JPH02300216A - Inorganic graft compound - Google Patents
Inorganic graft compoundInfo
- Publication number
- JPH02300216A JPH02300216A JP12054889A JP12054889A JPH02300216A JP H02300216 A JPH02300216 A JP H02300216A JP 12054889 A JP12054889 A JP 12054889A JP 12054889 A JP12054889 A JP 12054889A JP H02300216 A JPH02300216 A JP H02300216A
- Authority
- JP
- Japan
- Prior art keywords
- inorganic
- grafting
- diacetylene
- diacetylene compound
- 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.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title abstract 3
- -1 diacetylene compound Chemical class 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 15
- 125000000962 organic group Chemical group 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 12
- 239000006229 carbon black Substances 0.000 abstract description 7
- 238000000465 moulding Methods 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 239000012298 atmosphere Substances 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 229910002804 graphite Inorganic materials 0.000 abstract description 2
- 239000010439 graphite Substances 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 8
- 229910010272 inorganic material Inorganic materials 0.000 description 8
- 239000011147 inorganic material Substances 0.000 description 8
- 230000009257 reactivity Effects 0.000 description 8
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000003708 ampul Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- PTZRYAAOQPNAKU-UHFFFAOYSA-N 2-[(1-carboxy-3-cyanobutyl)diazenyl]-4-cyanopentanoic acid Chemical compound N#CC(C)CC(C(O)=O)N=NC(C(O)=O)CC(C)C#N PTZRYAAOQPNAKU-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- ANUZKYYBDVLEEI-UHFFFAOYSA-N butane;hexane;lithium Chemical compound [Li]CCCC.CCCCCC ANUZKYYBDVLEEI-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- AKOJBFZCIRFXBA-UHFFFAOYSA-N hexa-1,3-diyne Chemical compound CCC#CC#C AKOJBFZCIRFXBA-UHFFFAOYSA-N 0.000 description 1
- PCTCNWZFDASPLA-UHFFFAOYSA-N hexa-2,4-diyne Chemical compound CC#CC#CC PCTCNWZFDASPLA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011172 small scale experimental method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、精密機械部品やエレクトロニクス分野で利用
できる剛性、硬度、線膨張率、熱伝導率等に優れた材料
を与える無機−グラフト化物に関するものである。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to an inorganic grafted material that provides a material with excellent rigidity, hardness, coefficient of linear expansion, thermal conductivity, etc. that can be used in precision mechanical parts and the electronics field. It is something.
本発明者らは、これまでに種々の多官能性ジアセチレン
系化合物を用いて三次元的に高密度に架橋させた高弾性
率成形体の開発を行なってきた。The present inventors have so far developed high-modulus molded bodies that are three-dimensionally crosslinked with high density using various polyfunctional diacetylene compounds.
共有結合を用いた架橋によって三次元的に高弾性率を発
現させるためには、架橋基密度を可能な限り高くし、且
つ架橋基を規則的にかつ高収率で反応させねばならない
。本発明者らは１．これまでに、架橋基密度が高く、架
橋基の反応性に富んだジアセチレン系化合物をアミド基
やエステル基とジアセチレン基や炭素−炭素二重結合を
組合せることで可能にし、これらの素材の優れた固相反
応性を利用して高弾性率を達成してきた。In order to express a high elastic modulus three-dimensionally by crosslinking using covalent bonds, the density of crosslinking groups must be made as high as possible, and the crosslinking groups must be reacted regularly and in high yield. The inventors 1. Until now, diacetylene compounds with high crosslinking group density and high crosslinking group reactivity have been made possible by combining amide groups or ester groups with diacetylene groups or carbon-carbon double bonds, and these materials have been developed. High elastic modulus has been achieved by utilizing the excellent solid phase reactivity of
その中で、本発明者らは、特に特許請求の範囲に示した
構造式を有するジアセチレン化合物が二重結合もジアセ
チレン基も良好な反応性を有することを見出した。Among them, the present inventors have particularly found that a diacetylene compound having the structural formula shown in the claims has good reactivity in both the double bond and the diacetylene group.
しかしながら、該ジアセチレン化合物は、その良好な反
応性故に成形条件や反応条件によっては、急激な分解を
生じ安全な成形という面において大きな問題が生じた。However, due to the good reactivity of the diacetylene compound, depending on the molding conditions and reaction conditions, the diacetylene compound may rapidly decompose, causing a serious problem in terms of safe molding.
もちろん、成形条件を緩和すれば分解反応は生じ難くな
るが、生産性は大巾に低下する。そこで、安定な成形を
可能にし、しかも生産性を損わない解決策が必要となっ
た。又、特に該ジアセチレン化合物が液状の場合、金型
からしみ出して均質化した成形体を与えにくいこともし
ばしば起った。Of course, if the molding conditions are relaxed, decomposition reactions will be less likely to occur, but productivity will drop significantly. Therefore, a solution was needed that would enable stable molding without sacrificing productivity. Moreover, especially when the diacetylene compound is liquid, it often oozes out of the mold, making it difficult to obtain a homogenized molded product.
本発明の目的は、成形性にすぐれ、且つ成形中に分解反
応が生じ難い、しかも成形体とした場合に優れた緒特性
（高弾性率、良好な硬さ、寸法安定性）を与えうるジア
セチレン化合物の誘導体すなわちグラフト化物を提供す
ることにある。The object of the present invention is to provide a molded product that has excellent moldability, is difficult to cause decomposition reactions during molding, and can provide excellent properties (high modulus of elasticity, good hardness, and dimensional stability) when formed into a molded product. An object of the present invention is to provide a derivative, ie, a grafted product, of an acetylene compound.
〔課題を解決するための手段］
本発明者らは、このような課題を解決するために、無機
物の表面に該ジアセチレン化合物をグラフト化すること
を考えた。[Means for Solving the Problems] In order to solve these problems, the present inventors considered grafting the diacetylene compound onto the surface of an inorganic substance.
無機物のぬれ性及び／又は親和性を良くするためには、
無機物の表面改質及び／又は表面処理を行うことが必要
である。表面処理した無機物に更に、ジアセチレン化合
物をグラフト化することを鋭意検討した結果、ジアセチ
レン化合物を無機物の表面にグラフト化できることを見
出し本発明に至ったものである。In order to improve the wettability and/or affinity of inorganic materials,
It is necessary to perform surface modification and/or surface treatment of the inorganic material. As a result of intensive study on grafting a diacetylene compound to the surface-treated inorganic material, the inventors discovered that it is possible to graft a diacetylene compound onto the surface of the inorganic material, leading to the present invention.
すなわち本発明は、一般式（１）で示されるジアセチレ
ン化合物を、無機物の表面にグラフト化した無機−グラ
フト化物
Ｒ−Ｘ−Ａ−ＣミＣ（、：（、−Ａ’ −Ｘ’ −Ｒ’
（１）（ここで、Ｒ，Ｒ’は炭素数が２から８までの
二重結合を有する有機基であり、ｘ、ｘ’は−ＯＣ−又
は−〇−であり、Ａ、Ａ’は炭素数が１から６までの有
機基を示す。）
を提供するものである。That is, the present invention provides an inorganic-grafted product R-X-A-C (,: (, -A'-X' - R'
(1) (Here, R, R' are organic groups having a double bond with 2 to 8 carbon atoms, x, x' are -OC- or -〇-, and A, A' are represents an organic group having 1 to 6 carbon atoms).
本発明において用いられる無機物は、特に制限はなく、
金属、金属の酸化物、硫化物、炭酸塩、リン酸塩、炭化
物など、及びカーボンブラック、カーボンファイバー、
黒鉛、カーボンウィスカーなどの炭素材料などが用いら
れ、これらが官能基を持っていればより好ましく゛、こ
のような官能基としては、例えば水酸基、カルボン酸基
、スルホン酸基等であり、官能基をもっている無機物と
しては、例えば金属酸化物、硫化物、カーボンブランク
、カーボンファイバー、カーボンウィスカー等である。The inorganic substance used in the present invention is not particularly limited,
Metals, metal oxides, sulfides, carbonates, phosphates, carbides, etc., carbon black, carbon fiber,
Carbon materials such as graphite and carbon whiskers are used, and it is preferable that these have functional groups. Examples of such functional groups include hydroxyl groups, carboxylic acid groups, and sulfonic acid groups. Examples of inorganic substances having groups include metal oxides, sulfides, carbon blanks, carbon fibers, and carbon whiskers.
本発明において、無機物の表面にジアセチレン化合物を
グラフト化する場合、まず無機物の表面から触媒あるい
は活性化剤を用いて直接的にグラフトする方法、あるい
は無機物表面にある官能基を用いてこれにグラフト重合
する方法、更にはいったんシランカップリング剤、チタ
ン系カップリング剤などの官能性カップリング剤で処理
し、次いでこれからグラフト重合する方法、特に好まし
くはアゾ基のようなラジカル開始剤を付加し、これより
グラフト重合する方法である。In the present invention, when grafting a diacetylene compound onto the surface of an inorganic material, first, grafting is performed directly from the surface of the inorganic material using a catalyst or activator, or grafting is performed using a functional group on the surface of the inorganic material. A method of polymerization, further a method of first treating with a functional coupling agent such as a silane coupling agent or a titanium-based coupling agent, and then graft polymerizing from this, particularly preferably adding a radical initiator such as an azo group, This is a method of graft polymerization.
シランカップリング剤を用いる方法においては、用いる
シランカップリング剤は通常用いられるシランカップリ
ング剤で良く、例えばビニルトリエトキシシラン、ビニ
ルトリメトキシシラン、Ｔ−メタクリロキシプロピルト
リメトキシシラン、γ−グリシドキシブロピルトリメト
キシシラン、Ｔ−グリシドキシプロビルメチルジエトキ
シシラン等である。また、ラジカル開始剤を付加する場
合には、例えば４．４′−アゾビス（４−シアノバレリ
ン酸Ｌｌ、１’−アゾビス（シクロへキサン−１−カル
ボニトリル）、２．２’−アゾビス（２，４−ジメチル
バレロニトリル）等が用いられる。In the method using a silane coupling agent, the silane coupling agent used may be a commonly used silane coupling agent, such as vinyltriethoxysilane, vinyltrimethoxysilane, T-methacryloxypropyltrimethoxysilane, γ-glyside. These include xybropyltrimethoxysilane, T-glycidoxypropylmethyldiethoxysilane, and the like. In addition, when adding a radical initiator, for example, 4,4'-azobis(4-cyanovaleric acid Ll, 1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2, 4-dimethylvaleronitrile), etc. are used.
本発明において、無機物の表面にグラフト化するジアセ
チレン化合物としては、一般式（１）で示されるジアセ
チレン化合物であり、Ｒ，Ｒ’は炭素数が２から８まで
の二重結合を有する有機基であり、その例としては、Ｃ
Ｉｌ□−Ｃ１１−、ＣＩｌ□＝Ｃ−Ｃ１１゜
Ｃ１１□＝（ＪＩＣｌｈ−、Ｃ１１３ＣＩｌ＝ＣＩ＋−
、ＣＩｈＣｌ１・ＣＩＩ ＣＩ＋□＝。In the present invention, the diacetylene compound to be grafted onto the surface of an inorganic substance is a diacetylene compound represented by the general formula (1), and R and R' are organic compounds having a double bond of 2 to 8 carbon atoms. A group, an example of which is C
Il□-C11-, CIl□=C-C11゜C11□=(JIClh-, C113CIl=CI+-
, CIhCl1・CII CI+□=.
ＣＩｌ□＝ＣＨＣＩＩ□ＣＩ＋□−、ＣＩｈ＝ＣＣｔ！
ｚ−。CIl□=CHCII□CI+□-, CIh=CCt!
z-.
ＣＨｚ＝ＣＩＩＣＩｈＣＩＩ□Ｃ１ｌ□−、Ｃ）１．Ｃ
１１＝ＣＩＩＣＩＩ□ＣＩ＋□＝。CHz=CIICIhCII□C1l□-, C)1. C
11=CIICII□CI+□=.
Ｃ１１Ｚ、Ｃ−
Ｃ８３ＣＨ２Ｃ旧ＣＩ−ＣＩＩ□Ｃｌｌ２ＣＩｌ□Ｃ１
１３゜１；ｌｈにｌＩ；に（ｌｈ−、ＣＩｈＣｌ１ 、
ＣＬ（二１１２にＨ３。C11Z, C- C83CH2C Old CI-CII□Cll2CIl□C1
13゜1; lh to lI; to (lh-, CIhCl1,
CL (H3 on 2112.
等が挙げられ、高い反応性を有するという点におＣＨ！
・ＣＨＣＨｚ−が好ましく、合成のしやすさも考えＣｌ
ｈ
す
ると、特にＣ１１，・Ｃ１１−、ＣＩｌ□・Ｃ−が好ま
しい。etc., and CH! has high reactivity.
・CHCHHz- is preferable, and considering ease of synthesis, Cl
h In this case, C11, .C11- and CIl□.C- are particularly preferred.
の場合、ＲとＡ及びＲ′とΔ′との結合様式には特に制
限はない。In the case of , there is no particular restriction on the bonding mode between R and A and between R' and Δ'.
Ａ、Ａ’は炭素数が１から６までの有機基を示し、その
例としては、−Ｃｌｈ−、＋ＣＩＩ□−）Ｔｒ士ＣＩ□
廿、イーＣ１１！＋ｉ−９士Ｃ１１□廿、千〇６廿。A and A' represent an organic group having 1 to 6 carbon atoms, examples of which include -Clh-, +CII□-)
廿, E-C11! ＋i-9士C11□廿, 1006廿.
特に、ジアセチレン基の反応性を高め、合成しゃすいと
いう点で−ＣＨ，−が好ましい。In particular, -CH,- is preferred because it increases the reactivity of the diacetylene group and facilitates synthesis.
本発明において、一般式（１）で示されるジアセチレン
化合物の合成については、例えば特開昭６２−２６７２
４８号公報や特開昭６２−２６７２５１号公報等に示さ
れる合成方法を用いて容易に、高収率で合成できる。又
、精製も通常のクロマト法、蒸留法、再結晶法等により
行うことができる。In the present invention, for the synthesis of the diacetylene compound represented by the general formula (1), for example, JP-A-62-2672
It can be easily synthesized in high yield using the synthesis methods shown in Japanese Patent Application Publication No. 48 and Japanese Patent Application Laid-Open No. 62-267251. Further, purification can also be carried out by conventional chromatography, distillation, recrystallization, etc.
本発明において、無機物にジアセチレン化合物をグラフ
ト化する場合、各種の公知のグラフ１−化方法が使用で
きるが、ここに−例を示すと、真空封管下や不活性ガス
下など重合を抑制することのない雰囲気下で一定時間熱
処理することによりグラフト化することができる。真空
封管法としては、通常の真空封管法を用いることができ
、少量実験の場合は、ガラスアンプル管に、無機物とジ
アセチレン化合物を入れ、次いで真空にした後、ガラス
アンプル管を溶着して行う方法が簡便に用いられる。工
業的には、真空下あるいはＮＺ＋ Ａｒなとの不活性ガ
ス雰囲気下で攪拌槽を用いて行うことができる。In the present invention, when grafting a diacetylene compound onto an inorganic substance, various known graphing methods can be used. Grafting can be achieved by heat treatment for a certain period of time in an atmosphere where there is no oxidation. As for the vacuum sealing method, the usual vacuum sealing tube method can be used.For small-scale experiments, put the inorganic substance and diacetylene compound into a glass ampoule tube, then evacuate it, and then weld the glass ampoule tube. This method is easily used. Industrially, it can be carried out using a stirring tank under vacuum or under an inert gas atmosphere such as NZ+Ar.
反応温度は特に制限がなく、反応の様式によって選択で
きるが、一般に一１０°Ｃ〜２００ ’Ｃの範囲が好ま
しく、より好ましくはジアセチレン化合物の反応性から
Ｏ′Ｃ〜１３０°Ｃである。また、反応時間は特に制限
はないが、好ましくは０．５〜２４時間である。反応終
了後、反応物を有機溶剤、例えばメタノール、エーテル
、アセトン、ジメチルスルホキシド等で抽出及び洗浄を
くり返した後、乾燥させて無機−グラフト化物を得るこ
とができる。The reaction temperature is not particularly limited and can be selected depending on the mode of reaction, but is generally preferably in the range of -10°C to 200°C, more preferably in the range of 0'C to 130°C in view of the reactivity of the diacetylene compound. Further, the reaction time is not particularly limited, but is preferably 0.5 to 24 hours. After the reaction is completed, the reaction product is repeatedly extracted and washed with an organic solvent such as methanol, ether, acetone, dimethyl sulfoxide, etc., and then dried to obtain an inorganic grafted product.
グラフト重合物の確認方法としては、溶剤抽出後、反応
物と原料の重量差を測定する方法、あるいは反応物のＴ
Ｇ／ＤＴＡ熱分析装置によって室温から６００″Ｃ以下
の温度で分解し重量減少する量をグラフト化した有機物
として測定するＴＧＡ法等で確認することができる。本
発明の場合は、この重量測定法、ＴＧＡ法を用いてグラ
フト重合物の確認を行った。The graft polymer can be confirmed by measuring the weight difference between the reactant and the raw material after solvent extraction, or by measuring the T of the reactant.
It can be confirmed by the TGA method, etc., which measures the amount of grafted organic matter that decomposes and loses weight at temperatures from room temperature to 600"C or less using a G/DTA thermal analyzer. In the case of the present invention, this gravimetric measurement method The graft polymer was confirmed using the TGA method.
本発明の無機−グラフト化物は、無機物の表面に、ジア
セチレン化合物をグラフト重合することによって、ジア
セチレン化合物の問題点である急激な分解反応性が抑制
でき、且っジアセチレン化合物の硬化収縮性についても
大きく改善できた。By graft polymerizing a diacetylene compound onto the surface of an inorganic material, the inorganic-grafted product of the present invention can suppress rapid decomposition reactivity, which is a problem with diacetylene compounds, and can reduce curing shrinkage of diacetylene compounds. We were also able to make significant improvements.
更に、無機−グラフト化物をジアセチレン化合物と混合
して板状、棒状、管状等に成形する場合、無機−グラフ
ト化物とジアセチレン化合物の親和性が良くなり均一な
成形体を得ることができる。Furthermore, when an inorganic grafted product is mixed with a diacetylene compound and molded into a plate, rod, tube, etc., the affinity between the inorganic grafted product and the diacetylene compound is improved and a uniform molded product can be obtained.
又、得られた成形体は、強度、弾性率、剛性、耐熱性等
に優れているために、精密機械部品、超音波関連機械部
品、エレクトロニクス分野に関する部品、Ｆ２！擦摩耗
材に関連する部品等に極めて有用である。In addition, the obtained molded product has excellent strength, elastic modulus, rigidity, heat resistance, etc., so it can be used as precision mechanical parts, ultrasonic-related mechanical parts, parts related to the electronics field, and F2! It is extremely useful for parts related to abrasion materials.
〔実施、比較例］
以下、本発明を実施例、比較例により詳細に説明するが
、本発明はこれらに限定されるものではない。[Execution and Comparative Examples] Hereinafter, the present invention will be explained in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
実施例１
無機物として酸化チタン（チタン工業製 ５ＴＴ−３０
）を用い、シランカップリング剤としてγ−グリシドキ
シプロピルトリメトキシシランの５％トルエン溶液を用
いて、１２０°Ｃの温度で８時間攪拌して処理した。更
にメタノールでソックスレー抽出した後、１００°Ｃで
２４時間乾燥した。Example 1 Titanium oxide (Titan Kogyo 5TT-30) was used as an inorganic substance.
), using a 5% toluene solution of γ-glycidoxypropyltrimethoxysilane as a silane coupling agent, and stirring at a temperature of 120° C. for 8 hours. After further Soxhlet extraction with methanol, it was dried at 100°C for 24 hours.
次に、アゾ基の導入を行なった。アゾ化剤は４３４′−
アゾビス（４−シアノバレリン酸）ヲ用いて、Ｔ−ピコ
リン少量とジメチルスルホキシドを溶剤として、５０°
Ｃの温度で攪拌しながら６時間反応させた。反応終了後
メタノールで洗浄し、室温で４８時間真空乾燥を行なっ
た。このように表面処理した酸化チタン３ｇと、ジアセ
チレン化合物として１，６ジアクリレート２．４へキサ
ジイン２ ｍｌをアンプル管に入れ真空封管した。これ
を７０°Ｃの温度で１６時間反応させた。反応終了後、
アセトンで洗浄し、室温で４８時間真空乾燥した。Next, an azo group was introduced. The azotizing agent is 434′-
Using azobis(4-cyanovaleric acid) and a small amount of T-picoline and dimethyl sulfoxide as a solvent, 50°
The reaction was allowed to proceed for 6 hours while stirring at a temperature of C. After the reaction was completed, it was washed with methanol and vacuum dried at room temperature for 48 hours. 3 g of titanium oxide surface-treated in this manner and 2 ml of 1,6 diacrylate 2.4 hexadiyne as a diacetylene compound were placed in an ampoule tube and sealed under vacuum. This was reacted at a temperature of 70°C for 16 hours. After the reaction is complete,
Washed with acetone and vacuum dried at room temperature for 48 hours.
グラフト化する前の酸化チタンの仕込み重量と反応終了
後の反応物の重量差から２５％の重量増加が認められた
。更に、反応物をＴＧ／ＤＴＡ熱重量分析装置によって
分析した結果、２４％の収率で付着物量が認められた。A 25% weight increase was observed from the difference between the weight of titanium oxide charged before grafting and the weight of the reactant after completion of the reaction. Further, as a result of analyzing the reaction product using a TG/DTA thermogravimetric analyzer, the amount of deposits was observed at a yield of 24%.
次に、無機−グラフト化物の分解挙動について調べた。Next, the decomposition behavior of the inorganic-grafted product was investigated.
ジアセチレン化合物と無機−グラフト化物を別々の容器
に入れ、次いで１５０°Ｃの温度に制御されたオイルバ
ス中に同時に浸漬した結果、数分後にジアセチレン化合
物はガスを発生しながら急激に分解した。しかし無機−
グラフト化物は、何ら変化は見られなかった。更に、オ
・イルバスの温度を２００°Ｃにしたが何ら変化は見ら
れなかった。The diacetylene compound and the inorganic-grafted product were placed in separate containers and then immersed simultaneously in an oil bath controlled at a temperature of 150°C. As a result, the diacetylene compound rapidly decomposed with gas generation after a few minutes. . But inorganic-
No change was observed in the grafted product. Further, the temperature of the oil bath was increased to 200°C, but no change was observed.
実施例２
無機物として、酸化ケイ素、酸化ジルコニウムを用いた
他は、実施例１と同様の方法で行なった。Example 2 The same method as in Example 1 was carried out except that silicon oxide and zirconium oxide were used as the inorganic substances.
各反応物のＴＧ／ＤＴＡ熱重量分析を行なった結果、酸
化ケイ素グラフト化物、酸化ジルコニウムグラフト化物
ともに重量減少が見られ、酸化ケイ素は４６％、酸化ジ
ルコニウムについては１８％の付着物量が認められた。As a result of TG/DTA thermogravimetric analysis of each reactant, a weight decrease was observed for both the silicon oxide grafted product and the zirconium oxide grafted product, and the amount of deposits was observed to be 46% for silicon oxide and 18% for zirconium oxide. .
実施例１と同様に分解性を調べた結果、両者ともに２０
０°Ｃ，２５０°Ｃの温度に置いて、分解したと思われ
る現象は全く見られなかった。一方、ジアセチレン化合
物だけでは、直ぐに分解が生じた。As a result of examining the degradability in the same manner as in Example 1, both were found to be 20
When placed at temperatures of 0°C and 250°C, no phenomena that appeared to have decomposed were observed. On the other hand, when the diacetylene compound alone was used, decomposition occurred immediately.
実施例３
無機物として、カーボンブラックを用いてジアセチレン
化合物のグラフト重合を試みた。Example 3 Graft polymerization of a diacetylene compound was attempted using carbon black as an inorganic substance.
ドライボックス中で、カーボンブラック１．０ｇをフラ
スコに秤りとり、その中へトルエン１０ｍ１を加え、よ
くかきまぜなからブチルリチウム１５％ヘキサン溶液１
ｄを添加して、カーボンブラック表面を１時間処理した
。次いで、該カーボンブラック分散液をＯ″Ｃに冷却し
た後、ｌ、６ジアクリレート２，４ヘキサジインを２ｄ
加えて８時間重合させた。In a dry box, weigh 1.0 g of carbon black into a flask, add 10 ml of toluene to it, stir well, and then add 1 ml of 15% butyl lithium hexane solution.
d was added and the carbon black surface was treated for 1 hour. Then, after cooling the carbon black dispersion to O''C, 2d of l,6 diacrylate 2,4 hexadiyne
In addition, polymerization was continued for 8 hours.
反応終了後、反応物をアセトンで洗浄し、室温で４８時
間真空乾燥した。After the reaction was completed, the reaction product was washed with acetone and vacuum-dried at room temperature for 48 hours.
グラフト重合物の確認として、反応前のカーボンブラッ
ク重量と反応後の重量差から、４２％の重量増加が認め
られた。更に、反応物をＴＧ／ＤＴＡ熱重量分析装置に
よって分析した結果、４０％の収率で付着物量が認めら
れた。As confirmation of the graft polymer, a 42% weight increase was observed based on the difference between the weight of the carbon black before the reaction and the weight after the reaction. Furthermore, as a result of analyzing the reaction product using a TG/DTA thermogravimetric analyzer, the amount of deposits was observed at a yield of 40%.
実施例１．２と同様に、反応物の分解性を調べた結果、
２００°Ｃ及び２５０°Ｃの温度雰囲気においても分解
する様子は見られなかった。一方ジアセチレン化合物だ
けでは、直ぐに分解が生じた。As in Example 1.2, the decomposition properties of the reactants were investigated, and the results were as follows:
No decomposition was observed even in the temperature atmosphere of 200°C and 250°C. On the other hand, when the diacetylene compound alone was used, decomposition occurred immediately.
Claims (1)
グラフト重合した無機−グラフト化物。 Ｒ−Ｘ−Ａ−Ｃ≡ＣＣ≡Ｃ−Ａ′−Ｘ′−Ｒ′（１）（
ここで、Ｒ、Ｒ′は炭素数が２〜８までの二重結合を有
する有機基であり、Ｘ、Ｘ′は ▲数式、化学式、表等があります▼又は−Ｏ−であり、
Ａ、Ａ′は炭素数が１から６までの有機基を示す。）[Scope of Claims] An inorganic-grafted product obtained by graft polymerizing a diacetylene compound represented by the general formula (1) onto an inorganic substance. R-X-A-C≡CC≡C-A'-X'-R' (1) (
Here, R and R' are organic groups having a double bond with 2 to 8 carbon atoms, and X and X' are ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or -O-,
A and A' each represent an organic group having 1 to 6 carbon atoms. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12054889A JPH0660226B2 (en) | 1989-05-16 | 1989-05-16 | Inorganic-grafted product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12054889A JPH0660226B2 (en) | 1989-05-16 | 1989-05-16 | Inorganic-grafted product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02300216A true JPH02300216A (en) | 1990-12-12 |
| JPH0660226B2 JPH0660226B2 (en) | 1994-08-10 |
Family
ID=14789032
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12054889A Expired - Fee Related JPH0660226B2 (en) | 1989-05-16 | 1989-05-16 | Inorganic-grafted product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0660226B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0391515A (en) * | 1989-09-05 | 1991-04-17 | Asahi Chem Ind Co Ltd | Molding of grafted inorganic substance |
-
1989
- 1989-05-16 JP JP12054889A patent/JPH0660226B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0391515A (en) * | 1989-09-05 | 1991-04-17 | Asahi Chem Ind Co Ltd | Molding of grafted inorganic substance |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0660226B2 (en) | 1994-08-10 |
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