JPH01254709A - Crosslinked product containing diacetylene linkage - Google Patents
Crosslinked product containing diacetylene linkageInfo
- Publication number
- JPH01254709A JPH01254709A JP8134088A JP8134088A JPH01254709A JP H01254709 A JPH01254709 A JP H01254709A JP 8134088 A JP8134088 A JP 8134088A JP 8134088 A JP8134088 A JP 8134088A JP H01254709 A JPH01254709 A JP H01254709A
- Authority
- JP
- Japan
- Prior art keywords
- hydrocarbon group
- polymerization
- bond
- crosslinked product
- diacetylene
- 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
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 title 1
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- -1 acrylic ester Chemical class 0.000 abstract description 6
- 239000000047 product Substances 0.000 abstract description 6
- 239000000178 monomer Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 239000007870 radical polymerization initiator Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 230000005587 bubbling Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 2
- 230000008878 coupling Effects 0.000 abstract 2
- 238000010168 coupling process Methods 0.000 abstract 2
- 238000005859 coupling reaction Methods 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 2
- 230000003647 oxidation Effects 0.000 abstract 2
- 238000007254 oxidation reaction Methods 0.000 abstract 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 abstract 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 abstract 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 abstract 1
- 229910001882 dioxygen Inorganic materials 0.000 abstract 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003708 ampul Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VWXLCWNPSOUPPE-UHFFFAOYSA-N (1-amino-2-methylpropylidene)azanium;chloride Chemical compound Cl.CC(C)C(N)=N VWXLCWNPSOUPPE-UHFFFAOYSA-N 0.000 description 1
- YFZCNXJOYHYIGC-UHFFFAOYSA-N (2,2,2-trichloroacetyl) 2,2,2-trichloroethaneperoxoate Chemical compound ClC(Cl)(Cl)C(=O)OOC(=O)C(Cl)(Cl)Cl YFZCNXJOYHYIGC-UHFFFAOYSA-N 0.000 description 1
- NSYCJGRIGHDEMT-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-(1,1,2,2,3,3,4,4,4-nonafluorobutylperoxy)butane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)OOC(F)(F)C(F)(F)C(F)(F)C(F)(F)F NSYCJGRIGHDEMT-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-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
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000002794 monomerizing effect Effects 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【発明の詳細な説明】
（発明の利用技術分野）
本発明は、精密機械やエレクトロニクス分野で利用でき
る硬化反応性に優れた新規な架橋性素材としてのジアセ
チレン結合を含存した重合物に関するものである。Detailed Description of the Invention (Technical Field of Application of the Invention) The present invention relates to a polymer containing diacetylene bonds as a novel crosslinkable material with excellent curing reactivity that can be used in precision machinery and electronics fields. It is.
（従来技術）
近年、ジアセチレン結合の固相反応性が注目され、学術
的研究から各種の応用まで幅広く研究されている。これ
らの研究の多くは、ジアセチレン結合のトポ°ケミカル
反応に着目したものであるが、一方熱硬化性樹脂の架橋
基として用いた例もある。(Prior Art) In recent years, the solid phase reactivity of diacetylene bonds has attracted attention and has been widely studied from academic studies to various applications. Most of these studies have focused on topochemical reactions of diacetylene bonds, but there are also examples of their use as crosslinking groups in thermosetting resins.
（発明が解決しようとする問題点）
しかし、未だジアセチレン結合を持つ化合物の種類は多
いとは言えず、ジアセチレン結合の有するポテンシャル
を充分に引き出してはいない。本発明者らは、化学的架
橋によって共有結合からなる緻密なネットワークを形成
させ、３次元的な高弾性率体とするため、ジアセチレン
結合を架橋基として用いることを検討してきた。(Problems to be Solved by the Invention) However, there are still not many types of compounds having diacetylene bonds, and the potential of diacetylene bonds has not been fully exploited. The present inventors have investigated the use of diacetylene bonds as crosslinking groups in order to form a dense network consisting of covalent bonds through chemical crosslinking, resulting in a three-dimensional high elastic modulus body.
その結果、側鎖にジアセチレン結合のあるポリアクリル
酸エステル系の架橋体が、硬化反応性に優れた素材であ
ることを見い出し、更に鋭意検討の結果、本発明に到っ
た。As a result, it was discovered that a crosslinked polyacrylate ester having diacetylene bonds in the side chain is a material with excellent curing reactivity, and as a result of further intensive studies, the present invention was arrived at.
（問題点を解決するための手段）
即ち、本発明は一般式（１）で表わされる分子骨格を構
造単位として含有したジアセチレン結合を含む架橋体
吉・
占
（ここで、Ｘｌ＋ Ｘ、Ｘ、、Ｘ、’ 、Ｘ２’ 、
Ｘ３’は水素原子又は１価の炭化水素基、Ｒ，Ｒ’は２
価の炭化水素基を表わす）を提供するものである。(Means for Solving the Problems) That is, the present invention provides a cross-linked compound containing a diacetylene bond containing the molecular skeleton represented by the general formula (1) as a structural unit (herein, Xl + X, X, ,X,',X2',
X3' is a hydrogen atom or a monovalent hydrocarbon group, R and R' are 2
(representing a valent hydrocarbon group).
本発明において、−形成（１）中のＸ、、Ｘ、。In the present invention - X, , X, in the formation (1).
Ｘ ３＋ ＸＩ’ ＋ Ｘ２′＋ Ｘ３′は水素原子
又は１価の炭化水素基である。それを例示すると、Ｈ、
ＣＨ３、ＣｚＨｓ 、 Ｃ３ＨＴ 。X 3+ XI' + X2'+ X3' is a hydrogen atom or a monovalent hydrocarbon group. To illustrate, H,
CH3, CzHs, C3HT.
れる。また、Ｘ＋、Ｘｚ、Ｘ３．ＸＩ’ 、Ｘ２’ 、
Ｘ３’中の水素原子又は炭化水素基が他の結合に置換さ
れていてもよく、その結合手としてはエーテル結合、エ
ステル結合、アミド結合、イミド結合、アミノ結合、イ
ミノ結合、ウレタン結合等が挙げられる。その結合手を
有する炭化水素基を例示すると、
更に、ｘ、、ｘ２．ｘ、、ｘ、’ 、ｘ２’ 、ｘ、’
中の水素原子のいくつかが、ニトロ基、水酸基、シアノ
基、カルボキシル基、アミノ基、ハロゲン原子等で置換
されていてもよい。その際のＸ＋。It will be done. Also, X+, Xz, X3. XI', X2',
The hydrogen atom or hydrocarbon group in X3' may be substituted with another bond, and examples of the bond include an ether bond, ester bond, amide bond, imide bond, amino bond, imino bond, urethane bond, etc. It will be done. Examples of hydrocarbon groups having such bonds include x, , x2. x,,x,',x2',x,'
Some of the hydrogen atoms therein may be substituted with nitro groups, hydroxyl groups, cyano groups, carboxyl groups, amino groups, halogen atoms, etc. X+ at that time.
Ｘｚ、Ｘｚ、Ｘ＋’ 、Ｘｚ’ 、Ｘ３’を例示するな
らば、）１０−ＣＨ２−、ＨＯ士ＣＨｚす「。To illustrate Xz, Xz, X+', Xz', and X3', 10-CH2-, HO CHZ".
本発明において、−ｉ式（Ｉ）中のＲ，Ｒ’は２価の炭
化水素基である。In the present invention, R and R' in -i formula (I) are divalent hydrocarbon groups.
その例としては、 ＣＨ２、Ｃ２Ｈ４−１及び脂環式基
の複合した基が挙げられ、これらのＲ，Ｒ’中の水素原
子のいくつかが、ハロゲン原子、ニトロ基、水酸基、シ
アノ基、カルボキシル基、アミノ基、アミド基、エステ
ル基、カルボニル基、エーテル結合を有する基（例えば
アルコキシル基）等で置換されていてもよい。Examples include complex groups of CH2, C2H4-1, and alicyclic groups, in which some of the hydrogen atoms in R and R' are halogen atoms, nitro groups, hydroxyl groups, cyano groups, and carboxyl groups. It may be substituted with a group, an amino group, an amide group, an ester group, a carbonyl group, a group having an ether bond (for example, an alkoxyl group), or the like.
また、当該炭化水素基は、エーテル結合、スルホニル結
合、エステル結合、カルボニル結合等で結ばれてなる炭
化水素基でも良く、この具体例を挙げると
等がある。Further, the hydrocarbon group may be a hydrocarbon group connected by an ether bond, a sulfonyl bond, an ester bond, a carbonyl bond, etc., and the following are specific examples thereof.
これらのＲ，Ｒ’のうち好ましいのは、合成のしやすさ
と耐熱性の良さから、
が好ましい。Among these R and R', the following are preferable because of ease of synthesis and good heat resistance.
本発明における重合体は、−形成（Ｉ）で表わされる分
子骨格を構造単位として含有した重合体である。本発明
における重合体において、その構成する構造単位は全て
同一であっても、部分的に異なる構造単位を含んでいて
もよい。The polymer in the present invention is a polymer containing a molecular skeleton represented by -formation (I) as a structural unit. In the polymer of the present invention, all of the structural units constituting the polymer may be the same or may include partially different structural units.
即ち、−形成（１）で表わされる本発明の重合体を構成
する構造体のＸＩ、 Ｘ２． Ｘｆｆ、 Ｘｒ’
。That is, XI of the structure constituting the polymer of the present invention represented by -formation (1), X2. Xff, Xr'
.
Ｘ Ｚ’ ＋ Ｌ′又はＲ，Ｒ’が各構造単位において
全て同一であっても、異なるものが含まれていてもかま
わない。It does not matter if X Z' + L' or R and R' are all the same in each structural unit, or different units may be included.
又、本発明における重合体は、−形成（１）で表わされ
る構造単位の他、下記の一般式（Ｉ［）で表わされる分
子骨格を有する構造単位を一部含んでいてもよい。In addition to the structural unit represented by -formation (1), the polymer in the present invention may partially contain a structural unit having a molecular skeleton represented by the following general formula (I[).
（ここでｘ、、Ｘ２．Ｘｉ、Ｘ＋’ 、Ｘｚ’ 、Ｘｓ
’ 。(Here x,,X2.Xi,X+',Xz',Xs
'.
Ｒ，Ｒ’は前記の通りである）
本発明の架橋体を合成するには、既知の有機合成反応を
応用改良して合成することができる。(R and R' are as described above) The crosslinked product of the present invention can be synthesized by applying and improving known organic synthesis reactions.
合成法を類型化して例示するならば、末端に二重結合を
持ったジアセチレン結合を有する化合物（例えばＣＩＩ
ｚ＝ＣＩ−Ｃ−０−ＣＨｚ−ＣＥ Ｃ−Ｃ＝’ Ｃ−Ｃ
Ｈｚ−Ｑ−−Ｃ−ＣＩｌ・ＣＨ２）を単量体として、こ
の二重結合部を重合させ、例えば
と
占
占Ｈ２
占
で表わされる分子骨格を持った架橋体を合成できる。To give an example of a synthetic method, a compound having a diacetylene bond with a double bond at the terminal (for example, CII
z=CI-C-0-CHz-CE C-C=' C-C
By using Hz-Q--C-CIl.CH2) as a monomer and polymerizing the double bond, a crosslinked product having a molecular skeleton represented by, for example, H2 can be synthesized.
重合方法としては、例えばラジカル重合、カチオン重合
、アニオン重合などを用いることができる。ラジカル重
合においては、均−系で行なわれる塊状又は溶液重合や
、不均一系で行なわれる乳化又は懸濁重合等が一般的で
あるが、いずれも適用ができる。いずれの重合方法を用
いるかは、重合に用いる単量体の構造や目的に応じて選
べばよい。As the polymerization method, for example, radical polymerization, cationic polymerization, anionic polymerization, etc. can be used. In radical polymerization, bulk or solution polymerization carried out in a homogeneous system, emulsion or suspension polymerization carried out in a heterogeneous system, etc. are generally used, and either of them can be applied. Which polymerization method to use may be selected depending on the structure of the monomer used for polymerization and the purpose.
ラジカル重合において、重合時に用いる溶剤は待に限定
はない。又、ラジカル重合開始剤としては、重合時に用
いる溶剤により任意の既知のラジカル重合開始剤を用い
ることができ、油溶性ラジカル開始剤として、例えば、
ジイソプロピルパーオキシジカーボネート、ジー２−エ
チルヘキシルパーオキシジカーボネート、ベンゾイルパ
ーオキサイド、トリクロロアセチルパーオキサイド、パ
ーフルオロブチルパーオキサイド等の過酸化物、２．２
′−アゾビスイソブチロニトリル、２．２′−アゾビス
（２，４−ジメチルバレロニトリル）等のアゾ化合物が
挙げられ、また水溶性ラジカル重合開始剤としては、例
えば、過酸化水素等のハイドロ−パーオキサイド、過硫
酸カリウム等の過酸化物あるいは２，２′−アゾビス（
２−アミジノプロパン）塩酸塩等のアゾ化合物等を用い
ることができる。In radical polymerization, the solvent used during polymerization is not particularly limited. Further, as the radical polymerization initiator, any known radical polymerization initiator can be used depending on the solvent used during polymerization, and as the oil-soluble radical initiator, for example,
Peroxides such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, benzoyl peroxide, trichloroacetyl peroxide, perfluorobutyl peroxide, 2.2
Examples of water-soluble radical polymerization initiators include azo compounds such as '-azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylvaleronitrile). -peroxide, peroxide such as potassium persulfate, or 2,2'-azobis(
Azo compounds such as (2-amidinopropane) hydrochloride, etc. can be used.
これらの重合開始剤は２種類以上を混合して使用するこ
とも可能であり、さらにはクロムイオン、亜硫酸イオン
、ヒドロキシルアミン、ヒドラジン等を加えてレドック
ス系重合開始剤として使用することも可能である。また
、光重合も可能で光増感剤としてベンゾインイソブチル
エーテル等のカルボニル化合物、過酸化ベンゾイル等の
過酸化物、２，２′−アゾビスイソブチロニトリル等の
アゾ化合物も用いられる。またこれらの触媒と共に促進
剤として亜硫酸水素ナトリウム、チオ硫酸ナトリウム、
硫酸第一鉄アンモニウム等を併用してもよい。It is also possible to use a mixture of two or more of these polymerization initiators, and it is also possible to use them as a redox polymerization initiator by adding chromium ions, sulfite ions, hydroxylamine, hydrazine, etc. . Photopolymerization is also possible, and carbonyl compounds such as benzoin isobutyl ether, peroxides such as benzoyl peroxide, and azo compounds such as 2,2'-azobisisobutyronitrile are also used as photosensitizers. In addition to these catalysts, sodium bisulfite, sodium thiosulfate,
Ferrous ammonium sulfate or the like may be used in combination.
重合開始剤の添加量は通常、単量体に対し０．０５〜５
．０重量％が好ましい。The amount of polymerization initiator added is usually 0.05 to 5% relative to the monomer.
．． 0% by weight is preferred.
重合時の重合温度は、特に制限はなく、通常の重合の温
度範囲でよく、０〜１００″Ｃ１好ましくは２０〜８０
゛Ｃが適当である。The polymerization temperature during polymerization is not particularly limited and may be within the normal polymerization temperature range, and is preferably 0 to 100"C1, preferably 20 to 80"C1.
゛C is appropriate.
（発明の効果）
本発明のジアセチレン化合物は、硬化反応性に優れ、ま
た硬化物が良好な耐熱性及び機械物性を発現する。(Effects of the Invention) The diacetylene compound of the present invention has excellent curing reactivity, and the cured product exhibits good heat resistance and mechanical properties.
本発明のジアセチレン化合物は、これらの特性を生かし
、高度な剛性や耐熱性及び硬化反応性を要求される電子
部品や精密機械部品に利用できる。By taking advantage of these properties, the diacetylene compound of the present invention can be used for electronic parts and precision mechanical parts that require high rigidity, heat resistance, and curing reactivity.
（実施例） 本発明を実施例をもって、具体的に説明する。(Example) The present invention will be specifically explained with reference to Examples.
実施例１
ベンゼン中、Ｐ−１−ルエンスルホン酸とハイトロキノ
ンノ存在下、 ＨＣ＝：ＣＣＨ２０ＨとＣＨ２＝ＣＨＣ
０ＯＨを１０時間還流した。放冷後、水で希釈して有機
層を分離した。これを、炭酸水素ナトリウム水溶液で洗
い、乾燥後、濃縮し、得られたオイルを蒸留して
ＣＨｚ ”’ ＣＨＣＯＯＣＨｚ Ｃ＝ＣＨを得た。Example 1 In benzene, in the presence of P-1-luenesulfonic acid and hytroquinone, HC=:CCH20H and CH2=CHC
0OH was refluxed for 10 hours. After cooling, it was diluted with water and the organic layer was separated. This was washed with an aqueous sodium bicarbonate solution, dried, and concentrated, and the resulting oil was distilled to obtain CHz ``' CHCOOCHz C=CH.
次にこれをＣｕＣ１の存在下、ピリジン中で、酸素をバ
ブリングさせながら酸化カップリング反応させた。反応
後、エーテル抽出し、乾燥、濃縮後、淡かっ色のオイル
を得た。Next, this was subjected to an oxidative coupling reaction in pyridine in the presence of CuC1 while bubbling oxygen. After the reaction, the mixture was extracted with ether, dried, and concentrated to obtain a pale brown oil.
ＩＨ−ＮＭＲ，ＩＲより
ＣＩｌ□＝Ｃ１ｌ−ＣＯ−０−ＣＨｚ−Ｃ’Ｅ＝ Ｃ−
Ｃ＝Ｃ−ＣＨｚ−０−Ｃｏ−ＣＩＩ＝Ｃｔｌ□であるこ
とを確認した。From IH-NMR and IR, CIl□=C1l-CO-0-CHz-C'E= C-
It was confirmed that C=C-CHz-0-Co-CII=Ctl□.
内容積約２０ｄのガラスアンプルに得られたＣ１ｚ＝Ｃ
１ｌ−Ｇｏ−０−Ｃｔｌ□−ＣＥＣ−Ｃ＝Ｃ−ＣＨｚ−
０−Ｃｏ−ＣＨ＝ＣＨｚ５ ｍｌと０．０３ｇのアゾビ
スイソブチロニトリルを加えた。このアンプルを液体窒
素で冷却して、真空ポンプで脱気後、溶封した。これを
７５°Ｃの湯浴中で８時間静置させたところ内容物が固
化した。その後冷却し、アンプルを破壊して塊状物を得
た。これは、溶剤に溶解しなかった。C1z=C obtained in a glass ampoule with an internal volume of about 20 d
1l-Go-0-Ctl□-CEC-C=C-CHz-
5 ml of 0-Co-CH=CHz and 0.03 g of azobisisobutyronitrile were added. This ampoule was cooled with liquid nitrogen, degassed using a vacuum pump, and then melt-sealed. When this was allowed to stand for 8 hours in a 75°C water bath, the contents solidified. Thereafter, it was cooled and the ampoule was broken to obtain a lump. It did not dissolve in the solvent.
この塊状物を示差熱・熱重量曲線の測定を行ったところ
、１２０°Ｃ〜１６０°Ｃにおいて発熱のビークがみら
れた。When this lump was subjected to differential heat/thermogravimetric curve measurement, a peak of heat generation was observed at 120°C to 160°C.
実施例２
実施例１のＣＨｚ＝ＣＨＣ００１１（７）かわりニＣＩ
＋２＝Ｃ−ＣＯＯＨＨｓ
を用いて、同様の合成手段により
Ｃ１１３ＣＨ。Example 2 CHz=CHC0011(7) in Example 1 instead of 2 CI
C113CH by similar synthetic means using +2=C-COOHHs.
を得た。I got it.
得られたＣ１１ｚ＝Ｃ−ＣＯ−０−ＣＨｚ−Ｃ＝ Ｃ−
Ｃ＝ Ｃ−Ｃｌ１ｚ−０−ＣＨ＋
−ＣＯ−Ｃ＝ＣＨｚ ２ｇとｌ ’；’ ／−）Ｌｔｌ
ｏｇを、三っロフＣＨ。The obtained C11z=C-CO-0-CHz-C=C-
C= C-Cl1z-0-CH+ -CO-C=CHz 2g and l';' /-)Ltl
og, Sanroff CH.
ラスコ中でかく拌しなから湯浴で６０〜６３°Ｃに加熱
させた。フラスコ内で還流するのを確認してからあらか
じめ１ｇのメタノールに溶かし°たｏ、ｏｉｇのアゾビ
スイソブチルニトリルを加えた。８時間重合させたとこ
ろで冷却し、沈澱物を口側した。ＩＲスペクトルよりエ
ステル結合、３重結合が確認され、又、溶剤には不溶で
あった。The mixture was stirred in a flask and heated to 60-63°C in a water bath. After confirming that the flask was refluxing, o.o.g. of azobisisobutylnitrile, which had been previously dissolved in 1 g of methanol, was added. After polymerization for 8 hours, it was cooled and the precipitate was taken out. An ester bond and a triple bond were confirmed from the IR spectrum, and it was insoluble in the solvent.
この塊状物を示差熱・熱重量測定したところ、１１０
”０〜１７０°Ｃにおいて発熱のピークがみられた。When this lump was measured by differential heat and thermogravimetry, it was found to be 110
``An exothermic peak was observed between 0 and 170°C.
ｔt
Claims (1)
′、Ｘ＿３′は水素原子又は１価の炭化水素基、Ｒ、Ｒ
′は２価の炭化水素基を表わす。）[Claims] A crosslinked product containing a diacetylene bond containing the molecular skeleton represented by the general formula (I) as a structural unit▲There are mathematical formulas, chemical formulas, tables, etc.▼…………(I) (where , X_1, X_2, X_3, X_1', X_2
', X_3' are hydrogen atoms or monovalent hydrocarbon groups, R, R
' represents a divalent hydrocarbon group. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8134088A JPH01254709A (en) | 1988-04-04 | 1988-04-04 | Crosslinked product containing diacetylene linkage |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8134088A JPH01254709A (en) | 1988-04-04 | 1988-04-04 | Crosslinked product containing diacetylene linkage |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01254709A true JPH01254709A (en) | 1989-10-11 |
Family
ID=13743641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8134088A Pending JPH01254709A (en) | 1988-04-04 | 1988-04-04 | Crosslinked product containing diacetylene linkage |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01254709A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02150668A (en) * | 1988-12-01 | 1990-06-08 | Nippondenso Co Ltd | Refrigerating cycle |
-
1988
- 1988-04-04 JP JP8134088A patent/JPH01254709A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02150668A (en) * | 1988-12-01 | 1990-06-08 | Nippondenso Co Ltd | Refrigerating cycle |
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