+

WO2001092357A1 - Interpolymere sensiblement aleatoire greffe a un ou a plusieurs monomeres organiques alceniques - Google Patents

Interpolymere sensiblement aleatoire greffe a un ou a plusieurs monomeres organiques alceniques Download PDF

Info

Publication number
WO2001092357A1
WO2001092357A1 PCT/US2001/016934 US0116934W WO0192357A1 WO 2001092357 A1 WO2001092357 A1 WO 2001092357A1 US 0116934 W US0116934 W US 0116934W WO 0192357 A1 WO0192357 A1 WO 0192357A1
Authority
WO
WIPO (PCT)
Prior art keywords
graft
inteφolymer
monomer
ethylene
vinyl
Prior art date
Application number
PCT/US2001/016934
Other languages
English (en)
Inventor
Gabriele Goethel
Michael E. Rowland
Steve R. Betso
Martin J. Guest
Karin Katzer
Ronald Wevers
Thomas T. Allgeuer
Hari P. Reddy
Original Assignee
Dow Global Technologies Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies Inc. filed Critical Dow Global Technologies Inc.
Priority to EP01937723A priority Critical patent/EP1290049A1/fr
Priority to US10/276,087 priority patent/US20030216509A1/en
Priority to BR0111483-2A priority patent/BR0111483A/pt
Priority to JP2002500967A priority patent/JP2003535194A/ja
Priority to AU2001263430A priority patent/AU2001263430A1/en
Publication of WO2001092357A1 publication Critical patent/WO2001092357A1/fr

Links

Classifications

    • 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
    • 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
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent

Definitions

  • This invention relates to graft substantially random mterpolymers which have been grafted with one or more olefinically unsaturated organic monomers .
  • the substantially random mterpolymers comprise polymer units derived from at least one aliphatic olefin monomer having from 2 to 20 carbon atoms and polymer units derived from at least one vinyl or vinylidene aromatic monomer and or from at least one hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer.
  • the invention further relates to blends of such graft interpolymers with one or more olefin or non-olefin polymers, grafted or ungrafted.
  • This invention includes multilayer structures comprising at least one layer of a graft substantially random interpolymer and a composite comprising such interpolymer.
  • the invention also provides applications for the graft substantially random, for example in shaped and fabricated articles, including fibers.
  • the generic class of materials encompassing interpolymers prepared by polymerizing ethylene and/or an alpha-olefin and at least one aromatic or (cyclo)aliphatic vinyl or vinylidene monomer, including such interpolymers which are substantially random interpolymers, are known in the art.
  • substantially random ethylene/styrene interpolymers have been described in EP-A-416815, US-A- 5,703,187 and US-A-5,872,201.
  • US-A-6,015,625 relates to an adhesive resin composition containing at least a partially or wholly graft-modified alpha-olefin/aromatic vinyl compound random copolymer having a graft quantity of an unsaturated carboxylic acid or its derivatives ranging from 0.01 to 30 weight percent.
  • Grafted ethylene/ ⁇ -olefin copolymers are, for example, described in EP-A- 428 510, EP-A-439 079, EP-A-605 952, US-A-4,762,890 and US-A-5,705,565.
  • Polar modified isotactic polypropylenes are also known. Such polar modified polypropylene may be useful as coupling agents in thermoplast-fiberglass composites and as self-adherent coating material for metal surfaces.
  • there is a multitude of other potential uses for such graft polymers which are known to those skilled in the art.
  • Blends of, for example, maleic anhydride grafted olefin homo- and copolymers and polyolefins have been suggested for a broad range of applications, including, for example, food packaging films, especially multilayer films, flooring and carpet systems, or pipe coatings.
  • EP-A-442 950 discloses fibers containing maleic anhydride (MAH) grafted linear polyethylene, preferably MAH-grafted high density polyethylene HDPE g or MAH-grafted linear low density polyethylene (LLDPEg). Owing to their adhesion to performance fibers and wettability thereof, such fibers are reported to be particularly useful in binder fiber applications. As a result of the graft modification, the melt index of the graft polymers is reported to decrease significantly relative to the melt index of the non-grafted starting materials.
  • MAH maleic anhydride
  • LLDPEg MAH-grafted linear low density polyethylene
  • melt index of HDPE is found to decrease by a factor in the range of about 20 to about 70, depending on the graft level.
  • the significant decrease in melt index correlates with a substantial increase in molecular weight.
  • Such increase in molecular weight, e.g. resulting from cross-linking of the polymer, and the concomitant broadening of the molecular weight distribution are undesired side effects of the graft modification of the polymer, which adversely affect its processability during the fiber forming process.
  • conventional grafted polyethylenes as used e.g.
  • PET polyethylene/polyester terephtalate
  • This invention provides a process for the preparation of grafted substantially random interpolymers having new and advantageous properties.
  • This invention provides for the utilization of the grafted substantially random interpolymers in a broad range of applications which benefit from the new and improved performance attributes, e.g. from the improved compatibility or bonding between system components. It is also an object of the present invention to provide a continuous process for interpolymer modification using grafting technology, wherein the interpolymer molecular weight changes little, if at all, as a result of the graft modification.
  • the continuous process provided by the present invention involves the use of high shear and elevated temperatures, such as is encountered using extrusion technology.
  • the present invention pertains to novel graft polymers with a backbone of one or more substantially random interpolymers as defined hereinbelow, the polymer backbone being grafted with at least one olefinically unsaturated organic monomer.
  • the present invention pertains to a graft interpolymer comprising: ( 1 ) polymer units derived from; (a) at least one vinyl or vinylidene aromatic monomer, or
  • the interpolymer backbone is grafted with at least one olefinically unsaturated organic monomer.
  • the graft polymer is a graft substantially random interpolymer with a graft-modified backbone of one substantially random interpolymer.
  • the invention further relates to blends of the novel graft polymers with at least one other olefin or non-olefin polymer, which itself can be grafted or non-grafted.
  • the invention also relates to melt processing techniques to produce the graft polymer, especially a reactive extrusion process, and hot melt grafting processes to produce these novel graft interpolymers.
  • One embodiment of the present invention relates to a multilayer composite wherein at least one of the layers is composed of a graft interpolymer provided by the present invention, or a polymer blend comprising such graft interpolymer.
  • Another embodiment of the present invention pertains to fibers comprising graft substantially random interpolymer according to the invention, including fibers made of blends of the graft substantially random interpolymer with a polyolefin, and fabrics made from such fibers.
  • the amount of a component or a value of a process variable such as, for example, temperature, pressure, time and the like is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70
  • values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc. are expressly enumerated in this specification.
  • one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate.
  • copolymer as employed herein means a polymer wherein at at least two different monomers are polymerized to form the copolymer.
  • interpolymer is used herein to indicate a polymer wherein at least two different monomers are polymerized to make the interpolymer. This includes copolymers, terpolymers, etc.
  • reactive extrusion refers to the performance of chemical reactions during continuous extrusion of polymers and/or polymerizable monomers.
  • the reactants must be in a physical form suitable for extrusion processing. Reactions may be performed on molten polymers, on liquified monomers, or on polymers dissolved or suspended in or plasticized by solvent.
  • Reactive extrusion refers to the performance of chemical reactions in a continuous extrusion process with short residence times. Detailed teachings relating to reactive extrusion are, for example, provided in "Reactive Extrusion - Principles and Practice" edited by M. Xanthos, Carl Hanser Verlag, Kunststoff, Vienna, New York, Barcelona, 1992.
  • compositions "derived from” specified materials may be simple mixtures of the original materials, and may also include the reaction products of those materials, or may even be wholly composed of reaction or decomposition products of the original materials. This includes, but is not limited to, those products "derived from” the grafted organic monomer or organic acid monomer.
  • the acid moiety can, in the process of production, extrusion or fabrication, undergo one or more chemical reactions that might alter its structure. Specifically, the free carboxylic acid group can undergo reactions and be converted to an ester, or an anhydride, or acid salt.
  • the anhydride when starting with the anhydride moiety, can be converted to the free acid or an ester or an acid salt.
  • the anhydride readily recognizes that these are common occurrences when thermally treating and handling organic acid grafted polymers.
  • a maleic anhydride moiety can exist as the original anhydride, the free maleic acid, an ester or a metal salt formed through the reaction with another component in the polymeric composition and understand that all these structures are included in this invention.
  • the term "comprising as used herein means "including”. All parts and percentages are by weight unless indicated otherwise.
  • substantially random as used herein in reference to a substantially random interpolymer comprising polymer units derived from ethylene and/or one or more -olefin monomers and polymer units derived from one or more vinyl or vinylidene aromatic monomers and/or aliphatic or cycloaliphatic vinyl or vinylidene monomers, and to ethylene/styrene interpolymers in particular, means that the distribution of the monomers of said interpolymer can be generally described by the Bernoulli statistical model or by a first or second order Markovian statistical model, as described by J. C. Randall in POLYMER SEQUENCE DETERMINATION. Carbon-13 NMR Method, Academic Press New York, 1977, pp. 71-78.
  • substantially random interpolymers do not contain more than 15 percent of the total amount of vinyl or vinylidene aromatic monomer in blocks of vinyl or vinylidene aromatic monomer of more than 3 units. More preferably, the interpolymer is not characterized by a high degree (greater than 50 mole percent) of either isotacticity or syndiotacticity. This means that in the carbon-13 NMR spectrum of the substantially random interpolymer the peak areas corresponding to the main chain methylene and methine carbons representing either meso diad sequences or racemic diad sequences should not exceed 75 percent of the total peak area of the main chain methylene and methine carbons.
  • fiber is used in a general sense and includes, without limitation, monofilaments, referring to individual strands of denier greater than 15, typically grater than 30; fine denier fibers or filaments, referring to strands of denier less than 15; multi-filaments, referring to simultaneously formed fine denier filaments spun in a bundle of fibers, generally containing at least 3 up to several thousand filaments; staple fibers, referring to fine denier strands which have been formed at, or cut to, staple lengths of typically 2.
  • fibrils referring to super fine discrete filaments embedded in a more or less continuous matrix
  • multi-constituent fibers such as bi-constituent fibers, referring to fibers comprising at least two polymers in continuous and/or dispersed phases
  • multicomponent fibers such as bicomponent fibers, referring to a fiber comprising two or more polymer components, each in a continuous phase, e.g. side by side or in a sheath/core arrangement.
  • the interpolymers used to prepare the novel graft interpolymers of the present invention include the substantially random interpolymers prepared by polymerizing i) ethylene and or one or more ⁇ -olefin monomers and ii) one or more vinyl or vinylidene aromatic monomers and/or one or more sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers, and optionally iii) other polymerizable ethylenically unsaturated monomer(s).
  • Suitable ⁇ -olefins include, for example, ⁇ -olefins containing from 3 to about 20, preferably from 3 to about 12, more preferably from 3 to about 8 carbon atoms.
  • ⁇ -olefins do not contain an aromatic moiety.
  • Suitable vinyl or vinylidene aromatic monomers which can be employed to prepare the interpolymers include, for example, those represented by the following formula:
  • R 1 - C C(R 2 ) 2
  • R 1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to about 4 carbon atoms, preferably hydrogen or methyl
  • each R is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to about 4 carbon atoms, preferably hydrogen or methyl
  • Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C 1- -alkyl, and C 1- -haloalkyl
  • n has a value from zero to about 4, preferably from zero to 2, most preferably zero.
  • Exemplary vinyl aromatic monomers include styrene, vinyl toluene, ⁇ -methylstyrene, t-butyl styrene, chlorostyrene, including all isomers of these compounds, and the like. Particularly suitable such monomers include styrene and lower alkyl- or halogen-substituted derivatives thereof.
  • Preferred monomers include styrene, ⁇ - mefhyl styrene, the lower alkyl- ( - C 4 ) or phenyl-ring substituted derivatives of styrene, such as for example, ortho-, meta-, and para-methylstyrene, the ring halogenated styrenes, para- vinyl toluene or mixtures thereof, and the like.
  • the most preferred aromatic vinyl monomer is styrene.
  • Suitable "hindered" aliphatic or cycloaliphatic vinyl or vinylidene monomers are addition polymerizable vinyl or vinylidene monomers corresponding to the formula:
  • R 1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to about 4 carbon atoms, preferably hydrogen or methyl; each R is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to about 4 carbon atoms, preferably hydrogen or methyl; or alternatively R and A together form a ring system.
  • hindered denotes that the monomer bearing this substituent is normally incapable of addition polymerization by standard Ziegler-Natta polymerization catalysts at a rate comparable with ethylene polymerizations.
  • Aliphatic ⁇ -olefins having a simple linear structure including, for example, propylene, butene-1, 4-methyl-l-pentene, hexene-1 or octene-1 are not considered as hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers.
  • Preferred aliphatic or cycloaliphatic vinyl or vinylidene compounds are monomers in which one of the carbon atoms bearing ethylenic unsaturation is tertiary or quaternary substituted.
  • substituents include cyclic aliphatic groups such as cyclohexyl, cyclohexenyl, cyclooctenyl, or ring alkyl or aryl substituted derivatives thereof, tert-butyl, norbornyl, and the like.
  • Most preferred aliphatic or cycloaliphatic vinyl or vinylidene compounds are the various isomeric vinyl- ring substituted derivatives of cyclohexene and substituted cyclohexenes, and 5-ethylidene-2-norbornene. Especially suitable are 1-, 3-, and 4- vinylcyclohexene.
  • the substantially random interpolymer contains a vinyl or vinylidene aromatic monomer and a sterically hindered aliphatic or cycloaliphatic monomer in polymerized form, the weight ratio between these two monomer types is not critical.
  • the interpolymer comprises polymer units derived from either one or more vinyl or vinylidene aromatic monomers, or one or more hindered aliphatic or cycloaliphatic monomers. Vinyl or vinylidene aromatic monomers are preferred over hindered aliphatic or cycloaliphatic monomers.
  • Optional other polymerizable ethylenically unsaturated monomers include strained ring olefins such as norbornene and C1-C10 alkyl or C 6 -CIQ aryl substituted norbornenes.
  • one or more dienes can optionally be incorporated into the interpolymer to provide functional sites of unsaturation on the interpolymer useful, for example, to participate in crosslinking reactions. While conjugated dienes such as butadiene, 1,3-pentadiene (that is, piperylene), or isoprene may be used for this purpose, nonconjugated dienes are preferred.
  • Typical nonconjugated dienes include, for example the open-chain nonconjugated diolefins such as 1,4-hexadiene (see U.S. Patent No. 2,933,480), 1,9-decadiene and 7-methyl-l,6- octadiene (also known as MOCD); cyclic dienes; bridged ring cyclic dienes, such as dicyclopentadiene (see U.S. Patent No. 3,211,709); or alkylidene-norbornenes, such as methylenenorbornene or ethylidenenorbornene (see U.S. Patent No. 3,151,173).
  • open-chain nonconjugated diolefins such as 1,4-hexadiene (see U.S. Patent No. 2,933,480), 1,9-decadiene and 7-methyl-l,6- octadiene (also known as MOCD); cyclic dienes; bridged ring cyclic
  • the nonconjugated dienes are not limited to those having only two double bonds, but rather also include those having three or more double bonds.
  • the diene may be incorporated in the substantially random interpolymer in an amount of from 0 to 15 weight percent based on the total weight of the interpolymer.
  • the substantially random interpolymers include the pseudo-random interpolymers as described in EP-A-0,416,815 by James C. Stevens et al. and in US Patent No. 5,703,187 by Francis J. Timmers, both of which are incorporated herein by reference in their entirety.
  • the substantially random interpolymers also include the interpolymers of ethylene, one or more alpha-olefin monomers and at least one vinyl or vinylidene aromatic monomer as described in US Patent No. 5,872,201 by Yunwa W. Cheung et al, which is incorporated herein by reference in its entirety.
  • interpolymers may be prepared that incorporate relatively bulky or hindered monomers in substantially random manner at low concentrations, and at higher concentrations according to an ordered insertion logic.
  • the copolymers of ethylene or ⁇ - olefins and a hindered aliphatic vinyl or vinylidene monomer or a vinyl or vinylidene aromatic monomer are preferably described as "pseudo-random". That is, the interpolymers lack well defined blocks of either monomer, however, the respective monomers are limited to insertion according to certain rules. These rules can be deduced from certain experimental details resulting from an analysis of the interpolymers, e.g.
  • the polymers were analyzed by 13 C-NMR spectroscopy at 130°C with a Varian VXR-300 spectrometer at 75.4 MHz.
  • Samples of 200 to 250 mg of interpolymer were dissolved in 15 ml of hot o-dichlorobenzene/ 1,1,2,2- tetrachloroethane-d 2 (approximately 70/30, v/v) which was approximately 0.05 M in chromium (ID) tris(acetylacetonate)) and a portion of the resulting solution was added to a 10 mm NMR tube.
  • ID chromium
  • spectral width 16,500 Hz
  • acquisition time 0.090 s
  • pulse width 36°
  • delay 1.0 s with the decoupler gated off during the delay
  • FT size 32K
  • number of scans > 30,000
  • line broadening 3 Hz.
  • Spectra, as recorded were referenced to tetrachloroethane-d 2 ( ⁇ 73.77 ppm, TMS scale). Therefore, without wishing to be bound by any particular theory, the results of the foregoing experimental procedures indicate that a particular distinguishing feature of pseudorandom copolymers is the fact that all phenyl or bulky hindering groups substituted on the polymer backbone are separated by 2 or more methylene units.
  • the catalysts used in this invention do not homopolymerize styrene to any appreciable extent, while a mixture of ethylene and styrene is rapidly polymerized and may give high styrene content (typically up to about 65 mole % styrene) copolymers.
  • the substantially random interpolymers can be prepared by polymerizing a mixture of polymerizable monomers in the presence of one or more metallocene or constrained geometry catalysts in combination with various cocatalysts.
  • Preferred operating conditions for such polymerization reactions are pressures from atmospheric up to 3000 atmospheres and temperatures from -30°C to 200°C.
  • substantially random ⁇ -olefin/vinyl aromatic interpolymers can also be prepared by the methods described in JP 07/278230 employing compounds shown by the general formula
  • Cp and Cp are cyclopentadienyl groups, indenyl groups, fluorenyl groups, or substituents of these, independently of each other;
  • R 1 and R 2 are hydrogen atoms, halogen atoms, hydrocarbon groups with carbon numbers of 1-12, alkoxyl groups, or aryloxyl groups, independently of each other;
  • M is a group IV metal, preferably Zr or Hf, most preferably Zr; and R is an alkylene group or silanediyl group used to cross-link Cp and Cp .
  • the substantially random ⁇ -olefin/vinyl aromatic interpolymers can also be prepared by the methods described by John G. Bradfute et al. (W. R. Grace & Co.) in WO 95/32095; by R. B. Pannell (Exxon Chemical Patents, Inc.) in WO 94/00500; and in Plastics Technology, p. 25 (September 1992), all of which are incorporated herein by reference in their entirety. Also suitable are the substantially random interpolymers which comprise at least one ⁇ -olefin/vinyl aromatic/vinyl aromatic/ ⁇ -olefin tetrad disclosed in WO-A-98/09999 by Francis J. Timmers et al.
  • interpolymers contain additional signals in their carbon-13 NMR spectra with intensities greater than three times the peak to peak noise. These signals appear in the chemical shift range 43.70 - 44.25 ppm and 38.0 - 38.5 ppm. Specifically, major peaks are observed at 44.1, 43.9, and 38.2 ppm.
  • a proton test NMR experiment indicates that the signals in the chemical shift region 43.70 - 44.25 ppm are methine carbons and the signals in the region 38.0 - 38.5 ppm are methylene carbons. It is believed that these new signals are due to sequences involving two head-to-tail vinyl aromatic monomer insertions preceded and followed by at least one ⁇ -olefin insertion, e.g.
  • each R is independently, each occurrence, H, hydrocarbyl, silahydrocarbyl, or hydrocarbylsilyl, containing up to about 30 preferably from 1 to about 20 more preferably from 1 to about 10 carbon or silicon atoms or two R groups together form a divalent derivative of such group.
  • R independently each occurrence is (including where appropriate all isomers) hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl or silyl or
  • two such R groups are linked together forming a fused ring system such as indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, or octahydrofluorenyl.
  • catalysts include, for example, racemic-(dimethylsilanediyl)-bis- (2-methyl-4-phenylindenyl) zirconium dichloride, racemic-(dimethylsilanediyl)-bis-(2-methyl- 4-phenylindenyl) zirconium l,4-diphenyl-l,3-butadiene, racemic-(dimethylsilanediyl)-bis-(2- methyl-4-phenylindenyl) zirconium di-Cl-4 alkyl, racemic-(dimethylsilanediyl)-bis-(2-methyl- 4-phenylindenyl) zirconium di-Cl-4 alkoxide, or any combination thereof and the like. It is also possible to use the following titanium-based constrained geometry catalysts,
  • an amount of atactic vinyl aromatic homopolymer may be formed due to homopolymerization of the vinyl aromatic monomer at elevated temperatures.
  • the presence of vinyl aromatic homopolymer is, in general, not detrimental for the purposes of the present invention and can be tolerated.
  • the vinyl aromatic homopolymer may be separated from the intei-polymer, if desired, by extraction techniques such as selective precipitation from solution with a non solvent for either the inte olymer or the vinyl aromatic homopolymer.
  • a preferred graft substantially random interpolymer comprises the backbone of one or more, preferably one, substantially random interpolymer comprising
  • a graft polymer according to the present invention comprises, preferably consists essentially of, the graft-modified backbone of one substantially random interpolymer having a melt index ( I 2 ) of at least 0.01, preferably in the range of from aboutO.Ol to about 1000, more preferably from about 0.01 to about 50 g/10 min, and a molecular weight distribution (as reflected in the ratio of the weight average molecular weight and the number average molecular weight; M w M n ) of from about 1.5 to about 20, comprising ( 1 ) polymer units derived from
  • melt index of the graft- modified substantially random interpolymer is selected such that said interpolymer meets the needs of the desired end use application. Such selection is routine for the person skilled in the art.
  • the melt index (I 2 ) is determined by ASTM D-1238, condition 190°C/2.16 kg.
  • a further preferred graft polymer according to the invention comprises a backbone of a one or more, preferably one, substantially random interpolymers having an I 2 of about 0.01 to about 50 g/10 min, an Mw M n of about 1.5 to about 20, comprising
  • graft polymers according to the invention are those, wherein said graft-modified substantially random interpolymer has an M w /M n of about 1.5 to about 20 and comprises
  • R 1 - C CH 2
  • Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C ⁇ . 4-alkyl, and C 1-4 -haloalkyl, or (b) a hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer is represented by the following general formula
  • a 1 I R 1 - C C(R 2 ) 2
  • a 1 is a sterically bulky, aliphatic or cyclophatic substituent of up to 20 carbons
  • R is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to about 4 carbon atoms, preferably hydrogen or methyl
  • each R is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl, or alternatively R and A together from a ring system, or
  • a further preferred embodiment of the present invention is a graft polymer wherein said substantially random interpolymer has an Mw/M n from about 1.8 to about 20 and comprises
  • said vinyl or vinylidene aromatic monomer which comprises styrene, ⁇ - ethyl styrene, ortho-, meta-, and para-methylstyrene, and the ring halogenated styrenes, or
  • said aliphatic or cycloaliphatic vinyl or vinylidene monomers which comprises 5-ethylidene-2-norbornene or 1-vinylcyclo-hexene, 3-vinylcyclo-hexene, and 4-vinylcyclohexene, or (c) a combination of a and b, and
  • said ethylenically unsaturated polymerizable monomers other than those derived from (1) and (2) is norbornene.
  • the most preferred graft polymers according to the invention are those, wherein the graft-modified backbone is a substantially random interpolymer comprising one or more vinyl aromatic monomers in combination with ethylene or a combination of ethylene and one or more C 3 - Cs alpha olefin monomers, or a combination of ethylene and norbornene.
  • Such interpolymers include the substantially random interpolymers selected from the group consisting of ethylene/styrene, ethylene/propylene/styrene, ethylene/butene/styrene, ethylene/pentene/styrene, ethylene/hexene/styrene, or ethylene/octene/styrene.
  • one or more of the substantially random interpolymers are chemically modified, with an olefinically unsaturated monomer, e.g. a vinyl- containing reactive monomer, or a mixture of such monomers, preferably in a free-radical grafting reaction.
  • an olefinically unsaturated monomer e.g. a vinyl- containing reactive monomer, or a mixture of such monomers, preferably in a free-radical grafting reaction.
  • the graft-modification introduces (additional) functional groups on the interpolymer backbone.
  • olefinically unsaturated organic monomers that contain at least one carbonyl group are organic carboxylic acids, including monocarboxylic acids and dicarboxylic acids, their anhydrides, esters and salts, both metallic and nonmetallic.
  • the olefinically unsaturated organic monomer is characterized by at least one ethylenic unsaturation conjugated with a carbonyl group.
  • Preferred organic monomers include maleic acid , fumaric acid , acrylic acid , methacrylic acid, itaconic acid, crotonic acid, alpha-methyl crotonic acid and cinnamic acid and their anhydride, ester and salt derivatives.
  • Acrylic acid, maleic acid and maleic anhydride are the more preferred olefinically unsaturated organic monomers containing at least one ethylenic unsaturation and at least one carbonyl group, maleic anhydride being the most preferred monomer.
  • an especially preferred interpolymer of the invention is a maleic anhydride (MAH) grafted ethylene/styrene interpolymer or a maleic anhydride grafted ethylene/C 3 -C 8 alpha-olefin/styrene interpolymer.
  • MAH maleic anhydride
  • a peroxide or other free radical initiator is used to accelerate the grafting.
  • Suitable peroxides include, but are not limited to, aromatic diacyl peroxides; aliphatic diacyl peroxides; dibasic acid peroxides; ketone peroxides; alkyl peroxyesters; alkyl hydroperoxides; alkyl and dialkyl peroxides, such as diacetylperoxide, 2,5-bis (t-butylperoxy)- 2,5-dimethylhexane or 2,5-dimethyl-2,5di(t-butylperoxy)hexyne-3.
  • Grafting of the substantially random interpolymer backbone with the olefinically unsaturated organic monomer can be achieved reactive extrusion in the melt, by reaction with the solid state polymer, or in solutio.
  • the methods as described in US Patents 3,236,917; 4,762,890 and 5,194,509 are incorporated herein by reference.
  • the grafting reaction is free radical initiated, the free radicals being generated by UV, chemical or other techniques. Details of the grafting reaction are given in the above US Patents, which are relied upon for further teaching.
  • the grafting process may also be a solid phase grafting process.
  • the polymer is introduced into a two-roll mixer and mixed at a temperature of 60°C.
  • the unsaturated organic compound is then added along with a free radical initiator, such as, for example, benzoyl peroxide, and the components are mixed at 30°C until the grafting is completed.
  • a free radical initiator such as, for example, benzoyl peroxide
  • the procedure is similar except that the reaction temperature is higher, e.g. 210 to 300°C, and a free radical initiator is not used or is used at a reduced concentration.
  • the substantially random interpolymer and the olefinically unsaturated organic monomer are mixed and reacted within at suitable device, e.g. an extruder, such as a twin-screw devolatilizing extruder, at temperatures at which the reactants are molten or in liquid form and in the presence of a free radical initiator.
  • suitable device e.g. an extruder, such as a twin-screw devolatilizing extruder
  • the unsaturated organic monomer may be mixed and dissolved in a non-reactive solvent known in the art.
  • the unsaturated organic monomer is injected into a zone maintained under pressure within the extruder.
  • the graft polymers according to the invention are prepared by melt processing technology, especially in the temperature range of about 50°C to about 300°C.
  • This melt processing technology can be a batch-wise or a continuous melt processing technology.
  • a reactive extrusion technology is used. Graft interpolymers which are prepared by the above melt processing techniques are therefore preferred subjects of the present invention.
  • the substantially random graft interpolymers of the present invention are surprisingly found not to change, or not to change significantly, in molecular weight or molecular weight distribution upon or following their reactive extrusion or melt processing transformation.
  • the relative stability of the interpolymer molecular weight, as compared, e.g., to analogously grafted HDPE or LLDPE polymers, is reflected, for example, in the substantially unchanged melt index of the substantially random graft interpolymer.
  • the melt index of the resulting graft interpolymer remains substantially the same or, if at all, decreases only relatively slightly (depending on the graft content of the interpolymer).
  • the grafting process and conditions are selected and controlled such that the functional groups are introduced into the interpolymer via reaction with the olefinically unsaturated monomer without any or at least without any significant degree of crosslinking or scission of the polymer backbone.
  • the grafting process may induce changes in the molecular weight and molecular weight distribution of the grafted interpolymer.
  • changes in the molecular weight and molecular weight distribution of the grafted interpolymer One skilled in the art readily recognizes if these changes affect the desired performance of the grafted interpolymer and react accordingly.
  • it is advantageous and preferred in the present invention that no significant change in molecular weight of the interpolymer occurs as a result of the graft process there are some circumstances when change in molecular weight is useful for the desired application. Graft interpolymers which change molecular weight during the grafting process are therefore also the subject of this invention.
  • a preferred process for preparing the substantially random graft interpolymers according to the invention is a reactive extrusion process which satisfies the following conditions:
  • Equipment Any single or multiple screw, e.g. twin screw, extruder or any melting/hot melting mixing device capable of allowing the temperature and time (duration) of the process to be controlled and capable of allowing the addition of solid or liquid components as desired.
  • Temperature The temperature of the process must at some point be such that it is greater than the melting point of the interpolymer; or, if the interpolymer is amorphous, some temperature such that the interpolymer can be processed easily and without shear degradation on the equipment used.
  • the temperature of the process must be such that it is above the initiation-temperature of the peroxide being used, but not so high that total decomposition of peroxide occurs before it is sufficiently mixed with the other components.
  • the duration of the process should be such that it allows sufficient melt-mixing of all the reaction components, and greater than the time required to allow for 90-99% complete decomposition of the peroxide being used (this time can be calculated from the half-life characteristics of the peroxide being employed).
  • This time can be calculated from the half-life characteristics of the peroxide being employed.
  • the components added in the reactive extrusion process can be added in any of the following three ways: (1) the three components are added separately, with the substantially random interpolymer being added first, then the vinyl acid (VA), i.e. the olefinically unsaturated monomer, and finally the peroxide (ROOR); (2) the interpolymer is added first, then a mixture of the peroxide and the vinyl acid; and (3) all three components can be added together.
  • VA vinyl acid
  • ROOR peroxide
  • interpolymer denotes any substantially random interpolymers as defined herein, preferably those designated as prefen-ed, e.g. ethylene/styrene interpolymer, ethylene/alpha-olefin/styrene interpolymer, blends of substantially random interpolymers, e.g. blends of ethylene/styrene interpolymers with ethylene/ ⁇ -olefin copolymers.
  • This also comprises hydrogenated and partially hydrogenated random styrene/butadiene (SB) rubbers.
  • Vinyl acid includes, for example, any substituted or non- substituted, carboxylic acid or ester moiety containing a polymerizable double bond. This comprises, but is not limited to maleic acid or ester, fumaric acid or ester, and the like.
  • Peroxide is meant to encompass any organoperoxide compound. This comprises, but is not limited to, dicumyl peroxide, benzoyl peroxide, and the like.
  • any free radical initiator can be employed, such as an azocompound.
  • grafted interpolymers of the invention Since, using the preferred process for the preparation of the grafted interpolymers of the invention, products can be obtained, that show improved strength, appearance and other beneficial properties, e.g. those mentioned above, a substantially random graft interpolymer which is produced by a hot melting process, and especially a reactive extrusion process, is another subject of the present invention (including polymer compositions comprising such interpolymer).
  • the present invention also relates to a graft polymer composition
  • a graft polymer composition comprising the reaction product of a (backbone) substantially random interpolymer and an olefinically unsaturated organic monomer, for example maleic acid or maleic acid anhydride, in the presence of a free radical initiator, preferably a peroxide, characterized in that the reaction product contains more than about 0.1 weight percent, preferably more than about 0.5 weight percent to about 2 weight percent or more of the organic monomer (in covalently bonded form) along the interpolymer backbone, for example as succinic acid or succinic acid groups.
  • the novel substantially random graft interpolymers of the invention are used as compatibilizers for filled resinous products.
  • fillers e.g., silica, talc, glass, clay, carbon black, and the like, e.g. to enhance strength and or provide for another desirable property.
  • these fillers are only marginally compatible with the resinous matrix within which they are incorporated and as such, the amount of filler which can be incorporated into the matrix, i.e., the loading level, is limited.
  • Compatibilizers are used to coat or otherwise treat the filler to render it more compatible with the matrix, and thus allow a high loading to be achieved.
  • the graft-modified substantially random interpolymers of this invention are particularly desirable compatibilizers because higher loading levels can be achieved, i.e.
  • the compatibilizers of this invention impart desirable properties to the composition in both fabricated and pre-fabricated form.
  • the strength and impact properties are enhanced relative to fabricated compositions void of grafted substantially random polymer.
  • pre-fabricated form for example pellet, sheet, uncured packaging etc.
  • the processability of the compositions by batch or continuous methods is enhanced relative to compositions void of grafted substantially random polymer of the invention.
  • the graft interpolymer of the invention can also be used as a chemical coupling agent for thermoplast-fiberglass composites as a result of its improved adhesive properties to polar polymers or as self adherent polymeric coating material.
  • Such coating material can be applied, for example, to metal or other surfaces; another possibility is its use as primer component or as hot melt adhesive.
  • grafted substantially random interpolymers of the present invention are useful include, but are not limited to: flooring systems, for example to improve filler bonding and durability; carpet structures, for example to provide improved bonding between components such as fibers based on polyethylene terephthalate, polyamide and polypropylene, improved bonding to substrates and in the event of recycling, improved compatibility between carpet components; construction, including glazing systems, as a concrete additive, wall covering etc.; wire and cable systems, particularly those including fillers; multilayer container and film structures, and particularly those which impart a controlled atmosphere to packaged goods and food products, e.g.
  • film structures including polar polymer such as ethylene/vinyl acetate, ethylene/vinyl alcohol, ethylene/acrylate, polyamides and poly vinylidene chloride homo- or co-polymers; paintable/printable polyolefin structures such as films, sheets and molded articles; laminated structures for fluid containment such as fuel tanks and piping systems; polymer bound additives; bitumen compositions; laminated structures including a scrim material such as nylon or PET for e.g.
  • the interpolymers according to the present invention are further particularly useful in blends with one or more olefin or non-olefin polymers, which themselves may be grafted or non-grafted.
  • olefin or non-olefin polymers which themselves may be grafted or non-grafted.
  • examples for such polymers are nylon, polycarbonate, polyethylene and copolymers, polypropylene and copolymers, polystyrene and styrenic copolymers, SB- and other rubbers, etc.
  • the graft-modified substantially random interpolymer is dry blended or melt blended with another thermoplastic polymer, and then molded or extruded into a shaped article.
  • thermoplastic polymers include any polymer with which the grafted substantially random polymer is compatible, and include both olefins and non-olefin polymers, grafted and ungrafted.
  • examples of such polymers include high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra low density polyethylene (ULDPE), polypropylene, ethylene-propylene copolymer, ethylene-styrene copolymer, polyisobutylene, ethylene-propylene, thylene-propylene-diene monomer (EPDM) copolymer, polystyrene, styrene-acrylonitrile (SAN) colopymer, styrene-maleic anhydride (SMA) copolymer, acrylonitrile-butadiene-styrene (ABS) copolymer, ethylene/acrylic acid
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • EAA ethylene/vinyl acetate
  • EVA ethylene/vinyl alcohol
  • EPCO propylene and carbon monoxide
  • ECOAA acrylic acid
  • non-olefin polymers are the polyesters, polyvinyl chloride (PVC), epoxides, polyurethanes, polycarbonates, polyamides, and the like.
  • Suitable polyamides which can be employed herein include those prepared both by condensation and ring opening polymerization. These are often given the common name Nylon.
  • Suitable materials include, for example, nylon 6, nylon 11, and nylon 12.
  • Polyamides are also prepared by condensation methods, such as the reaction between a diamine and a diacid (or diacid derivative). The structure of materials prepared by this method are designated numerically with the number of carbons between the nitrogen atoms from the diamine portion followed by the number of carbon atoms in the diacid portion.
  • the polymer prepared from 1,6-diamino hexane and adipic acid is described as polyamide 66 or nylon 66.
  • Condensation polyamides include, for example, polyamides 46, 66, 69, 610, and 612. Blends of polyamides and MAH-grafted substantially random interpolymers provide particularly advantageous performance properties.
  • Blends of substantially random graft interpolymers of the present invention with other polymers preferably comprise from about 0.1 to about 99.9 weight percent of one or more additional polymeric component, based on the total weight of the composition, Preferred additional polymeric components are polyethylene homopolymer or copolymers or polypropylene homopolymer or copolymers, and polyamides, e.g. nylons.
  • the blends of this invention also include those composite systems comprising at least two dissimilar polymers in combination with one or more substantially random graft interpolymers, and in which the substantially random graft interpolymers act as a compatibilizer.
  • Such multicomponent systems employ the substantially random graft interpolymers preferably in amounts of from about 2 to about 30 weight percent.
  • Such blends can also be advantageously used for packaging purposes including food and industrial packaging and other uses taking advantage of the improved properties of the polymer blends, such uses being well known to one skilled in the art.
  • the graft substantially random interpolymers or blends of such graft interpolymers according to the present invention are further particularly useful in compositions with one or more fillers, e.g. compositions containing up to 95 weight percent of one or more fillers.
  • Many molded and extruded products contain fillers, e.g., silica, talc, glass, clay, carbon black, and the like, e.g. to enhance strength and/or provide for another desirable property.
  • the graft- modified substantially random interpolymers of this invention are particularly desirable components of composite systems, imparting desirable properties to the composition in both fabricated and pre-fabricated form, by providing enhanced bonding between the fillers and the polymer matrix comprising the graft-modified substantially random interpolymers.
  • fillers examples include glass, glass fibers, talc, calcium carbonate, clay, carbon black, marble dust, cement dust, feldspar, silica, fumed silica, silicates, alumina, magnesium, oxide, antimony oxide, zinc oxide, barium sulfate, aluminium silicate, calcium silicate, titanium oxides, glass microspheres, mica, clays, wollastaone and chalk, magnesium hydroxide, calcium hydroxide and aluminum trihydrate and the like.
  • Compositions of graft inte ⁇ olymers or blends of inte ⁇ olymers of the present invention with fillers and especially with fillers in an amount of 10 to 90 percent by weight of the composition are a further subject of the present invention.
  • Still a further subject of the present invention are multilayer composites containing at least one layer of the graft substantially random inte ⁇ olymer or a blend of inte ⁇ olymers of the present invention.
  • the graft inte ⁇ olymer of the present provides enhanced adhesion or compatibility between the different layers of the multilayer structure.
  • layers of polyethylene with layers of polar materials, as for example nylon or ethylene vinyl alcohol, using an intermediate layer of a graft polymer according to the invention.
  • the graft polymer combines properties of polar and nonpolar polymers and, hence, allows formation of an improved performance film or multilayer structures.
  • the materials of the present invention may contain one or more additives, for example, antioxidants (e.g.
  • hindered phenols such as, for example, Irganox 1010, a registered trademark of Ciba Geigy), phosphites (e.g., LgafosTM 168 a registered trademark of Ciba Geigy), U.V.
  • additives e.g., light stabilizers, such as hindered amines; plasticizers, such as dioctylphthalate or epoxidized soy bean oil; thermal stabilizers; mold release agents tackifiers, such as hydrocarbon tackifiers; waxes, such as polyethylene waxes; processing aids, such as oils, organic acids such as stearic acid, metal salts of organic acids; crosslinking agents, such as peroxides or silanes; colorants or pigments to the extent that they do not interfere with the desired physical or mechanical properties of the compositions of the present invention.
  • the above additives are employed in functionally equivalent amounts known to those skilled in the art, generally in amounts of up to about 30, preferably from about 0.01 to about 5, more preferably from about 0.02 to about 1 percent by weight, based upon the total weight of the composition.
  • the graft polymers, blends of polymers or multilayer composites of the present invention can be processed to fabricated articles by any suitable means known in the art.
  • they can be processed to films or sheets or to one or more layers of a multilayered structure by known processes, such as calendering, blowing, casting or extrusion including co- extrusion processes.
  • Injection molded, compression molded, extruded or blow molded parts can also be prepared from the compositions of the present invention.
  • the compositions can be processed to foams or fibers.
  • Useful temperatures for processing the inte ⁇ olymer(s) in combination with the filler(s) and optional additives to the fabricated articles generally are 100°C to 300°C, preferably from 120°C to 250°C, more preferably from 140°C to 200°C.
  • Such fabricated articles of the present invention may also be foamed.
  • the foam layer may be produced by an extrusion process or from expandable or foamable particles, moldable foam particles, or beads from which a sheet is formed by expansion and/or coalescing and welding of those particles.
  • Various additives may be inco ⁇ orated in the foam structure, such as stability control agents, nucleating agents, pigments, antioxidants, acid scavengers, ultraviolet absorbers, flame retardants, processing aids or extrusion aids. Some of the additives are described in more detail above.
  • the grafted inte ⁇ olymers and grafted inte ⁇ olymer blends and compositions, in the present invention may be crosslinked chemically or with radiation.
  • Suitable free radical crosslinking agents include organic peroxides such as dicumyl peroxide, hydrolyzed silanes, organic azides, or a combination thereof.
  • the grafted inte ⁇ olymer or inte ⁇ olymer blend or composition may be crosslinked via a process of the separate grafting of a silane moiety to the backbone followed by hydrolysis of the silane to form crosslinks between adjacent polymer chains via siloxane linkages.
  • the graft polymers or blends of polymers of the present invention can readily be coated, extruded, or layered onto a substrate.
  • Typical substrates include glass, metal, ceramic, wood, polymer-based materials, natural fibers, matting, and mixtures thereof.
  • the materials of the present invention can be extruded, milled, or calendered as unsupported films or sheets, for example for producing floor tiles, wall tiles, floor sheeting, wall coverings, or ceiling coverings. They are particularly useful as sound insulating or energy absorbing layers, films, sheets or boards. Films, sheets or boards of a wide thickness range can be produced. Depending on the intended end-use, useful thicknesses generally are from 0.5 to 20 mm, preferably from 1 to 10 mm.
  • injection molded parts or blow molded articles such as toys, containers, building and construction materials, automotive components, and other durable goods can be produced from the compositions of the present invention.
  • fibers comprising the novel graft substantially random inte ⁇ olymers particularly benefit from the improved properties of such inte ⁇ olymers, e.g. by means of improved processability and higher productivity in the fiber fo ⁇ riing processes, e.g. in the fiber spinning process (as compared to conventional fibers comprising graft polyolefin instead of graft substantially random inte ⁇ olymer).
  • Advantageously used in fibers are such graft substantially random inte ⁇ olymers which show no or only minimal levels of cross- linked or higher molecular weight inte ⁇ olymer as a result of the graft modification.
  • Such inte ⁇ olymers are characterized in that their melt index does not significantly change (decrease) as a result of the graft modification.
  • the present invention provides fibers comprising the above defined graft substantially random inte ⁇ olymers, in particular those indicated as being preferred.
  • fibers comprising such substantially random inte ⁇ olymers grafted with an ethylenically unsaturated carboxylic acid or its anhydride, preferably a dicarboxylic acid or a monocarboxylic acid, or an anhydride thereof, more preferably maleic acid or maleic anhydride. Grafting with maleic acid or maleic anhydride gives rise to succinic acid groups or succinic anhydride groups along the inte ⁇ olymer backbone, preferably with no or only minimal side reactions, such as crosslinking or chain scission.
  • graft substantially random inte ⁇ olymers having a melt index of at least about 5 or higher, preferably at least about 10 or higher, and is not significantly lower than the melt index of the substantially random inte ⁇ olymer before grafting.
  • the content of the functional group or groups, e.g. succinic acid groups and/or succinic anhydride groups, introduced in the grafting process is at least about 0.1 , preferably at least about 0.5, more preferably at least about 1 weight percent of the graft substantially random inte ⁇ olymer.
  • the content of residual (free) olefinically unsaturated organic monomer in the inte ⁇ olymer should be as low as possible.
  • the fibers of the invention can be prepared using known fiber forming technologies, e.g. melt spinning.
  • melt spinning the molten polymer or polymer mixture is expelled through a die, with subsequent drawing of the molten extrudate, solidification of the extrudate by heat transfer to a surrounding fluid medium, and taking up of the solid extrudate on a godet or another take-up surface, e.g. a belt.
  • the extmsion die may be a conventional die, for example, a spinnerette typically containing three or more orifices up to several hundred or several thousand orifices.
  • the spinnerette typically includes a filter element to remove gels and other impurities which might otherwise foul or clog the spinnerette orifices.
  • the spinnerette also includes a breaker plate to allow uniform distribution of the molten polymer mass which is supplied from an extruder and/or a gear pump, to all orifices of the spinnerette.
  • Melt spinning may also include cold drawing, heat treating and/or texturizing.
  • An important aspect of the fiber forming process is the orientation of the polymer molecules by drawing the polymer or polymer mixture in the molten state as it leaves the spinnerette.
  • the fiber fo ⁇ ning process may involve, for example, continuous filament forming, staple fiber forming, a spun bond or an air jet process or a melt blown process. It is desirable to spin the fiber at high speeds.
  • Preferred fibers of the invention comprise a blend of an ungrafted ethylene homopolymer or an ungrafted ethylene/C 3 -C 20 alpha-olefin copolymer with a graft substantially random inte ⁇ olymer .
  • Such fibers include multiconstituent, preferably biconstituent fibers as well as ,multicomponent fibers, preferably bicomponent fibers.
  • the biconstituent fibers of the present invention may comprise a continuous phase of either the graft inte ⁇ olymer or the ungrafted ethylene homopolymer or copolymer with the other component being dispersed therein in a matrix/fibril orientation.
  • Jxi multicomponent or bicomponent fibers with a sheath/core arrangement one or more graft substantially random inte ⁇ olymers are comprised in either the sheath or the core, or in both, advantageously blended with an ungrafted polymer, such as polypropylene homopolymer or copolymer, polystyrene, polyamide, substantially random inte ⁇ olymers or polyester terephthalate (PET).
  • Bicomponent fibers preferably comprise the grafted inte ⁇ olymer and an ungrafted polymer component in the same continuous phase. The ratio of ungrafted polymer to grafted substantially random inte ⁇ olymer generally depends on the graft level and the desired bonding level.
  • a suitable ratio for example is in the range of from about 95/5 to about 80/20 ungrafted polymer/graft substantially random inte ⁇ olymer.
  • the ungrafted and grafted blend components may be blended together prior to extrusion using methods and equipment generally known in the art, e.g. by melt blending or dryblending.
  • the fibers of the invention are typically fine denier filaments of 15 denier or less down to fractional deniers, depending on the desired properties and the specific application in which they are to be used.
  • the fibers of the present invention have a wide variety of applications.
  • Yet another aspect of the present invention relates to the fibers of the invention in a blend of fibers, e.g. additionally comprising performance fibers.
  • the fibers of the present invention are particularly useful in binder fiber applications with high tenacity performance fibers such as, for example, fibers from polyamides, polyesters, cotton, wool, silk, cellulosics, modified cellulosics such as rayon and rayon acetate, and the like.
  • the fibers of the present invention find particular advantage as binder fibers owing to their adhesion to performance fibers and wettability thereof which is enhanced by the presence of the functional (polar) groups in the graft inte ⁇ olymer and the relatively lower melting temperature or range of the grafted inte ⁇ olymer constituent relative to the perfomance fiber.
  • the present invention relates to a fabric, non-woven or woven, comprising the fibers of the invention, or fiber blends comprising the fibers of the invention.
  • the fibers may be formed into a batt and heat treated by calendaring on a heated, embossed roller to form a fabric.
  • the batts may also be heat bonded, for example, by infrared light, ultrasound or the like, to obtain a light loft fabric.
  • the fibers may also be employed in conventional textile processing such as carding, sizing, weaving and the like. Woven fabrics made from the fibers of the present invention may also be heat treated to alter the properties of the fabric.
  • Also useful for indicating the molecular weight of the substantially random inte ⁇ olymers used in the present invention is the Gottfert melt index (G, cm 3 / 10 min) which is obtained in a similar fashion as for melt index (I 2 ) using the ASTM D1238 procedure for automated plastometers, with the melt density set to 0.7632, the melt density of polyethylene at 190°C.
  • melt density to styrene content for ethylene-styrene inte ⁇ olymers was measured, as a function of total styrene content, at 190°C for arange of 29.8% to 81.8% by weight styrene. Atactic polystyrene levels in these samples was typically 10% or less. The influence of the atactic polystyrene was assumed to be minimal because of the low levels. Also, the melt density of atactic polystyrene and the melt densities of the samples with high total styrene are very similar.
  • Inte ⁇ olymer styrene content and the concentration of atactic polystyrene homopolymer impurity in the ESI are determined using proton nuclear magnetic resonance ( H NMR). All proton NMR samples are prepared in 1, 1, 2, 2-tetrachloroethane-d 2 (tce-d 2 ). The resulting solutions contain from about 1.6 to about 2.4 weight percent of inte ⁇ olymer. The inte ⁇ olymers are weighed directly into 5-mm sample tubes. A 0.75-ml aliquot of tce-d 2 is added by syringe and the tube is capped with a tight- fitting cap. The samples are heated at 85°C to soften the inte ⁇ olymer. To provide mixing, the capped samples are occasionally brought to reflux using a heat gun.
  • H NMR proton nuclear magnetic resonance
  • Proton NMR spectra are accumulated with the sample probe at 80°C, and referenced to the residual protons of tce-d 2 at 5.99 ppm. Data is collected in triplicate on each sample. The following instrumental conditions are used for analysis of the inte ⁇ olymer samples:
  • Sweep width 5000 Hz Acquisition time, 3.002 sec
  • Pulse width 8 ⁇ sec Frequency, 300 MHz Delay, 1 sec Transients, 16
  • the total analysis time per sample is about 10 minutes.
  • Polystyrene has five different types of protons that are distinguishable by proton NMR.
  • these protons are labeled b, branch; ⁇ , alpha; o, ortho; m, meta; p, para, as shown in figure 1.
  • b branch
  • ⁇ alpha
  • o ortho
  • m meta
  • p para
  • the NMR spectrum for polystyrene homopolymer includes a resonance centered around a chemical shift of about 7.1 ppm, which is believed to correspond to the three ortho and para protons. It includes another peak centered around a chemical shift of about 6.6 ppm. That peak corresponds to the two meta protons. Other peaks at about 1.5 and 1.9 ppm correspond to the three aliphatic protons (alpha and branch).
  • the relative intensities of the resonances for each of these protons are determined by integration.
  • the integral corresponding to the resonance at 7.1 ppm is designated PS 7 .1 below.
  • That con-esponding to the resonance at 6.6 ppm is designated PS 6 . 6
  • that corresponding to the aliphatic protons (integrated from 0.8-2.5 ppm) is designated PSai.
  • the theoretical ratio for PS 7 .r. PS 6 . 6 : PSai is 3:2:3, or 1.5:1:1.5.
  • An aliphatic ratio of 2 to 1 is predicted based on the protons labeled ⁇ and b respectively in figure 1. This ratio is also observed when the two aliphatic peaks are integrated separately. Further, the ratio of aromatic to aliphatic protons is measured to be 5 to 3, as predicted from theoretical considerations.
  • the 1H-NMR spectrum for the ESI inte ⁇ olymer is acquired.
  • This spectrum shows resonances centered at about 7.1 ppm, 6.6 ppm and in the aliphatic region.
  • the 6.6 ppm peak is relatively much weaker for the ESI inte ⁇ olymer than for the polystyrene homopolymer. The relative weakness of this peak is believed to occur because the meta protons in the ESI copolymer resonate in the 7.1 ppm region.
  • the only protons that produce the 6.6 ppm peak are meta protons associated with atactic polystyrene homopolymer that is an impurity in the ESI.
  • the peak centered at about 7.1 ppm thus includes ortho, meta and para protons from the aromatic rings in the ESI inte ⁇ olymer, as well as the ortho and para protons from the aromatic rings in the polystyrene homopolymer impurity.
  • the peaks in the aliphatic region include resonances of aliphatic protons from both the ESI inte ⁇ olymer and the polystyrene homopolymer impurity.
  • the relative intensities of the peaks are determined by integration.
  • the peak centered around 7.1 ppm is referred to below as I . ⁇ , that centered around 6.6 ppm is I 6 . 6 and that in the aliphatic regions is I .
  • I7.1 includes a component attributable to the aromatic protons of the aromatic protons of the
  • Wt% PS 100% * Wt% S * (I 2S). 100 - [Wt% S * (Ie. 6 /2S)]
  • the total styrene content was also determined by quantitative Fourier Transform Infrared spectroscopy (FTIR).
  • FTIR Fourier Transform Infrared spectroscopy
  • the eluent (stablized 1,2,4-trichlorobenzene) is degased on line.
  • the solvent flow rate is 1 ml/min.; 200 ⁇ l are injected.
  • the analysis are carried out at 140°C.
  • the vials are kept ready at 80°C until 1 h before analyzing.
  • the calibration of the columns was done via a calibration kit from Polymer Laboratories.
  • the molecular weights of the polystyrene standards were confirmed by light scattering measurements.
  • the polystyrene calibration curve was transformed into a calibration curve for polyethylene using the following Kuhn-Mark-
  • the grafted samples were prepared by feeding a mixture of polymer, reactive monomer and initiator into a Werner-Pfleiderer ZSK 30 twin screw extruder.
  • the reactive monomer was maleic anhydride
  • the initiator was 2,5-dimethyl-2,5-di(t-butylperoxy)hexane
  • the polymers were Ethylene Styrene Inte ⁇ olymers with different styrene content (30wt%, 70wt%) and with different melt index (Ig/lOmin and lOg/10 min).
  • the weight ratio of MAH/initiator/polymer was 1.5/0.05/98.45%.
  • the operating conditions of the twin screw extruder were: Barrel Temp. (1-5, Die) 80°C, 150°C, 200°C, 200°C, 150°C, 150°C Melt Temp. (4) 210°C Melt Temp. (Die) 150°C Screw speed 150 ⁇ m
  • melt index and maleic anhydride content of the graft-modified and unmodified (starting) inte ⁇ olymers are listed in the below table.
  • Substantially random ethylene/styrene inte ⁇ olymer (ESI) no.7 and substantially random ethylene/propylene/styrene inte ⁇ olyer (EPS) no. 1 were prepared in a continuously operating loop reactor.
  • An Ingersoll-Dresser twin screw pump provided the mixing.
  • the reactor ran liquid full at 475 psig (3,275 kPa).
  • Raw materials and catalyst/cocatalyst flows were fed into the reactor through injectors and Kenics static mixers in the loop reactor piping. From the discharge of the loop pump, the process flow went through two shell and tube heat exchangers before returning to the suction of the loop pump.
  • loop flow Upon exiting the last exchanger, loop flow returned through the injectors and static mixers to the suction of the pump. A second monomer/feed injector and mixer were used if available. Heat transfer oil or tempered water was circulated through the exchangers' jacket to control the loop temperature. The exit stream of the loop reactor was taken off between the two exchangers. The flow and solution density of the exit stream was measured by a Micro-MotionTM mass flow meter.
  • Solvent was injected to the reactor primarily as part of the feed flow to keep the ethylene in solution. A split stream from the pressurization pumps prior to ethylene injection was taken to provide a flush flow for the loop reactor pump seals. Additional solvent was added as a diluent for the catalyst. Feed solvent was mixed with uninhibited styrene monomer on the suction side of the pressurization pump. The pressurization pump supplies solvent and styrene to the reactor at approximately 650 psig (4,583 kPa). Fresh styrene flow was measured by a Micro-Motion mass flow meter, and total solvent/styrene flow was measured by a separate Micro-Motion mass flow meter.
  • Ethylene was supplied to the reactor at approximately 690 psig (4,865 kPa).
  • the ethylene stream was measured by a Micro-Motion mass flow meter.
  • a flow meter /controller was used to deliver hydrogen into the ethylene stream at the outlet of the ethylene control valve.
  • Propylene was added either as a high pressure stream after the solvent pressurization pump.
  • the ethylene/hydrogen mixture was at ambient temperature when it was combined with the solvent/styrene stream.
  • the temperature of the entire feed stream as it entered the reactor loop was lowered to approximately 2°C by a glycol cooled exchanger.
  • the catalyst system was a three component system composed of a titanium catalyst, an aluminum co-catalyst and a boron co-catalyst. Preparation of the three catalyst components takes place in three separate tanks.
  • the titanium catalyst was (1H- cyclopenta[ 1 ]phenanthrene-2-yl)dimethyl(t-butylamido)-silanetitanium
  • the aluminum co- catalyst component was a modified methylaluminoxane type 3A (MMAO-3A; CAS No. 146905-79-5) and the boron co-catalyst was tris(pentafluorophenyl)borane (FAB, CAS No. 001109-15-5).
  • MMAO-3A modified methylaluminoxane type 3A
  • FAB tris(pentafluorophenyl)borane
  • Fresh solvent and concentrated catalyst/co-catalyst/secondary co-catalyst premix were added and mixed into their respective run tanks and fed into the reactor via a variable speed PulsafeederTM diaphragm pumps.
  • the three component catalyst system entered the reactor loop through an injector and static mixer into the suction side of the twin screw pump.
  • the raw material feed stream was also fed into the reactor loop through an injector and static mixer upstream of the catalyst injection point or through a feed injector/mixer between the two exchangers.
  • This flashed polymer entered the devolatilization section of the process.
  • the volatiles flashing from the devolatilization were condensed with a glycol jacketed exchanger, passed through vacuum pump, and were discharged to vapor/liquid separation vessel.
  • solvent/styrene were removed from the bottom of this vessel as recycle solvent while unreacted ethylene exhausted from the top.
  • the ethylene stream was measured with a Micro-Motion mass flow meter.
  • the measurement of vented ethylene plus a calculation of the dissolved gases in the solvent/styrene stream were used to calculate the ethylene conversion.
  • the polymer and remaining solvent were pumped with a gear pump to a final devolatilizer.
  • the pressure in the second devolatilizer was operated at approximately 10 mmHg (1.4 kPa) absolute pressure to flash the remaining solvent.
  • the dry polymer ( ⁇ 1000 ppm total volatiles) was pumped with a gear pump to an underwater pelletizer, spin-dried, and collected.
  • Table 3 lists certain properties characterizing the inte ⁇ olymers used in the Examples. Inte ⁇ olymer styrene content, inte ⁇ olymer propylene content and content of atactic polystyrene were determined using the proton nuclear magnetic resonance method described hereinbefore. Table 3: Properties of ESI-7 and EPS-1
  • the olefinically unsaturated organic monomer was maleic anhydride (MAH), the radical initiator was 2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane (30 % solution in a mineral oil).
  • MAH maleic anhydride
  • the weight ratios of MAH/initiator/inte ⁇ olymer was 1.4/0.32/98.28 for ESI-7 and 1.4/0.5/98.1 for EPS-1.
  • the grafting process for ESI-7 and EPS-1 is performed analogously to Example 1.
  • MAH-graft ESI-7 had a melt index of 7.8 and a MAH graft content of 0.6 weight %; MAH-graft EPS-1 had a MAH graft content of 0.95 %.
  • the graft content was measured via FTIR spectroscopy on compression molded films with a thickness of about 0.1mm - free MAH was removed during the compression molded process.
  • Fibers comprising MAH-graft ESI-7 show superior Spinning Performance
  • Fibers comprising the MAH-graft ESI-7 were formed on a spinning line.
  • a blend of 10 % by weight of MAH graft ESI-7 and 90 weight percent of an ethylene/octene copolymer (0.95 g/ccm density; 17 Melt Index) was extruded on a standard screw extruder with an L/D of 28 and a compression ratio of 2.5 at 180°C.
  • the molten extrudate was fed through a gear pump into a spin pack including a three layer filter system of 0.065/0.030/0.16 micron and a spinnerette having 400 0.31 mm holes with an L/D of 6.8.
  • the molten filaments were drawn down to about 11 denier by the extensional force of a draw down godet at 120 m/min and winded up.
  • the maximum spinning speed (fiber drawing) before fiber break was 120 m/min (which reflects the machine limit).
  • the maximum spinning speed for analogously formed fibers consisting of 100 % of the ethylene/octene copolymer was only 90 m/min.
  • the maximum spinning speed for analogously formed fibers consisting of 10% of MAHgraft HDPE (0.953 density, melt index of grafted HDPE 9.8; melt index before grafting 65; MAH graft content of 1.17) and 90 % of the ethylene/octene copolymer was only 60 m/min.
  • Bicomponent Fibers incorporating MAH-graft ESI-7 Compositions comprising the MAHgraft ESI-7 were used to make bicomponent fibers.
  • the bicomponent fibers had a core/sheath arrangement, with the core made from polypropylene and the sheath formed from the below-identified blends comprising MAH graft ESI-7.
  • the above fibers were mixed in with cellulose pulp at a 12% by weight loading (of binder fiber) and using an air-laid process, 100 gsm cores/pads were fabricated. Following the fabrication of the air-laid cores/pads, the cores/pads were heated in a platen press for up to 60 seconds at both 275 F and 300 F to facilitate the binder fibers to bond to the cellulose pulp. Following this step, 5-6 tensile specimens were cut out from each core/pad (and each of the above three binder fiber compositions) and tested in an Instron machine at 0.5"/min testing speed. The dry tensile strength (or binding strength) of each composition from the above tests is reported below.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Textile Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Artificial Filaments (AREA)
  • Multicomponent Fibers (AREA)

Abstract

Le polymère greffé décrit dans cette invention contient un squelette composé d'un ou de plusieurs interpolymères sensiblement aléatoires. Ce polymère greffé comprend: (1) des unités polymériques provenant; (a) d'au moins un monomère aromatique vinylidène ou vinylique, ou (b) d'au moins un monomère contrarié vinylidène ou vinylique cycloaliphatique ou aliphatique, ou (c) d'une combinaison d'au moins un monomère vinylidène ou vinylique aromatique et d'au moins un monomère contrarié vinylidène ou vinylique cycloaliphatique ou aliphatique; et (2) des unités polymèriques provenant d'au moins un éthylène et/ou d'un α-oléfine C3-20; et (3) éventuellement des unités polymériques provenant d'un ou de plusieurs monomères polymérisables éthyléniquement non saturés, et qui sont différents des monomères provenant de (1) et (2); ledit squelette étant greffé avec un ou plusieurs monomères organiques alcéniques. Dans un mode de réalisation optimal, de tels polymères greffés sont préparés selon un procédé d'extrusion réactive.
PCT/US2001/016934 2000-05-26 2001-05-24 Interpolymere sensiblement aleatoire greffe a un ou a plusieurs monomeres organiques alceniques WO2001092357A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP01937723A EP1290049A1 (fr) 2000-05-26 2001-05-24 Interpolymere sensiblement aleatoire greffe a un ou a plusieurs monomeres organiques alceniques
US10/276,087 US20030216509A1 (en) 2000-05-26 2001-05-24 Substantially random interpolymer grafted witn one or more olefinically unsaturated organic monomers
BR0111483-2A BR0111483A (pt) 2000-05-26 2001-05-24 Composição de interpolìmero enxertado, seu uso e produtos obtidos
JP2002500967A JP2003535194A (ja) 2000-05-26 2001-05-24 １種以上のオレフィン性不飽和有機モノマーをグラフトした実質上ランダムなインターポリマー
AU2001263430A AU2001263430A1 (en) 2000-05-26 2001-05-24 Substantially random interpolymer grafted with one or more olefinically unsaturated organic monomers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP0004841 2000-05-26
EPPCT/EP00/04841 2000-05-26

Publications (1)

Publication Number Publication Date
WO2001092357A1 true WO2001092357A1 (fr) 2001-12-06

Family

ID=8163962

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2001/016934 WO2001092357A1 (fr) 2000-05-26 2001-05-24 Interpolymere sensiblement aleatoire greffe a un ou a plusieurs monomeres organiques alceniques

Country Status (6)

Country Link
JP (1) JP2003535194A (fr)
KR (1) KR20030005397A (fr)
CN (1) CN1430631A (fr)
AU (1) AU2001263430A1 (fr)
BR (1) BR0111483A (fr)
WO (1) WO2001092357A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005150098A (ja) * 2003-10-22 2005-06-09 Seiko Epson Corp 正孔輸送材料、層、有機エレクトロルミネッセンス素子および正孔輸送材料の精製方法
DE102007043972A1 (de) 2007-09-11 2009-05-20 Kometra Kunststoff-Modifikatoren Und -Additiv Gmbh Verfahren zur Herstellung carboxylierter Ethylenpolymerblends
DE102008019804A1 (de) 2008-04-15 2009-10-22 Kometra Kunststoff-Modifikatoren Und -Additiv Gmbh Funktionalisierte Ethylenpolymere mit hohem Haftvermögen und Verfahren zu ihrer Herstellung
WO2011032176A1 (fr) * 2009-09-14 2011-03-17 Dow Global Technologies Inc. Polymeres contenant des unites issues d'ethylene et de polyalcene
US8598276B2 (en) 2009-09-14 2013-12-03 Dow Global Technologies Llc Polymers comprising units derived from ethylene and poly(alkoxide)
US8691923B2 (en) 2009-09-14 2014-04-08 Dow Global Technologies Llc Interconnected copolymers of ethylene in combination with at least one polysiloxane
WO2014146773A1 (fr) 2013-03-20 2014-09-25 Byk Kometra Gmbh Procédé de production d'élastomères thermoplastiques fonctionnalisés
JP2016117842A (ja) * 2014-12-22 2016-06-30 日油株式会社 ポリアミド樹脂組成物およびその樹脂成形品
US9945071B2 (en) 2006-11-13 2018-04-17 Columbia Insurance Company Methods and systems from recycling carpet and carpets manufactured from recycled material

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017222981A1 (fr) * 2016-06-22 2017-12-28 Dow Global Technologies Llc Élimination du cobalt colloïdal d'une composition aqueuse
CN111482345A (zh) * 2020-03-18 2020-08-04 安徽昌发实业有限公司 一种铁艺工艺品表面耐腐蚀处理工艺

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4263193A (en) * 1978-03-17 1981-04-21 Showa Denko K.K. Aqueous emulsion of multi-component synethetic resin and process for production thereof
EP0317358A2 (fr) * 1987-11-20 1989-05-24 Sumitomo Chemical Company, Limited Résine de polyoléfine modifiée
US5082899A (en) * 1988-11-02 1992-01-21 The Dow Chemical Company Maleic anhydride-grafted polyolefin fibers
US5346963A (en) * 1993-04-28 1994-09-13 The Dow Chemical Company Graft-modified, substantially linear ethylene polymers and methods for their use
US5356950A (en) * 1991-03-25 1994-10-18 Exxon Chemical Patents Inc. Grafted polymers of an isomonoolefin and an alkylstyrene
EP0674325A2 (fr) * 1994-03-24 1995-09-27 Nippon Petrochemicals Co., Ltd. Composition polymère isolante électrique et fils ou câble utilisant cette composition
EP0676265A2 (fr) * 1994-04-04 1995-10-11 Bridgestone Corporation Verres caoutchoucs de vulcanisation ne collant pas aux caoutchoucs hydrocarbonés vulcanisés ou vulcanisants

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4263193A (en) * 1978-03-17 1981-04-21 Showa Denko K.K. Aqueous emulsion of multi-component synethetic resin and process for production thereof
EP0317358A2 (fr) * 1987-11-20 1989-05-24 Sumitomo Chemical Company, Limited Résine de polyoléfine modifiée
US5082899A (en) * 1988-11-02 1992-01-21 The Dow Chemical Company Maleic anhydride-grafted polyolefin fibers
US5356950A (en) * 1991-03-25 1994-10-18 Exxon Chemical Patents Inc. Grafted polymers of an isomonoolefin and an alkylstyrene
US5527170A (en) * 1992-06-29 1996-06-18 Bridgestone Corporation Rubber curing bladders having self release or low adhesion to curing or cured hydrocarbon rubbers
US5346963A (en) * 1993-04-28 1994-09-13 The Dow Chemical Company Graft-modified, substantially linear ethylene polymers and methods for their use
EP0674325A2 (fr) * 1994-03-24 1995-09-27 Nippon Petrochemicals Co., Ltd. Composition polymère isolante électrique et fils ou câble utilisant cette composition
EP0676265A2 (fr) * 1994-04-04 1995-10-11 Bridgestone Corporation Verres caoutchoucs de vulcanisation ne collant pas aux caoutchoucs hydrocarbonés vulcanisés ou vulcanisants

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005150098A (ja) * 2003-10-22 2005-06-09 Seiko Epson Corp 正孔輸送材料、層、有機エレクトロルミネッセンス素子および正孔輸送材料の精製方法
US9945071B2 (en) 2006-11-13 2018-04-17 Columbia Insurance Company Methods and systems from recycling carpet and carpets manufactured from recycled material
DE102007043972A1 (de) 2007-09-11 2009-05-20 Kometra Kunststoff-Modifikatoren Und -Additiv Gmbh Verfahren zur Herstellung carboxylierter Ethylenpolymerblends
DE102008019804A1 (de) 2008-04-15 2009-10-22 Kometra Kunststoff-Modifikatoren Und -Additiv Gmbh Funktionalisierte Ethylenpolymere mit hohem Haftvermögen und Verfahren zu ihrer Herstellung
WO2011032176A1 (fr) * 2009-09-14 2011-03-17 Dow Global Technologies Inc. Polymeres contenant des unites issues d'ethylene et de polyalcene
US8598276B2 (en) 2009-09-14 2013-12-03 Dow Global Technologies Llc Polymers comprising units derived from ethylene and poly(alkoxide)
US8691923B2 (en) 2009-09-14 2014-04-08 Dow Global Technologies Llc Interconnected copolymers of ethylene in combination with at least one polysiloxane
US8987385B2 (en) 2009-09-14 2015-03-24 Dow Global Technologies Llc Interconnected copolymers of ethylene in combination with one other polyalkene
WO2014146773A1 (fr) 2013-03-20 2014-09-25 Byk Kometra Gmbh Procédé de production d'élastomères thermoplastiques fonctionnalisés
US10189933B2 (en) 2013-03-20 2019-01-29 Byk-Chemie Gmbh Method for producing functionalized thermoplastic elastomers
JP2016117842A (ja) * 2014-12-22 2016-06-30 日油株式会社 ポリアミド樹脂組成物およびその樹脂成形品

Also Published As

Publication number Publication date
BR0111483A (pt) 2003-07-01
KR20030005397A (ko) 2003-01-17
CN1430631A (zh) 2003-07-16
JP2003535194A (ja) 2003-11-25
AU2001263430A1 (en) 2001-12-11

Similar Documents

Publication Publication Date Title
US6319969B1 (en) Interpolymer compositions for use in sound management
US6262161B1 (en) Compositions having improved ignition resistance
US6362270B1 (en) Thermoplastic compositions for durable goods applications
AU735403B2 (en) Filled polymer compositions
US6190768B1 (en) Fibers made from α-olefin/vinyl or vinylidene aromatic and/or hindered cycloaliphatic or aliphatic vinyl or vinylidene interpolymers
WO1998010160A1 (fr) Revetement pour plancher, mur ou plafond
CA2378322A1 (fr) Compositions interpolymeres utilisees dans la gestion du son
CN1419613A (zh) 具有高应变率拉伸的聚丙烯织物的制造方法及其使用方法
WO2001092357A1 (fr) Interpolymere sensiblement aleatoire greffe a un ou a plusieurs monomeres organiques alceniques
EP1157048B1 (fr) Procede d'elaboration a plusieurs systemes catalytiques pour la production d' interpolymeres d'alpha-olefines et de monomeres aromatoques insatures
US6365658B1 (en) Polymer compositions
US20030216509A1 (en) Substantially random interpolymer grafted witn one or more olefinically unsaturated organic monomers
EP1126969A1 (fr) Articles fabriques a partir de compositions interpolymeres d'alpha-olefine/vinyle ou de vinylidene aromatique et/ou de vinyle ou de vinylidene aliphatique ou cycloaliphatique encombres steriquement
WO1999046348A1 (fr) Ruban auto-adhesif deformable
EP1290049A1 (fr) Interpolymere sensiblement aleatoire greffe a un ou a plusieurs monomeres organiques alceniques
EP1141475A1 (fr) Interpolymeres aromatiques d'alpha-olefine/vinyle ou de vinylidene et/ou interpolymeres aliphatiques ou cycloaliphatiques de vinyle ou de vinylidene a empechement sterique destines a la fabrication de tapis
WO2000036021A1 (fr) Procede pour scier un composite de bois
MXPA99011695A (en) Filled polymer compositions
MXPA01005814A (en) Mel-bondable polypropylene/ethylene polymer fiber and composition for making the same
MXPA99005680A (en) Plasticized alpha-olefin/vinylidene aromatic monomer or hindered aliphatic or cycloaliphatic vinylidene monomer interpolymers

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2001937723

Country of ref document: EP

Ref document number: 10276087

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 1020027015950

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 018101526

Country of ref document: CN

Ref document number: PA/A/2002/011678

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 2001263430

Country of ref document: AU

WWP Wipo information: published in national office

Ref document number: 1020027015950

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 2001937723

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 2001937723

Country of ref document: EP

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载