JPS638418A - Production of heat-resistant polymer derived from aromatic diamine - Google Patents
Production of heat-resistant polymer derived from aromatic diamineInfo
- Publication number
- JPS638418A JPS638418A JP14959086A JP14959086A JPS638418A JP S638418 A JPS638418 A JP S638418A JP 14959086 A JP14959086 A JP 14959086A JP 14959086 A JP14959086 A JP 14959086A JP S638418 A JPS638418 A JP S638418A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic
- wet cake
- aromatic diamine
- compound
- 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.)
- Pending
Links
- 150000004984 aromatic diamines Chemical class 0.000 title claims abstract description 32
- 229920000642 polymer Polymers 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- -1 aromatic acidic compound Chemical class 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000002798 polar solvent Substances 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 5
- 125000006157 aromatic diamine group Chemical group 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract description 17
- 230000001588 bifunctional effect Effects 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000428 dust Substances 0.000 abstract description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052697 platinum Inorganic materials 0.000 abstract description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 238000003756 stirring Methods 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000843 powder Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000012452 mother liquor Substances 0.000 description 6
- 239000011550 stock solution Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000007868 Raney catalyst Substances 0.000 description 4
- 150000001491 aromatic compounds Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004811 liquid chromatography Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 3
- 229910000564 Raney nickel Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000004760 aramid Substances 0.000 description 3
- 229920003235 aromatic polyamide Polymers 0.000 description 3
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 3
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UCNVFOCBFJOQAL-UHFFFAOYSA-N DDE Chemical compound C=1C=C(Cl)C=CC=1C(=C(Cl)Cl)C1=CC=C(Cl)C=C1 UCNVFOCBFJOQAL-UHFFFAOYSA-N 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920005575 poly(amic acid) Polymers 0.000 description 2
- 229920002312 polyamide-imide Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- BNXZHVUCNYMNOS-UHFFFAOYSA-N 1-butylpyrrolidin-2-one Chemical compound CCCCN1CCCC1=O BNXZHVUCNYMNOS-UHFFFAOYSA-N 0.000 description 1
- GGYVTHJIUNGKFZ-UHFFFAOYSA-N 1-methylpiperidin-2-one Chemical compound CN1CCCCC1=O GGYVTHJIUNGKFZ-UHFFFAOYSA-N 0.000 description 1
- MWAGUKZCDDRDCS-UHFFFAOYSA-N 1-nitro-4-(4-nitrophenoxy)benzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1OC1=CC=C([N+]([O-])=O)C=C1 MWAGUKZCDDRDCS-UHFFFAOYSA-N 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003471 mutagenic agent Substances 0.000 description 1
- 231100000707 mutagenic chemical Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- CYFLXLSBHQBMFT-UHFFFAOYSA-N sulfamoxole Chemical group O1C(C)=C(C)N=C1NS(=O)(=O)C1=CC=C(N)C=C1 CYFLXLSBHQBMFT-UHFFFAOYSA-N 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polyamides (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、芳香族ジアミンを一原料成分とする耐熱性重
合体の製造方法の改善に関するものであり、特に製造工
程の安全性を高めることを目的としている。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to an improvement in a method for producing a heat-resistant polymer containing an aromatic diamine as a raw material component, and in particular to improving the safety of the production process. It is an object.
〈従来の技術〉
芳香族ジアミン類は耐熱性高分子製造用の必須成分とし
て広く実用化されている。最近先端産業技術分野におい
ては高性能高分子材料の必要性が急速に高まっており、
その−翼を担っているのが各種の耐熱性高分子群である
。その意味で芳香族ジアミン類の産業界における重要性
は一段と高まっている。<Prior Art> Aromatic diamines have been widely put into practical use as essential components for the production of heat-resistant polymers. Recently, the need for high-performance polymer materials has been rapidly increasing in the field of advanced industrial technology.
The wings are played by various heat-resistant polymer groups. In this sense, aromatic diamines are becoming increasingly important in industry.
耐熱性高分子類は、一般には、アミド系極性溶媒中、無
水条件下、室温で芳香族ジアミン類と二官能性芳香族酸
性化合物、たとえばピロメリット酸二無水物、無水トリ
メリット酸モノクロリド、テレフタル酸ジクロリド、イ
ソフタル酸ジクロリドなどを反応させることにより合成
される。Heat-resistant polymers are generally prepared by combining aromatic diamines and bifunctional aromatic acidic compounds such as pyromellitic dianhydride, trimellitic anhydride monochloride, etc. in an amide polar solvent under anhydrous conditions at room temperature. It is synthesized by reacting terephthalic acid dichloride, isophthalic acid dichloride, etc.
従来から、芳香族ジアミノ類の製造には芳香族ジニトロ
化合物を極性溶媒中、接触水素還元し、次いで加熱／熱
濾過後、必要に応じて濃縮し、晶析させて単離した後、
乾燥する方法が広く行なわれてきた。たと又は、英国特
許第１、２２８．７３８号、特開昭５６−２２．７５２
号公報、特開昭５７−１７６．９３５号公報など。Traditionally, aromatic diamino compounds have been produced by subjecting aromatic dinitro compounds to catalytic hydrogen reduction in a polar solvent, followed by heating/hot filtration, concentration as necessary, crystallization, and isolation.
Drying methods have been widely used. Totaka, British Patent No. 1, 228.738, JP 56-22.752
No. 57-176.935, etc.
そして芳香族ジアミン類は工業的には、乾燥した粉末ま
たはフレークの形状で供給されてきｔこ。Industrially, aromatic diamines are supplied in the form of dry powder or flakes.
〈発明が解決しようとする問題点〉
ところが、芳香族レアミノ類は一般に変異原生陽性（発
癌懸念性）の物質であるため取扱い作業には特別に厳重
な環境対策が必要である。<Problems to be Solved by the Invention> However, since aromatic rare aminos are generally mutagen-positive (cancer-causing substances), special environmental measures are required when handling them.
しかし、取扱い形状が粉末またはフレーク状であること
に関係してどうしても微細粉塵の発生があり、環境対策
にも自と限界があった。芳香族ンアミンの利用者がこの
問題を手取り早く解決する方法は、芳香族ジアミン製造
業者に、芳香族レアミンを重合用の溶媒に溶解してもら
い、芳香族レアミンを溶液として入手することであった
。しかし、この方法は、芳香族ジアミノ製造業者が芳香
族ジアミンを単離／乾燥して取扱う限り、粉塵取扱い作
業を利用者側から製造業者側へ転嫁したｔごけて、根本
的な解決策にはならないことは明白である。However, since it is handled in the form of powder or flakes, it inevitably generates fine dust, and there are limits to environmental measures. A quick way for users of aromatic amines to solve this problem was to have aromatic diamine manufacturers dissolve aromatic diamines in polymerization solvents and obtain aromatic diamines as a solution. . However, as long as aromatic diamine manufacturers handle aromatic diamines by isolating and drying them, this method does not provide a fundamental solution as it shifts the dust handling work from the user side to the manufacturer side. It is clear that this should not be the case.
この問題を解決するための手法の一つとして、芳香族ジ
ニトロ体を重合用溶媒中で接触還元した後、溶液状態で
副生水を除去して得られる芳香族ジアミン溶液をそのま
ま重合工程に活用するという方法が提案されている（た
とえば、特開昭６０−２１０６３０号公報など）。この
方法は、芳香族ジアミン粉体の取扱いがなくなるという
点では環境対策上、有効である。しかし、この方法の場
合、芳香族ンアミンの精製工程がカットされるため、低
沸および高沸不純物が残留してその品位が低下するとい
う問題がある。One method to solve this problem is to catalytically reduce the aromatic dinitro compound in a polymerization solvent and then remove the by-product water in the solution state, and use the resulting aromatic diamine solution as it is in the polymerization process. A method has been proposed (for example, Japanese Patent Laid-Open No. 60-210630). This method is effective in terms of environmental protection because it eliminates the need to handle aromatic diamine powder. However, in the case of this method, since the purification step of the aromatic amine is cut, there is a problem that low-boiling and high-boiling impurities remain and the quality is degraded.
また、ジアミン製造工場と重合工場が離れている場合、
貯蔵コストおよび輸送コストが高くつくという問題もあ
る。Also, if the diamine manufacturing factory and polymerization factory are far apart,
There is also the problem of high storage and transportation costs.
このように、これまでに提案された方法では芳香族ジア
ミンの環境対策とコスト／パフォーマンスの両立がむず
かしかったため、芳香族ジアミンから誘導される耐熱性
重合体の製造は意外にコスト高につくことが多かった。As described above, it has been difficult to achieve both environmental protection and cost/performance for aromatic diamines with the methods proposed so far, so the production of heat-resistant polymers derived from aromatic diamines can be surprisingly expensive. There were many.
そこで本発明者らは、芳香族ジアミンの環境対策とコス
ト／パフォーマンスε両立させ、その結果として耐熱性
重合体の製造コストを低下させることを目的として鋭意
検討した結果、本発明に到達した。Therefore, the present inventors have conducted intensive studies aimed at achieving both environmental protection and cost/performance ε of aromatic diamines, and as a result, reducing the manufacturing cost of heat-resistant polymers, and as a result, they have arrived at the present invention.
く問題点を解決するための手段〉
すなわち、本発明は重合反応阻害性のない中−ｔ＄；￥
−極性溶媒中、不均一系水添触媒の存在下に芳香族レニ
トロ化合物または芳香族モノニトロアミノ化合物を接触
還元した後、不均一系水添触媒を口過回収し、次に番肴
すキ芳香族ジアミノを晶析させて溶媒含有率３〜７０Ｍ
量％のウェットケーク状に単離することによって調製し
た芳香族レアミンウエットケークと二官能性芳香族酸性
化合物をアミド系極性溶媒中で反応させることを特徴と
する芳香族レアミンから誘導される耐熱性重合体の製造
方法を提供するものである。Means for Solving the Problems〉 That is, the present invention provides medium-t$;
- After catalytic reduction of an aromatic renitro compound or an aromatic mononitroamino compound in the presence of a heterogeneous hydrogenation catalyst in a polar solvent, the heterogeneous hydrogenation catalyst is recovered by mouth, and then the plate is prepared. Aromatic diamino is crystallized and the solvent content is 3 to 70M.
Heat resistance derived from aromatic reamin, which is characterized by reacting an aromatic reamin wet cake prepared by isolating % of aromatic reamin into a wet cake and a bifunctional aromatic acidic compound in an amide polar solvent. The present invention provides a method for producing a synthetic polymer.
本発明に用いられるアミド系極性溶媒は、芳香族ジアミ
ン化合物と二官能性芳香族酸性物質との重合反応を阻害
する性質を示さず、かつ分子内にアミド結合を有する極
性溶媒類であり、たとえば、Ｎ＠Ｎ−ジメチルアセトア
ミド、Ｎ・Ｎ−ジエチルアセトアミド、Ｎ−メチルピロ
リドン、Ｎ−エチルピロリドン、Ｎ−ブチルピロリドン
、Ｎ−シクロへキンルピロリドン、Ｎ−メチルピペリド
ン、１．３−ジメチル−２−イミダゾリジノン、ヘキサ
メチルホスホルアミドなどが挙げられる。特にＮ−メチ
ルピロリドンおよびＮ、Ｎ−ジメチルアセトアミドが有
用である。また、類似化合物であるＮ、Ｎ−ジメチルホ
ルムアミドは、酸クロリド類を利用する重合系において
重合阻害効果があり、本発明の目的には使えない。The amide polar solvent used in the present invention is a polar solvent that does not inhibit the polymerization reaction between the aromatic diamine compound and the bifunctional aromatic acidic substance and has an amide bond in the molecule, such as , N@N-dimethylacetamide, N·N-diethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, N-butylpyrrolidone, N-cyclohequinylpyrrolidone, N-methylpiperidone, 1,3-dimethyl-2- Examples include imidazolidinone and hexamethylphosphoramide. Particularly useful are N-methylpyrrolidone and N,N-dimethylacetamide. Further, N,N-dimethylformamide, which is a similar compound, has a polymerization inhibiting effect in polymerization systems that utilize acid chlorides, and cannot be used for the purpose of the present invention.
本発明に用いられる芳香族ジニトロ化合物または芳香族
モノニトロアミノ化合物は一般式Ｏ□Ｎ−Ａｒ−Ｎｏ□
またハ０２Ｎ−Ａｒ−ＮＨ２テ表ワサレる化合物であり
、 −Ａｒ−１訃一般式から選ばれた二価の芳香族残基
を示す。ここで、Ｒ，は炭素数１から４のアルキル基ま
たはアルコキン基、Ｘは直接結合 −〇−１−Ｓ−１Ｏ
ＣＨ３ＣＦ３
−Ｃ−１−ＳＯ，−１−Ｃ−１−〇−またはＣＨ３ＣＦ
３
Ｏ
ｌｌ
−Ｎ−Ｃ−１ａはＯまたは１〜４の整数、ｂはＯまたは
１−１２の整数を示す。−Ａｒ−の具体例を挙げろと次
のとおりである。The aromatic dinitro compound or aromatic mononitroamino compound used in the present invention has the general formula O□N-Ar-No□
It is also an interesting compound and represents a divalent aromatic residue selected from the general formula -Ar-1. Here, R, is an alkyl group or alkoxy group having 1 to 4 carbon atoms, and X is a direct bond -〇-1-S-1O
CH3CF3 -C-1-SO, -1-C-1-〇- or CH3CF
3 O ll -N-C-1a represents O or an integer of 1 to 4, and b represents O or an integer of 1 to 12. Specific examples of -Ar- are as follows.
すなわち
÷０（ΣＳ÷０÷、
ＨＯＯＨ
本発明で用いられる不均一系水添触媒は、一般に接触還
元に使用されている金属または金属酸化物触媒であり、
たとえば、白金、パラジウム、ロジウム、ルテニウム、
ニッケル、コバルト、銅、酸化白金、酸化パラジウム、
酸化ロジウムなどが挙げられる。これらの金属触媒は、
金属の状態でも使用することができるが、通常バカ−ホ
ン、硫酸バリウム、ノリカゲル、アルミナ等の担体表面
に付着させて用いたり、また、ニッケル、コバルト、銅
等はラネー触媒としても用いられる。触媒の使用量は原
料のニトロ化合物１００部に対して、金属分として０．
０１〜ＩＯ部であり、担体に付着させた場合は好ましく
は０．１〜５部である。That is, ÷0(ΣS÷0÷, HOOH) The heterogeneous hydrogenation catalyst used in the present invention is a metal or metal oxide catalyst that is generally used in catalytic reduction.
For example, platinum, palladium, rhodium, ruthenium,
Nickel, cobalt, copper, platinum oxide, palladium oxide,
Examples include rhodium oxide. These metal catalysts are
Although it can be used in the form of a metal, it is usually used by being attached to the surface of a carrier such as Vacphone, barium sulfate, Norica gel, or alumina, and nickel, cobalt, copper, or the like is also used as a Raney catalyst. The amount of catalyst used is 0.00 parts as metal content per 100 parts of the raw material nitro compound.
01 to IO parts, and preferably 0.1 to 5 parts when attached to a carrier.
反応温度は、特に限定はないが一般には２０〜２００℃
の範囲、特に５０〜１３０℃の範囲が好ましい。The reaction temperature is not particularly limited, but is generally 20 to 200°C.
A range of , particularly a range of 50 to 130°C is preferred.
また、反応に用いる水素の圧力は、通常ゲージ圧で０．
１〜５０に９／ｄであり、触媒の活性度により最適範囲
が異なる。たとえば５％パラジウム／活性炭、５％白金
／活性炭の場合ゲージ圧で０．１〜５ ｋｑ ／ ｄが
適当であるが、ラネーニッケルの場合１０〜５０ ｋｑ
／ ｄが適当である。Furthermore, the pressure of hydrogen used in the reaction is usually 0.00 gauge pressure.
The optimum range varies depending on the activity of the catalyst. For example, in the case of 5% palladium/activated carbon or 5% platinum/activated carbon, a gauge pressure of 0.1 to 5 kq/d is appropriate, but in the case of Raney nickel, it is 10 to 50 kq.
/d is appropriate.
本発明の水添反応においては −Ｎｏ２＋ ３Ｈ２−ｅ
−ＮＨ，＋ ２Ｈ２０の反応により１モルのＮＯ２基か
ら２モルの水が生成する。In the hydrogenation reaction of the present invention, -No2+ 3H2-e
The reaction of -NH, +2H20 produces 2 moles of water from 1 mole of NO2 groups.
ジアミノを晶析させる工程およびΩ晶析しｔこ芳香族ジ
アミンを口過分離して芳香族ジアミン結晶のウェットケ
ークを回収する工程を順次経由させる。ただし、Ｂ工程
で過度の濃縮を行なった場合は、Ｃ工程は不用となる。A step of crystallizing diamino and a step of separating aromatic diamine by filtration and recovering a wet cake of aromatic diamine crystals are sequentially performed. However, if excessive concentration is performed in step B, step C will be unnecessary.
そして、必要に応じてこれらのいずれかの工程の前、途
中または後に、水添反応における副生水を蒸留除去する
工程が加わってもよい。If necessary, a step of distilling and removing by-product water in the hydrogenation reaction may be added before, during, or after any of these steps.
この副生水の蒸留除去は、水添反応母液まｔ二はその晶
析母液を常圧または減圧下に加熱して低沸成分としての
水を留出させることによって行なわれる。その際、水は
、単蒸留の形式で溶媒と共沸留出させてもかまわないし
、精留塔を通して精留してもかまわない。前者の場合、
上記Ｂの濃縮操作と兼ねることができろ。This by-product water is removed by distillation by heating the hydrogenation reaction mother liquor or the crystallization mother liquor under normal pressure or reduced pressure to distill off water as a low-boiling component. In this case, water may be distilled off azeotropically with the solvent by simple distillation, or may be rectified through a rectification column. In the former case,
It can also be used as the concentration operation in B above.
また、効果的共沸助剤たとえばベンゼン、トルエン、キ
シレン、クロルベンゼンなどの芳香族炭化水素類および
芳香族ハロゲン化炭化水素類を併用することも有効であ
る。水添反応母液中には、芳香族ジニトロ体を原料とし
た場合、芳香族ジアミン１モル当り、水４モルが副生じ
ている。上記の副生水蒸留除去操作は、最終的に得られ
るウェットケーク中の水分が、芳香族ジアミン１モル当
り、０．５モル（好ましくは０、１モル）以下になるこ
とを目標に実施される。It is also effective to use effective azeotropic aids such as aromatic hydrocarbons and aromatic halogenated hydrocarbons such as benzene, toluene, xylene, and chlorobenzene. In the hydrogenation reaction mother liquor, when an aromatic dinitro compound is used as a raw material, 4 moles of water are produced as a by-product per 1 mole of aromatic diamine. The above-mentioned by-product water distillation removal operation is carried out with the aim of reducing the water content in the final wet cake to 0.5 mol (preferably 0.1 mol) or less per 1 mol of aromatic diamine. Ru.
ウェットケーク中の水分が、芳香族ジアミン１モル当り
０．５モルを越えろと、芳香族ジアミンウェットケーク
を二官能性芳香族酸性成分と直接反応させた場合の重合
活性が著しく低下するので好ましくない。It is not preferable for the water content in the wet cake to exceed 0.5 mole per mole of aromatic diamine, as this will significantly reduce the polymerization activity when the aromatic diamine wet cake is directly reacted with a difunctional aromatic acidic component. .
本発明における不溶性触媒を回収する工程および晶析し
た芳香族ジアミンを口過分離して芳香族ジアミン結晶の
ウェットケークを回収する工程は、通常の固／液分離装
置のいずれを用いても実施できる。それらの代表例とし
て、静置式加圧口過機、静置式減圧口過機、圧送式フィ
ルタープレス、遠心分離機、回転式ドラムフィルター、
回転式ベルトフィルターなどが挙げられる。この口過分
離操作は、得られろウェットケーク中の含液率が７０（
好ましくは６０）重量％以下になるように実施されろ。In the present invention, the step of recovering an insoluble catalyst and the step of separating the crystallized aromatic diamine by mouth to recover a wet cake of aromatic diamine crystals can be carried out using any conventional solid/liquid separator. . Typical examples include static pressurizing filters, static vacuum filters, pressure filter presses, centrifugal separators, rotating drum filters,
Examples include rotary belt filters. This separation operation results in a liquid content of 70 (
Preferably, the amount is 60% by weight or less.
含液率が７０重量％を越える場合は、夏場のように気温
が高くなると保存中に溶液相が分離する危険性が発生す
るので好ましくない。If the liquid content exceeds 70% by weight, it is not preferable because there is a risk that the solution phase will separate during storage when the temperature is high, such as in summer.
本発明で得られるウェットケークの含液率は、濃縮操作
を強化するかまたは分離回収後、乾燥工程にかけること
によってさらに低下させることができる。本発明の目的
の一つである芳香族ジアミン乾燥粉末の飛散防止効果が
得られるのは含液率３（好ましくは１０）重量％以上で
あす、本発明のウェットケークは含液率３〜７０（好ま
しくは１０〜６０）重量％の芳香族ジアミン結晶集合体
である。The liquid content of the wet cake obtained in the present invention can be further reduced by intensifying the concentration operation or by subjecting it to a drying process after separation and recovery. The effect of preventing the aromatic diamine dry powder from scattering, which is one of the objects of the present invention, can be obtained when the liquid content is 3 (preferably 10)% by weight or more, and the wet cake of the present invention has a liquid content of 3 to 70% by weight. (preferably 10 to 60% by weight) of aromatic diamine crystal aggregates.
本発明で用いられる二官能性芳香族酸性化合物は、一般
式
である。ここでＹは、水酸基、ハロゲン基、炭素数１〜
１２個のアルコキシ基、Ａｒ、Ａｒ’、Ａｒ−は炭素数
６〜４０個の芳香族基を示す。The difunctional aromatic acidic compound used in the present invention has the general formula: Here, Y is a hydroxyl group, a halogen group, or a carbon number of 1 to
The 12 alkoxy groups, Ar, Ar', and Ar- represent an aromatic group having 6 to 40 carbon atoms.
などが挙げられる。Examples include.
られる。It will be done.
れる。It will be done.
本発明における耐熱性重合体は上記の芳香族ジアミンウ
ェットケークと二官能性芳香族酸性化合物をアミド系極
性溶媒中で、実質的に等モル比（１／１±０．０５モル
比）で混合し、１００℃（好ましくは８０℃）以下の温
度条件下、０．１〜１０時間程度反応させることにより
合成される。そしてこの条件下で合成される耐熱性重合
体は、二官能性芳香族酸性化合物の覆類によって芳香族
ポリアミド、芳香族ポリアミド・アミド酸または芳香族
ポリアミド酸になる。芳香族ポリアミド・アミド酸およ
び芳香族ポリアミド酸は、続いて化学閉環または熱閉環
反応を起こさせることにより芳香族ポリアミドイミドお
よび芳香族ポリイミドに変化する。The heat-resistant polymer in the present invention is a mixture of the above-mentioned aromatic diamine wet cake and a bifunctional aromatic acidic compound in a substantially equimolar ratio (1/1±0.05 molar ratio) in an amide polar solvent. However, it is synthesized by reacting for about 0.1 to 10 hours at a temperature of 100°C (preferably 80°C) or lower. The heat-resistant polymer synthesized under these conditions becomes aromatic polyamide, aromatic polyamide/amic acid, or aromatic polyamic acid by coating with a difunctional aromatic acidic compound. Aromatic polyamide/amic acid and aromatic polyamic acid are subsequently converted into aromatic polyamide-imide and aromatic polyimide by causing a chemical ring-closing or thermal ring-closing reaction.
〈実施例〉 以下、実施例を挙げて本発明を詳述する。<Example> Hereinafter, the present invention will be explained in detail with reference to Examples.
実施例１
内容積５ｇのガラス製オートクレーブに４−４′−ジニ
トロジフェニルエーテル１８２ｆ （０，７モル）、日
本エンゲルハルト製５％白金カーボン粉末４ｙおよびＮ
−メチル−２−ピロリドン（以下、ＮＭＰと略称する）
１０００禽ｌを仕込み、オートクレーブ内の空気を窒素
で置換した後、水素で２０１１２０にダ／ｄゲージの中
間タンクを経由して３ ｋｇ ／ ｄゲージに加圧した
。Example 1 4-4'-dinitrodiphenyl ether 182f (0.7 mol), 5% platinum carbon powder 4y manufactured by Engelhard Japan, and N were placed in a glass autoclave with an internal volume of 5 g.
-Methyl-2-pyrrolidone (hereinafter abbreviated as NMP)
After charging 1,000 liters of chicken and replacing the air in the autoclave with nitrogen, it was pressurized to 3 kg/d gauge with hydrogen via an intermediate tank of 201,120 da/d gauge.
次にゆるやかに攪拌しながら３０分かけて９０℃に加熱
し、続いて攪拌を激しくして反応を開始した。その後、
オートクレーブ内には３ｋｆ／ｄゲージの水素圧をかけ
続けた。強力攪拌開始後、約１２０分で中間タンクのゲ
ージ圧の低下が止んｔごので続いて１時間攪拌して反応
を終了した。次に、内容物を吸引口過して、白金−カー
ボン粉末その他の不溶分を除去し、得られた口過母液を
精留管、窒素ガス導入管および攪拌機を備えた５ｇフラ
スコに移し、窒素ガスを流しながらトルエン５００ ｄ
を添加して約１２０〜１３０℃に加熱し、系中の水をト
ルエンとともに共沸留出させた。続いてトルエン５００
ｍｌを追添加し、最終的に実質上すべてのトルエンを
留出させて脱水操作を終了した。Next, the mixture was heated to 90° C. over 30 minutes with gentle stirring, and then the reaction was started with vigorous stirring. after that,
Hydrogen pressure of 3 kf/d gauge was continuously applied inside the autoclave. After about 120 minutes after the start of strong stirring, the gauge pressure in the intermediate tank stopped decreasing, so stirring was continued for 1 hour to complete the reaction. Next, the contents were passed through a suction port to remove platinum-carbon powder and other insoluble matter, and the obtained filtration mother liquor was transferred to a 5 g flask equipped with a rectifying tube, a nitrogen gas introduction tube, and a stirrer. 500 d of toluene while flowing gas
was added and heated to about 120 to 130°C, and the water in the system was azeotropically distilled together with toluene. followed by 500 toluene
ml was added, and finally substantially all of the toluene was distilled off to complete the dehydration operation.
得られた脱水液中の水分をカールフッシャー法で測定し
たところ３８０−であり、また、生成した４・４′−ジ
アミノジフェニルエーテル（以下、４−４’ −ＤＤＥ
と略称する）を液クロ法で分析したところ芳香族化合物
中に占める純度９８、９９６、収率９９．８％であった
。The water content of the obtained dehydrated solution was measured by the Karl Fuscher method and was found to be 380-.
When analyzed by liquid chromatography, the purity of the aromatic compounds was 98.996, and the yield was 99.8%.
次に、上記で得られた４・４’−ＤＤＥの脱水溶液を内
容積５１のガラス製ロータリーエバポレーターに仕込み
、４０ ｆｉＨｇの減圧下に濃縮操作を行なってＮＭＰ
を約８０ Ｑ ｍｌ留出させた後、室温に冷却したとこ
ろ、４＠４’−ＤＤＥの晶析スラリーが得られた。次に
、この晶析スラリーを遠心分離機にかけて結晶を回収し
たところＮＭＰを３７重量％含有したウェットケークが
約１５３１得られた。このウェットケーク中の４・４’
−ＤＤＥを液クロ法で分析したところ、芳香族化合物中
に占める純度が９９．６％というすぐれたものであった
。Next, the dehydrated solution of 4,4'-DDE obtained above was charged into a glass rotary evaporator with an internal volume of 51 cm, and concentrated under a reduced pressure of 40 fiHg to obtain NMP.
After about 80 Q ml of distilled water was cooled to room temperature, a crystallized slurry of 4@4'-DDE was obtained. Next, this crystallization slurry was centrifuged to collect crystals, and about 1,531 wet cakes containing 37% by weight of NMP were obtained. 4.4' in this wet cake
-DDE was analyzed by liquid chromatography and found to have an excellent purity of 99.6% among aromatic compounds.
次に、攪拌機を備えた内容積ＩＮの丸底フラスコに上記
で得られた４・４’−ＤＤＥのウェットケーク３Ｌ８ｆ
（ＤＤＥ換算０．１０モル）、メタフェニレンジアミン
４．３２ｙ（０，０４モル）およびＮ Ｍ Ｐ ３００
ｍｌを仕込んで均一溶解した。この溶液を氷水浴で冷
却しながら、攪拌下、固体粉末状の無水トリメリット酸
モノクロリド２９．５ｙ（Ｑ、１４モル）を、内部の温
度が３０℃を越えない速度で添加し、続いて１時間攪拌
を続行して重合体原液を得た。次に、この重合体原液を
強力攪拌下の水１０ｅ中に投入して重合体を析出させ、
水洗／脱水／乾燥してポリアミドイミド重合体粉末を得
た。得られた重合体の対数粘度ｐｉｎｈ （濃度：０
．５ｆ／ｄｌ、溶媒二Ｎ−メチルー２−ピロリドン、温
度：３０℃）を測定したところ０．８８という実用性の
高いものであった。Next, the wet cake 3L8f of 4,4'-DDE obtained above was placed in a round bottom flask with an internal volume of IN equipped with a stirrer.
(0.10 mol in terms of DDE), metaphenylenediamine 4.32y (0.04 mol) and N M P 300
ml was charged and uniformly dissolved. While cooling this solution in an ice-water bath, 29.5y (Q, 14 mol) of trimellitic anhydride monochloride in the form of a solid powder was added under stirring at a rate such that the internal temperature did not exceed 30°C, and then Stirring was continued for 1 hour to obtain a polymer stock solution. Next, this polymer stock solution was poured into water 10e under strong stirring to precipitate the polymer,
A polyamide-imide polymer powder was obtained by washing with water/dehydration/drying. Logarithmic viscosity pinh (concentration: 0
．． The measured value was 0.88, which was highly practical.
比較例１
水添反応溶媒および重合溶媒としてのＮＭＰのかわりに
Ｎ＠Ｎ−ジメチルホルムアミドを用いる以外すべて実施
例Ｉと同様の操作を行なったところ、得られた重合体の
′Ｐｉｎｈは０．２５という著しく低いものであった。Comparative Example 1 The same operations as in Example I were carried out except that N@N-dimethylformamide was used instead of NMP as the hydrogenation reaction solvent and polymerization solvent, and the resulting polymer had a 'Pinh of 0.25. This was extremely low.
実施例２
４・４′−ジニトロジフェニルエーテル１８２１ｃ０．
７モル）のかわりに、４−ニトロ−３′−アミノジフェ
ニルエーテル１６１Ｆ（０，７モル）を用いる以外すべ
て実施例１と同様の操作を行なったところ、ｐｉｎｈが
０．９１という実用性の高い重合体が得られた。Example 2 4,4'-dinitrodiphenyl ether 1821c0.
The same procedure as in Example 1 was carried out except that 4-nitro-3'-aminodiphenyl ether 161F (0.7 mol) was used instead of 4-nitro-3'-aminodiphenyl ether 161F (0.7 mol). A combination was obtained.
実施例３
内容積５ｇのガラス製オートクレーブに２゜２−ビス（
４−ｐ−ニトロフエノキシフエニＡ４）プロパン
３２９、７１ （０，７モル）、日本エンゲルハルト社
製５％パラジウム−カーボン粉末１４ＦおよびＮ、Ｎ−
ジメチルアセトアミド（以下、ＤＭＡＣと略称する３１
５００ｇ／を仕込み、オートクレーブ内の空気を窒素で
置換した後、水素で２０６．２０ｋｖ／ｄゲージの中間
タンクを経由して２ ｋｑ ／ ｃ４ゲージに加圧した
。次にゆるやかに攪拌しながら８０℃に加熱し、続いて
攪拌を激しくして反応を開始した。その後、オートクレ
ーブ内１こは２ ｋｑ ／ ｄゲージの水素圧をかけ続
けた。強力攪拌開始後、約５時間で中間タンクのケージ
圧の低下がほぼ止んｔごので続いて２時間攪拌して反応
を終了した。次に内容物を吸引口過して、パラジウム−
カーボン粉末その他の不溶分を除去し、得られた口過母
液を内容積５１のガラス製σ−タリーエバポレーターに
仕込み、４ Ｑ ｍＨｇの減圧下に濃縮操作を行なった
。Example 3 A 2° 2-screw (
4-p-Nitrophenoxyphenyl A4) Propane 329,71 (0.7 mol), 5% palladium-carbon powder 14F and N,N-
Dimethylacetamide (hereinafter abbreviated as DMAC)
After charging 500 g of autoclave and replacing the air in the autoclave with nitrogen, it was pressurized with hydrogen to 2 kq/c4 gauge via an intermediate tank of 206.20 kv/d gauge. Next, the mixture was heated to 80° C. with gentle stirring, and then the reaction was started with vigorous stirring. Thereafter, hydrogen pressure of 2 kq/d gauge was continued to be applied to one autoclave. About 5 hours after the start of strong stirring, the cage pressure in the intermediate tank almost stopped decreasing, so stirring was continued for 2 hours to complete the reaction. Next, the contents are passed through the suction port and palladium-
Carbon powder and other insoluble matter were removed, and the resulting filtration mother liquor was charged into a glass σ-tally evaporator with an internal volume of 51 cm, and concentrated under reduced pressure of 4 Q mHg.
この濃縮操作では初期には水が留出し、途中から水／Ｄ
ＭＡＣ共沸系が留出し、末期にはＤＭＡＣが留出し、全
留出量は約１．４５０ ｚｔであった。その結果、エバ
ポレーター内に、ＤＭＡＣを２８重量％含有したウェッ
トケークが３９０１残留した。このウェットケーク中の
２・２−ビス（４−ｐ−アミノフェノキシフェニル）プ
ロパノ（以下、ＰＯＤＡと略称する）を液クロ法で分析
したところ、芳香族化合物中に占める純度は９９．１％
であった。In this concentration operation, water is distilled out at the beginning, and water/D
The MAC azeotrope was distilled out, and at the end, DMAC was distilled out, and the total distilled amount was about 1.450 zt. As a result, 3901 pieces of wet cake containing 28% by weight of DMAC remained in the evaporator. When 2,2-bis(4-p-aminophenoxyphenyl)propano (hereinafter abbreviated as PODA) in this wet cake was analyzed by liquid chromatography, the purity of the aromatic compounds was 99.1%.
Met.
次に攪拌機を備えた内容積ｌｌの丸底フラスコに上記で
得られたＰＯＤＡのウェットケーク５７．１ｆ（ＰＯＤ
Ａ換算０．１０モル）およびＤＭ Ａ Ｃ４００ｍｌを
仕込んで均一溶解した。この溶液の入ったフラスコを氷
水浴につけ攪拌しながら固体粉末状のテレフタル酸ツク
ロリド／イソフタル酸ジクロリド（１Ｆ１モル比）混合
物２０．３Ｆ（０，１モル）を内部の温度が３０℃を越
丸ないような速度で添加し、続いて１時間攪拌を続行し
て重合体原液を得た。次に、この重合体原液を強力攪拌
下の水ｌＯ１中に投入して重合体を析出させ、水洗／脱
水／加熱乾燥してポリアミド重合体粉末を得た。得られ
た重合体の′Ｐｉｎｈ １．ｔ ０．７０という実用性
の高いものであつｔこ。Next, 57.1f of the wet cake of PODA obtained above (PODA
0.10 mol (calculated as A) and 400 ml of DM AC were charged and uniformly dissolved. Place the flask containing this solution in an ice water bath and add 20.3F (0.1 mol) of a solid powdered mixture of terephthalic acid chloride/isophthalic acid dichloride (1F 1 molar ratio) while stirring until the internal temperature exceeds 30°C. The polymer stock solution was obtained by adding the polymer at the same rate and then continuing stirring for 1 hour. Next, this polymer stock solution was poured into 1O1 water under strong stirring to precipitate the polymer, and the polymer was washed with water, dehydrated, and dried by heating to obtain a polyamide polymer powder. 'Pinh of the obtained polymer 1. It is highly practical with a t of 0.70.
実施例４
２．２−ビス（４−ｐ−ニトロフェノキンフェニル）プ
ロパノ３２９．７ｊ’（０，７モル）のかわりにビス（
４−ｐ−ニトロフェノキンフェニル）スルホノ
３４５．１ｙ（０，７モル）を用いる以外はすべて実施
例３と同様の操作を行なったところ、７＋ｉｎｈ実施例
５
内容積５ｇのガラス製オートクレーブに４゜３′−ジニ
トロベノズアミド
１４３．５ｙ（０，５モル）、ラネーニッケル水性ペー
スト３．５ノおよび１．３−ジメチル−２−イミダゾリ
ジノ７（以下、ＤＭＩと略称する）１５００ ｚｌを仕
込み、オートクレーブ内の空気を窒素で置換した後、水
素で２０１，２０＃／ｄゲージの中間タンクを経由して
８に９／Ｃ４ゲージに加圧した。次にゆるやかに攪拌し
ながら８０℃に加熱し、続いて攪拌を激しくして反応を
開始した。その後、９０℃に昇温しオートクレーブ内に
は３ ｋｇ ／ ｄゲージの水素圧をかけ続けた。強力
攪拌開始後約１０時間で中間タンクのゲージ圧の低下が
ほぼ止んだので続いて２時間攪拌して反応を終了した。Example 4 Bis(
All operations were performed in the same manner as in Example 3 except that 4-p-nitrophenoquinphenyl)sulfono 345.1y (0.7 mol) was used. 3'-dinitrobenozamide 143.5y (0.5 mol), Raney nickel aqueous paste 3.5y and 1,3-dimethyl-2-imidazolidino 7 (hereinafter abbreviated as DMI) 1500zl were charged and placed in an autoclave. After replacing the air with nitrogen, the tank was pressurized with hydrogen to 8 to 9/C4 gauge via a 201,20#/d gauge intermediate tank. Next, the mixture was heated to 80° C. with gentle stirring, and then the reaction was started with vigorous stirring. Thereafter, the temperature was raised to 90°C, and a hydrogen pressure of 3 kg/d gauge was continued to be applied inside the autoclave. Approximately 10 hours after the start of strong stirring, the gauge pressure in the intermediate tank almost stopped decreasing, so stirring was continued for 2 hours to complete the reaction.
次に内容物を吸引口過してラネーニッケルその他の不溶
分を除去し、得られた口過母液を精留管、および攪拌機
を備丸た５ｅフラスコに移し、キシレノ５００ ｍｌを
添加して、水流７スビレーターの減圧下に加熱して系中
の水をキシレノとともに共沸留出させた。続いてキシレ
ン５ Ｑ Ｑ ｔｔを追添加し、最終的に実質上すべて
のキシレノを留出させて脱水操作を終了した。Next, the contents were passed through a suction port to remove Raney nickel and other insoluble matter, and the resulting filtration mother liquor was transferred to a 5e flask equipped with a rectification tube and a stirrer, 500 ml of xyleno was added, and the water was The system was heated under reduced pressure using a subilator to azeotropically distill off the water in the system together with xyleno. Subsequently, xylene 5 Q Q tt was further added, and finally substantially all of the xylene was distilled off to complete the dehydration operation.
次に、上記脱水溶液を内容積５１のガラス製ロータリー
エバポレーターに仕込み、４０ｆｌＨｇの威圧下に濃縮
操作を行なってＤＭＩを約１２５０ ｘｌ留出させた後
、室温に冷却したところ４ｅ３′−ジアミノベンズアニ
リド（以下、４．３／−ＤＡＢＡと略称する）の晶析ス
ラリーが得られた。次に晶析スラリーを遠心分離機にか
けて結晶を回収したところ、ＤＭＩを４６重量％含有し
たウェットケークが約２０４Ｆ得られた。このウェット
ケーク中の４・３’−ＤＡＢＡを液クロ法で分析したと
ころ、芳香族化合物中に占める純度が９８．８％であっ
た。Next, the dehydrated solution was charged into a glass rotary evaporator with an internal volume of 51 cm, and concentrated under a pressure of 40 flHg to distill out about 1250 xl of DMI. When cooled to room temperature, 4e3'-diaminobenzanilide was obtained. (hereinafter abbreviated as 4.3/-DABA) was obtained. Next, the crystallization slurry was centrifuged to collect crystals, and a wet cake containing 46% by weight of DMI was obtained at about 204F. When 4,3'-DABA in this wet cake was analyzed by liquid chromatography, the purity of the aromatic compounds was 98.8%.
次に攪拌機を備えた内容積１４の丸底フラスコに上記で
得られた３・４’−ＤＡＢＡにｌ）ウェットケーク４２
ｇ（３−４’−ＤＡＢＡ換算０． ｌ ０モル）および
ＤＭＩ３ｏｏｍｚを仕込んで均一溶解した。この溶液の
入ったフラスコを氷水浴につけ攪拌しながら固体粉末状
の３・３′・４・４′−ベノゾフエノンテトラカルボン
酸二無水物３２．２Ｆ（０，１モル）を内部の温度が３
０℃を越えないような速度で添加し、続いて１時間攪拌
を続行して重合体原液を得た。次に、この重合体原液を
強力攪拌下の水１０１中に投入して重合体を析出させ水
洗／脱水／加熱乾燥してポリイミド重合体粉末を得た。Next, in a round bottom flask with an internal volume of 14 equipped with a stirrer, add the 3,4'-DABA obtained above to l) Wet cake 42
g (0.1 0 mol in terms of 3-4'-DABA) and DMI3oomz were charged and uniformly dissolved. The flask containing this solution was placed in an ice water bath, and while stirring, 32.2 F (0.1 mol) of solid powder 3,3',4,4'-benozophenonetetracarboxylic dianhydride was added until the internal temperature was reached. 3
The mixture was added at a rate that did not exceed 0° C., and stirring was continued for 1 hour to obtain a polymer stock solution. Next, this polymer stock solution was poured into water 101 under strong stirring to precipitate the polymer, which was then washed with water, dehydrated, and dried by heating to obtain a polyimide polymer powder.
得られた重合体の７ｉｎｈは０．６９という実用性の高
いものであった。The 7 inch of the obtained polymer was 0.69, which was highly practical.
〈発明の効果〉
本発明の途中で得られる芳香族ジアミノのウェットケー
クは、有害物質粉塵対策が不用かつコスト／パフォーマ
ンスがすぐれているため、そのまま極性溶媒中で二官能
性芳香族酸性化合物、たとえばピロメリット酸二無水物
、無水トリメリット酸モノクロリド、テレフタル酸ジク
ロリド、イソフタル酸ジクロリドなどと反応させろこと
により安全に実用的高重合度を有する耐熱性高分子類を
製造することができる。そして、これらの耐熱性高分子
類は、すぐれた耐熱性および力学特性を利用して、電気
・電子部品、航空φ宇宙機器部品、自動車用部品、事務
機器部品などの分野に広く活用される。<Effects of the Invention> The wet cake of aromatic diamino obtained during the process of the present invention does not require measures against harmful substance dust and has excellent cost/performance. By reacting with pyromellitic dianhydride, trimellitic anhydride monochloride, terephthalic acid dichloride, isophthalic acid dichloride, etc., heat-resistant polymers having a practically high degree of polymerization can be safely produced. Utilizing their excellent heat resistance and mechanical properties, these heat-resistant polymers are widely used in fields such as electrical and electronic parts, aerospace equipment parts, automobile parts, and office equipment parts.
Claims (1)
は芳香族モノニトロアミノ化合物を接触還元した後、不
均一系水添触媒をロ過回収し、次に芳香族ジアミンを晶
析させて溶媒 含有率３〜７０重量％のウェットケーク状に単離するこ
とによつて調製した芳香族ジアミンウェットケークと二
官能性芳香族酸性化合物をアミド系極性溶媒中で反応さ
せることを特徴とする芳香族ジアミンから誘導される耐
熱性重合体の製造方法。[Claims] After catalytically reducing an aromatic dinitro compound or an aromatic mononitroamino compound in the presence of a heterogeneous hydrogenation catalyst in a polar solvent that does not inhibit the polymerization reaction, the heterogeneous hydrogenation catalyst is Aromatic diamine wet cake and difunctional aromatic acidic compound prepared by collecting the aromatic diamine by filtration and then crystallizing the aromatic diamine and isolating it in the form of a wet cake with a solvent content of 3 to 70% by weight. 1. A method for producing a heat-resistant polymer derived from an aromatic diamine, which comprises reacting the following in an amide polar solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14959086A JPS638418A (en) | 1986-06-27 | 1986-06-27 | Production of heat-resistant polymer derived from aromatic diamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14959086A JPS638418A (en) | 1986-06-27 | 1986-06-27 | Production of heat-resistant polymer derived from aromatic diamine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS638418A true JPS638418A (en) | 1988-01-14 |
Family
ID=15478527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14959086A Pending JPS638418A (en) | 1986-06-27 | 1986-06-27 | Production of heat-resistant polymer derived from aromatic diamine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS638418A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010168502A (en) * | 2009-01-26 | 2010-08-05 | Mitsubishi Gas Chemical Co Inc | Polyamide |
| JP2014094889A (en) * | 2012-11-07 | 2014-05-22 | Toray Fine Chemicals Co Ltd | Diamine compound and its manufacturing method |
| JP2014094890A (en) * | 2012-11-07 | 2014-05-22 | Toray Fine Chemicals Co Ltd | Diamine compound and manufacturing method thereof |
| JP2014094888A (en) * | 2012-11-07 | 2014-05-22 | Toray Fine Chemicals Co Ltd | Diamine compound and manufacturing method thereof |
| WO2024013195A1 (en) * | 2022-07-11 | 2024-01-18 | Cap Iii B.V. | Process for the recovery of spandex and nylon 6 from spandex and nylon comprising materials |
-
1986
- 1986-06-27 JP JP14959086A patent/JPS638418A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010168502A (en) * | 2009-01-26 | 2010-08-05 | Mitsubishi Gas Chemical Co Inc | Polyamide |
| JP2014094889A (en) * | 2012-11-07 | 2014-05-22 | Toray Fine Chemicals Co Ltd | Diamine compound and its manufacturing method |
| JP2014094890A (en) * | 2012-11-07 | 2014-05-22 | Toray Fine Chemicals Co Ltd | Diamine compound and manufacturing method thereof |
| JP2014094888A (en) * | 2012-11-07 | 2014-05-22 | Toray Fine Chemicals Co Ltd | Diamine compound and manufacturing method thereof |
| WO2024013195A1 (en) * | 2022-07-11 | 2024-01-18 | Cap Iii B.V. | Process for the recovery of spandex and nylon 6 from spandex and nylon comprising materials |
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