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

由聚烯烴製造製成物件之方法 Method of manufacturing articles made from polyolefin

本發明係關於一種製備含碳物件之方法。 This invention relates to a method of making a carbonaceous article.

先前，諸如碳纖維之含碳物件已主要由聚丙烯腈(polyacrylonitrile；PAN)、瀝青或纖維素前驅物產生。製備含碳物件之方法藉由自前驅物形成製成物件(諸如纖維或膜)開始。可使用形成或模製聚合物之標準技術使前驅物形成製成物件。隨後使製成物件穩定化以使得製成物件在後續熱處理步驟期間基本上保留形狀；在不受理論限制的情況下，此類穩定化通常涉及氧化與加熱之組合且一般導致界定製成物件之前驅物之脫氫、成環、氧化及交聯。隨後，藉由在惰性氛圍中加熱經穩定之製成物件來將經穩定之製成物件轉化成含碳物件。雖然生產含碳物件之一般步驟與生產多種前驅物之步驟相同，但彼等步驟之細節視所選前驅物之化學組成而廣泛變化。 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.

已研究聚烯烴作為含碳物件之替代前驅物，但已證實難以實現適合及經濟可行之製備方法。備受關注的為鑑定由聚烯烴前驅物製備含碳物件之經濟方法。舉例而言，在穩定化及碳化步驟期間使質量保留率最大化為所關注的。 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.

本發明描述一種製備含碳物件之方法，包括：提供交聯聚烯烴製成物件；藉由空氣氧化使交聯聚烯烴製成物件穩定化以提供穩定製成物件；在至少一個前述步驟期間或中間用含硼液體(BCL)處理；以及對穩定製成物件進行碳化。在一種情況下，本發明描述一種製備穩定物件之方法。 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.

除非另外指示，否則數值範圍(例如「2至10」)包含界定所述範圍之數字(例如2及10)。 Numerical ranges (eg, "2 to 10") include numbers that define the ranges (eg, 2 and 10) unless otherwise indicated.

除非另外指明，否則比率、百分比、份及其類似者以重量計。 Unless otherwise indicated, ratios, percentages, parts, and the like are by weight.

除非另外指明，否則用於聚烯烴樹脂之可交聯官能基含量藉由可交聯官能基mol%特性化，其計算為可交聯官能基之莫耳數除以聚烯烴中所含有的單體單元的總莫耳數。 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.

除非另外指示，否則「單體」係指可進行聚合之分子，從而構成例如聚烯烴之大分子之基本結構的組成單元。在一個態樣中，本發明描述一種由聚烯烴樹脂產生含碳製成物件之方法。如本文中更詳細地描述，含碳製成物件藉由以下方法製備：(a)提供烯烴樹脂；(b)從烯烴樹脂形成製成物件；(c)交聯製成物件以提供交聯製成物件；(d)藉由空氣氧化使製成物件穩定化以提供穩定製成物件；(e)在至少一個前述步驟期間或中間用含硼液體(BCL)處理；和(f)對穩定製成物件進行碳化。 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.

適合的BCL包含液體，所述液體包含含硼物質。適合的含硼物質之實例包含硼烷、硼酸鹽、二烴基硼酸(borinic acid)、烴基硼酸(boronic acid)、硼酸(boric acid)、二烴基硼酸酯、烴基硼酸酯、硼氧雜環己烷、胺基硼烷、環硼氮烷、硼氫化物及其衍生物及組合。元素硼也為適合的含硼物質。硼酸之衍生物之實例包含偏硼酸及三氧化二硼。硼酸鹽衍生物之實例包含無機硼酸鹽，諸如硼酸鋅，及有機硼酸鹽，諸如三丁基硼酸鹽。在一種情況下，BCL僅藉由含硼物質製備。在一種情況下，BCL亦與含硼物質一起包含另一組分，且經選擇以使得另一組分與含硼物質可混溶，與其形成懸浮液或另外與其一起攜載且與總體製程相容。在一種情況下，另一組分為極性或非極性液體。舉例而言，醇(諸如異丙醇)為BCL之適合成分。在一種情況下，在BCL中以懸浮液形式攜載含硼物質的至少一部分。 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.

除非另外說明，否則可以任何順序進行本文所描述之任何方法或製程步驟。 Any of the methods or process steps described herein can be performed in any order, unless otherwise stated.

聚烯烴為一類由一或多種烯烴單體產生之聚合物。本文所描述之聚合物可由一或多種類型之單體形成。聚乙烯為較佳聚烯烴樹脂，但其他聚烯烴樹脂可取代。舉例而言，由乙烯、丙烯或其他α-烯烴(例如，1-丁烯、1-己烯、1-辛烯)或其組合產生之聚烯烴亦為適合的。本文中所描述之聚烯烴通常以樹脂形式提供，再分成具有適宜尺寸之球粒或顆粒以用於進一步熔融或溶液處理。在一種情況下，聚烯烴樹脂在形成為製成物件之前用BCL處理。聚烯烴樹脂可藉由此項技術中已知之任何機制，諸如噴霧、浸漬或吸收來用BCL 處理。BCL可以適合之液體形式，例如無溶劑形式，或作為溶液的一部分，或作為液體中的懸浮液引入。BCL可作為連續法的一部分或作為分批法的一部分引入。 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.

使本文所描述之聚烯烴樹脂經受交聯步驟。用於交聯聚烯烴之任何適合之方法為足夠的。在一種情況下，聚烯烴藉由照射(諸如藉由電子束處理)交聯。其他交聯方法為適合的，例如紫外線照射及γ照射。在一些情況下，引發劑(諸如二苯甲酮)可與照射結合使用以引發交聯。在一種情況下，聚烯烴樹脂已經改質以包含適用於反應而使聚烯烴樹脂交聯的可交聯官能基。在聚烯烴樹脂包括可交聯官能基之情況下，交聯可藉由已知方法，包含使用化學交聯劑、藉由加熱、藉由蒸汽或其他適合方法引發。在一種情況下，共聚物適合於提供具有可交聯官能基之聚烯烴樹脂，其中一或多種α-烯烴已與含有適用於充當可交聯官能基之基團的另一單體共聚合，例如二烯、一氧化碳、甲基丙烯酸縮水甘油酯、丙烯酸、乙酸乙烯酯、順丁烯二酸酐或乙烯基三甲氧基矽烷(VTMS)屬於適用於與α-烯烴共聚合之單體。此外，具有可交聯官能基之聚烯烴樹脂亦可由已藉由將官能基部分接枝至基質聚烯烴上而經改質之聚(α-烯烴)產生，其中官能基係基於其隨後實現給定聚烯烴之交聯之能力選擇。舉例而言，此類型之接枝可藉由使用自由基引發劑(諸如過氧化物)及乙烯基單體(諸如VTMS、二烯、乙酸乙烯酯、丙烯酸、甲基丙烯酸、丙烯酸酯及甲基丙烯酸酯(諸如甲基丙烯酸縮水甘油酯及甲基丙烯醯氧基丙基三甲氧基矽烷)、烯丙基胺、對胺基苯乙烯、甲基丙烯酸二甲基胺基乙酯)或經由疊氮基官能化 分子(諸如4-[2-(三甲氧基矽基)乙基)]苯磺醯基疊氮化合物)來進行。具有可交聯官能基之聚烯烴樹脂可由聚烯烴樹脂產生，或可商業上購買。市售可得之具有可交聯官能基之聚烯烴樹脂的實例包括The Dow Chemical Company出售之SI-LINK、The Dow Chemical Company出售之PRIMACOR、Kuraray出售之EVAL樹脂及Arkema出售之LOTADER AX8840。 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.

如上文所描述，處理聚烯烴樹脂以形成製成物件。製成物件為已由聚烯烴樹脂製造之物件。製成物件使用已知之聚烯烴製造技術形成，例如熔融或溶液紡絲以形成纖維、膜擠壓或膜鑄造或吹製膜法以形成膜、模擠壓或射出模製或壓縮成形以形成更複雜形狀，或溶液澆注。根據目標含碳物件之所需幾何形狀及該含碳物件之所需物理特性選擇製造技術。舉例而言，在所需含碳物件為碳纖維之情況下，纖維紡絲為適合的製造技術。作為另一實例，在所需含碳物件為碳膜之情況下，壓縮模製為適合的製造技術。在一種情況下，製成物件用BCL處理。在一種情況下，製成物件在交聯聚烯烴樹脂之前用BCL處理。製成物件可藉由此項技術中已知之任何機制，諸如噴霧、浸漬或吸收來用BCL處理。BCL可以適合之液體形式，例如無溶劑形式，或作為溶液的一部分，或作為液體中的懸浮液引入。BCL可作為連續法的一部分或作為分批法的一部分引入。 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.

如上文所提及，使至少一部分聚烯烴樹脂交聯以產生交聯製成物件。在一些實施例中，交聯經由化學交聯進行。因此，在一些實施例中，交聯製成物件為已用一或多種 化學劑處理以交聯聚烯烴樹脂之可交聯官能基的製成物件。此類化學劑用於引發可交聯官能基之間分子內化學鍵之形成或與可交聯官能基反應以形成分子內化學鍵，如此項技術中已知。化學交聯使可交聯官能基反應形成新鍵，形成界定具有可交聯官能基之聚烯烴樹脂的不同聚合物鏈之間的鍵。基於聚烯烴樹脂中包括之可交聯官能基的類型來選擇實現交聯之化學劑；已知經由分子間及分子內化學鍵交聯可交聯官能基之一系列不同的反應。選擇適合的化學劑，已知其交聯製成物件中所存在之可交聯官能基以產生經交聯之製成物件。舉例而言，在不限制本發明之情況下，若附接至聚烯烴之可交聯官能基為乙烯基，則適合的化學劑包括自由基引發劑，諸如過氧化物或偶氮基-雙腈化物，例如過氧化二異丙苯、過氧化二苯甲醯、過辛酸第三丁酯、偶氮二異丁腈及其類似物。若附接至聚烯烴之可交聯官能基為酸(諸如羧酸)或酐或酯或縮水甘油氧基，則適合的化學劑可為含有至少兩個親核基團之化合物，包括二親核試劑，諸如二胺、二醇、二硫醇，例如乙二胺、己二胺、丁二醇或己二硫醇。亦可使用含有兩個以上親核基團之化合物，例如丙三醇、山梨糖醇或六亞甲基四胺。混合型二親核試劑或高親核試劑(其含有至少兩個不同親核基團，例如乙醇胺)亦可為適合的化學劑。若附接至聚烯烴之可交聯官能基為單烷氧基矽烷基、二烷氧基矽烷基或三烷氧基矽烷基，則水及路易斯(Lewis)酸或布朗斯泰德(Bronsted)酸或鹼催化劑可用作適合的化學劑。舉例而言，在不限制本發明之情況下，路易斯酸或布朗斯泰德酸或鹼催化劑包括芳基磺酸、硫酸、氫氧化物、鋯醇鹽或錫試劑。 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.

交聯製成物件一般較佳以確保製成物件在後續處理步驟所需之高溫下保留其形狀。在不交聯之情況下，聚烯烴樹脂通常在高溫下軟化、熔融或者變形或分解。交聯增加製成物件之熱穩定性。在一種情況下，製成物件在交聯之後及在穩定之前用BCL處理。交聯製成物件可藉由此項技術中已知之任何機制，諸如噴霧、浸漬或吸收來用BCL處理。BCL可以適合之液體形式，例如無溶劑形式，或作為溶液的一部分，或作為液體中的懸浮液引入。BCL可作為連續法的一部分或作為分批法的一部分引入。 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.

在氧化環境中加熱交聯製成物件以產生穩定製成物件。在一些實施例中，用於使交聯製成物件穩定化之溫度為至少120℃，較佳至少190℃。在一些實施例中，用於使交聯製成物件穩定化之溫度不超過400℃，較佳不超過300℃。在一種情況下，將交聯製成物件引入已達到所需溫度之加熱室中。在另一情況下，將製成物件引入處於或接近環境溫度之加熱室中，隨後將該腔室加熱至所需溫度。在一些實施例中，加熱速率為至少1℃/分鐘。在其他實施例中，加熱速率不超過15℃/分鐘。在又一情況下，逐步加熱腔室，例如將腔室加熱至第一溫度持續一段時間(諸如120℃持續一小時)，隨後升高至第二溫度持續一段時間(諸如180℃持續一小時)，且第三次升高至固持溫度(諸如250℃持續10小時)。視製成物件之尺寸而定，穩定化方法涉及在給定溫度下固持經交聯之製成物件至多100小時之時間段。在一種情況下，製成物件在穩定化方法期間用BCL處理。交聯製成物件可藉由此項技術中已知之任何機制，諸如噴霧、浸漬或吸收在穩定化期間 用BCL處理。BCL可以適合之液體形式，例如無溶劑形式，或作為溶液的一部分，或作為液體中的懸浮液引入。BCL可作為連續法的一部分或作為分批法的一部分引入。穩定化方法產率經穩定化之製成物件，其為穩定化方法產生經硼處理之穩定製成物件，其為用於含碳物件之前驅物。在不受理論限制之情況下，穩定化方法氧化經交聯之製成物件，且使烴結構變化，其增加交聯密度，同時減小經交聯之製成物件之氫/碳比。在不受理論限制之情況下，在硼存在下之穩定化方法改質氧化化學且增加交聯密度。 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.

出乎意料地，已發現經由BCL在製成物件中引入硼提高隨後產生的穩定物件及含碳物件之質量保留。亦已發現用含硼物質處理製成物件改良隨後產生之含碳物件之保形性(form-retention)。 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.

在另一態樣中，本發明描述由聚烯烴前驅物(樹脂)形成之經硼處理之穩定製成物件。在一種情況下，經硼處理之穩定製成物件根據本文中所描述之方法形成。 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.

在又一態樣中，提供一種含碳物件及其之製備方法。含碳物件為富含碳之物件；碳纖維、碳薄片及碳膜為含碳物件之實例。含碳物件具有許多應用，例如碳纖維常用於加強複合材料，諸如用於經碳纖維加強之環氧樹脂複合物；而碳盤或墊用於高效能制動系統。 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.

本文所描述之含碳物件藉由經由在惰性環境中熱處理經硼處理之穩定製成物件對穩定製成物件進行碳化來製備。惰性環境為圍繞經硼處理之穩定製成物件、在高溫下顯示與碳之較小反應性之環境，較佳為高真空或氧-耗盡氛 圍，更佳為氮氣氛圍或氬氣氛圍。應理解，痕量氧氣可存在於惰性氛圍中。在一種情況下，惰性環境之溫度為600℃或高於600℃。較佳地，惰性環境之溫度為800℃或高於800℃。在一種情況下，惰性環境之溫度不超過3000℃。在一種情況下，溫度為1400-2400℃。處於或接近該範圍上端之溫度將產生處於或接近該範圍上端之溫度將產生石墨物件，而處於或接近該範圍下端之溫度將產生碳物件。 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.

為防止在碳化期間起泡或損害製成物件，較佳以漸進或逐步的方式加熱惰性環境。在一個實施例中，將經硼處理之穩定製成物件引入含有處於或接近環境溫度之惰性環境的加熱室中，隨後加熱腔室一段時間以實現所需最終溫度。在自腔室移出物件之前，加熱時程亦可包括在最終溫度或中間溫度或程式化冷卻速率下指定時間段之一或多個保持步驟。 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.

在又一實施例中，含有惰性環境之腔室再分成多個區，各藉由適當的控制裝置維持在所需溫度下，且經由適當的傳輸機制(諸如機動帶)以自一個區傳至下一區之逐步方式加熱經硼處理之穩定製成物件。在經硼處理之穩定製成物件為纖維之情況下，此傳輸機制可為在碳化方法之出口處向纖維施加牽引力，同時在入口處控制經穩定之纖維中之拉力。 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.

現將在以下實例中詳細描述本發明之一些實施例。 Some embodiments of the invention will now be described in detail in the following examples.

在實例中，將總質量產率計算為氧化質量產率與碳化質量產率(如以下所提供計算)之乘積。PHR係指每一 百份樹脂之份數(質量基礎)。MI係指熔融指數，其為熔體流動速率之量度。重量%係指每100總份之份數，質量基礎。PE係指聚乙烯。BA係指硼酸。MBA係指偏硼酸。BO係指氧化硼。ZB係指硼酸鋅。T₉₅%係指觀測到5%質量損失之溫度(℃)。T₅₀%係指觀測到50%質量損失之溫度(℃)。T₅%係指觀測到95%質量損失之溫度(℃)。量測產率之定義： 氧化質量產率： 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:

碳化質量產率： Carbonization mass yield:

總質量產率：Y _M =Y _O Y _C Total mass yield: Y _M = Y _O Y _C

總質量產率(每初始質量之PE的含碳物質量)： Total mass yield (carbonaceous mass per PE of initial mass):

其中m _PE 為聚乙烯之初始質量；m _OX 為在氧化之後剩餘的質量；m _CF 為在碳化之後剩餘的質量；M _%PE 為初始形成之物件中聚乙烯之質量%。 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.

索氏萃取(Soxhlet extraction)為測定交聯乙烯塑膠之凝膠含量及膨脹率之方法。如本文所用，根據ASTM標準D2765-11「用於測定交聯乙烯塑膠之凝膠含量及膨脹率之標準測試方法(Standard Test Methods for Determination of Gel Content and Swell Ratio of Crosslinked Ethylene Plastics)」來進行索氏萃取。在所採用之方法中，稱取0.050g與0.500g之間的經交聯之製成物件且將其置放於基於纖維素之套管中，隨後將該套管置放於具有足夠量的二甲苯之索氏萃取設備中。隨後用回流的二甲苯進行索氏萃取持續至少12小時。在萃取之後，移出套管且將經交聯之製成物件在真空烘箱中在80℃下乾燥至少12小時且隨後稱重，從而提供經索氏處理之物件。隨後自重量比(經索氏處理之物件)/(交聯製成物 件)計算凝膠含量(%)。 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 (%).

比較實例1 Comparative example 1

將乙烯/辛烯共聚物(密度=0.941g/cm³；MI=34g/10min，190℃/2.16kg)與乙烯基三甲氧基矽烷(VTMS)反應性擠壓以形成VTMS接枝之乙烯/辛烯共聚物(MI=19g/10min，190℃/2.16kg；1.4重量%接枝的矽烷含量，由¹³C NMR測定)前驅物樹脂。VTMS接枝的前驅物樹脂經熔融紡絲以形成具有以下特性之纖維：1573根長絲，1978.2總丹尼爾(denier)，2.31gf/den，12.94%斷裂伸長率。製備之纖維在含有異丙醇溶液之容器中連續處理30min，所述溶液具有5重量%由King Industries供應之芳基磺酸Nacure B201。使經處理之纖維乾燥固化3天。纖維隨後在80℃(100%相對濕度)下濕固化5天。凝膠分率藉由索氏萃取測定為61.4-61.9%。交聯纖維使用熱解重量分析(TGA)儀器，使用表1中概述之條件以10℃/min之溫度斜升速率氧化及碳化。表2報導在空氣氧化期間保留的質量及在氧化及碳化處理兩者之後的最終質量產率。 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.

實例1A Example 1A

將乙烯/辛烯共聚物(密度=0.941g/cm³；MI=34g/10min，190℃/2.16kg)與乙烯基三甲氧基矽烷(VTMS)反應性擠壓以形成VTMS接枝之乙烯/辛烯共聚物(MI=19g/10min，190℃/2.16kg；1.4重量%接枝的矽烷含量，由¹³C NMR測定)前驅物樹脂。VTMS接枝的前驅物樹脂經熔融紡絲以形成具有以下特性之纖維：1573根長絲，1978.2總丹尼爾，2.31gf/den，12.94%斷裂伸長率。製備的纖維在含有異丙醇溶液之容器中連續處理30min，所述溶液具有5重量%芳基磺酸Nacure B201。使經處理之纖維乾燥固化3天。纖維隨後在80℃(100%相對濕度)下濕固化5天。凝膠分率藉由索氏萃取測定為61.4-61.9%。交聯纖維隨後用硼酸於異丙醇中之5重量%溶液處理表3中報導之時間。在硼酸溶液處理之後，纖維在環境條件下在空氣中乾燥隔夜。硼酸處理之前/及之後的纖維質量及質量之相對改變報導於表4中。 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.

硼酸處理的交聯纖維使用熱解重量分析(TGA)儀器，使用表5中概述之條件以10℃/min之溫度斜升速率氧化及碳化。表6報導在空氣氧化期間保留的質量及在氧化及 碳化處理兩者之後的最終質量產率。 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.

實例1B Example 1B

將乙烯/辛烯共聚物(密度=0.941g/cm³；MI=34g/10min，190℃/2.16kg)與乙烯基三甲氧基矽烷(VTMS)反應性擠壓以形成VTMS接枝之乙烯/辛烯共聚物(MI=19g/10min，190℃/2.16kg；1.4重量%接枝的矽烷含量，由¹³C NMR測定)前驅物樹脂。VTMS接枝的前驅物樹脂經熔融紡絲以形成具有以下特性之纖維：1573根長絲，1978.2總丹尼爾，2.31gf/den，12.94%斷裂伸長率。製備的纖維在含有異丙醇溶液之容器中連續處理30min，所述溶液具有5重量%芳基磺酸Nacure B201。使經處理之纖維乾燥固化3天。纖維隨後在80℃(100%相對濕度)下濕固化5天。凝膠分率藉由索氏 萃取測定為61.4-61.9%。交聯纖維隨後用硼酸於異丙醇中之5重量%溶液處理表7中報導之時間。在硼酸溶液處理之後，纖維在環境條件下在空氣中乾燥隔夜。乾燥、經硼酸處理之纖維在真空烘箱中經歷熱處理(80℃)隔夜。硼酸處理之前/及之後的纖維質量及質量之相對改變報導於表8中。 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.

熱處理、硼酸處理的交聯纖維使用熱解重量分析(TGA)儀器，使用表9中概述之用於氧化及碳化方案之條件以10℃/min之溫度斜升速率氧化及碳化。 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.

表10報導在空氣氧化期間保持的質量及在氧化及碳化處理兩者之後的最終質量產率。 Table 10 reports the quality maintained during air oxidation and the final mass yield after both oxidation and carbonization treatments.

比較實例2 Comparative example 2

將乙烯/辛烯共聚物(密度=0.941g/cm³；MI=34g/10min，190℃/2.16kg)與乙烯基三甲氧基矽烷(VTMS)反應性擠壓以形成VTMS接枝之乙烯/辛烯共聚物(MI=19g/10min，190℃/2.16kg；1.4重量%接枝的矽烷含量，由¹³C NMR測定)前驅物樹脂。VTMS接枝的前驅物樹脂經熔融紡絲以形成具有以下特性之纖維：1573根長絲，1945.8總丹尼爾，2.25gf/den，12.17%斷裂伸長率。製備的纖維在含有異丙醇溶液之容器中連續處理5秒，所述溶液具有5重量%芳基磺酸Nacure B201。使經處理之纖維乾燥固化3天。纖維隨後在80℃(100%相對濕度)下濕固化5天。凝膠分率藉由索氏萃取測定為58.2-58.9%。交聯纖維使用熱解重量分析(TGA)儀器，使用表11中概述之條件以10℃/min之溫度斜升速率氧化及碳化。表12報導在空氣氧化期間保留的質量及在氧化及碳化處理兩者之後的最終質量產率。 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.

實例2A Example 2A

將乙烯/辛烯共聚物(密度=0.941g/cm³；MI=34g/10min，190℃/2.16kg)與乙烯基三甲氧基矽烷(VTMS)反應性擠壓以形成VTMS接枝之乙烯/辛烯共聚物(MI=19g/10min，190℃/2.16kg；1.4重量%接枝的矽烷含量，由¹³C NMR測定)前驅物樹脂。VTMS接枝的前驅物樹脂經熔融紡絲以形成具有以下特性之纖維：1573根長絲，1945.8總丹尼爾，2.25gf/den，12.17%斷裂伸長率。製備的纖維在含有異丙醇溶液之容器中連續處理5秒，所述溶液具有5重量%芳基磺酸Nacure B201。使經處理之纖維乾燥固化3天。纖維隨後在80℃(100%相對濕度)下濕固化5天。凝膠分率藉由索氏萃取測定為58.2-58.9%。交聯纖維隨後用硼酸於異丙醇中之5重量%溶液處理表13中報導之時間。在硼酸溶液處理之後，纖維在環境條件下在空氣中乾燥隔夜。乾燥、經硼酸處理之 纖維在真空烘箱中經歷熱處理(80℃)隔夜。硼酸處理之前/及之後的纖維質量及質量之相對改變報導於表14中。 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.

熱處理、硼酸處理的交聯纖維使用熱解重量分析(TGA)儀器，使用表15中概述之條件以10℃/min之溫度斜升速率氧化及碳化。表16報導在空氣氧化期間保留的質量及氧化及碳化處理兩者之後的最終質量產率。 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.

實例2B Example 2B

將乙烯/辛烯共聚物(密度=0.941g/cm³；MI=34g/10min，190℃/2.16kg)與乙烯基三甲氧基矽烷(VTMS)反應性擠壓以形成VTMS接枝之乙烯/辛烯共聚物(MI=19g/10min，190℃/2.16kg；1.4重量%接枝的矽烷含量，由¹³C NMR測定)前驅物樹脂。VTMS接枝的前驅物樹脂經熔融紡絲以形成具有以下特性之纖維：1573根長絲，1945.8總丹尼爾，2.25gf/den，12.17%斷裂伸長率。製備的纖維在含有異丙醇溶液之容器中連續處理5秒，所述溶液具有5重量%芳基磺酸Nacure B201。使經處理之纖維乾燥固化3天。纖維隨後在80℃(100%相對濕度)下濕固化5天。凝膠分率藉由索氏萃取測定為58.2-58.9%。交聯纖維隨後用硼酸於異丙醇中之5重量%溶液處理表17中報導之時間。在硼酸溶液處理之後，纖維在環境條件下在空氣中乾燥隔夜。乾燥、經硼酸處理之纖維在真空烘箱中經歷熱處理(80℃)隔夜。硼酸處理之前/及之後的纖維質量及質量之相對改變報導於表18中。 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.

經熱處理、硼酸處理的交聯纖維使用熱解重量分析(TGA)儀器，使用表19中概述之條件以10℃/min之溫度斜升速率氧化及碳化。表20報導在空氣氧化期間保留的質量及在氧化及碳化處理兩者之後的最終質量產率。 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.

比較實例3 Comparative example 3

將乙烯/辛烯共聚物(密度=0.941g/cm³；MI=34g/10min，190℃/2.16kg)與乙烯基三甲氧基矽烷(VTMS)反應性擠壓以形成VTMS接枝之乙烯/辛烯共聚物(MI=19g/10min，190℃/2.16kg；1.4重量%接枝矽烷含量，由¹³C NMR測定)前驅物樹脂。VTMS接枝的前驅物樹脂經熔融紡絲以形成具有以下特性之纖維：1573根長絲，1978.2總丹尼爾，2.31 gf/den，12.94%斷裂伸長率。製備的纖維在含有異丙醇溶液之容器中連續處理30min，所述溶液具有5重量%芳基磺酸Nacure B201。使經處理之纖維乾燥固化3天。纖維隨後在60℃(100%相對濕度)下濕固化5天。凝膠分率藉由索氏萃取測定為55.59-56.30%。交聯纖維使用熱解重量分析(TGA)儀器，使用表21中概述的條件以10℃/min的溫度斜升速率氧化及碳化。表22報導在空氣氧化期間保留的質量及在氧化及碳化處理兩者之後的最終質量產率。 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.

實例3A Example 3A

將乙烯/辛烯共聚物(密度=0.941g/cm³；MI=34g/10min，190℃/2.16kg)與乙烯基三甲氧基矽烷(VTMS)反應性擠壓以形成VTMS接枝之乙烯/辛烯共聚物(MI=19g/10min，190℃/2.16kg；1.4重量%接枝矽烷含量，由¹³C NMR測定)前驅物樹脂。VTMS接枝的前驅物樹脂經熔融紡絲以形成具有以下特性之纖維：1573根長絲，1978.2總丹尼爾，2.31gf/den，12.94%斷裂伸長率。製備的纖維在含有異丙醇溶液之容器中連續處理30min，所述溶液具有5重量%芳基磺酸Nacure B201。使經處理之纖維乾燥固化3天。纖維隨後在60℃(100% 相對濕度)下濕固化5天。凝膠分率藉由索氏萃取測定為55.59-56.30%。交聯纖維隨後用氧化硼於異丙醇中之飽和溶液處理表23中報導之時間。在氧化硼溶液處理之後，纖維在環境條件下在空氣中乾燥隔夜。氧化硼處理之前/及之後的纖維質量及質量之相對改變報導於表24中。 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.

氧化硼處理的交聯纖維使用熱解重量分析(TGA)儀器，使用表25中概述之條件以10℃/min之溫度斜升速率氧化及碳化。表26報導在空氣氧化期間保留的質量及氧化及碳化處理兩者之後的最終質量產率。 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.

實例3B Example 3B

將乙烯/辛烯共聚物(密度=0.941g/cm³；MI=34g/10min，190℃/2.16kg)與乙烯基三甲氧基矽烷(VTMS)反應性擠壓以形成VTMS接枝之乙烯/辛烯共聚物(MI=19g/10min，190℃/2.16kg；1.4重量%接枝矽烷含量，由¹³C NMR測定)前驅物樹脂。VTMS接枝的前驅物樹脂經熔融紡絲以形成具有以下特性之纖維：1573根長絲，1978.2總丹尼爾，2.31gf/den，12.94%斷裂伸長率。製備的纖維在含有異丙醇溶液之容器中連續處理30min，所述溶液具有5重量%芳基磺酸Nacure B201。使經處理之纖維乾燥固化3天。纖維隨後在60℃(100%相對濕度)下濕固化5天。凝膠分率藉由索氏萃取測定為55.59-56.30%。交聯纖維隨後用硼酸鋅(Firebrake ZB-XF)於異丙醇中之5重量%懸浮液處理表27中報導之時間。在硼酸鋅懸浮液處理之後，纖維在環境條件下在空氣中乾燥隔夜。乾燥、經硼酸鹽鋅處理之纖維在真空烘箱中經歷熱處理(80℃)隔夜。硼酸處理之前/及之後的纖維質量及質量之相對改變報導於表28中。 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.

硼酸鋅處理的交聯纖維使用熱解重量分析(TGA)儀器，使用表29中概述的條件以10℃/min的溫度斜 升速率氧化及碳化。 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.

表30報導在空氣氧化期間保持的質量及在氧化及碳化處理兩者之後的最終質量產率。 Table 30 reports the quality maintained during air oxidation and the final mass yield after both oxidation and carbonization treatments.

實例4 Example 4

將乙烯/辛烯共聚物(密度=0.941g/cm³；MI=34g/10min，190℃/2.16kg)與乙烯基三甲氧基矽烷(VTMS)反應性擠壓以形成VTMS接枝之乙烯/辛烯共聚物(MI=19g/10min，190℃/2.16kg；1.4重量%接枝矽烷含量，由¹³C NMR測定)前驅物樹脂。VTMS接枝的前驅物樹脂經熔融紡絲以形成具有以下特性之纖維：1573根長絲，1978.2總丹尼爾，2.31gf/den，12.94%斷裂伸長率。製備的纖維在含有異丙醇溶液之容器中連續處理30min，所述溶液具有5重量%芳基磺酸Nacure B201。使經處理之纖維乾燥固化3天。纖維隨後在80℃(100%相對濕度)下濕固化5天。凝膠分率藉由索氏萃取測定為61.4-61.9%。交聯纖維隨後用硼酸於異丙醇中之5重量%溶液處理表31中報導之時間。在硼酸溶液處理之後，纖維在環境條件下在空氣中乾燥隔夜。乾燥、經硼酸處理之纖維在真空 烘箱中經歷熱處理(80℃)隔夜。硼酸處理之前/及之後的纖維質量及質量之相對改變報導於表32中。 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.

經熱處理、硼酸處理的交聯纖維使用熱解重量分析(TGA)儀器，使用表33中概述之條件以10℃/min之溫度斜升速率氧化及碳化。表34報導在空氣氧化期間保留之質量及在氧化及碳化處理之後的最終質量產率。 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.

實例5 Example 5

將乙烯/辛烯共聚物(密度=0.941g/cm³；MI=34g/10min，190℃/2.16kg)與乙烯基三甲氧基矽烷(VTMS)反應性擠壓以形成VTMS接枝之乙烯/辛烯共聚物(MI=19g/10min，190℃/2.16kg；1.4重量%接枝矽烷含量，由¹³C NMR測定)前驅物樹脂。VTMS接枝的前驅物樹脂經熔融紡絲以形成具有以下特性之纖維：1573根長絲，1945.8總丹尼爾， 2.25gf/den，12.17%斷裂伸長率。在含有具有5重量%硼酸之異丙醇溶液的容器中持續處理纖維束。溶液中之纖維滯留時間為5秒。使經處理之纖維乾燥固化3天。纖維隨後在80℃(100%相對濕度)下濕固化1-5天，如表35中所報導。凝膠分率由索氏萃取測定。完整結果報導在表36中。 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.

製備及交聯之三個區段(A、B及C)用表37中報導之硼酸於甲醇中之15重量%溶液處理多次。在硼酸溶液處理之後，纖維在環境條件下在空氣中乾燥隔夜。乾燥、經硼酸處理之纖維隨後在真空烘箱中經歷熱處理(80℃)隔夜。在硼酸處理之前及之後的纖維質量及質量之相對變化報導在表38中。 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.

熱處理、硼酸處理的交聯纖維使用熱解重量分析(TGA)儀器，使用表39中概述之條件氧化及碳化。溫度斜升速率維持於10℃/min以用於氧化及碳化方案。表40報導在空氣氧化期間保留的質量及在氧化及碳化處理兩者之後的最終質量產率。 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.

比較實例6 Comparative example 6

乙烯基三甲氧基矽烷接枝之乙烯/辛烯共聚物(MI=7g/10min，190℃/2.16kg；1.6重量%接枝矽烷含量)用作前驅物樹脂。使用Carver壓機在180℃下將膜壓縮模製成藉由測微器量測為3毫米(76.2微米)厚之薄膜。藉由用 市售芳基磺酸催化劑(Nacure B-201，King Industries)在異丙醇溶液中處理膜12小時，隨後在60-80℃下濕固化72小時使所有膜交聯。凝膠分率藉由索氏萃取確定為81.8%。自所製備之膜切割九(9)個較小圓形膜且稱重。在空氣(21%氧氣含量)下在對流烘箱中在270℃下持續5小時對膜氧化。在空氣氧化之後將九(9)個膜稱重。在空氣氧化期間的質量保留率(氧化質量產率)報導在表41中。氧化膜隨後在氮氣下使用10℃/min之升溫速率自25℃至800℃碳化。在碳化期間的質量保留率(碳化質量產率)報導在表41中。計算之總質量產率報導在表41中。平均氧化質量產率、碳化質量產率及總質量產率分別為43.5%、45.7%及19.7%。 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.

實例6 Example 6

乙烯基三甲氧基矽烷接枝之乙烯/辛烯共聚物(MI=7g/10min，190℃/2.16kg；1.6重量%接枝矽烷含量)用作前驅物樹脂。使用Carver壓機在180℃下將膜壓縮模製成藉由測微器量測為3毫米(76.2微米)厚之薄膜。藉由用市售芳基磺酸催化劑(Nacure B-201，King Industries)在異丙醇溶液中處理膜12小時，隨後在60-80℃下濕固化72小時 使所有膜交聯。凝膠分率藉由索氏萃取確定為81.8%。標記為A-D之四(4)個膜浸沒於根據表42之含有二氯甲烷及硼酸三丁酯之溶液之小瓶中。膜在硼酸三丁酯溶液中處理隔夜。記錄用硼酸三丁酯處理之前及之後的膜重量。表43報導各膜之重量改變。在空氣(21%氧氣含量)下在對流烘箱中在270℃下持續5小時對膜氧化。在空氣氧化之後將膜稱重。在空氣氧化期間的質量保留率(氧化質量產率)報導在表44中。氧化膜隨後在氮氣下使用10℃/min之升溫速率自25℃至800℃碳化。在碳化期間的質量保留率(碳化質量產率)報導在表44中。相比於對照膜(比較實例6)，在氧化之前用硼酸三丁酯處理之膜之平均氧化質量產率增加5.5-42.1%。相比於對照膜(比較實例6)，在氧化及碳化之前用硼酸三丁酯處理之膜之平均碳化質量產率增加13.6-24.5%。相比於對照膜(比較實例6)，在氧化及碳化之前用硼酸三丁酯處理之膜之平均總質量產率增加25.4-78.2%。 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).

比較實例7 Comparative example 7

乙烯/辛烯共聚物(密度=0.950g/cm³；MI=17g/10min，190℃/2.16kg)在氮氣下在DSM Xplore 15微混配機中在160℃下熔融摻合。在160℃下使用Carver壓機壓縮模製一膜。在空氣(21%氧氣含量)下在對流烘箱中在250℃下持續10小時對膜氧化。在空氣氧化之後將膜稱重。在空氣氧化期間的質量保留率(氧化質量產率)報導在表45中。氧化膜隨後在氮氣下使用10℃/min之升溫速率自25℃至800℃碳化。在碳化期間的質量保留率(碳化質量產率)報導在表45中。計算的總質量產率報導在表45中。 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.

實例7A Example 7A

乙烯/辛烯共聚物(密度=0.950g/cm³；MI=17g/10min，190℃/2.16kg)與5重量%聚丁二烯(按獲自Sigma Aldrich原樣使用(平均M_n 1,530-2,070；目錄號434779))在氮氣下在DSM Xplore 15微混配機中在160℃下熔融摻合。在160℃下使用Carver壓機壓縮模製成膜。使膜在對流烘箱中在250℃下在空氣(21%氧氣含量)下氧化10小時。在空氣氧化之後將膜稱重。在空氣氧化期間的質量保留率(氧化 質量產率)報導在表46中。氧化膜隨後在氮氣下使用10℃/min之升溫速率自25℃至800℃碳化。在碳化期間的質量保留率(碳化質量產率)報導在表46中。計算的總質量產率報導在表46中。 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.

實例7B Example 7B

乙烯/辛烯共聚物(密度=0.950g/cm³；MI=17g/10min，190℃/2.16kg)與5重量%聚丁二烯(按獲自Sigma Aldrich原樣使用(平均M_n 1,530-2,070；目錄號434779))在氮氣下在DSM Xplore 15微混配機中在160℃下熔融摻合。在160℃下使用Carver壓機壓縮模製成膜。藉由將2.01mL於THF中之1M BH₃溶液溶解於300mL THF中在手套箱中製備300mL 6.66mM BH₃(硼烷)溶液。將膜浸沒於100mL BH₃溶液中隔夜。在自溶液移除之後，膜在手套箱氛圍中乾燥。在16h之後，自手套箱移除膜。使膜在對流烘箱中在250℃下在空氣(21%氧氣含量)下氧化10小時。在空氣氧化之後將膜稱重。在空氣氧化期間的質量保留率(氧化質量產率)報導在表47中。氧化膜隨後在氮氣下使用10℃/min之升溫速率自25℃至800℃碳化。在碳化期間的質量保留率(碳化質量產率)報導在表47中。計算的總質量產率報導在表47中。相比於對照膜(比較實例7及實例7A)，對於用硼烷處理之膜(實例7B)觀測到碳化質量產率之相對增量為221-261%。相比於對照膜(比較實例7及實例7A)，對於用硼烷處理之膜觀測 到總質量產率之相對增量為297-308%。 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)

一種製備含碳物件之方法，包括：(a)提供烯烴樹脂；(b)自所述烯烴樹脂形成製成物件；(c)交聯所述製成物件；(d)藉由空氣氧化對所述製成物件穩定化；(e)在至少一個前述步驟期間或中間用含硼液體(BCL)處理；以及(f)對所述穩定製成物件進行碳化。 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. 如申請專利範圍第1項所述之方法，其中所述BCL為適用於在所述製成物件中沈積硼之硼源。 The method of claim 1, wherein the BCL is a boron source suitable for depositing boron in the fabricated article. 如申請專利範圍第2項所述之方法，其中所述硼源為元素硼、硼烷、硼酸鹽、二烴基硼酸(borinic acid)、烴基硼酸(boronic acid)、硼酸(boric acid)、二烴基硼酸酯、烴基硼酸酯、硼氧雜環己烷、胺基硼烷、環硼氮烷、硼氫化物及其衍生物及組合。 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. 如申請專利範圍第1項至第3項中任一項所述之方法，其中步驟(d)包括在120℃下或高於120℃下加熱所述製成物件。 The method of any one of claims 1 to 3, wherein the step (d) comprises heating the finished article at 120 ° C or higher. 如申請專利範圍第1項至第4項中任一項所述之方法，其中步驟(b)包括藉由纖維紡絲、膜擠壓澆鑄、吹製膜處理、經由模之型材擠壓、射出模製、溶液澆鑄或壓縮模製將所述聚烯烴樹脂轉化成製成物件。 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. 一種製備含碳物件之方法，包括：(a)提供交聯聚烯烴製成物件； (b)藉由空氣氧化使所述交聯聚烯烴製成物件穩定化以提供穩定製成物件；(c)在至少一個前述步驟期間或中間用含硼液體(BCL)處理；以及(d)對所述穩定製成物件進行碳化。 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. 如申請專利範圍第6項所述之方法，其中所述BCL為適用於在所述製成物件中沈積硼之硼源。 The method of claim 6, wherein the BCL is a boron source suitable for depositing boron in the fabricated article. 如申請專利範圍第7項所述之方法，其中所述硼源為元素硼、硼烷、硼酸鹽、二烴基硼酸、烴基硼酸、硼酸、二烴基硼酸酯、烴基硼酸酯、硼氧雜環己烷、胺基硼烷、環硼氮烷、硼氫化物及其衍生物及組合。 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. 如申請專利範圍第1項至第3項中任一項所述之方法，其中步驟(b)包括在120℃下或高於120℃下加熱所述交聯製成物件。 The method of any one of claims 1 to 3, wherein the step (b) comprises heating the crosslinked article at 120 ° C or higher.