MOISTURE CURABLE, MELT PROCESSIBLE GRAFT ETHYLENE COPOLYMERS

Abstract: The present invention relates to high performance wire and cable compositions and to hot melt adhesives containing a silyl-grafted ethylene copolymer having particularly low levels of glycidyl acrylate termonomer. The preferred epoxy glycidyl methacrylate copolymerized into the polymer backbone provides a graft site for the aminosilane. Subsequent moisture crosslinking at the silyl site of the thermally stable graft copolymer provides compositions with attractive physical properties for wire and cable semicons, insulation, and jackets, as well as hot melt adhesives. The preferred aminosilane is N-cyclohexylaminopropyl trimethoxysilane.

Description: TITLE Moisture Curable, Melt Processible Graft Ethylene Copolymers BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to high performance wire and cable resins and to hot melt adhesives containing a silyl grafted ethylene copolymer having particularly low levels of a glycidyl acrylate termonomer. Description of Related Art U.S. Pat. Nos. 5,389,728 and 5,484,847 describe the preparation and use of moisture curable, melt processible, graft copolymers which are obtained by reacting certain ethylene copolymers having copolymerized therewith a glycidyl containing comonomer(s) which is then further reacted with a particular grafting agent selected from N-tert-butylaminopropyl trimethoxysilane. This particular class of grafted copolymers was described as sufficiently stable for coextrudable hot melt adhesive use. Wire and cable applications were also mentioned for this particular class. The above patent disclosures also clearly described certain substituted aminopropyl trimethoxy silanes grafted ethylene copolymers (ethylene/alkyl acrylate/glycidyl methacrylate as the direct copolymer) which were particularly unsuitable for hot melt adhesive use because of their thermal instability under hot melt adhesive use conditions. Included among the list of particularly unsuitable silanes utilized as a grafting reagent was N-cyclohexylaminopropyl trimethoxysilane as well as numerous others. Comparative Example 2 in U.S. Pat. No. 5,389,728 clearly shows the unsuitability of a copolymer having ethylene, an alkyl acrylate and a glycidyl termonomer grafted with N-cyclohexylaminopropyl trimethoxysilane. The only suitable N- alkylaminopropyl trimethoxysilane for hot melt adhesive use was the patented t- butyl derivative. Other comparative unsuitable examples were also described. The inventors have found that because of a specific low range of glycidyl monomer in the present invention, thermal stability is achieved for hot melt adhesive compositions having the claimed grafted copolymers therein. On the other hand, and with respect to vinyl acetate containing copolymers, U.S. Pat. No. 5,484,847 did not disclose any specific comparative examples showing other N-substituted aminopropyl trimethoxy silanes and only specifically disclosed an ethylene/vinyl acetate/glycidyl methacrylate copolymer containing 11.1 wt.% EVA and 7.4 wt.% glycidyl methacrylate with N-tert- butylaminopropyl trimethoxysilane grafted thereto. This patent disclosure did not teach anything about the use or potential use of other N-substituted aminopropyl trimethoxysilanes as grafting reagents with vinyl acetate containing ethylene copolymers-all comparative examples and/or teachings with respect to any reagent other than N-tert-butylaminopropyl trimethoxysilanes were directed to the alkyl acrylate containing copolymers. Both patent disclosures discussed above expressly or implicitly teach away from the use or potential use of ethylene copolymers having an alkyl acrylate or a vinyl acetate as a comonomer along with a glycidyl containing comonomer which is subsequently grafted with an aminosilane other than the specific t- butylaminopropyl trimethoxysilane. Furthermore, the above patent disclosures suggest that at lower percentages of glycidyl moiety in the disclosed compositions (equal to or less than 6 percent) grafting catalysts are required to speed up the grafting reaction. The present inventors have surprisingly found, on the other hand, that catalysts are unnecessary to effect the grafting reaction at these lower percentages of glycidyl monomer and have further found that moisture curing catalysts are also unnecessary. The present inventors have also found that the relative composition of the direct copolymer, wherein one of the monomers is vinyl acetate, affects the suitability of a grafted copolymer based thereon for wire and cable applications. The inventors have found that an ethylene vinyl acetate copolymer having a narrow, specific range of glycidyl comonomer which is subsequently grafted in an extruder with an N-substituted aminopropyl trimethoxysilane (excluding N-t- butyl) and subsequently formed into a coating for a wire or cable (or material suitable for forming a coating for a wire and cable) provides a particularly effective wire and cable coating with good moisture curing thermoset properties and, thus, further provides effective wire and cable products. There is a need to develop additional copolymers which provide good performance in hot melt adhesives as well as wire and cable applications which continue to demand reliable physical properties at extreme temperatures or wide temperature variations and which can be readily made in an extruder. In addition, prior art thermoset resins generally require continuous vulcanization (CV) tubes and/or radiation equipment to provide high performance thermoset properties and known vinyl silane moisture curable systems typically require peroxide, catalyst and high graft temperatures which can lead to undesired side crosslinking reactions and an increase in compound viscosity. The present inventors have discovered a thermally stable grafted terpolymer having a glycidyl moiety which contains an N-cyclohexylaminopropyl trimethoxysilane or other N-alkyl- or N- alkylarylaminopropyl trimethoxysilanes which were formerly thought to be unsuitable and which do not require a CV tube, peroxide, extruder catalyst addition or high graft temperatures. BRIEF SUMMARY OF THE INVENTION The present invention comprises or consists essentially of a grafted polymeric compound having units of the formula E/X/Y-(G) in random order, wherein E is ethylene; X comprises about 8-70 weight percent, preferably about 8-50 weight percent, most preferably about 8-46 weight percent, relative to the total weight of E/X/Y, and is selected from the group consisting of: a C r C g alkyl acrylate, a C,-C 8 alkyl methacrylate or vinyl acetate; Y comprises about 0.5-9 weight percent, preferably about 1-4 weight percent, relative to the total weight of E/X/Y, of a glycidyl containing monomer selected from the group consisting of glycidyl acrylate, glycidyl methacrylate and glycidyl vinyl ether, and G comprises from about 15-150 percent of a stoichiometric amount with respect to the weight of the glycidyl moiety, of a secondary aminosilane compound of the formula R-N(H)CH 2 -CH 2 CH 2 -Si(OCH 3 ) 3 wherein R is selected from a) a secondary radical of the formula HCR1R2 wherein Rl and R2 are independently selected from C,-C 6 alkyl or C,-C 6 alkylaryl wherein Rl and R2 may be joined to form a C 5 -C 9 cycloaliphatic ring; OR b) a primary radical of the formula HHCR3 wherein R3 is selected from a C 3 -C 12 alkyl group or a C r C 12 alkyl aryl group wherein, in the case of a C 3 -C 6 alkyl group, said alkyl moiety is branched, and wherein Rl, R2 or R3 may be unsubstituted or substituted with substituents selected from C,-C 4 alkyl. The grafted polymeric compound is thermally stable and has a melt index ranging from 1 to 2000. The melt index is preferably 1 to 60 for wire and cable applications and 50 to 2000 for hot melt adhesives. The present invention also comprises a thermally stable, melt-processible, moisture curable graft copolymer which comprises the reaction products of (A) a direct copolymer from monomers comprising: (i)ethylene; (ii) 8-70 wt.% of C,-C 8 alkyl acrylate or methacrylate or vinyl acetate; (iii) 0.5-9 wt.% of a glycidyl containing monomer selected from the group consisting of glycidyl acrylate, glycidyl methacrylate and glycidyl vinyl ether; and (B) from 15 to 150 percent of a stoichiometric amount with respect to the weight of the glycidyl moiety, of a secondary aminosilane of the formula R- N(H)CH 2 -CH 2 CH 2 -Si(OCH 3 ) 3 wherein R is selected from a) a secondary radical of the formula HCR1R2 wherein Rl and R2 are independently selected from C,-C 6 alkyl or C r C 6 alkylaryl wherein Rl and R2 may be joined to form a C 5 -C 9 cycloaliphatic ring; or b) a primary radical of the formula HHCR3 wherein R3 is selected from a C 3 -C 12 alkyl group or a C,-C 12 alkyl aryl group wherein, in the case of a C 3 -C 6 alkyl group, said alkyl moiety is branched, and wherein Rl, R2 or R3 may be unsubstituted or substituted with substituents selected from C 4 -C 4 alkyl wherein the grafted polymeric compound has a melt index of 1 to 2000 and is thermally stable. The present invention also relates to hot melt adhesive compositions or wire and cable compositions containing or comprising said grafted copolymers and to hot melt adhesive compositions and/or wires and cables which contain the post-extrusion, post-hydrolyzed crosslinked versions of said polymers. The invention herein also relates to improved methods for coating a wire comprising the steps of: (a) extruding a mixture of a direct ethylene copolymer containing epoxide groups and a grafting compound around a wire, wherein said direct ethylene copolymer is derived from monomers comprising: (i) ethylene; (ii) 8-70 weight percent of C r C 8 alkyl acrylate or methacrylate or vinyl acetate; (iii) 0.5 to 9 weight percent of a glycidyl containing monomer selected from the group consisting of glycidyl acrylate, glycidyl methacrylate and glycidyl vinyl ether; and said grafting compound comprises about 15 to 150 weight percent of a stoichiometric amount with respect to the weight of the glycidyl moiety of a secondary aminosilane of the formula R-N(H)CH 2 -CH 2 CH 2 -Si(OCH 3 ) 3 wherein R is selected from (i) a secondary radical of the formula HCR1R2, wherein Rl and R2 are independently selected from C,-C 6 alkyl or C r C 6 alkylaryl, wherein Rl and R2 may be joined to form a C 5 -C 9 cycloaliphatic ring; or (ii) a primary radical of the formula HHCR3 wherein R3 is selected from a C 3 -C 12 alkyl group or a C,-C 12 alky aryl group wherein, in the case of a C 3 -C 6 alkyl group said alkyl moiety is branched and wherein Rl, R2 or R3 may be unsubstituted or substituted with substituents selected from C,-C 4 alkyl; and (b) curing the coating on the wire by contacting the coated wire with water or air having a relative humidity of greater than 50%. The invention also relates to a method of improving the thermal stability of N-(substituted)aminopropyl trimethoxysilane grafted ethylene copolymers comprising selecting a direct copolymer prepared from (a) (i), (ii), and (iii) above to react with an N- (substituted)aminopropyl trimethoxysilane of the formula R- N(H)CH 2 -CH 2 CH 2 -Si(OCH 3 ) 3 wherein R is selected from a) a secondary radical of the formula HCR1R2 wherein Rl and R2 are independently selected from C,-C 6 alkyl or C,-C 6 alkylaryl wherein Rl and R2 may be joined to form a C 5 -C 9 cycloaliphatic ring; or b) a primary radical of the formula HHCR3 wherein R3 is selected from a C 3 -C 12 alkyl group or a C,-C, 2 alkyl aryl group wherein, in the case of a C 3 -C 6 alkyl group, said alkyl moiety is branched, and wherein Rl , R2 or R3 may be unsubstituted or substituted with substituents selected from C,-C 4 alkyl, to form a thermally stable N-substituted aminopropyl trimethoxysilane grafted ethylene copolymer. Definitions The term "direct copolymer" refers to a polymeric chain made from the respective monomeric units and serves as the base polymer for the "grafted copolymer" which includes a grafting reagent (or portion thereof) covalently bonded to the base polymer. The term "glycidyl" refers to a group derived from 2,3-epoxy-l-propanol and a glycidyl monomer is an epoxy containing monomer. The term "thermally stable" means that the grafted copolymer of the invention does not undesirably crosslink (or decompose) at the temperatures necessary to form or use the particular grafted direct copolymer without also negatively affecting the stability of the base direct copolymer or of the grafted polymer to the extent that such polymer cannot be satisfactorily used as a hot melt adhesive or as a wire and cable composition. The temperatures referred to above may vary depending upon the non-ethylene components in the direct copolymer (for example vinyl acetate versus alkyl acrylates) and also depends upon the nature of the silane grafting reagent. For suitability as a hot melt adhesive, the composition needs to be thermally stable in a hot melt container over an extended period of time at a temperature of, for example, 135 degrees Centigrade. The grafted polymers of this invention are thermally stable under these conditions. The vinyl acetate containing polymers are suitable as wire and cable compositions and are stable under the conditions necessary to form the compositions (in an extruder) for wire and cable applications. DETAILED DESCRIPTION The compositions of the invention are high performance polymeric compositions suitable for wire and cable and hot melt adhesive use. The recited compositions do not require special equipment (i.e. CV tubes) or peroxides, extruder catalysts or high graft temperatures to achieve significant thermoset properties suitable for wire and cable compositions and for hot melt adhesive compositions. The inventors have surprisingly found that lower levels of GMA or glycidyl moiety in the direct copolymer described herein coupled with the particular type of grafting material influences the temperature at which grafting occurs (e.g. grafting can occur at lower temperatures) and influences the variability of the grafting reaction in terms of graft level (e.g. provides more consistent-less variable-grafting levels). Grafting at lower temperatures is particularly suitable for wire and cable compositions because crosslinking side reactions are minimized. The compositions of the invention include thermally stable hot melt adhesive compositions and wire and cable compositions. The thermally stable hot melt adhesive compositions are N-substituted aminopropyl trimethoxysilane grafted ethylene alkyl acrylate or alkyl methacrylate copolymers also having as a third comonomer a low weight percentage of a hydroxy containing monomer beta to the nitrogen on the grafting agent. The wire and cable compositions are N- substituted aminopropyl trimethoxysilane grafted ethylene vinyl acetate copolymers also having as a third comonomer a low weight percentage of a hydroxy containing monomer beta to the nitrogen on the grafting agent. Secondary aminosilane compounds based on triethoxysilane composition comprise the invention also. The compositions of the invention are thermally-stable, graft copolymers which are the reaction products of a direct ethylene copolymer containing epoxide groups and a grafting compound which is a secondary aminosilane compound of the formula R-N(H)CH 2 -CH 2 CH 2 -Si(OCH 3 ) 3 wherein R is selected from a) a secondary radical of the formula HCR1R2 wherein Rl and R2 are independently selected from C C 6 alkyl or C,-C 6 alkylaryl wherein Rl and R2 may be joined to form a C 5 -C 9 cycloaliphatic ring; or b) a primary radical of the formula HHCR3 wherein R3 is selected from a C 3 -C 12 alkyl group or a C,-C 12 alkyl aryl group wherein, in the case of a C 3 -C 6 alkyl group, said alkyl moiety is branched (versus linear off the carbon atom of attachment), and wherein Rl, R2 or R3 may be unsubstituted or substituted with substituents selected from C,-C 4 alkyl. The direct ethylene copolymer The direct copolymer represented by the units of EXY in random order has a glycidyl monomer incorporated therein as defined above as the Y component in the percentage range of 0.5 to 9 wt. percent, preferably 1 to 4 weight percent. The glycidyl monomers are the glycidyl esters of acrylic and methacrylic acid and also glycidyl vinyl ether. Glycidyl methacrylate is especially preferred. In order to provide thermal stability to the grafted copolymers of the invention, the percentage of glycidyl monomer in the terpolymer needs to be carefully controlled and should preferably be between 0.5 and 9 weight percent, with the preferred percentage when the grafting reagent is selected from N- cyclohexylaminopropyl trimethoxy silane being approximately 4 wt.% or less for hot melt adhesive application and 2 wt.% or less for wire and cable. Surprisingly, no catalyst is required for grafting or eventual moisture cure of a thermoset composition containing the grafted copolymer. The X component of the direct ethylene copolymer is selected from C,-C 8 alkyl acrylates such as n-butyl acrylate or methacrylate and is present in a wt. percentage range relative to the other components in the direct copolymer of 8 to 70 weight percent, preferably 8 to 50 weight percent, most preferably 8 to 46 weight percent. The X component may also be selected from a vinyl acetate moiety in the same weight range. These copolymers containing the E/X/Y components in the weight percentages listed above are generally prepared by well known methods of preparing such copolymers. These methods typically use a continuous stirred reactor at high temperatures and pressures, as described in U.S. Pat. Nos. 4,351,931 and 3,780,140. The melt index of the direct copolymers used as precursors herein may have a melt index range of 1 to 2000. Preparation of an E/X/Y terpolymer of ethylene n-butyl acrylate glycidyl methacrylate of weight % composition 66.75/28/5.25 as may be used in this invention typically involves polymerization in a stirred autoclave reactor above 20,000 psi and at reactor temperatures above 150°C. Random monomer polymerization is initiated with peroxide free radicals. A telogen such as acetone is used to control molecular weight to the desired range. High and then low pressure separators are used to let down reactor pressure. Resin is isolated as pellets melt cut under water, dried, and packaged. The polymer described here is commercially available from DuPont as Elvaloy®AM resin, has a melt index of 12 g/10 min., crystalline melting point of 72°C, and density of 0.94 g/cm 3 . Stress strain properties by ASTM D638 with a 2 inch/min. pull rate are 750 psi (5.2 mPa) tensile strength, 950% elongation at break, and 73 Shore A durometer hardness. Preparation of an E/X/Y terpolymer of ethylene vinyl acetate glycidyl methacrylate of weight % composition 66.75/32/2 as may be used in this invention is carried out by polymerization in a stirred autoclave at 27,000 psi pressure, 168°C reactor temperature, and peroxide free radical initiation. An acetone telogen is used to control molecular weight to provide resin with melt index in the range of 3-50 g/10 min. isolated after pressure let down, melt pelletization, and drying. The direct copolymers utilized in this invention having a vinyl acetate component have a Melt Index range of between 1 and 60 g/10 min. and are suitable for wire and cable applications. The resulting grafted copolymers prepared from these direct copolymers should have an MI range that is similar to the precursor direct copolymer. No major change in MI properties should generally occur upon grafting; the MI of the grafted polymer is usually not more than 20%o different than the precursor copolymer. The Grafting Reagent As described above, the grafting reagent is selected from an N-substituted aminoalkyl trialkoxysilane which after grafting and upon moisture cure provides good thermoset and/or controlled crosslinking for the hot melt adhesive or the wire and cable composition. Generally these reagents are commercially available or made from commercially available precursors. The suitable aminosilanes are selected from a compound of the formula R- N(H)C r C 6 alkyl-Si(OC r C 6 alkyl) 3 wherein R is selected from a) a secondary radical of the formula HCR1R2 wherein Rl and R2 are independently selected from C,-C 6 alkyl or C,-C 6 alkylaryl wherein Rl and R2 may be joined to form a C 5 -C 9 cycloaliphatic ring; or b) a primary radical of the formula HHCR3 wherein R3 is selected from a C 3 -C 12 alkyl group or a C r C ]2 alkyl aryl group wherein, in the case of a C 3 -C 6 alkyl group, said alkyl moiety is branched, and wherein Rl, R2 or R3 may be unsubstituted or substituted with substituents selected from C,-C 4 alkyl. The secondary radicals are selected from, for example, isopropyl, isobutyl or cyclohexyl or C,-C 4 alkyl substituted versions thereof and are also selected from an alkylaryl such as benzyl, phenethyl and the like. The primary radicals are selected from moieties such as HHCC(CH 3 ) 2 or HHC(C 4 -C 12 ). The preferred aminosilane is selected from a compound of the formula R-N(H)C r C 6 alkyl- Si(OC r C 6 alkyl) 3 wherein, in order, R is cyclohexyl ( cycloaliphatic), C,-C 6 alkyl is propyl (C 3 alkyl) and OC,-C 6 is OCH 3 (OC,alkyl). The Resulting Grafted Ethylene Copolymer The grafted ethylene copolymer of the invention herein results from the reaction product(s) of the direct copolymer and the grafting reagent described above The glycidyl group reacts with the secondary amine (amino) group of the aminosilane. The stoichiometric amount of the secondary amino silane relative to the glycidyl moiety can vary considerably from 15 to 150 percent, based on weight. The skilled artisan can vary this according to the degree of crosslinking desired in the post-extruded, post-hydrolyzed product. The resulting crosslinking leads to high heat resistance, oil resistance, mechanical strength, good abrasion as well as cut resistance etc. In general, the grafting reaction occurs by contacting the direct copolymer and the aminosilane in, e.g., a high shear melt mixer such as an extruder equipped with a suitable mixing screw or other high shear mixers such as a Banbury, Brabender or Haake mixer, though any suitable mixer is contemplated. Melt temperatures above 110°C are used to allow sufficiently rapid reaction without increasing the possibility of undesirable side reactions. Stearic acid and triphenylphosphine may be further or additionally added to the reaction system to catalyze the reaction although, as indicated above, they are not required or necessary. Generally, reaction temperatures above 220 deg. C. are not suitable when vinyl acetate is in the polymer because of potential polymer degradation. No solvent is generally used and hold up times required for complete reaction are typically about 1 to 10 minutes depending upon the temperature, shear and/or catalyst system if present. While close to stoichiometric amounts of aminosilane and glycidyl moiety are most suitable, an aminosilane/glycidyl ratio of from 0.15/1 to 1.5/1 can be used. The process of preparation is that as described in the examples. In contrast to the use of t-butyl derivatives as described in the prior art, high temperatures were not required to graft the aminosilane. For wire and cable applications, the aminosilane is typically grafted to glycidyl methacrylate epoxy-containing polymers, such as ethylene vinyl acetate and ethylene n-butyl acrylate, by heating at 110 to 200°C in a high shear mixer such as a Banbury, Brabender, Haake, Buss co-kneader, or in a single or twin screw extruder for about 1-10 minutes, depending on the temperature. Grafting also takes place by compression or injection molding plaques containing the mixed compound of glycidyl methacrylate polymer and aminosilane. Reaction of N-cyclohexylaminopropyl trimethoxysilane with glycidyl methacrylate epoxy is rapid and complete at 150°C and even occurs at 110°C at reasonable rate. In the absence of moisture, crosslinking does not take place and the grafted compound is re-shapeable. If sufficient moisture is present in the grafted compound, as may be introduced with a filler, scorch or pre-cure may occur and result in increased compound viscosity and difficulty in subsequent processing, such as extrusion on to wire. Use of dry fillers or pre-drying of compound ingredients minimizes potential scorch. The grafted copolymers of the invention are suitable for use alone or in combination with other ingredients depending upon the final use/product. For example, they can be formulated with tackifiers or plasticizers or other excipients used in hot melt adhesives or in wire and cable compositions. These grafted copolymers may be used in neat form or blended with the stated excipients for either hot melt use or for wire and cable use. The grafted copolymers of the invention may further be processed and reshaped into the final configuration between 110°C and 170°C as long as moisture is avoided. For hot melt adhesive use, the neat grafted copolymer can be utilized as a hot melt adhesive or it can be formulated. There are many possible formulations, but a typical formulation might contain about one third polymer, one third of a hydrocarbon wax (paraffin or microcrystalline), one third of a tackifier resin and ppm level of an antioxidant package (e.g. phenolic and phosphite). Sometimes only polymer, tackifying resin and antioxidant are included in the formulation. Tackifier resins commonly used are C 5 and C 9 hydrocarbon resins and rosin esters. Hot melt adhesives are normally produced in high shear batch mixers such as sigma blades, Banburys, Brabenders, Haake, etc. There are many uses for moisture-curable adhesives, including automotive gaskets, auto interior trim, auto head and tail lamps, furniture assembly including edge banding, bookbinding and general product assembly. For wire and cable applications, the grafted copolymer is prepared by addition of aminosilane to the mixed compound in the wire coating extruder. Residence times of typically 3-5 minutes at temperatures of 150°C provide good conditions for grafting secondary aminosilanes inside the extruder during coating of the wire. No catalysts are needed for the grafting reaction. The coated wire is wound on a reel which then may be submerged in 75-80°C water for 8 to 24 hours to bring about moisture cure. Prior to cure some care in handling is required to avoid deformation. The water permeates through the coating to react with the trimethoxysilane groups on two separate polymers to form a Si-O-Si crosslink bond with elimination of methanol. For medium and high voltage power cable, an ethylene vinyl acetate- or n- butyl acrylate-glycidyl methacrylate semicon compound is extruded onto wire with grafting of aminosilane introduced in the wire line extruder. By the same procedure, an insulation compound of ethylene glycidyl methacrylate or other moisture cureable polyethylene insulation is extruded with a second extruder over the semicon again with aminosilane introduced. And finally in a third extruder, a second outer semicon of ethylene vinyl acetate- glycidyl methacrylate and aminosilane is extruded and grafted in the extruder while wire coating. These three layers, all of which contain grafted aminosilane can then be simultaneously cured by submersion in warm water. This moisture cure technology is especially effective in power cables where semicon compounds contain relatively low filler levels and the PE insulation is unfilled so moisture crosslinking during grafting is minimal because of low moisture content in the compounds. The same glycidyl epoxy/aminosilane technology provides moisture curable flame retardant non-halogen jackets and automotive primary wire. These compounds differ from power cable semicons in containing higher levels of mineral fillers so that greater care must be taken to assure dry compound ingredients to minimize pre-cure during grafting of the aminosilane. Any wire and cable compound containing an epoxy group - semicon, insulation, and/or jacket - can be grafted with an appropriate aminosilane and extruder conditions during wire line coating and subsequently moisture cured with water to provide cables with attractive physical properties. The resulting graft copolymers of this invention have a melt index (MI) of from 1 to 2,000. Higher melt index polymers are particularly suitable for hot melt adhesive use while the lower melt index polymers (e.g., vinyl acetate containing polymers) are suitable for wire and cable applications. Moisture curing occurs by crosslinking of the direct polymer through the silane groups. Crosslinking during moisture cure causes increased strength and modulus. The crosslinking reaction on moisture treatment of the grafted copolymer can occur at room temperature and at 50% humidity or higher, but is accelerated at higher temperatures and higher relative humidity. Total immersion in warm water provides commercially attactive cure rates for coated wire. Test Procedures: In the examples which follow, the preparation of the moisture curable ethylene graft copolymer is described. The rate of moisture cure is monitored by viscosity change and the thermal stability of the graft copolymers is determined. Melt Index (MI) is determined using ASTM D-1238 (2160 g. load/190 deg.C with values in units of g/10 min.). Viscosity stability for adhesives was measured using a Brookfield viscometer at 135°C and a shear rate of 0.1 sec-1. The polymer is kept at this temperature in an open cup, and viscosity change continuously monitored. This temperature is a typical melt processing temperature for adhesives. For adhesives, long hold up times in the melt are desired. In the test, a viscosity increase of less than 50%) over a period of eight hours is considered an indication of thermal stability and sufficient for adhesive use. Such a test is also indicative of stability at higher temperatures with shorter hold up times such as in an extrusion process where exposure to high temperature is generally in or over a several minute period. Curability-the ease at which the polymer crosslinks with moisture is determined in the following way. A 70 mil compression molded plaque was prepared using a press temperature of 120 deg. C. and a 5,000 pound load. The plaque was placed in a humidity chamber kept at 70 deg. C. and 95% relative humidity. After 24 hours, melt index tests are carried out. Low or no flow after this time indicates a good cure rate. Viscosity stability for wire and cable was measured on the compound using a Mooney viscometer after 1+4 minutes at 100°C with the large rotor by ASTM D1646. Compounds were stored at 23 °C in 50%> relative humidity and Mooney viscosity (ML) increase measured over time. Curability for wire and cable was determined by measurement of tensile properties by ASTM D412 of molded test plaques or coated wire. Volume resistivity, an important property for power cable semicons, was measured by ASTM D991. Volume resistivity for insulation material was measured by ASTM D257. Dielectric strength was measured by ASTM D149 in oil by increasing voltage at a rate of 500 volt/sec. Dielectric constant and dissipation factor were measured by ASTM DI 50. For wire and cable samples, grafting of aminosilane was carried out either in compression molded 2 mm plaques heated 5 minutes at 150 or 180 (or 177)°C or in a wire line extruder at 60-150°C during wire coating. Moisture crosslinking through the silane groups of the grafted aminosilane was carried out by submersion of test plaques and coated wire in water at 80°C for 24 hours. EXAMPLES The following example demonstrates that a lower glycidyl moiety percentage in an ethylene/alkyl acrylate terpolymer grafted with a substituted N- aminoalkyl trialkoxysilane has the physical properties which are indicative of a hot melt adhesive. Example 1 -Grafted Ethylene/n-Butyl Acrylate/GMA in Hot Melt Adhesive 45 g. of an ethylene/n-butylacrylate/glycidyl methacrylate containing 4 wt.%) GMA and 30 weight percent nBA and having a melt index of 1000 was reacted with 3.3 g. of N-cyclohexylaminopropyl trimethoxysilane in a Brabender mixer at 160 deg. C for 10 min. Rotor speed was 100 rpm. This represents a stoichiometric balance of aminosilane to the glycidyl moiety. The MI of the grafted product was 1098. This is above that of the direct copolymer which suggests that little or no crosslinking occured during the preparation of the grafted copolymer. Thermal stability of the product was determined. The Brookfield viscosity initially was 33,600 centipoise. Viscosity increased approximately 40%> in 8 hours indicating adequate thermal stability for hot melt adhesive use. Cure tests showed the resin to have no flow after the 24 hour moisture treatment at 70 deg. C. indicating the efficiency of the crosslinking by moisture. No catalyst was required for moisture cure or for preparation of the grafted product. Comparative Example 1 45 g. of an ethylene/-n-butyl acrylate/glycidyl methacrylate direct copolymer containing 25 wt.% n-butyl acrylate and 7.6 wt.%> glycidyl methacrylate and having an MI of 900 was reacted with 8.14 g. of N- cyclohexylaminopropyl trimethoxysilane using a 30%> molar excess of silane. Melt index of the grafted product was 1443. Cure was excellent, the resin exhibiting no flow after 24 hours under the conditions described above. Thermal stability was unacceptable or poor- viscosity increased from 22,000 by 100% in only 210 minutes. The above example demonstrates that the relative percentage of glycidyl methacrylate in the terpolymer makes a significant difference in the ultimate thermal stability of the grafted product formed therefrom. These examples also demonstrate that the ability to moisture cure is not negatively impacted by lowering the percentage of glycidyl groups and thus lowering the percentage of grafted sites or moisture cure crosslinking sites. Example 2 - Grafted Ethylene/n-Butyl Acrylate/GMA In Wire And Cable Semicon A semicon compound based on ethylene n-butyl acrylate glycidyl methacrylate (GMA) with 28 wt.% n-butyl acrylate and 5.25 wt.% GMA with 12 melt index (commercially DuPont Elvaloy®AM resin) was mixed in a lab-size banbury internal mixer with Black Pearls 3200, high purity fine particle size conductive furnace black from Cabot Corp., stearic acid, and Irganox 1010 hindered phenol antioxidant from Ciba-Geigy. The compound ingredients were mixed to 121 °C, held 2 minutes, dropped, sheeted, and allowed to cool. The compound formulation in parts per hundred rubber (phr) is listed in Table 1. Stearic acid is a process aid but also has a catalytic effect on the grafting reaction. A stoichiometric amount of n-cyclohexylaminopropyl trimethoxysilane and 38%> of the stoichiometric amount (Samples 1 and 2, respectively) were added to the compound on a 90°C two-roll mill along with a small amount of the carbon black which was held out of the banbury mix. The cyclohexylaminosilane was obtained from Huls America Inc. as PSX5411. The mixed stock was sheeted off the same day for Mooney viscosity and preparation of test plaques. Mooney viscosity biscuits were stored at 23 °C in a 50% relative humidity test lab and ML- 1+4 at 100°C periodically measured. Test plaques with 2 mm thickness were molded the same day of the mix for 5 minutes in a heated press at either 150°C (Condition A) or 180°C (Condition B) to graft the aminosilane to the GMA epoxy on the polymer. Test plaques were moisture cured by submersion for 24 hours in an 80°C water bath. Mooney viscosity, original and heat aged tensiles, and volume resistivity results are found in Table 1. Volume resistivity provides an important measure of the electrical suitability of the semicon for the application. The increase in stock viscosity measured by Mooney shows that moisture cure occurs slowly at ambient temperature in 50% relative humidity. All compounds are tightly cured as shown by the high tensile strength and low elongation values. The grafting reaction occurs at 150°C as well as it does at 180°C. A more optimum cure with higher elongation is possible with a resin with reduced glycidyl methacrylate than the 5.25 wt.% present in Elvaloy®AM. Volume resistivity results are well within the requirements for electrically conductive semicons. TABLE 1 Moisture Cured Semicon of Ethylene n-Butyl Acrylate Glycidyl Methacrylate with Stoichiometric And Less Than Stoichiometric n- Cvchohexylaminopropyl Trimethoxysilane phr Compound I 2 Elvaloy® AM 100 100 Black Pearls 3200 75 75 Stearic Acid 1 1 Irganox 1010 1.5 1.5 PSX 5411 Aminosilane 10.14 3.87 Test Plaques - 2 mm Graft Conditions: A - 5 min. at 150°C in press B - 5 min. at 180°C in press Moisture Cure Conditions: 24 Hours in 80°C water bath Results: ML - 1 +4 at 100°C Compound 1 2 1 Day after mix 41 63 2 Days after mix 58 78 8 Days after mix Off scale Off scale Stress/Strain Compound 1 Compound 2 Original A B A B Hardness, Shore A 87 91 91 89 T B , mPa 18.2 20.1 15.0 15.1 E B , % 56 58 83 84 Heat Aged 7 Days @ 150°C Hardness, Pts. Chg. 0 -12 -8 -4 T B , %> Retention 96 95 127 132 E B , % Retention 66 71 65 75 Volume Resistivity, ohm • meter 7 8 211 8 Example 3 - Grafted Ethylene/Ninyl Acetate/GMA In Wire And Cable Semicon A semicon compound based on ethylene vinyl acetate glycidyl methacrylate (GMA) with 32 wt.% vinyl acetate and 2.0 wt.% GMA with 26 melt index was mixed with the same ingredients, again in a lab-size banbury mixer in the same manner as in Example 2. A stoichiometric amount of n- cychohexylaminopropyl trimethoxysilane was added to the compound listed in Table 2 on a 90°C two-roll mill as before. The mixed stock was again sheeted off the same day for Mooney viscosity and preparation of test plaques. Results are found in Table 2. Curing takes place slowly at 23°C in 50% relative humidity as shown by the Mooney viscosity increase while curing is rapid in 80°C water as shown by the tensile results. Again, the grafting reaction was equally facile at 150 as at 180°C. The 2% GMA level in this polymer provides a more optimum cure state level as indicated by the original elongation values of well over 100%. TABLE 2 Moisture Cured Semicon of Ethylene Vinyl Acetate Glycidyl Methacrylate with n-Cychohexylaminopropyl Trimethoxysilane phr Compound 3 EVA GMA 100 Black Pearls 3200 75 Stearic Acid 1 Irganox 1010 1.5 PSX 5411 Aminosilane 3.87 Test Plaques - 2 mm Graft Conditions: A - 5 min. at 150°C in press B - 5 min. at 180°C in press Moisture Cure Conditions: 24 Hours in 80°C water bath Results: ML - l+4 at lOO°C 1 Day after mix 56 2 Days after mix 60 8 Days after mix 74 15 Days after mix Off scale Stress/Strain Original A B Hardness, Shore A 83 92 MlOO mPa 13.0 13.2 T B , mPa 13.1 13.4 E B , % 153 145 Heat Aged 7 Days @ 150°C Hardness, Pts. Chg. +4 0 M100, % Retention 134 131 T B , % Retention 140 137 E B , % Retention 83 88 Volume Resistivity, ohm • meter 3.3 1.3 Example 4 - Grafted Ethylene/Vinyl Acetate/GMA Semicon Extruded On Wire A semicon compound based on ethylene vinyl acetate glycidyl methacrylate (GMA) with 32 wt.% vinyl acetate and 2.0 wt.% GMA with 27 melt index was mixed with the same ingredients in a lab-size banbury internal mixer in the same manner as in Examples 2 & 3. A stoichiometric amount of n- cyclohexylaminopropyl trimethoxysilane was added to the compound listed in Table 3 on a 90°C two-roll mill as before. But here the mixed stock was extruded on to wire the same day of the mix. A Royal L/D = 15/1, 1-1/4 inch rubber extruder with a low compression general transition screw with crosshead for wire coating was used. The extruder temperature profile was 60 to 150°C. A breaker plate and 60 mesh screen pack were employed. An approximate 1mm thickness of compound with smooth surface was coated on the 12 gauge solid aluminum conductor with an extruder rpm of 13 and line speed of 7 m min. Grafting of the aminosilane to the GMA epoxy takes place in the extruder during wire coating. The estimated compound melt temperature was at least 125°C. Moisture cure in the extruder appeared minimal as indicated by the unchanged head pressure during this short extrusion run. Curing takes place slowly at 23 °C in 50% relative humidity as shown by the increase in modulus and tensile strength and decrease in elongation of coated uncured wire stored in our physical test lab and periodically tested over time (Table 3). Curing is rapid in 80°C water as shown by the tensile results. The 2% GMA level in this polymer and stoichiometric amount of aminosilane provide an optimum cure state level. TABLE 3 Moisture Cured Semicon of Ethylene Vinyl Acetate Glycidyl Methacrylate with n-Cychohexylaminopropyl Trimethoxysilane Extruded on Wire Phr Compound 4 EVA GMA 100 Black Pearls 3200 75 Stearic Acid 1 Irganox 1010 1.5 PSX 5411 Aminosilane 3.87 Wire coating - 1 mm Graft Conditions: Extrusion on wire - extruder profile 60-150°C Moisture Cure Conditions: 24 Hours in 80°C water bath Results: Uncured Wire (23°C, 50% rel. hum.) Days after Mix Stress/Strain 2 8 15 M 100, mPa 8.4 9.4 10.2 T B , mPa 9.3 10.1 11.1 E B , % 293 267 231 Cured Wire (80°C water for 24 hrs) Stress/Strain (Original) M 100, mPa 12.7 T B , % 13.6 E B , % 184 Stress/Strain (Heat Aged 7 Days @150°C) M 100, % Retention 159 T B , % Retention 151 E B , % Retention 57 Example 5 - Grafted Ethylene/GMA In Wire And Cable Insulation Unfilled low density polyethylene is used for low and medium voltage power cable. An insulation compound based on a copolymer of ethylene and 1.8 wt. % glycidyl methacrylate with 5 melt index was mixed with a stoichiometric amount of n-cyclohexylaminopropyl trimethoxysilane in a lab-size brabender at 50 rpm and 110°C for 5 minutes after the resin pellets were melted. Some grafting of aminosilane to GMA undoubtedly took place in the brabender as the temperature rose to 132°C. Grafting was completed by molding 2 mm test plaques in a 177°C press for 5 minutes. Test plaques were moisture cured by submersion for 24 hours in an 80°C water bath as previously. Results are found in Table 4. An adequate moisture cure is obtained for an insulation material as indicated by the original tensile results. Electrical properties, although not quite as good as for peroxide-cured medium voltage insulation, nonetheless, are attractive. TABLE 4 Moisture Cured Insulation of Ethylene Glycidyl Methacrylate with N-Cvclohexylaminopropyl Trimethoxysilane Phr Compound 5 EGMA 100 PSX 5411 Aminosilane 3.48 Test Plagues - 2 mm Graft Conditions: 5 min. at 177°C in press (Some grafting likely during brabender mix) Moisture Cure Conditions: 24 hours in 80°C water bath Results: Stress/Strain (Original) Hardness, Shore A 93 M 100, mPa 9.2 T B , mPa 11.7 E B , % 432 Electricals Volume Resistivity, ohm • cm X 10 16 7.6 Dielectric Strength (oil) kvolt/mm 27.2 (volt/mil) 691 Dielectric Constant at 1 rnHz 2.39 Dissipation Factor at 1 mHz 0.00254

Claims: WHAT IS CLAIMED IS: 1. A thermally-stable, grafted copolymer, comprising units of the formula E/X/Y-(G) in random order, wherein E is ethylene; X comprises from 8-70 weight percent relative to the total weight of E/X/Y and is selected from the group consisting of: a C r C 8 alkyl acrylate, a C r C 8 alkyl methacrylate, or vinyl acetate; Y comprises about 0.5 to 9 weight percent relative to the total weight of E/X/Y of a glycidyl containing monomer selected from the group consisting of glycidyl acrylate, glycidyl methacrylate and glycidyl vinyl ether; and G comprises about 15-150 percent of a stoichiometric amount with respect to the weight of the glycidyl moiety, of a secondary aminosilane compound of the formula R-N(H)C,-C 6 alkyl-Si(OC ] -C 6 alkyl) 3 wherein R is selected from a) a secondary radical of the formula HCR1R2 wherein Rl and R2 are independently selected from C,-C 6 alkyl or C,-C 6 alkylaryl wherein Rl and R2 may be joined to form a C 5 -C 9 cycloaliphatic ring; or b) a primary radical of the formula HHCR3 wherein R3 is selected from a C 3 -C ]2 alkyl group, or a C,-C ]2 alkylaryl group wherein, in the case of a C 3 -C 6 alkyl group, said alkyl moiety is branched, and wherein Rl , R2 or R3 may be unsubstituted or substituted with substituents selected from C,-C 4 alkyl. 2. The grafted copolymer according to Claim 1 having a melt index ranging from about 1 to about 2000. 3. The grafted copolymer according to Claim 1 wherein element X is vinyl acetate and Y is present in a percentage range of about 1 to 4 percent. 4. The grafted copolymer according to Claim 1 wherein element X is selected from the C,-C 8 alkyl acrylate or methacrylate and Y is present in a percentage range of about 1 to 4 percent. 5. The grafted copolymer according to claim 3 or 4 wherein G is N- cyclohexylaminopropyl trimethoxysilane. 6. A thermally-stable, melt-processible, moisture-curable, graft copolymer which comprises the reaction products of a direct ethylene copolymer containing epoxide groups and a grafting compound, wherein said grafting compound is a secondary aminosilane compound of the formula R-N(H)C,-C 6 alkyl-Si(OC,-C 6 alkyl) 3 . 7. The grafted copolymer of claim 6 wherein the direct ethylene copolymer is derived from monomers comprising: (a) ethylene; (b) 8-70 weight percent of C,-C 8 alkyl acrylate or methacrylate or vinyl acetate; (c) 0.5 to 9 weight percent of a glycidyl containing monomer selected from the group consisting of glycidyl acrylate, glycidyl methacrylate and glycidyl vinyl ether. 8. The grafted copolymer of claim 7 wherein the grafting compound comprises about 15 to 150 weight percent of a stoichiometric amount, with respect to the weight of the glycidyl moiety, of a secondary aminosilane of the formula R-N(H)CH 2 -CH 2 CH 2 -Si(OCH 3 ) 3 wherein R is selected from (a) a secondary radical of the formula HCR1R2, wherein Rl and R2 are independently selected from C,-C 6 alkyl or C,-C 6 alkylaryl, wherein Rl and R2 may be joined to form a C 5 -C 9 cycloaliphatic ring; or (b) a primary radical of the formula HHCR3 wherein R3 is selected from a C 3 -C 12 alkyl group or a C r C ]2 alky aryl group wherein, in the case of a C 3 -C 6 alkyl group said alkyl moiety is branched and wherein Rl, R2 or R3 may be unsubstituted or substituted with substituents selected from C,-C 4 alkyl. 9. The grafted copolymer of claim 8 having a melt index ranging from about 1 to 2000. 10. The grafted copolymer of claim 8 wherein the direct copolymer is ethylene/n-butyl acrylate/glycidyl methacrylate and the secondary aminosilane is N-cyclohexylaminopropyl trimethoxysilane. 11. The grafted copolymer of claim 8 wherein the direct copolymer is ethylene/vinyl acetate /glycidyl methacrylate and the secondary aminosilane is N-cyclohexylaminopropyl trimethoxysilane. 12. A thermally-stable, hot melt adhesive comprising the copolymer according to claim 1 or claim 8 after extrusion and hydrolysis such that the resulting copolymer is crosslinked. 13. A wire and cable composition comprising the copolymer according to claim 1 or claim 8 after extrusion and hydrolysis such that the resulting copolymer is crosslinked. 14. An article comprising the copolymer according to claim 1 after extrusion and hydrolysis such that the resulting copolymer is crosslinked, said article selected from the group consisting of: a power cable, a primary auto wire, a wire jacket and a semicon. 15. An article comprising the copolymer according to claim 8 after extrusion and hydrolysis such that the resulting copolymer is crosslinked, said article selected from the group consisting of: a power cable, a primary auto wire, a wire jacket and a semicon. 16. A method for coating a wire comprising the steps of: (a) extruding a mixture of a direct ethylene copolymer containing epoxide groups and a grafting compound around a wire, wherein said direct ethylene copolymer is derived from monomers comprising: (i) ethylene; (ii) 8-70 weight percent of C r C 8 alkyl acrylate or methacrylate or vinyl acetate; (iii) 0.5 to 9 weight percent of a glycidyl containing monomer selected from the group consisting of glycidyl acrylate, glycidyl methacrylate and glycidyl vinyl ether, and and said grafting compound comprises about 15 to 150 weight percent of a stoichiometric amount with respect to the weight of the glycidyl moiety of a secondary aminosilane of the formula R-N(H)CH 2 -CH 2 CH 2 -Si(OCH 3 ) 3 wherein R is selected from (i) a secondary radical of the formula HCR1R2, wherein Rl and R2 are independently selected from C,-C 6 alkyl or C r C 6 alkylaryl, wherein Rl and R2 may be joined to form a C 5 -C 9 cycloaliphatic ring; or (ii) a primary radical of the formula HHCR3 wherein R3 is selected from a C 3 -C 12 alkyl group or a C,-C 12 alky aryl group wherein, in the case of a C 3 -C 6 alkyl group said alkyl moiety is branched and wherein Rl, R2 or R3 may be unsubstituted or substituted with substituents selected from C,-C 4 alkyl; and (b) curing the coating on the wire by contacting the coated wire with water or air having a relative humidity of greater than 50%. 17. A method to improve the thermal stability of N-(substituted) aminopropyl trimethoxysilane grafted ethylene compolymers comprising: (a) selecting a direct ethylene copolymer derived from monomers comprising: (i) ethylene; (ii) 8-70 weight percent of C,-C 8 alkyl acrylate or methacrylate or vinyl acetate; (iii) 0.5 to 9 weight percent of a glycidyl containing monomer selected from the group consisting of glycidyl acrylate, glycidyl methacrylate and glycidyl vinyl ether, and (b) contacting the copolymer of a with a grafting compound comprising about 15 to 150 weight percent of a stoichiometric amount with respect to the weight of the glycidyl moiety of a secondary aminosilane of the formula R-N(H)CH 2 -CH 2 CH 2 -Si(OCH 3 ) 3 wherein R is selected from (i) a secondary radical of the formula HCR1R2, wherein Rl and R2 are independently selected from C,-C 6 alkyl or C,- C 6 alkylaryl, wherein Rl and R2 may be joined to form a C 5 -C 9 cycloaliphatic ring; or (ii) a primary radical of the formula HHCR3 wherein R3 is selected from a C 3 -C 12 alkyl group or a alky aryl group wherein, in the case of a C 3 -C 6 alkyl group said alkyl moiety is branched and wherein Rl , R2 or R3 may be unsubstituted or substituted with substituents selected from C,-C 4 alkyl, to form a thermally-stable, N-(substituted) aminopropyl trimethoxysilane grafted ethylene copolymer.

Inventors: ARHART RICHARD JAMES, PREJEAN GEORGE WYATT, ARHART, RICHARD, JAMES, PREJEAN, GEORGE, WYATT
Applicants: DU PONT, E.I. DU PONT DE NEMOURS AND COMPANY
Application year: 2000
Main classification: C08F8
IPC codes: C08F8, C09J151, H01B7