TW201638004A - Process for making a fabricated article from polyolefin - Google Patents

Abstract

In one instance, the present disclosure describes a method for preparing a carbonaceous article comprising: providing a crosslinked polyolefin fabricated article; stabilizing the crosslinked polyolefin fabricated article by air oxidation to provide a stabilized fabricated article; treating with a boron-containing liquid (BCL) during or intermediate to at least one of the preceding steps; and carbonizing the stabilized fabricated article. In one instance the present disclosure describes a method for preparing a stabilized article.

Description

Method of manufacturing articles made from polyolefin

This invention relates to a method of making a carbonaceous article.

Previously, carbonaceous articles such as carbon fibers have been produced primarily from polyacrylonitrile (PAN), asphalt or cellulose precursors. The method of preparing a carbonaceous article begins by forming a article, such as a fiber or film, from the precursor. The precursor can be formed into articles using standard techniques for forming or molding the polymer. The finished article is then stabilized such that the finished article retains substantially the shape during the subsequent heat treatment step; without being bound by theory, such stabilization typically involves a combination of oxidation and heating and generally results in defining the finished article prior to Dehydrogenation, ring formation, oxidation and crosslinking of the drive. Subsequently, the stabilized article is converted into a carbonaceous article by heating the stabilized article in an inert atmosphere. While the general steps for producing carbonaceous articles are the same as those for producing a plurality of precursors, the details of those steps vary widely depending on the chemical composition of the selected precursor.

Polyolefins have been investigated as an alternative precursor to carbonaceous articles, but it has proven difficult to achieve suitable and economically viable preparation methods. Of particular interest is the identification of an economical method for preparing carbonaceous articles from polyolefin precursors. For example, maximizing mass retention during stabilization and carbonization steps is of concern.

The present invention describes a method of preparing a carbonaceous article comprising: providing a crosslinked polyolefin article; stabilizing the crosslinked polyolefin article by air oxidation to provide a stable article; during at least one of the preceding steps or The intermediate is treated with a boron-containing liquid (BCL); and the stabilized article is carbonized. In one aspect, the invention features a method of making a stable article.

Numerical ranges (eg, "2 to 10") include numbers that define the ranges (eg, 2 and 10) unless otherwise indicated.

Unless otherwise indicated, ratios, percentages, parts, and the like are by weight.

Unless otherwise indicated, the crosslinkable functional group content for the polyolefin resin is characterized by the crosslinkable functional group mol%, which is calculated as the number of moles of the crosslinkable functional group divided by the single contained in the polyolefin. The total number of moles of the body unit.

Unless otherwise indicated, "monomer" refers to a molecule that can be polymerized to form a constituent unit of the basic structure of a macromolecule such as a polyolefin. In one aspect, the invention describes a method of producing a carbon-containing article from a polyolefin resin. As described in more detail herein, a carbon-containing article is prepared by (a) providing an olefin resin; (b) forming an article from an olefin resin; and (c) crosslinking the article to provide a cross-linking system. (d) stabilizing the article by air oxidation to provide a stable article; (e) treating with a boron-containing liquid (BCL) during or between at least one of the preceding steps; and (f) stabilizing The object is carbonized.

Suitable BCLs comprise a liquid comprising a boron-containing material. Examples of suitable boron-containing materials include borane, borate, boronic acid, boronic acid, boric acid, dihydrocarbyl borate, hydrocarbyl borate, boron oxocycle Hexane, aminoborane, borazine, borohydride and derivatives and combinations thereof. Elemental boron is also a suitable boron-containing material. Examples of the derivative of boric acid include metaboric acid and boron trioxide. Examples of borate derivatives include inorganic borate salts such as zinc borate, and organoborates such as tributyl borate. In one case, the BCL is prepared solely from the boron-containing material. In one instance, the BCL also contains another component with the boron-containing material and is selected such that the other component is miscible with the boron-containing material, forms a suspension with it or otherwise carried with it and is associated with the overall process. Rong. In one case, the other component is a polar or non-polar liquid. For example, an alcohol such as isopropanol is a suitable component of BCL. In one case, at least a portion of the boron-containing material is carried as a suspension in the BCL.

Any of the methods or process steps described herein can be performed in any order, unless otherwise stated.

Polyolefins are a class of polymers produced from one or more olefin monomers. The polymers described herein can be formed from one or more types of monomers. Polyethylene is a preferred polyolefin resin, but other polyolefin resins can be substituted. For example, polyolefins derived from ethylene, propylene or other alpha-olefins (e.g., 1-butene, 1-hexene, 1-octene), or combinations thereof, are also suitable. The polyolefins described herein are typically provided in the form of a resin which is subdivided into pellets or granules of suitable size for further melting or solution processing. In one case, the polyolefin resin is treated with BCL prior to being formed into a finished article. The polyolefin resin can be BCL by any mechanism known in the art, such as spraying, dipping or absorbing. deal with. The BCL may be in a suitable liquid form, such as in the form of a solvent free, or as part of a solution, or as a suspension in a liquid. The BCL can be introduced as part of a continuous process or as part of a batch process.

The polyolefin resin described herein is subjected to a crosslinking step. Any suitable method for crosslinking the polyolefin is sufficient. In one case, the polyolefin is crosslinked by irradiation, such as by electron beam treatment. Other crosslinking methods are suitable, such as ultraviolet irradiation and gamma irradiation. In some cases, an initiator such as benzophenone can be used in combination with irradiation to initiate crosslinking. In one case, the polyolefin resin has been modified to include a crosslinkable functional group suitable for the reaction to crosslink the polyolefin resin. Where the polyolefin resin comprises a crosslinkable functional group, the crosslinking can be initiated by known methods, including the use of a chemical crosslinking agent, by heating, by steam or other suitable means. In one case, the copolymer is suitable for providing a polyolefin resin having a crosslinkable functional group in which one or more alpha-olefins have been copolymerized with another monomer having a group suitable for acting as a crosslinkable functional group, For example, dienes, carbon monoxide, glycidyl methacrylate, acrylic acid, vinyl acetate, maleic anhydride or vinyltrimethoxydecane (VTMS) are monomers suitable for copolymerization with alpha-olefins. Further, the polyolefin resin having a crosslinkable functional group may also be produced from a poly(α-olefin) which has been modified by grafting a functional group moiety onto a matrix polyolefin, wherein the functional group is based on its subsequent realization. The ability to select the crosslinking of polyolefins. For example, this type of grafting can be achieved by the use of free radical initiators (such as peroxides) and vinyl monomers (such as VTMS, dienes, vinyl acetate, acrylic acid, methacrylic acid, acrylates, and methyl groups). Acrylates (such as glycidyl methacrylate and methacryloxypropyltrimethoxydecane), allylamine, p-aminostyrene, dimethylaminoethyl methacrylate) or via stacks Nitrogen functionalization A molecule such as 4-[2-(trimethoxyindolyl)ethyl)]benzenesulfonyl azide compound is used. The polyolefin resin having a crosslinkable functional group may be produced from a polyolefin resin or may be commercially available. Examples of commercially available polyolefin resins having crosslinkable functional groups include SI-LINK sold by The Dow Chemical Company, PRIMACOR sold by The Dow Chemical Company, EVAL resin sold by Kuraray, and LOTADER AX8840 sold by Arkema.

The polyolefin resin is processed to form a finished article as described above. The finished article is an article that has been made of a polyolefin resin. The finished article is formed using known polyolefin manufacturing techniques, such as melt or solution spinning to form fibers, film extrusion or film casting or blown film forming to form a film, die extrusion or injection molding or compression forming to form more Complex shapes, or solution casting. The manufacturing technique is selected based on the desired geometry of the target carbonaceous article and the desired physical properties of the carbonaceous article. For example, where the desired carbonaceous article is a carbon fiber, fiber spinning is a suitable manufacturing technique. As another example, where the desired carbonaceous article is a carbon film, compression molding is a suitable manufacturing technique. In one case, the finished article is treated with BCL. In one case, the finished article is treated with BCL prior to crosslinking the polyolefin resin. The finished article can be treated with BCL by any mechanism known in the art, such as spraying, dipping or absorbing. The BCL may be in a suitable liquid form, such as in the form of a solvent free, or as part of a solution, or as a suspension in a liquid. The BCL can be introduced as part of a continuous process or as part of a batch process.

As mentioned above, at least a portion of the polyolefin resin is crosslinked to produce a crosslinked article. In some embodiments, the crosslinking is carried out via chemical crosslinking. Thus, in some embodiments, the cross-linked article is one or more A chemical agent is used to treat a finished article of a crosslinkable functional group of a polyolefin resin. Such chemistries are used to initiate the formation of intramolecular chemical bonds between crosslinkable functional groups or to react with crosslinkable functional groups to form intramolecular chemical bonds, as is known in the art. Chemical crosslinking causes the crosslinkable functional groups to react to form new bonds, forming bonds between different polymer chains that define the polyolefin resin having crosslinkable functional groups. The chemical agent that achieves crosslinking is selected based on the type of crosslinkable functional group included in the polyolefin resin; it is known that a series of different reactions of crosslinkable functional groups are crosslinked via intermolecular and intramolecular chemical bonds. A suitable chemical agent is selected which is known to be crosslinked to form crosslinkable functional groups present in the article to produce a crosslinked article. For example, without limiting the invention, if the crosslinkable functional group attached to the polyolefin is a vinyl group, suitable chemical agents include free radical initiators such as peroxides or azo-bisnitriles. Compounds such as dicumyl peroxide, benzamidine peroxide, tert-butyl peroctoate, azobisisobutyronitrile and the like. If the crosslinkable functional group attached to the polyolefin is an acid such as a carboxylic acid or an anhydride or a glycidoxy group, suitable chemical agents may be compounds containing at least two nucleophilic groups, including dinucleophilic Reagents such as diamines, diols, dithiols such as ethylenediamine, hexamethylenediamine, butanediol or hexanedithiol. Compounds containing two or more nucleophilic groups such as glycerol, sorbitol or hexamethylenetetramine may also be used. Mixed dinucleophiles or high nucleophiles (which contain at least two different nucleophilic groups, such as ethanolamine) may also be suitable chemical agents. If the crosslinkable functional group attached to the polyolefin is a monoalkoxyalkyl, dialkoxyalkyl or trialkoxyalkyl, water and Lewis acid or Bronsted acid Or a base catalyst can be used as a suitable chemical agent. For example, without limiting the invention, the Lewis acid or Bronsted acid or base catalyst comprises an aryl sulfonic acid, sulfuric acid, hydroxide, zirconium alkoxide or tin reagent.

Cross-linked articles are generally preferred to ensure that the finished article retains its shape at the elevated temperatures required for subsequent processing steps. In the case of no crosslinking, the polyolefin resin is usually softened, melted or deformed or decomposed at a high temperature. Crosslinking increases the thermal stability of the finished article. In one case, the finished article is treated with BCL after crosslinking and prior to stabilization. The crosslinked article can be treated with BCL by any mechanism known in the art, such as spraying, dipping or absorbing. The BCL may be in a suitable liquid form, such as in the form of a solvent free, or as part of a solution, or as a suspension in a liquid. The BCL can be introduced as part of a continuous process or as part of a batch process.

The cross-linked articles are heated in an oxidizing environment to produce a stable finished article. In some embodiments, the temperature used to stabilize the crosslinked article is at least 120 ° C, preferably at least 190 ° C. In some embodiments, the temperature used to stabilize the crosslinked article is no more than 400 ° C, preferably no more than 300 ° C. In one case, the crosslinked article is introduced into a heating chamber that has reached the desired temperature. In another case, the finished article is introduced into a heating chamber at or near ambient temperature, which is then heated to the desired temperature. In some embodiments, the heating rate is at least 1 °C/minute. In other embodiments, the heating rate does not exceed 15 ° C / minute. In yet another case, the chamber is gradually heated, for example, by heating the chamber to a first temperature for a period of time (such as 120 ° C for one hour), and then to a second temperature for a period of time (such as 180 ° C for one hour). And the third time is raised to the holding temperature (such as 250 ° C for 10 hours). Depending on the size of the article being made, the stabilization method involves holding the crosslinked article at a given temperature for a period of up to 100 hours. In one case, the finished article is treated with BCL during the stabilization process. Crosslinked articles can be stabilized during any stabilization by any mechanism known in the art, such as spraying, dipping or absorption. Treated with BCL. The BCL may be in a suitable liquid form, such as in the form of a solvent free, or as part of a solution, or as a suspension in a liquid. The BCL can be introduced as part of a continuous process or as part of a batch process. Stabilization Process The yield stabilized article is a stabilized process that produces a boron treated stabilized article that is used for a carbonaceous article precursor. Without being bound by theory, the stabilizing process oxidizes the crosslinked articles and changes the hydrocarbon structure, which increases the crosslink density while reducing the hydrogen/carbon ratio of the crosslinked articles. Without being bound by theory, the stabilization process in the presence of boron upgrades the oxidation chemistry and increases the crosslink density.

Unexpectedly, it has been discovered that the incorporation of boron into the finished article via BCL enhances the quality retention of subsequently produced stable and carbonaceous articles. It has also been found that treatment of articles made with boron-containing materials improves the form-retention of subsequently produced carbonaceous articles.

In another aspect, the invention features a boron treated stabilized article formed from a polyolefin precursor (resin). In one case, the boron-treated stabilized article is formed according to the methods described herein.

In yet another aspect, a carbonaceous article and a method of making the same are provided. Carbonaceous articles are carbon-rich articles; carbon fibers, carbon flakes, and carbon films are examples of carbonaceous articles. Carbonaceous articles have many applications, such as carbon fiber, which is commonly used to reinforce composite materials, such as for carbon fiber reinforced epoxy resin composites, and carbon disks or pads for high performance braking systems.

The carbonaceous articles described herein are prepared by carbonizing a stabilized article by heat treating a boron treated stable article in an inert environment. The inert environment is an environment that surrounds the boron-treated stable article and exhibits less reactivity with carbon at high temperatures, preferably a high vacuum or oxygen-depleted atmosphere. Preferably, it is a nitrogen atmosphere or an argon atmosphere. It should be understood that traces of oxygen may be present in an inert atmosphere. In one case, the temperature of the inert environment is 600 ° C or higher. Preferably, the temperature in the inert environment is 800 ° C or higher. In one case, the temperature of the inert environment does not exceed 3000 °C. In one case, the temperature is 1400-2400 °C. Temperatures at or near the upper end of the range will produce temperatures at or near the upper end of the range that will produce graphite articles, while temperatures at or near the lower end of the range will produce carbon articles.

To prevent foaming or damage to the finished article during carbonization, it is preferred to heat the inert environment in a progressive or stepwise manner. In one embodiment, the boron treated stabilized article is introduced into a heating chamber containing an inert environment at or near ambient temperature, followed by heating the chamber for a period of time to achieve the desired final temperature. The heating schedule may also include one or more holding steps for a specified period of time at the final or intermediate temperature or stylized cooling rate prior to removal of the item from the chamber.

In yet another embodiment, the chamber containing the inert environment is subdivided into a plurality of zones, each maintained at a desired temperature by suitable control means, and passed from one zone to the appropriate via a suitable transport mechanism, such as a motorized belt. A stepwise manner in the next zone heats the stabilized article that has been treated with boron. In the case where the boron-treated stabilized article is a fiber, the transport mechanism can be to apply traction to the fiber at the exit of the carbonization process while controlling the tension in the stabilized fiber at the inlet.

Some embodiments of the invention will now be described in detail in the following examples.

In the examples, the total mass yield is calculated as the product of the oxidized mass yield and the carbonized mass yield (as calculated below). PHR refers to the number of parts per part of resin (quality basis). MI refers to the melt index, which is a measure of the melt flow rate. Weight% means the number of parts per 100 parts, based on mass. PE means polyethylene. BA refers to boric acid. MBA refers to metaboric acid. BO means boron oxide. ZB refers to zinc borate. T ₉₅ % refers to the temperature at which 5% mass loss is observed (°C). T ₅₀ % means the temperature at which 50% mass loss is observed (°C). T ₅ % refers to the temperature at which 95% mass loss is observed (°C). Definition of measurement yield: Oxidation mass yield:

Carbonization mass yield:

Total mass yield: Y _M = Y _O Y _C

Total mass yield (carbonaceous mass per PE of initial mass):

Where m _PE is the initial mass of polyethylene; m _OX is the mass remaining after oxidation; m _CF is the mass remaining after carbonization; M _%PE is the mass % of polyethylene in the initially formed article.

Soxhlet extraction is a method for determining the gel content and expansion ratio of crosslinked ethylene plastics. As used herein, the standard test method for Determination of Gel Content and Swell Ratio of Crosslinked Ethylene Plastics is used in accordance with ASTM Standard D2765-11 "Standard Test Methods for Determination of Gel Content and Swell Ratio of Crosslinked Ethylene Plastics". Extraction. In the method employed, between 0.050 g and 0.500 g of the cross-linked finished article is weighed and placed in a cellulose-based sleeve, which is then placed in a sufficient amount. Soxhlet extraction equipment for xylene. Soxhlet extraction with refluxing xylene followed by at least 12 hours. After extraction, the sleeve was removed and the cross-linked article was dried in a vacuum oven at 80 ° C for at least 12 hours and then weighed to provide a Soxhlet-treated article. Subsequent to weight ratio (Soxhed article) / (crosslinked product) Piece) Calculate the gel content (%).

Comparative example 1

The ethylene/octene copolymer (density = 0.941 g/cm ³ ; MI = 34 g/10 min, 190 ° C / 2.16 kg) was reactively extruded with vinyl trimethoxydecane (VTMS) to form VTMS grafted ethylene / Octene copolymer (MI = 19 g/10 min, 190 ° C / 2.16 kg; 1.4 wt% grafted decane content, determined by ¹³ C NMR) precursor resin. The VTMS grafted precursor resin was melt spun to form fibers having the following characteristics: 1573 filaments, 1978.2 total denier, 2.31 gf/den, 12.94% elongation at break. The prepared fibers were continuously treated for 30 min in a vessel containing an isopropyl alcohol solution having 5 wt% of arylsulfonic acid Nacure B201 supplied by King Industries. The treated fibers were dried and cured for 3 days. The fibers were then moisture cured at 80 ° C (100% relative humidity) for 5 days. The gel fraction was determined by Soxhlet extraction to be 61.4-61.9%. The crosslinked fibers were oxidized and carbonized using a thermogravimetric analysis (TGA) instrument using the conditions outlined in Table 1 at a ramp rate of 10 ° C/min. Table 2 reports the quality retained during air oxidation and the final mass yield after both oxidation and carbonization treatments.

Example 1A

The ethylene/octene copolymer (density = 0.941 g/cm ³ ; MI = 34 g/10 min, 190 ° C / 2.16 kg) was reactively extruded with vinyl trimethoxydecane (VTMS) to form VTMS grafted ethylene / Octene copolymer (MI = 19 g/10 min, 190 ° C / 2.16 kg; 1.4 wt% grafted decane content, determined by ¹³ C NMR) precursor resin. The VTMS grafted precursor resin was melt spun to form fibers having the following characteristics: 1573 filaments, 1978.2 total denier, 2.31 gf/den, 12.94% elongation at break. The prepared fibers were continuously treated in a vessel containing an isopropyl alcohol solution for 30 minutes, and the solution had 5% by weight of arylsulfonic acid Nacure B201. The treated fibers were dried and cured for 3 days. The fibers were then moisture cured at 80 ° C (100% relative humidity) for 5 days. The gel fraction was determined by Soxhlet extraction to be 61.4-61.9%. The crosslinked fibers were then treated with a 5 wt% solution of boric acid in isopropanol to treat the times reported in Table 3. After treatment with the boric acid solution, the fibers were dried overnight in air under ambient conditions. The relative changes in fiber quality and quality before/after boric acid treatment are reported in Table 4.

The borated acid-treated crosslinked fibers were oxidized and carbonized using a thermogravimetric analysis (TGA) instrument using the conditions outlined in Table 5 at a ramp rate of 10 ° C/min. Table 6 reports the quality retained during oxidation of air and in oxidation and Final mass yield after both carbonization treatments.

Example 1B

The ethylene/octene copolymer (density = 0.941 g/cm ³ ; MI = 34 g/10 min, 190 ° C / 2.16 kg) was reactively extruded with vinyl trimethoxydecane (VTMS) to form VTMS grafted ethylene / Octene copolymer (MI = 19 g/10 min, 190 ° C / 2.16 kg; 1.4 wt% grafted decane content, determined by ¹³ C NMR) precursor resin. The VTMS grafted precursor resin was melt spun to form fibers having the following characteristics: 1573 filaments, 1978.2 total denier, 2.31 gf/den, 12.94% elongation at break. The prepared fibers were continuously treated in a vessel containing an isopropyl alcohol solution for 30 minutes, and the solution had 5% by weight of arylsulfonic acid Nacure B201. The treated fibers were dried and cured for 3 days. The fibers were then moisture cured at 80 ° C (100% relative humidity) for 5 days. The gel fraction was determined by Soxhlet extraction to be 61.4-61.9%. The crosslinked fibers were then treated with a 5% by weight solution of boric acid in isopropanol for the time reported in Table 7. After treatment with the boric acid solution, the fibers were dried overnight in air under ambient conditions. The dried, boric acid treated fibers were subjected to heat treatment (80 ° C) overnight in a vacuum oven. The relative changes in fiber quality and quality before/after boric acid treatment are reported in Table 8.

The heat treated, boric acid treated crosslinked fibers were oxidized and carbonized using a thermogravimetric analysis (TGA) instrument using the conditions outlined in Table 9 for the oxidation and carbonization scheme at a ramp rate of 10 ° C/min.

Table 10 reports the quality maintained during air oxidation and the final mass yield after both oxidation and carbonization treatments.

Comparative example 2

The ethylene/octene copolymer (density = 0.941 g/cm ³ ; MI = 34 g/10 min, 190 ° C / 2.16 kg) was reactively extruded with vinyl trimethoxydecane (VTMS) to form VTMS grafted ethylene / Octene copolymer (MI = 19 g/10 min, 190 ° C / 2.16 kg; 1.4 wt% grafted decane content, determined by ¹³ C NMR) precursor resin. The VTMS grafted precursor resin was melt spun to form fibers having the following characteristics: 1573 filaments, 1945.8 total denier, 2.25 gf/den, 12.17% elongation at break. The prepared fibers were continuously treated in a vessel containing an isopropyl alcohol solution for 5 seconds, and the solution had 5% by weight of arylsulfonic acid Nacure B201. The treated fibers were dried and cured for 3 days. The fibers were then moisture cured at 80 ° C (100% relative humidity) for 5 days. The gel fraction was determined by Soxhlet extraction to be 58.2-58.9%. The crosslinked fibers were oxidized and carbonized using a thermogravimetric analysis (TGA) instrument using the conditions outlined in Table 11 at a ramp rate of 10 ° C/min. Table 12 reports the mass retained during air oxidation and the final mass yield after both oxidation and carbonization treatments.

Example 2A

The ethylene/octene copolymer (density = 0.941 g/cm ³ ; MI = 34 g/10 min, 190 ° C / 2.16 kg) was reactively extruded with vinyl trimethoxydecane (VTMS) to form VTMS grafted ethylene / Octene copolymer (MI = 19 g/10 min, 190 ° C / 2.16 kg; 1.4 wt% grafted decane content, determined by ¹³ C NMR) precursor resin. The VTMS grafted precursor resin was melt spun to form fibers having the following characteristics: 1573 filaments, 1945.8 total denier, 2.25 gf/den, 12.17% elongation at break. The prepared fibers were continuously treated in a vessel containing an isopropyl alcohol solution for 5 seconds, and the solution had 5% by weight of arylsulfonic acid Nacure B201. The treated fibers were dried and cured for 3 days. The fibers were then moisture cured at 80 ° C (100% relative humidity) for 5 days. The gel fraction was determined by Soxhlet extraction to be 58.2-58.9%. The crosslinked fibers were then treated with the 5% by weight solution of boric acid in isopropanol for the time reported in Table 13. After treatment with the boric acid solution, the fibers were dried overnight in air under ambient conditions. The dried, boric acid treated fibers were subjected to heat treatment (80 ° C) overnight in a vacuum oven. The relative changes in fiber quality and quality before/after boric acid treatment are reported in Table 14.

The heat treated, boric acid treated crosslinked fibers were oxidized and carbonized using a thermogravimetric analysis (TGA) instrument using the conditions outlined in Table 15 at a ramp rate of 10 ° C/min. Table 16 reports the mass quality retained during air oxidation and the final mass yield after both oxidation and carbonization treatments.

Example 2B

The ethylene/octene copolymer (density = 0.941 g/cm ³ ; MI = 34 g/10 min, 190 ° C / 2.16 kg) was reactively extruded with vinyl trimethoxydecane (VTMS) to form VTMS grafted ethylene / Octene copolymer (MI = 19 g/10 min, 190 ° C / 2.16 kg; 1.4 wt% grafted decane content, determined by ¹³ C NMR) precursor resin. The VTMS grafted precursor resin was melt spun to form fibers having the following characteristics: 1573 filaments, 1945.8 total denier, 2.25 gf/den, 12.17% elongation at break. The prepared fibers were continuously treated in a vessel containing an isopropyl alcohol solution for 5 seconds, and the solution had 5% by weight of arylsulfonic acid Nacure B201. The treated fibers were dried and cured for 3 days. The fibers were then moisture cured at 80 ° C (100% relative humidity) for 5 days. The gel fraction was determined by Soxhlet extraction to be 58.2-58.9%. The crosslinked fibers were then treated with the 5% by weight solution of boric acid in isopropanol for the time reported in Table 17. After treatment with the boric acid solution, the fibers were dried overnight in air under ambient conditions. The dried, boric acid treated fibers were subjected to heat treatment (80 ° C) overnight in a vacuum oven. The relative changes in fiber quality and quality before/after boric acid treatment are reported in Table 18.

The heat treated, boric acid treated crosslinked fibers were oxidized and carbonized using a thermogravimetric analysis (TGA) instrument using the conditions outlined in Table 19 at a ramp rate of 10 ° C/min. Table 20 reports the mass retained during air oxidation and the final mass yield after both oxidation and carbonization treatments.

Comparative example 3

The ethylene/octene copolymer (density = 0.941 g/cm ³ ; MI = 34 g/10 min, 190 ° C / 2.16 kg) was reactively extruded with vinyl trimethoxydecane (VTMS) to form VTMS grafted ethylene / Octene copolymer (MI = 19 g/10 min, 190 ° C / 2.16 kg; 1.4 wt% grafted decane content, determined by ¹³ C NMR) precursor resin. The VTMS grafted precursor resin was melt spun to form fibers having the following characteristics: 1573 filaments, 1978.2 total denier, 2.31 gf/den, 12.94% elongation at break. The prepared fibers were continuously treated in a vessel containing an isopropyl alcohol solution for 30 minutes, and the solution had 5% by weight of arylsulfonic acid Nacure B201. The treated fibers were dried and cured for 3 days. The fibers were then moisture cured at 60 ° C (100% relative humidity) for 5 days. The gel fraction was determined by Soxhlet extraction to be 55.59-56.30%. The crosslinked fibers were oxidized and carbonized using a thermogravimetric analysis (TGA) instrument using the conditions outlined in Table 21 at a ramp rate of 10 ° C/min. Table 22 reports the mass retained during air oxidation and the final mass yield after both oxidation and carbonization treatments.

Example 3A

The ethylene/octene copolymer (density = 0.941 g/cm ³ ; MI = 34 g/10 min, 190 ° C / 2.16 kg) was reactively extruded with vinyl trimethoxydecane (VTMS) to form VTMS grafted ethylene / Octene copolymer (MI = 19 g/10 min, 190 ° C / 2.16 kg; 1.4 wt% grafted decane content, determined by ¹³ C NMR) precursor resin. The VTMS grafted precursor resin was melt spun to form fibers having the following characteristics: 1573 filaments, 1978.2 total denier, 2.31 gf/den, 12.94% elongation at break. The prepared fibers were continuously treated in a vessel containing an isopropyl alcohol solution for 30 minutes, and the solution had 5% by weight of arylsulfonic acid Nacure B201. The treated fibers were dried and cured for 3 days. The fibers were then moisture cured at 60 ° C (100% relative humidity) for 5 days. The gel fraction was determined by Soxhlet extraction to be 55.59-56.30%. The crosslinked fibers were then treated with a saturated solution of boron oxide in isopropanol to treat the times reported in Table 23. After treatment with the boron oxide solution, the fibers were dried overnight in air under ambient conditions. The relative changes in fiber quality and quality before/after the boron oxide treatment are reported in Table 24.

The boron oxide treated crosslinked fibers were oxidized and carbonized using a thermogravimetric analysis (TGA) instrument using the conditions outlined in Table 25 at a ramp rate of 10 ° C/min. Table 26 reports the mass quality retained during air oxidation and the final mass yield after both oxidation and carbonization treatments.

Example 3B

The ethylene/octene copolymer (density = 0.941 g/cm ³ ; MI = 34 g/10 min, 190 ° C / 2.16 kg) was reactively extruded with vinyl trimethoxydecane (VTMS) to form VTMS grafted ethylene / Octene copolymer (MI = 19 g/10 min, 190 ° C / 2.16 kg; 1.4 wt% grafted decane content, determined by ¹³ C NMR) precursor resin. The VTMS grafted precursor resin was melt spun to form fibers having the following characteristics: 1573 filaments, 1978.2 total denier, 2.31 gf/den, 12.94% elongation at break. The prepared fibers were continuously treated in a vessel containing an isopropyl alcohol solution for 30 minutes, and the solution had 5% by weight of arylsulfonic acid Nacure B201. The treated fibers were dried and cured for 3 days. The fibers were then moisture cured at 60 ° C (100% relative humidity) for 5 days. The gel fraction was determined by Soxhlet extraction to be 55.59-56.30%. The crosslinked fibers were then treated with a 5 wt% suspension of zinc borate (Firebrake ZB-XF) in isopropanol for the time reported in Table 27. After treatment with the zinc borate suspension, the fibers were dried overnight in air under ambient conditions. The dried, zinc borate treated fibers were subjected to heat treatment (80 ° C) overnight in a vacuum oven. The relative changes in fiber quality and quality before/after boric acid treatment are reported in Table 28.

The zinc borate treated crosslinked fibers were subjected to a thermogravimetric analysis (TGA) instrument using the conditions outlined in Table 29 at a temperature of 10 ° C/min. Rate-up oxidation and carbonization.

Table 30 reports the quality maintained during air oxidation and the final mass yield after both oxidation and carbonization treatments.

Example 4

The ethylene/octene copolymer (density = 0.941 g/cm ³ ; MI = 34 g/10 min, 190 ° C / 2.16 kg) was reactively extruded with vinyl trimethoxydecane (VTMS) to form VTMS grafted ethylene / Octene copolymer (MI = 19 g/10 min, 190 ° C / 2.16 kg; 1.4 wt% grafted decane content, determined by ¹³ C NMR) precursor resin. The VTMS grafted precursor resin was melt spun to form fibers having the following characteristics: 1573 filaments, 1978.2 total denier, 2.31 gf/den, 12.94% elongation at break. The prepared fibers were continuously treated in a vessel containing an isopropyl alcohol solution for 30 minutes, and the solution had 5% by weight of arylsulfonic acid Nacure B201. The treated fibers were dried and cured for 3 days. The fibers were then moisture cured at 80 ° C (100% relative humidity) for 5 days. The gel fraction was determined by Soxhlet extraction to be 61.4-61.9%. The crosslinked fibers were then treated with the 5% by weight solution of boric acid in isopropanol for the time reported in Table 31. After treatment with the boric acid solution, the fibers were dried overnight in air under ambient conditions. The dried, boric acid treated fibers were subjected to heat treatment (80 ° C) overnight in a vacuum oven. The relative changes in fiber quality and quality before/after boric acid treatment are reported in Table 32.

The heat treated, boric acid treated crosslinked fibers were oxidized and carbonized using a thermogravimetric analysis (TGA) instrument using the conditions outlined in Table 33 at a ramp rate of 10 ° C/min. Table 34 reports the quality retained during air oxidation and the final mass yield after oxidation and carbonization.

Example 5

The ethylene/octene copolymer (density = 0.941 g/cm ³ ; MI = 34 g/10 min, 190 ° C / 2.16 kg) was reactively extruded with vinyl trimethoxydecane (VTMS) to form VTMS grafted ethylene / Octene copolymer (MI = 19 g/10 min, 190 ° C / 2.16 kg; 1.4 wt% grafted decane content, determined by ¹³ C NMR) precursor resin. The VTMS grafted precursor resin was melt spun to form fibers having the following characteristics: 1573 filaments, 1945.8 total denier, 2.25 gf/den, 12.17% elongation at break. The fiber bundle was continuously treated in a vessel containing a solution of isopropyl alcohol having 5% by weight of boric acid. The fiber residence time in the solution was 5 seconds. The treated fibers were dried and cured for 3 days. The fibers were then wet cured at 80 ° C (100% relative humidity) for 1-5 days as reported in Table 35. The gel fraction was determined by Soxhlet extraction. The full results are reported in Table 36.

The three sections (A, B and C) prepared and crosslinked were treated multiple times with a 15% by weight solution of boric acid in methanol reported in Table 37. After treatment with the boric acid solution, the fibers were dried overnight in air under ambient conditions. The dried, boric acid treated fibers were then subjected to heat treatment (80 ° C) overnight in a vacuum oven. The relative changes in fiber quality and quality before and after boric acid treatment are reported in Table 38.

The heat treated, boric acid treated crosslinked fibers were oxidized and carbonized using a thermogravimetric analysis (TGA) instrument using the conditions outlined in Table 39. The temperature ramp rate was maintained at 10 ° C/min for oxidation and carbonization schemes. Table 40 reports the quality retained during air oxidation and the final mass yield after both oxidation and carbonization treatments.

Comparative example 6

A vinyltrimethoxydecane grafted ethylene/octene copolymer (MI = 7 g/10 min, 190 ° C / 2.16 kg; 1.6 wt% grafted decane content) was used as the precursor resin. The film was compression molded at 180 ° C using a Carver press into a film measuring 3 mm (76.2 μm) thick by a micrometer. By using A commercially available arylsulfonic acid catalyst (Nacure B-201, King Industries) was treated with a film in an isopropanol solution for 12 hours, followed by moisture curing at 60-80 ° C for 72 hours to crosslink all of the films. The gel fraction was determined by Soxhlet extraction to be 81.8%. Nine (9) smaller circular membranes were cut from the prepared membrane and weighed. The membrane was oxidized in air (21% oxygen content) in a convection oven at 270 °C for 5 hours. Nine (9) films were weighed after air oxidation. The mass retention rate (oxidation mass yield) during air oxidation is reported in Table 41. The oxide film was then carbonized from 25 ° C to 800 ° C under a nitrogen gas at a temperature increase rate of 10 ° C / min. The mass retention rate (carbonization mass yield) during carbonization is reported in Table 41. The calculated total mass yield is reported in Table 41. The average oxidation mass yield, carbonization mass yield, and total mass yield were 43.5%, 45.7%, and 19.7%, respectively.

Example 6

A vinyltrimethoxydecane grafted ethylene/octene copolymer (MI = 7 g/10 min, 190 ° C / 2.16 kg; 1.6 wt% grafted decane content) was used as the precursor resin. The film was compression molded at 180 ° C using a Carver press into a film measuring 3 mm (76.2 μm) thick by a micrometer. The membrane was treated in a solution of isopropanol with a commercially available arylsulfonic acid catalyst (Nacure B-201, King Industries) for 12 hours, followed by wet curing at 60-80 ° C for 72 hours. All membranes were crosslinked. The gel fraction was determined by Soxhlet extraction to be 81.8%. Four (4) membranes labeled A-D were immersed in a vial containing a solution of dichloromethane and tributyl borate according to Table 42. The membrane was treated overnight in a solution of tributyl borate. The film weight before and after treatment with tributyl borate was recorded. Table 43 reports the weight change of each film. The membrane was oxidized in air (21% oxygen content) in a convection oven at 270 °C for 5 hours. The film was weighed after air oxidation. The mass retention rate (oxidation mass yield) during air oxidation is reported in Table 44. The oxide film was then carbonized from 25 ° C to 800 ° C under a nitrogen gas at a temperature increase rate of 10 ° C / min. The mass retention rate (carbonization mass yield) during carbonization is reported in Table 44. The average oxidation mass yield of the film treated with tributyl borate prior to oxidation increased by 5.5-42.1% compared to the control film (Comparative Example 6). The average carbonization mass yield of the film treated with tributyl borate prior to oxidation and carbonization was increased by 13.6-24.5% compared to the control film (Comparative Example 6). The average total mass yield of the film treated with tributyl borate prior to oxidation and carbonization was increased by 25.4-78.2% compared to the control film (Comparative Example 6).

Comparative example 7

The ethylene/octene copolymer (density = 0.950 g/cm ³ ; MI = 17 g/10 min, 190 ° C / 2.16 kg) was melt blended under nitrogen at 160 ° C in a DSM Xplore 15 micromixer. A film was compression molded at 160 ° C using a Carver press. The membrane was oxidized in air (21% oxygen content) in a convection oven at 250 ° C for 10 hours. The film was weighed after air oxidation. The mass retention rate (oxidation mass yield) during air oxidation is reported in Table 45. The oxide film was then carbonized from 25 ° C to 800 ° C under a nitrogen gas at a temperature increase rate of 10 ° C / min. The mass retention rate (carbonization mass yield) during carbonization is reported in Table 45. The calculated total mass yields are reported in Table 45.

Example 7A

Ethylene / octene copolymer (density ^{= 0.950g / cm 3; MI =} 17g / 10min, 190 ℃ / 2.16kg) and 5% by weight of polybutadiene (Press was used as obtained from Sigma Aldrich (average M _n 1,530-2,070 ; Cat. No. 434779)) Melt blending at 160 ° C in a DSM Xplore 15 micromixer under nitrogen. The film was compression molded at 160 ° C using a Carver press. The membrane was oxidized in a convection oven at 250 ° C for 10 hours under air (21% oxygen content). The film was weighed after air oxidation. The mass retention rate (oxidation mass yield) during air oxidation is reported in Table 46. The oxide film was then carbonized from 25 ° C to 800 ° C under a nitrogen gas at a temperature increase rate of 10 ° C / min. The mass retention rate (carbonization mass yield) during carbonization is reported in Table 46. The calculated total mass yields are reported in Table 46.

Example 7B

Ethylene / octene copolymer (density ^{= 0.950g / cm 3; MI =} 17g / 10min, 190 ℃ / 2.16kg) and 5% by weight of polybutadiene (Press was used as obtained from Sigma Aldrich (average M _n 1,530-2,070 ; Cat. No. 434779)) Melt blending at 160 ° C in a DSM Xplore 15 micromixer under nitrogen. The film was compression molded at 160 ° C using a Carver press. A 300 mL 6.66 mM BH ₃ (borane) solution was prepared in a glove box by dissolving 2.01 mL of a 1 M BH ₃ solution in THF in 300 mL of THF. The membrane was immersed in 100 mL of BH ₃ solution overnight. After removal from the solution, the film was dried in a glove box atmosphere. After 16 h, the film was removed from the glove box. The membrane was oxidized in a convection oven at 250 ° C for 10 hours under air (21% oxygen content). The film was weighed after air oxidation. The mass retention rate (oxidation mass yield) during air oxidation is reported in Table 47. The oxide film was then carbonized from 25 ° C to 800 ° C under a nitrogen gas at a temperature increase rate of 10 ° C / min. The mass retention rate (carbonization mass yield) during carbonization is reported in Table 47. The calculated total mass yields are reported in Table 47. The relative increase in carbonization mass yield was observed to be 221-261% for the borane treated membrane (Example 7B) compared to the control membrane (Comparative Example 7 and Example 7A). The relative increase in total mass yield observed for the borane treated membrane was 297-308% compared to the control membrane (Comparative Example 7 and Example 7A).

Claims (9)

A method of preparing a carbonaceous article, comprising: (a) providing an olefin resin; (b) forming a finished article from the olefin resin; (c) crosslinking the article; (d) by air oxidation The article is stabilized; (e) treated with a boron-containing liquid (BCL) during or between at least one of the foregoing steps; and (f) carbonized the stabilized article. The method of claim 1, wherein the BCL is a boron source suitable for depositing boron in the fabricated article. The method of claim 2, wherein the boron source is elemental boron, borane, borate, boronic acid, boronic acid, boric acid, dihydrocarbyl. Borate esters, hydrocarbyl borate esters, boroxanes, amine boranes, borazines, borohydrides and derivatives and combinations thereof. The method of any one of claims 1 to 3, wherein the step (d) comprises heating the finished article at 120 ° C or higher. The method of any one of the preceding claims, wherein the step (b) comprises: fiber spinning, film extrusion casting, blown film processing, extrusion through a die, injection Molding, solution casting or compression molding converts the polyolefin resin into a finished article. A method of preparing a carbonaceous article, comprising: (a) providing a crosslinked polyolefin article; (b) stabilizing the crosslinked polyolefin article by air oxidation to provide a stable article; (c) treating with a boron containing liquid (BCL) during or between at least one of the preceding steps; and (d) The stabilized article is carbonized. The method of claim 6, wherein the BCL is a boron source suitable for depositing boron in the fabricated article. The method of claim 7, wherein the boron source is elemental boron, borane, borate, dihydrocarbylboronic acid, hydrocarbylboronic acid, boric acid, dihydrocarbyl borate, hydrocarbyl borate, boron oxalate Cyclohexane, amine borane, borazine, borohydride and derivatives and combinations thereof. The method of any one of claims 1 to 3, wherein the step (b) comprises heating the crosslinked article at 120 ° C or higher.