JPH0198626A - Molding of polyamide having diacetylene group - Google Patents
Molding of polyamide having diacetylene groupInfo
- Publication number
- JPH0198626A JPH0198626A JP25461087A JP25461087A JPH0198626A JP H0198626 A JPH0198626 A JP H0198626A JP 25461087 A JP25461087 A JP 25461087A JP 25461087 A JP25461087 A JP 25461087A JP H0198626 A JPH0198626 A JP H0198626A
- Authority
- JP
- Japan
- Prior art keywords
- molding
- diacetylene
- group
- formula
- 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.)
- Granted
Links
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000004952 Polyamide Substances 0.000 title claims abstract description 21
- 229920002647 polyamide Polymers 0.000 title claims abstract description 21
- 238000000465 moulding Methods 0.000 title abstract description 22
- 125000000962 organic group Chemical group 0.000 claims abstract description 12
- 125000005843 halogen group Chemical group 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 4
- 238000005520 cutting process Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000006068 polycondensation reaction Methods 0.000 abstract description 3
- -1 diamine compound Chemical class 0.000 abstract description 2
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 abstract description 2
- 239000012776 electronic material Substances 0.000 abstract description 2
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 238000003754 machining Methods 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 150000002367 halogens Chemical class 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 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
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 101150077323 GPA2 gene Proteins 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- AIYPMVLGZIAKRM-UHFFFAOYSA-N hexa-2,4-diyne-1,6-diamine Chemical compound NCC#CC#CCN AIYPMVLGZIAKRM-UHFFFAOYSA-N 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Polyamides (AREA)
Abstract
Description
【発明の詳細な説明】
〔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。Detailed Description of the Invention [Technical Field of Application of the Invention] The present invention relates to a molded article of polyamide containing diacetylene groups, and more particularly, to a molded article of polyamide containing diacetylene groups that can be easily crosslinked in the polymer main chain. This invention relates to a polyamide molded article with a high elastic modulus.
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っ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ョン）、
シかし、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、（マクロモレキュル
ケミストリ（Ｍａｋｕｒｏｍｏｌ、Ｃｈｅｍ、）、１３
４．２１９（１９７０） 、ジャーナル オブ ポリマ
ー サイエンス ポリマーケミストリー エデイジョン
（Ｊ、Ｐｏｌｙｍ、Ｓｃｉ、Ｐｏｌｙｍ。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 light (topochemical polymerization).
However, most research has focused on diacetylene compounds, which are monomers, and there has been little research on polymers containing diacetylene groups (macromolecules).
Chemistry (Makuromol, Chem,), 13
4.219 (1970), Journal of Polymer Science Polymer Chemistry Edition (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った。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
性能を持った成形体を得るに到っていない。Chem, Ed.), 19.1154 (1981)
) [Problems to be Solved by the Invention] However, there has been no attempt to develop a polymer capable of isotropically exhibiting a high elastic modulus using a diacetylene compound. 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.
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、鋭意研究を行なってきた。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
に到った。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, a diacetylene polymer molded article containing an amide bond was discovered and the present invention was completed.
即ち、本発明は、下記−紋穴（ｒ）で示されるジアセチ
レン基を含有するポリアミドの高剛性成形体を提供する
ものである。That is, the present invention provides a highly rigid molded article of polyamide containing a diacetylene group represented by the following symbol (r).
（式中、Ｙ、 、Ｙ、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、ｚ、、
ｚｔ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２以上の整数を示す、）
本発明において、ＹＩ、Ｙｚ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
異種であっても良い。ハロゲン原子としては、Ｆ、 Ｃ
１，Ｂｒ、 Ｉである。炭素数１から１２の１価の有機
基としてはＣ１１ｓ、ＣＪｓ、ＣＪフ。(In the formula, Y, Y, is the same or different monovalent organic group having 1 to 12 carbon atoms, halogen atom, hydrogen atom, z,
zt is the same or different type of divalent organic group having 1 to 24 carbon atoms; n is an integer of 2 or more;) In the present invention, YI and Yz are hydrogen atoms, halogen atoms, and 1 having 1 to 12 carbon atoms; It represents a valent organic group, and may be the same or different types. As halogen atoms, F, C
1, Br, I. Monovalent organic groups having 1 to 12 carbon atoms include C11s, CJs, and CJ.
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。Part or all of the atoms 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.
本発明において、２い２□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、−ＣＨ，−。In the present invention, 2□ is a divalent organic group having 1 to 24 carbon atoms, and examples thereof include -CH, -.
ＣＨｚＧＨｚ 、 Ｃ２Ｈ４−２−Ｃ４Ｈｓ−１Ｃ
ｓＨ＋。−９−ＣｉＨ＋ｇ−、−Ｃ１Ｈ＋ａ−、−Ｃ＋
ｏＬ。−、−ＣＨｚ−ｃＨ−ｌｌｓ
ＣＨ３
芳香族基が挙げられ、該２価の有機基が、 Ｃｈ 。CHzGHz, C2H4-2-C4Hs-1C
sH+. -9-CiH+g-, -C1H+a-, -C+
oL. -, -CHz-cH-lls CH3 aromatic group is mentioned, and the divalent organic group is Ch.
ＣＩ ＣＮ
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価の有機基がようにエーテル結合、エス
テル結合、アミド結合、カルボニル基、スルホニル基、
チオエーテル結合等で連結されていても良い。Part or all of the CI CN atoms 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 addition, the divalent organic group may be an ether bond, an ester bond, an amide bond, a carbonyl group, a sulfonyl group,
They may be linked by a thioether bond or the like.
本発明に用いるジアセチレン基を含有するポリアミドは
ホモポリマーでも良く、また共重合体の一部に導入され
ていても良い。The polyamide containing diacetylene groups used in the present invention may be a homopolymer, or may be incorporated into a part of the copolymer.
本発明に用いるジアセチレン基を含有するポリ本発明の
成形体に用いるジアセチレン基含有ポリアミドの製造方
法は、特願昭６２−１０８９７４号明細書に開示した下
記−紋穴（ｎ）で示されるジアセチレン基含有ジカルボ
ン酸誘導体と、
（式中、Ｘはハロゲン原子、水酸基であり、ＹいＹ！は
前述と同じである。）
一般式（Ｉ［［）
％式％（［［）
（式中、ＺＩ、Ｚｚは前述と同じである。）で示される
ジアミン化合物とから低温溶液重縮合法、界面溶液重縮
合法等によって製造できる。Diacetylene group-containing polyamide used in the present invention The method for producing the diacetylene group-containing polyamide used in the molded article of the present invention is shown in the following - pattern hole (n) disclosed in Japanese Patent Application No. 108974/1982. A diacetylene group-containing dicarboxylic acid derivative, (wherein, X is a halogen atom or a hydroxyl group, and Y! is the same as above.) ZI and Zz are the same as above.
低温溶液重縮合法の場合、溶媒としてはＮ−メチルピロ
リドン、Ｎ、Ｎ−ジメチルホルムアミド、Ｎ、Ｎ−ジメ
チルアセトアミド、ヘキサメチルホスホルアミド、゛ジ
メチルスルホキシド等の非プロトン性極性溶媒が好まし
い。また、重合溶媒中に塩化リチウム、塩化カルシウム
等の塩類を共存させても良い。重合温度については特に
制限はないが、−２０℃から１００℃で行なうことがで
きる。重合反応終了後、反応液をポリマーの貧溶媒中に
注ぎ重合物を析出させ、ろ過洗浄後減圧下にて乾燥させ
ることによって目的とするジアセチレン基含有ポリアミ
ドを得ることができる。In the case of the low temperature solution polycondensation method, the solvent is preferably an aprotic polar solvent such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, hexamethylphosphoramide or dimethylsulfoxide. Furthermore, salts such as lithium chloride and calcium chloride may be present in the polymerization solvent. There are no particular restrictions on the polymerization temperature, but it can be carried out at -20°C to 100°C. After the polymerization reaction is completed, the reaction solution is poured into a poor solvent for the polymer to precipitate a polymer, which is then filtered, washed, and dried under reduced pressure to obtain the desired diacetylene group-containing polyamide.
本発明の成形体に用いるジアセチレン基含有ポリアミド
の別途製造方法としては、下記−紋穴（式中、Ｙｌ、Ｙ
２、ｚは前述と同じ。）で示されるビスエチニル化合物
を触媒存在下、酸化的にカップリングさせ重合すること
によって製造することができる。用いる触媒としては銅
塩類、マンガン塩類、コバルト塩類、助触媒としてはア
ミン類、アルカリ性化合物等を用いることができる。好
ましい触媒系としては、塩化第１ｗ４／Ｎ、Ｎ、Ｎ ’
、Ｎ ’−テトラメチルエチレンジアミン、塩化第１
銅／ピリジン、塩化第２銅／ピリジン、塩化マンガン／
α−ベンゾイルオキシム等である。As a separate method for producing the diacetylene group-containing polyamide used in the molded article of the present invention, the following method can be used:
2. z is the same as above. ) can be produced by oxidatively coupling and polymerizing the bisethynyl compounds shown in the following in the presence of a catalyst. As the catalyst to be used, copper salts, manganese salts, and cobalt salts can be used, and as the co-catalyst, amines, alkaline compounds, etc. can be used. Preferred catalyst systems include 1st chloride w4/N, N, N'
, N'-tetramethylethylenediamine, monochloride
Copper/pyridine, cupric chloride/pyridine, manganese chloride/
α-benzoyloxime and the like.
使用する触媒量はモノマーに対して０．１％から１００
％の範囲で重合を行なうことができる。好ましくは１％
から３０％の範囲である。The amount of catalyst used is from 0.1% to 100% based on the monomer.
%. Preferably 1%
The range is from to 30%.
重合溶媒としては、モノマー及び生成するポリマーの良
溶媒であり、触媒に対して不活性であれば特に制限はな
い。好ましい溶媒としてはジクロロベンゼン、ニトロベ
ンゼン、Ｎ−メチルピロリドン、Ｎ、Ｎ−ジメチルアセ
トアミド、 １．４−ジオキサン等である。The polymerization solvent is not particularly limited as long as it is a good solvent for the monomer and the polymer to be produced and is inert to the catalyst. Preferred solvents include dichlorobenzene, nitrobenzene, N-methylpyrrolidone, N,N-dimethylacetamide, and 1,4-dioxane.
重合に使用する酸素はそのままあるいは窒素等の不活性
ガスで希釈することができ、また、空気も使用すること
ができる。好ましくは酸素気流下で重合を実施する。Oxygen used in polymerization can be used as is or diluted with an inert gas such as nitrogen, and air can also be used. Polymerization is preferably carried out under an oxygen stream.
重合温度は高々１００℃までであり通常は２０℃から８
０℃の範囲で実施されるが、望ましくは副反応を防止す
るため高温での重合は避けるべきである。The polymerization temperature is at most 100℃, usually from 20℃ to 8℃.
The polymerization is carried out at a temperature in the range of 0°C, but preferably high temperature polymerization should be avoided to prevent side reactions.
本発明のジアセチレン基を含有するポリアミドの成形体
は、−紋穴（１）
（式中、Ｙｌ、Ｙ２は同種または異種の炭素数１から１
２の１価の有機基、ハロゲン原子、水素原子、Ｚ＋ 、
Ｚ！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２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成形
することにより得られる。発現される弾性率の値は、成
形の方法、条件によって異なるが、好ましい方法を用い
れば、６ ＧＰａ以上の弾性率を発現することもできる
。The molded article of the polyamide containing diacetylene groups of the present invention has the following structure: -More (1)
2 monovalent organic group, halogen atom, hydrogen atom, Z+,
Z! are the same or different divalent organic groups having 1 to 24 carbon atoms, and n is an integer of 2 or more. ) It can be obtained by molding a polyamide containing a diacetylene group shown in the following. The value of the elastic modulus developed varies depending on the molding method and conditions, but if a preferred method is used, an elastic modulus of 6 GPa or more can be developed.
本発明における成形物の形状は、特に制限はなく任意の
形状に成形されたものであり、例えば板状、塊状、棒状
、球状あるいは繊維状、フィルム状であっても良く、用
途に応じた形態と大きさを有するものである。The shape of the molded product in the present invention is not particularly limited and may be molded into any shape, such as a plate, a block, a rod, a sphere, a fiber, or a film, depending on the purpose. It has a size of .
本発明における弾性率は、成形物の形状により、曲げ弾
性率、圧縮弾性率あるいは引っ張り弾性率が適用できる
。As the elastic modulus in the present invention, bending elastic modulus, compressive elastic modulus, or tensile elastic modulus can be applied depending on the shape of the molded product.
本発明において、成形体を成形する方法としては、例え
ば押出し成形、射出成形、圧縮成形、フィルムの圧延成
形などが用いられる。本発明のジアセチレン基−含有ポ
リマーはアミド基を含有するため、分子間力が大きく、
ジアセチレン基の反応性が高く、上記成形方法により架
橋反応が進み、高弾性率が発現されると考えられる。従
って、より好ましい成形方法としては、架橋反応を促進
させるため、圧力、熱、紫外線゛、放射線等の励起エネ
ルギーを単独、また、組み合わせて与えることが効果的
である。これらの励起エネルギーは、形状を付与した後
、また付与すると同時に与えることができる。In the present invention, methods for forming the molded article include, for example, extrusion molding, injection molding, compression molding, film rolling, and the like. Since the diacetylene group-containing polymer of the present invention contains an amide group, the intermolecular force is large.
It is thought that the reactivity of the diacetylene group is high, and the above-mentioned molding method progresses the crosslinking reaction, resulting in the development of a high modulus of elasticity. Therefore, as a more preferable molding method, it is effective to apply excitation energy such as pressure, heat, ultraviolet rays, radiation, etc. singly or in combination in order to promote the crosslinking reaction. These excitation energies can be applied after or simultaneously with imparting the shape.
特に、高弾性率を発現させる方法としては高圧下で成形
する方法が好ましく、例えば、プレス成形や静水圧加圧
等の加圧方法を使用できる。加圧圧力には特に制限はな
いが、３００気圧以上あれば良く、上限は特にない、好
ましくは１０００気圧から２００００気圧である。また
、加工時には大気圧下で加圧することによって成形可能
であるが、空隙のない成形物を得るためには加圧時に加
圧容器内や試料空隙の空気を排気し、減圧ないし真空状
態にして加圧成形することが好ましい。In particular, as a method for developing a high elastic modulus, a method of molding under high pressure is preferable, and for example, a pressurizing method such as press molding or hydrostatic pressing can be used. The pressurizing pressure is not particularly limited, but it may be 300 atm or more, and there is no particular upper limit, preferably 1000 atm to 20000 atm. Additionally, during processing, molding is possible by pressurizing under atmospheric pressure, but in order to obtain a molded product without voids, the air in the pressurized container and sample voids is evacuated during pressurization, and the pressure is reduced or a vacuum is created. Pressure molding is preferred.
加圧成形時の温度は、特に制限はないがジアセチレン基
含有ポリアミドの溶融温度以下であれば良い。好ましく
は室温（２０℃）から４００℃の範囲であれば良く、特
に好ましくは５０℃から３５０℃の範囲であれば良い。The temperature during pressure molding is not particularly limited as long as it is below the melting temperature of the diacetylene group-containing polyamide. The temperature range is preferably from room temperature (20°C) to 400°C, particularly preferably from 50°C to 350°C.
フィルム状成形物を得るには、フィルム形態を付与した
後あるいは付与と同時に圧力、熱、紫外線、放射線等の
励起エネルギーを与えることが好ましく、延伸等により
配向させ一方向の弾性率を向上させながら、また、させ
た後、これらのエネルギーを与えることも効果的であり
、より弾性率の向上した成形物を得ることができる。In order to obtain a film-like molded product, it is preferable to apply excitation energy such as pressure, heat, ultraviolet rays, or radiation after or simultaneously with imparting the film form, and while improving the elastic modulus in one direction by orienting it by stretching etc. In addition, it is also effective to apply these energies after the molding, and it is possible to obtain a molded product with a further improved modulus of elasticity.
また、ジアセチレン基含有ポリアミドの成形時に無機あ
るいは有機充填材、顔料、′紫外線吸収材、安定材等を
配合して成形することも可能である。It is also possible to mix inorganic or organic fillers, pigments, ultraviolet absorbers, stabilizers, etc. when molding the diacetylene group-containing polyamide.
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
って緻密に架橋した、熱的性質にも優れた高剛性成形体
であり、特に好ましい成形方法を用いれば６ ＧＰａ以
上の弾性率を発現できる。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. If used, an elastic modulus of 6 GPa or more can be achieved.
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用材料として有用である
。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. It is useful as a material for
次に本発明を実施例を以って具体的に示す。Next, the present invention will be specifically illustrated with reference to Examples.
文中、すべて重量部を以って示す。なお、実施例は、本
発明の範囲を拘束するものではない。In the text, all parts are expressed in parts by weight. Note that the examples do not limit the scope of the present invention.
参考例１
攪拌装置、窒素導入管、温度計を装着した１１４０フラ
スコに３，３′−ジアミノジフェニルブタジイン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−クロロホルミルフェニル）−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。Reference Example 1 3,3'-diaminodiphenylbutadiine was added to a 1140 flask equipped with a stirrer, a nitrogen inlet tube, and a thermometer.
2 parts (0.1 mol) were dissolved in 300 parts of dry N-methylpyrrolidone under a nitrogen stream 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.
メタノールで洗浄後、減圧下で乾燥させた。After washing with methanol, it was dried under reduced pressure.
ポリマーの収量はほぼ定量的であった。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であった。The yield of polymer was almost quantitative. It was confirmed from the IR spectrum that it was the desired diacetylene group-containing polyamide. The logarithmic viscosity of the polymer was 0.32.
参考例２
実施例１の３，３−ジアミノジフェニルブタジインの代
わりに３．３′−ジアミノジフェ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と同様に行なった
。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であった。Reference Example 2 Except that 3,3'-diaminodiphenylbutadiine was used instead of 3,3-diaminodiphenylbutadiine in Example 1, and 5% by weight of lithium chloride was added to the dry N-methylpyrrolidone solvent. was carried out in the same manner as in Example 1. It was confirmed from the IR spectrum that it was the desired diacetylene group-containing polyamide. Logarithmic viscosity of polymer is 0
．． It was 29.
参考例３
実施例１の３，３−ジアミノジフェ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と同様に行なった。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であった。Reference Example 3 The same procedure as in Example 1 was carried out except that 2,4-hexadiyne-1,6-diamine was used instead of 3,3-diaminodiphenylbutadiine. It was confirmed from the IR spectrum that it was the desired diacetylene group-containing polyamide. The logarithmic viscosity of the polymer was 0.36.
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ｔｏｏｏ
ｏ気圧、温度３００℃、２時間加圧加熱し成形を行なっ
た。得られた成形体は直径３．５ Ｃ！１１の黒色円盤
状であった。Example 1 The diacetylene group-containing polyamide obtained in Reference Example 1 was filled into the cylinder of the molding die shown in FIG.
Molding was carried out by heating under pressure at 300° C. for 2 hours. The obtained molded body has a diameter of 3.5 C! It was in the shape of 11 black discs.
得られた成形体を高さ２ｍ、幅５龍、長さ３．３１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パイブロンＤＤＶ−Ｉ［［（株式
会社オリエンチック）を用いて曲げ弾性率の測定を行っ
たところ成形体の弾性率は？、 ８ ＧＰａであった。The obtained molded body was cut into a rectangular parallelepiped with a height of 2 m, a width of 5 mm, and a length of 3.3 mm to prepare a test piece. The flexural modulus of the cut out test piece was measured using a dynamic viscoelasticity automatic measuring device Pyblon DDV-I (manufactured by Orientic Co., Ltd.).What was the modulus of elasticity of the molded product? , 8 GPa.
実施例２〜４ 成形条件を変更した以外は、実施例１と同様に行った。Examples 2-4 The same procedure as in Example 1 was carried out except that the molding conditions were changed.
結果を表に示す。The results are shown in the table.
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。Examples 5 to 8 Examples 1 to 8 except that the polymer obtained in Reference Example 2 was used.
A molded body was obtained in the same manner as in 4. The results are shown in the table.
実施例９〜ｌＯ
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。Example 9-lO Example 1-1 except that the polymer obtained in Reference Example 3 was used
A molded body was obtained in the same manner as in 4. The results are shown in the table.
１ １０．０００ａｔｍ ３００℃ ２時間
？、 ６ ＧＰａ２ １０，０００ ３００
４ ７．８３ １５．０００
２８０ ２ ７．６４ １
５．０００ ３００ ２ ８．
０５ １０．０００ ３００ ２
７．３６ １０．０００ ３００
４ ７．４７ １０．０００
３２０ ２ ７．６８ １５
．０００ ３００ ２ ７．６
９ １０．０００ １００ ２
６．８１０ １５．０００ １００
２ ７．９1 10,000atm 300℃ 2 hours
? , 6 GPa2 10,000 300
4 7.83 15.000
280 2 7.64 1
5.000 300 2 8.
05 10.000 300 2
7.36 10.000 300
4 7.47 10.000
320 2 7.68 15
．． 000 300 2 7.6
9 10.000 100 2
6.810 15.000 100
2 7.9
【図面の簡単な説明】
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
。
特許出層人工業技術院長
第１図BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view of a mold used in Examples. Patent issued by the Director of the Institute of Industrial Science and Technology Figure 1
Claims (1)
ら１２の１価の有機基、ハロゲン原子、水素原子、Ｚ＿
１、Ｚ＿２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２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の成形
体[Claims] The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I) (In the formula, Y_1 and Y_2 are the same or different monovalent organic compounds having 1 to 12 carbon atoms) group, halogen atom, hydrogen atom, 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 2 or more. ) Molded polyamide containing diacetylene groups
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 true JPH0198626A (en) | 1989-04-17 |
| JPH0349290B2 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) |
Cited By (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 |
| WO2010036175A1 (en) * | 2008-09-23 | 2010-04-01 | Nexam Chemicals | Moulded article obtained from acetylenic polyamide |
Citations (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
Patent Citations (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 |
Cited By (4)
| 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 |
| JPH0359088B2 (en) * | 1987-10-29 | 1991-09-09 | Kogyo Gijutsuin | |
| WO2010036175A1 (en) * | 2008-09-23 | 2010-04-01 | Nexam Chemicals | Moulded article obtained from acetylenic polyamide |
| US8492507B2 (en) | 2008-09-23 | 2013-07-23 | Nexam Chemical Ab | Acetylenic polyamide |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0349290B2 (en) | 1991-07-29 |
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