WO2010074916A1 - Compositions isolantes durcissant à température et humidité ambiantes et procédés associés - Google Patents

Compositions isolantes durcissant à température et humidité ambiantes et procédés associés Download PDF

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WO2010074916A1
WO2010074916A1 PCT/US2009/066598 US2009066598W WO2010074916A1 WO 2010074916 A1 WO2010074916 A1 WO 2010074916A1 US 2009066598 W US2009066598 W US 2009066598W WO 2010074916 A1 WO2010074916 A1 WO 2010074916A1
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silane
composition
copolymer
ethylene
sulfonic acid
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PCT/US2009/066598
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Michael B. Biscoglio
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Dow Global Technologies Inc.
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • 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
    • C08F246/00—Copolymers in which the nature of only the monomers in minority is defined
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • 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
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
    • 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
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers

Definitions

  • This invention relates to an ambient temperature (e.g., about 1O 0 C to about 3O 0 C) and ambient humidity (e.g., about 30% to about 70% relative humidity (RH)) curing polymer compositions and to novel or crosslinking processes curing catalysts used therein. More specifically, the invention relates to crosslinkable polymer compositions containing a silane- functional polymer and at least one silanol condensation catalyst.
  • ambient temperature e.g., about 1O 0 C to about 3O 0 C
  • ambient humidity e.g., about 30% to about 70% relative humidity (RH)
  • RH relative humidity
  • crosslinking improves properties of the polymer such as its mechanical strength and heat resistance.
  • Polymers normally considered to be thermoplastics, and not crosslinkable can also be crosslinked by introducing crosslinkable groups into the polymer.
  • An example thereof is the crosslinking of polyolefins, such as polyethylene.
  • a silane compound can be introduced as a crosslinkable group, e.g. by grafting the silane compound onto the prepared polyolefin, or by copolymerization of the polyolefinic and the silane compound.
  • Silane-crosslinkable polymers and compositions comprising those polymers, are well known in the art, e.g., USP 6,005,055, WO 02/12354 and WO 02/12355.
  • the polymer is typically a polyolefin, e.g., polyethylene, into which one or more unsaturated silane compounds, e.g., vinyl trimethoxysilane, vinyl triethoxysilane, vinyl dimethoxyethoxysilane, etc., have been incorporated.
  • the polymer is crosslinked upon exposure to moisture typically in the presence of a catalyst.
  • Silane crosslinked polymers have a myriad of uses, particularly in the preparation of insulation coatings in the wire and cable industry.
  • the crosslinking of polymers with hydrolysable silane groups is carried out by so-called moisture curing.
  • the silane groups are hydrolyzed under the influence of water, resulting in the splitting-off of alcohol and the formation of silanol groups.
  • the silanol groups are crosslinked by a condensation reaction splitting off water.
  • a so-called silanol condensation catalyst is used as catalyst.
  • Prior-art silanol condensation catalysts include carboxylates of metals, such as tin, zinc, iron, lead and cobalt; organic bases; inorganic acids; and organic acids.
  • silanol condensation systems and in particular ones based on tin carboxylates e.g., di-n-butyltin dilaurate (DBTDL) and reactor based silane/ ⁇ -olefin copolymers, are frequently used in the crosslinking of polymer compositions containing silanol groups, they are disadvantageous in some respects. Thus, efforts are being made to find silanol condensation systems reducing or obviating these disadvantages.
  • DBTDL di-n-butyltin dilaurate
  • silane/ ⁇ -olefin copolymers are frequently used in the crosslinking of polymer compositions containing silanol groups.
  • prior-art silanol condensation catalysts function satisfactorily only at elevated temperatures in the order of 80-100 0 C and give a poor performance at normal ambient temperature and relative humidity, e.g., room temperature (lOoC to 30oC) and 30% RH to 70% RH.
  • room temperature e.g., room temperature (lOoC to 30oC)
  • 30% RH to 70% RH e.g., room temperature (lOoC to 30oC) and 30% RH to 70% RH.
  • room temperature room temperature
  • LV low voltage
  • the degree of crosslinking of the polymer composition is measured as the gel content after crosslinking at a certain temperature for a certain period of time.
  • crosslinking at room temperature for four days should result in a gel content of at least 65% and a catalyst loading of 1 mmol/kg composition.
  • crosslinking can be measured by hot creep.
  • Hot Creep here and in the example is maximum elongation under load found in the hot set test described in IEC 60811-2-1 International Standard when performed at 200 0 C. See also ICEA T-28-562 "Test Method for Measurement of Hot Creep of Polymeric Insulations. This is not achieved by existing silanol condensation catalysts, and it would therefore be a considerable step forward to provide a silanol condensation catalyst meeting this requirement.
  • silane crosslinkable polymer compositions comprise (i) at least one silane-functional polymer, e.g., silane-grafted copolymer, and mixtures thereof, and (ii) a catalytic amount of at least one substituted, preferably poly-substituted, aromatic sulfonic acid (PASA).
  • PASA poly-substituted, aromatic sulfonic acid
  • the numerical ranges in this disclosure are approximate, and thus may include values outside of the range unless otherwise indicated. Numerical ranges include all values from and including the lower and the upper values, in increments of one unit, provided that there is a separation of at least two units between any lower value and any higher value. As an example, if a compositional, physical or other property, such as, for example, molecular weight, viscosity, melt index, etc., is from 100 to 1,000, it is intended that all individual values, such as 100, 101, 102, etc., and sub ranges, such as 100 to 144, 155 to 170, 197 to 200, etc., are expressly enumerated.
  • a compositional, physical or other property such as, for example, molecular weight, viscosity, melt index, etc.
  • a catalyst of this invention comprises a component of the formula (I):
  • the aryl group is an alkyl-substituted benzene ring with the alkyl substituent containing 8-20 carbon atoms.
  • the catalysts of the compositions of this invention are preferably poly-substituted aromatic sulfonic acid (PASA) catalysts.
  • PASA catalyst of this invention may be introduced e.g., as a component of a catalyst masterbatch or deployed during polymer extension.
  • Various other approaches to mixing, admixing, or commingling the selected reactants will be readily apparent in view of this disclosure.
  • the preferred PASA catalysts of this invention are of formula (II):
  • m is 1 to 3; R, is (CH 2 ) n CH 3 ; n is 0 to 3; Each R x is the same or different than Ri ; and Ar is an aromatic moiety; and
  • m is 0 to 3;
  • R 1 is (CH 2 ) n CH 3 ;
  • n is greater than 20;
  • Each R x is the same or different than Ri ; and Ar is an aromatic moiety.
  • the catalysts of the second instance demonstrate lower water solubility than the catalysts of the first instance (the longer the length of the Ri alkyl chain and the more alkyl chains on the aromatic moiety, the more compatible the catalyst is with the organic media of the polymer).
  • the catalysts of the first instance are readily prepared as sulfonated derivatives of alkylated toluene, ethyl benzene and xylene materials.
  • the aromatic moiety can be heterocyclic, e.g., a pyridine or quinoline, but preferably is benzene or naphthalene.
  • the catalysts of the second instance include ⁇ -olefin sulfonates, alkane sulfonates, is ethionates (ethers or esters of 2-hydroxyethylsulfonic acid also known as isethionic acid), and propane sulfone derivatives, e.g., oligomers or copolymers of acrylamide propane sulfonic acid. While the maximum value of n is limited only by practical considerations such as economics, catalyst mobility and the like, preferably the maximum value of n is 80, more preferably 50.
  • the PASA typically comprises from 0.01 to 1, preferably from 0.03 to 0.5 and more preferably from 0.05 to t 0.2, weight percent of the composition based upon the total weight of the composition.
  • the invention is further directed to a process for crosslinking silane functional polyolefins by adding an alkylated naphthalene monosulfonic acid or an arylalkyl sulfonic acid or a hydrolyzable derivative thereof or a metal salt thereof as a crosslinking catalyst.
  • the number of carbons in each substituent alkyl group of the alkylated naphthalene and the arylalkyl group will depend on their size and degree of branching. For alkylated naphthalene monosulfonic acids and the derivatives thereof, the total number of carbons in the alkyl groups is in the range of 20-80.
  • the number of carbons in each alkyl group is in the range of 5-20, preferably the alkyl group on the naphthalene ring is a linear or branched alkyl with 10- 18 carbons, and most preferably a linear alkyl of 10 to 18 carbons.
  • the number of alkyl groups on the naphthalene rings is 2 or 3.
  • the total number of carbons in the alkyl groups on the naphthalene rings is in the range of 24 to 50.
  • the aryl group may be phenyl or naphthyl, preferably phenyl, substituted with at least two alkyl groups with the total number of carbons in the alkyl group(s) being 12-80, preferably 24-50.
  • Each of the alkyl groups may be same or different, and preferably the alkyl group is linear with 5-20 carbons, preferably 9-14 carbons.
  • the crosslinking catalyst may be a mixture of alkylated naphthalene monosulfonic acids or a mixture of the arylalkyl sulfonic acids.
  • the derivative of the alkylated naphthalene monosulfonic acid or arylalkyl sulfonic acid is selected from the group consisting of the anhydrides, esters, acetylates, epoxy-blocked esters and amine salts thereof which are hydrolyzable to the corresponding alkylated naphthalene monosulfonic acid or the arylalkyl sulfonic acid.
  • Such derivatives include sulfonic acid anhydrides, alkyl sulfonic acid esters, epoxy blocked sulfonic acids, acetylated sulfonic acids, and amine salts of the alkylated naphthalene monosulfonic acids or arylalkyl sulfonic acids.
  • the sulfonic acid group of the epoxy-blocked sulfonic acid is reacted with an epoxide to provide a beta-hydroxy sulfonic acid ester.
  • Suitable epoxy compounds for preparing an epoxy- blocked sulfonic acid include diglycidyl ethers of bisphenol A or bisphenol F; diglycidyl ethers of a glycol, such as ethylene glycol, propylene glycol or butanediol; monoglycidyl ethers of Ci to C 18 alpha-olefin epoxides and 1,2-epoxycyclohexane.
  • the derivatives of the sulfonic acid crosslinking catalysts of the present invention may be prepared from the sulfonic acid in accordance with procedures well known in the art.
  • the process for making an ester or acetylate typically involves condensation of the sulfonic acid group with a hydroxy functioning group such as an alcohol, or an acetyl alcohol.
  • the anhydride of a sulfonic acid is prepared by heating a sulfonic acid compound to remove H 2 O causing two sulfonic acid groups to condense to form an anhydride.
  • the epoxy blocked esters are prepared by reacting the sulfonic acid with an epoxy compound.
  • the metal salt of the alkylated naphthylene monosulfonic acid or the arylalkyl sulfonic acid can be prepared from the corresponding sulfonic acid using well known procedures.
  • the process typically involves reaction of the corresponding sulfonic acid with a metal oxide or metal hydroxide in a suitable solvent such as methanol.
  • the amine salt is prepared by reacting ammonia or an alcohol amine with the sulfonic acid group.
  • the metal or arylalkyl acid salt is selected from the group consisting of aluminum, tin, copper, and zinc. Particularly preferred are zinc, tin, and aluminum, In one particularly preferred embodiment of the invention the catalyst is the zinc salt of a predominantly dinonylnaphthalene monosulfonic acid.
  • the crosslinking catalyst is the zinc salt of a mixture of didodecylnaphthalene monosulfonic acid, tridodecylnaphthalene monosulfonic acid and tetradodecylnaphthalene monosulfonic acid, or a zinc salt of (tetradecylphenyl) tetradecyl sulfonic acid.
  • the metal salts, of the present invention are highly compatible with polyethylene and form a single phase therewith.
  • the silane crosslinking catalysts useful in the invention are alkylated naphthalene monosulfonic acids as well as their corresponding derivatives and metal salts and arylalkyl sulfonic acids as well as their corresponding derivatives and metal salts.
  • the catalyst is a mixture of didodecylnaphthalene monosulfonic acid and tridodecylnaphthalene monosulfonic acid and tetradodecyl-naphthalene sulfonic acid wherein the ratio of di, tri, and tetra-alkylated naphthalene sulfonic acids is in a ratio of 2: 1 : 1.
  • the silanol condensation catalyst is distinguished by being a benzene or naphthalene sulphonic acid that is sufficiently lipophilic to be compatible with the polymer composition to be crosslinked, e.g. polyethylene containing hydrolysable silane groups.
  • the hydrocarbon group of the alkylaryl sulphonic acid must have a certain size and must, e.g. in the case where the acid is a benzene sulphonic acid, have an alkyl substituent containing at least 8 carbon atoms, as indicated in the foregoing. If the alkyl group does not have such a size that the lipophilicity requirement is met, the catalyst is not compatible with the polymer composition but will be released therefrom upon crosslinking in aqueous solution, thus impairing crosslinking efficiency.
  • Ar preferably is an alkyl-substituted aryl group containing a benzene or naphthalene ring, substituted by an alkyl group, the size of which is 8-20 carbon atoms in the benzene case and 4-18 carbon atoms in the naphthalene case. Due to commercial availability, it is most preferred that the aryl group is a benzene ring, substituted with an alkyl substituent containing 12 carbon atoms.
  • the currently most preferred compounds of formula I are dodecyl benzene sulphonic acid and tetrapropyl benzene sulphonic acid.
  • the silanol condensation catalyst may also be a precursor of a compound of formula I, i.e. a compound that is converted by hydrolysis to a compound of formula I.
  • a precursor is the acid anhydride of the sulphonic acid compound of formula I.
  • Another instance is a sulphonic acid of formula I that has been provided with a hydrolysable protective group, e.g. an acetyl group, which can be removed by hydrolysis to give the sulphonic acid of formula I.
  • the amount of silanol condensation catalyst present in the crosslinkable polymer composition generally is in the order of 0.0001-3% by weight, preferably 0.001-2% by weight and most preferably 0.005-1% by weight, as based on the amount of silanol- group containing polymers in the composition. It will be appreciated that the effective amount of catalyst depends on the molecular weight of the catalyst. Thus, a smaller amount is required of a catalyst having a low molecular weight, than of a catalyst having a high molecular weight.
  • the catalyst is preferably added to the crosslinkable polymer in the form of a master batch, i.e., mixed with a polymer, such as a homo- or copolymer of ethylene, e.g. LDPE, EEA or EBA containing 3-30% by weight of alkyl acrylate comonomer.
  • the master batch contains a minor amount of the catalyst, generally 0.02-5% by weight, preferably 0.05-2% by weight.
  • the catalyst may be used in the crosslinkable polymer composition alone or combined with other silanol condensation catalysts, such as other catalysts of the formula I or conventional silanol condensation catalysts, e.g. carboxylic acid salts of the metals tin, zinc, iron, lead and cobalt; hydrolysis products of alkyl tin trichlorides; organic bases; inorganic acids; and organic acids.
  • the silane crosslinkable polymer compositions of this invention comprise (i) at least one silane-functionalized or silane functional polymer, e.g., a silane derivatized ⁇ -olefinic polymer, and (ii) a catalytic amount of at least one substituted aromatic sulfonic acid, preferably PASA.
  • Silane-functionalized olefinic polymers include but are not limited to silane- functionalized polyethylene, polypropylene, etc., and various blends of these polymers.
  • Preferred silane-functionalized olefinic polymers include (i) the copolymers of ethylene and a hydrolysable silane, (ii) a copolymer of ethylene, one or more C 3 or higher ⁇ -olefins or unsaturated esters, and a hydrolysable silane, (iii) a homopolymer of ethylene having a hydrolysable silane grafted to its backbone, and (iv) a copolymer of ethylene and one or more C 3 or higher ⁇ -olefins or unsaturated esters, the copolymer having a hydrolysable silane grafted to its backbone.
  • Each of these groups is described in greater detail below.
  • Polyethylene polymer as here used is a homopolymer of ethylene or a copolymer of ethylene and a minor amount of one or more ⁇ -olefins of 3 to 20 carbon atoms, preferably of 4 to 12 carbon atoms, and, optionally, a diene or a mixture or blend of such homopolymers and copolymers.
  • the mixture can be either an in situ blend or a post-reactor (or mechanical) blend.
  • Exemplary ⁇ -olefins include propylene, 1-butene, 1-hexene, 4-methyl-l-pentene and 1-octene.
  • Examples of a polyethylene comprising ethylene and an unsaturated ester are copolymers of ethylene and vinyl acetate or an acrylic or methacrylic ester.
  • the polyethylene can be homogeneous or heterogeneous. Homogeneous polyethylenes typically have a polydispersity (Mw/Mn) of about 1.5 to about 3.5, an essentially uniform comonomer distribution, and a single, relatively low melting point as measured by differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • the heterogeneous polyethylenes typically have a polydispersity greater than 3.5 and lack a uniform comonomer distribution. Mw is weight average molecular weight, and Mn is number average molecular weight.
  • the polyethylenes have a density in the range of 0.850 to 0.970 g/cc, preferably in the range of 0.870 to 0.950 g/cc. They also have a melt index (I 2 ) in the range of 0.01 to 2000, preferably 0.05 to 1000 and more preferably 0.10 to 50, g/10 min. If the polyethylene is a homopolymer, then its I 2 is 0.5 to 5.0 g/10mm, preferably 0.75 to 3 g/10 min. The I 2 is determined under ASTM D-1238, Condition E and measured at 190 C and 2.16 kg.
  • the polyethylenes used in the practice of this invention can be prepared by any process including high-pressure, solution, slurry and gas phase using conventional conditions and techniques.
  • Catalyst systems include Ziegler-Natta, Phillips, and the various single-site catalysts, e.g., metallocene, constrained geometry, etc.
  • the catalysts are used with and without supports.
  • Useful polyethylenes include low density homopolymers of ethylene made by high pressure processes (HP-LDPE), linear low density polyethylenes (LLDPE), very low density polyethylenes (VLDPE), ultra low density polyethylenes (ULDPE), medium density polyethylenes (MDPE), high density polyethylene (HDPE), and metallocene and constrained geometry copolymers.
  • HP-LDPE high pressure processes
  • LLDPE linear low density polyethylenes
  • VLDPE very low density polyethylenes
  • ULDPE ultra low density polyethylenes
  • MDPE medium density polyethylenes
  • HDPE high density polyethylene
  • metallocene and constrained geometry copolymers metallocene and constrained geometry copolymers.
  • High-pressure processes are typically free radical initiated polymerizations and conducted in a tubular reactor or a stirred autoclave.
  • the pressure is within the range of 25,000 to 45,000 psi and the temperature is in the range of 200 to 35O 0 C.
  • the pressure is in the range of 10,000 to 30,000 psi and the temperature is in the range of 175 to 250 0 C.
  • Copolymers comprised of ethylene and unsaturated esters are well known and can be prepared by conventional high-pressure techniques.
  • the unsaturated esters can be alkyl acrylates, alkyl methacrylates, or vinyl carboxylates.
  • the alkyl groups typically have 1 to
  • the carboxylate groups typically have 2 to
  • the portion of the copolymer attributed to the ester comonomer can be in the range of 5 to 50 percent by weight based on the weight of the copolymer, preferably in the range of about 15 to about 40 percent by weight.
  • the acrylates and methacrylates are ethyl acrylate, methyl acrylate, methyl methacrylate, t-butyl acrylate, n-butyl acrylate, n-butyl methacrylate, and 2-ethylhexyl acrylate.
  • Examples of the vinyl carboxylates are vinyl acetate, vinyl propionate, and vinyl butanoate.
  • the melt index of the ethylene/unsaturated ester copolymers is typically in the range of 0.5 to 50 g/10min, preferably in the range of 2 to 25 g/10min.
  • the VLDPE or ULDPE is typically a copolymer of ethylene and one or more ⁇ -olefins having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms.
  • the density of the VLDPE or ULDPE is typically in the range of 0.870 to 0.915 g/cc.
  • the melt index of the VLDPE or ULDPE is typically in the range of 0.1 to 20 g/10min, preferably in the range of 0.3 to 5 g/10min.
  • the portion of the VLDPE or ULDPE attributed to the comonomer(s), other than ethylene, can be in the range of 1 to 49 percent by weight based on the weight of the copolymer, preferably in the range of 15 to 40 percent by weight.
  • a third comonomer can be included, e.g., another ⁇ -olefin or a diene such as ethylidene norbornene, butadiene, 1 ,4-hexadiene or a dicyclopentadiene.
  • Ethylene/propylene copolymers are generally referred to as EPRs
  • ethylene/propylene/diene terpolymers are generally referred to as an EPDM.
  • the third comonomer is typically present in an amount of 1 to 15 percent by weight based on the weight of the copolymer, preferably present in an amount of 1 to 10 percent by weight.
  • the copolymer contains two or three comonomers inclusive of ethylene.
  • the LLDPE can include VLDPE, ULDPE, and MDPE, which are also linear, but, generally, have a density in the range of 0.916 to 0.925 g/cc.
  • the LLDPE can be a copolymer of ethylene and one or more ⁇ -olefins having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms.
  • the melt index is typically in the range of 1 to 20 g/10min, preferably in the range of 3 to 8 g/10min.
  • HDPE, MDPE, blends of polyethylene(s) LLDPE/LDPE, high (e.g., 3-10) and low (0.5 to 0.9) melt index materials will readily be suggested to one skilled in this art.
  • Any polypropylene may be used in these compositions. Examples include homopolymers of propylene, copolymers of propylene and other olefins, and terpolymers of propylene, ethylene, and dienes (e.g. norbornadiene and decadiene). Additionally, the polypropylenes may be dispersed or blended with other polymers such as EPR or EPDM. Suitable polypropylenes include thermoplastic elastomers (TPE), thermoplastic olefins (TPO) and thermoplastic vulcanates (TPV). Examples of polypropylenes are described in Polypropylene Handbook: Polymerization, Characterization, Properties, Processing, Applications 3-14, 113-176 (E. Moore, Jr. ed., 1996).
  • a silane-functional polymer of this invention is preferably a graft polymer of a silane- functional group grafted onto, e.g., polyethylene.
  • Preferred polyethylene reactants are LLDPE or LDPE having a density in the range of 0.90 to 0.94 g/cc.
  • the grafted silane component (if a graft polymer is used) should generally comprise about 0.5 to about 5% by weight, preferably 1.0% to 2.0% by weight of the graft polymer.
  • silane-functional group can be bound to or incorporated into the backbone or to-be-cross-linked-polymer (to create a silane-functional polymer) in various ways. Whether a graft polymer or silane/ ⁇ -olefin copolymer is used will depend upon the end use of the cross-linked material and its physical characteristics. For example, silane- functional copolymer (as distinguished from graft polymer) will generally have silane-functional groups that are less sterically hindered than their graft-polymer analogies. Both chemical and processing equipment issues (as well as the resulting cross-linked polymer's characteristics) will be considered in deciding upon which of the various synthetic routes to use.
  • Vinyl alkoxysilanes are suitable silane compounds for grafting or copolymerization to form the silane-functionalized olefinic polymer.
  • Copolymers of ethylene and vinyl silanes may also be used.
  • suitable silanes are vinyltrimethoxysilane and vinyltriethoxysilane.
  • Such polymers are typically made using a high-pressure process.
  • Ethylene vinylsilane copolymers are particularly well suited for moisture-initiated crosslinking.
  • compositions of this invention may contain other components such as antioxidants, colorants, corrosion inhibitors, lubricants, anti-blocking agents, flame retardants, and processing aids.
  • Suitable antioxidants include (a) phenolic antioxidants, (b) thio-based antioxidants, (c) phosphate-based antioxidants, and (d) hydrazine-based metal deactivators.
  • Suitable phenolic antioxidants include methyl-substituted phenols. Other phenols, having substituents with primary or secondary carbonyls, are suitable antioxidants.
  • One preferred phenolic antioxidant is isobutylidene bis(4,6-dimethylphenol).
  • One preferred hydrazine-based metal deactivator is oxalyl bis(benzylidiene hydrazine). These other components or additives are used in manners and amounts known in the art.
  • the antioxidant is typically present in amount between 0.05 and 10 weight percent based on the total weight of the polymeric composition.
  • the invention is a fabricated article such as a wire or cable construction prepared by applying the polymeric composition over a wire or cable, e.g., by extrusion.
  • Other constructions include fiber, film, foam, ribbons, tapes, adhesives, footwear, apparel, packaging, automotive parts, refrigerator linings and the like.
  • the composition may be formed, applied and used in any manner known in the art.
  • the invention is a process of curing a composition comprising a silane-crosslinkable polymer using a PASA.
  • the cure can be effected in any one of a number of known processes and under a variety of conditions.
  • Sn Masterbatch 1 is a catalyst masterbatch containing 2.5% of DBTDL and additional antioxidants.
  • SA Masterbatch 1 is catalyst masterbatch containing 2.8% of a sulfonic acid based catalyst and additional antioxidants.
  • Reactor copolymer 1 is a commercially available reactor based high pressure copolymer from Dow Chemical (1.5 melt index LDPE), it contains -1.5% by wt. of VTMS.
  • Sn Masterbatch 2 is a catalyst masterbatch containing 0.25% of DBTDL and additional antioxidants and flame retardants.
  • Grafted copolymer 1 is a LLDPE grafted with ⁇ 1.5% VTMS via reactive extrusion with peroxide.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

La présente invention concerne des compositions de polymères de silane réticulables comprenant (i) au moins un polymère à fonction silane, par exemple un copolymère à greffage silane, et des mélanges de tels polymères, et (ii) une quantité catalytique d'au moins un acide sulfonique aromatique substitué, de préférence polysubstitué (PASA).
PCT/US2009/066598 2008-12-23 2009-12-03 Compositions isolantes durcissant à température et humidité ambiantes et procédés associés WO2010074916A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10040888B1 (en) 2013-06-14 2018-08-07 Cooper-Standard Automotive Inc. Composition including silane-grafted polyolefin
US10100139B2 (en) 2013-08-01 2018-10-16 Cooper-Standard Automotive Inc. Hose, composition including silane-grafted polyolefin, and process of making a hose
US10371292B2 (en) 2014-07-02 2019-08-06 Cooper-Standard Automotive Inc. Hose, abrasion resistant composition, and process of making a hose
US10570236B2 (en) 2016-12-10 2020-02-25 Cooper-Standard Automotive Inc. Combined seals, compositions, and methods of making the same
US10779608B2 (en) 2016-12-10 2020-09-22 Cooper-Standard Automotive, Inc. Polyolefin elastomer compositions and methods of making the same
WO2024110589A1 (fr) * 2022-11-23 2024-05-30 Borealis Ag Câble comprenant une couche de composition de polyéthylène réticulable à vitesse de réticulation améliorée

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6005055A (en) * 1993-12-20 1999-12-21 Borealis Holding A/S Polyethylene compatible sulphonic acids as silane crosslinking catalysts
WO2002012354A1 (fr) * 2000-08-03 2002-02-14 King Industries, Inc. Catalyseurs d'acide monosulfonique alkylaryle et arylalkyle pour la reticulation de polyethylene
WO2006017391A2 (fr) * 2004-08-05 2006-02-16 Dow Global Technologies Inc. Composition de réticulation à base de silane réticulable par l’humidité

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6005055A (en) * 1993-12-20 1999-12-21 Borealis Holding A/S Polyethylene compatible sulphonic acids as silane crosslinking catalysts
WO2002012354A1 (fr) * 2000-08-03 2002-02-14 King Industries, Inc. Catalyseurs d'acide monosulfonique alkylaryle et arylalkyle pour la reticulation de polyethylene
WO2006017391A2 (fr) * 2004-08-05 2006-02-16 Dow Global Technologies Inc. Composition de réticulation à base de silane réticulable par l’humidité

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10253127B2 (en) 2013-06-14 2019-04-09 Cooper-Standard Automotive, Inc. Composition including silane-grafted polyolefin
US10774168B2 (en) 2013-06-14 2020-09-15 Cooper-Standard Automotive, Inc. Composition including silane-grafted polyolefin
US10040888B1 (en) 2013-06-14 2018-08-07 Cooper-Standard Automotive Inc. Composition including silane-grafted polyolefin
US10774955B2 (en) 2013-08-01 2020-09-15 Cooper-Standard Automotive, Inc. Hose, composition including silane-grafted polyolefin, and process of making a hose
US10100139B2 (en) 2013-08-01 2018-10-16 Cooper-Standard Automotive Inc. Hose, composition including silane-grafted polyolefin, and process of making a hose
US10371292B2 (en) 2014-07-02 2019-08-06 Cooper-Standard Automotive Inc. Hose, abrasion resistant composition, and process of making a hose
US10895335B2 (en) 2014-07-02 2021-01-19 Cooper-Standard Automotive, Inc. Hose, abrasion resistant composition, and process of making a hose
US10689471B2 (en) 2016-12-10 2020-06-23 Cooper-Standard Automotive, Inc. Microdense seals, compositions, and methods of making the same
US10689470B2 (en) 2016-12-10 2020-06-23 Cooper-Standard Automotive, Inc. Static seals, compositions, and methods of making the same
US10779608B2 (en) 2016-12-10 2020-09-22 Cooper-Standard Automotive, Inc. Polyolefin elastomer compositions and methods of making the same
US10570236B2 (en) 2016-12-10 2020-02-25 Cooper-Standard Automotive Inc. Combined seals, compositions, and methods of making the same
US11377514B2 (en) 2016-12-10 2022-07-05 Cooper-Standard Automotive, Inc. Combined seals, compositions, and methods of making the same
US11684115B2 (en) 2016-12-10 2023-06-27 Cooper-Standard Automotive Inc. Roofing membranes, compositions, and methods of making the same
WO2024110589A1 (fr) * 2022-11-23 2024-05-30 Borealis Ag Câble comprenant une couche de composition de polyéthylène réticulable à vitesse de réticulation améliorée

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