CA2180012A1 - Lldpe resin blends - Google Patents
Lldpe resin blendsInfo
- Publication number
- CA2180012A1 CA2180012A1 CA002180012A CA2180012A CA2180012A1 CA 2180012 A1 CA2180012 A1 CA 2180012A1 CA 002180012 A CA002180012 A CA 002180012A CA 2180012 A CA2180012 A CA 2180012A CA 2180012 A1 CA2180012 A1 CA 2180012A1
- Authority
- CA
- Canada
- Prior art keywords
- blend
- lldpe
- weight
- copolymer
- low density
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08L23/08—Copolymers of ethene
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
A resin blend of LLDPE produced using a metallocene catalyst system and low density, high pressure polyethylene can be extruded into films exhibiting improved optical properties and impact strength.
Description
wo 95n~00s 2 1 8 0 0 1 2 I~DPE RIZRIN BLEND8 The invention relates to blends of linear low density copolymers of ethylene (LLDPE), and films thereof , which exhibit excellent optical properties.
Application of conventional linear low density polyethylene (LLDPE) in films which require ~Y~-Pl 1 Pnt optical properties i5 limited because of inherent optical properties of the resin. The haze value of conventional LLDPE is generally greater than 10 [as measured by ASTM D-1003 ] .
Ethylene polymers which can be employed in applications requiring ~Ycpl 1 Pnt optical properties are referred to as low density polyethylene (LDPE), which is pru-luct:d at higher ~ a~DUL.~S than the pressure employed to produce LLDPE. For example, LDPE is stated to be produced at 150-300 MPa [1500-3000 atm] at 200-300-C, while LLDPE is produced at 0.3-1.0 MPa [or 3 to 10 di ,'-res] at 70-90-C
(see KIRK-OTHMER, ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, Vol.
16, page 433 tThird Edition. ] ) . However, LDPE resins exhibit very low impact resistance.
Recently, new linear low density products have been produced with r ~l l oCpnp catalysts. This invention relates to the addition of high ~ ur ~ PE resins and antiblocking agents, i . e . microtalc, to the new met~ l l ocpnp LLDPE resins to achieve P~'~'Pl 1 Pnt optical properties with acceptable blocking characteristics. This invention is made possible because of the narrow molecular weight distribution and more uniform short chain branching distribution of the metallocene resin rather than the conventional LLDPE
resins.
The invention resides in a blend of 70 to 98 weight percent of an as-synthesized composition which is dry and solvent-free and comprises spherical, non-porous particles, which has an average particle size of 0.05 to 0.11 cm (0.02 to 0 . 045 inches), and a settled bulk density of 400 to 580 kg/m3 (25 to 36 lb/ft3), and which is a copolymer of ethylene and an alpha olefin, having a density of 0.902 to WO 9512700~ ,., 5. ' 1 0.929, a MFR Or 15 to 25, and a MW/Mn Or 2.0 to 3.0; and 2 to 30 weight percent of low density polyethylene ~ duced at 150-300 MPa [1500-3000 atm] and 200-300'C, wherein the haze value of the blend is less than 5 as measured by ASTM
D-1003 and the dart drop impact resistance measured by ASTM
D-1709 is greater than 400.
The LLDPE resin containing blends of the invention can be ~ocessed readily on commercial LLDPE film extruders without modifications. Films produced from the blends exhibit _Yr_l l_nt impact properties which far exceed the impact properties of the LDPE.
The Low DensitY PolYefhYlene tLDPE) C ~.-nt The LDPE ~ t employed in the blend of the invention is conventional and is produced at higher ~L.2SDU. ~S than those employed to produce LLDPE. Thus the LDPE is ~L-,du.:ed at 150-300 MPa [1500-3000 atm] and 200-300~C, while LLDPE is typically produced at 0.3-1.0 MPa [or 3 to lo d; ~ ~es] and 70-loO C. Without the addition of the LLDPE . _ I_, the LDPE resin exhibits very low impact resistance.
Co,,olYmer C~ ,~
The copolymer, , --t of the blend of the invention is linear low density polyethylene (LLDPE) having a density of 0.902 to 0.929, most preferably ranging 0.915 to 0.922.
The LLDPE ~ , L of the blend of invention is different from conventional LLDPE in that it eYhibits a haze value as measured by ASTM D-1003 of less than about 20, preferably from 3 to 10, most preferably from 5 to 7.
By comparison, the haze value of conventional LLDPE is greater than 10.
The LLDPE ~ _ snt contains 0 .1 to 2 ppm of Zr ( ~rom the catalyst used in its synthesis) and has an average particle size Or 0 . 05 to 0 . 11 cm (0 . 02 to 0 . 045 inches), and a settled bulk density of 400 to 580 kg/m' (25 to '!
.
Application of conventional linear low density polyethylene (LLDPE) in films which require ~Y~-Pl 1 Pnt optical properties i5 limited because of inherent optical properties of the resin. The haze value of conventional LLDPE is generally greater than 10 [as measured by ASTM D-1003 ] .
Ethylene polymers which can be employed in applications requiring ~Ycpl 1 Pnt optical properties are referred to as low density polyethylene (LDPE), which is pru-luct:d at higher ~ a~DUL.~S than the pressure employed to produce LLDPE. For example, LDPE is stated to be produced at 150-300 MPa [1500-3000 atm] at 200-300-C, while LLDPE is produced at 0.3-1.0 MPa [or 3 to 10 di ,'-res] at 70-90-C
(see KIRK-OTHMER, ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, Vol.
16, page 433 tThird Edition. ] ) . However, LDPE resins exhibit very low impact resistance.
Recently, new linear low density products have been produced with r ~l l oCpnp catalysts. This invention relates to the addition of high ~ ur ~ PE resins and antiblocking agents, i . e . microtalc, to the new met~ l l ocpnp LLDPE resins to achieve P~'~'Pl 1 Pnt optical properties with acceptable blocking characteristics. This invention is made possible because of the narrow molecular weight distribution and more uniform short chain branching distribution of the metallocene resin rather than the conventional LLDPE
resins.
The invention resides in a blend of 70 to 98 weight percent of an as-synthesized composition which is dry and solvent-free and comprises spherical, non-porous particles, which has an average particle size of 0.05 to 0.11 cm (0.02 to 0 . 045 inches), and a settled bulk density of 400 to 580 kg/m3 (25 to 36 lb/ft3), and which is a copolymer of ethylene and an alpha olefin, having a density of 0.902 to WO 9512700~ ,., 5. ' 1 0.929, a MFR Or 15 to 25, and a MW/Mn Or 2.0 to 3.0; and 2 to 30 weight percent of low density polyethylene ~ duced at 150-300 MPa [1500-3000 atm] and 200-300'C, wherein the haze value of the blend is less than 5 as measured by ASTM
D-1003 and the dart drop impact resistance measured by ASTM
D-1709 is greater than 400.
The LLDPE resin containing blends of the invention can be ~ocessed readily on commercial LLDPE film extruders without modifications. Films produced from the blends exhibit _Yr_l l_nt impact properties which far exceed the impact properties of the LDPE.
The Low DensitY PolYefhYlene tLDPE) C ~.-nt The LDPE ~ t employed in the blend of the invention is conventional and is produced at higher ~L.2SDU. ~S than those employed to produce LLDPE. Thus the LDPE is ~L-,du.:ed at 150-300 MPa [1500-3000 atm] and 200-300~C, while LLDPE is typically produced at 0.3-1.0 MPa [or 3 to lo d; ~ ~es] and 70-loO C. Without the addition of the LLDPE . _ I_, the LDPE resin exhibits very low impact resistance.
Co,,olYmer C~ ,~
The copolymer, , --t of the blend of the invention is linear low density polyethylene (LLDPE) having a density of 0.902 to 0.929, most preferably ranging 0.915 to 0.922.
The LLDPE ~ , L of the blend of invention is different from conventional LLDPE in that it eYhibits a haze value as measured by ASTM D-1003 of less than about 20, preferably from 3 to 10, most preferably from 5 to 7.
By comparison, the haze value of conventional LLDPE is greater than 10.
The LLDPE ~ _ snt contains 0 .1 to 2 ppm of Zr ( ~rom the catalyst used in its synthesis) and has an average particle size Or 0 . 05 to 0 . 11 cm (0 . 02 to 0 . 045 inches), and a settled bulk density of 400 to 580 kg/m' (25 to '!
.
wogs/27005 _3_ P~ 5 36 lb/ft3)- The as-8ynthesized resin is dry and solvent-free and comprises spherical, non-porous particles.
The LLDPE ~ eilt of the invention blend exhibits a melt flow ratio (MFR) range of 15 to 25, preferably 15 to 20 and most preferably 16 to 18. MFR is the ratio I21/I2 [wherein I21 is measured at 190-C in accordance with ASTM
D-1238, Condition F and I2 is measured at l90-C in accordance with ASTM D-1238, Condition E. ]
The LLDPE ~ -nrnt exhibits an MI of 0. 01 to 5, generally 0 .1 to 5, and preferably 0 . 5 to 4, and most preferably 0. 8 to 2 . 0 . For blown film, the MI of the copolymer is preferably 0 . 5 to 1. 5 .
The melting point of the LLDPE - _ --t ranges from 95-C to 130-C. Furth~ ~e, the hexane extractables content is very low, typically ranging from 0 . 3 to 1. 0 wt. 96 . The MW/Mn of the LLDPE ,rnt ranges from 2 . o to 3 0; Mw is the weight average - l~clllAr weight and Mn is the number average molecular weight, each of which is calculated from 1~ r weight distribution measured by GPC (gel permeation chromatography).
If the LLDPE ~ ~ is ~ocessed into a film, without blending with LDPE in accordance with the invention, the film would exhibit bA7 An -~fl tear strength, as measured by ASTM D1922, ranging from 50 to 600, preferably from 220 to 420 for machine direction and from 200 to 700, preferably from 200 to 600 for the transverse direction. The film would also exhibit high modulus, ~s measured by ASTM D882 ranging from 7 x 10 to 48 x 104 kPa (1 x 104 to 6 x 104 psi), preferably from 15 to 31 x 104 kPa (2.2 to 4.5 x 104 psi) and high tensile yield, as measured by ASTM D882, ranging ~rom 4800 to 21000 kPa (700 to 3000 psi), preferably from 12000 to 16000 kPa (1800 to 2300 psi).
If the LLDPE component is processed into a film, 35 without blending with LDPE in accordance with the invention, the film would exhibit optical qualities as =` 2~ 8Q01 2 . .
Wo 95~7005 r~
_~_ det-ormin~cl by haze studies, measured by AST~ D-1003 between 3 and 20, preferably from 4 to 10. Films of inferior haze properties exhibit a haze of greater than 10. The importance of the optical properties of LLDPE depend on the 5 intended application of the LLDPE resin. It is generally accepted that the poor optical properties of normal LLDPEs (haze >10 and gloss <50) severely limits their use in applications where optical perf~r--n~ is important.
The copolymer ~ ~nt of the resin blend of the 10 invnetion is a copolymer of ethylene and one or more C3-C10 alpha-olefins, which preferably contains at least 80 weight ~ ethylene unlts. Suitable alpha olei~ins include propylene, butene-l, pentene-1, hexene-l, 4-methylpentene-1, heptene-1 and octene-l. Preferably, the alpha-olefin 15 ~_ -r is 1- butene, l-hexene, and l-octene. The most preferred alpha olefin is hexene-l. Thus, copolymers having two ~ ~~ ic units are possible as well as terpolymers having three monomeric units. Particular examples of such polymers include ethylene/l-butene 20 copolymers, ethylene/1-hexene copolymers, ethylene/4-methyl-l-pentene copolymers, ethylene/l-butene/l-hexene terpolymers, ethylene/propylene/1-hexene terpolymers and ethylene/propylene/l-butene terpolymers.
The LLDPE copolymer used in this invention is prepared 25 from a new class of polyolefin catalyst comprising a carrier, an all~m; no~rAn~ and at least one metallocene.
The catalyst carrier material is a solid, particulate, porous, inorganic or organic material, preferably inorganic material, such as an oxide of silicon and/or of aluminum.
30 The carrier material is used in the form of a dry powder having an average particle size of 1 to 250 microns, preferably 10 to 150 microns. If n~c~Cc~ry~ the treated carrier material may be sieved to insure that the particles have an average particle size of preferably less than 150 35 microns. This is highly desirable in forming narrow molecular weight LLDPE, to reduce gels. The surface area wo ssn700s 218 ~ 012 of the carrier is at lea6t about 3 m2/gm, and preferably at least 50 m /gm up to 350 m /gm. When the carrier i5 6ilica, it is preferably heated to 100-C to 850 C and most preferably at about 250-C. The carrier material used to 5 produce the catalyst composition should have at least some active hydroxyl (OH) groups.
In the most preferred Pm~o~ , the carrier is silica which, prior to the use thereof, is dehydrated by fluidizing it with nitrogen and heating at about 250-C for 10 about 4 hours to achieve a surface hydroxyl group .,o~lc~..L.~tion of about 1.8 milli--les per gram (mmols/gm).
The silica of the most preferred P~ s~lir l. is a high surface area, _~hous silica (surface area = 300 m2/gm;
pore volume of 1. 65 cm3/gm) marketed under the tr~
of Davison 952-1836, Davison 952 or Davison 955 by the Davison fhPmi~-Al Division of W.R. Grace and Company. The silica is in the form of spherical particles, e.g., as obtained by a spray-drying process.
The alllminnYInP used in the LLDPE catalyst composition comprises ~ ric linear and/or cyclic alkyl Illlm;n(~Y~npc represented by the formula:
R-(Al(R)-O)n-AlR2 for oli~, ic, linear al~min~YlnP~c- and (-Al(R)-O-)m for oligomeric cyclic aluminr~y;!np wherein n is 1-40, preferably 10-20, m is 3-40, preferably 3-20 and R is a Cl-C8 alkyl group and preferably methyl. Methylalumin-oxane (MAO) is a miYture of oligomers with a very wide distribution of molecular weights and usually with an average molecular weight of about 1000. MAO is typically kept in solution in toluene.
The metallocene c _ ~ has the formula CpmMAnBp in which Cp is an unsubstituted or substituted cyclopentadienyl group, M is a transition metal selected from zirconium or hafnium and A and B belong to the group ;n~ ;n ~ a halogen atom, hydrogen or an alkyl group. In the above formula of the metallocene compound, the preferred transition metal atom M is zirconium. In the ~ 2180012 Wo 95/2700s PC r/US95/03564 above formula of the metallocene, _ ', the Cp group i8 an unsubstituted, a mono- or a polysubstituted cyclopentadienyl group. The substituents on the cyclopentadienyl group can be preferably straight-chain or 5 branched Cl-C6 alkyl groups. The cyclopentadienyl group can be also a part of a bicyclic or a tricyclic moiety such a8 indenyl, tetrahydroindenyl, fluorenyl or a partially l.ydLv~ ated fluorenyl group, as well as a part of a substituted bicyclic or tricyclic moiety. In the case when 10 m in the above formula of the metallocene _ _ ul.d i8 equal to 2, the cyclopentadienyl groups can be also bridged by polymethylene or dialkylsilane groups, such as -CH2-, -CH2-CH2-, -CR'R"- and -CR'R"-CR'R"- where R' and R" are short alkyl groups or l~yd~v~n, -Si(cH3)2-~ Si(CH3)2~CH2~CH2~
15 Si(CH3)2- and similar bridge groups. If the A and B
substituents in the above formula of the metallocene ' are halogen atoms, they belong to the group of fluorine, chlorine, bromine or iodine. If the substituents A and B in the above formula of the metAlloC~nF~ ~ ~
20 are alkyl or aromatic groups, they are preferably straight-chain or branched Cl-C8 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl or n-octyl.
Suitable metallocene ~_ __u.-ds include bis(cyclo-25 pentadienyl)metal dihalides, bis(cyclopentadienyl)metal hydrirl~h;~ c, bis(cyclop~ntA~ nyl~metal monoalkyl monohalides, bis(cyclopentadienyl)metal dialkyls and bis(indenyl)metal dihalides wherein the metal is titanium, zirconium or hafnium, halide groups are preferably chlorine 30 and the alkyl groups are Cl-C6 alkyls. Illustrative, but non-limiting examples of metallocenes include bis (cyclo-pentadienyl) zirconium dichloride, bis (cyclopentadienyl) -hafnium dichloride, bis(cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) hafnium dimethyl, 35 bis(cyclopenta-dienyl) zirconium hydridochloride, bis (cyclopentadienyl) hafnium hydridochloride, :~ 2180012 W0 95/27005 .
bis (pentamethylcyclopentadienyl) zirconium dichloride, bis ( pentamethylcyclcpentadienyl ) haf nium dichloride, bis ( n-butylcyclopentadienyl)zirconium dichloride, bis(isobutyl-cyclopentadienyl) zirconium dichloride, cyclopenta-dienyl-5 zirconium trichloride, bis(indenyl) zirconium dichloride,bis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, and ethylene-tbis(4,5,6,7-tetrahydro-1-indenyl) ] zirconium dichloride .
The mole ratio of al~minoY~n~ provided aluminum, 10 expressed as Al, to metallocene metal expressed as ~ (e.g.
Zr), ranges from 50 to 500, preferably 75 to 300, and most preferably 100 to 200. An added advantage of the present invention is that this Al: Zr ratio can be directly controlled. In a preferred ~ the alllmi nny~n~o and 15 metallocene compound are mixed together in a suitable co-solvent at a t~. r,eL~Lu e of 20 to 80-C, for 0.1 to 6.0 hours, prior to reaction with the carrier. The co-solvent for the metallocene and al~minnY in(~ can be aromatic hydrocarbons, halogenated hydrocarbon or halogenated 20 aromatic hydrocarbons, preferably toluene.
A particularly desirable method for producing linear low density polyethylene polymers is in a single fluid bed reactor such as that described in U . S . Patent No .
The LLDPE ~ eilt of the invention blend exhibits a melt flow ratio (MFR) range of 15 to 25, preferably 15 to 20 and most preferably 16 to 18. MFR is the ratio I21/I2 [wherein I21 is measured at 190-C in accordance with ASTM
D-1238, Condition F and I2 is measured at l90-C in accordance with ASTM D-1238, Condition E. ]
The LLDPE ~ -nrnt exhibits an MI of 0. 01 to 5, generally 0 .1 to 5, and preferably 0 . 5 to 4, and most preferably 0. 8 to 2 . 0 . For blown film, the MI of the copolymer is preferably 0 . 5 to 1. 5 .
The melting point of the LLDPE - _ --t ranges from 95-C to 130-C. Furth~ ~e, the hexane extractables content is very low, typically ranging from 0 . 3 to 1. 0 wt. 96 . The MW/Mn of the LLDPE ,rnt ranges from 2 . o to 3 0; Mw is the weight average - l~clllAr weight and Mn is the number average molecular weight, each of which is calculated from 1~ r weight distribution measured by GPC (gel permeation chromatography).
If the LLDPE ~ ~ is ~ocessed into a film, without blending with LDPE in accordance with the invention, the film would exhibit bA7 An -~fl tear strength, as measured by ASTM D1922, ranging from 50 to 600, preferably from 220 to 420 for machine direction and from 200 to 700, preferably from 200 to 600 for the transverse direction. The film would also exhibit high modulus, ~s measured by ASTM D882 ranging from 7 x 10 to 48 x 104 kPa (1 x 104 to 6 x 104 psi), preferably from 15 to 31 x 104 kPa (2.2 to 4.5 x 104 psi) and high tensile yield, as measured by ASTM D882, ranging ~rom 4800 to 21000 kPa (700 to 3000 psi), preferably from 12000 to 16000 kPa (1800 to 2300 psi).
If the LLDPE component is processed into a film, 35 without blending with LDPE in accordance with the invention, the film would exhibit optical qualities as =` 2~ 8Q01 2 . .
Wo 95~7005 r~
_~_ det-ormin~cl by haze studies, measured by AST~ D-1003 between 3 and 20, preferably from 4 to 10. Films of inferior haze properties exhibit a haze of greater than 10. The importance of the optical properties of LLDPE depend on the 5 intended application of the LLDPE resin. It is generally accepted that the poor optical properties of normal LLDPEs (haze >10 and gloss <50) severely limits their use in applications where optical perf~r--n~ is important.
The copolymer ~ ~nt of the resin blend of the 10 invnetion is a copolymer of ethylene and one or more C3-C10 alpha-olefins, which preferably contains at least 80 weight ~ ethylene unlts. Suitable alpha olei~ins include propylene, butene-l, pentene-1, hexene-l, 4-methylpentene-1, heptene-1 and octene-l. Preferably, the alpha-olefin 15 ~_ -r is 1- butene, l-hexene, and l-octene. The most preferred alpha olefin is hexene-l. Thus, copolymers having two ~ ~~ ic units are possible as well as terpolymers having three monomeric units. Particular examples of such polymers include ethylene/l-butene 20 copolymers, ethylene/1-hexene copolymers, ethylene/4-methyl-l-pentene copolymers, ethylene/l-butene/l-hexene terpolymers, ethylene/propylene/1-hexene terpolymers and ethylene/propylene/l-butene terpolymers.
The LLDPE copolymer used in this invention is prepared 25 from a new class of polyolefin catalyst comprising a carrier, an all~m; no~rAn~ and at least one metallocene.
The catalyst carrier material is a solid, particulate, porous, inorganic or organic material, preferably inorganic material, such as an oxide of silicon and/or of aluminum.
30 The carrier material is used in the form of a dry powder having an average particle size of 1 to 250 microns, preferably 10 to 150 microns. If n~c~Cc~ry~ the treated carrier material may be sieved to insure that the particles have an average particle size of preferably less than 150 35 microns. This is highly desirable in forming narrow molecular weight LLDPE, to reduce gels. The surface area wo ssn700s 218 ~ 012 of the carrier is at lea6t about 3 m2/gm, and preferably at least 50 m /gm up to 350 m /gm. When the carrier i5 6ilica, it is preferably heated to 100-C to 850 C and most preferably at about 250-C. The carrier material used to 5 produce the catalyst composition should have at least some active hydroxyl (OH) groups.
In the most preferred Pm~o~ , the carrier is silica which, prior to the use thereof, is dehydrated by fluidizing it with nitrogen and heating at about 250-C for 10 about 4 hours to achieve a surface hydroxyl group .,o~lc~..L.~tion of about 1.8 milli--les per gram (mmols/gm).
The silica of the most preferred P~ s~lir l. is a high surface area, _~hous silica (surface area = 300 m2/gm;
pore volume of 1. 65 cm3/gm) marketed under the tr~
of Davison 952-1836, Davison 952 or Davison 955 by the Davison fhPmi~-Al Division of W.R. Grace and Company. The silica is in the form of spherical particles, e.g., as obtained by a spray-drying process.
The alllminnYInP used in the LLDPE catalyst composition comprises ~ ric linear and/or cyclic alkyl Illlm;n(~Y~npc represented by the formula:
R-(Al(R)-O)n-AlR2 for oli~, ic, linear al~min~YlnP~c- and (-Al(R)-O-)m for oligomeric cyclic aluminr~y;!np wherein n is 1-40, preferably 10-20, m is 3-40, preferably 3-20 and R is a Cl-C8 alkyl group and preferably methyl. Methylalumin-oxane (MAO) is a miYture of oligomers with a very wide distribution of molecular weights and usually with an average molecular weight of about 1000. MAO is typically kept in solution in toluene.
The metallocene c _ ~ has the formula CpmMAnBp in which Cp is an unsubstituted or substituted cyclopentadienyl group, M is a transition metal selected from zirconium or hafnium and A and B belong to the group ;n~ ;n ~ a halogen atom, hydrogen or an alkyl group. In the above formula of the metallocene compound, the preferred transition metal atom M is zirconium. In the ~ 2180012 Wo 95/2700s PC r/US95/03564 above formula of the metallocene, _ ', the Cp group i8 an unsubstituted, a mono- or a polysubstituted cyclopentadienyl group. The substituents on the cyclopentadienyl group can be preferably straight-chain or 5 branched Cl-C6 alkyl groups. The cyclopentadienyl group can be also a part of a bicyclic or a tricyclic moiety such a8 indenyl, tetrahydroindenyl, fluorenyl or a partially l.ydLv~ ated fluorenyl group, as well as a part of a substituted bicyclic or tricyclic moiety. In the case when 10 m in the above formula of the metallocene _ _ ul.d i8 equal to 2, the cyclopentadienyl groups can be also bridged by polymethylene or dialkylsilane groups, such as -CH2-, -CH2-CH2-, -CR'R"- and -CR'R"-CR'R"- where R' and R" are short alkyl groups or l~yd~v~n, -Si(cH3)2-~ Si(CH3)2~CH2~CH2~
15 Si(CH3)2- and similar bridge groups. If the A and B
substituents in the above formula of the metallocene ' are halogen atoms, they belong to the group of fluorine, chlorine, bromine or iodine. If the substituents A and B in the above formula of the metAlloC~nF~ ~ ~
20 are alkyl or aromatic groups, they are preferably straight-chain or branched Cl-C8 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl or n-octyl.
Suitable metallocene ~_ __u.-ds include bis(cyclo-25 pentadienyl)metal dihalides, bis(cyclopentadienyl)metal hydrirl~h;~ c, bis(cyclop~ntA~ nyl~metal monoalkyl monohalides, bis(cyclopentadienyl)metal dialkyls and bis(indenyl)metal dihalides wherein the metal is titanium, zirconium or hafnium, halide groups are preferably chlorine 30 and the alkyl groups are Cl-C6 alkyls. Illustrative, but non-limiting examples of metallocenes include bis (cyclo-pentadienyl) zirconium dichloride, bis (cyclopentadienyl) -hafnium dichloride, bis(cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) hafnium dimethyl, 35 bis(cyclopenta-dienyl) zirconium hydridochloride, bis (cyclopentadienyl) hafnium hydridochloride, :~ 2180012 W0 95/27005 .
bis (pentamethylcyclopentadienyl) zirconium dichloride, bis ( pentamethylcyclcpentadienyl ) haf nium dichloride, bis ( n-butylcyclopentadienyl)zirconium dichloride, bis(isobutyl-cyclopentadienyl) zirconium dichloride, cyclopenta-dienyl-5 zirconium trichloride, bis(indenyl) zirconium dichloride,bis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, and ethylene-tbis(4,5,6,7-tetrahydro-1-indenyl) ] zirconium dichloride .
The mole ratio of al~minoY~n~ provided aluminum, 10 expressed as Al, to metallocene metal expressed as ~ (e.g.
Zr), ranges from 50 to 500, preferably 75 to 300, and most preferably 100 to 200. An added advantage of the present invention is that this Al: Zr ratio can be directly controlled. In a preferred ~ the alllmi nny~n~o and 15 metallocene compound are mixed together in a suitable co-solvent at a t~. r,eL~Lu e of 20 to 80-C, for 0.1 to 6.0 hours, prior to reaction with the carrier. The co-solvent for the metallocene and al~minnY in(~ can be aromatic hydrocarbons, halogenated hydrocarbon or halogenated 20 aromatic hydrocarbons, preferably toluene.
A particularly desirable method for producing linear low density polyethylene polymers is in a single fluid bed reactor such as that described in U . S . Patent No .
4,481,301. The process conditions would include a 25 temperature below the sintering t~ ULa of the polymer particles, preferably 60- to 115-C, and more preferably 75-to 95-C, and a ~res~ulla of 150 to 350 psig (1100 to 2500 kPa ) .
A "diluent" gas nonreactive under the conditions in 30 the polymerization reactor, such as nitrogen, argon, helium, methane, or ethane, is preferably present during the copolymerization of the LLDPE. Hydrogen can also be present as a chain transfer agent.
W0 95127005 ~ ; 2 1 8 0 0 1 2 r~
Th~ Tnvention Blends The blends of the invention comprise 70 to 98, preferably 90 to 98, and most preferably 95 to 98 weight percent of the LI,DPE copolymers described above and 2 to 30, preferably 2 to 10, and most prefera~ly 2 to 5 weight percent of conventional LDPE resin.
The blends products may also contain any of various additives conventionally added to polymer compositions such as lubricants, microtalc, stabilizer, anti~y;rl~nts~
compa~ih;lt7~rs, pigments, etc. These additivess can be employed to stabilize the products against oxidation. For example, additive r~C k~PC comprising 400-1200 ppm hindered phenol(s); 700-2000 ppm phosphites; 250 to 1000 ppm antistats and 250-1000 ppm stearates, for addition to the resin powders, can be used for pelletization.
The polymer blend can be added directly to a blown film extruder, e.g., a Sterling ~:X~L lder, to produce ~ilms having a thirlrno~ for example of 0.5 to 5 mils (0.013 to 0 . 13 mm) .
Films ~Ivduced from the blend of the invention have ;, LVVt:d optical properties (haze <5 and gloss >70) . Films produced from the invention blend also exhibit Dart Drop Impact values as measured by ASTM D-1709 greater than 400, generally from 500 to 1500 .
The following Examples further illustrate the essential features of the invention.
The properties of the polymers produced in the Examples were det~-rm;nFfI by the following test methods:
Density ASTM D-1505 - a pla~ue is made and conditioned for one hour at lOO-C to approach equilibrium crystallinity.
Mea:,uL- l. for density is then made in a density gradient column; reported as gms/cc.
Melt Index ASTM D-1238 - Condition E
(MI), I Measured at l90-C - reported as grams per 10 2 minutes.
21800~2 wo ssn700s . r~
g High Load ASTM D-1238 - Condition F
Nelt Index Measured at 10 . 5 times the weight used in (HLMI), I21 the melt index te6t above.
Melt Flow Ratio (MFR) 2 Ex~m~le 1 A 1 I2 ~ . 918 density pilot plant LLDPE metallocene resin produced in accordance with Example A, below, was ~_ _ '^d on a Banbury mixer using 1000 ppm Irganox 1010, 2000 ppm Irgafos 168, 1000 ppm Erucamide, 5000 ppm ABT
2500, 500 ppm AS990 and 500 ppm ZnSt. The pelletized metallocene resin was then blended with a ~ ~;ial high pre6sure ethylene low density resin (Mobil LBA-133) of 2 I2, 0.924 density at three different levels -0%, 5% and 10% . A 1 mil (0 . 03 mm) film was then ~L~,duced from each blend using a 2.5 inch (6.4 cm) Brampton blown film extruder at 440-C, 100 mil (2.5 mm) die gap, and a resin ~eed of 150 lbs/hr (68 kg/hr). A broader molecular weight distribution commercial LLDPE resin, Mobil NTX-095, was also blended at with LBA-133 two levels, for comparison purposes. These results were then compared with a 1 mil film made from Rexene 1065 (1.9 I2, 0.924 density), a commercial high clarity LDPE resin.
The results (see Table I) show that at the 5% LLDPE
blend level, the metallocene/LDPE blend gave comparable haze to that of Rexene 1065 (4 . 4 vs. 4 . 6 for Rexene) while offering superior impact properties (i.e. dart impact of 750 vs 64 gms for Rexene 1065). Furth~ , at the same LDPE blend level, impact properties of the metallocene/LDPE
blend were superior to those of NTX-095/LDPE blend. The metallocene blend offered lower haze (4.4% vs 10.3% for NTX-095 blend) and superior dart impact ~L~ L Ly (750 gms vs 166 gms for the NTX-095 blend).
` - 2180012 Wo 95127005 r.~
~2L~
~igh clArity M~t~llo_- -- Blen~ 8tutly Base ~esin % LDPE % Haze DDI, gms Metallocene 5 4 . 4 750 5Produced Res in ( a ) Metallocene 0 7. 0 >800 Produced Res in ( a ) NTX--095 5 10. 0 166 NTX--095 0 17.0 264 10Rexene 1065 (b) 0 4 . 6 64 (a) Produced as in Example A.
(b) Rexene 1065 was run on the Brampton film extruder at 360-C and 40 mil (1 mm) die gap, with other conditions being the same.
r 1~ A
Raw material6 used in catalyst preparation included 504 g of Davison 952-1836 silica, 677 g of methyl-all-minnYAn~ in toluene solution (30 wt.96 MA0), 7.136 g of bis ln-butylcyclopentadienyl ) zirconium dichloride.
The steps of the catalyst preparation are set forth below:
1. Dehydrate the 952-1836 silica at 250-C for 4 hours using air to purge. Then purge with nitrogen on cooling.
2. Transfer the silica to a mix-vessel.
3. Add 7.136 g of l~is(n-butylcyclopentadienyl) zirconium dichloride and 677 g of methylall~min~YAn~ to a bottle.
4. Agitate the catalyst solution in the bottle until the metallocene dissolves in the MA0 solution.
A "diluent" gas nonreactive under the conditions in 30 the polymerization reactor, such as nitrogen, argon, helium, methane, or ethane, is preferably present during the copolymerization of the LLDPE. Hydrogen can also be present as a chain transfer agent.
W0 95127005 ~ ; 2 1 8 0 0 1 2 r~
Th~ Tnvention Blends The blends of the invention comprise 70 to 98, preferably 90 to 98, and most preferably 95 to 98 weight percent of the LI,DPE copolymers described above and 2 to 30, preferably 2 to 10, and most prefera~ly 2 to 5 weight percent of conventional LDPE resin.
The blends products may also contain any of various additives conventionally added to polymer compositions such as lubricants, microtalc, stabilizer, anti~y;rl~nts~
compa~ih;lt7~rs, pigments, etc. These additivess can be employed to stabilize the products against oxidation. For example, additive r~C k~PC comprising 400-1200 ppm hindered phenol(s); 700-2000 ppm phosphites; 250 to 1000 ppm antistats and 250-1000 ppm stearates, for addition to the resin powders, can be used for pelletization.
The polymer blend can be added directly to a blown film extruder, e.g., a Sterling ~:X~L lder, to produce ~ilms having a thirlrno~ for example of 0.5 to 5 mils (0.013 to 0 . 13 mm) .
Films ~Ivduced from the blend of the invention have ;, LVVt:d optical properties (haze <5 and gloss >70) . Films produced from the invention blend also exhibit Dart Drop Impact values as measured by ASTM D-1709 greater than 400, generally from 500 to 1500 .
The following Examples further illustrate the essential features of the invention.
The properties of the polymers produced in the Examples were det~-rm;nFfI by the following test methods:
Density ASTM D-1505 - a pla~ue is made and conditioned for one hour at lOO-C to approach equilibrium crystallinity.
Mea:,uL- l. for density is then made in a density gradient column; reported as gms/cc.
Melt Index ASTM D-1238 - Condition E
(MI), I Measured at l90-C - reported as grams per 10 2 minutes.
21800~2 wo ssn700s . r~
g High Load ASTM D-1238 - Condition F
Nelt Index Measured at 10 . 5 times the weight used in (HLMI), I21 the melt index te6t above.
Melt Flow Ratio (MFR) 2 Ex~m~le 1 A 1 I2 ~ . 918 density pilot plant LLDPE metallocene resin produced in accordance with Example A, below, was ~_ _ '^d on a Banbury mixer using 1000 ppm Irganox 1010, 2000 ppm Irgafos 168, 1000 ppm Erucamide, 5000 ppm ABT
2500, 500 ppm AS990 and 500 ppm ZnSt. The pelletized metallocene resin was then blended with a ~ ~;ial high pre6sure ethylene low density resin (Mobil LBA-133) of 2 I2, 0.924 density at three different levels -0%, 5% and 10% . A 1 mil (0 . 03 mm) film was then ~L~,duced from each blend using a 2.5 inch (6.4 cm) Brampton blown film extruder at 440-C, 100 mil (2.5 mm) die gap, and a resin ~eed of 150 lbs/hr (68 kg/hr). A broader molecular weight distribution commercial LLDPE resin, Mobil NTX-095, was also blended at with LBA-133 two levels, for comparison purposes. These results were then compared with a 1 mil film made from Rexene 1065 (1.9 I2, 0.924 density), a commercial high clarity LDPE resin.
The results (see Table I) show that at the 5% LLDPE
blend level, the metallocene/LDPE blend gave comparable haze to that of Rexene 1065 (4 . 4 vs. 4 . 6 for Rexene) while offering superior impact properties (i.e. dart impact of 750 vs 64 gms for Rexene 1065). Furth~ , at the same LDPE blend level, impact properties of the metallocene/LDPE
blend were superior to those of NTX-095/LDPE blend. The metallocene blend offered lower haze (4.4% vs 10.3% for NTX-095 blend) and superior dart impact ~L~ L Ly (750 gms vs 166 gms for the NTX-095 blend).
` - 2180012 Wo 95127005 r.~
~2L~
~igh clArity M~t~llo_- -- Blen~ 8tutly Base ~esin % LDPE % Haze DDI, gms Metallocene 5 4 . 4 750 5Produced Res in ( a ) Metallocene 0 7. 0 >800 Produced Res in ( a ) NTX--095 5 10. 0 166 NTX--095 0 17.0 264 10Rexene 1065 (b) 0 4 . 6 64 (a) Produced as in Example A.
(b) Rexene 1065 was run on the Brampton film extruder at 360-C and 40 mil (1 mm) die gap, with other conditions being the same.
r 1~ A
Raw material6 used in catalyst preparation included 504 g of Davison 952-1836 silica, 677 g of methyl-all-minnYAn~ in toluene solution (30 wt.96 MA0), 7.136 g of bis ln-butylcyclopentadienyl ) zirconium dichloride.
The steps of the catalyst preparation are set forth below:
1. Dehydrate the 952-1836 silica at 250-C for 4 hours using air to purge. Then purge with nitrogen on cooling.
2. Transfer the silica to a mix-vessel.
3. Add 7.136 g of l~is(n-butylcyclopentadienyl) zirconium dichloride and 677 g of methylall~min~YAn~ to a bottle.
4. Agitate the catalyst solution in the bottle until the metallocene dissolves in the MA0 solution.
5. Transfer the MA0 and metallocene solution into the mix-vessel containing the dehydrated 955 silica slowly while agitating the silica bed vigorously to make sure that the catalyst solution is well dispersed into the silica bed.
W0 95/27005 r~
W0 95/27005 r~
6. After the addition, continue to agitate the catalyst for 1/2 hours.
7. Start drying the catalyst by purging with nitrogen for 5 hours at 45 C.
8. Sieve the catalyst to remove particles larger than 150 micron.
9. The catalyst has the following analysis:
Yield = 767 g catalyst (from 500 g of silica) Al = 9.95 wt.%
Zr = 0 .19 wt . %
LLDPE resin was ~Lvduced from the above catalyst in a fluid bed gas phase reactor using the following process conditions:
Process Conditions:
15 Fluidization velocity 1.7 ft/sec tO.5 m/sec) Residence time 2 . 5 hours Temperature 8 4 C
Ethylene 220 psi EIexene 3 . 6 psi 20 Isopentane 50 psi Carbon dioxide 3 ppm Ash 200-300 ppm The resulting resin had the following characteristics:
25 density 0 . 918 Mw/Mn 2 . 6 ~FR 18 Melting point 115-C
Yield = 767 g catalyst (from 500 g of silica) Al = 9.95 wt.%
Zr = 0 .19 wt . %
LLDPE resin was ~Lvduced from the above catalyst in a fluid bed gas phase reactor using the following process conditions:
Process Conditions:
15 Fluidization velocity 1.7 ft/sec tO.5 m/sec) Residence time 2 . 5 hours Temperature 8 4 C
Ethylene 220 psi EIexene 3 . 6 psi 20 Isopentane 50 psi Carbon dioxide 3 ppm Ash 200-300 ppm The resulting resin had the following characteristics:
25 density 0 . 918 Mw/Mn 2 . 6 ~FR 18 Melting point 115-C
Claims (6)
1. A blend comprising 70 to 98 weight percent of an as-synthesized composition which is dry and solvent-free and comprises spherical, non-porous particles, which has an average particle size of 0.05 to 0.11 cm (0.02 to 0.045 inches), and a settled bulk density of 400 to 580 kg/m3 (25 to 36 lb/ft3), and which is a copolymer of ethylene and an alpha olefin, having a density of 0.902 to 0.929, a MFR of 15 to 25, and a NW/Mn of 2.0 to 3.0; and 2 to 30 weight percent of low density polyethylene produced at 150-300 NPa [1500-3000 atm]
and 200-300°C, wherein the haze value of the blend is less than 5 as measured by ASTN D-1003 and the dart drop impact resistance measured by ASTM D-1709 is greater than 400.
and 200-300°C, wherein the haze value of the blend is less than 5 as measured by ASTN D-1003 and the dart drop impact resistance measured by ASTM D-1709 is greater than 400.
2. The blend of Claim 1, wherein said alpha olefin of said copolymer has 3 to 10 carbon atoms.
3. The blend of Claim 1, wherein the alpha olefin selected from butene, hexene, octene and admixtures thereof.
4. The blend of any preceding claim comprising 90-98 weight% of said copolymer and 2-10 weight% of said low density polyethylene.
5. The blend of any preceding claim comprising 95-98 weight% of said copolymer and 2-5 weight% of said low density polyethylene.
6. A film formed from the blend as claimed in any preceding claim.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US22056194A | 1994-03-31 | 1994-03-31 | |
| US08/220,561 | 1994-03-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2180012A1 true CA2180012A1 (en) | 1995-10-12 |
Family
ID=22824029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002180012A Abandoned CA2180012A1 (en) | 1994-03-31 | 1995-03-21 | Lldpe resin blends |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0753026A4 (en) |
| JP (1) | JPH09511273A (en) |
| KR (1) | KR970701758A (en) |
| CN (1) | CN1145082A (en) |
| AU (1) | AU686370B2 (en) |
| CA (1) | CA2180012A1 (en) |
| WO (1) | WO1995027005A1 (en) |
| ZA (1) | ZA952648B (en) |
Families Citing this family (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5792560A (en) * | 1995-09-28 | 1998-08-11 | Norton Performance Plastics Corporation | Thermoplastic interlayer film |
| US6159608A (en) * | 1995-09-28 | 2000-12-12 | Saint-Gobain Performance Plastics Corporation | Thermoplastic interlayer film |
| DE19548788A1 (en) † | 1995-12-27 | 1997-07-03 | Hoechst Ag | Foils and layers |
| US6017832A (en) * | 1996-09-04 | 2000-01-25 | Kimberly-Clark Worldwide, Inc. | Method and composition for treating substrates for wettability |
| US6204208B1 (en) | 1996-09-04 | 2001-03-20 | Kimberly-Clark Worldwide, Inc. | Method and composition for treating substrates for wettability and skin wellness |
| EP0970143A1 (en) * | 1997-03-25 | 2000-01-12 | Exxon Chemical Patents Inc. | Olefin polymer compositions containing metal carboxylate cross-linking retarders |
| DE19723003A1 (en) | 1997-06-02 | 1998-12-03 | Basf Ag | Polymer blend |
| US6096668A (en) * | 1997-09-15 | 2000-08-01 | Kimberly-Clark Worldwide, Inc. | Elastic film laminates |
| DE19745047A1 (en) | 1997-10-11 | 1999-04-15 | Basf Ag | Polymer mixture, especially for production of film |
| US6072005A (en) * | 1997-10-31 | 2000-06-06 | Kimberly-Clark Worldwide, Inc. | Breathable films and process for producing them |
| CN1313526C (en) * | 1998-03-10 | 2007-05-02 | 三井化学株式会社 | Ethylene copolymer composition and use thereof |
| TW460485B (en) | 1998-06-19 | 2001-10-21 | Japan Polyolefins Co Ltd | Ethylene.Α-olefin copolymer, and combinations, films and use thereof |
| US7335716B1 (en) | 1999-06-17 | 2008-02-26 | Mitsui Chemicals, Inc. | Ethylene (co)polymers and uses thereof |
| PL200524B1 (en) | 1999-08-13 | 2009-01-30 | Basell Polyolefine Gmbh | COPOLYMERS OF ETHYLENE WITH C₃ -C₉ $g(a) OLEFINS and uses as well as application of monoindenyl- or monofluorenyl complexes of chromium |
| US6388017B1 (en) † | 2000-05-24 | 2002-05-14 | Phillips Petroleum Company | Process for producing a polymer composition |
| EP1225201A1 (en) | 2001-01-12 | 2002-07-24 | ATOFINA Research | High shrink polyethylene films |
| EP1312624A1 (en) * | 2001-11-14 | 2003-05-21 | Atofina Research S.A. | Metallocene film resin |
| CN1246349C (en) * | 2001-01-12 | 2006-03-22 | 阿托菲纳研究公司 | Metallocene film resin |
| EP1260541A1 (en) * | 2001-05-21 | 2002-11-27 | Atofina Research S.A. | Polyethylene films with improved processability and optical properties |
| WO2004056481A1 (en) | 2002-12-20 | 2004-07-08 | Basell Polyolefine Gmbh | Monocyclopentadienyl complexes |
| MXPA05006583A (en) | 2002-12-20 | 2005-12-14 | Basell Polyolefine Gmbh | COPOLYMERS OF ETHYLENE WITH alpha-OLEFINS. |
| US7238748B2 (en) * | 2003-08-20 | 2007-07-03 | Dupont Performance Elastomers L.L.C. | Process aid for metallocene catalyzed linear low density polyethylene polymers |
| DE102004020524A1 (en) | 2004-04-26 | 2005-11-10 | Basell Polyolefine Gmbh | Polyethylene for film, e.g. stretch film, used in carrier bags, contains ethylene homopolymers and/or copolymers of ethylene with 1-alkenes |
| DE102004027332A1 (en) | 2004-06-04 | 2005-12-22 | Basell Polyolefine Gmbh | New organometallic transition metal compound useful as catalyst constituents of catalyst systems for the polymerization of ethylene |
| CA2479190A1 (en) * | 2004-08-26 | 2006-02-26 | Nova Chemicals Corporation | Polyethylene blends |
| DE102005057559A1 (en) | 2005-11-30 | 2007-05-31 | Basell Polyolefine Gmbh | New transition pyrazole metal compound useful for e.g. the oligomerization, polymerization or copolymerization of polyolefin, preferably ethylene |
| DE102006001959A1 (en) | 2006-01-13 | 2007-07-19 | Basell Polyolefine Gmbh | Preparation of monoimine compound, useful in the polymerization of olefin, comprises reacting dicarbonyl compound with an aniline compound in presence of an aliphatic, non-aromatic solvent |
| DE102007017903A1 (en) | 2007-04-13 | 2008-10-16 | Basell Polyolefine Gmbh | Polyethylene and catalyst composition and process for its preparation |
| US8435911B2 (en) | 2008-10-16 | 2013-05-07 | Basell Polyolefine Gmbh | Hybrid catalyst composition for polymerization of olefins |
| EP3630886B1 (en) * | 2017-05-31 | 2022-08-17 | Univation Technologies, LLC | Blends of linear low density polyethylenes |
| US20210395480A1 (en) * | 2020-06-22 | 2021-12-23 | Total American Services | Extruded Non-Crosslinked Polyethylene Foam |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4243619A (en) * | 1978-03-31 | 1981-01-06 | Union Carbide Corporation | Process for making film from low density ethylene hydrocarbon copolymer |
| ZA832777B (en) * | 1982-04-27 | 1984-11-28 | Bp Chem Int Ltd | Polyethylene blend and film |
| US4833111A (en) * | 1988-01-14 | 1989-05-23 | Mobil Oil Corporation | Catalyst composition for polymerizing alpha-olefin polymers of narrow molecular weight distribution |
| DE68928100T2 (en) * | 1988-09-30 | 1997-11-06 | Exxon Chemical Patents Inc | LINEAR ETHYLENE-COPOLYMER MIXTURES OF COPOLYMERS WITH TIGHT MOLECULAR WEIGHT AND COMPOSITION DISTRIBUTIONS |
| EP0575123B2 (en) * | 1992-06-17 | 2008-02-13 | Mitsui Chemicals, Inc. | Ethylene copolymer composition |
| DE69433347T2 (en) * | 1993-01-29 | 2004-04-15 | Dow Global Technologies, Inc., Midland | Ethylene copolymerization |
-
1995
- 1995-03-21 KR KR1019960705055A patent/KR970701758A/en not_active Application Discontinuation
- 1995-03-21 CN CN95192353A patent/CN1145082A/en active Pending
- 1995-03-21 EP EP95915393A patent/EP0753026A4/en not_active Withdrawn
- 1995-03-21 WO PCT/US1995/003564 patent/WO1995027005A1/en not_active Application Discontinuation
- 1995-03-21 CA CA002180012A patent/CA2180012A1/en not_active Abandoned
- 1995-03-21 AU AU22287/95A patent/AU686370B2/en not_active Ceased
- 1995-03-21 JP JP7525743A patent/JPH09511273A/en not_active Ceased
- 1995-03-30 ZA ZA952648A patent/ZA952648B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0753026A1 (en) | 1997-01-15 |
| CN1145082A (en) | 1997-03-12 |
| AU2228795A (en) | 1995-10-23 |
| AU686370B2 (en) | 1998-02-05 |
| KR970701758A (en) | 1997-04-12 |
| EP0753026A4 (en) | 1998-06-10 |
| ZA952648B (en) | 1996-09-30 |
| JPH09511273A (en) | 1997-11-11 |
| WO1995027005A1 (en) | 1995-10-12 |
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