- the reactors may be in tandem or parallel operation.
- the first polymerization reactor preferably operates at lower temperature.
- the residence time in each reactor will depend on the design and the capacity of the reactor. Generally the reactors should be operated under conditions to achieve a thorough mixing of the reactants. In addition, it is preferred that from 20 to 60 weight % of the final polymer is polymerized in the first reactor, with the balance being polymerized in the second reactor.
- a particularly useful solution polymerization process uses at least two
- the polymerization temperature in the first reactor is from about 80°C to about 180°C (preferably from about 120°C to 160°C) and the second reactor is preferably operated at a higher temperature (up to about 220°C).
- the most preferred reaction process is a "medium pressure process", meaning that the pressure in each reactor is preferably less than about 6,000 psi (about 42,000 kilopascals or kPa), most preferably from about 2,000 psi to 3,000 psi (about 14,000 22,000 kPa).
- Mn, Mw and Mz were determined by high temperature Gel Permeation Chromatography (GPC) with differential refractive index detection using universal calibration (e.g. ASTM-D646-99).
- GPC Gel Permeation Chromatography
- Mz differential refractive index detection using universal calibration (e.g. ASTM-D646-99).
- Mw weight average molecular weight
- Mn number average molecular weight
- GPC-FTIR was used to determine the comonomer content as a function of molecular weight. After separation of the polymer by GPC an on-line FTIR measures the concentration of the polymer and methyl end groups. Methyl end groups are used in the branch frequency calculations. Conventional calibration allows for the calculation of a molecular weight distribution.
- the short chain branch frequency (SCB per 1000 carbon atoms) of copolymer samples was determined by Fourier Transform Infrared Spectroscopy (FTIR) as per ASTM D6645-01 .
- FTIR Fourier Transform Infrared Spectroscopy
- a Thermo-Nicolet 750 Magna-IR Spectrophotometer was used for the measurement.
- FTIR was also used to determine internal, side chain and terminal levels of unsaturation.
- Comonomer content can also be measured using 13 C NMR techniques as discussed in Randall Rev. Macromol. Chem. Phys., C29 (2&3), p.285; U.S. Patent No. 5,292,845 and WO 2005/121239.
- Polyethylene composition density (g/cm 3 ) was measured according to ASTM
- the density and melt index of the first and second ethylene polymers that comprise the polyethylene composition were determined based on composition models. The following equations were used to calculate the density and melt index I2
- Plaques molded from the polyethylene compositions were tested according to the following ASTM methods: Bent Strip Environmental Stress Crack Resistance (ESCR), ASTM D1693; Flexural properties, ASTM D 790; Tensile properties, ASTM D 638.
- ESCR Bent Strip Environmental Stress Crack Resistance
- Rotomolded parts were prepared in a rotational molding machine sold under the tradename Rotospeed RS3-160 by Ferry Industries Inc.
- the machine has two arms which rotate about a central axis within an enclosed oven.
- the arms are fitted with plates which rotate on an axis that is roughly perpendicular to the axis of rotation of the arm.
- Each arm is fitted with six cast aluminum molds that produce plastic cubes having dimensions of 12.5 inches (31 .8 cm) x 12.5 inches x 12.5 inches.
- the arm rotation was set to about 8 revolutions per minute (rpm) and the plate rotation was set to about 2 rpm.
- molds produce parts having a nominal thickness of about 0.25 inches (0.64 cm) when initially filled with a standard charge of about 3.7 kg of polyethylene resin in powder form (35 US mesh size). The temperature within the enclosed oven was maintained at a temperature of 560°C. The molds and their content were heated for specified period of time, until full powder densification is achieved. The molds were subsequently cooled in a controlled environment prior to removing the parts.
- Specimens were collected from the molded parts for density and color measurements
- the ARM impact test was performed in accordance with ASTM D5628 at a test temperature of -40°C.
- Bimodal polyethylene compositions were prepared at a dual reactor pilot plant.
- the content of the first reactor flows into the second reactor, both of which are well mixed.
- the process operates using continuous feed streams.
- the catalyst cyclopentadienyl Ti tri tert.butly phosphimine di chloride
- the overall production rate was about 90 kg/hr.
- the polymerization conditions are provided in Table 1 .
- the polymer compositions prepared at the pilot plant were stabilized using a conventional additive package for rotational molding applications prior to carrying out plaque testing trials.
- the invention Compared to examples with similar densities, the invention combines both high comonomer content and reverse comonomer distribution.
- the molecular attributes of the invention are critical in maintaining a combination of good rotomolding
- the resins of the present invention have good flow properties and high environmental stress crack resistance and are useful in rotomolding plastic parts.
Abstract
Description
Claims
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MX2016004602A MX370346B (en) | 2013-11-18 | 2014-11-06 | Enhanced escr bimodal rotomolding resin. |
DK14802198.3T DK3071643T3 (en) | 2013-11-18 | 2014-11-06 | Bimodal rotational casting resin with improved ESCR |
JP2016553750A JP6445578B2 (en) | 2013-11-18 | 2014-11-06 | Improved ESCR bimodal rotational molding resin |
CN201480062852.1A CN105705572B (en) | 2013-11-18 | 2014-11-06 | The bimodal rotational moulding resin that ESCR is improved |
EP14802198.3A EP3071643B1 (en) | 2013-11-18 | 2014-11-06 | Enhanced escr bimodal rotomolding resin |
EP19172134.9A EP3540007B1 (en) | 2013-11-18 | 2014-11-06 | Enhanced escr bimodal rotomolding resin |
ES14802198T ES2749153T3 (en) | 2013-11-18 | 2014-11-06 | Bimodal rotational molding resin with improved ESCR |
KR1020167013706A KR102256256B1 (en) | 2013-11-18 | 2014-11-06 | Enhanced escr bimodal rotomolding resin |
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WO2018089195A1 (en) * | 2016-11-08 | 2018-05-17 | Univation Technologies, Llc | Bimodal polyethylene |
WO2020240401A1 (en) * | 2019-05-31 | 2020-12-03 | Nova Chemicals (International) S.A. | Enhanced escr and ductility bimodal rotomolding resin |
WO2021014244A1 (en) * | 2019-07-25 | 2021-01-28 | Nova Chemicals (International) S.A. | Rotomolded parts prepared from bimodal polyethylene |
US11746220B2 (en) | 2020-06-12 | 2023-09-05 | Braskem S.A. | High flow rotomolding compositions, processes thereof, and articles therefrom |
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CA2834068C (en) * | 2013-11-18 | 2020-07-28 | Nova Chemicals Corporation | Enhanced escr bimodal rotomolding resin |
JP6778481B2 (en) * | 2015-11-11 | 2020-11-04 | 旭化成株式会社 | Polyethylene-based polymer and its production method, polyethylene-based polymer composition, and crosslinked pipe |
US9783664B1 (en) * | 2016-06-01 | 2017-10-10 | Nova Chemicals (International) S.A. | Hinged component comprising polyethylene composition |
KR101958015B1 (en) | 2016-11-08 | 2019-07-04 | 주식회사 엘지화학 | Ethylene/alpha-olefin copolymer |
WO2018093078A1 (en) | 2016-11-15 | 2018-05-24 | 주식회사 엘지화학 | Ethylene/alpha-olefin copolymer exhibiting excellent environmental stress crack resistance |
CN110540690A (en) * | 2019-09-04 | 2019-12-06 | 浙江大学 | Double-peak high-density polyethylene resin and preparation method thereof |
WO2021214584A1 (en) * | 2020-04-20 | 2021-10-28 | Nova Chemicals (International) S.A. | Rotomolding compositions with low relative elasticity |
EP4298161A1 (en) | 2021-02-24 | 2024-01-03 | Nova Chemicals (International) S.A. | Bimodal polyethylene composition |
BR112023018965A2 (en) | 2021-03-19 | 2023-10-17 | Nova Chem Int Sa | HIGH DENSITY POLYETHYLENE COMPOSITION |
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ES2749153T3 (en) | 2020-03-19 |
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US20160002448A1 (en) | 2016-01-07 |
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CA2834068C (en) | 2020-07-28 |
US9181422B2 (en) | 2015-11-10 |
US9540505B2 (en) | 2017-01-10 |
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US20150141579A1 (en) | 2015-05-21 |
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