Abstract:
A combination of vinyl trimethoxysilane and vinyl triethoxysilane can be grafted onto polyethylene to produce a polyethylene graft terpolymer that can be crosslinked without a significant reduction in crosslinking rates relative to vinyl triemethoxysilane grafted polyethylene. The combination of vinyl trimethoxysilane and vinyl triethoxysilane apparently act synergistically. While byproduct methanol from crosslinking with trimethoxysilane is very undesirable in some products, byproduct ethanol from crosslinking is less hazardous, especially at ppm levels.

Description:
RELATED APPLICATION 
       [0001]    This application claims the benefit of U.S. Provisional Application No. 61/347,859, filed on May 25, 2010. The entire teachings of the above application are incorporated herein by reference. 
     
    
     FIELD OF THE INVENTION 
       [0002]    This invention relates to crosslinkable polyethylene composition that can be utilized in manufacturing various articles of manufacture. This crosslinkable polyethylene composition is of particular value for utilization in manufacturing crosslinked polyethylene pipe for the distribution of potable water since a reduced level of methanol is generated in cases where it is employed in making such pipe. 
       BACKGROUND OF THE INVENTION 
       [0003]    Various articles of manufacture are made utilizing polyethylene which is crosslinked after being molded or extruded during the manufacturing process. For instance, the “sioplas” process and the “monosil” process are widely used in manufacturing articles which are comprised of crosslinked polyethylene, such as polyethylene pipe. However, one significant drawback associated with the sioplas process and monosil process is that methanol is generated as a by-product of the crosslinking reaction. This is of particular concern in cases where the article manufactured is intended for use in applications where it comes in contact with potable water. For instance, residual methanol in a crosslinked polyethylene pipe can migrate into water flowing through the pipe and can result in an unacceptable level of contamination. 
         [0004]    Crosslinked polyethylene (PEX) offers an excellent array of physical characteristics, cost advantages, and long service life that make it highly desirable for utilization in water pipes. In particular, crosslinking of polyethylene has been shown to increase maximum useful service temperature, reduce creep, improve chemical resistance, increase abrasion resistance, improve memory characteristics, improve impact resistance, and improve environmental stress cracking resistance as compared to uncrosslinked polyethylene. However, the problem associated with residual methanol migration into the water conveyed through such PEX pipes continues to be of concern. U.S. Pat. No. 6,284,178 appreciates this problem associated with high levels of residual methanol and notes that methanol levels can be reduced by increasing the curing time employed in manufacturing the PEX article. The techniques revealed in this patent is reported to be useful in making PEX having a low enough methanol extraction value (using the ANSI/NSF 61 standard) to qualify for use in potable water systems. Even though this approach is technically viable it is not universally acceptable from a commercial standpoint since its implementation would lead to reduced manufacturing throughput and increased manufacturing cost. 
         [0005]    One other possible approach to the problem of contamination with residual methanol would be to replace the vinyl trimethoxysilane which is normally used in the sioplas process and the monosil process with vinyl triethoxysilane. Such a substitution of vinyl triethoxysilane into the process in place of vinyl trimethoxysilane would result in the formation of ethanol rather than methanol. This would be greatly advantageous since ethanol (ethyl alcohol) is not toxic at low levels and its metabolism by humans and animals is well understood. However, vinyl triethoxysilane cannot simply be substituted into the sioplas process or the monosil process in place of vinyl methoxysilane because it participates in the crosslinking step of the process at a commercially unacceptable rate. 
         [0006]    Many techniques for producing articles of manufacture that are comprised of crosslinked polyethylene are known in the art. For instance, U.S. Pat. No. 4,117,195 discloses a method for producing PEX pipe using silane grafted PEX. In this process, the polyethylene is metered into a screw extrusion machine together with compounding ingredients comprising a hydrolysable unsaturated silane, a free-radical generator and a silanol condensation catalyst. The compounding ingredients are blended with the polymer in the barrel of the extruder and the mixture is heated sufficiently to effect grafting of silane groups to the polymer, the amount of free-radical generator being sufficiently low to limit direct free-radical crosslinking to a level that will not prevent extrusion of the material. The reaction mixture is extruded directly from the same extruder through an extrusion die to form an elongate shaped product and crosslinking is effected by subjecting the shaped product to the action of moisture. 
         [0007]    U.S. Pat. No. 5,756,023 reveals a method of producing reformed crosslinked polyethylene articles wherein the reformed crosslinked articles are free of visible and objectionable folds, seams, and interfaces on reformed surfaces thereof. A preferred embodiment of the method described in U.S. Pat. No. 5,656,023 includes the steps of extruding a silane-grafted polyethylene tube, heating an end of the tube, reforming the end of the tube to produce a radially enlarged sealing surface thereon, cooling the reformed tube, and curing the reformed tube to produce an increase in the degree of crosslinking of the polyethylene material. 
         [0008]    U.S. Pat. No. 7,086,421 discloses a multilayer crosslinked polyethylene (“PEX”) pipe comprising: (a) an inner tubular core of high density polyethylene (“HDPE”) having a maximum wall thickness from about 28 to 100 times smaller than the nominal diameter of pipe in the range from 7 mm (0.25″) to 152 mm (6″), ratio  28  being attributable to small diameter non-SDR-9 piping, and ratio  100  being attributable to the larger diameter SDR-9 pipe, wherein the HDPE has a density in the range from 0.941 g/cc to 0.963 g/cc; and, (b) an outer tubular sheath of at least one layer of a crosslinked polyethylene contiguous with the outer surface of the inner core layer, wherein said PEX is crosslinked to a gel level of at least 65% by a silane grafting process. 
         [0009]    U.S. Pat. No. 7,255,134 discloses pipe or tubing of crosslinked polyethylene (PEX) that includes carbon black at a level of less than 2% to improve resistance to oxidizing agents, such as chlorine and hypochlorous acid in water. This patent more specifically reveals a pipe of crosslinked polyethylene having a wall of substantially uniform thickness in the range from 1.78 mm to 17.29 mm having dispersed therein from 0.1 to about 1.25% by weight of carbon black having a particle size less than 27 nm (nanometers), and wherein said PEX is crosslinked by a method selected from the addition of AZO compounds and silane grafting process said pipe including, an inner tubular core of protective polymer selected from the group consisting of high density polyethylene (HDPE) and chlorinated polyethylene (CPE) contiguous with the inner surface of the crosslinked PEX, the core having a substantially uniform wall thickness in the range from 0.025 mm (1 mil) to 1.52 mm (0.06″), and a maximum wall thickness in the range from about 28 to 100 times smaller than the nominal diameter of the pipe in the range from 7 mm (0.25″) to 152 mm (6″), ratio  28  being attributable to small diameter non-SDR-9 piping, and ratio  100  being attributable to the larger diameter SDR-9 pipe, wherein the HDPE has a density in the range from 0.941 g/cc to 0.963 g/cc, and the chlorinated polyethylene has a chlorine content in the range from 5 to about 50% by weight. 
         [0010]    United States Patent Publication No. 2007/0184227 A1 discloses silane crosslinked polyolefin tubes having a minimum crosslinking degree of 60% that are intended for drinking water and/or water for industrial use and which are resistant to a chlorine content between 0.1 and 5 ppm. These polyolefin tubes are manufactured by a single-stage process which is characterized by the polyolefin composition comprises (A) a polyolefin, (B) a mixture of an organic silane of the general formula RSiX 3  with a radical-generating constituent and a catalyst (B3), and with a stabilizer mixture of a high melting point, high-molecular phenolic constituent with a sulfur-containing constituent, a phosphorus-containing processing stabilizer and a metal deactivator. 
       SUMMARY OF THE INVENTION 
       [0011]    The problem associated with residual methanol being in products made with crosslinked polyethylene continues to be of concern today. This problem is of particular relevance in cases where the product made with the crosslinked polyethylene comes in contact with potable water. For instance, it is important for crosslinked polyethylene pipes utilized in the conveyance of potable water to contain no more than a very low level of residual methanol. More specifically, a maximum level of 20 ppm of extractable methanol is frequently demanded today. However, for technical, commercial, and economic reasons a good solution to this problem has been elusive. There is, accordingly, a long felt need for a commercially viable low cost technique for producing crosslinked polyethylene articles, such as crosslinked polyethylene water pipes and tubes. 
         [0012]    This invention is based upon the unexpected finding that a combination of vinyl trimethoxysilane and vinyl triethoxysilane can be grafted onto polyethylene to produce a polyethylene graft terpolymer that can be crosslinked without any significant change in crosslinking rates. The combination of vinyl trimethoxysilane and vinyl triethoxysilane acts to attain a rate of crosslinking that far exceeds the rate that would be expected in a polyethylene polymer containing a given level of vinyl triethoxysilane units grafted thereto. In any case, the crosslinkable polyethylene graft terpolymers of this invention which are comprised of polyethylene with both vinyl trimethoxysilane units and vinyl triethoxysilane units grafted thereon can be utilized in a commercially viable process to manufacture articles of manufacture having a reduced level of residual methanol. Articles of manufacture made utilizing the graft polyethylene and technique of this invention also offer all of the other chemical and physical characteristics of products made utilizing conventional technology. This is because the crosslinked polyethylene made by the method of this invention is essentially identical to the polymer that results by practicing conventional technology except, of course, in that it offers the advantage of containing a lower level of residual methanol. 
         [0013]    The present invention more specifically discloses a crosslinkable polyethylene graft terpolymer which is comprised of polyethylene wherein the polyethylene has vinyl trimethoxysilane units grafted thereon, wherein the polyethylene has vinyl triethoxysilane units grafted thereon, and wherein the weight ratio of vinyl triethyoxysilane units to vinyl tirmethoxysilane units is at least 0.25:1. 
         [0014]    The subject invention further reveals a process for synthesizing a crosslinkable polyethylene graft terpolymer which comprises (1) dispersing vinyl trimethoxysilane, vinyl triethyoxysilane, and a free radical generator into a polyethylene resin at a temperature above the melting point of the polyethylene resin to produce polymeric reaction mixture, wherein the weight ratio of vinyl triethyoxysilane units to vinyl tirmethoxysilane units is at least 0.25:1, and (2) maintaining the polymeric reaction mixture at an elevated temperature (which is typically above the decomposition temperature of free radical initiator utilized, typically above about a temperature of 150° C.) above a temperature of about 170° C. to allow the vinyl trimethoxysilane and the vinyl triethyoxysilane to graft onto the polyethylene to produce the crosslinkable graft terpolymer. 
         [0015]    The present invention also discloses a process for manufacturing polyethylene pipe which comprises (1) extruding a crosslinkable polyethylene graft terpolymer composition into a the form of an uncured pipe, wherein the crosslinkable polyethylene graft terpolymer is comprised of polyethylene wherein the polyethylene has vinyl trimethoxysilane units grafted thereon, wherein the polyethylene has vinyl triethoxysilane units grafted thereon, and wherein the weight ratio of vinyl triethyoxysilane units to vinyl tirmethoxysilane units is at least 0.25:1, (2) curing uncured pipe at an elevated temperature of at least about 150° F. in the presence of moisture to produce a cured pipe, and (3) allowing the cured pipe to cool to ambient temperature (about 70° F.) to produce the crosslinked polyethylene pipe. 
         [0016]    The subject invention further reveals a process for manufacturing polyethylene pipe which comprises (1) extruding a crosslinkable polyethylene graft terpolymer composition into a the form of an uncured pipe, wherein the crosslinkable polyethylene graft terpolymer is comprised of polyethylene wherein the polyethylene has vinyl trimethoxysilane units grafted thereon, wherein the polyethylene has vinyl triethoxysilane units grafted thereon, and wherein the weight ratio of vinyl triethyoxysilane units to vinyl tirmethoxysilane units is at least 0.25:1, (2) curing uncured pipe at an elevated temperature of at least about 150° F. in the presence of moisture to produce a cured pipe, and (3) allowing the cured pipe to cool to ambient temperature to produce the crosslinked polyethylene pipe. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0017]      FIG. 1  is a graph of percentage gel versus cure time for the crosslinkable polyethylene samples evaluated in Examples 1-6. 
       
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0018]    The crosslinkable polyethylene graft terpolymers of this invention are made by simply grafting both vinyl trimethoxysilane and vinyl triethoxysilane onto polyethylene. The polyethylene used will typically be high density polyethylene (HDPE) and is usually a polyethylene homopolymer. It should be noted that polyethylene is generally regarded as being high density polyethylene if it has a density of at least 0.941 g/cc (see Encyclopedia of Chemical Technology by Kirk &amp; Othmer, Vol. 17, page 704, 1996). The polyethylene can contain processing aids, stabilizers, antioxidants, antiozonants, pigments, lubricants, flow control agents, and the like in amounts that are normally within the range of about 10 ppm to about 7 parts per 100 parts of polymer. Hindered phenols, such as Irganox® 1010, Irganox®  1076 , and Irganox® 1330, are preferred primary antioxidants that can be employed in the polyethylene. Irgafos® 168 and IrganoxPS802 are secondary antioxidants that can be utilized in the polyethylene as thermal processing aids. Carbon black is an example of a black pigment and titanium dioxide is an example of a white pigment that can be used in the polyethylene to attain a desired color. 
         [0019]    The vinyl trimethoxysilane and vinyl triethoxysilane can be grafted onto the polyethylene in accordance with this invention via the utilization of free radical reactions. This is accomplished by mixing the vinyl trimethoxysilane and vinyl triethoxysilane throughout the polyethylene. This mixing step is conducted at a temperature which is above the melting point of the polyethylene to attain a relatively homogeneous mixture. This mixing can be conducted in an extruder, such as a twin screw extruder, and is preferably done under low moisture conditions. For instance, a dry inert gas, such as nitrogen, can be introduced into the extruder to displace moist air. 
         [0020]    After the vinyl trimethoxysilane and vinyl triethoxysilane have been dispersed throughout polyethylene, free radicals are generated in the polyethylene composition by exposing it to radiation, such as electron beams, a source of gamma radiation, or ultra-violet light. However, it is normally preferred to incorporate a chemical free radical generator into the polyethylene to ensure a fast and uniform rate of grafting. This can be accomplished by adding the chemical free radical generator to the mixer or extruder used to disperse the vinyl trimethoxysilane and vinyl triethoxysilane into the polyethylene resin. The chemical free radical generator can also be added via a separate feed stream as long as good mixing is attained. 
         [0021]    The free radical generator will typically be an alkylperoxide, actylperoxide, ketoneperoxide, hydroperoxide, peroxocarbonate, persters, peroxoketal, peroxooligomer, or azo compound. In most applications it is highly preferred to employ a peroxide that does not generate any toxic species as reaction by-products. In many cases, the free radical generator will be an organic alkylperoxide selected from the group consisting of 2,5-dimethyl-2,5-di(tertiary-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tertiary-butylperoxy)-3-hexine, di(tertiarybutyl)peroxide, 1,3-di(tertiary-butyl-peroxyiso-propyl)benzol, dicumylperoxide, tertiary-butylcumylperoxide. Such peroxides are typically employed at a level which is within the range of 0.01 weight percent to about 0.12 weight percent, based upon the total weight of the polymeric composition. It is normally preferred for the peroxide to be present at a level which is within the range of 0.02 weight percent to about 0.1 weight percent with a level which is within the range of 0.04 weight percent to about 0.08 weight percent being more typical. 
         [0022]    The reaction scheme used to graft the vinyl trimethoxysilane and vinyl triethoxysilane onto the polyethylene can be depicted as follows: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0023]    As is illustrated in the reaction scheme shown above, vinyl methoxysilane, CH 2 ═CHSi(OCH 3 ) 3 , and vinyl ethoxysilane, CH 2 ═CHSi(OCH 2 CH 3 ) 3 , are grafted onto the backbone of the polyethylene in the presence of free radicals at an elevated temperature. In cases where chemical free radical generators are used, it is important for the elevated temperature utilized to be high enough to generate free radicals at a reasonable rate. This elevated temperature will be above the decomposition temperature of the chemical free radical generator in cases where a chemical free radical generator is employed. This temperature will normally be above about 150° C. and will often be above about 170° C. As the reaction proceeds, grafting occurs and vinyl trimethoxysilane units (—CH 2 CH 2 Si(OCH 3 ) 3 ) and vinyl triethoxysilane units (—CH 2 CH 2 Si(OCH 2 CH 3 ) 3 ) are grafted onto the backbone of the polyethylene. The distribution of vinyl trimethoxysilane units and vinyl triethoxysilane units along the polyethylene backbone is essentially random in order. 
         [0024]    The weight ratio of vinyl triethyoxysilane units to vinyl tirmethoxysilane units that are grafted onto the polyethylene will be at least 0.25:1. In most cases, the weight ratio of vinyl triethyoxysilane units to vinyl tirmethoxysilane units grafted onto the polyethylene will within the range of 0.25:1 to 9:1. Typically, the weight ratio of vinyl triethyoxysilane units to vinyl tirmethoxysilane units grafted onto the polyethylene will be within the range of 0.3:1 to 9:1. More typically, the weight ratio of vinyl triethyoxysilane units to vinyl tirmethoxysilane units grafted onto the polyethylene will be within the range of 0.4:1 to 6:1. In many cases, the weight ratio of vinyl triethyoxysilane units to vinyl trimethoxysilane units will be within the range of 0.5:1 to 3:1. Preferably, the weight ratio of vinyl triethyoxysilane units to vinyl tirmethoxysilane units grafted onto the polyethylene will be within the range of 0.6:1 to 2:1. More preferably, the weight ratio of vinyl triethyoxysilane units to vinyl trimethoxysilane units grafted onto the polyethylene will be within the range of 0.8:1 to 3:2. 
         [0025]    The sum of the weight of the vinyl triethyoxysilane units and vinyl trimethoxysilane units in the polyethylene terpolymer represents from about 0.5 weight percent to about 4 weight percent of the total weight of the polymer. Typically, the sum of the weight of the vinyl triethyoxysilane units and vinyl tirmethoxysilane units in the polyethylene terpolymer will represent from about 1 weight percent to about 3 weight percent of the total weight of the polymer. More typically, the sum of the weight of the vinyl triethyoxysilane units and vinyl tirmethoxysilane units in the polyethylene terpolymer will represent from about 1.5 weight percent to about 2.5 weight percent of the total weight of the polymer. 
         [0026]    After the graft polyethylene polymer has been synthesized, it is typically palletized and stored for later use in moisture free environment. For instance, the resin can be advantageously stored in bags that inhibit moisture penetration, such as foil-lined bags, to protect the crosslinkable graft polyethylene from moisture to prevent premature crosslinking. 
         [0027]    A catalyst is then typically added to the crosslinkable graft polyethylene, it is then molded or extruded into a desired shape and is then subsequently cured (crosslinked) via conventional techniques. Such techniques are disclosed in U.S. Pat. No. 6,284,178 and U.S. Pat. No. 7,086,421. The teachings of U.S. Pat. No. 6,284,178 and U.S. Pat. No. 7,086,421 are incorporated herein by reference for the purpose of teaching techniques for manufacturing articles which are comprised of crosslinked polyethylene. Generally, in such techniques a catalyst or catalyst masterbatch is blended into the crosslinkable graft polyethylene. This can conveniently be done in a single screw extruder having a L/D which is within the range of 18-32. The catalyst is typically a tin catalyst, such as dibutyltindilaurate, dibutyltinoxide, tinoctoate, dibutyltinmaleate or titanylacetonate. A primary antioxidant, such as a hindered phenol, a secondary antioxidant, a hindered amine light stabilizer, such as Tinuvin® 111, and/or a pigment can optionally also be added to the crosslinkable graft polyethylene during this mixing step. 
         [0028]    The crosslinkable graft polyethylene with a catalyst blended therein is then molded or extruded into a desired form, such as that of a pipe or tube. Pipes or tubes made in such a manner can then optionally be reformed. For instance, an enlarged sealing surface may be formed on a tubular product as described in U.S. Pat. No. 5,879,723, the teachings of which are hereby incorporated herein by reference. If such a sealing surface is to be formed on the product, preferably the product is heated to an elevated temperature and then reformed between a pair of mating dies. However, it should be understood that other procedures may be followed for reforming the product without departing from the principles of the present invention. 
         [0029]    The formed article is then cured by subjecting it to an elevated temperature and moisture, in the form of liquid water, water vapor or steam. This can be accomplished by heating the formed article to a temperature of at least about 160° F. and preferably at least  180 ° F. Steam is typically introduced into the vessel wherein the article is cured to ensure that a sufficient quantity of water is present to allow for an efficient cure cycle. The cure reaction involves a hydrolysis step which consumes water and which produces methanol or ethanol depending upon whether the silane unit participating in the reaction is a vinyl trimethyoxysilane unit or a vinyl triethoxysilane unit. This hydrolysis step can be depicted as follows: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0030]    The hydrolysis step is followed by a condensation step which provides a crosslink between polyethylene chains and which produces water. This hydrolysis step between vinyl trimethoxysilane units on adjacent polyethylene chains can be depicted as follows: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0031]    This reaction crosslinks polyethylene chains within the polymer structure which results in increased maximum useful service temperature, reduced creep, improved chemical resistance, increased abrasion resistance, improved memory characteristics, improved impact resistance, and improved environmental stress cracking resistance as compared to uncrosslinked polyethylene. By utilizing the technique of this invention, the amount of methanol generated is reduced by approximately the ratio of vinyl triethoxysilane units to total vinyl trialkylsilane units in the polyethylene. 
         [0032]    This invention is illustrated by the following examples that are merely for the purpose of illustration and are not to be regarded as limiting the scope of the invention or the manner in which it can be practiced. Unless specifically indicated otherwise, parts and percentages are given by weight. 
       Examples 1-6 
       [0033]    In this series of experiments, Sclair® high density polyethylene was crosslinked with 100% vinyl trimethoxysilane (VTMO), 75% VTMO/25% VTEO, 50% VTMO/50% VTEO, 33% VTMO/67% VTEO, 25% VTMO/75% VTEO, and 100% vinyl triethoxysilane (VTEO). The percentage of gel/crosslink level attained versus cure time is shown in  FIG. 1 . As can been seen after 4 hours of cure time, a gel contain of greater than 65% was attained in all of the polyethylene compositions that contained at least 33% VTMO. After a cure time of 4 hours, the polyethylene composition that contained 25% VTMO reached a gel contain of almost 65%. This series of experiments shows that all of the cure formulations containing VTEO cured at a much faster rate than would be predicted. In other words, the substitution of VTEO for VTMO reduced the rate of crosslinking much less than was expected based upon crosslinking rates that are attained utilizing solely VTMO or VTEO for curing. Thus, this series of experiments shows that a reasonable level of crosslinking (65%) can be attained without significantly increasing cure cycle times or adding to or significantly effecting manufacturing costs. 
         [0034]    The crosslinked polyethylene samples made in this series of experiments were tested by NSF 61 extraction to determine the level of residual methanol and residual ethanol present. The level of residual methanol and residual ethanol detected in this series of crosslinked polyethylene samples is reported in Table 1. 
         [0000]    
       
         
               
               
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                   
                 TABLE 1 
               
             
             
               
                   
                   
               
               
                   
                   
                 Total Alcohol 
               
             
          
           
               
                   
                 Sample 
                 % Methanol 
                 % Ethanol 
               
               
                   
                   
               
             
          
           
               
                   
                 100% VTMO 
                 100 
                 0 
               
               
                   
                  75% VTMO/25% VTEO 
                 63.8 
                 36.2 
               
               
                   
                  50% VTMO/50% VTEO 
                 37.1 
                 62.9 
               
               
                   
                  33% VTMO/67% VTEO 
                 16.7 
                 83.3 
               
               
                   
                  25% VTMO/75% VTEO 
                 18.8 
                 81.2 
               
               
                   
                 100% VTEO 
                 0 
                 100 
               
               
                   
                   
               
             
          
         
       
     
         [0035]    This series of experiments shows that residual methanol levels can be greatly reduced by practicing the technology of this invention without significantly impacting cure cycle times or manufacturing costs. 
         [0036]    While certain representative embodiments and details have been shown for the purpose of illustrating the subject invention, it will be apparent to those skilled in this art that various changes and modifications can be made therein without departing from the scope of the subject invention.