JPS63146920A - Production of raw material pitch for carbon material - Google Patents
Production of raw material pitch for carbon materialInfo
- Publication number
- JPS63146920A JPS63146920A JP14416087A JP14416087A JPS63146920A JP S63146920 A JPS63146920 A JP S63146920A JP 14416087 A JP14416087 A JP 14416087A JP 14416087 A JP14416087 A JP 14416087A JP S63146920 A JPS63146920 A JP S63146920A
- Authority
- JP
- Japan
- Prior art keywords
- pitch
- catalyst
- raw material
- polymerization
- hydrogen fluoride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002994 raw material Substances 0.000 title claims abstract description 29
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 17
- -1 polycyclic hydrocarbon Chemical class 0.000 claims abstract description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 8
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract description 28
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 abstract description 16
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 abstract description 10
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 9
- 239000004917 carbon fiber Substances 0.000 abstract description 9
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 abstract description 8
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 3
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 2
- LEMQFBIYMVUIIG-UHFFFAOYSA-N trifluoroborane;hydrofluoride Chemical compound F.FB(F)F LEMQFBIYMVUIIG-UHFFFAOYSA-N 0.000 abstract 2
- 239000011295 pitch Substances 0.000 description 45
- 238000006116 polymerization reaction Methods 0.000 description 20
- 238000000034 method Methods 0.000 description 15
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002641 tar oil Substances 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 210000004185 liver Anatomy 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 208000006558 Dental Calculus Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000035425 carbon utilization Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ナフタレン、アントラセン、フェナントレン
、アセナフテン等の縮合多環炭化水素を重合させ、炭素
繊維及びその他の高機能性炭素材料の原料として好適な
ピッチを製造する方法に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention polymerizes condensed polycyclic hydrocarbons such as naphthalene, anthracene, phenanthrene, acenaphthene, etc., and is suitable as a raw material for carbon fibers and other highly functional carbon materials. The present invention relates to a method of manufacturing pitch.
（従来の技術）
ナフタレンその他の炭化水素を重合させてメソフェスピ
ッチないし等方性ピッチを製造する方法は、塩化アルミ
ニウム等のルイス酸触媒存在下で１００〜３００°Ｃで
熱処理した後、溶媒抽出法、沈澱法あるいは濾過法等に
より添加触媒を除去し、更に３００〜５００°Ｃで熱処
理する方法が知られており、特公昭５３−７５３３号、
Ｊｏｕｒｎａｌ ｏｆ ｍａｔｅｒｉａｌｓ ５ｃｉｅ
ｎｃｅ 刈ｐ３１７７〜３１８３ （１９８５）、特
開昭６１−８３３１７号等に記載されている。(Prior art) The method for producing mesophasic pitch or isotropic pitch by polymerizing naphthalene and other hydrocarbons involves heat treatment at 100 to 300°C in the presence of a Lewis acid catalyst such as aluminum chloride, followed by solvent extraction. A method is known in which the added catalyst is removed by a precipitation method, a precipitation method, a filtration method, etc., and then heat-treated at 300 to 500°C.
Journal of materials 5cie
nce Kari p3177-3183 (1985), JP-A-61-83317, etc.
（発明が解決しようとする問題点）
これらの塩化アルミ触媒触媒を用いる方法は、高温下で
反応が行われるため、一部脱水素反応が進行し生成ピッ
チの品質を低下させることの他、使用した塩化アルミ触
媒をピッチ中から回収再使用することが困難であると云
う欠点を有する。(Problems to be Solved by the Invention) In these methods using aluminum chloride catalysts, since the reaction is carried out at high temperatures, some of the dehydrogenation reaction proceeds, reducing the quality of the pitch produced, and the use of aluminum chloride catalysts. The drawback is that it is difficult to recover and reuse the aluminum chloride catalyst from the pitch.
更に炭素繊維のプリカーサ−ピンチとしての致命的な欠
陥として、微量の塩化アルミニウムまたはその誘導体が
炭素繊維中に残存し、仮焼あるいは黒鉛化時に、炭素繊
維の強度等の物性を著しく劣化させる。このような塩化
アルミニウムまたはその誘導体をピッチまたは繊維中か
ら除去することは極めて困難である。Furthermore, a fatal defect of precursor pinch in carbon fibers is that trace amounts of aluminum chloride or its derivatives remain in carbon fibers, which significantly deteriorates physical properties such as strength of carbon fibers during calcination or graphitization. It is extremely difficult to remove such aluminum chloride or its derivatives from pitch or fibers.
（問題点を解決するための手段）
発明者等は、ナフタレン、アントラセン、フェナントレ
ン、アセナフテン、ピレン等の縮合多環炭化水素の重合
反応について検討し、これらの化合物が、強力なプロト
ン酸触媒である弗化水素・三弗化硼素触媒の存在下で極
めて容易に重合が行われ、その重合生成物が炭素利料用
原料ピッチまたはそのプリカーサ−ピッチとして優れた
性質を有することを見出し、本発明に至った。(Means for Solving the Problems) The inventors have studied polymerization reactions of condensed polycyclic hydrocarbons such as naphthalene, anthracene, phenanthrene, acenaphthene, and pyrene, and have found that these compounds are strong protonic acid catalysts. It was discovered that polymerization can be carried out extremely easily in the presence of a hydrogen fluoride/boron trifluoride catalyst, and that the polymerization product has excellent properties as a raw material pitch for carbon utilization or its precursor pitch, and the present invention has been made based on the present invention. It's arrived.
即ち本発明は、縮合多環炭化水素またはこれを含有する
物質を弗化水素・三弗化硼素触媒の存在下で重合させる
ことを特徴とする炭素材料用原料ピッチの製造法である
。That is, the present invention is a method for producing raw material pitch for carbon materials, which is characterized by polymerizing a condensed polycyclic hydrocarbon or a substance containing the same in the presence of a hydrogen fluoride/boron trifluoride catalyst.
本発明において用いる原料としては、ナフタレン、アン
トラセン、フェナントレン、アセナフテン、アセナフチ
レン、ピレン等の縮合多環炭化水素およびこれらの混合
物ないしこれらを含有する物質であって、種々の石油留
分、石油加工工程の残油および石炭タール留分等も含ま
れる。The raw materials used in the present invention include condensed polycyclic hydrocarbons such as naphthalene, anthracene, phenanthrene, acenaphthene, acenaphthylene, and pyrene, mixtures thereof, and substances containing these, which are used in various petroleum fractions and petroleum processing processes. Also included are residual oil and coal tar fractions.
これらの原料は、重合触媒である弗化水素・三弗化硼素
と強く結合する塩基性化合物である窒素化合物、硫黄化
合物および酸素化合物の含有濃度が低いものが特に原料
として適している。These raw materials are particularly suitable as raw materials that contain low concentrations of nitrogen compounds, sulfur compounds, and oxygen compounds, which are basic compounds that strongly bind to hydrogen fluoride and boron trifluoride, which are polymerization catalysts.
重合触媒量は、縮合多環炭化水素１モルに対し弗化水素
を３〜２０モル、三弗化硼素を０．１〜１．０モルであ
る。重合触媒は弗化水素単独または三弗化硼素単独では
有効でない。The amount of polymerization catalyst is 3 to 20 moles of hydrogen fluoride and 0.1 to 1.0 mole of boron trifluoride per mole of condensed polycyclic hydrocarbon. Hydrogen fluoride or boron trifluoride alone are not effective as polymerization catalysts.
弗化水素（肝）は、三弗化硼素（ＢＰ３）と共に用いる
ことにより強いプロトン酸を形成し、塩基である縮合多
環炭化水素（Ａｒ）と錯体を形成する。Hydrogen fluoride (liver) forms a strong protic acid when used with boron trifluoride (BP3), and forms a complex with the base fused polycyclic hydrocarbon (Ar).
八ｒ ＋ ＩＩＦ ＋ ＢＰ＊ −〉
Ｈ” ＡｒＢＦ、＋ （１）式（１）
で生成した錯体は、過剰に用いるＩＩＦに溶解し錯体溶
液を形成する。重合反応はＨＦ溶液において、温和な条
件で極めて円滑に進行する。このように肝は重合を円滑
に進行させるための溶媒としての機能を有し、過剰に用
いるが、２０倍モル以上の使用は不要である。8r + IIF + BP* −>
H'' ArBF, + (1) Formula (1)
The complex formed is dissolved in IIF used in excess to form a complex solution. The polymerization reaction proceeds extremely smoothly in an HF solution under mild conditions. As described above, liver has a function as a solvent for smoothly proceeding polymerization, and is used in excess, but it is not necessary to use 20 times the mole or more.
重合反応の温度は０〜１５０°Ｃであり、好ましくは３
０〜１００°Ｃである。最適の反応温度は、原料の種類
により選定されるが、重合を過度に進める条件は、後の
触媒回収を困難にするため避ける必要がある。The temperature of the polymerization reaction is 0 to 150°C, preferably 3
It is 0-100°C. The optimal reaction temperature is selected depending on the type of raw material, but conditions that promote polymerization excessively must be avoided because they will make it difficult to recover the catalyst later.
重合に要する時間は、原料の種類、温度および触媒量に
よって変化するが、通常５〜３００分であり、好ましく
は１５〜１８０分である。The time required for polymerization varies depending on the type of raw materials, temperature and amount of catalyst, but is usually 5 to 300 minutes, preferably 15 to 180 minutes.
重合反応は、撹拌機を備えた耐蝕性の反応器中に原料お
よび触媒を供給し、撹拌混合下で行う。The polymerization reaction is carried out by supplying the raw materials and catalyst into a corrosion-resistant reactor equipped with a stirrer and stirring the mixture.
反応操作は、回分操作でも連続操作でも良い。反応器へ
の原料供給を容易にする目的で、固体原料を適当な不活
性溶媒に溶解して用いることができる。この不活性溶媒
には、ベンゼン、トルエン、キシレンなどの芳香族炭化
水素が好適である。The reaction operation may be a batch operation or a continuous operation. For the purpose of facilitating the supply of raw materials to the reactor, solid raw materials can be used after being dissolved in a suitable inert solvent. Aromatic hydrocarbons such as benzene, toluene, and xylene are suitable for this inert solvent.
原料の縮合多環炭化水素は、触媒と混合することにより
錯体を形成し、ＩＩＦ相中に熔解した後、速やかに重合
反応が進行し、重合体（（Ａｒ）。］の錯錯体液に転化
する。即ち錯体は次の平衡関係を保っている。The raw material condensed polycyclic hydrocarbon forms a complex by mixing it with a catalyst, and after being dissolved in the IIF phase, the polymerization reaction proceeds rapidly and is converted into a complex liquid of the polymer ((Ar).) That is, the complex maintains the following equilibrium relationship.
１（Ｆ ＋ ＢＰ３ ＋ （Ａｒ）、、＝コＨ” （Ａ
ｒ）、ｌＢＦ、 （２）従って揮発成分であるＨＦ、
ＢＰ、を加熱藤発、留去することで触媒を回収し、同時
に重合ピッチを分離することができる。1(F + BP3 + (Ar),,=koH” (A
r), lBF, (2) Therefore, HF, which is a volatile component,
By heating the BP and distilling it off, the catalyst can be recovered and the polymerized pitch can be separated at the same time.
触媒１１Ｆ、ＢＦ３のピッチからの分離回収は、具体的
に以下の方法で実施できる。The separation and recovery of the catalysts 11F and BF3 from the pitch can be carried out specifically by the following method.
回分的に触媒を分離する方法としては、重合体の肝−Ｂ
Ｆ３錯体溶液からなる反応液を適当な圧力下で加熱し、
ＨＦ、ＢＦ３を気相として反応器から抜出し、重合体は
最終的に溶融ピッチとして回収する。As a method for separating the catalyst batchwise, polymer liver-B
Heating the reaction solution consisting of the F3 complex solution under appropriate pressure,
HF and BF3 are extracted from the reactor as a gas phase, and the polymer is finally recovered as molten pitch.
この操作をより円滑に進めるため、ピッチを良く溶解し
、且つ適度な蒸気圧を有し、更にＨＦ、ＢＰ、に対して
比較的不活性な助剤、例えばベンゼン、トルエン、ハロ
ゲン化芳香族炭化水素等を系内に供給または共存させて
加熱し、これらの助剤蒸気と共にＨＰ、ＢＦ３を蒸発気
化する方法も採られる。加熱の方法は、外部よりジャケ
ット等を通して加熱するか、または前述の助剤の蒸気を
供給して直接加熱により実施しても良い。In order to proceed with this operation more smoothly, auxiliary agents that dissolve pitch well, have appropriate vapor pressure, and are relatively inert to HF and BP, such as benzene, toluene, halogenated aromatic carbonized A method may also be adopted in which hydrogen or the like is supplied or allowed to coexist in the system and heated to evaporate HP and BF3 together with these auxiliary agent vapors. The heating may be performed by heating from the outside through a jacket or the like, or by direct heating by supplying the vapor of the auxiliary agent described above.
連続的に触媒を分離する方法では、蒸留塔を用い、還流
される前述の不活性な助剤中に重合反応液を連続的に供
給し、塔頂から気化したＨＦ、ＢＦ３を抜出し、塔底か
らピッチを助剤溶液として回収する。In the method of continuously separating the catalyst, a distillation column is used, the polymerization reaction liquid is continuously fed into the above-mentioned inert auxiliary agent that is refluxed, vaporized HF and BF3 are extracted from the top of the column, and the vaporized HF and BF3 are extracted from the bottom of the column. The pitch is recovered as an auxiliary solution.
どちらの方法においても、重合物錯体溶液を加熱分解し
てＨＦ、ＢＦ３を回収するのに必要な温度は、１００〜
２５０°Ｃであり、好ましくは１２０〜１８０°Ｃであ
る。１００°Ｃ以下の温度では触媒分離を満足な程度ま
で進めることが困難であり、また２５０°Ｃ以」二の高
温は必要としない。In both methods, the temperature required to thermally decompose the polymer complex solution and recover HF and BF3 is 100 to
The temperature is 250°C, preferably 120-180°C. At temperatures below 100°C, it is difficult to proceed with catalyst separation to a satisfactory degree, and high temperatures above 250°C are not necessary.
１１Ｆ、ＢＦ：ｌを回収するための操作圧力はＯ〜１０
気圧、好ましくは１〜５気圧である。操作圧力が高い程
、ピッチからのＩＩＰ、ＢＦ３の分離が困難となるが、
回収触媒、特にガス状のＢＦ３の再利用が容易となる。11F, BF: The operating pressure for recovering l is O~10
Atmospheric pressure, preferably 1 to 5 atm. The higher the operating pressure, the more difficult it becomes to separate IIP and BF3 from the pitch.
The recovered catalyst, especially gaseous BF3, can be easily reused.
ここで得られるピッチは、実質的にＨＦ、ＢＦ３を含有
せす、蒸留、溶媒抽出、加熱処理およびこれらの組合せ
操作を加えることにより炭素繊組、用原料ピッチ、また
はその他の原料ピッチとして好適な性状を有するものに
加工することができる。The pitch obtained here can be made into a material suitable for carbon fiber assembly, raw material pitch, or other raw material pitch by adding substantially HF, BF3, distillation, solvent extraction, heat treatment, and combination operations thereof. It can be processed into something with specific properties.
また本発明により合成したピッチは、特開昭５６−１０
１９１５号、特開昭５８−１８５６１２号などに記載さ
れている既知の加熱処理法などにより、容易にメソフェ
ーズを生成し、種々の炭素材料用ピッチまたはそのプリ
カーサ−として優れた性質を有するピッチが得られる。Moreover, the pitch synthesized according to the present invention is
1915, JP-A No. 58-185612, etc., it is possible to easily generate mesophase and obtain pitches having excellent properties as pitches for various carbon materials or as precursors thereof. It will be done.
（効果）
本発明の方法によれば、ナフタレン、アントラセン、フ
ェナントレン、アセナフテン、ピレン等の縮合多環炭化
水素を極めて容易に重合することができ、次のような利
点がある。(Effects) According to the method of the present invention, condensed polycyclic hydrocarbons such as naphthalene, anthracene, phenanthrene, acenaphthene, and pyrene can be extremely easily polymerized, and the method has the following advantages.
（１）原料は前述した種々の縮合多環炭化水素を単一成
分として用いることができるが、同時にこれらを混合物
として用い、特性の異なるピッチを意図的に得ることが
できる。またこれらの縮合多環炭化水素を含有する種々
のタール油等を原料とすることもできる。(1) As the raw material, the various condensed polycyclic hydrocarbons described above can be used as a single component, but at the same time, pitches with different characteristics can be intentionally obtained by using them as a mixture. Moreover, various tar oils containing these condensed polycyclic hydrocarbons can also be used as raw materials.
（２）本発明の方法では、触媒のＨＦ、ＢＦ３が容易に
分離され、また分離されたＩＩＰ、ＢＦ３は触媒として
再利用することができる。(2) In the method of the present invention, HF and BF3 of the catalyst can be easily separated, and the separated IIP and BF3 can be reused as a catalyst.
（３）触媒のＨＦ、ＢＦ３が完全に除去されたピッチが
得られるので、本発明によるピッチは炭素繊維用原料ま
たはその他の高機能性炭素材料用原料として極めて優れ
た性質を有している。(3) Since pitch is obtained in which the catalysts HF and BF3 are completely removed, the pitch according to the present invention has extremely excellent properties as a raw material for carbon fibers or other highly functional carbon materials.
（４）本発明の方法により製造したピッチは、前述の如
き既知の方法にまり高収率でメソフェースピンチを調製
できる。ここで得られるメソフェースピンチは、容易に
紡糸可能であって、紡糸後に不融化、炭化更に必要に応
じ黒鉛化を経て、高強度の炭素繊維もしくは黒鉛化繊維
を製造できる。(4) The pitch produced by the method of the present invention can be used to prepare mesoface pinch in high yield by using the known method as described above. The mesoface pinch obtained here can be easily spun, and after spinning, it can be made infusible, carbonized, and optionally graphitized to produce high-strength carbon fibers or graphitized fibers.
（５）本発明によるピッチは、適度の活性水素を保有し
ており、その不融化処理が容易である。(5) The pitch according to the present invention has an appropriate amount of active hydrogen and can be easily rendered infusible.
以上による本発明の工業的意義が大きい。The present invention as described above has great industrial significance.
（実施例）
次に実施例により本発明を更に具体的に説明する。もち
ろん本発明はこれらの実施例により制限されるものでは
無い。(Example) Next, the present invention will be explained in more detail with reference to Examples. Of course, the present invention is not limited to these examples.
実施例１
ナフタレン１モル、ＩＩＰ ８モルをオートクレーブに
仕込み、ゆっくり撹拌しながら、ＢＦ３０．５モルを約
２分間で供給した。ＢＦ３の供給に伴ってナフタレンは
溶解し直ちに重合を開始した。オートクレーブの温度を
４０’Ｃに加温し、なお３０分間撹拌し反応を完結した
後、反応液を冷水中に抜出し、遊離したピッチを温キシ
レンに溶解し、温水で３回洗浄し、次に減圧下でキシレ
ンを蒸発留去してピッチを得た。このピッチの軟化点は
約６０°Ｃであり、ピンチ中にナフタレンは検出しなか
ったが、ピッチの元素分析結果は、Ｃ９２，１χ、Ｉ＋
７．９χであり、−３，）フレ７０）理論値（Ｃ９２
，３Ｚ 、）１７．７２） ４ｍはぼ一致した。Example 1 1 mol of naphthalene and 8 mol of IIP were charged into an autoclave, and 30.5 mol of BF was fed over about 2 minutes while stirring slowly. As BF3 was supplied, naphthalene was dissolved and polymerization started immediately. After heating the temperature of the autoclave to 40'C and stirring for 30 minutes to complete the reaction, the reaction solution was extracted into cold water, the liberated pitch was dissolved in warm xylene, washed three times with warm water, and then Pitch was obtained by evaporating the xylene under reduced pressure. The softening point of this pitch is approximately 60°C, and naphthalene was not detected during pinching, but the elemental analysis results of the pitch are C92,1χ, I+
7.9χ, -3,) Frequency 70) Theoretical value (C92
, 3Z, ) 17.72) 4m were almost identical.
実施例２
実施例１と同様の操作で、ナフタレン１モル、１１Ｆ５
モル、ＢＦ３０．５モルを温度２０°Ｃ６０分間重合さ
せて得られたピッチは、軟化点４５°Ｃ１元素分析値Ｃ
９２，２χ、Ｈ７，８χであった。Example 2 In the same manner as in Example 1, 1 mol of naphthalene, 11F5
Pitch obtained by polymerizing 30.5 moles of BF at a temperature of 20°C for 60 minutes has a softening point of 45°C1 elemental analysis value C
The results were 92.2χ and H7.8χ.
実施例３
ナフタレン１モル、ＨＦ５モル、ＢＦ２０．４モルを１
００°Ｃ６０分間重合させて得たピッチを窒素ガスの流
通下に３８０°Ｃで１０時間処理し、異方性組織が実質
的に１００″Ａのメソフェースピッチを４０重景％の収
率で得た。Example 3 1 mole of naphthalene, 5 moles of HF, 20.4 moles of BF
The pitch obtained by polymerizing at 00°C for 60 minutes was treated at 380°C for 10 hours under nitrogen gas flow to produce mesoface pitch with an anisotropic structure of substantially 100″A at a yield of 40%. Obtained.
この加工後のメソフェーズピッチの軟化点は３００°Ｃ
であり、３５０’Ｃで容易に紡糸可能であった。The softening point of mesophase pitch after this processing is 300°C
and could be easily spun at 350'C.
このピッチは、所定の不融化、炭化処理後、高品質の炭
素繊維が得られた。After this pitch was subjected to prescribed infusibility and carbonization treatments, high-quality carbon fibers were obtained.
実施例４
内容積２００ｍ ｊ２の撹拌機付オートクレーブを用い
第１表に示す種々の縮合多環炭化水素を原料として重合
を実施した。Example 4 Polymerization was carried out using various condensed polycyclic hydrocarbons shown in Table 1 as raw materials using an autoclave equipped with a stirrer and having an internal volume of 200 m2.
原料の縮合多環炭化水素を０．５ｍｆｆ１をオートクレ
ーブに仕込み、ＨＦ３ｍ ｌを加え、ゆっくり撹拌しな
がらＢＦ３ガス０．２５モルを送入することにより原料
はＢＦ３を吸収しながら溶解した。0.5 mff1 of condensed polycyclic hydrocarbon as a raw material was charged into an autoclave, 3 ml of HF was added, and 0.25 mol of BF3 gas was introduced while stirring slowly, so that the raw material was dissolved while absorbing BF3.
外部ジャケットにより所定温度に制御しながら３時間保
持し重合反応させた後、オートクレーブのベントを開放
し、常圧において１８０〜２００°Ｃ迄徐々に加熱し、
実質的に全量のＨＦ、ＢＦ３をガス状で回収し、その後
溶融状態のピッチを抜出した。After holding the polymerization reaction for 3 hours while controlling the temperature at a predetermined temperature using an external jacket, the vent of the autoclave was opened and the temperature was gradually heated to 180 to 200°C at normal pressure.
Substantially all of the HF and BF3 were recovered in gaseous form, and then the molten pitch was extracted.
各原料における重合反応条件、収率および得られたピッ
チの物性を第１表に示す。なお収率は１、得られたピッ
チをエタノールで洗浄し、未反応物等を除去した後のピ
ッチの原料に対する重量％である。Table 1 shows the polymerization reaction conditions, yield, and physical properties of the pitch obtained for each raw material. Note that the yield is 1, which is % by weight based on the pitch raw material after washing the obtained pitch with ethanol and removing unreacted substances.
第１表 ＊固体のまま取り出した。Table 1 *Taken out as a solid.
実施倒覆
実施例１および実施例４で合成したピッチを炭素化して
評価を行った。ピッチの炭素化は、常圧６００°Ｃで２
時間焼成した場合と、１０ｋｇ／ｃｍ２Ｇの加圧下、５
５０°Ｃで２時間焼成した場合とした。The pitch synthesized in Practical Overturning Example 1 and Example 4 was carbonized and evaluated. Carbonization of pitch takes place at normal pressure of 600°C.
When fired for 5 hours and under a pressure of 10 kg/cm2G,
The case was calculated by firing at 50°C for 2 hours.
各原料よりのピッチの炭素化による炭素収率を第２表に
示す。生成した炭素は、偏光顕微鏡による観察で流れ構
造が見られ、メソフェーズ化を経由して炭素化したこと
を示していた。Table 2 shows the carbon yield by carbonization of pitch from each raw material. The produced carbon showed a flow structure when observed using a polarizing microscope, indicating that it was carbonized through mesophase formation.
第２表
実施例６
内容積５００ｍ Ｉ！、の撹拌機付オートクレーブ中に
ナフタレン１モル（１２８ｇ）、アントラセン０．１モ
ル（１７，８ｇ）を仕込み、１ｌＦ６モル（２００ｇ）
を加え、その後ＢＰ３０．６モルを吸収させ、温度８０
°Ｃで３時間重合させた。重合後容器を常圧に開放し、
ヘンゼン２００ｇを加え外部より加熱し、ヘンゼンの全
量を触媒蒸気と共に留去した。分離したピンチは、更に
減圧化で未反応ナフタレンを蒸留分離した。得られた・
ピッチの重量収率は、ナフタレン＋アントラセンの重量
に対して９５″Ａであった。またこのピッチの融点は１
１０°Ｃ１ＩＩ／Ｃ元素比率は０．７９であった。Table 2 Example 6 Internal volume 500m I! 1 mol (128 g) of naphthalene and 0.1 mol (17.8 g) of anthracene were placed in an autoclave with a stirrer, and 6 mol (200 g) of 11F was charged.
was added, then 30.6 moles of BP was absorbed, and the temperature was 80
Polymerization was carried out for 3 hours at °C. After polymerization, open the container to normal pressure,
200 g of Hensen was added and heated from the outside, and the entire amount of Hensen was distilled off along with the catalyst vapor. The separated pinch was further distilled to remove unreacted naphthalene under reduced pressure. Obtained
The weight yield of pitch was 95″A based on the weight of naphthalene + anthracene. Also, the melting point of this pitch was 1
The 10°C1II/C element ratio was 0.79.
実施例７
石炭タールの蒸留によって得られるアントラセン２５Ｗ
ｔＸを含有するタール油（留分範囲２００〜３７０°
Ｃ）を原料とし、実施例６と同じオートクレーブにより
重合を実施した。原料タール油２００ｇを仕込み、ＨＦ
１２０ｇ、 ＢＦ：＋０．６モルを加えて８０°Ｃで３
時間重合を行った。重合後宮圧下で２００°Ｃまで加熱
し触媒のＩＰ、ＢＦ３を気化分離した後、重合油を抜出
し、真空下で未反応油を蒸留分離し、原料タール油に対
し６１χの重合ピッチを得た。ピッチの融点は５９°Ｃ
であり、Ｈ／Ｃ比は０．７５であった。Example 7 Anthracene 25W obtained by distillation of coal tar
Tar oil containing tX (distillation range 200-370°
C) was used as a raw material, and polymerization was carried out in the same autoclave as in Example 6. Prepare 200g of raw material tar oil and HF
120g, BF: +0.6mol added and heated at 80°C
Time polymerization was performed. After the polymerization stage was heated to 200°C under pressure to vaporize and separate the catalyst IP and BF3, the polymerized oil was extracted and unreacted oil was distilled off under vacuum to obtain a polymer pitch of 61χ based on the raw material tar oil. The melting point of pitch is 59°C
The H/C ratio was 0.75.
Claims (1)
・三弗化硼素触媒の存在下で重合させることを特徴とす
る炭素材料用原料ピッチの製造法A method for producing raw material pitch for carbon materials, which comprises polymerizing a condensed polycyclic hydrocarbon or a substance containing it in the presence of a hydrogen fluoride/boron trifluoride catalyst.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP87110624A EP0257303B1 (en) | 1986-07-29 | 1987-07-22 | Process for producing pitch used as starting material for the making of carbon materials |
| DE8787110624T DE3774035D1 (en) | 1986-07-29 | 1987-07-22 | METHOD FOR PRODUCING PECH, RECOVERABLE FOR PRODUCING CARBON BODIES. |
| US07/077,211 US4789455A (en) | 1986-07-29 | 1987-07-24 | Process for producing pitch used as starting material for the making of carbon materials |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61-176704 | 1986-07-29 | ||
| JP17670486 | 1986-07-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63146920A true JPS63146920A (en) | 1988-06-18 |
| JP2526585B2 JP2526585B2 (en) | 1996-08-21 |
Family
ID=16018289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62144160A Expired - Lifetime JP2526585B2 (en) | 1986-07-29 | 1987-06-11 | Manufacturing method of raw material pitch for carbon material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2526585B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01254796A (en) * | 1988-04-04 | 1989-10-11 | Mitsubishi Gas Chem Co Inc | Mesophase pitch for carbonaceous material |
| US5484520A (en) * | 1993-12-09 | 1996-01-16 | Mitsubishi Gas Chemical Company, Inc. | Self-adhesive carbonaceous grains and process for producing high-density and high-strength carbon artifacts showing a fine mosaic texture of optical anisotropy derived from such grains |
| JP2007534815A (en) * | 2004-04-26 | 2007-11-29 | メルク パテント ゲーエムベーハー | Electroluminescent polymers and uses thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1657730A3 (en) | 2004-11-15 | 2007-05-30 | Mitsubishi Gas Chemical Company, Inc. | Electrode sheet and electric double layer capacitor using the same |
| KR101869647B1 (en) | 2017-03-21 | 2018-06-21 | 국방과학연구소 | Manufacturing method of mesophase pitch by heterogeneous fluorination reaction and mesophase pitch by the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6397624A (en) * | 1986-10-15 | 1988-04-28 | Sumitomo Metal Ind Ltd | Production of condensed polycyclic aromatic resin |
-
1987
- 1987-06-11 JP JP62144160A patent/JP2526585B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6397624A (en) * | 1986-10-15 | 1988-04-28 | Sumitomo Metal Ind Ltd | Production of condensed polycyclic aromatic resin |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01254796A (en) * | 1988-04-04 | 1989-10-11 | Mitsubishi Gas Chem Co Inc | Mesophase pitch for carbonaceous material |
| US5484520A (en) * | 1993-12-09 | 1996-01-16 | Mitsubishi Gas Chemical Company, Inc. | Self-adhesive carbonaceous grains and process for producing high-density and high-strength carbon artifacts showing a fine mosaic texture of optical anisotropy derived from such grains |
| US5609800A (en) * | 1993-12-09 | 1997-03-11 | Mitsubishi Gas Chemical Company, Inc. | Process for producing high-density and high-strength carbon artifacts showing a fine mosaic texture of optical anisotropy |
| JP2007534815A (en) * | 2004-04-26 | 2007-11-29 | メルク パテント ゲーエムベーハー | Electroluminescent polymers and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2526585B2 (en) | 1996-08-21 |
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