JPH0588258B2 - - Google Patents
Info
- Publication number
- JPH0588258B2 JPH0588258B2 JP8037785A JP8037785A JPH0588258B2 JP H0588258 B2 JPH0588258 B2 JP H0588258B2 JP 8037785 A JP8037785 A JP 8037785A JP 8037785 A JP8037785 A JP 8037785A JP H0588258 B2 JPH0588258 B2 JP H0588258B2
- Authority
- JP
- Japan
- Prior art keywords
- membered heterocyclic
- oxidizing agent
- particles
- heterocyclic compound
- inorganic compound
- 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.)
- Expired - Lifetime
Links
- 239000002245 particle Substances 0.000 claims description 18
- 239000007800 oxidant agent Substances 0.000 claims description 17
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 16
- 150000002484 inorganic compounds Chemical class 0.000 claims description 14
- 229910010272 inorganic material Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 229920000128 polypyrrole Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- 150000000565 5-membered heterocyclic compounds Chemical class 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003233 pyrroles Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は複素５員環式化合物重合体組成物の製
造方法に関する。詳しくは無機化合物粒子上に複
素５員環式化合物重合体を担持させた組成物の製
造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a five-membered heterocyclic compound polymer composition. Specifically, the present invention relates to a method for producing a composition in which a five-membered heterocyclic compound polymer is supported on inorganic compound particles.
複素５員環式化合物が酸化剤によつて重合体を
生成することはすでに知られておりピロール及び
その誘導体が無機酸、塩化鉄、ベンゾキノン、オ
ゾンなどによりポリピロールを生成することが
Advances in Heterocyclic Chemistry 15巻、
67ページ（1973）に示されており、又、こうして
得られるポリピロールが不溶不融で成形が困難で
ある上にかさ比重も小さく取り扱いが固難である
という問題があり、これに対しては特開昭59−
168010で示されるような、特定の粒子状担体の存
在下にピロールを電解重合する方法が知られてい
る。
It is already known that five-membered heterocyclic compounds can form polymers when treated with oxidizing agents, and pyrrole and its derivatives can form polypyrroles when treated with inorganic acids, iron chloride, benzoquinone, ozone, etc.
Advances in Heterocyclic Chemistry Volume 15,
67 (1973), and the polypyrrole obtained in this way has the problem that it is insoluble and infusible, difficult to mold, and has a small bulk specific gravity, making it difficult to handle. 1977-
A method of electropolymerizing pyrrole in the presence of a specific particulate carrier, as shown in No. 168010, is known.
上述の粒子状担体の存在下にピロールを電解重
合する方法は特別な装置及び電解質を必要とする
問題があり、その上溶液中で反応させるため、重
合反応した後高価な電解質の回収再利用などに問
題があつた。
The above-mentioned method of electrolytically polymerizing pyrrole in the presence of a particulate carrier has the problem of requiring special equipment and an electrolyte, and on top of that, since the reaction is carried out in a solution, it is difficult to recover and reuse the expensive electrolyte after the polymerization reaction. There was a problem.
本発明者らは上記問題を解決して簡便に安価に
複素５員環式化合物重合体組成物を製造する方法
について鋭意検討した結果、特定の方法を採用す
ることで簡便に無機化合物粒子上に複素５員環式
化合物重合体を担持せしめた組成物が得られるこ
とを見い出し本発明を完成した。
The present inventors have conducted intensive studies on a method for easily and inexpensively producing a 5-membered heterocyclic compound polymer composition by solving the above problems. The present invention was completed by discovering that a composition supporting a polymer of a five-membered heterocyclic compound can be obtained.
即ち本発明は酸化剤を含浸させた粒子径が
0.01μm〜10mmの無機化合物粒子を複素五員環式
化合物を含む溶液と接触せしめることを特徴とす
る複素五員環式化合物重合体組成物の製造方法で
ある。 That is, in the present invention, the diameter of the particles impregnated with the oxidizing agent is
This is a method for producing a five-membered heterocyclic compound polymer composition, which comprises bringing inorganic compound particles of 0.01 μm to 10 mm into contact with a solution containing the five-membered heterocyclic compound.
本発明において担体となる無機化合物粒子とし
ては特に制限はなくどのようなものであつても良
く、金属の酸化物、水酸化物、炭酸塩が挙げら
れ、中でも、酸化物、例えば、酸化マグネシウ
ム、アルミナ、シリカ、酸化亜鉛、酸化鉄、酸化
チタン、酸化バリウム、それらの混合物および共
晶体が好ましい。共晶体としては例えばタルク、
マイカ、ハイドロタルサイト、それらを加熱処理
して結晶水或いは付着水を除去したものなどが示
される。 The inorganic compound particles serving as a carrier in the present invention are not particularly limited and may be of any kind, and include metal oxides, hydroxides, and carbonates. Among them, oxides such as magnesium oxide, Alumina, silica, zinc oxide, iron oxide, titanium oxide, barium oxide, mixtures and eutectics thereof are preferred. Examples of eutectics include talc,
Examples include mica, hydrotalcite, and those obtained by heat treatment to remove crystallized water or attached water.
上記無機化合物の粒子径としては0.01μm〜10
mmのものが使用でき、樹脂のフイラーとして利用
する場合は0.1〜1000μm程度、また触媒として流
動床式或いは固定床用に利用する場合は100μm〜
10mmのものを用いるのが好ましい。 The particle size of the above inorganic compound is 0.01 μm to 10
0.1 to 1000 μm when used as a resin filler, and 100 μm to 100 μm when used as a catalyst in a fluidized bed or fixed bed.
It is preferable to use one with a diameter of 10 mm.
本発明において使用する酸化剤としては、無機
酸、金属化合物が有効であり、硫酸、塩酸、硝
酸、クロルスルホン酸などが無機酸の具体例とし
て挙げられる。金属化合物としてはルイス酸とし
て知られる化合物が好ましく用いられ、アルミニ
ウム、錫、チタン、ジルコニウム、クロム、マン
ガン、鉄、銅、モリブデン、タングステン、ルテ
ニウム、パラジウム、白金等の金属の塩化物、硫
酸塩、硝酸塩、アセチルアセトナート化合物など
が具体例として挙げられる。その他の酸化剤とし
てベンゾキノン、ジアゾニウム塩などの有機化合
物も使用できる。これらの酸化剤は、１種あるい
は２種以上混合して用いることも可能である。特
に、鉄、チタンの塩化物、硫酸塩が好ましく用い
られる。 Inorganic acids and metal compounds are effective as the oxidizing agent used in the present invention, and specific examples of the inorganic acids include sulfuric acid, hydrochloric acid, nitric acid, and chlorosulfonic acid. As the metal compound, compounds known as Lewis acids are preferably used, and metal chlorides, sulfates, Specific examples include nitrates and acetylacetonate compounds. Organic compounds such as benzoquinone and diazonium salts can also be used as other oxidizing agents. These oxidizing agents may be used alone or in combination of two or more. In particular, chlorides and sulfates of iron and titanium are preferably used.
これらの酸化剤を上述の無機化合物粒子に含浸
せしめる方法としては、酸化剤と無機化合物粒子
を共粉砕する方法、酸化剤を溶解した溶液中に上
述の無機化合物粒子を分散混合し、次いで過或
いは溶媒を蒸発除去する方法、さらには酸化剤の
蒸気下に無機化合物を分散し、酸化剤を吸着せし
める方法などが挙げられる。 Methods for impregnating the above-mentioned inorganic compound particles with these oxidizing agents include a method of co-pulverizing the oxidizing agent and the inorganic compound particles, a method of dispersing and mixing the above-mentioned inorganic compound particles in a solution in which the oxidizing agent is dissolved, and then filtration or Examples include a method in which the solvent is removed by evaporation, and a method in which an inorganic compound is dispersed in the vapor of an oxidizing agent to adsorb the oxidizing agent.
酸化剤と無機化合物粒子の量比については特に
制限はないが、通常は無機化合物粒子に対し
0.0001〜1wt比であるのが一般的である。 There is no particular restriction on the ratio of the oxidizing agent to the inorganic compound particles, but it is usually
Generally, the ratio is 0.0001 to 1wt.
本発明において使用する複素五員環式化合物と
しては、ピロール、フラン、チオフエン及びそれ
らの誘導体が挙げられる。中でもピロール、Ｎ−
アルキルピロール、Ｎ−アリールピロール、３及
び／又は４位にアルキル基又はハロゲン原子の置
換したピロールなどのピロール誘導体が反応性の
点から有利である。 The five-membered heterocyclic compounds used in the present invention include pyrrole, furan, thiophene, and derivatives thereof. Among them, pyrrole, N-
Pyrrole derivatives such as alkylpyrrole, N-arylpyrrole, and pyrrole substituted with an alkyl group or a halogen atom at the 3- and/or 4-position are advantageous from the viewpoint of reactivity.
これらの複素五員環式化合物を上述の酸化剤を
含浸せしめた無機化合物粒子と接触させる際に用
いる溶媒としては、複素五員環式化合物が可溶で
かつ上記の酸化剤及び無機化合物粒子が難溶であ
るものなら特に制限はなく、脂肪族及び芳香族炭
化水素などの有機化合物が好ましく使用できる。
具体的には、ペンタン、ヘキサン、ヘプタン、デ
カンなどの脂肪族炭化水素或いはベンゼン、トル
エン、キシレン、エチルベンゼンなどの芳香族炭
化水素或いはそれらの混合物が挙げられる。 The solvent used when bringing these five-membered heterocyclic compounds into contact with the inorganic compound particles impregnated with the above-mentioned oxidizing agent is one that is soluble in the five-membered heterocyclic compound and that is compatible with the above-mentioned oxidizing agent and inorganic compound particles. There is no particular restriction as long as it is poorly soluble, and organic compounds such as aliphatic and aromatic hydrocarbons can be preferably used.
Specifically, aliphatic hydrocarbons such as pentane, hexane, heptane, and decane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; and mixtures thereof.
複素五員環式化合物と溶媒の混合比については
特に制限はないが、通常は溶媒に対して0.001〜
0.1wt比であるのが一般的である。 There is no particular restriction on the mixing ratio of the five-membered heterocyclic compound and the solvent, but it is usually 0.001 to 0.001 to the solvent.
Generally, the ratio is 0.1wt.
接触温度および時間についても特に制限はな
く、接触温度としては室温でも良く、接触時間に
ついては複素五員環式化合物重合体の比率が所望
の値となるよう任意に定めれば良い。 There are no particular limitations on the contact temperature and time, and the contact temperature may be room temperature, and the contact time may be arbitrarily determined so that the ratio of the five-membered heterocyclic compound polymer becomes a desired value.
本発明の組成物は導電性のフイラーとして無機
化合物粒子の機械的強度と複素五員環式化合物重
合体の導電性をあわせ持つ複合体として利用可能
であり、又、酸化剤を除去或いは除去することな
く複素五員環式化合物の触媒効果を利用した担持
型の接触としての用途が期待できる。
The composition of the present invention can be used as a conductive filler as a composite that has both the mechanical strength of inorganic compound particles and the conductivity of a five-membered heterocyclic compound polymer, and can also be used to remove or eliminate oxidizing agents. It can be expected to be used as a supported contact using the catalytic effect of five-membered heterocyclic compounds.
以下、実施例を挙げ本発明を説明する。 The present invention will be explained below with reference to Examples.
実施例 １
タルクの粉末（日本タルク株式会社製、グレー
ドMS）4.0ｇを塩化第二鉄1.0ｇと共粉砕し、酸
化剤含浸タルクを用意した。シクロヘキサン100
mlにピロール2.5mlを溶解し、撹拌しながら、上
記の酸化剤含浸タルクを少量ずつ加えた。３時間
反応した後生成した複合体を取し、シクロヘキ
サン20mlで３回洗浄し、未反応モノマーを除去し
た。その後乾燥して約0.6ｇのポリピロールを担
持した黒色粉末を得た。このものをそのまま500
Kg／cm2でプレス成形し、タブレート状とし、電気
電導度を四探針法で測定したところ、1.4×102Ω
cmであつた。Example 1 4.0 g of talc powder (manufactured by Nippon Talc Co., Ltd., grade MS) was co-pulverized with 1.0 g of ferric chloride to prepare talc impregnated with an oxidizing agent. Cyclohexane 100
2.5 ml of pyrrole was dissolved in 2.5 ml of pyrrole, and the above oxidizing agent-impregnated talc was added little by little while stirring. After reacting for 3 hours, the resulting complex was taken and washed three times with 20 ml of cyclohexane to remove unreacted monomers. Thereafter, it was dried to obtain a black powder supporting about 0.6 g of polypyrrole. 500 as is this thing
Kg/cm 2 was press-molded into a tablate shape, and the electrical conductivity was measured using the four-point probe method, and it was 1.4 × 10 2 Ω.
It was cm.
実施例 ２、３
無機化合物として、ケイ酸カルシウム（浅田製
粉株式会社製、実施例２）、炭酸カルシウム（竹
化学工業株式会社製、サンマイト＃800、実施例
３）を用いた他は実施例１と同様にし色の粒子を
それぞれ5.3ｇ、5.4ｇを得た。タブレツト状とし
たものの電気電導度はそれぞれ2.7×102Ωcm、3.4
×103Ωcmであつた。Examples 2 and 3 Example 1 except that calcium silicate (manufactured by Asada Seifun Co., Ltd., Example 2) and calcium carbonate (Manufactured by Take Kagaku Kogyo Co., Ltd., Sunmite #800, Example 3) were used as inorganic compounds. In the same manner as above, 5.3 g and 5.4 g of colored particles were obtained, respectively. The electrical conductivity of the tablet-shaped tablets is 2.7×10 2 Ωcm and 3.4, respectively.
It was ×10 3 Ωcm.
実施例 ４、５
無機化合物として、乾燥したシリカゲル（＃40
〜＃60、実施例４）、活性アルミナ粒子（実施例
５）をそれぞれ4.5ｇ用い、塩化第二鉄0.5ｇとメ
タノール中で混合した後にメタノールを蒸発させ
て酸化剤含浸担体を作り、その粒子を用いて実施
例１と同様に反応させた。得られた色粒子をソツ
クスレー抽出器を用いてメタノールで５時間抽出
して大部分の塩化第二鉄を除去し、乾燥して、そ
れぞれ4.9ｇ及び5.2ｇの組成物を得た。また、こ
れらの元素分析を行よたところＣ、Ｈ、Ｎの比は
73.4：4.9：21.7及び73.1：5.0：21.9であり、ポリ
ピロールが担持されていると推定できる。Examples 4 and 5 Dried silica gel (#40
~ #60, Example 4) and activated alumina particles (Example 5), 4.5 g each, were mixed with 0.5 g of ferric chloride in methanol, the methanol was evaporated, an oxidizing agent impregnated carrier was prepared, and the particles were mixed with 0.5 g of ferric chloride in methanol. The reaction was carried out in the same manner as in Example 1. The obtained colored particles were extracted with methanol using a Soxhlet extractor for 5 hours to remove most of the ferric chloride, and dried to obtain 4.9 g and 5.2 g of compositions, respectively. In addition, when these elemental analyzes were conducted, the ratio of C, H, and N was
73.4:4.9:21.7 and 73.1:5.0:21.9, and it can be assumed that polypyrrole is supported.
実施例 ６、７
複素五員環式化合物として、Ｎ−メチルピロー
ル（実施例６）、チオフエン（実施例７）を用い
た他は実施例１と同様にし、それぞれ黒色粉末を
5.5ｇ、5.2ｇ得た。タブレツトでの電気電導度は
それぞれ7.4×104Ωcm、1.8×105Ωcmであつた。Examples 6 and 7 The same procedure as in Example 1 was carried out except that N-methylpyrrole (Example 6) and thiophene (Example 7) were used as the five-membered heterocyclic compound, and black powder was used for each.
5.5g and 5.2g were obtained. The electrical conductivity of the tablet was 7.4×10 4 Ωcm and 1.8×10 5 Ωcm, respectively.
Claims (1)
の無機化合物粒子を複素五員環式化合物溶液と接
触せしめることを特徴とする複素五員環式化合物
重合体組成物の製造方法。1 Particle size impregnated with oxidizing agent is 0.01 μm to 10 mm
A method for producing a five-membered heterocyclic compound polymer composition, which comprises contacting inorganic compound particles with a five-membered heterocyclic compound solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8037785A JPS61238819A (en) | 1985-04-17 | 1985-04-17 | Production of composition of five-membered heterocyclic compound polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8037785A JPS61238819A (en) | 1985-04-17 | 1985-04-17 | Production of composition of five-membered heterocyclic compound polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61238819A JPS61238819A (en) | 1986-10-24 |
| JPH0588258B2 true JPH0588258B2 (en) | 1993-12-21 |
Family
ID=13716587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8037785A Granted JPS61238819A (en) | 1985-04-17 | 1985-04-17 | Production of composition of five-membered heterocyclic compound polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61238819A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3001408U (en) * | 1994-02-09 | 1994-08-30 | 株式会社シマノ | Top guide for hollow rods |
-
1985
- 1985-04-17 JP JP8037785A patent/JPS61238819A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3001408U (en) * | 1994-02-09 | 1994-08-30 | 株式会社シマノ | Top guide for hollow rods |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61238819A (en) | 1986-10-24 |
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