JPS59206434A - Production of polyamic acid - Google Patents

Abstract

PURPOSE:To produce a polyamic acid excellent in heat resistance, mechanical strength, abrasion resistance, chemical resistance, and flexibility, by reacting a tetracarboxylic acid dianhydride purified with acetic anhydride with a diamine in a dehydrated organic solvent. CONSTITUTION:A crude tetracarboxylic acid dianhydride of an impurity content of 0.5-30wt% is immersed in 1-1.5 times, by weight, as much acetic anhydride for about a night. After removing most of the acetic anhydride, the mixture is dried at 100-150 deg.C for several hours to obtain a purified tetracarboxylic acid dianhydride. This dianhydride is reacted with a diamine, e.g., 2,2-bis(4-aminophenyl)propane, in an organic solvent (e.g., N-methyl-2-pyrrolidone) dehydrated over zeolite to a moisture content <=500ppm.

Description

[Detailed Description of the Invention] This invention relates to a method for producing polyamic acid using tetracarboxylic dianhydride and diamine as raw materials, and its purpose is to perform a ring-closing treatment at a double price. Pholamide foam has a variety of heat resistance, mechanical strength, abrasion resistance, system resistance, and burnability, and is useful as electrical insulation materials, detonators, soothing agents, molded products, and film materials. I decided to make an offering.

Conventionally, the method for obtaining polyamic acid is to use tetracarboxylic dianhydride, diamine, aprotic acid, and 5 in a bath medium.
I did not know that the reaction takes place at low temperatures below 0°C.
In order to obtain a high molecular angle polymer, the molar ratio of tetracarboxylic dianhydride and diamine is approximately equal to that of pure monomers prepared by highly advanced methods such as sublimation, and anhydrous bath medium dehydrated and distilled. I decided to use 0 and other words equally.

Tetracarboxylic dianhydride 1J1, yx r:J, ridges on ice, I bought it, and if it is stored for a long time, it will react with moisture in the air and open the ring. When ring-opened tetracarboxylic dianhydride is used as a raw material for polyamic acid, only a low-grade polymer solution is obtained, and polyimide molded products made from this product have no resistance to oxidation. It has poor strength, wear resistance, wear resistance, and compatibility! However, it is difficult to put it into practical use.

In order to avoid such a flat part 8, the conventional Teton Calho 7 trianhydride v! The ring is opened by crystallizing J with acetic anhydride.
There was one case in which the fc part grapes were almost never in operation. However, the operation of this writing crystal is extremely complicated'1
However, since the recovery rate of tetracarboxylic dianhydride was also low, as a result, it was still possible to complete one cycle.

On the other hand, 11) Moisture used in the reaction is small (l<γ). Conventionally, a dehydration bath H'< is obtained by dehydrating phosphorus pentoxide or calcium hydride blue, or by dehydrating it with zero force and then distilling it under reduced pressure. . However, this operation rμ was similarly complicated with VC and was a first-year high school song.

In order to improve the problem of delivery to Fuminyoshi and others, we conducted a thorough investigation and obtained crude tetracarboxylic acid dianhydride anhydride vinegar.
It was discovered that a high molecular weight polyamic acid can be obtained by reacting purified tetracarboxylic dianhydride with a diamine in an organic solvent dehydrated with zeolite.

The uninvented % song is C6ic except for one complicated song called A monomer's redigit crystal, common medium's dehydration #, and tame.
iru. Shun soaked in anhydrous vinegar, most of the scorched water vinegar removed, heated and dried! Shirusuke's atonecarboxylic dianhydride and zeolite)'
kms katana p left sealed for 1 day and added fc solvent bj
According to c and V, it is possible to use a high molecular weight polyamide # such as a case where a re-crystallized monomer and a dehydrated distilled solvent are added.

The crude tetone carbon dianhydride used in the present invention contains impurities of 20.5 to 6 % and is of poor quality, including those with a lump-colored rostrum and ring-opened polycarboxylic acid. Even tetracarboxylic dianhydride that has been recrystallized can last for a long time.
``Tetracarboxylic dianhydride, which is partially ring-opened due to moisture in the wall air, is also subject to non-invention.''

Examples of the types of tetracarboxylic dianhydrides used in the invention include acid anhydrides, and dicarboxylic dianhydrides such as those that produce anhydride 'f'//) in the molecule; Examples of the groups f and lI/'1 may also be used.

The following are examples of two-anhydride-one-name Vs that are uninvented and convenient for use.

Pyromellitic acid, 3.3', 4.4'
-Zinenyltetracarboxylic dianhydride, 1.2.
5.6. -su2 talenttet2rikirubonenemynianhydro'wJ%
2.3.6゜Z-naphthalenetetracarboxylic dianhydride'ms 2゜2', 3.5'-diphenyltetracarboxylic dianhydride; water, 2.2-bis(3,4,-dicarboxylic dianhydride Eninolipropanihydride, bis(3,4-dicarboxyphenyl)sulfo/dianhydride, 5.4.9.
10-perylenetetracarboxylic dianhydride, bis(3,
4-dicarpoxin-yl)ether dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,6-ditaloluna Atalene-1,4゜5.8-tetracarboxylic dianhydride, 2.7-cycloluna-2crene-
1,4,5,8,-tetracarboxylic dianhydride, 2,5
,6.7-chitratalolnaphthalene/-1,4,5,8-
The unrivaled genuine tetracarbone, phenanthrene-1,8,
9,10-tetracarboxylic dianhydride, 2,2-bis(
2,3-dicarboxinenyl) crovanni-free 7F-'
l1l), 2,2-bis(2,3-dicarboxienyl)hexa2-fluoroflobanni anhydride q=, 1.1-
Bis(2,3-dicarboxyphenyl)ethanihydride, 1,1-bis(3,4-dicarboxy-2enyl)ethanihydride, bis(2,3-dicarboxyenyl)
Methane dianhydride, bis(3,4-dicarboxycinenyl)methane dianhydride, bis(5,4-dicarboxyphenyl)sulfone dianhydride, benzene-1,2,3,4
-titracarboxylic dianhydride, -ffi, 4.5'
4'-benzophenonetetracarboxylic dianhydride, 2
, 3.2'3'-benzophenonetetracarboxylic dianhydride, 2,3.5'4'-benzonetetracarboxylic acid dianhydride, vinjin-2,3,5,6-tetracarboxylic acid Acid dianhydride, thionene-2,3,4,5-
Tetracarboxylic dianhydride, Tetracarbon dianhydride, Decahydronaphthalene-1,4,5,8-
Tetracarboxylic dianhydride, 4,8-dimethyl-i,
2.3.5.6.7-hexahydros2talene-1,2
゜5.6-Tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride,
Pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, dicyclo-(2,2,2)-otato(7)-ene- 2
, 3,5,6-tetracarboxylic dianhydride 2,6,6-4'-biphenylnatracarboxylic dianhydride, 6,
4.5'4'-vinenyltetracarboxylic dianhydride,
2,3,2ζ6'-biphenylnatracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)dimetersilanihydride, bis(6°4-dicarboxyphenyl)
Methyl 2-enylsilanhydride, bis(3,4-dicarboxyphenyl)di-2enylsilanhydride, bis(2
,3-dicarphoxinenyl) dinotersilani anhydrous 9
Of course, 1,4-bis(3,4-dihydrofoxyfluoride/L
= Benzene jtl & 71m1
．． 1.3-bis(3+4-dicarboxyphenyl)
-1,1,5゜6, -tetosimethyldisilosane two groups (sword < thing, p-enylene bis (trimellitic acid mo/Esthe Jb Fengyo Suimono), ethylene glycol bis (trimellitic acid anhydride vA) + 2 .2-bis(6,4-dicarboxyphenyl)hexafluoroglolobanni anhydride, 2.2-bis(4-(3,4,-dicarboxyphenoxy)phenyl)hexaneroloroglobanni 7XvtJ
, 4,4'-His(3,4-dicarboxy:7
enoxy) diphenyl sulfide dianhydride, His(4-
(6,4-dicarboxyphenoxy)phenyl]sulfone dianhydride, 4,4'-(1,4-phenylene)bis(
5,5,6-t') phenyl ditalic anhydride), 4.4
'-(oxydi1.4-, phenine/)bis(s,
s, 6-tri-2-enylntalic acid scorched water) 0 anhydrous vinegar During the free time, there is some vinegared rice, gran, and other acids of the basic propionic acid base, and the missing items of the anhydrous temple. In addition, even if the anhydrous safflower used once in the treatment of the present invention has the same monogonal anhydride size, it may be used repeatedly. Tori-ni-sho-suimono is called anhydrous counting. If the total amount of water is immersed in an acid, an acid sword (1 to 15 times the water content (weight ratio) is also sufficient for H → 7L. Since there are a lot of cases, preferably 72.

At the time of reconnaissance + 41], I did not fall asleep at times, but -2 at night
It is enough to get +1 to the degree of concentration (the presentation of the inkstone is enough to change the purpose).

Anhydrous U1 was given Vc, so due to the mistake of a detonation, Fc except for Anhydrous meter I'9c,
It is best to keep the kiln dry and dry at 100-150°G for a long time.
Well, it seems like it's W if it sticks to 6 o'clock + Wj or more at 160℃ 0 It's not enough to remove the anhydrous enemy with a hardness lower than 100℃ (by sublimation with a sieve moderation than 150℃) dissipation and heat]
Side reaction of Japanese name-C! However, I don't like it.

There are no particular limitations on the diamines that are suitable for use in the invention. Examples of suitable diamines for use in the invention include the following: 2,2-his(4-amino-phenyl)propane; 2
, 6-diamitohyridine, bis-(4-aminoneenyl)diethyl 7rane, bis-(4-amitouf,yl)jinjenylsilane, benzidine, 6,6'-dichloro-pendecine, 3,3'-dimethoxybenzidine, and No(4-amino-phenyl)etherphosphine oxide, His-(4-amino-2enyl)-N-phtelamine, Bis-(4-amino-2enyl)-N-methylamine, 3.3'-dumenal -4,4'-diaminop2=
3.
6'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylmethane, 6,5'-jethoxy-4,4'-diaminodiphenylmethane.

6.6'-dicarboxy-4,4'-diaminodiphenylmethane, 3.3'-cyclo4,4'-diaminodienylmethane, 3.5'-dichloro-4,4'-diaminodiphenylmethane, 3,6 '-dibrome-4,4'
-diaminodiphenylmethane, 6,6'-dihydroxy-4,4'-diaminodiphenylmethane, 6,5'-disulfo-4,4'-diaminodiphenylmethane.

3.5'-dimethyl-4,4'-diaminodiphenyl ether, 3,5'-dimethoxy-4,4'-diaminodiphenyl ether, 3,6'-jethoxy-4,4'-
Diaminodiphenyl ether, 5,5'-dicarboxy-4,4'-diaminodiphenyl nial, 3゜5'-
Cycloro 4.4'-cy7minodine enyl ether, 3
．． 3'-dihydroxy-4,4'-diaminodiphenyl ether, 3.3'-disulfo-4,4'-diaminodiphenyl ether, 3j'-dimethyl-4,4'-diaminodiphenyl sulfone, 3. ．． 5'-dimethoxy-4
, 4'-diaminodiphenylsulfone.

6.6'-jethoxy-4,4'-diaminodiphenylsulfone, 3.3'-dicarboxy-4,4'-diaminodiphenylsulfone, 3.3'-dichloro-4,4'
-diaminodi2enyl sulfone, 6,5'-dihydroxy-4,4'-diaminodiphenylsulfone.

5.5'-disulfo-4,4'-diaminodiphenylsulfone, 5.5'-dimethyl-4,4'-diaminodienylgloban, 6.5'-dimethoxy-4,4'-diaminodieneylgloban, 3. 3'-Jetoxy-4
, 4'-cyaminodineenylgloban, 6.3'-dicarboxy-4,4'-diaminodienylgloban%
6.37-dichloro-4,4'-cyaminodiphenylgloban, 3.5'-dihydroxy-4,4'-cyamodi2enylgloban, 5.5'-disulfo-4,4'
-diaminodiphenylmethaney, 5,6'-dimethyl-
4,4'-diaminodiphenyl sulfide, 3.3'
-dimethoxy-4,4'-diaminodiphenylmethaneide% 6.6'-jethoxy-4,4'-diaminodiphenyl sulfide, 5.6'-dicarboxy-4,
4'-diaminodiphenylsul 2ite, 3,3'-dichloro-4,4'-cya e-nodineenyl, X/l,
:7ite, 3,6'-dihydroquine-4,4'-
Diaminocinenyl sulfide, 3,3'-disul*
-4,4'-diaminodiphenylsul211d,3
．． 3'-diaminodiphenylmethane, 3.3'-diaminodiphenyl ether, 3.3'-diaminodiphenylsulfone, 3.3'-diaminodienylcroban, 6
．． 5'-cyaminodiphenylsrunide, 6.5'-
Diaminobenzo 2-enone, 2,4-diaminotoluene,
2,6-diaminotoluene, buff-7znylenediamine, meta-2enylenediamine, 4,4'-diaminodi2enylgloban, 4,4'-diaminodienylmethane, 4,4'-diaminodienyl srunite s
4.4'-cyaminodine enyl sulfone, 4.
4'-Diamino-diphenyl ether, 6,4'-cyamino-dialnylether, 1,5-cyamino/-1-IL/, 6,6'-dimethoxybezidine, 2,4-bis(beta-amino- t-7tel) toluene, bis-
(buff-beta-amino-t-funal-2enyl)ether, bis-(ham-beta-amino-t-funal-2enyl)benzene, his-par-(1,1-cyfnal-5-anobennal)benzene, 1- Innorohiru-2,4-metaphenylenediamine, m-quinene diamine, hexamenalediamine, hegtamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, diaminoglobiltetonemethylenediamine, 6-Menalhebutamethylenediamine, 4.4'-Dinonalhebutamethylenediamine, 2.1
1-diamino-dodecane, 1,2-bis-(6-amituglophoquine)ethane, 2,2-dimeteroglobylene diabane.

6-medoxyhexamethylenediamine, 6,5'-dimethylbenzidine, 2,5-dimethylhexamethylenediamine, 2I5-dimethylhexamethylenecyamine,
5-methyl-nonamethylenediamine, 2.17-diamino-icosatecan, 1゜4-diaminocyclohexane, 1.10-diamino-1,10-dimethyldecane,
1.12-Diamino-oftatecan. Used in non-invention
The zeolite used may be naturally produced or synthetically produced. Moreover, it does not have to contain a kasudai agent. The pore size of the zeolite is about the same as that of water molecules, and the solvent molecules are also smaller than 77 times. A pellet-like spherical shape is preferred.

- Biolite's Xutoguchi and the number of days left unused and 1J inverse comparison? It would be better to try out the LTV station first and decide on the number 2, since it is in a relationship with the 1st flight digit line.

The moisture absorption in the solvent with the thickness removed is preferably less than 500,
Descendantly r Work 1
'[Not more than 100 sirs. If the duty is more than 500p, the molecular protein of polyamic acid is not enough.

Is it okay to use a holamide bath or anything else that is suitable for use as a line? N-methyl-2-pyrrolidone s iN
, N-dimethylacetamide, N.

N-dimethylformamide, N,N-dimethylformamide, cymetersulfoquinde, sulfolane, methylsulfolane, tetramethylsilver, hexamethylphosphoramide, butyrocytaton's aprotic aprotic solvents are preferred. , These digit lines may be used in combination, or two or more buildings may be used in combination. Menalimbutergone, cresol, dioxin, and cyclohexamonochloride may be used for toilet use by applying abrasive force to the extent that the solvent does not precipitate.

The polyamic acid obtained according to the present invention is subjected to stress at a temperature of 100°C or higher, or dehydration is performed, for example, by treatment with acetic anhydride-pyridine, resulting in di-ring closure and mechanical strength. It can be applied to polyimide which has excellent abrasion resistance, chemical resistance and workability.

The following will be explained in more detail using examples of non-inventions, but the scope of non-inventions will be limited to the following examples.
Yes.

Example 1 Crude pyromellitic dianhydride (purity 92%) 100 gK
150 g of grapes were added and left to stand overnight, filtered under reduced pressure, and dried in an oven at 160° C. for 8 hours for simple purification of pyromellitic dianhydride. The yield of pyromellitic dianhydride was 94.9%, and the recovery of acetic anhydride was 894%.

-100g of Molecular Thief 5A in 11,000N, N-dimethylacetamide? 11% Toro Shun 5 Hyuga The moisture M2S waste was left to dehydrate N,N-dimethylacetamide by re-sealing.

Vorticity meter, stirrer 2 and calcium chloride a busy 30
200 g of 4,4'-diaminodine enyl ether and dehydrated N with soil were placed in 114 round flasks.

256.9 g of N-dimethylacetamide was added to make a homogeneous solution. The purified pyromellitic dianhydride obtained above was heated to 10°C or lower by placing the flask in an ice bath.
Gradually add the grapes. When the reaction mixture was finished, the reaction solution was vortexed at 15°C and allowed to react for 7 hours. The reduction and deterioration of the varnish in the 7-hour reaction wave was measured at 4.58 dl/g (solvent N
, N-dimethylacetamide, concentration 0.1 g/di,
Temperature 25.0℃, comparison of Aono example described below? +1 Moko 1 (same soup stock) and had a sufficiently high molecular weight. l
The hue was 6. When this reaction bath was cast onto a glass plate and the wires were removed, a strong film made of polyamic acid was formed.

The second film was further heat treated at 200°C and 400°C to create a polyimide film with excellent heat resistance, mechanical strength, abrasion resistance and 90% durability.

Comparative substance 1 Crude pyromellit without any refining operation @(
(purity 92%) and water content 980pp without dehydration
The reaction was carried out in the same manner as in Example 1 except that N,N-dimethylacetamide of II was used, but the viscosity of the solution did not increase.0 Still the hue was slightly Gardner Hue 11.0 Example 2 Coarse 3. s; 4. Yield of 0 anhydride made in the same manner as in Example 1 except for use in 4'-benzo2ninonetetracarboxylic dianhydride (purity 95%): 95.8
%, and the recovery rate of acetic anhydride was 91.5%.

On the other hand, N-methyl-2-pyrrolid type 71 has PyritT.
-144 (manufactured by Bayer) 100g Dehydrated N
-Methyl-2-pyrrolidone. Temperature H↑, stirring rock P
Calcium chloride tube? 4.4'-Schifbanodine enyl ether in 14 flasks of 500 m 17.6
0g of P-21 dilenediamine and 225.9g of dehydrated N-methyl-2-pyrrolidone obtained above. FC Shun, Example 1
And my colleague and samurai purified pyromeri torinanhydro? 1171
9.1 ag and clay samurai rq made 6,3. '4,4'-
Benzophenone tetracarboxylic anhydride 28.114
Gradually, the 0-piece DP "j' 1 anti-upper Otsu) Liquid polarity '/X:: The temperature was set to 20°C and the reaction was carried out for 8 hours. At 8 o'clock, the reaction was carried out for 8 hours. Reduction of the varnish of the reactant When I measured the viscosity, it was 6°07 dl/g, indicating that it had become a cylinder molecule.

This polyimide film has improved heat resistance, wall stability, and stability when treated in the same manner as in the reaction bath number τ(IJ1). 2. Crude pyromellits without any refining operations. 5, 6. Reaction coating was carried out in the same manner as in σ Example 2, except that '4,4'-benzoneenonetetracarboxylic dianhydride and grapevine rind were used. At 8:00 IMj, the reduced viscosity of the varnish in the reaction zone was 60-28 dl/g. This reaction bath solution was insufficient in mechanical processing properties of a polyimide film obtained by processing in the same manner as in Example 1.

Rifle Example 6 Pyromelli Tori Muzui 100g1/(: Mubo Boi Enemy 500
Add 20 g of activated charcoal and reflux for 60 minutes.
The resulting assembly was dyed by vacuum filtration. Pure IZ
99.96%, yield 51.8% fc.

10,000, add 6g of phosphorus pentoxide to N,N-dimethylacetamide 11, add 7J of phosphorus to 115 pl of water by reducing the pressure, add 115 pl of water, IQ-dimethylacetamide/ζ.

In addition to using pyromellitic dianhydride obtained by tanphase crystallization and de-7KN,N-dinotylacetamide obtained by distillation VC, I also carried out a reaction with a co-worker of K'Hya Ri111. 7 o'clock 1i + 41y,, the original viscosity of Ogo's varnish was D4.26d17g, and the Gardner hue was 6 to 1 hue. By dehydrating the monomers and the amount of the monomers, the
It is clear that the polyamide synthesized from the bathing medium, the nanatsuma obtained by crystallization, and the common medium obtained by steaming, and the madder molecular shield polyamic acid of Il: T1 or higher, are produced by the samurai. It is.

Also by an inventive method! The yield of coffin-made grains and the recovery rate of anhydrous vinegar are also shown in Figure 3 for comparison.
= Considering the same costs, etc., the uninvented method has continuity and is behind H9 (ζ Obviously 'C
be.

Claims (1)

[Claims] 1. Crude tetracarboxylic dianhydride was soaked in anhydrous vinegar, most of the acetic anhydride removed, heated and dried, and then purified with purified tetracarboxylic anhydride and diamine. A process for producing polyamic acid, which is dehydrated with zeolite and then stirred in an FC bath medium to give a χ 2. The A8 solvent is an aprotic bath medium. 3. The method for manufacturing polyamic acid described in Paragraph 1 of Kari dT Sabimu's Article 3. The water content 11 of the dehydrated shoulder bathing medium shall be 500 pμ or less. Scope 04 of polyamic acid according to item 1 or 2, % of the zeolite being Tainobo zeolite. =1'
A method for producing polyamic acid according to claim 1.