JPH0253824A - Thermotropic liquid crystalline polymeric material - Google Patents
Thermotropic liquid crystalline polymeric materialInfo
- Publication number
- JPH0253824A JPH0253824A JP20539688A JP20539688A JPH0253824A JP H0253824 A JPH0253824 A JP H0253824A JP 20539688 A JP20539688 A JP 20539688A JP 20539688 A JP20539688 A JP 20539688A JP H0253824 A JPH0253824 A JP H0253824A
- Authority
- JP
- Japan
- Prior art keywords
- thermotropic liquid
- liquid crystal
- skeleton structure
- copolyesteramide
- polymer material
- 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
- 239000007788 liquid Substances 0.000 title abstract description 13
- 239000000463 material Substances 0.000 title abstract description 7
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000006850 spacer group Chemical group 0.000 claims abstract description 6
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract 2
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 13
- 239000004974 Thermotropic liquid crystal Substances 0.000 claims description 12
- 239000002861 polymer material Substances 0.000 claims description 12
- 229920001634 Copolyester Polymers 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 description 9
- 239000004973 liquid crystal related substance Substances 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000004760 aramid Substances 0.000 description 6
- 229920003235 aromatic polyamide Polymers 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- -1 oxypropylene chain Chemical group 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 3
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000002535 lyotropic effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- NUVBSKCKDOMJSU-UHFFFAOYSA-N ethylparaben Chemical compound CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- CWLGEPSKQDNHIO-JOBJLJCHSA-N (e)-n-[(e)-benzylideneamino]-1-phenylmethanimine Chemical compound C=1C=CC=CC=1/C=N/N=C/C1=CC=CC=C1 CWLGEPSKQDNHIO-JOBJLJCHSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- ZVSKZLHKADLHSD-UHFFFAOYSA-N benzanilide Chemical compound C=1C=CC=CC=1C(=O)NC1=CC=CC=C1 ZVSKZLHKADLHSD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000010228 ethyl p-hydroxybenzoate Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- UVEWQKMPXAHFST-UHFFFAOYSA-N n,1-diphenylmethanimine Chemical compound C=1C=CC=CC=1C=NC1=CC=CC=C1 UVEWQKMPXAHFST-UHFFFAOYSA-N 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 1
Landscapes
- Polyamides (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の技術分野〕
本発明は、液晶特性を示す高分子材料に関し、さらに詳
しくは、サーモトロピック液晶性を有し、しかも力学的
特性、成形加工特性ならびに熱的特性にすぐれたサーモ
トロピック液晶高分子材料に関する。[Detailed Description of the Invention] [Technical Field of the Invention] The present invention relates to a polymer material exhibiting liquid crystal properties, and more particularly, to a polymer material having thermotropic liquid crystal properties and having good mechanical properties, molding properties, and thermal properties. This invention relates to thermotropic liquid crystal polymer materials with excellent properties.
従来、全芳香族ポリアミドおよび全芳香族ポリエステル
などの高分子材料が、高強度高弾性ならびに耐熱性液晶
高分子材料として工業的に使用されている（たとえば、
Ｐ、Ｗ、Ｍｏｒｇａｎ、Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ
、１０．１３８１（１９７７）、またはＪ、Ｐｏｌｙｍ
、Ｓｅｔ。Conventionally, polymeric materials such as wholly aromatic polyamides and wholly aromatic polyesters have been used industrially as high strength, high elasticity, and heat resistant liquid crystal polymer materials (for example,
P.W.Morgan, Macromolecules
, 10.1381 (1977), or J. Polym.
, Set.
Ｐｏｌｙｍ、Ｃｈｅｍ、Ｅｄ、、１４，２０４３゜（１
９７６）など）。Polym, Chem, Ed, 14,2043° (1
976) etc.).
上記の内、全芳香族ポリアミドは、ライオトロピック液
晶性を示すため、液晶紡糸によって繊維の形態にするこ
ともできる。一方、全芳香族ポリエステルはサーモトロ
ピック液晶性（すなわち、加熱ないし冷却することによ
って液晶状態が形成される液晶）を有しており、溶融状
態での成形が可能であるため、射出成形など方法を用い
て所望形状に成形することができる。Among the above, wholly aromatic polyamides exhibit lyotropic liquid crystallinity and can therefore be formed into fibers by liquid crystal spinning. On the other hand, fully aromatic polyester has thermotropic liquid crystallinity (i.e., a liquid crystal that forms a liquid crystal state when heated or cooled) and can be molded in a molten state, so it can be molded using methods such as injection molding. It can be molded into a desired shape.
しかしながら、上述した全芳香族ポリアミドは、比較的
機械的特性においてすぐれているものの、ライオトロピ
ック液晶性（すなわち、溶媒を加えて溶液化することに
よって液晶状態が形成される液晶）しか示さないので、
これを繊維の形態に成形する場合、液晶を一旦、溶液状
態にしてから紡糸するという成形加工方法を採らざるを
得ず、したがって成形加工性の点で問題がある。However, although the above-mentioned wholly aromatic polyamide has relatively excellent mechanical properties, it only exhibits lyotropic liquid crystallinity (i.e., a liquid crystal in which a liquid crystal state is formed by adding a solvent to form a solution).
When molding this into a fiber, it is necessary to adopt a molding method in which the liquid crystal is once in a solution state and then spun, which poses a problem in terms of moldability.
一方、上述した全芳香族ポリエステルは、液晶としては
サーモトロピック性を示すためこれをそのまま溶融した
状態での成形が可能であり、上記の全芳香族ポリアミド
に比べて成形特性においてすぐれているということがで
きるが、機械的強度、熱的特性においては十分満足のい
くものではないとい問題がある。On the other hand, the above-mentioned fully aromatic polyester exhibits thermotropic properties as a liquid crystal, so it can be molded in its molten state, and has superior molding properties compared to the above-mentioned fully aromatic polyamide. However, there is a problem that the mechanical strength and thermal properties are not fully satisfactory.
本発明は上述した点に鑑みてなされたものであり、サー
モトロピック液晶性を有し、かつ、力学的・熱的特性な
らびに成形性の双方にすぐれた液晶高分子材料を提供す
ることを目的としている。The present invention has been made in view of the above-mentioned points, and an object of the present invention is to provide a liquid crystal polymer material that has thermotropic liquid crystal properties and is excellent in both mechanical and thermal properties and moldability. There is.
上述した目的を達成するため、本発明に係るサーモトロ
ピック液晶高分子材料は、メソーゲン基とスペーサーか
らなる繰返し単位を骨格構造とし、かつ、該骨格構造中
にアミド結合を有するコポリエステルアミドからなるこ
とを特徴としている。In order to achieve the above-mentioned object, the thermotropic liquid crystal polymer material according to the present invention is composed of a copolyester amide having a skeleton structure consisting of a repeating unit consisting of a mesogen group and a spacer, and having an amide bond in the skeleton structure. It is characterized by
さらに、本発明に係るサーモトロピック液晶高分子材料
は、好ましくは、コポリエステルアミド中のアミド結合
の導入量が、６０モル％以下、さらに好ましくは２５モ
ル％以下であることを特徴としている。Further, the thermotropic liquid crystal polymer material according to the present invention is preferably characterized in that the amount of amide bonds introduced into the copolyesteramide is 60 mol% or less, more preferably 25 mol% or less.
以下、本発明を、実施例を含めてさらに詳細に説明する
。Hereinafter, the present invention will be described in further detail including Examples.
本発明のサーモトロピック液晶高分子材料は、基本的に
は、メソーゲン基とスペーサーからなる繰返し単位を骨
格構造とし、かつ、該骨格構造中にアミド結合を有する
コポリエステルアミドからなる。The thermotropic liquid crystal polymer material of the present invention basically consists of a copolyesteramide having a skeleton structure of repeating units consisting of a mesogen group and a spacer, and having an amide bond in the skeleton structure.
本発明のコポリエステルアミドは、所定のスぺ一ザー、
重合後にメソーゲン基となるカルボキシル基、水酸基、
酸塩化物あるいはアセチル基などの官能基を有する芳香
族二官能性モノマーと、メソーゲン基となるアミノ基を
有する芳香族二官能性モノマーとを重縮合反応させるこ
とによって得られる。The copolyesteramide of the present invention has a predetermined sprayer,
carboxyl group, hydroxyl group, which becomes mesogen group after polymerization,
It is obtained by polycondensation reaction between an aromatic bifunctional monomer having a functional group such as an acid chloride or an acetyl group and an aromatic bifunctional monomer having an amino group that becomes a mesogen group.
本発明の材料における芳香族化合物は、従来の液晶高分
子の骨格構造として用いられてきたものを使用すること
ができる。具体的には、ベンゼン、ナフタレン、ターフ
ェニル、ビフェニル、ジフェニルエーテル、アゾベンゼ
ン、ベンジリデンアニリン、ベンゾイルアニリン、ジフ
ェニルスルホン、トランスシクロヘキサン環、フェニル
ベンゾエート、ベンジリデンアセトフェノン、ベンジリ
デンアジンなどを用いることができる。As the aromatic compound in the material of the present invention, those that have been used as the skeleton structure of conventional liquid crystal polymers can be used. Specifically, benzene, naphthalene, terphenyl, biphenyl, diphenyl ether, azobenzene, benzylideneaniline, benzoylaniline, diphenylsulfone, transcyclohexane ring, phenylbenzoate, benzylideneacetophenone, benzylideneazine, and the like can be used.
また、スペーサーとなる分子鎖には、メチレン鎖、オキ
シエチレン鎖、オキシプロピレン鎖、オキシテトラメチ
レン鎖、シロキサン鎖などが導入されつる。In addition, a methylene chain, an oxyethylene chain, an oxypropylene chain, an oxytetramethylene chain, a siloxane chain, or the like can be introduced as a molecular chain to serve as a spacer.
得られるコポリエステルアミドの具体例を挙げると、た
とえば以下の一般式で表される高分子がある。Specific examples of the resulting copolyesteramide include polymers represented by the following general formula.
上式中、Ｒ１−Ｒ５は水素またはハロゲン、アルコキシ
、アルキルフェニルなどの炭化水素基であり、ｎ−２〜
１８、ｗ＝４〜２５、Ｘ＝０〜２、ｙ−０〜２０．２＝
０〜２である。In the above formula, R1-R5 are hydrogen or a hydrocarbon group such as halogen, alkoxy, alkylphenyl, etc., and n-2 to
18, w=4-25, X=0-2, y-0-20.2=
It is 0-2.
一般に、全芳香族ポリアミドはライオトロピック液晶性
を有するが、分子間の相互作用が強いため、全芳香族ポ
リエステルのようにサーモトロピック液晶性を示さず、
成形加工性が極めて乏しく、このため、たとえば繊維の
形態にするためには溶液から紡糸する方法を採らざるを
得ない。しかし、全芳香族ポリアミドは、たとえばケブ
ラに代表されるように分子間相互作用が大きいために、
力学的・熱的性質は、サーモトロピック液晶性を有する
全芳香族ポリエステルよりもすぐれている。In general, wholly aromatic polyamides have lyotropic liquid crystallinity, but due to strong interactions between molecules, they do not exhibit thermotropic liquid crystallinity like wholly aromatic polyesters.
Molding processability is extremely poor, and for this reason, in order to form fibers, for example, a method of spinning from a solution must be adopted. However, fully aromatic polyamides have large intermolecular interactions, as typified by Kevlar, so
The mechanical and thermal properties are superior to fully aromatic polyesters with thermotropic liquid crystallinity.
本発明の祠料においては、上記の問題の双方を解決する
ために、上記のようにコポリエステル中にアミド結合を
導入することによって液晶性と力学的・熱的性質の双方
において、その改善を図ろうとするものである。しかし
ながら、本発明者らの研究によれば、上記アミノ結合の
導入量によっては目的とする特性が得られないことが判
明している。In order to solve both of the above problems, the abrasive material of the present invention improves both liquid crystallinity and mechanical/thermal properties by introducing amide bonds into the copolyester as described above. This is what we are trying to achieve. However, according to the research conducted by the present inventors, it has been found that the desired properties cannot be obtained depending on the amount of the amino bond introduced.
すなわち、本発明のサーモトロピック液晶高分子材料は
、高分子中のアミド結合の量を、特に６０モル％以下、
さらに好ましくは２５モル％以下に制限することが肝要
である。本発明者らの知見によれば、高分子中のアミド
結合の導入量が６０モル％を超えると、力学的・熱的性
質は向上するもののサーモトロピック液晶性が著しく減
少するので好ましくない。That is, in the thermotropic liquid crystal polymer material of the present invention, the amount of amide bonds in the polymer is preferably 60 mol% or less,
More preferably, it is important to limit the amount to 25 mol% or less. According to the findings of the present inventors, if the amount of amide bonds introduced into the polymer exceeds 60 mol %, although the mechanical and thermal properties are improved, the thermotropic liquid crystallinity is significantly reduced, which is not preferable.
本発明においては、上記のアミド結合量は、重合開始前
の各成分モル比から計算により求めたものである。In the present invention, the above amide bond amount is calculated from the molar ratio of each component before the start of polymerization.
本発明のサーモトロピック液晶高分子材料は、サーモト
ロピック液晶性を有するとともに、機械的強度ならびに
熱的性質にもすぐれているので、本発明によれば、溶融
状態での成形加工が可能であり、しかも全芳香族ポリエ
ステルよりも力学的・熱的性質が一層向上した高分子祠
料が提供される。また、本発明のサーモトロピック液晶
高分子材料は分子中にアミド結合を特定量有しているの
で、従来の全芳香族ポリエステルにおいて問題となって
いた繊維軸と垂直方向の強度が著しく向上する点におい
てもすぐれている。The thermotropic liquid crystal polymer material of the present invention has thermotropic liquid crystallinity and also has excellent mechanical strength and thermal properties, so according to the present invention, it can be molded in a molten state, Moreover, a polymer abrasive material is provided which has even better mechanical and thermal properties than wholly aromatic polyester. In addition, since the thermotropic liquid crystal polymer material of the present invention has a specific amount of amide bonds in its molecules, the strength in the direction perpendicular to the fiber axis, which was a problem with conventional wholly aromatic polyesters, is significantly improved. It is also excellent in terms of
以下、本発明を実施例に基づいて説明するが本発明はこ
れら実施例の記載によって制限されるものではない。Hereinafter, the present invention will be explained based on Examples, but the present invention is not limited by the description of these Examples.
第１図に示す反応式に従ってコポリエステルアミドを合
成した。A copolyester amide was synthesized according to the reaction formula shown in FIG.
すなわち、エチル−４−ヒドロキシベンゾエートと１，
１０−ジブロムデカンのＷｉ Ｉ Ｉ ｌａｎ＋ｓｏｎ
のエチル合成に伴って化合物（１）を得たのち、加水分
解して４，４′−ジカルボキシ−１，１０−ジフェニル
デカン（２）を得た。That is, ethyl-4-hydroxybenzoate and 1,
Wi I I lan+son of 10-dibromedecane
Compound (1) was obtained by ethyl synthesis, and then hydrolyzed to obtain 4,4'-dicarboxy-1,10-diphenyldecane (2).
上記化合物（２）とジアセチル化−ｐ−フェニレンジア
ミン（３）とジアセチル化ハイドロキノン（４）を所定
量重合管に加え、オイル浴中で１００℃でｌｈｒ、１５
０℃でｌｈｒ、２４０°Ｃでｌｈｒ、３００℃で５ｈｒ
昇温しつつ加熱反応させた。さらに真空下で３００℃で
２ｈｒ重合を続は生成したポリマーは重合管をわって取
り出した。Predetermined amounts of the above compound (2), diacetylated p-phenylenediamine (3), and diacetylated hydroquinone (4) were added to a polymerization tube, and the mixture was heated in an oil bath at 100°C for 15 hours.
1hr at 0℃, 1hr at 240℃, 5hr at 300℃
A heating reaction was carried out while increasing the temperature. Further, polymerization was carried out at 300° C. for 2 hours under vacuum, and the resulting polymer was taken out through the polymerization tube.
第１図に示す生成物であるコポリエステルアミドの各繰
返し単位数に、１．およびｍの値を重縮合条件によって
変化させた場合の各種合成高分子について、熱的特性を
測定した。測定結果を下記第１表に示す。For each repeating unit number of the product copolyesteramide shown in FIG. The thermal properties of various synthetic polymers were measured when the values of and m were varied depending on the polycondensation conditions. The measurement results are shown in Table 1 below.
第１表
上記表中 Ｋ： 結晶化温度
Ｎ： ネマチック相転移温度
ｌ： イソトロピック相転移温度
Ｔ ｉ −Ｔｍ ： メソ相の温度範囲上記第１表に
示すように、たとえば、ｐ−アミノフェノールを２０％
含有するコポリエステルアミド（例２）におては、２３
２℃でネマチック相であり、３２４℃においてはイソト
ロピック相を示す。一方、同様の構造のポリエステル（
アミノフェノールは有さない）である例１においては、
対応するコポリエステルアミドよりも、７℃高いネマチ
ック温度を示し、２℃だけ低いイソトロピツク温度を示
す。このように、ｐ−アミノフェノール部分の導入量が
増加すると、ネマチック温度が高くなり、反対にｐ−ア
ミノフェノール部分の導入量が減少すると、イソトロピ
ック温度が低くなる。そして、ｐ−アミノフェノール部
分の導入量が５０％までの場合には、サーモトロピック
液晶性を示すコポリエステルアミドを与えるが、ｐ−ア
ミノフェノール部分が６０％含有するコポリエステルア
ミドは、もはやサーモトロピック液晶性を示さない。In Table 1 above, K: Crystallization temperature N: Nematic phase transition temperature l: Isotropic phase transition temperature T i -Tm: Temperature range of meso phase As shown in Table 1 above, for example, when p-aminophenol is 20%
In the copolyesteramide containing (Example 2), 23
It exhibits a nematic phase at 2°C and an isotropic phase at 324°C. On the other hand, polyester with a similar structure (
In Example 1, which has no aminophenol:
It exhibits a 7° C. higher nematic temperature and a 2° C. lower isotropic temperature than the corresponding copolyester amide. Thus, when the amount of p-aminophenol moiety introduced increases, the nematic temperature increases, and conversely, when the amount of p-aminophenol moiety introduced decreases, the isotropic temperature decreases. When the amount of p-aminophenol moiety introduced is up to 50%, a copolyesteramide exhibiting thermotropic liquid crystallinity is obtained, but a copolyesteramide containing 60% p-aminophenol moiety is no longer thermotropic. Does not exhibit liquid crystallinity.
同定
上記実施例で得られた合成高分子の同定は、ＮＭＲ，な
らびにＩＲによって行なった。Identification The synthetic polymer obtained in the above example was identified by NMR and IR.
下記第２表は、上記の例２と例５について、同相ならび
に溶液状態での６７．８ＭＨｚ”’Ｃ化学シフトの測定
結果を示すものである。ただし、化学シフトの基準物質
としては、固相スペクトルにおいてはテトラメチルシラ
ンを用い、溶液スペクトルは１． １． ２． ２−テ
トラクロロエタン−ｄ （ＴＣＥ−６２）とペンタ
フルオロフェノ−ル（Ｐ Ｐ Ｐ）との混合物中にて測
定した（２７℃）第２図に、高分子中の炭素の位置関係
を示す。Table 2 below shows the measurement results of 67.8 MHz'''C chemical shifts in the same phase and solution state for Examples 2 and 5 above.However, as a reference material for chemical shifts, solid phase Tetramethylsilane was used in the spectra, and the solution spectra were measured in a mixture of 1. 1. 2. 2-tetrachloroethane-d (TCE-62) and pentafluorophenol (P P P) (27 ℃) Figure 2 shows the positional relationship of carbon in the polymer.
第３図に、例２のコポリエステルアミドのＮＭＲスペク
トルを示す。第４図は、例５ならびに例１の溶液スペク
トルであり、第５図は、例１、例２および例５の溶液ス
ペクトルである。FIG. 3 shows the NMR spectrum of the copolyesteramide of Example 2. FIG. 4 is the solution spectrum of Example 5 and Example 1, and FIG. 5 is the solution spectrum of Example 1, Example 2, and Example 5.
また、例２のコポリエステルアミドについて、示差熱分
析を行った結果を第７図に示す。この場合の測定は、昇
温度速度ならびに冷却速度を各々２０℃／分で行った。Furthermore, the results of differential thermal analysis of the copolyesteramide of Example 2 are shown in FIG. In this case, the measurement was performed at a temperature increase rate and a cooling rate of 20° C./min.
第１図は重合過程を示す化学反応式、第２図はコポリエ
ステルアミドの炭素の位置を示す化学構造式、第３図〜
第５図はＮＭＲスペクトルのチャート図、第６図はＩＲ
スペクトルのチャート図、第７図は示差熱分析で得られ
たチャート図である。Figure 1 is a chemical reaction formula showing the polymerization process, Figure 2 is a chemical structural formula showing the carbon positions of copolyesteramide, and Figures 3-
Figure 5 is a chart of the NMR spectrum, Figure 6 is the IR spectrum.
The spectrum chart, FIG. 7, is a chart obtained by differential thermal analysis.
Claims (1)
格構造とし該骨格構造中にアミド結合を有するコポリエ
ステルアミドからなることを特徴とする、サーモトロピ
ック液晶高分子材料。 ２、コポリエステルアミド中のアミド結合の導入量が、
２５モル％以下であることを特徴とする、請求項１のサ
ーモトロピック液晶高分子材料。 ３、パラ結合芳香族ジアミンあるいはｐ−アミノフェノ
ールを含むことを特徴とする、請求項１のサーモトロピ
ック液晶高分子材料。[Scope of Claims] 1. A thermotropic liquid crystal polymer material, characterized in that it is made of a copolyesteramide whose skeleton structure is a repeating unit consisting of a mesogen group and a spacer, and which has an amide bond in the skeleton structure. 2. The amount of amide bond introduced into the copolyester amide is
The thermotropic liquid crystal polymer material according to claim 1, characterized in that the content is 25 mol% or less. 3. The thermotropic liquid crystal polymer material according to claim 1, characterized in that it contains a para-bonded aromatic diamine or p-aminophenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20539688A JPH0253824A (en) | 1988-08-18 | 1988-08-18 | Thermotropic liquid crystalline polymeric material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20539688A JPH0253824A (en) | 1988-08-18 | 1988-08-18 | Thermotropic liquid crystalline polymeric material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0253824A true JPH0253824A (en) | 1990-02-22 |
Family
ID=16506135
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20539688A Pending JPH0253824A (en) | 1988-08-18 | 1988-08-18 | Thermotropic liquid crystalline polymeric material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0253824A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100305685B1 (en) * | 1999-08-25 | 2001-09-24 | 조남홍 | Device for piercing the hole which exhaust residual gas of can container |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6390001A (en) * | 1986-10-01 | 1988-04-20 | Polyplastics Co | Head shell |
| JPS63105027A (en) * | 1986-10-22 | 1988-05-10 | Polyplastics Co | Liquid crystal polymer |
| JPS63105025A (en) * | 1986-10-22 | 1988-05-10 | Polyplastics Co | Liquid crystal polymer |
| JPH01319534A (en) * | 1988-06-21 | 1989-12-25 | Mitsubishi Kasei Corp | Aromatic polyester amide and production thereof |
| JPH03501030A (en) * | 1987-07-06 | 1991-03-07 | アライド‐シグナル・インコーポレーテッド | Aliphatic-aromatic poly(ester amide) alternation |
-
1988
- 1988-08-18 JP JP20539688A patent/JPH0253824A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6390001A (en) * | 1986-10-01 | 1988-04-20 | Polyplastics Co | Head shell |
| JPS63105027A (en) * | 1986-10-22 | 1988-05-10 | Polyplastics Co | Liquid crystal polymer |
| JPS63105025A (en) * | 1986-10-22 | 1988-05-10 | Polyplastics Co | Liquid crystal polymer |
| JPH03501030A (en) * | 1987-07-06 | 1991-03-07 | アライド‐シグナル・インコーポレーテッド | Aliphatic-aromatic poly(ester amide) alternation |
| JPH01319534A (en) * | 1988-06-21 | 1989-12-25 | Mitsubishi Kasei Corp | Aromatic polyester amide and production thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100305685B1 (en) * | 1999-08-25 | 2001-09-24 | 조남홍 | Device for piercing the hole which exhaust residual gas of can container |
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