JPH02188418A - Thermally expandable graphite - Google Patents
Thermally expandable graphiteInfo
- Publication number
- JPH02188418A JPH02188418A JP1008343A JP834389A JPH02188418A JP H02188418 A JPH02188418 A JP H02188418A JP 1008343 A JP1008343 A JP 1008343A JP 834389 A JP834389 A JP 834389A JP H02188418 A JPH02188418 A JP H02188418A
- Authority
- JP
- Japan
- Prior art keywords
- graphite
- alkaline earth
- thermally expandable
- earth metal
- expandable graphite
- 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.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 56
- 239000010439 graphite Substances 0.000 title claims abstract description 56
- 150000004679 hydroxides Chemical class 0.000 claims abstract description 6
- 150000001341 alkaline earth metal compounds Chemical group 0.000 claims description 16
- -1 inorganic acid salts Chemical class 0.000 claims description 9
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 10
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 9
- 238000010306 acid treatment Methods 0.000 abstract description 6
- 230000004580 weight loss Effects 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 5
- 238000002485 combustion reaction Methods 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910004014 SiF4 Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 235000011835 quiches Nutrition 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は熱膨張性黒鉛に関する。熱膨張性黒鉛は、高温
に加熱すると瞬時に元の体積の数十倍から数百倍に膨張
し、これをプレスすることによりバインダーを使用する
ことなく可撓性に優れた黒鉛シートか得られることから
工業的に重要な素材としてよ（知られている。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to thermally expandable graphite. When thermally expandable graphite is heated to high temperatures, it instantly expands to tens to hundreds of times its original volume, and by pressing it, a highly flexible graphite sheet can be obtained without using a binder. Therefore, it is known as an industrially important material.
熱膨張性黒鉛は、通常、天然黒鉛、熱分解黒鉛、キッシ
ュ黒鉛などの黒鉛を、濃硫酸と強い酸化剤との混合物で
処理（以下、この処理を酸処理という）した後、水洗し
、乾燥することによって得られる。酸処理方法としては
、濃硫酸に硝酸及びその塩を併用する方法（特公昭５４
−２５９１３号）Ｍ他剤として過マンガン酸カリ（特開
昭５５−９５６０９号）、過ハロゲン酸塩（特開昭５１
−９６７９３号）を用いる方法、或は黒鉛を電解反応に
より陽極酸化を行なう方法（特公昭５６−１８３５２号
）が知られている。Thermally expandable graphite is usually produced by treating graphite such as natural graphite, pyrolytic graphite, or quiche graphite with a mixture of concentrated sulfuric acid and a strong oxidizing agent (hereinafter, this treatment is referred to as acid treatment), followed by washing with water and drying. obtained by doing. As an acid treatment method, a method using concentrated sulfuric acid together with nitric acid and its salts (Japanese Patent Publication No. 54
-25913) M Other agents include potassium permanganate (JP-A No. 55-95609), perhalogenate (JP-A No. 51-Sho.
96793) or a method of anodic oxidation of graphite by electrolytic reaction (Japanese Patent Publication No. 18352/1983).
このようにして得られた熱膨張性黒鉛を加工するには、
黒鉛の膨張性を高め、さらに膨張時に発生する硫酸を含
む酸性ガスを除去するために熱膨張性黒鉛を８００〜１
５００℃の高温下に数秒〜数十秒間滞留させることが必
要であるが、その際、黒鉛成分の燃焼に起因すると考え
られる製品の歩留りの低下という問題が生じる。即ち、
熱膨張性黒鉛は５００℃程度の温度では空気雰囲気中で
ゆるやかに酸化され、７００℃程度になると明らかに重
量減少が認められる程度に燃焼する。本明細書では、こ
の重ｔＸ少の程度を「耐酸化性」といつＯ
〔課題を解決するための手段〕
本発明者らは高温処理の際に重量減少の少ない熱膨張性
黒鉛、即ち、耐酸化性の優れた熱膨張性黒鉛につき鋭意
検討を重ねた結果、熱膨張性黒鉛にアルカリ土類金属化
合物を含有させることにより上述の課題を解決しうろこ
とを見出した。即ち本発明はアルカリ土類金属の酸化物
、水酸化物、無機酸塩、有機酸塩よりなる群から選ばれ
た少なくとも一種のアルカリ土類金属化合物を含有して
いるこ上を特徴とする熱膨張性黒鉛を要旨とするもので
ある。To process the thermally expandable graphite obtained in this way,
In order to increase the expandability of graphite and further remove acidic gases containing sulfuric acid generated during expansion, thermally expandable graphite is added to
It is necessary to retain the product at a high temperature of 500° C. for several seconds to several tens of seconds, but at that time, a problem arises in that the yield of the product decreases, which is thought to be caused by combustion of the graphite component. That is,
Thermal expandable graphite is slowly oxidized in an air atmosphere at a temperature of about 500°C, and burns to the extent that a weight loss is clearly observed at a temperature of about 700°C. In this specification, this degree of weight tX is referred to as "oxidation resistance". As a result of extensive research into thermally expandable graphite with excellent oxidation resistance, we have found that the above-mentioned problems can be solved by incorporating an alkaline earth metal compound into thermally expandable graphite. That is, the present invention provides a heat treatment method characterized by containing at least one alkaline earth metal compound selected from the group consisting of alkaline earth metal oxides, hydroxides, inorganic acid salts, and organic acid salts. The main theme is expandable graphite.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の熱膨張性黒鉛はアルカリ土類金属化合物を含有
するものである。アルカリ土類金属化合物としてはＭｇ
、Ｃａ、Ｂａの酸化物、水酸化物、硫酸、硝酸、塩酸、
炭酸、リン酸、珪酸等の無機酸の塩、ギ酸、酢酸、シュ
ウ酸、コハク酸、酒石酸、クエン酸等の有機酸の塩が挙
げられる。これらの中ではＣａ及びＢａの水酸化物、硫
酸塩、炭酸塩、硝酸塩が好ましい。The thermally expandable graphite of the present invention contains an alkaline earth metal compound. Mg as an alkaline earth metal compound
, Ca, Ba oxides, hydroxides, sulfuric acid, nitric acid, hydrochloric acid,
Examples include salts of inorganic acids such as carbonic acid, phosphoric acid, and silicic acid, and salts of organic acids such as formic acid, acetic acid, oxalic acid, succinic acid, tartaric acid, and citric acid. Among these, hydroxides, sulfates, carbonates, and nitrates of Ca and Ba are preferred.
本発明の熱膨張黒鉛は、例えば、約２０〜１００メツシ
ユに粉砕された黒鉛を、９８％硫酸と６０％過酸化水素
水の混合物中に添加し、４５℃以下の温度で１０〜３０
分接触させて酸処理を行ない、生成物を水洗し、濾別し
た後乾燥する際、水洗工程或は水洗してから濾別後にア
ルカリ土類金属化合物を黒鉛と接触させることにより製
造される。即ち、酸処理後の黒鉛を水洗する際、水洗の
最終工程で、アルカリ土類金属化合物を添加するか、水
洗後濾過した湿潤状態の黒鉛のケーキに、粒状或は粉砕
したアルカリ土類金属化合物を添加混合することにより
、アルカリ土類金属化合物を黒鉛に含有させる。The thermally expandable graphite of the present invention can be produced, for example, by adding graphite crushed into about 20 to 100 meshes into a mixture of 98% sulfuric acid and 60% hydrogen peroxide,
It is produced by contacting the alkaline earth metal compound with graphite during the water washing process or after washing with water and filtering, when the product is washed with water, filtered and then dried. That is, when acid-treated graphite is washed with water, an alkaline earth metal compound is added in the final step of water washing, or a granular or pulverized alkaline earth metal compound is added to the wet graphite cake that has been filtered after washing with water. By adding and mixing, an alkaline earth metal compound is incorporated into graphite.
アルカリ土類金属化゛合物は上記のような粒状あるいは
粉状のものをそのまま、或は水と混合したもの、または
メタノール、エタノール等のアルコール類、アセトン、
メチルエチルケトン等のケトン類、酢酸メチル等のエス
テル類、塩化メチレン等のハロゲン化炭化水素等の有機
溶媒に溶解或は分散させて黒鉛と接触させる。Alkaline earth metal compounds can be used in the form of granules or powders as described above, as they are, or mixed with water, alcohols such as methanol and ethanol, acetone,
It is dissolved or dispersed in an organic solvent such as a ketone such as methyl ethyl ketone, an ester such as methyl acetate, or a halogenated hydrocarbon such as methylene chloride, and brought into contact with graphite.
この際、アルカリ土類金属化合物は、熱膨張性黒鉛に含
まれる遊離硫酸との反応により形成されるアルカリ土類
金属の硫酸塩として黒鉛に付着した状態で含有されるが
、一部は過剰のアルカリ土類金属化合物が付着物として
含有されていてもよい。なお、本発明でいう「′ｔ１離
硫酸」とは黒鉛の内部にとりこまれ黒鉛層間化合物を形
成している硫酸以外の付着硫酸を意味する。At this time, the alkaline earth metal compound is contained as an alkaline earth metal sulfate formed by the reaction with the free sulfuric acid contained in the thermally expandable graphite, and is attached to the graphite. An alkaline earth metal compound may be contained as a deposit. In addition, "'t1 sulfuric acid" as used in the present invention means attached sulfuric acid other than sulfuric acid that is incorporated into graphite and forms a graphite intercalation compound.
本発明の熱膨張性黒鉛の製造法の好ましい態様としては
、原料黒鉛を酸処理後、酸処理生成物を洗浄する際、被
洗浄物固形分に対し、遊離硫酸の量がＩ ｍｏｌ／ｋｇ
以下となるまで洗浄し、濾別して得られる湿潤状のケー
キをアルカリ土類金属水酸化物と水との混合物と混合し
た後濾別し、次いで乾燥するか、或はアルカリ土類金属
水酸物と水との混合物を添加後、濾別せずに撹拌しなが
ら乾燥させる方法が挙げられる。In a preferred embodiment of the method for producing thermally expandable graphite of the present invention, when the raw graphite is acid-treated and the acid-treated product is washed, the amount of free sulfuric acid is I mol/kg based on the solid content of the object to be washed.
The wet cake obtained by washing and filtration is mixed with a mixture of alkaline earth metal hydroxide and water, filtered, and then dried; An example of a method is to add a mixture of water and water, and then dry the mixture with stirring without filtering.
この際、酸処理生成物の洗浄を、被洗浄物固形分に対す
る遊離硫酸の量が１ｍｏｌ／ｋｇ以下となるまで行なわ
ずにアルカリ土類金属水酸化物と接触させると、原料黒
鉛に含有されていたＦｅ等の各種元素が、黒鉛の酸処理
により酸処理液中に溶出し、これらがアルカリ土類金属
水酸化物と反応して、水酸化物を形成し、熱膨張性黒鉛
の特性を低下させるばかりでなく、酸処理生成物を水洗
後濾過する際に濾材の目づまりを引き起こし、濾過性を
低下させることがあるので好ましくない。At this time, if the acid treatment product is brought into contact with the alkaline earth metal hydroxide without washing the acid-treated product until the amount of free sulfuric acid is 1 mol/kg or less based on the solid content of the material to be washed, the acid treatment product may be washed with the alkaline earth metal hydroxide. Various elements such as Fe are eluted into the acid treatment solution when graphite is treated with acid, and these react with alkaline earth metal hydroxides to form hydroxides, which deteriorate the properties of thermally expandable graphite. Not only this, but also the filter medium may become clogged when the acid-treated product is filtered after washing with water, which may reduce the filterability, which is not preferable.
アルカリ土類金属化合物の含有量は、元素の種類或いは
熱膨張黒鉛中に含有される遊離硫酸の量によっても異な
るが、アルカリ土類金属として０゜１〜ｌＯ重量％の範
囲で含有されていることが好ましい。The content of alkaline earth metal compounds varies depending on the type of element or the amount of free sulfuric acid contained in thermally expandable graphite, but it is contained in the range of 0.1 to 10% by weight as alkaline earth metals. It is preferable.
アルカリ土類金属の含有量が０．１重世％未満では熱膨
張性黒鉛の耐酸化性の向上が十分でなく、一方、１０重
量％を超えても含有量に見合う効果が発現されないこと
があり、かつ、経済性の点からも好ましくない。If the alkaline earth metal content is less than 0.1% by weight, the oxidation resistance of thermally expandable graphite will not be improved sufficiently, while if it exceeds 10% by weight, the effect commensurate with the content may not be expressed. Yes, and also unfavorable from an economic point of view.
本発明において、熱膨張性黒鉛中の遊離硫酸の量、アル
カリ土類金属の量及び耐酸化性の測定は次のようにして
行なった。In the present invention, the amount of free sulfuric acid, amount of alkaline earth metal, and oxidation resistance in thermally expandable graphite were measured as follows.
熱膨張性黒鉛５ｇを熱風循環式乾燥器中で１０５℃で２
時間乾燥後、デシケーク−中で冷却したものを水に分散
させた状態で約１０分間保持した後、アルカリ滴定によ
り測定する。水分散液の濃度は１〜５重量％にすること
がアルカリ滴定操作上好ましい。5g of thermally expandable graphite was dried at 105℃ in a hot air circulation dryer for 2 hours.
After drying for a period of time, the mixture was cooled in a desiccant, kept dispersed in water for about 10 minutes, and then measured by alkaline titration. It is preferable for the concentration of the aqueous dispersion to be 1 to 5% by weight in terms of alkaline titration operation.
（ｌｌＢａ元素の場合
試料約１ｇを容量１００ｍｌの白金皿にとり、精秤した
後電気マツフル炉中に４００℃で５〜１０分間保持し、
次いで炉温を８００℃に昇温しで約５時間保持して燃焼
、灰化する。灰化物を放冷後、これに濃硫酸２〜３滴及
びフン酸約１０ｍｌを加え加熱乾固させ、天分中のシリ
カ分をＳｉＦ４として揮発させて除去する。この操作を
３回くり返した後、得られた固形物に１８Ｎ塩酸を約２
０ｍｌ加えて加熱し、塩酸可溶分を溶出させ、１ｋ５−
Ｃの濾紙を用いて濾別する。残渣を１８Ｎ塩酸及び温水
で洗浄後、濾紙とともに磁性坩堝に入れて燃焼し、常法
に従って硫酸バリウムとして分析し、Ｂａの量を測定す
る。(In the case of llBa element, take about 1 g of the sample in a 100 ml platinum dish, weigh it accurately, and hold it in an electric Matsufuru furnace at 400°C for 5 to 10 minutes.
Next, the furnace temperature is raised to 800°C and held for about 5 hours to burn and incinerate. After the ash is allowed to cool, 2 to 3 drops of concentrated sulfuric acid and about 10 ml of hydronic acid are added to it and heated to dryness, and the silica in the ash is removed by volatilization as SiF4. After repeating this operation three times, add 18N hydrochloric acid to the obtained solid for about 2 hours.
Add 0ml and heat to elute the hydrochloric acid soluble content, 1k5-
Filter using C filter paper. After washing the residue with 18N hydrochloric acid and hot water, it is placed in a magnetic crucible together with a filter paper and burned, and analyzed as barium sulfate according to a conventional method to measure the amount of Ba.
（２）Ｃａ元素及びＭｇ元素の場合
試料約１ｇを精秤し、５０ｍｌの５Ｎ塩酸を加えて１０
分間加熱し、冷却後容１１００ｍｌのメスフラスコでメ
スアップする。次いで階１３１濾祇で濾過した濾液を水
で希釈し、原子吸光分析によりＣａ及びＭｇの濃度を測
定する。(2) In the case of Ca element and Mg element, accurately weigh approximately 1 g of the sample, add 50 ml of 5N hydrochloric acid, and add 50 ml of 5N hydrochloric acid.
Heat for a minute, cool, and then make up the volume using a 1100 ml volumetric flask. Next, the filtrate filtered through the filtration filter No. 131 is diluted with water, and the concentrations of Ca and Mg are measured by atomic absorption spectrometry.
（１）熱膨張性黒鉛５ｇを１０５℃に設定された熱風循
環式乾燥器中に２時間保持する。(1) 5 g of thermally expandable graphite is held in a hot air circulation dryer set at 105° C. for 2 hours.
（２１（１）の処理を施した熱膨張性黒鉛１ｇを容ｆｆ
１ｌＱ Ｑｍｊ！の白金皿にとり、４００℃に設定され
た電気マツフル炉中に４５分間保持した後、炉よりとり
出し、デシケータ−中で３０分間放冷する。(1 g of thermally expandable graphite treated according to 21(1)
1lQ Qmj! The mixture was placed in a platinum plate and kept in an electric Matsufuru furnace set at 400°C for 45 minutes, then taken out from the furnace and left to cool in a desiccator for 30 minutes.
（３） （２１の処理後の熱膨張性黒鉛を７５０℃に
設定された電気マツフル炉に５分間保持した後、炉より
とり出し、デシケータ−中で１時間放冷する。このよう
に熱膨張性黒鉛を５分間加熱し、１時間放冷する操作を
繰返し、加熱時間の積算時間が１５分（加熱回数が３回
目）のときの放冷後の重量（ｍ、）及び３０分（加熱回
数が６回目）のときの放冷後の重Ｍ （ｍｚ ）を測定
し、次式のように加熱積算時間が１５分から３０分に至
る１５分間の重量減少速度を計算し、耐酸化性を示すパ
ラメーターとする。(3) (The thermally expandable graphite treated in step 21 is held in an electric Matsufuru furnace set at 750°C for 5 minutes, then taken out of the furnace and left to cool in a desiccator for 1 hour. Repeat the operation of heating the graphite for 5 minutes and leaving it to cool for 1 hour, and calculate the weight (m, ) after leaving it to cool when the cumulative heating time is 15 minutes (the 3rd heating time) and the weight (m, ) after 30 minutes (the number of heating times). (6th time), measure the weight M (mz) after standing to cool, calculate the weight loss rate for 15 minutes from 15 minutes to 30 minutes using the following formula, and show the oxidation resistance. Take it as a parameter.
重量減少速度が小さいほど耐酸化性が優れていることを
表わす。The smaller the weight loss rate, the better the oxidation resistance.
次に実施例により本発明をさらに詳細に説明するが、本
発明はその要旨をこえない限り以下の実施例に限定され
るものではない。なお、実施例中、部は重量部を示す。Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof. In addition, in the examples, parts indicate parts by weight.
実施例１〜６、比較例１〜３
固定炭素分９０％、灰分８％のカナダ産出の天然鱗片状
黒鉛（粒度：３６〜８０メツシユ）４００部を、９８％
硫酸１５００部と６０％過酸化水素水２０部の混合液に
加えて３０〜３５℃で１５分間反応させた。次いで反応
生成物に３０％硫酸１５００部を加えて希釈した後、ガ
ラス繊維濾紙（ＧＡｌｏｏ）を用いて吸引濾過した。得
られた残渣から５０部づつを６回に分けてとり、それぞ
れを６００部の水中に加えて３０秒間攪拌し洗浄した後
吸引濾過した。得られた６種類の残渣の各々からそれぞ
れ５部をとり、これらを熱風循環式乾燥器中で１０５℃
で２時間乾燥したものについてアルカリ滴定を行ない、
遊離硫酸の含有量を測定した。Examples 1 to 6, Comparative Examples 1 to 3 400 parts of natural flaky graphite (particle size: 36 to 80 mesh) produced in Canada with a fixed carbon content of 90% and an ash content of 8% was mixed with 98%
It was added to a mixed solution of 1,500 parts of sulfuric acid and 20 parts of 60% hydrogen peroxide solution, and reacted at 30 to 35°C for 15 minutes. Next, the reaction product was diluted by adding 1500 parts of 30% sulfuric acid, and then filtered with suction using glass fiber filter paper (GAloo). Fifty parts of the resulting residue were taken in six portions, each portion was added to 600 parts of water, stirred for 30 seconds, washed, and filtered with suction. Take 5 parts from each of the six types of residues obtained and dry them at 105°C in a hot air circulation dryer.
After drying for 2 hours, alkaline titration was carried out.
The content of free sulfuric acid was measured.
５部を分取した残りの残渣６種類のうち、４種類につい
てそれぞれ４０部をとり、乾燥処理を施さずにこれに１
０００部の水と第１表に示す種類及び量のアルカリ土類
金属化合物との混合物を加えて１０分間攪拌した後、ガ
ラス繊維濾紙（ＧＡｌｏｏ）を用いて吸引濾過し、得ら
れた残渣を熱風ｗｉ環式乾燥器中で１０５℃で９０分間
乾燥して熱膨張性黒鉛を得た。（実施例１〜４）また、
前記６種類の残渣の残りの２種類に対しては乾燥処理を
施さずに、それぞれに第１表に示す量の硝酸カルシウム
・４水塩（実施例５）及び炭酸カルシウム（実施例６）
を各々２０部のメタノール中ですりつぶして得られたス
ラリーを添加し、約１００℃のホットプレート上で攪拌
しながら乾燥した後、さらに熱風循環式乾燥話中で１０
５℃で２時間加熱して熱膨張性黒鉛を得た。Of the 6 types of residue remaining after separating 5 parts, 40 parts of each of 4 types were taken and 1 part was added to this without drying.
A mixture of 1,000 parts of water and an alkaline earth metal compound of the type and amount shown in Table 1 was added, stirred for 10 minutes, filtered with suction using glass fiber filter paper (GAloo), and the resulting residue was blown with hot air. Thermal expandable graphite was obtained by drying at 105° C. for 90 minutes in a wi-ring dryer. (Examples 1 to 4) Also,
The remaining two types of the six types of residues were not subjected to drying treatment, and were treated with calcium nitrate tetrahydrate (Example 5) and calcium carbonate (Example 6) in the amounts shown in Table 1.
The slurry obtained by grinding each in 20 parts of methanol was added, dried on a hot plate at about 100°C with stirring, and further dried for 10 parts in a hot air circulation dryer.
Thermal expandable graphite was obtained by heating at 5° C. for 2 hours.
一方、実施例１〜６と同様に原料黒鉛を酸処理後水洗、
濾過した残渣に、アルカリ土類金属化合物を添加せずに
乾燥させるか（比較例工）、或はアルカリ土類金属化合
物の代りにＮ１５苛性ソーダ水溶液（比較例２）又はＮ
１５アンモニア水（比較例３）を添加して熱膨張性黒鉛
を得た。On the other hand, similarly to Examples 1 to 6, raw graphite was treated with acid and then washed with water.
The filtered residue was dried without adding an alkaline earth metal compound (comparative example), or N15 caustic soda aqueous solution (comparative example 2) or N was added instead of the alkaline earth metal compound.
15 ammonia water (Comparative Example 3) was added to obtain thermally expandable graphite.
得られた熱膨張性黒鉛について、前述の方法に従ってア
ルカリ土類金属の含有量及び耐酸化性を測定した。結果
を第１表に示す。The alkaline earth metal content and oxidation resistance of the obtained thermally expandable graphite were measured according to the method described above. The results are shown in Table 1.
なお、比較例２の熱膨張性黒鉛については、その１ｇを
１００ｍ１のメスフラスコにとり、５０ｍ２の脱イオン
水を加えて１０分間振盪した後、脱イオン水を加えて１
００ｍｌにメスアップし、隘１３１の濾紙で濾過し、濾
液に塩酸を加えて常法に従い原子吸光分析によりＮａの
含有量を測定した。Regarding the thermally expandable graphite of Comparative Example 2, 1 g of it was placed in a 100 m volumetric flask, 50 m2 of deionized water was added, and the mixture was shaken for 10 minutes.
The volume was increased to 0.00 ml, filtered through a filter paper with a diameter of 131, hydrochloric acid was added to the filtrate, and the Na content was measured by atomic absorption spectrometry according to a conventional method.
本発明の熱膨張性黒鉛は、高温下で膨張させる際、酸化
燃焼による重量減少が少なく、これを可撓性黒鉛シート
等に加工する際の製品の歩留りが向上する。When the thermally expandable graphite of the present invention is expanded at high temperatures, there is little weight loss due to oxidative combustion, and the yield of products when processed into flexible graphite sheets and the like is improved.
Claims (1)
び有機酸塩よりなる群から選ばれた少なくとも１種のア
ルカリ土類金属化合物を含有していることを特徴とする
熱膨張性黒鉛。1. Thermal expandability characterized by containing at least one alkaline earth metal compound selected from the group consisting of alkaline earth metal oxides, hydroxides, inorganic acid salts, and organic acid salts. graphite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1008343A JPH02188418A (en) | 1989-01-17 | 1989-01-17 | Thermally expandable graphite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1008343A JPH02188418A (en) | 1989-01-17 | 1989-01-17 | Thermally expandable graphite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02188418A true JPH02188418A (en) | 1990-07-24 |
Family
ID=11690568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1008343A Pending JPH02188418A (en) | 1989-01-17 | 1989-01-17 | Thermally expandable graphite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02188418A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6406612B1 (en) | 1999-05-20 | 2002-06-18 | Graftech Inc. | Expandable graphite and method |
| US6669919B1 (en) | 2000-11-16 | 2003-12-30 | Advanced Energy Technology Inc. | Intercalated graphite flakes exhibiting improved expansion characteristics and process therefor |
| JP2004182593A (en) * | 2002-12-05 | 2004-07-02 | Hilti Ag | Method for controlling expansion characteristics of graphite sulfate particle freely expandable by heat and method for using it |
| JP2007063434A (en) * | 2005-08-31 | 2007-03-15 | Air Water Inc | Flame-retardant polymer composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5580711A (en) * | 1978-12-02 | 1980-06-18 | Teruhisa Kondo | Production of flexible graphite product |
| JPS583966B2 (en) * | 1979-10-29 | 1983-01-24 | 日本黒鉛工業株式会社 | Method for manufacturing graphite compression molded bodies for high-temperature packing |
| JPS6369705A (en) * | 1986-09-12 | 1988-03-29 | Sumitomo Metal Ind Ltd | Production of expanded graphite |
-
1989
- 1989-01-17 JP JP1008343A patent/JPH02188418A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5580711A (en) * | 1978-12-02 | 1980-06-18 | Teruhisa Kondo | Production of flexible graphite product |
| JPS583966B2 (en) * | 1979-10-29 | 1983-01-24 | 日本黒鉛工業株式会社 | Method for manufacturing graphite compression molded bodies for high-temperature packing |
| JPS6369705A (en) * | 1986-09-12 | 1988-03-29 | Sumitomo Metal Ind Ltd | Production of expanded graphite |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6406612B1 (en) | 1999-05-20 | 2002-06-18 | Graftech Inc. | Expandable graphite and method |
| US6669919B1 (en) | 2000-11-16 | 2003-12-30 | Advanced Energy Technology Inc. | Intercalated graphite flakes exhibiting improved expansion characteristics and process therefor |
| JP2004182593A (en) * | 2002-12-05 | 2004-07-02 | Hilti Ag | Method for controlling expansion characteristics of graphite sulfate particle freely expandable by heat and method for using it |
| JP2007063434A (en) * | 2005-08-31 | 2007-03-15 | Air Water Inc | Flame-retardant polymer composition |
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