CN107532340A - The method of product is made up of polyolefin - Google Patents

The method of product is made up of polyolefin Download PDF

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Publication number
CN107532340A
CN107532340A CN201680023492.3A CN201680023492A CN107532340A CN 107532340 A CN107532340 A CN 107532340A CN 201680023492 A CN201680023492 A CN 201680023492A CN 107532340 A CN107532340 A CN 107532340A
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Prior art keywords
product
boron
fiber
boric acid
processing
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Inventor
E·J·胡可坎恩
B·E·巴尔顿
G·F·比洛维奇
J·T·巴顿
E·尼科利
T·H·彼得森
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
    • D01F11/124—Boron, borides, boron nitrides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
    • D06M11/82—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides with boron oxides; with boric, meta- or perboric acids or their salts, e.g. with borax
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

In one example, the disclosure describes a kind of method for preparing carbonaceous article, comprising：Product is made in the polyolefin for providing crosslinking；The polyolefin of the crosslinking is made by air oxidation, and product is stable stable to be made product to provide；During at least one in abovementioned steps or middle boron-bearing liquid (BCL) is handled；And the product that is made of the stabilization is set to be carbonized.In one example, the disclosure describes a kind of method for being used to prepare stable product.

Description

The method of product is made up of polyolefin
Background technology
Before this, carbonaceous article, as carbon fiber has mainly been manufactured by polyacrylonitrile (PAN), pitch or cellulose precursor.System The technique for making carbonaceous article starts to be formed by the precursor product is made, such as fiber or film.Precursor can be used to be formed or molded and gather The standard technique of compound forms and product is made.Then make product stabilization is made to allow to be made product in the subsequent thermal processing step phase Between be kept substantially shape；Without being bound by theory, such stabilisation is usually directed to oxidation and the combination of heat, and logical Often cause restriction that the dehydrogenation of the precursor of product is made, ring is formed, is aoxidized and is crosslinked.Pass through the system of thermal-stable in an inert atmosphere Into product, the product that is made of the stabilization is then converted into carbonaceous article.Although the general step of carbonaceous article is manufactured with regard to a variety of It is identical for precursor, but the details of those steps differs widely, and this depends on the chemical composition of selected precursor.
Probe into out the carbonaceous article precursor that polyolefin is a kind of replacement, but be adapted to and economically viable preparation side Method but confirms to be difficult to.What is received much concern is to confirm a kind of be used for by the economic of polyolefin precursor preparation carbonaceous article Method.For example, it is contemplated that retaining quality during stabilizing with carburising step reaches maximum.
The content of the invention
The disclosure describes a kind of method for preparing carbonaceous article, comprising：Product is made in the polyolefin for providing crosslinking；It is logical Cross air oxidation the polyolefin of the crosslinking is made product is stable stable to be made product to provide；In abovementioned steps extremely During one item missing or middle boron-bearing liquid (BCL) is handled；And the product that is made of the stabilization is set to be carbonized.In an example In, the disclosure describes a kind of method for being used to prepare stable product.
Embodiment
Except as otherwise noted, otherwise number range (such as in " 2 to 10 ") include define the scope numeral (such as 2 and 10).
Except as otherwise noted, otherwise ratio, percentage, part etc. are by weight.
Except as otherwise noted, otherwise the crosslinkable functionality content of vistanex passes through mol% crosslinkable functionality tables Sign, it is calculated as the molal quantity for mole keeping count of divided by being contained in the monomeric unit in the polyolefin sum of crosslinkable functionality.
Except as otherwise noted, otherwise " monomer " refers to a kind of molecule, and it can undergo polymerization, so as to promote component units to be formed The basic structure of macromolecular (such as polyolefin).In an aspect, contained the present disclosure describes one kind by vistanex manufacture The method that product is made in carbon.As being more fully described herein, the carbon containing product that is made is prepared by the following method：(a) provide Olefin resin；(b) formed by the olefin resin and product is made；(c) product that is made is made to be crosslinked to provide being made for crosslinking Product；(d) make described to be made that product is stable stable to be made product to provide by air oxidation；(e) in abovementioned steps During at least one or middle boron-bearing liquid (BCL) is handled；And (f) makes the product that is made of the stabilization be carbonized.
Suitable BCL includes including the liquid containing boron substance.The suitable example containing boron substance includes borine, boric acid Salt, borinic acid, boric acid (boronic acid), boric acid (boric acid), borine acid esters, borate, boroxin, ammonia Base borine, boron nitrogen alkynes, boron hydride and its derivative and combination.Element boron is also suitable to contain boron substance.Boronic acid derivatives Example include metaboric acid and boron oxide.The example of borate derivative includes inorganic borate (such as Firebrake ZB) and organic boronic Salt (such as tri butyl boron hydrochlorate).In one example, BCL is only prepared with containing boron substance.In one example, BCL also includes another A kind of component causes another component with miscible containing boron substance, to be suspended with the formation containing boron substance with containing boron substance, and by selection Liquid, or otherwise by being carried containing boron substance, and with whole process compatible.In one example, another component be polarity or Nonpolar liquid.For example, alcohol (such as isopropanol) is BCL suitable component.In one example, containing boron substance at least A part is carried in BCL with form of suspension.
Unless otherwise indicated, otherwise any method as described herein or processing step can be carried out in any order.
Polyolefin is a kind of polymer manufactured by one or more olefinic monomers.Polymer as described herein can be by one kind Or polytype monomer is formed.Polyethylene is preferable vistanex, but other vistanexes are alternative.Citing comes Say, be also by ethene, propylene or other alpha-olefins (such as 1- butylene, 1- hexenes, 1- octenes) or the polyolefin of its combination manufacture Suitable.Polyolefin as described herein generally provides as a resin, is subdivided into size and is easy to add for further melt or solution The spherolite or particle of work.In one example, vistanex before being formed as that product is made with BCL processing.Polyolefin tree Fat can be by any mechanism as known in the art (such as spraying, dipping or imbibition) with BCL processing.The liquid that BCL can be adapted to Form (such as pure) or a part as solution introduce as the suspension in liquid.BCL can be used as continuous processing A part or as batch process a part introduce.
Vistanex as described herein undergoes cross-linking step.Any method suitable for cross-linked polyolefin all meets will Ask.In one example, by irradiation, such as it is crosslinked polyolefin by electron beam process.Other cross-linking methods, for example, it is ultraviolet Line irradiates and gamma-radiation is suitable.In some instances, irradiation can be combined and uses initiator, trigger friendship such as benzophenone Connection.In one example, vistanex has been modified with including being suitable for reaction with the cross-linking of crosslinked polyolefin resin Functional group.In the case where vistanex includes crosslinkable functionality, crosslinking can be triggered by known method, including the use of change Learn crosslinking agent, by heating, passing through steam or other suitable methods.In one example, copolymer is adapted to provide for having The vistanex of crosslinkable functionality, one or more of which alpha-olefin with containing being adapted to act as crosslinkable functionality Another monomer copolymerization of group, such as diene, carbon monoxide, GMA, acrylic acid, vinyl acetate Ester, maleic anhydride or vinyltrimethoxy silane (VTMS) are suitable for the monomer with alpha-olefin copolymer.In addition, have The vistanex of crosslinkable functionality can also by by by function regiment headquarters point be grafted on basic polyolefin it is modified it is poly- (α- Alkene) manufacture, wherein functional group then realizes that ability of the crosslinking of given polyolefin is selected based on it.For example, this The grafting of type can be by using radical initiator (such as peroxide) and vinyl monomer (such as VTMS, diene, acetic acid Vinyl acetate, acrylic acid, methacrylic acid, acrylate and methacrylate, such as GMA and methyl Acryloxypropyl trimethoxy silane, allyl amine, p-aminophenyl ethene, dimethylaminoethyl methacrylate) or it is logical Cross azido functionalized molecule (such as 4- [2- (trimethoxy silane base) ethyl)] benzenesulfonyl azide) carry out.Have The vistanex of crosslinkable functionality can be by vistanex manufacture or commercially available.With the commercially available of crosslinkable functionality Vistanex example is included by the SI-LINK of Dow Chemical (The Dow Chemical Company) sale, by making pottery Family name chemical company sell PRIMACOR, by Kuraray (Kuraray) sell EVAL resins and by A Kema (Arkema) The LOTADER AX8840 of sale.
As described above, vistanex is processed and product is made in formation.It is via vistanex that product, which is made, Manufactured product.Product is made using known polyolefins manufacturing technology (for example, melt or solution-polymerized SBR are to form fiber, film squeezes Go out or film is cast or blown film process is to form film, mould extrusion or injection moulding or compression forming to form more complicated shape, Or solution-cast) formed.According to the expectation geometry of target carbonaceous article and its it is expected physical characteristic selection manufacturing technology.Lift For example, when it is carbon fiber it is expected carbonaceous article, fibre spinning is suitable manufacturing technology.As another example, in institute In the case that desired carbonaceous article is carbon film, compression forming is suitable manufacturing technology.In one example, product use is made BCL processing.In one example, product is made before vistanex is crosslinked with BCL processing.Product, which is made, can pass through this Known any mechanism (such as spraying, dipping or imbibition) is with BCL processing in field.Liquid form that BCL can be adapted to (such as it is pure It is net) or a part as solution or as the suspension introducing in liquid.BCL can be as the part or work of continuous processing Introduced for a part for batch process.
It is as noted above, make the crosslinking of at least a portion vistanex that product be made with what is be crosslinked.In some realities Apply in example, be crosslinked and carried out via chemical crosslinking.Therefore, in certain embodiments, the product that is made of crosslinking is with a kind of or more Kind chemical reagent is handled so that product is made with what the crosslinkable functionality of vistanex was crosslinked.Such chemical reagent plays initiation The effect or reacted with crosslinkable functionality to form intramolecular chemical that intramolecular chemical key between crosslinkable functionality is formed Key, as known in the art.Chemical crosslinking causes crosslinkable functionality to react to form new keys, can so as to have in restriction Formed between the various polymer chains of the vistanex of crosslinking functionality bonded.Based on (one be included in vistanex Kind or it is a variety of) type selecting of crosslinkable functionality makes the chemical reagent that crosslinking occurs；It is known make crosslinkable functionality via point A series of different reactions being crosslinked between son with intramolecular chemical key.Can make to be present in known to selection be made it is cross-linking in product Functional group is crosslinked to produce the suitable chemical reagent that product is made of crosslinking.For example, the disclosure is not being limited In the case of, if connected to the crosslinkable functionality of polyolefin is vinyl, then suitable chemical reagent draws including free radical Agent is sent out, such as peroxide or the double nitriles of azo, such as dicumyl peroxide, dibenzoyl peroxide, tert-butyl peroctoate, azo two Isobutyronitrile etc..If connected to the crosslinkable functionality of polyolefin is sour (such as carboxylic acid) or acid anhydrides or ester or glycidoxypropyl, So suitable chemical reagent can be the compound containing at least two nucleophilic groups, including two nucleophiles, such as diamines, glycol, two Mercaptan, such as ethylenediamine, hexamethylene diamine, butanediol or ethanthiol.It can also use containing the chemical combination for having more than two nucleophilic groups Thing, such as glycerine, D-sorbite or hexa.The nucleophilic of mixed type two examination containing at least two different nucleophilic groups Agent or higher nucleopilic reagent (such as monoethanolamine) can also be suitable chemical reagent.If connected to the cross-linking official of polyolefin It can roll into a ball as monoalkoxysilane base, dialkoxy silicane base or trialkoxy silane base, then water and Louis (Lewis) or cloth Lanace spy (Bronsted) acid or base catalyst can be used as suitable chemical reagent.For example, the feelings of the disclosure are not being limited Under condition, Louis or bronsted acid or base catalyst include aryl sulfonic acid, sulfuric acid, hydroxide, alcohol zirconium or tin reagent.
It is typically preferably to be protected with ensuring to be made product at a high temperature of needed for subsequent process steps to make product crosslinking is made Hold its shape.In the case of without crosslinking, vistanex generally softens, melts or is otherwise deformed or divides at high temperature Solution.Be crosslinked increases heat endurance for product is made.In one example, product is made after crosslinking and before stabilisation With BCL processing.Crosslinking is made product and can use BCL (such as spraying, dipping or imbibition) by any mechanism as known in the art Processing.The liquid form (such as pure) that BCL can be adapted to or the part as solution or as the suspension in liquid Introduce.The part that BCL can be as continuous processing or the part introducing as batch process.
Crosslinking be made that product heats to be stablized in an oxidizing environment product is made.In certain embodiments, make The stable temperature of product that is made of crosslinking is at least 120 DEG C, preferably at least 190 DEG C.In certain embodiments, the system of crosslinking is made The temperature stable into product is no more than 400 DEG C, preferably no more than 300 DEG C.In one example, the product that is made of crosslinking is drawn Enter in the heating chamber at desired temperature.In another example, product will be made and introduce at or approximately at environment temperature In the heating chamber of degree, then by oven heats to desired temperature.In certain embodiments, the rate of heat addition be at least 1 DEG C/ Minute.In other embodiments, the rate of heat addition is no more than 15 DEG C/min.In another example again, the room is progressively heated, Such as the room is heated to the first temperature and maintains a period of time, such as 120 DEG C maintain one hour, are then raised to second temperature dimension Hold a period of time, such as 180 DEG C maintain one hour, and the 3rd is increased to keeping temperature, and such as 250 DEG C maintain 10 hours.Stabilize Technique is related to the period for product being made 100 hours being remained up under assigned temperature for making crosslinking, and this depends on being made The size of product.In one example, product is made during stabilization process with BCL processing.The product that is made of crosslinking can be steady By any mechanism as known in the art (such as spraying, dipping or imbibition) with BCL processing during fixedization.What BCL can be adapted to Liquid form (such as pure) or a part as solution introduce as the suspension in liquid.BCL can be used as continuous A part for technique or the part introducing as batch process.Stabilization process generation is as the precursor of carbonaceous article through boron Product is made in the stabilization of processing.Without being bound by theory, stabilization process makes the product that is made of crosslinking that oxygen occur Change and cause hydrocarbon structure to change, so as to increase crosslink density, while reduce hydrogen/carbon ratio that product is made of crosslinking. Without being bound by theory, stabilization process changes oxidation chemistry property and increase crosslink density in the presence of boron.
Unexpectedly, it has been found that the product of the stabilization then manufactured can be improved by introducing boron in product is made via BCL With the quality retention rate of carbonaceous article.It has also been discovered that product, which is made, with the processing containing boron substance can improve the carbon containing system that then manufactures The conformality of product.
In another aspect, the stabilization handled through boron that disclosure description one kind is formed by polyolefin precursor (resin) Product is made.In one example, the product that is made of the stabilization handled through boron is formed according to process as described herein.
In yet other aspects, there is provided carbonaceous article and its manufacture method.Carbonaceous article is the product that rich carbon contains；Carbon is fine Dimension, carbon plate and carbon film are the example of carbonaceous article.Carbonaceous article has many applications, for example, carbon fiber be generally used for strengthening it is compound Material, such as carbon fiber-reinforced type ring complex oxide, and carbon disk or carbon pad are used for high-performance brakes.
Carbonaceous article as described herein is to carry out heat by the product that is made of the stabilization in inert environments to being handled through boron Handle and make the stable product that is made be carbonized to prepare.Inert environments are to show to lack enclosing for reactivity with carbon electrode at high temperature Pile warp boron processing stabilization the environment that product is made, preferably high vacuum or lack oxygen atmosphere, more preferably nitrogen atmosphere or Argon gas atmosphere.It will be appreciated that there may be the oxygen of trace in inert atmosphere.In one example, the temperature of inert environments is in Or higher than 600 DEG C.Preferably, the temperature of inert environments is at or greater than 800 DEG C.In one example, the temperature of inert environments No more than 3000 DEG C.In one example, temperature is 1400-2400 DEG C.It will be produced at or approximately at the temperature of that scope upper end Raw graphite product, and will produce carbon product at or approximately at the temperature of scope lower end.
In order to prevent during carbonization bubble or damage product is made, preferably by it is progressive or progressively in a manner of heated inert ring Border.In one embodiment, the product introducing that is made of the stabilization handled through boron is contained into inertia at or approximately at environment temperature In the heating chamber of environment, then by oven heats for a period of time to reach desired final temperature.Heat time table may be used also Including before removing product from heating chamber, making one or more holding steps under final temperature or medium temperature or by program Change the period as defined in cooldown rate maintenance.
In another embodiment, the room containing inert environments is subdivided into multiple areas, will be every by appropriate control device Individual area maintains at the desired temperature, and by passing through via appropriate transport mechanism (such as motor-driven conveyer belt) from an area The stabilization handled through boron is in a step-wise fashion heated to next area product is made.The stabilization handled wherein through boron is made Product are in the example of fiber, and this transport mechanism can apply tractive force to fiber in the exit of carbonization technique, and enter The pulling force of the stable fiber of control at mouthful.
Some embodiments of the present invention now will be described in detail in following instance.
In instances, oeverall quality yield calculates (following article institute by the product of oxidation quality yield and the quality yield that is carbonized There is provided and calculate).PHR refers to the resin (by mass) of part/100.MI refers to melt index, and it is measured for melt flow rate.Weight Amount % refers to the total part in part/100, by mass.PE refers to polyethylene.BA refers to boric acid.MBA refers to metaboric acid.BO refers to aoxidize Boron.ZB refers to Firebrake ZB.T95% refers to the temperature (DEG C) for observing 5% mass loss.T50% refers to observe 50% mass damage The temperature (DEG C) of mistake.T5% refers to the temperature (DEG C) for observing 95% mass loss.The definition of measured yield：
Oxidation quality yield：
Be carbonized quality yield：
Oeverall quality yield：YM=YOYC
Oeverall quality yield (per the carbonaceous quality of PE initial masses)：
Wherein mPEFor the initial mass of polyethylene；mOXFor remaining quality after oxidation；mCFFor remaining matter after carbonization Amount；M%PEFor the quality % of polyethylene in the product that is originally formed.
Surname extraction (Soxhlet extraction) is gel content and the swelling of a kind of vinyl plastics for determining crosslinking The method of ratio.As used herein, surname extraction " is used for the solidifying of the vinyl plastics of measure crosslinking according to ASTM standard D2765-11 Standard method of test (the Standard Test Methods for Determination of Gel of glue content and swelling ratio Content and Swell Ratio of Crosslinked Ethylene Plastics) " carry out.In the method for use In, the product that is made of the crosslinking between 0.050 and 0.500g is weighed and is put into cellulose family sleeve pipe, then will described in Sleeve pipe is put into the surname extraction equipment of the dimethylbenzene with sufficient amount.Then in the case of backflow dimethylbenzene at least 12 is small Perform surname extraction.After extraction, sleeve pipe is removed and dries being made in vacuum drying oven of the product at 80 DEG C for crosslinking At least 12 hours, and then weigh, so as to provide the product of Soxhlet processing.Then by weight ratio (product of Soxhlet processing)/(friendship Product is made in connection) calculated for gel content (%).
Comparative example 1
Ethylene/octene (density=0.941g/cm3；MI=34g/10min, 190 DEG C/2.16kg) it is to use ethene Base trimethoxy silane (VTMS) Reaction extrusion, to form the ethylene/octene (MI=19g/ of VTMS grafting 10min, 190 DEG C/2.16kg；The silane contents of 1.4 weight % grafting, are utilized13C NMR are determined) precursor resin.VTMS grafting Precursor resin forms the fiber with following characteristic by melt-spun：1573 long filaments, 1978.2 total daniers, 2.31gf/ denier, 12.94% elongation at break.Prepared fiber is containing with 5 weight % aryl sulfonic acids (Nacure B201, by Jin Shi works Industry (King Industries) is supplied) aqueous isopropanol container in continuous processing 30 minutes.Make the fiber through processing solid Change 3 days.Then make the fiber moisturecuring under 80 DEG C (100% relative humidity) 5 days.Gel fraction is determined by surname extraction For 61.4-61.9%.The fiber of crosslinking is using thermogravimetry (TGA) instrument using the condition summarized in table 1 with 10 DEG C/minute The temperature ramp rate oxidation and carbonization of clock.Table 2 reports the quality that retains during air oxidation and is aoxidizing and be carbonized two Final mass yield after kind processing.
Table 1
Table 2
Example 1A
Ethylene/octene (the g/cm of density=0.9413；MI=34 g/10 min, 190 DEG C/2.16 kg) it is to use Vinyltrimethoxy silane (VTMS) Reaction extrusion, to form the ethylene/octene (MI=19 of VTMS grafting G/10 min, 190 DEG C/2.16 kg；The silane contents of 1.4 weight % grafting, are utilized13C NMR are determined) precursor resin.VTMS connects The precursor resin of branch forms the fiber with following characteristic by melt-spun：1573 long filaments, 1978.2 total daniers, 2.31 gf/ Denier, 12.94% elongation at break.Prepared fiber is containing the isopropyl with 5 weight % aryl sulfonic acids (Nacure B201) Continuous processing 30 minutes in the container of alcoholic solution.Make fiber solidization 3 days through processing.Then at 80 DEG C, (100% is relatively wet Degree) under make the fiber moisturecuring 5 days.Gel fraction is determined as 61.4-61.9% by surname extraction.The fiber of crosslinking is subsequent Continue the time reported in table 3 with solution processing of the 5 weight % boric acid in isopropanol.After boric acid solution processing, fiber It is dried overnight at ambient conditions in atmosphere.Before boric acid processing/and fiber quality afterwards and the relative change of quality Change is reported in table 4.
Table 3
Table 4
Through boric acid handle crosslinking fiber using thermogravimetry (TGA) instrument using the condition summarized in table 5 with 10 DEG C/min of temperature ramp rate oxidation and carbonization.Table 6 report the quality that retains during air oxidation and in oxidation and Final mass yield after two kinds of processing of carbonization.
Table 5
Table 6
Example 1B
Ethylene/octene (density=0.941g/cm3；MI=34g/10min, 190 DEG C/2.16kg) it is to use ethene Base trimethoxy silane (VTMS) Reaction extrusion, to form the ethylene/octene (MI=19g/ of VTMS grafting 10min, 190 DEG C/2.16kg；The silane contents of 1.4 weight % grafting, are utilized13C NMR are determined) precursor resin.VTMS grafting Precursor resin forms the fiber with following characteristic by melt-spun：1573 long filaments, 1978.2 total daniers, 2.31gf/ denier, 12.94% elongation at break.Prepared fiber is containing the isopropanol with 5 weight % aryl sulfonic acids (Nacure B201) Continuous processing 30 minutes in the container of solution.Make fiber solidization 3 days through processing.Then 80 DEG C (100% relative humidity) Under make the fiber moisturecuring 5 days.Gel fraction is determined as 61.4-61.9% by surname extraction.The fiber of crosslinking is then with 5 Solution processing of the weight % boric acid in isopropanol continues the time reported in table 7.After boric acid solution processing, fiber is in sky It is dried overnight at ambient conditions in gas.The dry fiber handled through boric acid undergoes heat treatment (80 DEG C) mistake in vacuum drying oven Night.Before boric acid processing/be reported in fiber quality afterwards and the relative change of quality in table 8.
Table 7
Table 8
The thermally treated, fiber of crosslinking that is handled through boric acid is using thermogravimetry (TGA) instrument using being summarized in table 9 Condition for the scheme that aoxidizes and be carbonized 10 DEG C/min of temperature ramp rate oxidation and carbonization.
Report the quality retained during air oxidation and the final mass after the two kinds of processing that aoxidize and be carbonized obtains Rate.
Table 9
Table 10
Comparative example 2
Ethylene/octene (density=0.941g/cm3；MI=34g/10min, 190 DEG C/2.16kg) it is to use ethene Base trimethoxy silane (VTMS) Reaction extrusion, to form the ethylene/octene (MI=19g/ of VTMS grafting 10min, 190 DEG C/2.16kg；The silane contents of 1.4 weight % grafting, are utilized13C NMR are determined) precursor resin.VTMS grafting Precursor resin forms the fiber with following characteristic by melt-spun：1573 long filaments, 1945.8 total daniers, 2.25gf/ denier, 12.17% elongation at break.Prepared fiber is containing the isopropanol with 5 weight % aryl sulfonic acids (Nacure B201) Continuous processing 5 seconds in the container of solution.Make fiber solidization 3 days through processing.Then make under 80 DEG C (100% relative humidity) The fiber moisturecuring 5 days.Gel fraction is determined as 58.2-58.9% by surname extraction.The fiber of crosslinking uses pyrolysis weight Amount analysis (TGA) instrument is aoxidized using the condition summarized in table 11 with 10 DEG C/min of temperature ramp rate and carbonization.Table 12 is reported The quality and the final mass yield after the two kinds of processing that aoxidize and be carbonized that road retains during air oxidation.
Table 11
Table 12
Example 2A
Ethylene/octene (density=0.941g/cm3；MI=34g/10min, 190 DEG C/2.16kg) it is to use ethene Base trimethoxy silane (VTMS) Reaction extrusion, to form the ethylene/octene (MI=19g/ of VTMS grafting 10min, 190 DEG C/2.16kg；1.4 the silane contents of weight % grafting, are utilized13C NMR are determined) precursor resin.VTMS grafting Precursor resin forms the fiber with following characteristic by melt-spun：1573 long filaments, 1945.8 total daniers, 2.25gf/ denier, 12.17% elongation at break.Prepared fiber is containing the isopropanol with 5 weight % aryl sulfonic acids (Nacure B201) Continuous processing 5 seconds in the container of solution.Make fiber solidization 3 days through processing.Then make under 80 DEG C (100% relative humidity) The fiber moisturecuring 5 days.Gel fraction is determined as 58.2-58.9% by surname extraction.The fiber of crosslinking is then with 5 weights Measure solution processing of the % boric acid in isopropanol and continue the time reported in table 13.After boric acid solution processing, fiber is in sky It is dried overnight at ambient conditions in gas.The dry fiber handled through boric acid undergoes heat treatment (80 DEG C) mistake in vacuum drying oven Night.Before boric acid processing/be reported in fiber quality afterwards and the relative change of quality in table 14.
Table 13
Table 14
The fiber of crosslinking thermally treated, through boric acid processing is used general in table 15 using thermogravimetry (TGA) instrument The condition stated is aoxidized with 10 DEG C/min of temperature ramp rate and carbonization.Table 16 reports the matter retained during air oxidation Amount and the final mass yield after the two kinds of processing that aoxidize and be carbonized.
Table 15
Table 16
Example 2B
Ethylene/octene (density=0.941g/cm3；MI=34g/10min, 190 DEG C/2.16kg) it is to use ethene Base trimethoxy silane (VTMS) Reaction extrusion, to form the ethylene/octene (MI=19g/ of VTMS grafting 10min, 190 DEG C/2.16kg；The silane contents of 1.4 weight % grafting, are utilized13C NMR are determined) precursor resin.VTMS grafting Precursor resin forms the fiber with following characteristic by melt-spun：1573 long filaments, 1945.8 total daniers, 2.25gf/ denier, 12.17% elongation at break.Prepared fiber is containing the isopropanol with 5 weight % aryl sulfonic acids (Nacure B201) Continuous processing 5 seconds in the container of solution.Make fiber solidization 3 days through processing.Then make under 80 DEG C (100% relative humidity) The fiber moisturecuring 5 days.Gel fraction is determined as 58.2-58.9% by surname extraction.The fiber of crosslinking is then with 5 weights Measure solution processing of the % boric acid in isopropanol and continue the time reported in table 17.After boric acid solution processing, fiber is in sky It is dried overnight at ambient conditions in gas.The dry fiber handled through boric acid undergoes heat treatment (80 DEG C) mistake in vacuum drying oven Night.Before boric acid processing/be reported in fiber quality afterwards and the relative change of quality in table 18.
Table 17
Table 18
The fiber of crosslinking thermally treated, through boric acid processing is used general in table 19 using thermogravimetry (TGA) instrument The condition stated is aoxidized with 10 DEG C/min of temperature ramp rate and carbonization.Table 20 reports the matter retained during air oxidation Amount and the final mass yield after the two kinds of processing that aoxidize and be carbonized.
Table 19
Table 20
Comparative example 3
Ethylene/octene (density=0.941g/cm3；MI=34g/10min, 190 DEG C/2.16kg) it is to use ethene Base trimethoxy silane (VTMS) Reaction extrusion, to form the ethylene/octene (MI=19g/ of VTMS grafting 10min, 190 DEG C/2.16kg；The silane contents of 1.4 weight % grafting, are utilized13C NMR are determined) precursor resin.VTMS grafting Precursor resin forms the fiber with following characteristic by melt-spun：1573 long filaments, 1978.2 total daniers, 2.31gf/ denier, 12.94% elongation at break.Prepared fiber is containing the isopropanol with 5 weight % aryl sulfonic acids (Nacure B201) Continuous processing 30 minutes in the container of solution.Make fiber solidization 3 days through processing.Then 60 DEG C (100% relative humidity) Under make the fiber moisturecuring 5 days.Gel fraction is determined as 55.59-56.30% by surname extraction.The fiber of crosslinking uses Thermogravimetry (TGA) instrument is aoxidized using the condition summarized in table 21 with 10 DEG C/min of temperature ramp rate and carbonization. Table 22 reports the quality retained during air oxidation and the final mass yield after the two kinds of processing that aoxidize and be carbonized.
Table 21
Table 22
Example 3A
Ethylene/octene (density=0.941g/cm3；MI=34g/10min, 190 DEG C/2.16kg) it is to use ethene Base trimethoxy silane (VTMS) Reaction extrusion, to form the ethylene/octene (MI=19g/ of VTMS grafting 10min, 190 DEG C/2.16kg；The silane contents of 1.4 weight % grafting, are utilized13C NMR are determined) precursor resin.VTMS grafting Precursor resin forms the fiber with following characteristic by melt-spun：1573 long filaments, 1978.2 total daniers, 2.31gf/ denier, 12.94% elongation at break.Prepared fiber is containing the isopropanol with 5 weight % aryl sulfonic acids (Nacure B201) Continuous processing 30 minutes in the container of solution.Make fiber solidization 3 days through processing.Then 60 DEG C (100% relative humidity) Under make the fiber moisturecuring 5 days.Gel fraction is determined as 55.59-56.30% by surname extraction.The fiber of crosslinking is subsequent Continue the time reported in table 23 with saturated solution processing of the boron oxide in isopropanol.It is fine after boron oxide soln processing Dimension is dried overnight at ambient conditions in atmosphere.Before boron oxide processing/and fiber quality afterwards and the phase of quality Change is reported in table 24.
Table 23
Table 24
The fiber of the crosslinking of oxidized boron processing uses the condition summarized in table 25 using thermogravimetry (TGA) instrument With 10 DEG C/min of temperature ramp rate oxidation and carbonization.Table 26 reports the quality that retains during air oxidation and in oxygen Final mass yield after two kinds of processing of change and carbonization.
Table 25
Table 26
Example 3B
Ethylene/octene (density=0.941g/cm3；MI=34g/10min, 190 DEG C/2.16kg) it is to use ethene Base trimethoxy silane (VTMS) Reaction extrusion, to form the ethylene/octene (MI=19g/ of VTMS grafting 10min, 190 DEG C/2.16kg；The silane contents of 1.4 weight % grafting, are utilized13C NMR are determined) precursor resin.VTMS grafting Precursor resin forms the fiber with following characteristic by melt-spun：1573 long filaments, 1978.2 total daniers, 2.31gf/ denier, 12.94% elongation at break.Prepared fiber is containing the isopropanol with 5 weight % aryl sulfonic acids (Nacure B201) Continuous processing 30 minutes in the container of solution.Make fiber solidization 3 days through processing.Then 60 DEG C (100% relative humidity) Under make the fiber moisturecuring 5 days.Gel fraction is determined as 55.59-56.30% by surname extraction.The fiber of crosslinking is subsequent Continue the time reported in table 27 with suspension processing of the 5 weight % Firebrake ZBs (Firebrake ZB-XF) in isopropanol. After the processing of Firebrake ZB suspension, fiber is dried overnight at ambient conditions in atmosphere.The dry fibre handled through Firebrake ZB Dimension (80 DEG C) of experience heat treatment in vacuum drying oven is stayed overnight.Before boric acid processing/and fiber quality afterwards and quality Relative change is reported in table 28.
Table 27
Table 28
The fiber of the crosslinking handled through Firebrake ZB uses the condition summarized in table 29 using thermogravimetry (TGA) instrument With 10 DEG C/min of temperature ramp rate oxidation and carbonization.Table 30 reports the quality that retains during air oxidation and in oxygen Final mass yield after two kinds of processing of change and carbonization.
Table 29
Table 30
Example 4
Ethylene/octene (density=0.941g/cm3；MI=34g/10min, 190 DEG C/2.16kg) it is to use ethene Base trimethoxy silane (VTMS) Reaction extrusion, to form the ethylene/octene (MI=19g/ of VTMS grafting 10min, 190 DEG C/2.16kg；The silane contents of 1.4 weight % grafting, are utilized13C NMR are determined) precursor resin.VTMS grafting Precursor resin forms the fiber with following characteristic by melt-spun：1573 long filaments, 1978.2 total daniers, 2.31gf/ denier, 12.94% elongation at break.Prepared fiber is containing the isopropanol with 5 weight % aryl sulfonic acids (Nacure B201) Continuous processing 30 minutes in the container of solution.Make fiber solidization 3 days through processing.Then 80 DEG C (100% relative humidity) Under make the fiber moisturecuring 5 days.Gel fraction is determined as 61.4-61.9% by surname extraction.The fiber of crosslinking is then with 5 Solution processing of the weight % boric acid in isopropanol continues the time reported in table 31.After boric acid solution processing, fiber exists It is dried overnight at ambient conditions in air.The dry fiber handled through boric acid undergoes heat treatment (80 DEG C) in vacuum drying oven Overnight.Before boric acid processing/be reported in fiber quality afterwards and the relative change of quality in table 32.
Table 31
Table 32
The fiber of crosslinking thermally treated, through boric acid processing is used general in table 33 using thermogravimetry (TGA) instrument The condition stated is aoxidized with 10 DEG C/min of temperature ramp rate and carbonization.Table 34 reports the matter retained during air oxidation Amount and the final mass yield after the two kinds of processing that aoxidize and be carbonized.
Table 33
Table 34
Example 5
Ethylene/octene (density=0.941g/cm3；MI=34g/10min, 190 DEG C/2.16kg) it is to use ethene Base trimethoxy silane (VTMS) Reaction extrusion, to form the ethylene/octene (MI=19g/ of VTMS grafting 10min, 190 DEG C/2.16kg；The silane contents of 1.4 weight % grafting, are utilized13C NMR are determined) precursor resin.VTMS grafting Precursor resin forms the fiber with following characteristic by melt-spun：1573 long filaments, 1945.8 total daniers, 2.25gf/ denier, 12.17% elongation at break.Fibre bundle continuous processing in the container containing the aqueous isopropanol with 5 weight % boric acid. The residence time of fiber in the solution is 5 seconds.Make fiber solidization 3 days through processing.Then at 80 DEG C, (100% is relative for fiber Humidity) under moisturecuring 1-5 days, as reported in table 35.Gel fraction is determined by surname extraction.Whole results are reported in table 36 In.
Table 35
Table 36
Prepared and crosslinking three kinds of segments (A, B and C) are handled with solution of the 15 weight % boric acid in methanol continues table The different time reported in 37.After boric acid solution processing, fiber is dried overnight at ambient conditions in atmosphere.Dry The fiber handled through boric acid then stay overnight in vacuum drying oven by (80 DEG C) of experience heat treatment.Fibre before and after boric acid processing The relative change of dimension quality and quality is reported in table 38.
Table 37
Table 38
The fiber of crosslinking thermally treated, through boric acid processing is used general in table 39 using thermogravimetry (TGA) instrument The condition oxidation and carbonization stated.For the scheme that aoxidizes and be carbonized, temperature ramp rate is maintained under 10 DEG C/min.Table 40 is reported The quality and the final mass yield after the two kinds of processing that aoxidize and be carbonized retained during air oxidation.
Table 39
Table 40
Comparative example 6
Using vinyltrimethoxy silane be grafted ethylene/octene (MI=7g/10min, 190 DEG C/ 2.16kg；The silane contents of 1.6 weight % grafting) it is used as precursor resin.Using card, not pressing machine shortens mould at 180 DEG C Type measures the film that thickness is 3 millimeters (76.2 microns) into by micrometer.By using commercially available aryl sulfonic acid catalyst The solution process film of (Nacure B-201, Jin Shi industry) in isopropanol continues 12 hours, wet solid at 60 DEG C -80 DEG C afterwards Change 72 hours to be crosslinked all films.Gel fraction is determined as 81.8% by surname extraction.Nine (9) are partitioned into from prepared film Individual less circular membrane is simultaneously weighed.Film is set to aoxidize 5 at 270 DEG C in convection oven under air (21% oxygen content) Hour.The individual film in nine (9) is weighed after air oxidation.Quality retention rate (oxidation quality yield) report during air oxidation Road is in table 41.Then oxide-film is set to be carbonized from 25 DEG C to 800 DEG C using 10 DEG C/min of even variable Rate under a nitrogen.Carbonization The quality retention rate (carbonization quality yield) of period is reported in table 41.The oeverall quality yield calculated is reported in table 41. Average oxidation quality yield, carbonization quality yield and oeverall quality yield are 43.5%, 45.7% and 19.7% respectively.
Table 41
Example 6
Using vinyltrimethoxy silane be grafted ethylene/octene (MI=7g/10min, 190 DEG C/ 2.16kg；The silane contents of 1.6 weight % grafting) it is used as precursor resin.Using card, not pressing machine shortens mould at 180 DEG C Type measures the film that thickness is 3 millimeters (76.2 microns) into by micrometer.By using commercially available aryl sulfonic acid catalyst The solution process film of (Nacure B-201, Jin Shi industry) in isopropanol continues 12 hours, wet solid at 60 DEG C -80 DEG C afterwards Change 72 hours to be crosslinked all films.Gel fraction is determined as 81.8% by surname extraction.Mark the A-D individual film submergence in four (4) In the dichloromethane and the bottle of the solution of butyl borate containing with good grounds table 42.Film treats in butyl borate solution Night.Before being handled with butyl borate and afterwards recording film weight.Table 43 reports the weight change of each film.In air Film is set to aoxidize 5 hours at 270 DEG C in convection oven under (21% oxygen content).Film is weighed after air oxidation. Quality retention rate (oxidation quality yield) during air oxidation is reported in table 44.10 DEG C/min are then used under a nitrogen Even variable Rate oxide-film is carbonized from 25 DEG C to 800 DEG C.Quality retention rate (carbonization quality yield) during carbonization is reported in In table 44.Compared with control film (comparative example 6), the average oxidation quality of the film handled before the oxidation with butyl borate obtains Rate improves 5.5-42.1%.Compared with control film (comparative example 6), with the film of butyl borate processing before oxidation and carbonization Average carbonization quality yield improve 13.6-24.5%.Compared with control film (comparative example 6), used before oxidation and carbonization The average oeverall quality yield of the film of butyl borate processing improves 25.4-78.2%.
Table 42
Table 43
Table 44
Comparative example 7
Ethylene/octene (density=0.950g/cm3；MI=17g/10min, 190 DEG C/2.16kg) at 160 DEG C Melting blends under a nitrogen in 15 miniature blending machines of DSM Xplore.Using card, not pressing machine is compressed into film at 160 DEG C Type.Film is set to aoxidize 10 hours at 250 DEG C in convection oven under air (21% oxygen content).To film after air oxidation Weighed.Quality retention rate (oxidation quality yield) during air oxidation is reported in table 45.Then use under a nitrogen 10 DEG C/min of even variable Rate makes oxide-film be carbonized from 25 DEG C to 800 DEG C.(carbonization quality obtains quality retention rate during carbonization Rate) it is reported in table 45.The oeverall quality yield calculated is reported in table 45.
Table 45
Example 7A
Ethylene/octene (density=0.950g/cm3；MI=17g/10min, 190 DEG C/2.16kg) and 5 weight % Polybutadiene (the average M used as it is from Sigma-Aldrich (Sigma Aldrich)n1,530-2,070； Catalog number (Cat.No.) 434779) melting blends under a nitrogen in 15 miniature blending machines of DSM Xplore at 160 DEG C.Film uses card not Pressing machine compression forming at 160 DEG C.Film is set to aoxidize 10 at 250 DEG C in convection oven under air (21% oxygen content) Hour.Film is weighed after air oxidation.Quality retention rate (oxidation quality yield) during air oxidation is reported in table In 46.Then oxide-film is set to be carbonized from 25 DEG C to 800 DEG C using 10 DEG C/min of even variable Rate under a nitrogen.During carbonization Quality retention rate (carbonization quality yield) is reported in table 46.The oeverall quality yield calculated is reported in table 46.
Table 46
Example 7B
Ethylene/octene (density=0.950g/cm3；MI=17g/10min, 190 DEG C/2.16kg) and 5 weight % Polybutadiene (the average M used as it is from Sigma-Aldrichn1,530-2,070；Catalog number (Cat.No.) 434779) Melting blends under a nitrogen in 15 miniature blending machines of DSM Xplore at 160 DEG C.Film using card not pressing machine at 160 DEG C Compression forming.By by 2.01mL 1M BH in glove box3Solution in THF is dissolved in 300mL THF to prepare 300mL 6.66mM BH3(borine) solution.Film is immersed in 100mL BH3In solution overnight.After being removed from solution, in gloves Desciccator diaphragm in case atmosphere.After 16 hours, membrane removal is gone from glove box.Under air (21% oxygen content) in convection oven Film is set to aoxidize at 250 DEG C 10 hours.Film is weighed after air oxidation.Quality retention rate (oxygen during air oxidation Change quality yield) it is reported in table 47.Then make oxygen from 25 DEG C to 800 DEG C using 10 DEG C/min of even variable Rate under a nitrogen Change film carbonization.Quality retention rate (carbonization quality yield) during carbonization is reported in table 47.The oeverall quality yield calculated It is reported in table 47.Compared with control film (comparative example 7 and example 7A), for the film (example 7B) handled with borine, observation 221-261% is improved to carbonization quality yield is relative.Compared with control film (comparative example 7 and example 7A), for at borine The film of reason, it was observed that oeverall quality yield is relative to improve 297-308%.
Table 47

Claims (9)

1. a kind of method for preparing carbonaceous article, comprising：
(a) olefin resin is provided；
(b) formed by the olefin resin and product is made；
(c) it is crosslinked the product that is made；
(d) stablize the product that is made by air oxidation；
(e) in abovementioned steps at least one of during or middle boron-bearing liquid (BCL) handle；And
(f) make the stabilization is made product carbonization.
2. according to the method for claim 1, wherein the BCL applies to boron being deposited on the boron being made in product Source.
3. according to the method for claim 2, wherein the boron source is element boron, borine, borate, borinic acid, boric acid (boronic acid), boric acid (boric acid), borine acid esters, borate, boroxin, amino borane, boron nitrogen alkynes, boron Hydride and its derivative and combination.
4. the method according to any claim in Claim 1-3, wherein step (d) are included in 120 DEG C or are higher than Product is made described in 120 DEG C of heating.
5. the method according to any claim in claim 1 to 4, wherein step (b) are included by fibre spinning, film Extrusion casting, blown film are processed, by described in mould carry out type face extrusion, injection moulding, solution-cast or compression forming general Vistanex, which changes into, is made product.
6. a kind of method for preparing carbonaceous article, comprising：
(a) product is made in the polyolefin for providing crosslinking；
(b) polyolefin of the crosslinking is made by air oxidation product is stable stable to be made product to provide；
(c) in abovementioned steps at least one of during or middle boron-bearing liquid (BCL) handle；And
(d) make the stabilization is made product carbonization.
7. according to the method for claim 6, wherein the BCL applies to boron being deposited on the boron being made in product Source.
8. according to the method for claim 7, wherein the boron source is element boron, borine, borate, borinic acid, boric acid (boronic acid), boric acid (boric acid), borine acid esters, borate, boroxin, amino borane, boron nitrogen alkynes, boron Hydride and its derivative and combination.
9. the method according to any claim in Claim 1-3, wherein step (b) are included in 120 DEG C or are higher than Product is made in 120 DEG C of heating crosslinkings.
CN201680023492.3A 2015-04-27 2016-04-07 The method of product is made up of polyolefin Pending CN107532340A (en)

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WO2015042387A1 (en) * 2013-09-19 2015-03-26 Dow Global Technologies Llc Polyolefin-derived carbon fibers containing boron

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WO2015042387A1 (en) * 2013-09-19 2015-03-26 Dow Global Technologies Llc Polyolefin-derived carbon fibers containing boron

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Application publication date: 20180102

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