JPH01229033A - Condensed copolymer with liquid crystal property - Google Patents
Condensed copolymer with liquid crystal propertyInfo
- Publication number
- JPH01229033A JPH01229033A JP5266588A JP5266588A JPH01229033A JP H01229033 A JPH01229033 A JP H01229033A JP 5266588 A JP5266588 A JP 5266588A JP 5266588 A JP5266588 A JP 5266588A JP H01229033 A JPH01229033 A JP H01229033A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- acid
- liquid crystal
- dimethyl
- solvent
- 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
- 239000004973 liquid crystal related substance Substances 0.000 title abstract description 9
- 229920001577 copolymer Polymers 0.000 title 1
- 229920000642 polymer Polymers 0.000 claims abstract description 42
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 9
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims description 7
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 6
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 4
- OMNHTTWQSSUZHO-UHFFFAOYSA-N 4-hydroxy-3,5-dimethylbenzoic acid Chemical compound CC1=CC(C(O)=O)=CC(C)=C1O OMNHTTWQSSUZHO-UHFFFAOYSA-N 0.000 abstract description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 18
- -1 thus useful for e.g. Substances 0.000 abstract description 5
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 abstract description 5
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 abstract description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 abstract description 3
- ASWXNYNXAOQCCD-UHFFFAOYSA-N dichloro(triphenyl)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(Cl)(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 ASWXNYNXAOQCCD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- YSJWNEDBIWZWOI-UHFFFAOYSA-N 2-hydroxy-3,4-dimethylbenzoic acid Chemical compound CC1=CC=C(C(O)=O)C(O)=C1C YSJWNEDBIWZWOI-UHFFFAOYSA-N 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000006068 polycondensation reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 8
- 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
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-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
- GDBUZIKSJGRBJP-UHFFFAOYSA-N 4-acetoxy benzoic acid Chemical compound CC(=O)OC1=CC=C(C(O)=O)C=C1 GDBUZIKSJGRBJP-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical class CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Liquid Crystal Substances (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、液晶性を有する共縮合重合体に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to a cocondensation polymer having liquid crystal properties.
共縮合重合体の原料の一つにｐ−オキシ安息香酸、また
は３．５−ジメチル−４−ヒドロキシ−安息香酸がある
。ｐ−オキシ安息香酸の縮合重合体は剛直で、耐熱性の
あるポリマーであるが、溶媒に溶解しない為、例えばキ
ャスティング等によるフィルム化が不可能であるなど、
溶液状態の加工ができない。また３、５−ジメチル−４
−ヒドロキシ−安息香酸の縮合重合体は各種の溶媒に可
溶であるが、ホモポリマーでは溶液液晶性を示さない。One of the raw materials for the cocondensation polymer is p-oxybenzoic acid or 3,5-dimethyl-4-hydroxybenzoic acid. The condensation polymer of p-oxybenzoic acid is a rigid and heat-resistant polymer, but because it does not dissolve in solvents, it is impossible to make it into a film by, for example, casting.
Processing in solution state is not possible. Also, 3,5-dimethyl-4
-Hydroxy-benzoic acid condensation polymers are soluble in various solvents, but homopolymers do not exhibit solution liquid crystallinity.
従ってｐ−オキシ安息香酸と３．５−ジメチル−４−ヒ
ドロキシ−安息香酸の長所を合わせ持つ共縮合重合体を
製造する研究も行われている。すなわち、高分子論文集
３３，６９３ （１９７６）にはｐ−オキシ安息香酸の
誘導体であるｐ−アセトキシ安息香酸、および３．５−
ジメチル−４−ビトロキシ−安息香酸の誘導体である３
、５−ジメチル−４−アセトキシ安息香酸を使用した共
縮合重合体の研究である。しかし得られた共縮合重合体
は溶液粘度が小さく、しかも分解温度も低い。Therefore, research is being conducted to produce cocondensation polymers that have both the advantages of p-oxybenzoic acid and 3,5-dimethyl-4-hydroxybenzoic acid. That is, in Kobunshi Ronsen 33, 693 (1976), p-acetoxybenzoic acid, which is a derivative of p-oxybenzoic acid, and 3.5-
3, a derivative of dimethyl-4-bitroxy-benzoic acid
, a study of cocondensation polymers using 5-dimethyl-4-acetoxybenzoic acid. However, the obtained cocondensation polymer has a low solution viscosity and a low decomposition temperature.
本発明の目的は、ｐ−オキシ安息香酸と３．５−ジメチ
ル−４−ヒドロキシ−安息香酸を原料とする共縮合重合
体であって、且つこの重合体が耐熱性に優れ、且つ特定
の溶媒に溶解した溶液が液晶性を示す新規な共縮合重合
体を得ることにある。The object of the present invention is to provide a cocondensation polymer made from p-oxybenzoic acid and 3,5-dimethyl-4-hydroxybenzoic acid, which has excellent heat resistance, and which is compatible with a specific solvent. The object of the present invention is to obtain a novel cocondensation polymer which exhibits liquid crystallinity when dissolved in a solution thereof.
（課題を解決するための手段〕
本発明者らは、前記課題を解決するため鋭意研究を行い
、本発明を完成するに到った。(Means for Solving the Problems) In order to solve the above problems, the present inventors have conducted extensive research and have completed the present invention.
すなわち、本発明の共縮合重合体は、ｐ−オキシ安息香
酸（ａ）と ３，５−ジメチル−４−ヒドロキシ−安息
香酸（ｂ）との共縮合重合体において、共縮合重合体の
組成比 （ａ）／（ｂ）カｏ、３５１０．６５〜０．６
５１０．３５であり、該共縮合重合体を溶剤にオルソク
ロロフェノールを使用し、５０℃で１０重量％溶解させ
た溶液が液晶性を有することを特徴とする共縮合重合体
である。That is, the cocondensation polymer of the present invention is a cocondensation polymer of p-oxybenzoic acid (a) and 3,5-dimethyl-4-hydroxybenzoic acid (b), and the composition ratio of the cocondensation polymer is (a)/(b) Kao, 3510.65-0.6
510.35, and is a cocondensation polymer characterized in that a solution obtained by dissolving the cocondensation polymer at 10% by weight at 50° C. using orthochlorophenol as a solvent has liquid crystallinity.
本発明における組成比（モル％）がｏ３５１０．６５〜
０．６５１０．３５である共縮合重合体は、ポリマー構
造上ランダム重合体であることが好ましく、また重合方
法はランダム重合体を少なくとも部分的に生成しつるも
のであれば如何なる方法でもよいか、次の方法により製
造する共縮合重合体が特に好ましい。The composition ratio (mol%) in the present invention is o3510.65~
The cocondensation polymer having a molecular weight of 0.6510.35 is preferably a random polymer in terms of polymer structure, and any polymerization method may be used as long as it at least partially produces a random polymer. Particularly preferred are cocondensation polymers produced by the following method.
すなわち、重合溶媒として、（１）塩素系溶媒、例えば
多塩素化エタン、多塩素化プロパン、クロルヘンゼン、
ジクロルベンゼン等、（２）非プロトン性強極性溶媒、
例えばニトロベンゼン、Ｎ−メチルピロリドン、ジメチ
ルイミダゾリジノン、ジメチルスルホキシド、ジメチル
ホルムアモト、ジメチルアセトアミド等の溶媒をそれぞ
れ単独であるいは混合して用いる。That is, as a polymerization solvent, (1) a chlorinated solvent such as polychlorinated ethane, polychlorinated propane, chlorhenzene,
dichlorobenzene etc., (2) aprotic strong polar solvent,
For example, solvents such as nitrobenzene, N-methylpyrrolidone, dimethylimidazolidinone, dimethylsulfoxide, dimethylformamoto, and dimethylacetamide are used alone or in combination.
次いで、これらの溶媒にトリフェニルフォスフインオキ
シドを加え、これに更にフォスゲンまたは蓚酸クロライ
ドを加え、溶媒中で触媒として作用するトリフェニルフ
ォスフインジクロライドを生成させる。Next, triphenylphosphine oxide is added to these solvents, and phosgene or oxalic acid chloride is further added thereto to generate triphenylphosphine dichloride which acts as a catalyst in the solvent.
フォスゲンまたは蓚酸クロライドは、通常、トリフェニ
ルフォスフインオキシドに対し、モル比で５〜１０％多
く使用する。またトリフェニルフォスフインジクロライ
トは加熱により、トリフェニルフォスフインオキシドに
分解するため、上記の反応はてきるだけ短時間で行う必
要があり、好まし、くは１５分以内である。トリフェニ
ルフォスフインジクロライドの使用量は、所望とする共
縮合重合体の分子量により変動させるが、通常上ツマ−
の合計量に対し１．１モル倍使用するのが好ましい。Phosgene or oxalic acid chloride is usually used in a molar ratio of 5 to 10% more than triphenylphosphine oxide. Furthermore, since triphenylphosphine dichlorite is decomposed into triphenylphosphine oxide by heating, the above reaction needs to be carried out in as short a time as possible, preferably within 15 minutes. The amount of triphenylphosphine dichloride to be used varies depending on the molecular weight of the desired cocondensation polymer, but it is usually
It is preferable to use 1.1 times the total amount by mole.
トリフェニルフォスフインジクロライトが生成した段階
でｐ−オキシ安息香酸と ３．５−ジメチル−４−ヒド
ロキシ安息香酸を所定量を加え、加熱して共縮合重合を
行わせる。この場合共縮合重合反応を促進させる為に、
酸受容体として塩基を添加することが好ましい。この場
合の塩基としては三級アミンか好ましく、トリエチルア
ミン、ピリジン類、Ｎ−アルキルモルフォリン、 Ｎ、
Ｎ−ジアルキルアニリン等であるが特にトリエチルアミ
ン、ピリジンまたはそれ等の混合物が良い。At the stage when triphenylphosphine dichlorite is produced, predetermined amounts of p-oxybenzoic acid and 3,5-dimethyl-4-hydroxybenzoic acid are added and heated to carry out cocondensation polymerization. In this case, in order to promote the cocondensation polymerization reaction,
Preference is given to adding a base as an acid acceptor. In this case, the base is preferably a tertiary amine, such as triethylamine, pyridines, N-alkylmorpholine, N,
N-dialkylaniline, etc., particularly triethylamine, pyridine, or a mixture thereof are preferred.
トリエチルアミンの使用では、反応が激しくおこり、重
合液の粘度が急上昇するが、トリエチルアミンとピリジ
ンを混合して用いると反応速度を調節できる為、好適で
ある。When triethylamine is used, the reaction occurs violently and the viscosity of the polymerization solution increases rapidly, but it is preferable to use a mixture of triethylamine and pyridine because the reaction rate can be adjusted.
反応温度は高ければ共縮合重合反応は速く進むが、−膜
内には５０℃以上２５０℃以下であり、使用する溶媒と
酸受容体との混合物の沸点までの温ＪＸで行うのが良い
。The higher the reaction temperature, the faster the cocondensation polymerization reaction will proceed, but the temperature within the membrane should be 50°C or higher and 250°C or lower, and it is preferable to carry out the reaction at a temperature up to the boiling point of the mixture of the solvent and acid acceptor used.
反応時間は１５分〜１２時間、好ましくは３０分〜４時
間で反応は完結し、高収率で目的の共縮合重合体か得ら
れる。反応物はそのまま冷却するか、反応に用いた溶媒
を加えて希釈後、攪拌下に冷メタノール中にそそぎ共縮
合重合体を析出させる。The reaction is completed in 15 minutes to 12 hours, preferably 30 minutes to 4 hours, and the desired cocondensation polymer is obtained in high yield. The reaction product is either cooled as it is, or diluted by adding the solvent used in the reaction, and then poured into cold methanol with stirring to precipitate a cocondensation polymer.
その組成比 （ａ）／ （ｂ） （モル比）が０．３
５７０．６５〜０．６５１０．３５のときに生成する共
縮合重合体は、モノクロロ酢酸、オルソクロルフェノー
ル、テトラクロロエタン／フェノール混合溶媒等に可溶
であり、５０℃で約４０重量％まで可溶であり、その濃
厚溶液は液晶性を示し、その溶液から溶媒を蒸発等によ
り除くことにより、分子鎖の配向したフィルムまたは繊
維を得ることができる。Ｐ−オキシ安息香酸（ａ）が０
．６５ （モル比）より多い場合には上記溶媒に溶解し
なくなり、また逆に３．５＝ジメチル−４−ヒドロキシ
−安息香酸（ｂ）が０．６５（モル比）より多い場合に
は共縮合重合体の耐熱性か低下しまた溶媒に溶解させて
も液晶性を示さない。Its composition ratio (a)/(b) (molar ratio) is 0.3
The cocondensation polymer produced when 570.65 to 0.6510.35 is soluble in monochloroacetic acid, orthochlorophenol, tetrachloroethane/phenol mixed solvent, etc., and is soluble up to about 40% by weight at 50°C. The concentrated solution exhibits liquid crystallinity, and by removing the solvent from the solution by evaporation or the like, a film or fiber with oriented molecular chains can be obtained. P-oxybenzoic acid (a) is 0
．． If the amount is more than 65 (molar ratio), it will not dissolve in the above solvent, and conversely, if the amount of 3.5=dimethyl-4-hydroxy-benzoic acid (b) is more than 0.65 (molar ratio), cocondensation will occur. The heat resistance of the polymer decreases, and it does not exhibit liquid crystallinity even when dissolved in a solvent.
また組成比 （ａ）／ （ｂ） （モル比）が０．３
５７０．６５〜０．６５１０．３５を有する共重縮合体
はオルソクロロフェノールに溶解させ、粘度ηｓｐ／Ｃ
を測定したところ０．５以上の値を示し、ざらにＧＰＣ
測定により分子量を測定したところ、（標準ポリスチレ
ン換算より）いずれも１００，０００以上であった。Also, the composition ratio (a)/(b) (molar ratio) is 0.3
The copolycondensate having a viscosity of 570.65 to 0.6510.35 was dissolved in orthochlorophenol, and the viscosity ηsp/C
When measured, it showed a value of 0.5 or more, and roughly GPC
When the molecular weights were measured, they were all 100,000 or more (based on standard polystyrene standards).
以上のような本発明の共縮合重合体は、先に述べたよう
に、分子鎖の配向したフィルムまたは繊維として加工で
き、例えば液晶表示素子、液晶テレビ等の用途に有用で
ある。As mentioned above, the cocondensation polymer of the present invention can be processed into a film or fiber with oriented molecular chains, and is useful for, for example, applications such as liquid crystal display elements and liquid crystal televisions.
以下、本発明を実施例により具体的に説明する。 Hereinafter, the present invention will be specifically explained with reference to Examples.
実施例１
１００ｍＩＬの四つロフラスコに攪拌器、滴下ロート、
還流冷却器、窒素パージ用導入管をとりつけ、フラスコ
内を乾燥窒素で十分に置換した後、１０ｏ＋ＩＬのクロ
ルベンゼンと １０ｍＪＺのＮ−メチルピロリドンおよ
び８．９４ｇ（０，０３２ｍｏｌ）のトリフェニルフォ
スフインオキシドを加え攪拌した。次に４．１０ｇ（０
，０３２ｍｏｌ）の蓚酸クロライドと １０ｍ２のクロ
ルベンゼンの混合液を１０分間で滴下した。滴下により
発生するガスは窒素と共に系外に搬出させ、アルジオキ
シフォスフオニウムクロライドを生成させた。ガス発生
停止後、ｐ−オキシ安息香酸２．０７ｇ（０，０１５０
Ｉｏｌ）と３．５−ジメチル−４−ヒドロキシ安息香酸
２．４９ｇ（０，Ｏ１５ｍｏｌ）の混合物を加え、反応
液を２５℃に冷却して、３．０３ｇ（０，０３ｍｏｌ）
のトリエチルアミンと２．３７ｇ（０，０３ｍｏｌ）の
とリジンの混合物を酸受容体として加え、 １２５℃で
１時間攪拌し反応させた。Example 1 A 100 mL four-loop flask was equipped with a stirrer, a dropping funnel,
Attach a reflux condenser and a nitrogen purge inlet pipe, and after thoroughly purging the inside of the flask with dry nitrogen, add 10o+IL of chlorobenzene, 10mJZ of N-methylpyrrolidone, and 8.94g (0,032mol) of triphenylphosphine oxide. was added and stirred. Next, 4.10g (0
, 032 mol) of oxalic acid chloride and 10 m2 of chlorobenzene were added dropwise over 10 minutes. The gas generated by the dropping was carried out of the system together with nitrogen to generate aldioxyphosphonium chloride. After the gas generation stopped, 2.07 g of p-oxybenzoic acid (0,0150
A mixture of 2.49 g (0.015 mol) of 3.5-dimethyl-4-hydroxybenzoic acid and 3.03 g (0.03 mol) was added, and the reaction solution was cooled to 25°C.
A mixture of 2.37 g (0.03 mol) of triethylamine and 2.37 g (0.03 mol) of lysine was added as an acid acceptor, and the mixture was stirred at 125° C. for 1 hour to react.
反応物を１２の冷メタノール中に攪拌下に滴下し、ポリ
マーを析出させた。析出したポリマーを濾別し真空乾燥
させた。ポリマー収率は装入原料に対して８９％であり
ポリマーの組成は元素分析よりｐ−オキシ安息香酸５２
ｍｏ１％、３．５−ジメチル−４−ヒドロキシ安息香酸
４８ｍｏ１％を含んでいた。。The reactant was added dropwise to 12 liters of cold methanol under stirring to precipitate a polymer. The precipitated polymer was filtered off and dried under vacuum. The polymer yield was 89% based on the charged raw material, and the composition of the polymer was determined by elemental analysis to be 52 p-oxybenzoic acid.
It contained 48 mo1% of 3.5-dimethyl-4-hydroxybenzoic acid. .
ポリマー０．１ｇをオルソクロルフェノールｌＯｍｆｌ
に溶解しオストワルト粘度計により３０℃で測定した結
果ηｓｐ／Ｃは１．０３であり、フィルム繊維用に適す
るものであった。またポリマーの熱分解開始温度（昇温
速度５℃／ｍｉｎで昇温したときの、５％重量減少温度
）は４５０℃であり、溶剤としてオルソクロロフェノー
ルを使用し、５０℃で１０重量％溶解させた溶液を偏光
顕微鏡により観察した結果、液晶による偏光が検出され
た。Add 0.1 g of polymer to orthochlorophenol
The η sp/C was measured at 30° C. using an Ostwald viscometer and was found to be 1.03, which was suitable for film fibers. The thermal decomposition initiation temperature of the polymer (temperature at which 5% weight loss occurs when the temperature is increased at a heating rate of 5°C/min) is 450°C, and orthochlorophenol is used as a solvent, and 10% by weight is dissolved at 50°C. As a result of observing the solution using a polarizing microscope, polarized light due to the liquid crystal was detected.
また液晶溶液より溶媒を留去したフィルムは引張り強度
、低収縮率の点です、ぐれていた。In addition, the film obtained by distilling off the solvent from the liquid crystal solution was inferior in terms of tensile strength and low shrinkage rate.
実施例２〜３および比較例１〜４
モノマー組成比（ｍｏ１％）を表のように変化させて、
実施例１と同様にして合成し高収率で共縮合重合体を得
た。Examples 2 to 3 and Comparative Examples 1 to 4 By changing the monomer composition ratio (mo1%) as shown in the table,
It was synthesized in the same manner as in Example 1 to obtain a cocondensation polymer in high yield.
得られたポリマーは元素分析の結果、装入原料モル比と
ほとんど一致した。As a result of elemental analysis, the molar ratio of the obtained polymer almost matched the molar ratio of the charged raw materials.
実施例１と同様にして、粘度、溶液の液晶性、オルソク
ロロフェノール（５０℃）に対する溶解性、熱分解開始
温度をそれぞれ測定して第１表に示した。In the same manner as in Example 1, the viscosity, liquid crystallinity of the solution, solubility in orthochlorophenol (50°C), and thermal decomposition initiation temperature were measured and shown in Table 1.
第１表に示す実施例および比較例より、Ｐ−ヒドロキシ
安息香酸と３．５−ジメチル−４−ヒドロキシ安息香酸
のモル組成比がそれぞれ０．６５７０．３５〜０．３５
／ ０．６５の範囲のものが、溶解性に優れ、溶液は液
晶性を示し、また粘度及び熱分解開始温度共に高いこと
を確認できた。From the examples and comparative examples shown in Table 1, the molar composition ratio of P-hydroxybenzoic acid and 3.5-dimethyl-4-hydroxybenzoic acid is 0.6570.35 to 0.35, respectively.
/0.65 had excellent solubility, the solution exhibited liquid crystallinity, and it was confirmed that both the viscosity and the thermal decomposition initiation temperature were high.
（発明の効果）
Ｐ−ヒドロキシ安息香酸と ３．５−ジメチル−４−ヒ
ドロキシ−安息香酸のモル組成比がそれぞれ０．６５７
０．３５〜０．３５７０．６５の範囲にある共縮合取合
体は特定の溶媒に溶解させたときに、液晶性を示す。ま
た、配向状態でフィルム、ｍ維等にすることにより高強
度、耐熱性、低収縮性を示す芳香族系重合体として極め
て有用である。(Effect of the invention) The molar composition ratio of P-hydroxybenzoic acid and 3.5-dimethyl-4-hydroxybenzoic acid is 0.657, respectively.
A co-condensed aggregate in the range of 0.35 to 0.3570.65 exhibits liquid crystallinity when dissolved in a specific solvent. In addition, it is extremely useful as an aromatic polymer that exhibits high strength, heat resistance, and low shrinkage when made into a film, m-fiber, etc. in an oriented state.
特許出願人 五井東圧化学株式会社 代 理 人 弁理士 若 林 忠Patent applicant: Goi Toatsu Chemical Co., Ltd. Representative Patent Attorney Tadashi Wakabayashi
Claims (1)
４−ヒドロキシ−安息香酸（ｂ）との共縮合重合体にお
いて、共縮合重合体の組成比（ａ）／（ｂ）が０．３５
／０．６５〜０．６５／０．３５であり、該共縮合重合
体を溶剤にオルソクロロフェノールを使用し、５０℃で
１０重量％溶解させた溶液が液晶性を有することを特徴
とする共縮合重合体。(1) p-oxybenzoic acid (a) and 3,5-dimethyl-
In the cocondensation polymer with 4-hydroxy-benzoic acid (b), the composition ratio (a)/(b) of the cocondensation polymer is 0.35.
/0.65 to 0.65/0.35, and a solution obtained by dissolving the cocondensation polymer at 10% by weight at 50°C using orthochlorophenol as a solvent has liquid crystallinity. Cocondensation polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5266588A JPH01229033A (en) | 1988-03-08 | 1988-03-08 | Condensed copolymer with liquid crystal property |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5266588A JPH01229033A (en) | 1988-03-08 | 1988-03-08 | Condensed copolymer with liquid crystal property |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01229033A true JPH01229033A (en) | 1989-09-12 |
Family
ID=12921166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5266588A Pending JPH01229033A (en) | 1988-03-08 | 1988-03-08 | Condensed copolymer with liquid crystal property |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01229033A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5092390A (en) * | 1973-12-21 | 1975-07-23 |
-
1988
- 1988-03-08 JP JP5266588A patent/JPH01229033A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5092390A (en) * | 1973-12-21 | 1975-07-23 |
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