JPH0257057B2 - - Google Patents
Info
- Publication number
- JPH0257057B2 JPH0257057B2 JP18994083A JP18994083A JPH0257057B2 JP H0257057 B2 JPH0257057 B2 JP H0257057B2 JP 18994083 A JP18994083 A JP 18994083A JP 18994083 A JP18994083 A JP 18994083A JP H0257057 B2 JPH0257057 B2 JP H0257057B2
- Authority
- JP
- Japan
- Prior art keywords
- aromatic
- polyimide
- acid
- aromatic diamine
- diamine
- 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 - Lifetime
Links
- 229920001721 polyimide Polymers 0.000 claims description 50
- 239000004642 Polyimide Substances 0.000 claims description 45
- 125000003118 aryl group Chemical group 0.000 claims description 36
- 150000004984 aromatic diamines Chemical class 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- -1 aromatic tetracarboxylic acid Chemical class 0.000 claims description 15
- 230000007062 hydrolysis Effects 0.000 claims description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 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 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000006068 polycondensation reaction Methods 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- RCZJVHXVCSKDKB-UHFFFAOYSA-N tert-butyl 2-[[1-(2-amino-1,3-thiazol-4-yl)-2-(1,3-benzothiazol-2-ylsulfanyl)-2-oxoethylidene]amino]oxy-2-methylpropanoate Chemical compound N=1C2=CC=CC=C2SC=1SC(=O)C(=NOC(C)(C)C(=O)OC(C)(C)C)C1=CSC(N)=N1 RCZJVHXVCSKDKB-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910001868 water Inorganic materials 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 235000011118 potassium hydroxide Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 239000003112 inhibitor Substances 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
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Description
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ãããæãã圹å²ã¯å€§ãããDETAILED DESCRIPTION OF THE INVENTION In recent years, aromatic polyimides have played a major role as highly functional heat-resistant materials.
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ãªããŒãå®çšã«äŸãããŠãããManufactured by a polycondensation reaction between an aromatic tetracarboxylic acid dianhydride having one or more aromatic rings in the molecule and an aromatic diamine having one or more aromatic rings in the molecule. Aromatic polyimides generally have the following structure, and from the viewpoint of the strength of the formed film, the logarithmic viscosity measured at 50°C using P-chlorophenol as a solvent is 2.0 or more, especially 2.0 or more. Polymers polycondensed to about 4.0 are in practical use.
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ããã (However, R and R' are residues containing an aromatic ring.) However, since aromatic polyimide is a material that requires high functionality, aromatic There are strict requirements for the performance of polyimide, and a considerable amount of polyimide is discarded as non-standard products due to the presence of a small amount of gel or minute pinholes in the formed film. Also, during film production, both ends of the film serve as gripping margins for the machine, so they are later cut and discarded, but both aromatic tetracarboxylic dianhydride and aromatic diamine, which are raw materials for aromatic polyimide, are extremely These are expensive chemicals, and these discarded parts have a large impact on the manufacturing cost of aromatic polyimide.
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æ³ã¯ç¥ãããŠããªãã It is known that these aromatic polyimides are decomposed by heating in the presence of an alkali, but they are completely decomposed into monomer units of aromatic tetracarboxylic acid and aromatic diamine, which can then be reused. There is no known method for using it as a condensation raw material that can be subjected to a polycondensation reaction.
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ãšãåºæ¥ãã The reason for this is that when imide bonds are dissociated by hydrolysis, an elimination reaction of carboxyl groups accompanies, and under mild decomposition conditions that do not cause elimination of carboxyl groups, imide bonds are The dissociation of bonds is not completed completely and polyimide oligomers remain, and furthermore, the recovered aromatic tetracarboxylic acid and aromatic diamine are significantly colored (brown). The presence of polyimide oligomers can be confirmed as methanol-insoluble components of the recovered material.
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ãã補é ããããšã¯äžå¯èœã§ããã Decarboxylation components such as aromatic tetracarboxylic acid and aromatic dicarboxylic acid, which are generated by the elimination of carboxyl groups mixed into the recovered raw material, and polyimide oligomers are inhibitors of the polycondensation reaction, and these are substances that inhibit the polycondensation reaction. If recovered raw materials containing more than % of the raw materials are used, it is impossible to produce an aromatic polyimide with a logarithmic viscosity of 2.0 or more through a polycondensation reaction.
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ã«ã€ããŠéæç 究ããçµæãæ¬çºæãå®æããã The present inventors completed the present invention as a result of intensive research into a method for recovering aromatic tetracarboxylic dianhydride and aromatic diamine, which have high polycondensation reactivity and can be reused as raw materials for aromatic polyimide.
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ã³è³éŠæãžã¢ãã³ã®ååæ¹æ³ã«é¢ããã That is, the present invention provides a method for simultaneously recovering an aromatic tetracarboxylic dianhydride and an aromatic diamine by hydrolysis from an aromatic polyimide that can no longer be used as a molded product. Aromatic polyimide is hydrolyzed at a temperature of 150 to 230°C in the presence of 4.0 to 4.8 times the mole of alkali to the extent that substantially no imide bonds remain, and the resulting reaction product is filtered to obtain aromatic tetracarboxylic acid. After separating into an alkaline aqueous solution (liquid A) and an aromatic diamine as a filter cake, an acid aqueous solution is further added to the filter cake to form an acid aqueous solution of aromatic diamine (liquid B), and the liquids A and B are respectively separated. The aromatic tetracarboxylic acid and the aromatic diamine are precipitated by contacting with activated carbon, and then the aromatic tetracarboxylic acid and the aromatic diamine are precipitated by adding acid and alkali in an amount equal to or more than the neutralization equivalent.The aromatic tetracarboxylic acid is further heated and dehydrated to precipitate the aromatic tetracarboxylic acid and the aromatic diamine. The present invention relates to a method for recovering aromatic tetracarboxylic dianhydrides and aromatic diamines, which is characterized in that they are recovered as anhydrides.
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ãŠã¯èç±æ§ãæãããã®ã§ããã°å¶éã¯ãªãã The aromatic polyimide used in this invention is not limited as long as it has heat resistance.
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ãã To specifically explain the method of the present invention, an alkali such as caustic soda, caustic potash, or ammonia, and water in an amount of 4.0 to 4.8 times the mole of aromatic polyimide and polyimide units are charged into a pressure-resistant reactor such as an autoclave, and the air is heated. After replacing the phase with an inert gas such as nitrogen or carbon dioxide, the polyimide is hydrolyzed by heating to a temperature in the range of 150 to 230°C until substantially no imide bonds are present.
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äºç¡æ°Žç©ãååããããšãåºæ¥ãã The aromatic tetracarboxylic acid produced by hydrolysis is present in the aqueous solution as an alkali salt, and the aromatic diamine is precipitated at the bottom of the autoclave after cooling and is filtered out. After decolorizing the filtrate with activated carbon, add an inorganic acid such as hydrochloric acid or sulfuric acid or an organic acid such as formic acid or acetic acid to acidify the liquid to precipitate aromatic tetracarboxylic acid, filter, wash with water, and dry. collected by. Here, during the precipitation of the aromatic tetracarboxylic acid from the alkaline solution, it is particularly necessary to make the solution acidic by adding an acid in an amount equal to or more than the neutralization equivalent in order to remove the mixed diamine component. The recovered aromatic tetracarboxylic acid is heated and dehydrated in an inert gas stream to form aromatic tetracarboxylic dianhydride, which can then be used as a raw material for aromatic polyimide. A purification operation may be added later.
In this way, from substandard aromatic polyimide,
Aromatic tetracarboxylic dianhydride can be recovered with a high yield of 90% or more.
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ã®åŠçãè¡ãªãã On the other hand, the precipitate filtered out after hydrolysis is aromatic diamine, and is subjected to the following treatment to remove foreign substances and decolorize it.
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ã¡ããæè¯ç²Ÿè£œçã®ç²Ÿè£œæäœãå ããŠãè¯ãã First, the precipitate is made into an aqueous acid solution such as hydrochloric acid, sulfuric acid, formic acid, acetic acid, etc., and the solution is decolorized with activated carbon and filtered. Next, an alkali such as caustic soda, caustic potash, or ammonia is added to the filtrate to make the liquid alkaline. The precipitated aromatic diamine is collected by filtration, washing with water, and drying. Here, when the aromatic diamine is precipitated from the acidic solution, it is particularly necessary to make the solution alkaline by adding an alkali equivalent to or more than the neutralization equivalent in order to remove the mixed carboxylic acid component.
In this way, from substandard aromatic polyimide,
Aromatic diamines can be recovered with a yield of over 90%. The recovered aromatic diamine can be used as it is as a raw material for polycondensation, but of course a purification operation such as sublimation purification may be added.
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åã§ããã In this invention, the alkali used for hydrolysis may be caustic soda, caustic potash, or ammonia, but the amount used is based on the polyimide unit.
It is necessary to add 4.0 times the mole or more; if it is less than this, the decomposition reaction will not proceed completely and a low molecular weight oligomer having a polyimide bond will be produced. In addition, excessive use is undesirable because it promotes decarboxylation reaction, and 4.0 to 4.0
Approximately 4.8 times the molar amount is optimal. The amount of water during hydrolysis is sufficient as long as it is sufficient to dissolve the alkali salt of aromatic tetracarboxylic acid produced, but generally it is 5 to 20% water based on the weight of the polyimide that has not yet been charged. About twice the amount is sufficient.
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æéã230âã§2.5æéãé©åœã§ããã In addition, in this invention, when hydrolyzing polyimide, the decomposition time until imide bonds are substantially no longer present varies depending on the hydrolysis temperature: 150°C for 7 hours, 170°C for 5 hours, 200°C at 3.5
Appropriate time is 2.5 hours at 230°C.
以äžã«å®æœäŸããã³æ¯èŒäŸã瀺ãã Examples and comparative examples are shown below.
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ã§ãã€ããExample 1 3,3',4,4'-biphenyltetracarboxylic dianhydride (hereinafter abbreviated as BPDA) and diaminodiphenyl ether (hereinafter abbreviated as DADE)
Aromatic polyimide produced by polycondensation of 30g of gripping margin during film formation [logarithmic viscosity (ηinh) at 50â is 3.5], 11.5g of caustic soda
(4.4 times the mole per polyimide unit), 300ml of distilled water
was placed in an autoclave with an internal volume of 430 ml. After the gas phase was purged with nitrogen, the temperature was raised to 190° C. and the mixture was stirred for 4 hours for hydrolysis. After cooling, the contents of the autoclave were filtered. Add 1 g of powdered activated carbon to the filtrate and
After stirring for several minutes, the activated carbon was separated by filtration, and 40 ml of concentrated hydrochloric acid was added to the filtrate. The precipitate was filtered, washed with water, dried under reduced pressure at 60°C overnight, and a portion was methyl esterified. Elemental analysis and gas chromatography analysis revealed that 3,3',4,4'-biphenyltetracarboxylic acid ( (hereinafter abbreviated as BPTA). Furthermore, gas chromatography analysis after esterification revealed that the concentration of the decarboxylated component was as small as 0.014%.
In addition, the recovered BPDA was completely dissolved in methanol and did not contain any insoluble matter, so it was confirmed that it did not contain any oligomers having polyimide bonds. 16 hours at 240â in nitrogen flow
The recovery rate after heating and dehydrating BPTA to form BPDA was 92.6% based on the charged aromatic polyimide.
It was hot.
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å§ä¹Ÿç¥ããçœè²ç²ç¶ç©ãåŸãã Further, after the hydrolysis, 30 ml of concentrated hydrochloric acid and 270 ml of distilled water were added to the filtered solid to dissolve it, and 1 g of powdered activated carbon was added and stirred for 30 minutes, after which the activated carbon was separated by filtration. 15 g of caustic soda was added to the filtrate and stirred, and the precipitate precipitated was filtered, washed with water, and dried under reduced pressure at 60° C. overnight to obtain a white powder.
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ãã€ãã Elemental analysis and gas chromatography analysis of a portion revealed that the frame was pure.
It was confirmed that it was DADE. The recovery rate was 91.1%.
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ãã 5.88 g (20 mmol) of BPDA and 4.01 g (20 mmol) of DADE recovered in the manner described above were
When polycondensation was performed at 160°C for 1 hour using 91.6 g of P-chlorophenol as a solvent by the method described in Publication No. 65227, the logarithmic viscosity (ηinh) at 50°C was
An aromatic polyimide having a value of 2.83 was obtained. This value indicates that condensation was sufficiently high.
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ã§ãã€ãã ηinh.=ln(η/η.)/c where η: Viscosity η of the polyimide solution. : Viscosity of solvent (P-chlorophenol) C: Concentration of polyimide (g/100g) A film with a thickness of 30ÎŒ was prepared from the obtained polyimide by the method described in JP-A-55-65227, and When the strength and elongation (at break) were measured, they were 23.9 Kg/mm 2 and 83%, respectively.
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ã§ãã€ããExample 2 In the same manner as in Example 1, 30 g of a substandard aromatic polyimide film was hydrolyzed at 150°C for 7 hours.
Recovery rates for BPDA and DADE were 91.1% and 93.3%, respectively.
Obtained in %. The concentration of the decarboxylated component in the recovered BPDA was sufficiently low at 0.011%, and it did not contain any polyimide oligomer. When polycondensation was carried out in the same manner as in Example 1 using these recovered raw materials,
The logarithmic viscosity at 50°C was 3.02, which was a fully satisfactory value, and the tensile strength and elongation of the polyimide film were 24.1 Kg/mm 2 and 85%.
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ã§åŸããExample 3 BPDA and DADE were prepared in the same manner as in Example 1, except that aromatic polyimide was hydrolyzed at a temperature of 230°C for 2.5 hours and formic acid was used instead of hydrochloric acid.
were obtained with recoveries of 93.4% and 92.6%, respectively.
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ã§ãã€ãã The concentration of decarboxylated components in the recovered BPDA is 0.018
%, and contained no polyimide oligomer at all. When polycondensation was carried out in the same manner as in Example 1 using these recovered raw materials, the logarithmic viscosity at 50°C was 2.97, which was a fully satisfactory value, and the polyimide film had a tensile strength of 23.6 Kg/mm 2 and an elongation of 82%
It was hot.
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ã§ãã€ããComparative Example 1 The same experiment as in Example 1 was conducted except that 26.2 g of caustic soda (10 times the mole relative to the polyimide unit) was used, and BPTA and DADE were obtained with a recovery rate of 92.4% and 92.1%, respectively. Analysis of the recovered BPTA revealed that polyimide oligomers were not present, but the concentration of decarboxylated components was as high as 0.43%. Furthermore, when polycondensation was carried out in the same manner as in Example 1, the logarithmic viscosity of the polycondensate was as low as 1.63, which was not a satisfactory value. The tensile strength of polyimide film is 13.7
Kg/mm 2 and elongation was 45%.
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šãäžæããªãã€ããComparative Example 2 Hydrolysis was carried out at 130° C. for 15 hours using the method of Example 1, and 67.3% of BPTA and 55.1% of DADE were recovered. As a result of BPTA analysis, the concentration of decarboxylated components was 0.00%, but polyimide oligomer
It was also contaminated by 7.3%. The recovered BPTA was anhydrified to form BPDA, and then polycondensed in the same manner as in Example 1, but the viscosity after the reaction did not increase at all.
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ãšäœããæºè¶³åºæ¥ãå€ã§ã¯ãªãã€ããComparative Example 3 Hydrolysis was carried out at 250°C for 1 hour in the same manner as in Example 1, and BPTA and DADE were reduced to 94.6% and 94.6%, respectively.
A recovery rate of 94.1% was obtained. Analysis of BPTA revealed that no polyimide oligomer was mixed in, but the concentration of decarboxylated components was 1.65%. As a result of the polycondensation test, the logarithmic viscosity at 50â was 1.16, the tensile strength of the polyimide film was 7.6 Kg/mm 2 , and the elongation was 23%.
This was a low and unsatisfactory value.
Claims (1)
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ã³ã®ååæ¹æ³ã1 In a method for simultaneously recovering aromatic tetracarboxylic dianhydride and aromatic diamine by hydrolysis from aromatic polyimide that can no longer be used as a molded product, 4.0 to 4.8 times the molar amount per polyimide unit of the aromatic polyimide. in the presence of alkali
Hydrolyzing aromatic polyimide at a temperature of 150 to 230°C to the extent that virtually no imide bonds remain,
After filtering the obtained reaction product and separating it into an alkaline aqueous solution of aromatic tetracarboxylic acid (liquid A) and an aromatic diamine as a filter cake, an acid aqueous solution is further added to the filter cake to separate the aromatic diamine acid. Aqueous solution (B solution)
Then, the A liquid and the B liquid are brought into contact with activated carbon, and then acid and alkali in an amount equal to or more than the neutralization equivalent are added to precipitate aromatic tetracarboxylic acid and aromatic diamine. A method for recovering aromatic tetracarboxylic dianhydride and aromatic diamine, which comprises further heating and dehydrating the tetracarboxylic acid to recover the dianhydride.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58189940A JPS6081154A (en) | 1983-10-13 | 1983-10-13 | Recovering process |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58189940A JPS6081154A (en) | 1983-10-13 | 1983-10-13 | Recovering process |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6081154A JPS6081154A (en) | 1985-05-09 |
JPH0257057B2 true JPH0257057B2 (en) | 1990-12-03 |
Family
ID=16249749
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP58189940A Granted JPS6081154A (en) | 1983-10-13 | 1983-10-13 | Recovering process |
Country Status (1)
Country | Link |
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JP (1) | JPS6081154A (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6450876A (en) * | 1987-08-21 | 1989-02-27 | Ube Industries | Production of high-purity biphenyltetracarboxylic acid dianhydride |
JP3087993B2 (en) * | 1988-06-25 | 2000-09-18 | å®éšèç£æ ªåŒäŒç€Ÿ | Method for producing aromatic polyamic acid |
JP4985085B2 (en) * | 2007-05-10 | 2012-07-25 | æ±æŽçŽ¡çžŸæ ªåŒäŒç€Ÿ | Decomposition and recovery method of polyimide |
JP5029222B2 (en) * | 2007-08-28 | 2012-09-19 | æ±æŽçŽ¡çžŸæ ªåŒäŒç€Ÿ | Decomposition and recovery method of polyimide |
JP4952441B2 (en) * | 2007-08-28 | 2012-06-13 | æ±æŽçŽ¡çžŸæ ªåŒäŒç€Ÿ | Decomposition and recovery method of polyimide |
JP2013087148A (en) * | 2011-10-14 | 2013-05-13 | Toray Ind Inc | Method for alkaline hydrolysis of polyimide and method for recovery of low molecular weight compound and metal from polyimide metal laminate |
KR101492894B1 (en) | 2012-06-12 | 2015-02-12 | ê°ë¶ìí€ê°ìŽì€ ëê¹í ìœí | Compound containing imido group, solution of compound containing imido group and method for producing of compound containing imido group |
KR101643071B1 (en) | 2013-11-27 | 2016-08-10 | ê°ë¶ìí€ê°ìŽì€ ë칎í ìœí | Solution of compound containing imido group and method for producing of polyimide film derived from solution of compound containing imido group |
WO2019181145A1 (en) | 2018-03-20 | 2019-09-26 | æ ªåŒäŒç€Ÿä»²ç°ã³ãŒãã£ã³ã° | Aqueous treatment agent, method for producing aqueous treatment agent, and method of using aqueous treatment agent |
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1983
- 1983-10-13 JP JP58189940A patent/JPS6081154A/en active Granted
Also Published As
Publication number | Publication date |
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JPS6081154A (en) | 1985-05-09 |
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