JPS6310724B2 - - Google Patents
Info
- Publication number
- JPS6310724B2 JPS6310724B2 JP57011875A JP1187582A JPS6310724B2 JP S6310724 B2 JPS6310724 B2 JP S6310724B2 JP 57011875 A JP57011875 A JP 57011875A JP 1187582 A JP1187582 A JP 1187582A JP S6310724 B2 JPS6310724 B2 JP S6310724B2
- Authority
- JP
- Japan
- Prior art keywords
- diisocyanate
- formula
- mol
- tricyclic
- reaction
- 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
Links
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000004952 Polyamide Substances 0.000 claims description 13
- 229920002647 polyamide Polymers 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 10
- -1 diisocyanate compound Chemical class 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000001302 tertiary amino group Chemical group 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 16
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 14
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- 239000004760 aramid Substances 0.000 description 3
- 229920003235 aromatic polyamide Polymers 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- NFBOHOGPQUYFRF-UHFFFAOYSA-N oxanthrene Chemical compound C1=CC=C2OC3=CC=CC=C3OC2=C1 NFBOHOGPQUYFRF-UHFFFAOYSA-N 0.000 description 3
- GJSGGHOYGKMUPT-UHFFFAOYSA-N phenoxathiine Chemical compound C1=CC=C2OC3=CC=CC=C3SC2=C1 GJSGGHOYGKMUPT-UHFFFAOYSA-N 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- GVIJJXMXTUZIOD-UHFFFAOYSA-N thianthrene Chemical compound C1=CC=C2SC3=CC=CC=C3SC2=C1 GVIJJXMXTUZIOD-UHFFFAOYSA-N 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 2
- SDFLTYHTFPTIGX-UHFFFAOYSA-N 9-methylcarbazole Chemical compound C1=CC=C2N(C)C3=CC=CC=C3C2=C1 SDFLTYHTFPTIGX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- XKEFYDZQGKAQCN-UHFFFAOYSA-N 1,3,5-trichlorobenzene Chemical compound ClC1=CC(Cl)=CC(Cl)=C1 XKEFYDZQGKAQCN-UHFFFAOYSA-N 0.000 description 1
- ICFDTWPLDBJRBV-UHFFFAOYSA-N 10-methylphenoxazine Chemical compound C1=CC=C2N(C)C3=CC=CC=C3OC2=C1 ICFDTWPLDBJRBV-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- QYKONCJMGHXSRX-UHFFFAOYSA-N 2,7-dimethyldibenzo-p-dioxin Chemical compound CC1=CC=C2OC3=CC(C)=CC=C3OC2=C1 QYKONCJMGHXSRX-UHFFFAOYSA-N 0.000 description 1
- LIJMFNWKSNVCIF-UHFFFAOYSA-N 2,7-dimethylphenoxathiine Chemical compound CC1=CC=C2OC3=CC(C)=CC=C3SC2=C1 LIJMFNWKSNVCIF-UHFFFAOYSA-N 0.000 description 1
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- JCELWOGDGMAGGN-UHFFFAOYSA-N N=C=O.N=C=O.C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 JCELWOGDGMAGGN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- RHFUXPCCELGMFC-UHFFFAOYSA-N n-(6-cyano-3-hydroxy-2,2-dimethyl-3,4-dihydrochromen-4-yl)-n-phenylmethoxyacetamide Chemical compound OC1C(C)(C)OC2=CC=C(C#N)C=C2C1N(C(=O)C)OCC1=CC=CC=C1 RHFUXPCCELGMFC-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- WKFBZNUBXWCCHG-UHFFFAOYSA-N phosphorus trifluoride Chemical compound FP(F)F WKFBZNUBXWCCHG-UHFFFAOYSA-N 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Description
[発明の目的]
(産業業上の利用分野)
本発明は、三環式複素縮合環を有するポリアミ
ドの新規な製造法に関し、更に詳しくは、三環式
複素縮合環化合物をジアミノ化することなく、該
化合物から直接に一工程で、しかも副生成物を生
じることなく三環式複素縮合環を有するポリアミ
ドを製造する方法に関する。
(従来の技術)
従来、芳香族ポリアミドの基本的な製造法は、
芳香族ジアミン化合物と芳香族ジカルボン酸化合
物もしくはその酸ハロゲン化合物との重縮合反応
を利用するものであつた。得られた芳香族ポリア
ミドは、優れた耐熱性及び機械的強度特性をもつ
が、その反面、有機溶剤に対する溶解性が悪く、
また、高融点かつ高結晶性であつて、射出・成形
が不可能であつた。従つて、繊維、フイルム、塗
膜等への成形が極めて困難であるという、著しい
実用上の制約を受けていた。
このため、優れた成形加工性をも有する芳香族
ポリアミドの研究が進められ、例えば米国特許第
3503931号明細書にみられるように芳香族ポリエ
ーテルアミドが、またジヤーナル・オブ・ポリマ
ー・サイエンス:ポリマー・ケミストリイ・エデ
イシヨン、第18巻、2163頁、1980年[Journal of
Polymer Science:Polymer Chemistry
Edition,Vol.18,2163(1980)]等にみられるよ
うに、三環式複素縮合環を有するポリアミドが提
案されている。これらのうち、後者によるポリア
ミドは、優れた耐熱性、成形加工性を有するもの
である。
これは次の反応式:
で表わされるように、三環式複素縮合環化合物の
ジアミノ化体[]をN―メチル―ピロリドン等
の溶媒中で、芳香族ジ酸クロライド体[]と重
縮合反応させ、三環式複素縮合環を有するポリア
ミド[]を得るものである。
しかし、この反応には下述する重大な欠点があ
つた。
第1に、この反応に先立つて、三環式複素縮合
環化合物をジアミノ化するための多くの工程を要
するため、全体としてコスト高になることであ
る。
第2に、この反応は重縮合反応であるから、副
生成物として塩化水素が生じることである。この
塩化水素は重縮合反応を阻害し、かつ反応装置を
腐食するので、工業的には不利である。
第3に、反応試剤のジアミノ化体[]及びジ
酸クロライド体[]が共に不安定なので、これ
らの保存、取扱いが困難なことである。
(発明が解決しようとする問題点)
本発明は、三環式複素縮合環を有するポリアミ
ドの製造法における上記の欠点を解消したもの
で、三環式複素縮合環化合物をジアミノ化するこ
となく、該化合物から直線に一工程で、しかも副
生成物を生じることなく三環式複素縮合環を有す
るポリアミドを製造する方法を提供することを目
的とするものである。
[発明の構成]
(問題点を解決するための手段及び作用)
本発明は、ジイソシアナート化合物と;
次式:
[Object of the invention] (Field of industrial application) The present invention relates to a novel method for producing a polyamide having a tricyclic heterofused ring, and more specifically, a method for producing a polyamide having a tricyclic heterofused ring without diaminating the tricyclic heterofused ring compound. , relates to a method for producing polyamides having tricyclic heterofused rings directly from said compounds in one step and without producing by-products. (Conventional technology) Conventionally, the basic manufacturing method for aromatic polyamide is as follows:
It utilized a polycondensation reaction between an aromatic diamine compound and an aromatic dicarboxylic acid compound or its acid halide. The obtained aromatic polyamide has excellent heat resistance and mechanical strength properties, but on the other hand, it has poor solubility in organic solvents.
Furthermore, it had a high melting point and high crystallinity, making injection and molding impossible. Therefore, it is extremely difficult to form into fibers, films, coatings, etc., which is a significant practical limitation. For this reason, research into aromatic polyamides, which also have excellent moldability, has been progressing, and for example, US Patent No.
3503931, Journal of Polymer Science: Polymer Chemistry Editions, Volume 18, Page 2163, 1980 [Journal of Polymer Science: Polymer Chemistry Editions]
Polymer Science: Polymer Chemistry
Edition, Vol. 18, 2163 (1980)], polyamides having tricyclic heterofused rings have been proposed. Among these, the latter polyamide has excellent heat resistance and moldability. This is the following reaction equation: As expressed by A polyamide [] having a ring is obtained. However, this reaction had serious drawbacks as described below. First, prior to this reaction, many steps are required to diaminate the tricyclic condensed heterocyclic compound, resulting in an overall high cost. Second, since this reaction is a polycondensation reaction, hydrogen chloride is produced as a by-product. This hydrogen chloride inhibits the polycondensation reaction and corrodes the reaction equipment, which is industrially disadvantageous. Thirdly, both the diaminated form [] and the diacid chloride form [] of the reaction reagent are unstable, making it difficult to store and handle them. (Problems to be Solved by the Invention) The present invention solves the above-mentioned drawbacks in the method for producing a polyamide having a tricyclic condensed heterocyclic ring. The object of the present invention is to provide a method for producing a polyamide having a tricyclic condensed heterocyclic ring from the compound in a straight line in one step without producing by-products. [Structure of the invention] (Means and effects for solving the problems) The present invention provides a diisocyanate compound and the following formula:
【式】
又は
(式中、X1,X2及びX3は、それぞれ―O―、
―S―、[Formula] or (In the formula, X 1 , X 2 and X 3 are respectively -O-,
-S-,
【式】を表わし;R1,R2,R3及び
R4は、それぞれ炭素数1〜5のアルキル基、―
OR6で示されるアルコキシ基、[Formula]; R 1 , R 2 , R 3 and R 4 are each an alkyl group having 1 to 5 carbon atoms, -
an alkoxy group represented by OR 6 ,
【式】で示さ
れる第三アミノ基を表わし;R5,R6,R7及びR8
は、それぞれ炭素数1〜5のアルキル基を表わ
し;n1,n2,n3及びn4は、それぞれ0〜3の整数
を表わす。また、X1及びX2、R1及びR2,R3及び
R4並びにR7及びR8は、それぞれ同一であつても
異なつていてもよく、n1,n2,n3及びn4が2〜3
の整数であるとき、複数個のR1,R2,R3及びR4
は、それぞれ同一であつても異なつていてもよ
い)。
で示される三環式複素縮合環化合物のうちの少な
くとも一種とを;
フリーデル―クラフツ型触媒の存在下、重付加
反応させることを特徴とする。
本発明に用いるジイソシアナート化合物として
は、m―フエニレンジイソシアナート、p―フエ
ニレンジイソシアナート、2,4―トリレンジイ
ソシアナート、2,6―トリレンジイソシアナー
ト、2,6―キシレン―1,4―ジイソシアナー
ト等のフエニルジイソシアナート及びその誘導
体;ビフエニル―4,4′―ジイソシアナート、ジ
フエニルメタン―4,4′―ジイソシアナート、
2,2′―ジメチルジフエニルメタン―4,4′―ジ
イソシアナート、ジフエニルエーテル―4,4′―
ジイソシアナート、ジフエニルスルフイド―4,
4′―ジイソシアナート、ジフエニルスルホン―
4,4′―ジイソシアナート等のジフエニルジイソ
シアナート及びその誘導体;ナフタリン―1,5
―ジイソシアナート等のナフタリンジイソシアナ
ート及びその誘導体;トリフエニルメタン―4,
4′―ジイソシアナート等のトリフエニルメタンジ
イソシアナート及びその誘導体;又は、ヘキサメ
チレンジイソシアナート等のポリメチレンジイソ
シアナート及びその誘導体;が挙げられる。
これらのうち、本発明方法においては、m―フ
エニレンジイソシアナート、p―フエニレンジイ
ソシアナート、2,4―トリレンジイソシアナー
ト、2,6―トリレンジイソシアナート、ジフエ
ニルメタン―4,4′―ジイソシアナート、ナフタ
リン―1,5―ジイソシアナートが好ましい。
本発明に用いる三環式複素縮合環化合物として
は、ジベンゾ―p―ジオキシン、2,7―ジメチ
ル―ジベンゾ―p―ジオキシン、フエノキサチイ
ン、2,7―ジメチルフエノキサチイン、チアン
トレン、2,8―ジメチルアミノ―チアントレ
ン、N―メチル―フエノキサジン、N―メチル―
フエノチアジン、ジフエニレンオキシド、ジフエ
ニレンスルフイド、N―メチル―カルバゾール等
が例示される。
これらのうち、本発明方法においては、ジフエ
ニレンオキシド、ジフエニレンスルフイド、ジベ
ンゾ―p―ジオキシン、チアントレン、フエノキ
サチインが好ましい。
尚、三環式複素縮合環化合物において、R1〜
R8で表わされる炭素数1〜5のアルキル基の具
体例としては、メチル、エチル、プロピル、i―
プロピル、n―ブチル、t―ブチル、アミル等が
挙げられる。
また、本発明に用いるフリーデル―クラフツ型
触媒としては、塩化アルミニウム、塩化第二鉄、
塩化スズ、塩化チタン、塩化亜鉛、塩化アンチモ
ン、塩化インジウム、塩化銅、三フツ化ホウ素、
三フツ化リン、五酸化リン、フルオロホウ酸、フ
ルオロリン酸、塩酸、硫酸、ヘテロポリ酸等の無
機酸又はp―トルエンスルホン酸等の有機酸が挙
げられる。
本発明の製造法としては、常用されている重付
加反応方法であればいずれも適用できる。好まし
くは、塊状重合、溶液重合である。かかる重付加
反応を反応式で表すと次のとおりである。
又は、
[上記の反応式中、R9はアルキル基で置換も
しくは置換されないアルキレン基、アリレン基
(−(CH2)−o,[Formula] represents a tertiary amino group; R 5 , R 6 , R 7 and R 8
each represents an alkyl group having 1 to 5 carbon atoms; n 1 , n 2 , n 3 and n 4 each represent an integer of 0 to 3. Also, X 1 and X 2 , R 1 and R 2 , R 3 and
R 4 and R 7 and R 8 may be the same or different, and n 1 , n 2 , n 3 and n 4 are 2 to 3.
is an integer of R 1 , R 2 , R 3 and R 4
may be the same or different). It is characterized by carrying out a polyaddition reaction with at least one of the tricyclic heterofused ring compounds represented by: in the presence of a Friedel-Crafts type catalyst. The diisocyanate compounds used in the present invention include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,6-xylene -1,4-diisocyanate and other phenyl diisocyanates and their derivatives; biphenyl-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate,
2,2'-dimethyldiphenylmethane-4,4'-diisocyanate, diphenyl ether-4,4'-
Diisocyanate, diphenyl sulfide-4,
4'-diisocyanate, diphenyl sulfone-
Diphenyl diisocyanate and its derivatives such as 4,4'-diisocyanate; naphthalene-1,5
-Naphthalene diisocyanate and its derivatives such as diisocyanate; triphenylmethane-4,
Examples include triphenylmethane diisocyanate and its derivatives such as 4'-diisocyanate; or polymethylene diisocyanate and its derivatives such as hexamethylene diisocyanate. Among these, in the method of the present invention, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4' -diisocyanate and naphthalene-1,5-diisocyanate are preferred. The tricyclic heterofused ring compounds used in the present invention include dibenzo-p-dioxin, 2,7-dimethyl-dibenzo-p-dioxin, phenoxathiin, 2,7-dimethylphenoxathiin, thianthrene, 2,8- Dimethylamino-thianthrene, N-methyl-phenoxazine, N-methyl-
Examples include phenothiazine, diphenylene oxide, diphenylene sulfide, and N-methyl-carbazole. Among these, diphenylene oxide, diphenylene sulfide, dibenzo-p-dioxin, thianthrene, and phenoxathiin are preferred in the method of the present invention. In addition, in the tricyclic heterofused ring compound, R 1 ~
Specific examples of the alkyl group having 1 to 5 carbon atoms represented by R 8 include methyl, ethyl, propyl, i-
Examples include propyl, n-butyl, t-butyl, amyl, and the like. In addition, the Friedel-Crafts type catalyst used in the present invention includes aluminum chloride, ferric chloride,
Tin chloride, titanium chloride, zinc chloride, antimony chloride, indium chloride, copper chloride, boron trifluoride,
Examples include inorganic acids such as phosphorus trifluoride, phosphorus pentoxide, fluoroboric acid, fluorophosphoric acid, hydrochloric acid, sulfuric acid, and heteropolyacid, and organic acids such as p-toluenesulfonic acid. As the production method of the present invention, any commonly used polyaddition reaction method can be applied. Preferably, bulk polymerization or solution polymerization is used. The polyaddition reaction is expressed as follows. Or [In the above reaction formula, R9 is an alkylene group substituted or unsubstituted with an alkyl group, an arylene group (-( CH2 ) -o ,
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】)(nは整数である)
を表わす]
これらのうち、塊状重合の場合には、反応試剤
及び触媒を攪拌しながら加熱して均一状態とした
後、重合させることが好ましい。0℃〜200℃、
1〜20時間の反応で高分子量のポリアミドが得ら
れる。
溶液重合の場合には、反応試剤及び反応中間体
を溶解し、かつ反応試剤と副反応を起こさない溶
媒を使用することが好ましい。−40℃〜200℃、1
〜30時間の反応で高分子量のポリアミドが得られ
る。
上記した溶媒としては、o―ジクロロベンゼ
ン、1,3,5―トリクロロベンゼン、ニトロベ
ンゼン、ニトロメタン、四塩化炭素等が例示され
る。また溶媒の使用量は、反応試剤に対し重量比
で2〜40倍であることが好ましい。
上記したいずれの重合法にあつても、使用する
ジイソシアナート化合物と三環式複素縮合環化合
物の配合比は、等モル量であることが、重付加反
応を円滑に進める上で好ましい。
フリーデル―クラフツ型触媒の使用量は、反応
試剤、重合条件により異なるが、使用するジイソ
シアナート化合物のイソシアナート基に対して
0.3〜1.5当量の範囲であることが好ましい。
本発明方法にあつては、上記した重付加反応が
終了した後の処理法の一例を掲げると、まずメタ
ノールを加えて残存イソシアナート基を分解し、
氷水に注入後、沈殿を別、洗浄、乾燥等の常法
の処理を施して、目的とするポリアミドを得るこ
とができる。
(実施例)
実施例 1
窒素ガス導入管、還流冷却器、温度計及び攪拌
棒を備えた四ツ口フラスコに、窒素ガス雰囲気中
で、2,4―トリレンジイソシアナート69.7g
(0.4モル)及び無水塩化アルミニウム106.7g
(0.8モル)を入れ、攪拌しながらジベンゾ―p―
ジオキシン73.7g(0.4モル)を少量ずつ約30分
間で投入し、その後80℃に加熱して4時間反応を
行なつた。
暗赤色で固形のポリマーが得られた。これにメ
タノール100mlを加えて残存イソシアナート基と
反応させた後、3の氷水に攪拌しながら注入し
た。次に全体を過して沈殿を別し、この沈殿
をメタノール、アセトンで洗浄した後乾燥し、次
いでジメチルホルムアミド(DMF)に溶解して、
得られた溶液を2の水に注入した。更に全体を
過して沈殿を別後、乾燥して白色粉末121.9
g(収率85%)を得た。
このポリマーからは、溶融により強靭なフイル
ムを成形できた。また、IRスペクトル(KBr錠
剤法)では、1655cm-1,3300cm-1に強いアミド基
の吸収を示した。融点(m.p)は354℃、固有粘
度[η]1.05(0.5g/100mlDMF中、30℃)、示差
熱天秤による加熱減量測定(5℃/min、空気
中)では、420℃まで重量減少しなかつた(以下、
加熱重量減少開始温度をTdで表わす)。
実施例 2
2,4―トリレンジイソシアナート69.7g
(0.4モル)とフエノキサチイン80.1g(0.4モル)
を、無水塩化アルミニウム106.7g(0.8モル)存
在下、90℃、10時間反応させた後、実施例1と同
様に後処理して白色粉末121.3g(収率81%)を
得た。
このポリマーは、m.p:321℃、η:1.33、
Td:382℃であつた。
実施例 3
2,4―トリレンジイソシアナート69.7g
(0.4モル)とチアントレン86.5g(0.4モル)を、
無水塩化アルミニウム106.7g(0.8モル)存在
下、120℃、6時間反応させた後、実施例1と同
様に後処理して白色粉末118.7g(収率76%)を
得た。
このポリマーは、N,N―ジメチルアセトアミ
ド、N―メチル―ピロリドン、m―クレゾール等
に可溶で、溶融により強靭なフイルムを成形する
ことが可能であつた。m.p:298℃、η:1.51、
Td:350℃であつた。
実施例 4
ニトロベンゼン1中で、2,4―トリレンジ
イソシアナート69.7g(0.4モル)とN―メチル
カルバゾール72.5g(0.4モル)を、無水塩化ア
ルミニウム106.7g(0.8モル)存在下、100℃、
10時間反応させた後、実施例1と同様に後処理し
て黄色粉末118.0g(収率83%)を得た。
このポリマーは、η:0.61、Td:475℃であつ
た。
実施例 5
2,4―トリレンジイソシアナート69.7g
(0.4モル)とジフエニレンオキシド67.3g(0.4モ
ル)を、無水塩化アルミニウム106.7g(0.8モ
ル)存在下、100℃、8時間反応させた後、実施
例1と同様に後処理して白色粉末126.0g(収率
92%)を得た。
このポリマーからは、溶融により強靭なフイル
ムを成形できた。m.p:372℃、η:1.13、Td:
437℃であつた。
実施例 6
ニトロベンゼン100ml中で、ジベンゾ―p―ジ
オキシン18.4g(0.1モル)とジフエニルメタン
ジイソシアナート25.0g(0.1モル)を、無水塩
化アルミニウム26.7g(0.2モル)存在下、100
℃、5時間反応させた後、実施例1と同様に後処
理して白色粉末38.6g(収率89%)を得た。
このポリマーからは、溶融により強靭なフイル
ムを成形できた。IRスペクトル:1650cm-1、
3312cm-1、m.p:375℃、η:0.84、Td:380℃で
あつた。
実施例 7
2,4―トリレンジイソシアナートの代わりに
ジフエニルスルホン―4,4′―ジイソシアナート
120.1g(0.4モル)を用いた他は実施例3と同様
に処理して白色粉末200.4g(収率97%)を得た。
このポリマーは、η:1.26、Td:462℃であつ
た。
実施例 8
2,4―トリレンジイソシアナートの代わりに
m―フエニレンジイソシアナート64.1g(0.4モ
ル)を用いた他は実施例3と同様に処理して白色
粉末138.6g(収率92%)を得た。
このポリマーは、η:1.21、Td:438℃であつ
た。
実施例 9
2,4―トリレンジイソシアナートの代わりに
1,5―ナフタレンジイソシアナート84.1g
(0.4モル)を用いた他は実施例3と同様に処理し
て白色粉末145.0g(収率85%)を得た。
このポリマーは、η:0.87、Td:445℃であつ
た。
[発明の効果]
本発明によれば、三環式複素縮合環化合物をジ
アミノ化する工程を必要とせず、該化合物から直
接に一工程で三環式複素縮合環を有するポリアミ
ドを製造できる。また、本発明は重付加反応であ
るから、水、塩化水素等の副生成物を生じること
がない。従つて、反応操作が簡便であり、また副
生成物による反応装置等の腐食も起こらないの
で、工業的価値は大である。[Formula]) (n is an integer) Among these, in the case of bulk polymerization, it is preferable to heat the reaction reagent and catalyst while stirring to make a homogeneous state, and then polymerize. 0℃~200℃,
A high molecular weight polyamide can be obtained in a reaction time of 1 to 20 hours. In the case of solution polymerization, it is preferable to use a solvent that dissolves the reaction reagent and the reaction intermediate and does not cause side reactions with the reaction reagent. -40℃~200℃, 1
A high molecular weight polyamide is obtained in ~30 hours of reaction. Examples of the above-mentioned solvents include o-dichlorobenzene, 1,3,5-trichlorobenzene, nitrobenzene, nitromethane, and carbon tetrachloride. The amount of solvent used is preferably 2 to 40 times the weight of the reaction reagent. In any of the above-mentioned polymerization methods, it is preferable that the diisocyanate compound and tricyclic fused ring compound used be in equimolar amounts in order to smoothly proceed with the polyaddition reaction. The amount of Friedel-Crafts type catalyst used varies depending on the reaction reagent and polymerization conditions, but it is based on the isocyanate group of the diisocyanate compound used.
It is preferably in the range of 0.3 to 1.5 equivalents. In the method of the present invention, an example of a treatment method after the completion of the polyaddition reaction described above is as follows: first, methanol is added to decompose the remaining isocyanate groups;
After pouring into ice water, the desired polyamide can be obtained by separating the precipitate and performing conventional treatments such as washing and drying. (Example) Example 1 69.7 g of 2,4-tolylene diisocyanate was placed in a four-necked flask equipped with a nitrogen gas inlet tube, a reflux condenser, a thermometer, and a stirring bar in a nitrogen gas atmosphere.
(0.4 mol) and anhydrous aluminum chloride 106.7 g
(0.8 mol) and dibenzo-p-
73.7 g (0.4 mol) of dioxin was added little by little over about 30 minutes, and then the mixture was heated to 80°C and reacted for 4 hours. A dark red solid polymer was obtained. After adding 100 ml of methanol to react with the remaining isocyanate groups, the mixture was poured into the ice water in step 3 with stirring. Next, the whole was filtered to separate the precipitate, and this precipitate was washed with methanol and acetone, dried, and then dissolved in dimethylformamide (DMF).
The resulting solution was poured into 2 water. After further filtering the whole to separate the precipitate, dry it to obtain a white powder of 121.9
g (yield 85%) was obtained. A strong film could be formed from this polymer by melting it. In addition, the IR spectrum (KBr tablet method) showed strong absorption of amide groups at 1655 cm -1 and 3300 cm -1 . The melting point (mp) is 354℃, the intrinsic viscosity [η] 1.05 (0.5g/100ml DMF, 30℃), and the weight loss measurement using a differential thermal balance (5℃/min, in air) shows that there is no weight loss up to 420℃. (Hereafter,
The temperature at which heating weight starts to decrease is expressed as Td). Example 2 2,4-tolylene diisocyanate 69.7g
(0.4 mol) and phenoxathiin 80.1g (0.4 mol)
was reacted at 90° C. for 10 hours in the presence of 106.7 g (0.8 mol) of anhydrous aluminum chloride, and then post-treated in the same manner as in Example 1 to obtain 121.3 g (yield: 81%) of white powder. This polymer has mp: 321℃, η: 1.33,
Td: It was 382℃. Example 3 2,4-tolylene diisocyanate 69.7g
(0.4 mol) and thianthrene 86.5g (0.4 mol),
After reacting at 120° C. for 6 hours in the presence of 106.7 g (0.8 mol) of anhydrous aluminum chloride, the mixture was post-treated in the same manner as in Example 1 to obtain 118.7 g (yield: 76%) of white powder. This polymer was soluble in N,N-dimethylacetamide, N-methyl-pyrrolidone, m-cresol, etc., and could be molded into a strong film by melting. mp: 298℃, η: 1.51,
Td: It was 350℃. Example 4 In nitrobenzene 1, 69.7 g (0.4 mol) of 2,4-tolylene diisocyanate and 72.5 g (0.4 mol) of N-methylcarbazole were added at 100°C in the presence of 106.7 g (0.8 mol) of anhydrous aluminum chloride.
After reacting for 10 hours, the mixture was post-treated in the same manner as in Example 1 to obtain 118.0 g of yellow powder (yield: 83%). This polymer had η: 0.61 and Td: 475°C. Example 5 2,4-tolylene diisocyanate 69.7g
(0.4 mol) and 67.3 g (0.4 mol) of diphenylene oxide were reacted at 100°C for 8 hours in the presence of 106.7 g (0.8 mol) of anhydrous aluminum chloride, and then post-treated in the same manner as in Example 1 to give a white color. Powder 126.0g (yield
92%). A strong film could be formed from this polymer by melting it. mp: 372℃, η: 1.13, Td:
It was 437℃. Example 6 In 100 ml of nitrobenzene, 18.4 g (0.1 mol) of dibenzo-p-dioxin and 25.0 g (0.1 mol) of diphenylmethane diisocyanate were added in the presence of 26.7 g (0.2 mol) of anhydrous aluminum chloride.
After reacting at ℃ for 5 hours, the mixture was post-treated in the same manner as in Example 1 to obtain 38.6 g of white powder (yield: 89%). A strong film could be formed from this polymer by melting it. IR spectrum: 1650cm -1 ,
The temperature was 3312 cm -1 , mp: 375°C, η: 0.84, and Td: 380°C. Example 7 Diphenylsulfone-4,4'-diisocyanate instead of 2,4-tolylene diisocyanate
200.4 g (yield: 97%) of white powder was obtained by the same treatment as in Example 3 except that 120.1 g (0.4 mol) was used. This polymer had η: 1.26 and Td: 462°C. Example 8 138.6 g of white powder (yield 92%) was prepared in the same manner as in Example 3 except that 64.1 g (0.4 mol) of m-phenylene diisocyanate was used instead of 2,4-tolylene diisocyanate. ) was obtained. This polymer had η: 1.21 and Td: 438°C. Example 9 1,5-naphthalene diisocyanate 84.1g instead of 2,4-tolylene diisocyanate
(0.4 mol) was used in the same manner as in Example 3 to obtain 145.0 g of white powder (yield: 85%). This polymer had η: 0.87 and Td: 445°C. [Effects of the Invention] According to the present invention, a polyamide having a tricyclic heterofused ring can be produced directly from the tricyclic heterofused ring compound in one step without requiring a step of diaminating the tricyclic heterofused ring compound. Furthermore, since the present invention is a polyaddition reaction, by-products such as water and hydrogen chloride are not produced. Therefore, the reaction operation is simple and the reaction apparatus is not corroded by by-products, so it is of great industrial value.
Claims (1)
―S―、【式】を表わし;R1,R2,R3及び R4は、それぞれ炭素数1〜5のアルキル基、―
OR6で示されるアルコキシ基、【式】で示さ れる第三アミノ基を表わし;R5,R6,R7及びR8
は、それぞれ炭素数1〜5のアルキル基を表わ
し;n1,n2,n3及びn4は、それぞれ0〜3の整数
を表わす。また、X1及びX2、R1及びR2,R3及び
R4並びにR7及びR8は、それぞれ同一であつても
異なつていてもよく、n1,n2,n3及びn4が2〜3
の整数であるとき、複数個のR1,R2,R3及びR4
は、それぞれ同一であつても異なつていてもよ
い。) で示される三環式複素縮合環化合物のうちの少な
くとも一種とを; フリーデル―クラフツ型触媒の存在下、重付加
反応させることを特徴とする三環式複素縮合環を
有するポリアミドの製造法。[Claims] 1. A diisocyanate compound; and the following formula: [Formula] or (In the formula, X 1 , X 2 and X 3 are respectively -O-,
-S-, represents [Formula]; R 1 , R 2 , R 3 and R 4 are each an alkyl group having 1 to 5 carbon atoms, -
OR represents an alkoxy group represented by 6 , a tertiary amino group represented by [Formula]; R 5 , R 6 , R 7 and R 8
each represents an alkyl group having 1 to 5 carbon atoms; n 1 , n 2 , n 3 and n 4 each represent an integer of 0 to 3. Also, X 1 and X 2 , R 1 and R 2 , R 3 and
R 4 and R 7 and R 8 may be the same or different, and n 1 , n 2 , n 3 and n 4 are 2 to 3.
is an integer of R 1 , R 2 , R 3 and R 4
may be the same or different. ) with at least one type of tricyclic heterofused ring compound represented by; A method for producing a polyamide having a tricyclic heterofused ring, which is characterized by carrying out a polyaddition reaction in the presence of a Friedel-Crafts type catalyst. .
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP57011875A JPS58129017A (en) | 1982-01-29 | 1982-01-29 | Preparation of polyamide having hetero condensed ring of tricyclic type |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP57011875A JPS58129017A (en) | 1982-01-29 | 1982-01-29 | Preparation of polyamide having hetero condensed ring of tricyclic type |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS58129017A JPS58129017A (en) | 1983-08-01 |
JPS6310724B2 true JPS6310724B2 (en) | 1988-03-09 |
Family
ID=11789893
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP57011875A Granted JPS58129017A (en) | 1982-01-29 | 1982-01-29 | Preparation of polyamide having hetero condensed ring of tricyclic type |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS58129017A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3026426U (en) * | 1995-12-28 | 1996-07-12 | 株式会社酒井機材製作所 | Cable support |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4843870B2 (en) * | 2001-05-31 | 2011-12-21 | 旭硝子株式会社 | Novel polyarylene ether, process for producing the same and use thereof |
-
1982
- 1982-01-29 JP JP57011875A patent/JPS58129017A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3026426U (en) * | 1995-12-28 | 1996-07-12 | 株式会社酒井機材製作所 | Cable support |
Also Published As
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JPS58129017A (en) | 1983-08-01 |
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