Classifications

• • C—CHEMISTRY; METALLURGY
  • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/04—Polymers provided for in subclasses C08C or C08F
  • C08F290/042—Polymers of hydrocarbons as defined in group C08F10/00
• • C—CHEMISTRY; METALLURGY
  • 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
  • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
  • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
• • C—CHEMISTRY; METALLURGY
  • 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
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/04—Anhydrides, e.g. cyclic anhydrides
  • C08F222/06—Maleic anhydride
• • C—CHEMISTRY; METALLURGY
  • 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
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• • C—CHEMISTRY; METALLURGY
  • 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
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
• • C—CHEMISTRY; METALLURGY
  • 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
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

• This invention relates to grafted ethylene copolymers, compositions comprising the grafted ethylene copolymers, and a process to make the grafted ethylene copolymers.
• U.S. 5,346,963 describes substantially linear olefin polymers produced by Dow Chemical Company's "constrained geometry" catalysts grafted with an unsaturated organic compound which exhibit adhesive properties as well as imparting desirable impact properties to various thermoplastic polymer blends. These polymers however do not achieve high levels of grafting without an increase in viscosity.
• EPA 0 440 506 discloses derivatized ethylene alpha-olefin polymers useful as multifunctional viscosity index improvers. These polymers however are generally only functionalized at the chain end and have thus only one functionality per chain. The chemistry used in this case generally leads to too low functionalization levels for the typical medium viscosity polymers used to modify engineering thermoplastics.
• This invention relates to a grafted ethylene copolymer comprising ethylene and an alpha-olefin grafted with 0.1 weight% or more of an unsaturated acid or anhydride wherein the copolymer prior to grafting is characterized by: 1) a vinylidene to vinyl end chain unsaturation ratio of 3 or less, and 2) a CDBI of 60 % or more if the polymer has a density of 0.90g/cc or more or a reactivity ratio between 0.5 and 1.5 or less if the polymer has a density of less than 0.90 g/cc, and wherein the grafted copolymer is characterized by a number of unsaturated acid or anhydride molecules per chain of 2 or more as calculated according to the following formula: [Mn* UAA (wt%)] / [UAA(Mw)] wherein Mn is the number average molecular weight as measured by GPC, UAA(wt%) is the weight percent of the unsaturated acid or anhydride as measured by
• Figure 1 is a graph of the MFR increase during grafting for examples 1-8. (Cond.l is example 1 and so on).
• Figure 2 is a graph of the MFR increase during grafting for examples 9-11. (Cond.9 is example 9 and so on).
• This invention relates to a grafted ethylene copolymer comprising ethylene and an alpha-olefin grafted with 0.1 weight % or more of an unsaturated acid or anhydride wherein the copolymer prior to grafting:
• Mn is the number average molecular weight as measured by GPC
• UAA(wt%) is the weight percent of the unsaturated acid or anhydride as measured by FTIR spectroscopy
• UAA(Mw) is the molecular weight of the unsaturated acid or anhydride, and optionally 4) an Mw/Mn greater than (I ⁇ o/I 2 )-4.63.
• the ethylene copolymer prior to grafting is a copolymer of ethylene and an ⁇ -olefin, preferably a C3 to C40 -olefin, even more preferably a C3 to Cjg ⁇ -olefin, even more preferably a C3 to a Ci 2 ⁇ -olefin.
• the ethylene polymer has a molecular weight distribution (Mw/Mn) of 4 or less, preferably 3 or less, even more preferably 2 or less, even more preferably between 2 and 1.
• the ethylene copolymer has a Composition Distribution Breadth Index (CDBI)of 50 % or more, preferably 60% or more, even more preferably 70% or more, even more preferably 80% or more, even more preferably 90% or more.
• Composition Distribution Breadth Index (CDBI) is a measure of the composition distribution of monomer within the polymer chains and is measured by the procedure described in PCT publication WO 93/03093, published February 18, 1993 including that fractions having a weight average molecular weight (Mw) below 15,000 are ignored when determining CDBI.
• the ethylene copolymer prior to grafting may have an Melt Index of 150 g/lOmin or less, preferably 20 g/lOmin or less, even more preferably 10 g/lOmin or less, even more preferably 5 g lOmin or less.
• the ethylene copolymer prior to grafting has a number average molecular weight of 10,000 or more, more preferably 20,000 or more even more preferably 30,000 or more, even more preferably between 30,000 and 150,000.
• the ethylene copolymer prior to grafting has a ratio of methylenes to tertiary carbon atoms of 18 or less, more preferably 17 or less. In a particularly preferred embodiment the ratio is 18 or less and the alpha-olefin is a C3 to C6 alpha-olefin, preferably butene, pentene, or hexene.
• the grafted ethylene copolymer has a number of unsaturated acid or anhydride molecules per chain of 2 or more as calculated according to the following formula: [Mn* UAA (wt%)] / [UAA(Mw)] wherein Mn is the number average molecular weight as measured by GPC, UAA(wt%) is the weight percent of the unsaturated acid or anhydride as measured by FTIR spectroscopy and UAA(Mw) is the molecular weight of the unsaturated acid or anhydride, preferably 3 or more, even more preferably 5 or more, even more preferably 10 or more.
• the ethylene copolymer further comprises an unsaturated acid or anhydride.
• unsaturated acid or anhydride include any unsaturated organic compound containing at least one double bond and at least one carbonyl group.
• Representative acids include carboxylic acids, anhydrides, esters and their salts, both metallic and non-metallic.
• the unsaturated acid or anhydride is preferably present at about 0.1 weight % to about 20 weight %, preferably at about 0.2 weight % to about 10 weight %, even more preferably at about 0.3 to about 5 weight %, based upon the weight of the ethylene copolymer and the unsaturated acid or anhydride.
• This invention can also be practiced with any unsaturated monomer which can be grafted in a reaction with peroxide.
• Ethylene copolymers useful herein can be produced by the methods described in US 5,055,438; US 5,507,475; US 5,096,867; US 5,264,405; US 5,324,800; US 5,017,714; U.S.5,240,894; US 5,198,401; US 5,153,157; WO 92 00333; WO 94 03506; EPA 520,732; EPA 129,368; EPA 277,003; EPA 277,004; and CA
• the ethylene copolymers are produced using one or more mono- or bis-cyclopentadienyl transition metal (preferably group 4) catalysts in combination with an activator of alumoxane and/or a non-coordinating anion, preferably in solution, slurry or gas phase.
• the catalyst may be supported or unsupported and the cyclopentadienyl rings by may substituted or unsubstituted.
• Unsaturated acid or anhydride content is measured by FTIR (Fourrier Transformed Infrared Spectroscopy).
• FTIR Frerier Transformed Infrared Spectroscopy
• the reaction products are compressed at temperature of 165°C into thin films from which infrared spectra were taken using a Mattson
• the number of unsaturated acid or anhydride (UAA) molecules per polymer chain is obtained by multiplying the total unsaturated acid or anhydride content as measured by FTIR spectroscopy by the number average molecular weight divided by the unsaturated acid or anhydride molecular weight as described in equation: [Mn* UAA (wt%)] / [ UAA(Mw)] wherein Mn is the number average molecular weight as measured by GPC, UAA(wt%) is the weight percent of the unsaturated acid or anhydride as measured by FTIR spectroscopy and UAA(Mw) is the molecular weight of the unsaturated acid or anhydride
• Unsaturations (vinylidene, vinyls chain end unsaturation, etc) in polyolefins are measured by proton NMR at 125°C. 100 mg of polymer is dissolved in lcc of trichlorobenzene and 0.2 cc of deuterobenzene.
• the instrument is preferably a VariantTM Unity plus 300 MHz. The following parameters are preferably used: aquisition time: 3 sec, spectral window: 6000 Hz, pulse width: 30°, delay Dl: 5 sec, number of transients: 1024, spinning rate: 17 Hz.
• Reactivity ratio is measured by the 13 C NMR procedure described in K. Soga, Polymer Bulletin, 1983, Vol 10. pg 168.
• grafted copolymers described herein include benefits derived from the lower viscosity ratios. Lower ratios translate into more stable operation conditions during processing of the polymers both during manufacturing and processing applications.
• the grafted polymers of this invention can be used in blends with engineering thermoplastics possessing a functional group susceptible of chemically reacting or interacting through polar interactions or hydrogen bounding with the unsaturated monomer which has been grafted to the backbone.
• thermoplastics corresponding to this definition are polyamide-6, polyamide-6,6 , polybuthylene terephtalate, polyethylene terephtalate, polycarbonate, polyphenylene oxide, polyphenylene ether, polyoxymethylene, polyvinyl alcohol, ethylene acrylic acid copolymers, ethylene methylacrylate copolymers, ethylene acrylic acid methylacrylate terpolymers and polyvinyl chloride. These polymers can also be used in any of the previous compositions also containing fillers such as silica, talc, calcium carbonate, carbon black or glass fibers.
• Polymers of this invention can also be used as compatibilizers for blends of polyolefinic polymers and polar thermoplastics as the ones mentionned above. These polymers can be added to polyolefinic compositions containing fillers such as talc, calcium carbonate, silica, carbon black and glass fibers where they will insure increased interaction with the filler and hence higher physical properties. Finally they can serve as adhesion promotors to polar substrates such as polar polymers, metal, aluminium, glass when used pure or in blends with other polyolefinic polymers but also thermoset rubber compounds.
• Mw and Mn are measured by gel permeation chromotography using monodisperse polystyrene standards on a Waters 150 gel permeation chromatograph (GPC)coupled with a DRI detector and a Chromatix KMX-6 on line light scattering photometer.
• GPC Waters 150 gel permeation chromatograph
• the system is used at 135 °C with 1,2,4-trichlorobenzene as the mobile phase.
• EXACTTM 4049 is an ethylene-butene copolymer produced with a single site metallocene catalyst which contains 26 wt% of butene and has a melt index (MI at
• EXACTTM 4033 is an ethylene butene copolymer containing 21.8 wt% butene and having a melt index (MI at 190°C, 2.16 kg ) of 0.8 g/10 min and a density of 0.88 g/cm 3 .
• ENGAGETM 8100 is an ethylene octene copolymer containing 35.5 wt% of octene and having a melt index (MI at 190°C, 2.16 kg ) of 1 g/10 min and a density of 0.87 g/cm 3 .
• ENGAGETM 8200 is an ethylene octene copolymer containing 36.3 wt% of octene and having a melt index (MI at 190°C, 2.16 kg ) of 4.7 g/10 min and a density of 0.87 g/cm 3 .
• MFR ratio is the ratio of the MFR of the ungrafted copolymer to the MFR of the grafted copolymer.
• MA maleic anhydride.
• the polymer and the maleic anhydride were simultaneouysly added to the feed hopper; after melting, the peroxide (Luperox 130) at a 10% concentration in mineral oil was added. Unreacted maleic anhydride and decomposition products of the peroxide are removed with vacuum prior to polymer recovery.
• the individual experiment proportions of maleic anhydride and peroxide are reported in Table 3.
• the characteristics of the grafted polymers are reported in Table 4.
• maleic anhydride (MA) content was measured by FTIR (Fourrier Transformed Infrared Spectroscopy).
• the reaction products are compressed at temperature of 165°C into thin films from which infrared spectra were taken using a Mattson PolarisTM Fourrier Transformed Infrared Spectrometer at 2 cm “1 resolution with the accumulation of 100 scans.
• the relative peak height of the anhydride absorption bond at 1790 cm “1 and of the acid absorption (coming from the anhydride hydrolysis in the air) at 1712 cm “1 compared with a bond at 4328 cm “1 serving as internal standard is taken as a measurement of the MA content.
• %MA (total MA content) k (A1790 + A1712)/A4328, k being determined after internal calibration with a series of standards and having a value of 0.258 in this case.
• the number of unsaturated acid or anhydride molecules per polymer chain is obtained by multiplying the total MA content as measured by FTIR spectroscopy by the number average molecular weight divided by the MA molecular weight as described in equation: [Mn* MA (wt%)] / [ MA(Mw)] wherein the Mn is the number average molecular weight as measured by GPC, MA(wt%) is the weight percent of the maleic anhydride as measured by FTIR spectroscopy and MA(Mw) is the molecular weight of the maleic anhydride.
• Unsaturations (vinylidene, vinyl chain end unsaturation, etc) in polyolefins were measured by proton NMR at 125°C.
• the 100 mg of polymer were dissolved in lcc of trichlorobenzene and 0.2 cc of deuterobenzene.
• the instrument was a VariantTM Unity plus 300 MHz. The following parameters were used: aquisition time: 3 sec, spectral window: 6000 Hz, pulse width: 30°, delay Dl: 5 sec, number of transients: 1024, spinning rate: 17 Hz.
• Table 5 reports the characterization for the four ungrafted polymers.
• the grafted copolymers of this invention achieve a Similar level of grafting with less increase in viscosity versus known polymers. Note that in Figure 1 the copolymers of the invention had a much lower MFR ratio.

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• 1998
  • 1998-03-19 JP JP54583998A patent/JP2001518137A/ja active Pending
  • 1998-03-19 KR KR1019997008587A patent/KR20010005528A/ko not_active Application Discontinuation
  • 1998-03-19 BR BR9808027-0A patent/BR9808027A/pt not_active Application Discontinuation
  • 1998-03-19 AU AU65753/98A patent/AU6575398A/en not_active Abandoned
  • 1998-03-19 WO PCT/US1998/005552 patent/WO1998042760A1/en not_active Application Discontinuation
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