JPH0618828B2 - Method for producing crosslinked molded article - Google Patents
Method for producing crosslinked molded articleInfo
- Publication number
- JPH0618828B2 JPH0618828B2 JP63141495A JP14149588A JPH0618828B2 JP H0618828 B2 JPH0618828 B2 JP H0618828B2 JP 63141495 A JP63141495 A JP 63141495A JP 14149588 A JP14149588 A JP 14149588A JP H0618828 B2 JPH0618828 B2 JP H0618828B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- butadiyne
- diacetylene
- double bond
- hydrocarbon group
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 claims description 37
- 150000002430 hydrocarbons Chemical group 0.000 claims description 22
- 238000000465 moulding Methods 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000000748 compression moulding Methods 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 description 27
- 239000000463 material Substances 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 13
- -1 butadiyne compound Chemical class 0.000 description 9
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 125000005647 linker group Chemical group 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000012719 thermal polymerization Methods 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 101150065749 Churc1 gene Proteins 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 102100038239 Protein Churchill Human genes 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F38/00—Homopolymers and copolymers of compounds having one or more carbon-to-carbon triple bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 本発明は、成形時に分解することなく、大型のブタジイ
ン系化合物の架橋成形体を製造する方法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a large-sized cross-linked molded article of a butadiyne compound without decomposing during molding.
近年、固相重合によるトポケミカル反応を用いた単結晶
ポリマーの合成は、注目されており、この手法を用い
て、種々の高弾性率を有する高結晶性高分子の開発が試
みられている。（例えば、「有機非線形光学材料」、シ
ーエムシー（1985）、マクロモレキユル ケミストリー
第134巻、第219頁（1970）、ジャーナル オブ ポリ
マーサイエンス 第Ｂ９巻、第133頁（1971）、ジャー
ナル オブ ポリマー サイエンス ポリマーフィジク
スエディション第12巻、第1511頁(1974)。） 本発明者らも、すでに種々のブタジイン化合物を合成
し、これらを用いて高弾性率を有する高分子成形体を種
々合成してきた。In recent years, attention has been paid to the synthesis of a single crystal polymer using a topochemical reaction by solid-state polymerization, and attempts have been made to develop highly crystalline polymers having various high elastic moduli using this method. (For example, “Organic Nonlinear Optical Materials”, CMC (1985), Macromorekiur Chemistry, Vol. 134, 219 (1970), Journal of Polymer Science, Volume B9, 133 (1971), Journal of Polymer Science, Polymer Physics. Cus Edition, Vol. 12, p. 1511 (1974).) The present inventors have already synthesized various butadiyne compounds, and have used these to synthesize various polymer moldings having a high elastic modulus.
本発明者らは、二重結合を有するブタジイン系モノマ
ー、オリゴマー及びポリマーを架橋成形することによ
り、高弾性率や高耐熱性を有する成形体を製造すること
に成功してきた（特願昭61-241515号、特願昭61-241516
号）。The present inventors have succeeded in producing a molded product having a high elastic modulus and high heat resistance by cross-linking and molding a butadiyne-based monomer, oligomer and polymer having a double bond (Japanese Patent Application No. 61- 241515, Japanese Patent Application No. 61-241516
issue).
しかしながら、これらのブタジイン化合物は、ジアセチ
レン基及び二重結合が固相反応に優れているため、架橋
成形する時に、大量の熱が発生してしばしば分解するこ
とがあり、又、大型成形体が蓄熱や発熱のため製造しに
くいなどの問題があった。このような発熱分解は、新た
に合成したブタジイン化合物の保存時や成形のための予
備調整（例えば、分粒、乾燥など）段階にも生じる場合
があり、安定した成形体製造への大きな障害となってい
た。However, since these butadiyne compounds have excellent solid-phase reaction in the diacetylene group and the double bond, a large amount of heat may be generated and often decomposed during cross-linking molding. There was a problem that it was difficult to manufacture due to heat storage and heat generation. Such exothermic decomposition may occur during the storage of the newly synthesized butadiyne compound and also during the preconditioning (eg, sizing, drying, etc.) for molding, which is a major obstacle to stable molding production. Was becoming.
本発明者らは、上述の問題を解決するために種々検討し
た結果、成形前に部分的、あるいは全てのジアセチレン
基を重合せしめれば、成形時に大きな発熱を伴わず、そ
の結果、安定した架橋成形体の製造や大型成形体を容易
に得ることができる可能性を見い出した。この場合、ジ
アセチレン基を反応させる時も大量に扱うとやはり蓄熱
するため分解が生じる可能性があるので、熱を逃しなが
ら反応させなければならない。そこで、熱を逃がしなが
ら反応させるために、低温で光照射する方法、溶剤に分
散させながら熱処理する方法等を見い出し、さらに研究
を重ねた結果、本発明に到達した。The present inventors have conducted various studies in order to solve the above-mentioned problems, and if a partial or all diacetylene groups are polymerized before molding, a large amount of heat is not generated during molding, and as a result, it is stable. We have found the possibility of easily producing cross-linked molded products and obtaining large-sized molded products. In this case, when a large amount of diacetylene group is treated, heat may still be accumulated and decomposition may occur. Therefore, it is necessary to react while distilling heat. Then, in order to react while radiating heat, a method of irradiating light at a low temperature, a method of heat treatment while dispersing in a solvent, and the like have been found out, and as a result of further research, the present invention has been achieved.
すなわち、本発明は、下記のブタジイン系化合物の架橋
成形体を製造するにあたり、予め原料のブタジイン系化
合物のジアセチレン基の３０〜９６％を重合させた後、
圧縮成形することを特徴とする架橋成形体の製造方法。That is, in the present invention, in producing a cross-linked molded article of the following butadiyne compound, after polymerizing 30 to 96% of the diacetylene group of the butadiyne compound as a raw material in advance,
A method for producing a crosslinked molded article, which comprises compression molding.
R-COO-R1-C≡C-C≡C-R2-OOC-R、 R-CONH-R1-C≡C-C≡C-R2-NHOC-R、 または （ここで、Ｒは、二重結合を有する一価の炭化水素基、
Ｒ１、Ｒ２は二価の有機基、Ｘは二重結合を有する二価
の炭化水素基である。） を提供するものである。R-COO-R 1 -C≡CC≡CR 2 -OOC-R, R-CONH-R 1 -C≡CC≡CR 2 -NHOC-R, Or (Here, R is a monovalent hydrocarbon group having a double bond,
R 1 and R 2 are divalent organic groups, and X is a divalent hydrocarbon group having a double bond. ) Is provided.
本発明において、Ｒ１，Ｒ２は、同種又は異種の２価の
有機基であり、その例としては、−C2H4-、−C3H6-、 等の脂肪族基、 等の芳香族基、及び 等の芳香族基及び脂肪族基の複合した基が挙げられる。In the present invention, R 1, R 2 is a divalent organic radical the same or different, examples, -C 2 H 4 -, - C 3 H 6 -, Aliphatic groups such as Aromatic groups such as And a group in which an aromatic group and an aliphatic group are combined.
これらのＲ１，Ｒ２のうち好ましいのは、合成のしやす
さと耐熱性のよさから、−CH2-、 であり、特に−CH2-、 が好ましい。Of these R 1 and R 2 , preferred are —CH 2 —, because of ease of synthesis and good heat resistance. And especially --CH 2- , Is preferred.
本発明における炭素−炭素二重結合を有する炭化水素基
ＲまたはＸは、一般に炭素数１〜20の１価、又は２価の
炭化水素基であり、その例としては、Ｈ２Ｃ＝ＣＨ−、 Ｈ２Ｃ＝ＣＨ−ＣＨ＝ＣＨ−、Ｈ２Ｃ＝ＣＨ−ＣＨ
２−、 −ＨＣ＝ＣＨ−、 −ＨＣ＝ＣＨ−ＣＨ＝ＣＨ−、−ＣＨ２−ＨＣ＝ＨＣ−
ＣＨ２−、等の炭素−炭素二重結合と水素原子又は脂肪
族基の組合せで構成された基、 等の炭素−炭素二重結合と芳香族基で構成された基、 等の炭素−炭素二重結合が環構造中に含まれる基等が挙
げられる。The hydrocarbon group R or X having a carbon-carbon double bond in the present invention is generally a monovalent or divalent hydrocarbon group having 1 to 20 carbon atoms, and examples thereof include H 2 C = CH-. , H 2 C = CH-CH = CH-, H 2 C = CH-CH
2- , -HC = CH-, -HC = CH-CH = CH - , - CH 2 -HC = HC-
A group composed of a carbon-carbon double bond such as CH 2 — and a hydrogen atom or an aliphatic group, A group composed of a carbon-carbon double bond and an aromatic group such as Groups having a carbon-carbon double bond contained in the ring structure thereof and the like.
これらの炭素−炭素二重結合を有する炭化水素基の中で
好ましいものは、硬化反応性から Ｈ２Ｃ＝ＣＨ−、 Ｈ２Ｃ＝ＣＨ−ＣＨ２−、−ＨＣ＝ＣＨ−、−ＣＨ２−
ＨＣ＝ＣＨ−ＣＨ２−、 等である。Among these hydrocarbon groups having a carbon-carbon double bond, preferred is H 2 C = CH-, because of curing reactivity. H 2 C = CH-CH 2 -, - HC = CH -, - CH 2 -
HC = CH-CH 2 -, Etc.
本発明において、重合前のブタジイン系化合物は、ジア
セチレン基含有炭化水素基と炭素−炭素二重結合を有す
る炭化水素基とを連結する連結基が構成単位として含ま
れる。その連結基としては、アミド結合、エステル結合
である。In the present invention, the butadiyne compound before polymerization contains a linking group as a structural unit, which links the diacetylene group-containing hydrocarbon group and the hydrocarbon group having a carbon-carbon double bond. The linking group is an amide bond or an ester bond.
本発明において、重合前のブタジイン系化合物は、前記
したようにジアセチレン基含有炭化水素基と炭素−炭素
二重結合を有する炭化水素基が、上記連結基によって一
分子中に結合されてなる化合物であるが、一分子中に存
在するジアセチレン基含有炭化水素の数に制限はなく、
１つだけ含む低分子化合物であっても、繰り返し単位と
して２つ以上含むオリゴマー更にポリマーであってもよ
く、又、繰り返し単位として含まれる場合、ジアセチレ
ン基含有炭化水素基は、同種であっても、異種であって
もよい。In the present invention, the butadiyne-based compound before polymerization is a compound in which a diacetylene group-containing hydrocarbon group and a hydrocarbon group having a carbon-carbon double bond are bound in one molecule by the linking group as described above. However, the number of diacetylene group-containing hydrocarbons present in one molecule is not limited,
It may be a low molecular weight compound containing only one or an oligomer or a polymer containing two or more repeating units, and when it is contained as a repeating unit, the diacetylene group-containing hydrocarbon group is the same kind. Or may be different.
本発明において、重合前のブタジイン系化合物は、ジア
セチレン基含有炭化水素基及び炭素−炭素二重結合を有
する炭化水素基の他に、構成要件以外の炭化水素基が連
結基によって連結された有機基を構成単位として部分的
に含んでいてもよい。構成要件以外の炭化水素基を例示
するならば、ＣＨ３−、−ＣＨ２−、 （ｍは２以上の整数）、 等であり、更に、これらの炭化水素基のいくつかが、ニ
トロ基、シアノ基、水酸基、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。これらの
構成要件以外の炭化水素基を導入することは、硬化反応
性と成形性をバランスする上で、効果を有する場合があ
る。In the present invention, the butadiyne-based compound before polymerization is, in addition to a hydrocarbon group having a diacetylene group-containing hydrocarbon group and a carbon-carbon double bond, an organic group in which a hydrocarbon group other than the constituents is linked by a linking group. The group may be partially contained as a constitutional unit. To exemplify a hydrocarbon group other than the constituent requirements, CH 3 —, —CH 2 —, (M is an integer of 2 or more), Further, some of these hydrocarbon groups may be substituted with a nitro group, a cyano group, a hydroxyl group, a carboxyl group, an amino group, a halogen atom or the like. Introducing a hydrocarbon group other than these constituent requirements may be effective in balancing the curing reactivity and the moldability.
本発明で、重合前のブタジイン系化合物において、ジア
セチレン基含有炭化水素基と炭素−炭素二重結合を有す
る炭化水素基の存在する比率については特に制限はない
が、好ましい範囲は硬化反応性が顕著であるモル比が0.
2〜５である。In the present invention, in the butadiyne-based compound before polymerization, the ratio of the hydrocarbon group having a diacetylene group-containing hydrocarbon group and the hydrocarbon group having a carbon-carbon double bond is not particularly limited, but a preferable range is that the curing reactivity is The significant molar ratio is 0.
It is 2-5.
更に、その比が0.5〜２のとき最も顕著な効果がみら
れ、特に好ましい。Further, when the ratio is 0.5 to 2, the most remarkable effect is observed, which is particularly preferable.
本発明のジアセチレン化合物を例示するならば、 Ｈ２Ｃ＝ＣＨＣＨ２ＣＯＮＨＣＨ２Ｃ≡ＣＣ≡ ≡ＣＣＨ２ＮＨＣＯＣＨ２ＣＨ＝ＣＨ２ ＣＨ３−ＣＨ＝ＣＨＣＨ２ＣＯＮＨＣＨ２Ｃ≡ＣＣ≡ ≡ＣＣＨ２ＣＯＮＨＣＨ２ＣＨ＝ＣＨＯＨ３ Ｈ２Ｃ＝ＣＨＣＯＮＨＣＨ２Ｃ≡ＣＣ≡ ≡ＣＣＨ２ＮＨＣＯＣＨ＝ＣＨ２ Ｈ２Ｃ＝Ｃ（ＣＨ３）−ＣＯＮＨＣＨ２Ｃ≡ＣＣ≡ ≡ＣＣＨ２ＮＨＣＯ（ＣＨ３）Ｃ＝ＣＨ２ 更に、以下の繰り返し単位を持つオリゴマー、ポリマー
等が挙げられる。Exemplifying the diacetylene compound of the present invention, H 2 C = CHCH 2 CONHCH 2 C≡CC≡ ≡CCH 2 NHCOCH 2 CH = CH 2 CH 3 -CH = CHCH 2 CONHCH 2 C≡CC≡ ≡CCH 2 CONHCH 2 CH = CHOH 3 H 2 C = CHCONHCH 2 C≡CC≡ ≡CCH 2 NHCOCH = CH 2 H 2 C = C (CH 3 ) -CONHCH 2 C≡CC≡≡CCH 2 NHCO (CH 3 ) C = CH 2 Furthermore, oligomers, polymers, etc. having the following repeating units can be mentioned.
等があげられる。 Etc.
本発明において、重合前のブタジイン系化合物の合成
は、特願昭61-241515号や特願昭61-241516号に開示され
ている方法にて合成できる。In the present invention, the butadiyne compound before polymerization can be synthesized by the method disclosed in Japanese Patent Application Nos. 61-241515 and 61-241516.
本発明のブタジイン系素材は、全ジアセチレン基量の30
〜96％の範囲内で重合されており、重合したジアセチレ
ン基の多い方が、より分解性は少ないが、成形時に一体
化しにくいなどの問題が生じる。そこで、分解反応を抑
制しうる点では50〜96％、成形性の点からは30〜80％が
好ましく、特に好ましくは、50〜80％である。The butadiyne-based material of the present invention has a total diacetylene group content of 30.
Polymerized within the range of up to 96%, and the more polymerized diacetylene groups are, the less decomposable, but problems such as difficulty in integration during molding occur. Therefore, it is preferably 50 to 96% from the viewpoint of suppressing the decomposition reaction, 30 to 80% from the viewpoint of moldability, and particularly preferably 50 to 80%.
ジアセチレン基の重合形式としては、トポケミカル重
合、ランダム重合、二重結合との共反応でも良く、又、
ジアセチレン基の重合処理によって二重結合や非共役三
重結合の一部又は全部が反応していても良く、分解反応
を抑制するにはむしろこれらの不飽和基が反応した方が
好ましい。The diacetylene group may be polymerized by topochemical polymerization, random polymerization, co-reaction with a double bond, or
A part or all of the double bond or non-conjugated triple bond may be reacted by the polymerization treatment of the diacetylene group, and it is preferable that these unsaturated groups are reacted in order to suppress the decomposition reaction.
ジアセチレン基の重合した割合を測定する方法として
は、ジアセチレン基を反応させるための処理をした後、
原料モノマーの良溶媒で、未反応のモノマーを洗い流す
方法や、示差熱測定や熱量測定で、処理前後で、ジアセ
チレン基の反応による発熱量の変化から求める方法、吸
収スペクトルの変化量等から求めることができる。As a method for measuring the polymerized ratio of the diacetylene group, after the treatment for reacting the diacetylene group,
Method to wash away unreacted monomer with a good solvent of raw material monomer, differential calorimetry or calorimetric measurement, change from calorific value due to reaction of diacetylene group before and after treatment, change from absorption spectrum, etc. be able to.
ジアセチレン基の重合方法としては、例えば、特開昭62
-267249号公報等で開示されている方法を用いることが
できる。すなわち、光重合法では、水銀ランプを用いて
のＵＶ照射、電子線照射、γ線照射法、プラズマ法等を
適用できる。熱重合法では、該ブタジイン系素材の融点
又は分解点以下の温度で一定時間熱処理することにより
重合できる。一方、加圧法としては、該ブタジイン系素
材を高圧下、一定時間加圧処理することにより合成でき
る。The diacetylene group can be polymerized by, for example, JP-A-62-62.
The method disclosed in Japanese Patent No. 267249 can be used. That is, in the photopolymerization method, UV irradiation using a mercury lamp, electron beam irradiation, γ-ray irradiation method, plasma method and the like can be applied. In the thermal polymerization method, polymerization can be carried out by heat treatment for a certain period of time at a temperature below the melting point or decomposition point of the butadiyne-based material. On the other hand, as a pressurizing method, the butadiyne-based material can be synthesized by pressurizing the butadiyne-based material under high pressure for a certain time.
上記の光重合法、熱重合法、加圧法を単独で用いてもよ
いが、２つ以上組み合せてもよく、例えば、加熱しなが
ら加圧法で製造するといった方法も適用できる。The above-mentioned photopolymerization method, thermal polymerization method, and pressure method may be used alone, but two or more may be combined, and, for example, a method of producing by a pressure method while heating can also be applied.
また、上記の光重合法、熱重合法、加圧法において、過
酸化物、アゾ化合物、ジスルフィド、ハロゲン化合物、
カルボニル化合物等の重合促進剤を用いてもよい。Further, in the above photopolymerization method, thermal polymerization method, pressure method, a peroxide, an azo compound, a disulfide, a halogen compound,
A polymerization accelerator such as a carbonyl compound may be used.
光重合法の場合、用いる光源、光源の出力、光源と原料
モノマーの距離については制限はない。また、反応時間
についても制限はないが、好ましくは１秒から10時間で
ある。In the case of the photopolymerization method, there is no limitation on the light source used, the output of the light source, and the distance between the light source and the raw material monomer. The reaction time is not limited, but is preferably 1 second to 10 hours.
一方、熱重合法において、反応温度は特に制限はない
が、好ましくは該ブタジイン系素材の融点または分解点
より50℃低い温度から分解点までであり、反応時間につ
いても制限はないが、好ましくは10分から10時間であ
る。On the other hand, in the thermal polymerization method, the reaction temperature is not particularly limited, but is preferably a temperature 50 ° C lower than the melting point or the decomposition point of the butadiyne-based material to the decomposition point, and the reaction time is not limited, but preferably 10 minutes to 10 hours.
一方、加圧法において、圧力は特に制限はないが、好ま
しくは常圧以上から10,000atmであり、反応時間につい
ては制限はないが、好ましくは0.1時間から10時間であ
る。On the other hand, in the pressurizing method, the pressure is not particularly limited, but is preferably atmospheric pressure or more to 10,000 atm, and the reaction time is not limited, but is preferably 0.1 hour to 10 hours.
これらの重合方法のうち特に好ましい方法としては、重
合による発熱を蓄積させないために、溶剤に懸濁させて
光照射、加熱、又は加圧する方法や、低温で光照射、又
は加圧する方法が挙げられる。Among these polymerization methods, particularly preferable methods include a method of suspending in a solvent and irradiating with light, heating, or pressurizing, or a method of irradiating with light or pressurizing at a low temperature in order to prevent accumulation of heat generated by the polymerization. .
本発明の製造方法によると、ブタジイン系素材は、その
ジアセチレン基の一部又は全部が予め重合されているの
で成形時に架橋による発熱があまりなく、分解しない。
そのため、従来、ブタジイン系素材をそのまま成形した
のでは、厚物の成形体を製造しにくかったが、本発明の
製造方法を用いることにより厚物の大型成形体を製造す
ることが容易になる。According to the production method of the present invention, a part or all of the diacetylene group of the butadiyne-based material is preliminarily polymerized, so there is little heat generation due to crosslinking during molding, and it does not decompose.
Therefore, it has been difficult to manufacture a thick molded product by molding the butadiene-based material as it is, but it becomes easy to manufacture a thick large molded product by using the manufacturing method of the present invention.
したがって、本発明の製造方法は、機能性素子や導電性
材料のみならず、機械部品から構造材料の製造方法まで
巾広く利用できる。Therefore, the manufacturing method of the present invention can be widely used not only for functional elements and conductive materials, but also for manufacturing mechanical parts to structural materials.
以下、実施例を挙げて本発明を説明するが、本発明は、
これらの実施例のみには限定されない。Hereinafter, the present invention will be described with reference to examples.
It is not limited to these examples only.
〔実施例１〕 以下のブタジイン系アミド素材１〜７を10ｇづつ100ml
の80℃の熱水に入れ、１時間攪拌し、ジアセチレン基の
反応率は、未反応物をＮＮ−ジメチルアセトアミドで洗
い流し、その残存量から求めた。その結果を表１に示
す。[Example 1] 100 g of the following butadiyne-based amide materials 1 to 7 in increments of 10 g
The reaction rate of the diacetylene group was determined by washing off the unreacted material with NN-dimethylacetamide and measuring the remaining amount. The results are shown in Table 1.
これらの処理した素材を、直径30mm、深さ60mmの金型に
詰めて、500atm、220℃で１時間圧縮成形したところ、
すべての素材は、黒色の成形体を与えた。しかし、熱処
理せずに圧縮成形すると、１，２，５，７の素材は完全
に炭化分解し、３，４，６の素材は、一部分解したきわ
めてもろい成形体しか与えなかった。 When these treated materials were packed in a mold with a diameter of 30 mm and a depth of 60 mm and compression molded at 500 atm and 220 ° C for 1 hour,
All materials gave black shaped bodies. However, when compression molding was performed without heat treatment, the raw materials 1, 2, 5, and 7 were completely carbonized and the raw materials 3, 4, and 6 gave only a partially decomposed extremely brittle molded body.
〔実施例２〕 以下のブタジイン系エステル素材８〜14を10ｇ、100ml
の50℃の水に入れ、１時間、５cmの距離から254nmのＵ
Ｖ照射しながら攪拌した。ジアセチレン基の反応率は、
未反応物をジメチルスルホキシドで洗い流し、その残存
量から求めた。その結果を表２に示す。[Example 2] 10 g, 100 ml of the following butadiyne ester materials 8 to 14
In water of 50 ℃ for 1 hour, from a distance of 5cm to 254nm U
The mixture was stirred under V irradiation. The reaction rate of the diacetylene group is
Unreacted substances were washed out with dimethylsulfoxide, and it was determined from the remaining amount. The results are shown in Table 2.
これらの処理した素材を直径30mm、深さ60mmの金型に詰
めて、500atm、150℃で１時間圧縮成形したところ、す
べての素材は黒色の成形体を与えた。 When these treated materials were packed in a mold having a diameter of 30 mm and a depth of 60 mm and compression-molded at 500 atm and 150 ° C. for 1 hour, all materials gave a black molded product.
しかし、未処理物のみを同条件で圧縮した場合、すべて
の素材は途中で炭化分解した。However, when only the untreated material was compressed under the same conditions, all the materials were carbonized and decomposed on the way.
Claims (1)
製造するにあたり、予め原料のブタジイン系化合物のジ
アセチレン基の３０〜９６％を重合させた後、圧縮成形
することを特徴とする架橋成形体の製造方法。 R-COO-R1-C≡C-C≡C-R2-OOC-R、 R-CONH-R1-C≡C-C≡C-R2-NHOC-R、 または （ここで、Ｒは、二重結合を有する一価の炭化水素基、
Ｒ１、Ｒ２は二価の有機基、Ｘは二重結合を有する二価
の炭化水素基である。）1. A cross-linked molding characterized by comprising preliminarily polymerizing 30 to 96% of a diacetylene group of a raw material butadiyne-based compound and then compression-molding the cross-linked molding of the following butadiyne-based compound. Body manufacturing method. R-COO-R 1 -C≡CC≡CR 2 -OOC-R, R-CONH-R 1 -C≡CC≡CR 2 -NHOC-R, Or (Here, R is a monovalent hydrocarbon group having a double bond,
R 1 and R 2 are divalent organic groups, and X is a divalent hydrocarbon group having a double bond. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63141495A JPH0618828B2 (en) | 1988-06-10 | 1988-06-10 | Method for producing crosslinked molded article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63141495A JPH0618828B2 (en) | 1988-06-10 | 1988-06-10 | Method for producing crosslinked molded article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01311107A JPH01311107A (en) | 1989-12-15 |
| JPH0618828B2 true JPH0618828B2 (en) | 1994-03-16 |
Family
ID=15293262
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63141495A Expired - Lifetime JPH0618828B2 (en) | 1988-06-10 | 1988-06-10 | Method for producing crosslinked molded article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0618828B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02150668A (en) * | 1988-12-01 | 1990-06-08 | Nippondenso Co Ltd | Refrigerating cycle |
| US7364670B2 (en) * | 2003-07-17 | 2008-04-29 | Fujifilm Corporation | Liquid crystalline compound, liquid crystalline composition and retardation film |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62263719A (en) * | 1986-05-09 | 1987-11-16 | Matsushita Electric Ind Co Ltd | AD converter |
-
1988
- 1988-06-10 JP JP63141495A patent/JPH0618828B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01311107A (en) | 1989-12-15 |
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