JPS63195104A - Production of thermally expandable graphite - Google Patents
Production of thermally expandable graphiteInfo
- Publication number
- JPS63195104A JPS63195104A JP62026154A JP2615487A JPS63195104A JP S63195104 A JPS63195104 A JP S63195104A JP 62026154 A JP62026154 A JP 62026154A JP 2615487 A JP2615487 A JP 2615487A JP S63195104 A JPS63195104 A JP S63195104A
- Authority
- JP
- Japan
- Prior art keywords
- sulfuric acid
- thermally expandable
- expandable graphite
- slurry
- reaction
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000010439 graphite Substances 0.000 title claims abstract description 48
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 133
- 239000012066 reaction slurry Substances 0.000 claims abstract description 20
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract 3
- 239000012895 dilution Substances 0.000 abstract 1
- 238000010790 dilution Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 11
- 239000002699 waste material Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000283986 Lepus Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- -1 hydrogen peroxide Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 235000011835 quiches Nutrition 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は熱膨張性黒鉛の製造法に関するものであシ、詳
しくは熱膨張性黒鉛の製造に際し多量に使用される硫酸
を、価値ある副産物として回収する方法に関するもので
ある。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a method for producing thermally expandable graphite. Specifically, the present invention relates to a method for producing thermally expandable graphite. This article relates to a method of recovering wastewater.
〈従来技術〉
熱膨張性黒鉛の製造法は公知である。通常は濃硫酸に、
濃硝酸、過塩素酸、クロム酸、リン酸等の無機酸やその
塩類あるいは過酸化水素等の酸化剤を添加した反応液に
、天然黒鉛、キッシュ黒鉛、熱分解黒鉛等を浸漬して反
応させることによシ裂造される。生成した熱膨張性黒鉛
は多量の水を加えて水洗し、残余の反応液を充分に除去
した稜乾燥して製品とされる。<Prior Art> Methods for producing thermally expandable graphite are known. Usually concentrated sulfuric acid,
Natural graphite, Quiche graphite, pyrolytic graphite, etc. are immersed in a reaction solution containing inorganic acids such as concentrated nitric acid, perchloric acid, chromic acid, phosphoric acid, their salts, or oxidizing agents such as hydrogen peroxide, and allowed to react. Especially when it is broken. The generated thermally expandable graphite is washed with a large amount of water, and the remaining reaction liquid is sufficiently removed and the product is dried.
なかでも酸化剤として過酸化水素水を用いる方法は、酸
化剤に起因する有毒物質の発生が無く、がつ廃硫酸の処
理も容易なので工業的に有利な方法とされている（’Ｉ
？公昭≦Ｏ−お１９λ号参照）。Among these, the method of using hydrogen peroxide as an oxidizing agent is considered to be an industrially advantageous method because it does not generate toxic substances caused by the oxidizing agent and it is easy to treat waste sulfuric acid ('I
? Kimiaki ≦ O-O (see No. 19λ).
〈発明が解決しようとする問題点〉
熱膨張性黒鉛製造の際の問題点の一つは多量の廃硫酸が
排出されることである。硫酸は黒鉛に対して重量比で３
乃至１０倍も使用されるが、反応液を水洗によって除去
するため、廃硫酸が低濃度で用途が限定されている。<Problems to be Solved by the Invention> One of the problems in producing thermally expandable graphite is that a large amount of waste sulfuric acid is discharged. The weight ratio of sulfuric acid to graphite is 3
Although it is used 10 to 10 times more often, since the reaction solution is removed by washing with water, the concentration of waste sulfuric acid is low and its uses are limited.
〈問題点を解決するための手段〉
本発明は、生成した熱膨張性黒鉛を反応液から分離する
際に、反応スラリーを希硫酸と混合し廃硫酸を高濃度で
回収するものである。すなわち本発明によれば、−硫啼
とば化剤を混合した反応液と黒鉛を反応させ、生成した
熱膨張性黒鉛を含む反応スラリーから所望によりｍ硫酸
の一部を分離した後、これに希硫酸を混合して低粘度ス
ラリーとし、これを熱膨張性黒鉛と硫り
酸とに分離することによフ、熱膨張性黒鉛％製造すると
同時に廃硫酸を高Ａｌで回収することができる。<Means for Solving the Problems> In the present invention, when the generated thermally expandable graphite is separated from the reaction liquid, the reaction slurry is mixed with dilute sulfuric acid to recover waste sulfuric acid at a high concentration. That is, according to the present invention, a reaction solution mixed with a sulfuric acid and graphite is reacted, and a part of m-sulfuric acid is optionally separated from the generated reaction slurry containing thermally expandable graphite. By mixing dilute sulfuric acid to form a low-viscosity slurry and separating this into thermally expandable graphite and sulfuric acid, it is possible to produce thermally expandable graphite and at the same time recover waste sulfuric acid with a high Al content.
液と黒鉛との反応自体は温性に従って行われる。The reaction itself between the liquid and graphite takes place according to the temperature.
たとえば、酸化剤として過酸化水素を用いる場合には、
黒鉛１００部（重量部、本明細書においては峙記しない
限）、部は重量部を意味する）を、−〜ご部の過酸化水
素水（Ｈ２Ｏ２換算）を含む濃硫酸３００−１００部中
に投入し、攪拌しながら数十分〜１時間程度保持すれば
よい。For example, when using hydrogen peroxide as the oxidizing agent,
100 parts of graphite (parts by weight, unless otherwise specified herein, parts mean parts by weight) in 300-100 parts of concentrated sulfuric acid containing ~ parts of hydrogen peroxide (H2O2 equivalent) It is sufficient to put the mixture into a container and hold it for about several tens of minutes to about 1 hour while stirring.
反応によシ生成した熱膨張性黒鉛と濃硫酸とから成る反
応スラリーは、擬塑性流体であシ粘度が高く、熱膨張性
黒鉛と濃硫酸の比重も違わないため、両者の分離が困難
である。本発明では、この反応スラリーに希硫酸を混合
して、反応スラリー中の硫酸濃度を低下させる。硫酸濃
度を低下させることにより、スラリーの粘度は低下し、
比重差も大きくなシ、かつスラリー濃度も低下して取扱
が容易になる６反応スラリーに対する希硫酸の混合北軍
および希硫酸の濃度は、低粘度スラリー中の硫酸濃度お
よびスラリー一度が目標の値となるように設定する０通
常は回収硫酸の濃度が６０％以上、好ましくは６０〜♂
Ｏ％となるように希硫酸を混合する。The reaction slurry consisting of thermally expandable graphite and concentrated sulfuric acid produced by the reaction is a pseudoplastic fluid with high viscosity, and the specific gravity of thermally expandable graphite and concentrated sulfuric acid is the same, so it is difficult to separate the two. be. In the present invention, dilute sulfuric acid is mixed with this reaction slurry to reduce the sulfuric acid concentration in the reaction slurry. By reducing the sulfuric acid concentration, the viscosity of the slurry decreases,
The difference in specific gravity is large, and the slurry concentration is also reduced, making it easier to handle 6. Mixing dilute sulfuric acid with the reaction slurry and the concentration of dilute sulfuric acid are the target values for the sulfuric acid concentration in the low viscosity slurry and the slurry once. Set so that the concentration of recovered sulfuric acid is usually 60% or more, preferably 60~♂
Dilute sulfuric acid is mixed so that the amount is 0%.
希硫酸としては、通常３０〜６０％硫酸を用いる。低粘
度スラリーは常用の一過装置で熱膨張性黒鉛と硫酸に分
離され、熱膨張性黒鉛は水洗、中和等の工程をへて、乾
燥され製品とされる。As the dilute sulfuric acid, 30 to 60% sulfuric acid is usually used. The low-viscosity slurry is separated into thermally expandable graphite and sulfuric acid using a commonly used passing-through device, and the thermally expandable graphite is washed with water, neutralized, etc., and then dried to form a product.
本発明の好ましい実施態様の一つにおいては、低粘度ス
ラリーから熱膨張性黒鉛を分離して得られた回収硫酸の
一部を所定の濃度に希釈して、反応スラリーと混合する
希硫酸として用いる。In one of the preferred embodiments of the present invention, a part of the recovered sulfuric acid obtained by separating thermally expandable graphite from a low viscosity slurry is diluted to a predetermined concentration and used as diluted sulfuric acid to be mixed with the reaction slurry. .
またこの際、回収硫酸の希釈を、熱膨張性黒鉛の水洗工
程から得られる極〈薄い硫酸で行うと、全体で回収され
る硫酸の回収率を最大にすることができる。Furthermore, at this time, if the recovered sulfuric acid is diluted with extremely dilute sulfuric acid obtained from the step of washing thermally expandable graphite with water, the overall recovery rate of sulfuric acid recovered can be maximized.
本発明の更に好ましい実施態様の一つにおいては、反応
スラリーを希硫酸と混合する前に、真空濾過装置や遠心
分離ａ等てあらく固液分離して硫酸の一部をｍｔ晦酸と
して回収し、次いでｌＡりのｍ硫酸と熱膨張性黒鉛との
混合物を希硫酸と混合して低粘度スラリーとし、ζｎか
ら６０〜？θ％（ｌｉｉｔ酸を回収する。このようにし
て回収さｎた濃硫酸は、発煙ａｍ等で濃度調整し、再び
反応に供することができる。In one of the more preferred embodiments of the present invention, before mixing the reaction slurry with dilute sulfuric acid, a portion of the sulfuric acid is recovered as mt acetic acid by performing solid-liquid separation using a vacuum filtration device or centrifugation a. Then, a mixture of lA m sulfuric acid and thermally expandable graphite is mixed with dilute sulfuric acid to form a low viscosity slurry, and the ζn is 60~? The concentrated sulfuric acid thus recovered can be adjusted in concentration with a fuming ampere or the like and subjected to the reaction again.
〈実施例〉
次に本発明を実施例により更に具体的に説明するが、本
発明は以下の実施例に限定されるものではない。なお、
以下の実施例においては、生成した熱膨張性黒鉛を評価
する方法として膨張度を用いている。膨張度は、単位重
量の熱膨張性黒鉛が急激々加熱によシどの位の体積に膨
張するかを示したもので、測定は試料を目盛付きの石英
管に入れ、これを７０００℃に保持されている電気炉中
に装入し膨張させ、その体積を石英管の目盛で読取るこ
とによって行われる。<Examples> 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. In addition,
In the following examples, the degree of expansion is used as a method for evaluating the generated thermally expandable graphite. The degree of expansion indicates how much volume a unit weight of thermally expandable graphite expands due to rapid heating.Measurement is carried out by placing a sample in a quartz tube with a scale and holding it at 7000℃. This is done by charging the tube into an electric furnace, allowing it to expand, and reading its volume on a scale on a quartz tube.
実施例／
粒度３２〜１０θメツシユのマダガスカル産焦鉛／θθ
部を、り／％濃硫ＩＭ３６０部と６０−過酸化水素水？
、！部で調整した反応液（約７０℃）に約７０分間で投
入し、その後−２０分間放置した。反応スラリーは１０
？θ部の６１％硫酸中に投入した。７０分間攪拌を行つ
九のぢ一過して約６ｒ％濃度の硫酸７２００部を回収し
た。熱膨張性黒鉛は水洗し、次いでアンモニア水で中和
した後、１００±３℃の温度で乾燥した。このものの膨
張度はコ／ ｏ 〔ｘｉ／ｊｌであった。Example / Madagascar scorched lead with particle size of 32 to 10 θ mesh / θθ
360 parts of concentrated sulfur IM and 60 parts of hydrogen peroxide?
,! The mixture was poured into a reaction solution (approximately 70° C.) prepared in 20 minutes for approximately 70 minutes, and then left to stand for -20 minutes. The reaction slurry is 10
? It was put into 61% sulfuric acid in the θ section. After 90 minutes of stirring for 70 minutes, 7200 parts of sulfuric acid with a concentration of about 6% was recovered. The thermally expandable graphite was washed with water, then neutralized with aqueous ammonia, and then dried at a temperature of 100±3°C. The degree of expansion of this material was ko/o [xi/jl.
実施例コ
実施例／と全く同様にして反応を行った後、反応スラリ
ーは真空ヌツチェによって戸遇し、濃硫酸７２０部を回
収した。炉滓は１４１０部の！ｒチ硫酸中に投入し、７
０分間攪拌を行ったのち再び真空ヌツテエで濾過し、約
６？チ濃度の硫酸１０θ部を回収した。熱膨張性黒鉛は
、実施例／と全く同様に後処理した。このものの膨張度
は、／り０〔Ｉｔｌ／ｌ〕であった。Example 4 After carrying out the reaction in exactly the same manner as in Example 1, the reaction slurry was passed through a vacuum nutsche, and 720 parts of concentrated sulfuric acid was recovered. There are 1410 pieces of furnace slag! Put it into sulfuric acid,
After stirring for 0 minutes, it was filtered again using a vacuum filter, and the mixture was stirred for about 6 minutes. 10θ parts of sulfuric acid with a concentration of The thermally expandable graphite was post-treated in exactly the same manner as in Example. The swelling degree of this product was 0 [Itl/l].
次に、上記で回収した７２０部の濃硫酸を、発煙硫酸と
濃硫酸で９／％に＃度調整したものを用いて、上記と全
く同様の操作を繰り返し、回収した濃硫酸の使用が熱膨
張性黒鉛の膨張度へ及ぼす影響を調べた。表−／にその
結果を示す。Next, using 720 parts of the concentrated sulfuric acid recovered above, which was adjusted to 9% with fuming sulfuric acid and concentrated sulfuric acid, the same operation as above was repeated, and the use of the recovered concentrated sulfuric acid was heated. The influence of expandable graphite on the degree of expansion was investigated. The results are shown in Table-/.
表−／ 繰シ返し反応の影響
表−／から明らかなように、回収された濃硫酸を含む硫
陽を用いて反応を行なっても、生成する熱膨張性黒鉛に
は殆んど悪影響を与えない。As is clear from Table - / Effect of repeated reactions - /, even if the reaction is carried out using sulfur chloride containing recovered concentrated sulfuric acid, it has almost no adverse effect on the thermally expandable graphite produced. do not have.
〈効 果〉
本発明によれば、反応に供した硫酸奢価値の高い比較的
高濃度の硫酸として回収することができる。また、反応
スラリーから濃硫酸を回収して再使用すると、上記に加
えて反応に供する新しい硫酸の食を角）約することがで
きる。<Effects> According to the present invention, the sulfuric acid used in the reaction can be recovered as relatively highly concentrated sulfuric acid with a high value. Furthermore, if concentrated sulfuric acid is recovered from the reaction slurry and reused, in addition to the above, the amount of fresh sulfuric acid used in the reaction can be saved.
９１出願人 日本化成株式会社 代 理 人 弁理士 長谷用 − ほか／名91 Applicant: Nippon Kasei Co., Ltd. Representative Patent Attorney Hase - Others/names
Claims (6)
せ、生成した熱膨張性黒鉛を含む反応スラリーから所望
により濃硫酸の一部を分離した後、これに希硫酸を混合
して低粘度スラリーとし、これを熱膨張性黒鉛と硫酸と
に分離することを特徴とする熱膨張性黒鉛の製造法。(1) A reaction mixture of concentrated sulfuric acid and an oxidizing agent is reacted with graphite, and a portion of the concentrated sulfuric acid is optionally separated from the generated reaction slurry containing thermally expandable graphite, and then diluted sulfuric acid is mixed therewith. A method for producing thermally expandable graphite, which is characterized by forming a low-viscosity slurry and separating this into thermally expandable graphite and sulfuric acid.
法において、低粘度スラリーから分離された硫酸の一部
を水ないしは薄い硫酸と混合したものを反応スラリーと
混合する希硫酸として用いることを特徴とする熱膨張性
黒鉛の製造法。(2) In the method for producing thermally expandable graphite according to claim 1, a portion of the sulfuric acid separated from the low viscosity slurry is mixed with water or dilute sulfuric acid as dilute sulfuric acid to be mixed with the reaction slurry. A method for producing thermally expandable graphite, characterized in that it is used.
法において、低粘度スラリーから分離された熱膨張性黒
鉛を水洗して得た３０（重量）％濃度以下の薄い硫酸を
反応スラリーと混合する希硫酸の調整に用いることを特
徴とする熱膨張性黒鉛の製造法。(3) In the method for producing thermally expandable graphite according to claim 2, dilute sulfuric acid with a concentration of 30% (by weight) or less obtained by washing thermally expandable graphite separated from a low viscosity slurry with water is reacted. A method for producing thermally expandable graphite, which is characterized in that it is used for adjusting dilute sulfuric acid to be mixed with a slurry.
記載の熱膨張性黒鉛の製造法において、低粘度スラリー
から分離回収される硫酸の濃度が少なくとも６０（重量
）％以上となるように反応スラリーに希硫酸を混合する
ことを特徴とする熱膨張性黒鉛の製造法。(4) In the method for producing thermally expandable graphite according to any one of claims 1 to 3, the concentration of sulfuric acid separated and recovered from the low viscosity slurry is at least 60% (by weight) or more. A method for producing thermally expandable graphite, which is characterized by mixing dilute sulfuric acid with a reaction slurry.
記載の熱膨張性黒鉛の製造法において、反応スラリーか
ら濃硫酸の一部を分離した後、希硫酸と混合することを
特徴とする熱膨張性黒鉛の製造法。(5) The method for producing thermally expandable graphite according to any one of claims 1 to 4, characterized in that after separating a portion of concentrated sulfuric acid from the reaction slurry, it is mixed with dilute sulfuric acid. A method for producing thermally expandable graphite.
法において、反応スラリーから回収した濃硫酸を、反応
液の一部として用いることを特徴とする熱膨張性黒鉛の
製造法。(6) A method for producing thermally expandable graphite according to claim 5, characterized in that concentrated sulfuric acid recovered from the reaction slurry is used as a part of the reaction liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62026154A JPH0788208B2 (en) | 1987-02-06 | 1987-02-06 | Method for producing thermally expandable graphite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62026154A JPH0788208B2 (en) | 1987-02-06 | 1987-02-06 | Method for producing thermally expandable graphite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63195104A true JPS63195104A (en) | 1988-08-12 |
| JPH0788208B2 JPH0788208B2 (en) | 1995-09-27 |
Family
ID=12185615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62026154A Expired - Fee Related JPH0788208B2 (en) | 1987-02-06 | 1987-02-06 | Method for producing thermally expandable graphite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0788208B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5132171A (en) * | 1990-07-06 | 1992-07-21 | Sanwa Kako Company Limited | Non-flammable open-cell cross-linked polyolefin foam and method for production thereof |
| CN1039801C (en) * | 1993-11-05 | 1998-09-16 | 宋克敏 | Manufacturing method of low-sulfur expansible black lead |
-
1987
- 1987-02-06 JP JP62026154A patent/JPH0788208B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5132171A (en) * | 1990-07-06 | 1992-07-21 | Sanwa Kako Company Limited | Non-flammable open-cell cross-linked polyolefin foam and method for production thereof |
| CN1039801C (en) * | 1993-11-05 | 1998-09-16 | 宋克敏 | Manufacturing method of low-sulfur expansible black lead |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0788208B2 (en) | 1995-09-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |