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Distannoxane catalysts for silane crosslinking and condensation reactions

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Distannoxane catalysts for silane crosslinking and condensation reactions


A fabricated article (e.g., jacketed or insulated wire or cable) is prepared by a process comprising the steps of: applying a coating of a moisture-curable composition onto a wire or cable; and reacting the moisture-curable composition with water, wherein the moisture-curable composition comprises at least one resin having hydrolysable reactive silane groups and a tin catalyst characterized by the tin having a +4 oxidation state and a bis(alkoxide) ligand. The product of the process includes a wire or cable comprising a jacket, wherein the jacket comprises at least one poly olefin resin having hydrolysable reactive silane groups and a tin catalyst, the tin catalyst having a bis(alkoxide) ligand and characterized by the tin having a +4 oxidation state. The product of the process also includes a wire or cable comprising a jacket wherein the jacket comprises (i) the reaction product of at least one polyolefin resin having hydrolysable reactive silane groups and water, and (ii) at least one tin catalyst, the tin catalyst having a bis(alkoxide) ligand and characterized by the tin having a +4 oxidation state.
Related Terms: Ligand Condensation Resin Olefin Silane

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USPTO Applicaton #: #20130319725 - Class: 174110SR (USPTO) - 12/05/13 - Class 174 


Inventors: Francis J. Timmers, Bharat Indu Chaudhary, Michael J. Mullins, Roger L. Kuhlman

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The Patent Description & Claims data below is from USPTO Patent Application 20130319725, Distannoxane catalysts for silane crosslinking and condensation reactions.

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FIELD OF THE INVENTION

This invention relates to silane crosslinking compositions and condensation reactions. In one aspect, the invention relates to moisture-curable, silane crosslinking compositions while in another aspect, the invention relates to such compositions comprising a distannoxane catalyst. In yet another aspect, the invention relates to silane crosslinked articles that were moisture-cured through the action of a distannoxane catalyst.

BACKGROUND OF THE INVENTION

Silane-crosslinkable polymers, and compositions comprising these polymers, are well known in the art, e.g., U.S. Pat. No. 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. These polymers have found a myriad of uses, particularly as insulation coatings in the wire and cable industry.

Important in the use of silane-crosslinkable polymers is their rate of cure. Generally, the faster the cure rate, the more efficient is their use. Polymer cure or crosslinking rate is a function of many variables not the least of which is the catalyst. Many catalysts are known for use in crosslinking polyolefins which bear unsaturated silane functionality, and among these are metal salts of carboxylic acids, organic bases, and inorganic and organic acids. Exemplary of the metal carboxylates is di-n-butyldilauryl tin (DBTDL), of the organic bases is pyridine, of the inorganic acids is sulfuric acid, and of the organic acids are the toluene and naphthalene didistannoxanes. While all of these catalysts are effective to one degree or another, new catalysts are of continuing interest to the industry, particularly to the extent that they are faster, or less water soluble, or cause less discoloration to the crosslinked polymer, or offer an improvement in any one of a number of different ways over the catalysts currently available for this purpose.

BRIEF

SUMMARY

OF THE INVENTION

In one preferred embodiment, the invention is an article that comprises at least one polymer or resin, preferably a poly olefin resin, having hydrolysable reactive silane groups and a tin catalyst, the tin catalyst having a bis(alkoxide) ligand and characterized by the tin having a +4 oxidation state. In certain embodiments, the inventive articles can be wire or cable jackets, insulation or semi-conductive layers; pipes; and foams.

In another preferred embodiment, the invention is an article that comprises (i) the reaction product of at least one polymer or resin, preferably a polyolefin resin, having hydrolysable reactive silane groups and water, and (ii) at least one tin catalyst, the tin catalyst having a bis(alkoxide) ligand and characterized by the tin having a +4 oxidation state. In certain embodiments, the inventive articles can be wire or cable jackets, insulation or semi-conductive layers; pipes; and foams.

In yet another preferred embodiment, the invention is a process for preparing a jacketed or insulated wire or cable, the process comprising the steps of: applying a coating of a moisture-curable composition onto a wire or cable; and reacting the moisture-curable composition with water, wherein the moisture-curable composition comprises at least one resin having hydrolysable reactive silane groups and a tin catalyst characterized by the tin having a +4 oxidation state and a bis(alkoxide) ligand.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the chemical structure of penta-coordinate and hexa-coordinate tin catalysts.

FIG. 2 is a graph comparing the viscosity over time of a silane-grafted ethylene-octene copolymer catalyzed by either a distannoxane or stannous octoate.

FIG. 3 is a graph showing the viscosity over time of a silane-grafted ethylene-octene copolymer catalyzed stannous octoate wherein the stannous octoate was subjected to a cycle of preheating.

FIG. 4 is a graph demonstrating the effect of temperature on the cross-linking reaction.

DETAILED DESCRIPTION

OF THE INVENTION

The silane crosslinkable polymer compositions of this invention comprise (i) at least one silane crosslinkable polymer, and (ii) a catalytic amount of at least one distannoxane catalyst. The silane crosslinkable polymers include silane-functionalized olefinic polymers such as 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 C3 or higher α-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 C3 or higher α-olefins or unsaturated esters, the copolymer having a hydrolysable silane grafted to its backbone.

Polyethylene polymer as here used is a homopolymer of ethylene or a copolymer of ethylene and a minor amount of one or more α-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 α-olefins include propylene, 1-butene, 1-hexene, 4-methyl-1-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). 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 about 0.850 to about 0.970 g/cc, preferably in the range of about 0.870 to about 0.930 g/cc. They also have a melt index (I2) in the range of about 0.01 to about 2000 g/10 min, preferably about 0.05 to about 1000 g/10 min, and most preferably about 0.10 to about 50 g/10 min. If the polyethylene is a homopolymer, then its I2 is preferably about 0.75 to about 3 g/10 min. The I2 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 solution, slurry, high-pressure 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-LDPEs), linear low density polyethylenes (LLDPEs), very low density polyethylenes (VLDPEs), ultra low density polyethylenes (ULDPEs), medium density polyethylenes (MDPEs), high density polyethylene (HDPE), and metallocene and constrained geometry copolymers.

High-pressure processes are typically free radical initiated polymerizations and conducted in a tubular reactor or a stirred autoclave. In the tubular reactor, the pressure is within the range of about 25,000 to about 45,000 psi and the temperature is in the range of about 200 to about 350C. In the stirred autoclave, the pressure is in the range of about 10,000 to about 30,000 psi and the temperature is in the range of about 175 to about 250C.



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stats Patent Info
Application #
US 20130319725 A1
Publish Date
12/05/2013
Document #
13926527
File Date
06/25/2013
USPTO Class
174110SR
Other USPTO Classes
528 56, 427117
International Class
01B3/30
Drawings
2


Ligand
Condensation
Resin
Olefin
Silane


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