JPH0349290B2 - - Google Patents
Info
- Publication number
- JPH0349290B2 JPH0349290B2 JP62254610A JP25461087A JPH0349290B2 JP H0349290 B2 JPH0349290 B2 JP H0349290B2 JP 62254610 A JP62254610 A JP 62254610A JP 25461087 A JP25461087 A JP 25461087A JP H0349290 B2 JPH0349290 B2 JP H0349290B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- group
- diacetylene
- groups
- polymer
- 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
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 claims description 17
- 239000004952 Polyamide Substances 0.000 claims description 11
- 229920002647 polyamide Polymers 0.000 claims description 11
- 125000000962 organic group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 238000000748 compression moulding Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- GRRYWLJOGFTFJH-UHFFFAOYSA-N 4-[4-(4-carbonochloridoylphenyl)buta-1,3-diynyl]benzoyl chloride Chemical compound C1=CC(C(=O)Cl)=CC=C1C#CC#CC1=CC=C(C(Cl)=O)C=C1 GRRYWLJOGFTFJH-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- -1 diacetylene compound Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polyamides (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Description
〔発明の利用技術分野〕
本発明は、ジアセチレン基を含有するポリアミ
ドの成形体に関する、更に詳しくは、ポリマー主
鎖中に容易に架橋し得るジアセチレン基を含有し
たポリアミドの高弾性率成形体に関するものであ
る。
〔従来の技術〕
特定のジアセチレン化合物は結晶状態で熱及び
γ線または紫外線等の高エネルギー線によつて重
合することは良く知られている（トポケミカルポ
リメリゼーシヨン）。しかし、多くの研究は単量
体であるジアセチレン化合物に関するものが主で
あり、ジアセチレン基を含有するポリマーについ
ての研究は少ない。（マクロモレキユル ケミス
トリ（Makuromol.Chem.），134，219（1970）、
ジヤーナル オブ ポリマー サイエンス ポリ
マー ケミストリー エデイシヨン（J.Polym.
Sci.Polym.Chem.Ed.），19，1154（1981））
〔発明が解決しようとしている問題点〕
しかしながら、ジアセチレン化合物を用いて等
方的に高弾性率が発現できるポリマーを開発する
試みはなかつた。また、これまで研究されてきた
トポケミカル重合性を有するジアセチレン化合物
は、ウレタン結合、エーテル結合を有するものに
限られ、耐熱性にも限界があり、十分満足し得る
性能を持つた成形体を得るに到つていない。
本発明者らは、ジアセチレン基の反応性を生か
し等方的に高剛性を発現し、耐熱性にも優れた成
形体を得ることを目指し、鋭意研究を行なつてき
た。その結果、アミド結合含有ジアセチレンポリ
マー成形体を見いだし本発明に到つた。
〔問題点を解決するための手段〕
即ち、本発明は、下記の一般式（Ｉ）で示され
るジアセチレン基を含有するポリアミドを300気
圧以上で圧縮成形して得られる弾性率6GPa以上
の高剛性成形体を提供するものである。
（式中、Y1、Y2は同種または異種の炭素数１か
ら12の１価の有機基、ハロゲン原子、水素原子、
Z1、Z2は同種または異種の炭素数１から24までの
２価の有機基、ｎは20以上の整数を示す。）
本発明の成形体の製造に用いられる前記式
（Ｉ）で示されるジアセチレン基を含有するポリ
アミドにおいて、Y1、Y2は水素原子、ハロゲン
原子、炭素数１から12の１価の有機基を示し、同
種または異種であつても良い。ハロゲン原子とし
てはＦ、Cl、Br、Ｉである。炭素数１から12の
１価の有機基としてはCH3、C2H5、C3H7、
C4H9、C5H11 -、C6H13 -、
[Technical Field of Application of the Invention] The present invention relates to a molded article of polyamide containing diacetylene groups, more specifically, a molded article of high elastic modulus of polyamide containing diacetylene groups that can be easily crosslinked in the polymer main chain. It is related to. [Prior Art] It is well known that certain diacetylene compounds can be polymerized in a crystalline state by heat and high-energy rays such as gamma rays or ultraviolet rays (topochemical polymerization). However, most of the research has focused on diacetylene compounds, which are monomers, and there has been little research on polymers containing diacetylene groups. (Makuromol.Chem., 134 , 219 (1970),
Journal of Polymer Science Polymer Chemistry Edition (J.Polym.
Sci.Polym.Chem.Ed.), 19, 1154 (1981)) [Problems to be solved by the invention] However, attempts were made to develop a polymer capable of isotropically exhibiting a high elastic modulus using a diacetylene compound. I stopped talking. In addition, the diacetylene compounds with topochemical polymerizability that have been studied so far are limited to those with urethane bonds and ether bonds, and their heat resistance is also limited, making it difficult to obtain molded products with sufficiently satisfactory performance. has not been reached. The present inventors have conducted extensive research with the aim of obtaining a molded product that exhibits high rigidity isotropically by taking advantage of the reactivity of diacetylene groups and also has excellent heat resistance. As a result, they discovered a diacetylene polymer molded article containing an amide bond and arrived at the present invention. [Means for Solving the Problems] That is, the present invention provides a polyamide with a high elastic modulus of 6 GPa or more obtained by compression molding a polyamide containing a diacetylene group represented by the following general formula (I) at 300 atmospheres or more. This provides a rigid molded body. (In the formula, Y 1 and Y 2 are the same or different monovalent organic groups having 1 to 12 carbon atoms, halogen atoms, hydrogen atoms,
Z 1 and Z 2 are the same or different divalent organic groups having 1 to 24 carbon atoms, and n is an integer of 20 or more. ) In the polyamide containing a diacetylene group represented by the formula (I) used for producing the molded article of the present invention, Y 1 and Y 2 are a hydrogen atom, a halogen atom, or a monovalent organic compound having 1 to 12 carbon atoms. represents a group and may be the same or different. The halogen atoms are F, Cl, Br, and I. Monovalent organic groups having 1 to 12 carbon atoms include CH 3 , C 2 H 5 , C 3 H 7 ,
C 4 H 9 , C 5 H 11 - , C 6 H 13 - ,
【式】【formula】
【式】【formula】
【式】【formula】
【式】等が挙げられる。これらの有機基の
水素原子の１部または全部がハロゲン原子、ニト
ロ基、アミノ基、シアノ基、カルボニル基、カル
ボキシル基、アルコキシル基、アミド基等の官能
基で置換されていても良い。
本発明において、Z1、Z2は炭素数１から24の２
価の有機基であり、その例としては、−CH2−、−
CH2CH2−、−C3H6−、−C4H8−、−C5H10−、−
C6H12−，−C8H16−、−C10H20−，
Examples include [Formula]. Part or all of the hydrogen atoms of these organic groups may be substituted with a functional group such as a halogen atom, nitro group, amino group, cyano group, carbonyl group, carboxyl group, alkoxyl group, or amide group. In the present invention, Z 1 and Z 2 are 2 having 1 to 24 carbon atoms.
is a valent organic group, examples of which are -CH 2 -, -
CH 2 CH 2 −, −C 3 H 6 −, −C 4 H 8 −, −C 5 H 10 −, −
C 6 H 12 −, −C 8 H 16 −, −C 10 H 20 −,
【式】等の脂肪族基、及びAliphatic groups such as [Formula], and
【式】【formula】
【式】等、及 び[Formula], etc. Beauty
【式】【formula】
【式】【formula】
【式】【formula】
【式】等の芳香族基が挙
げられ、該２価の有機基が、−CF2−，−C2F4−，
−C3F6−，Examples include aromatic groups such as [Formula], and the divalent organic group is -CF 2 -, -C 2 F 4 -,
−C 3 F 6 −,
【式】【formula】
【式】
等のように水素原子の１部または全部がハロゲン
原子、ニトロ基、アミノ基、シアノ基、カルボニ
ル基、カルボキシル基、アルコキシル基、アミド
基等の官能基で置換されていても良い。また、該
２価の有機基が[Formula] A part or all of the hydrogen atoms may be substituted with a functional group such as a halogen atom, a nitro group, an amino group, a cyano group, a carbonyl group, a carboxyl group, an alkoxyl group, an amide group, etc. Moreover, the divalent organic group is
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
この様にして得られる本発明のジアセチレン基
含有ポリアミド成形体は、ジアセチレン基を架橋
させることによつて緻密に架橋した、熱的性質に
も優れた高剛性成形体であり、6GPa以上の弾性
率を発現できる。本発明の成形体は、この様に優
れた物性を有し、構造材料として有用である。ま
た、必要に応じて加熱処理したり、切削や切断等
の機械加工が可能で任意の形状に加工できるた
め、歯車、カム等の精密機械部品や電子材料等の
高度の物性を要求される部品材料として有用であ
る。
次に本発明を実施例を以つて具体的に示す。
文中、すべて重量部を以つて示す。なお、実施
例は、本発明の範囲を拘束するものではない。
参考例 １
の製造
撹拌装置、窒素導入管、温度計を装着した１
４口フラスコに３，3′−ジアミノジフエニルブタ
ジイン23.2部（0.1モル）を窒素気流下乾燥Ｎ−
メチルピロリドン300部に溶解させ、５℃に冷却
した。この溶液に１，４−ビス（４−クロロホル
ミルフエニル）−ブタジイン32.7部（0.1モル）を
添加し、５℃で１時間反応させた。引続き室温で
３時間反応させ、得られた反応溶液を大過剰のメ
タノール中に投入しポリマーを析出させた。メタ
ノールで洗浄後、減圧下で乾燥させた。
ポリマーの収量はほぼ定量的であつた。IRス
ペクトルより目的のジアセチレン基含有ポリアミ
ドであることが確認された。ポリマーの対数粘度
は0.32であつた。
参考例 ２
の製造
参考例１の３，３−ジアミノジフエニルブタジ
インの代わりに３，3′−ジアミノジフエニルブタ
ジインを用い、また、溶媒の乾燥Ｎ−メチルピロ
リドン中に塩化リチウムを５重量％加えた以外は
実施例１と同様に行なつた。IRスペクトルより
目的のジアセチレン基含有ポリアミドであること
が確認された。ポリマーの対数粘度は0.29であつ
た。
参考例 ３
の製造
実施例１の３，３−ジアミノジフエニルブタジ
インの代わりに２，４−ヘキサジイン−１，６−
ジアミンを用いた以外は実施例１と同様に行なつ
た。IRスペクトルより目的のジアセチレン基含
有ポリアミドであることが確認された。ポリマー
の対数粘度は0.36であつた。
実施例 １
参考例１で得られたジアセチレン基含有ポリア
ミドを第１図に示す成形金型のシリンダー内に充
填し、熱板間が減圧脱気できる油圧プレス上に置
き、加圧圧力10000気圧、温度300℃、２時間加圧
加熱し成形を行なつた。得られた成形体は直径
3.5cmの黒色円盤状であつた。
得られた成形体を高さ２mm、幅５mm、長さ3.3
cmの直方体に切り出し試験片とした。切り出され
た試験片を動的粘弾性自動測定装置バイブロン
DDV−（株式会社オリエンテツク）を用いて
曲げ弾性率の測定を行つたところ成形体の弾性率
は7.8GPaであつた。
実施例 ２〜４
成形条件を変更した以外は、実施例１と同様に
行つた。結果を表に示す。
実施例 ５〜８
参考例２で得られたポリマーを用いた以外は実
施例１〜４と同様に行い成形体を得た。結果を表
に示す。
実施例 ９〜10
参考例３で得られたポリマーを用いた以外は実
施例１〜４と同様に行い成形体を得た。結果を表
に示す。
The diacetylene group-containing polyamide molded product of the present invention thus obtained is a highly rigid molded product that is densely crosslinked by crosslinking the diacetylene groups and has excellent thermal properties. Can exhibit elastic modulus. The molded article of the present invention has such excellent physical properties and is useful as a structural material. In addition, it can be processed into any shape by heat treatment and machining such as cutting and cutting as necessary, so it can be processed into any shape, such as precision mechanical parts such as gears and cams, and parts that require high physical properties such as electronic materials. Useful as a material. Next, the present invention will be specifically illustrated with reference to Examples. In the text, all parts are expressed in parts by weight. Note that the examples do not limit the scope of the present invention. Reference example 1 Manufacturing 1 equipped with a stirring device, nitrogen inlet tube, and thermometer
In a 4-necked flask, 23.2 parts (0.1 mol) of 3,3'-diaminodiphenylbutadiyne was dried under a nitrogen stream.
It was dissolved in 300 parts of methylpyrrolidone and cooled to 5°C. 32.7 parts (0.1 mol) of 1,4-bis(4-chloroformylphenyl)-butadiyne was added to this solution, and the mixture was reacted at 5°C for 1 hour. Subsequently, the reaction was allowed to proceed at room temperature for 3 hours, and the resulting reaction solution was poured into a large excess of methanol to precipitate a polymer. After washing with methanol, it was dried under reduced pressure. The yield of polymer was almost quantitative. The IR spectrum confirmed that it was the desired diacetylene group-containing polyamide. The logarithmic viscosity of the polymer was 0.32. Reference example 2 Production of 3,3'-diaminodiphenylbutadiine was used instead of 3,3-diaminodiphenylbutadiine in Reference Example 1, and 5% by weight of lithium chloride was added to the dry N-methylpyrrolidone solvent. The procedure was the same as in Example 1 except for this. The IR spectrum confirmed that it was the desired diacetylene group-containing polyamide. The logarithmic viscosity of the polymer was 0.29. Reference example 3 Production of 2,4-hexadiyne-1,6-instead of 3,3-diaminodiphenylbutadiyne in Example 1
The same procedure as in Example 1 was carried out except that diamine was used. The IR spectrum confirmed that it was the desired diacetylene group-containing polyamide. The logarithmic viscosity of the polymer was 0.36. Example 1 The diacetylene group-containing polyamide obtained in Reference Example 1 was filled into the cylinder of the mold shown in Figure 1, placed on a hydraulic press capable of reducing pressure and degassing between the hot plates, and applying a pressure of 10,000 atm. The molding was carried out by heating under pressure at a temperature of 300°C for 2 hours. The obtained compact has a diameter
It was 3.5 cm in the shape of a black disc. The obtained molded body is 2 mm high, 5 mm wide, and 3.3 mm long.
A test piece was cut into a rectangular parallelepiped of cm in size. The cut out test piece was measured using the dynamic viscoelasticity automatic measuring device Vibron.
When the bending elastic modulus was measured using DDV- (Orientek Co., Ltd.), the elastic modulus of the molded product was 7.8 GPa. Examples 2 to 4 The same procedure as Example 1 was carried out except that the molding conditions were changed. The results are shown in the table. Examples 5 to 8 Molded bodies were obtained in the same manner as Examples 1 to 4 except that the polymer obtained in Reference Example 2 was used. The results are shown in the table. Examples 9-10 Molded articles were obtained in the same manner as Examples 1-4 except that the polymer obtained in Reference Example 3 was used. The results are shown in the table.
【表】【table】
第１図は実施例で用いた成形金型の断面を示す
図である。
FIG. 1 is a diagram showing a cross section of a molding die used in Examples.
Claims (1)
ら12の１価の有機基、ハロゲン原子、水素原子、
Z1、Z2は同種または異種の炭素数１から24までの
２価の有機基、ｎは20以上の整数を示す。） で示されるジアセチレン基を含有するポリアミド
を300気圧以上で圧縮成形して得られる弾性率
6GPa以上の成形体。[Claims] 1 The following general formula (I) (In the formula, Y 1 and Y 2 are the same or different monovalent organic groups having 1 to 12 carbon atoms, halogen atoms, hydrogen atoms,
Z 1 and Z 2 are the same or different divalent organic groups having 1 to 24 carbon atoms, and n is an integer of 20 or more. ) Elastic modulus obtained by compression molding polyamide containing diacetylene groups at 300 atmospheres or more
Molded objects of 6GPa or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25461087A JPH0198626A (en) | 1987-10-12 | 1987-10-12 | Molding of polyamide having diacetylene group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25461087A JPH0198626A (en) | 1987-10-12 | 1987-10-12 | Molding of polyamide having diacetylene group |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0198626A JPH0198626A (en) | 1989-04-17 |
| JPH0349290B2 true JPH0349290B2 (en) | 1991-07-29 |
Family
ID=17267425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25461087A Granted JPH0198626A (en) | 1987-10-12 | 1987-10-12 | Molding of polyamide having diacetylene group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0198626A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01115929A (en) * | 1987-10-29 | 1989-05-09 | Agency Of Ind Science & Technol | Polyamide containing diacetylene group |
| US8492507B2 (en) * | 2008-09-23 | 2013-07-23 | Nexam Chemical Ab | Acetylenic polyamide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6426636A (en) * | 1987-07-23 | 1989-01-27 | Agency Ind Science Techn | Amide polymer containing diacetylene group |
-
1987
- 1987-10-12 JP JP25461087A patent/JPH0198626A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0198626A (en) | 1989-04-17 |
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