DE2247733A1 - NEW AROMATIC POLYIMIDES WITH CARBINOL CHAINS, THE PROCESS FOR THEIR PRODUCTION AND THEIR APPLICATION - Google Patents

Description

September 15 DR. GERHARD RATZEL 68 Mannheim ι,

Seckenheimer Sfr. 36a Tel. (0621) 400315 PATENT ADVOCATE

Postal checking account! Frankfurt / M. No. 8293 Bank. Deutsche Bank Mannheim No. 72/00Οίό

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INSTITUT PHANCAIS DU PETROLE ■ ^ ₉

DES OARBUMNTS ET LUBRIi ¹ IANTS ./^4 / 733

1 & 4, avenue de Bois-Preau 9 2 ^ RUEIL-MALMISON / ffRANKRlCIQH

New aromatic polyimides with carbinol chain linkage, Process for their production and their application

The flauptpatent .. .. «> ......... _: ..... (patent application

P 20 05 5Ü7.2) relates to a process for the production of aromatic polyimides with carbinol chain linkage, which is characterized in that at a temperature between about 100 and ZfOO ° C at least one tetraester of metaphenylene-bis (hydroxymethylene-Zf-phthalic acid) der general formula

RO ₂ C CO R

MU _n U - ^ * ^ , CD —.H

2 2

in which R denotes a monovalent hydrocarbon radical and R »denotes hydrogen or a monovalent hydrocarbon radical, with ι i Mfvn nri mary diamine of the formula

H ₂ N - M - NH ₂

i η dar moines divalent aliphatic, alicyclic, aroma; iti already, alky, aromatic, carbocyclic or heterocyclic means radical .

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BATH

It was known that these polyimides have good properties, especially good solubility in various polar organic solvents, so that these polyimides are mainly used in the production of composite bodies (laminated bodies), adhesives, lacquers, cast bodies, films, fibers or porous substances can be used advantageously.

In a first additional application it was stated that this Polyimides also from the metaphenylene-bis (hydroxymethylene-4— phthalic acid) can be produced by yourself.

It has now been found that paraphenylene-bis-hydroxymethylene-4-phthalene compounds) Can produce polyimides with at least as interesting properties.

The carbinol chain-linked aromatic polyimides of the present invention Additional registrations are characterized in that they contain repeating units of the following general formula:

GHOH-

I "Il

CHOH

(VIII)

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BAO & iGiNÄt

in wriohor M oi.non by oi.notn alinhali.schon, alicyclinchen, aromatic or alky! aromatic (homocyclic or heterocyclic) Biprinnary diamine derived divalent radical with preferably Represents 6 to 30 carbon atoms.

Dor I? Oat H can be composed of different atoms or groups of atoms, e.g. with chlorine or fluorine atoms or alkyl or alkoxy-j in particular Methyl or methoxy groups may be substituted.

"Numerous examples of such biprimary diamines sin. in · the Called main patent.

Dioso have aromatic polyimides with carbinol chain linkage generally an inherent viscosity, measured at 30 ° C in a 0.5% strength by weight solution in N-methylpyrrolidone, of at least 0.1 dl / g and in particular of at least 0.2 dl / g.

You can use any conventional method and in particular in the same way as in the main patent and the first additional application can be obtained. You can, for example, by polycondensation of a diacid diester mixture of the formula given above (VI) and a biprimary diamine of the formula NH ^ - M - NHp a temperature usually between 100 and 200 ° C are obtained, where M has the same meaning as given above. The implementation is generally in a polar Solvents such as dimethylformamide, dimethylacetamide, the N-Methy! pyrrolidone, the pyridine, the phenol or carried out a cresol. A preferred procedure uses a cresol which is very common in industry is. You can also work without a solvent and simply melt the reaction components.

A prepolymer can also be used for certain uses separate, which has a low molecular weight and is soluble and meltable. This prepolymerization is, as In that Main patent, based on the diester, either in

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BAD OiRrGINAi

or in the melt, carried out at an average temperature of 100 to 200 ° C; the reaction is stopped, for example, when the intrinsic viscosity, measured at 30 ° C. and 0.5% in N-methylpyrrolidone, is 0.05 to 0.50 dl / g.

The polyimides of the present additional application can also be prepared from the tetraesters of the above formula (VII) by heating them with a biprimary diamine, as defined above, for example to a temperature between 200 and 300.degree. A mixture of ester amides is then obtained, which by further heating, for example on a Ternpe:
being transformed.

e.g. to a temperature between 200 and 350 ° C in polyimides

The polyimides of the present supplementary application can also be prepared directly from the paraphenylene-bis-hydroxymethylene - ^ - phthalic acid) by mixing the acid mentioned and a biprimary diamine of the type described above in a polar solvent such as dimethylformamide, dimethylsulfoxy, dimethylacetamide , N-methylpyrrolidone, pyridine, phenol or a cresol. The reaction is generally carried out at a temperature between 100 and 250 ° C. until a solution with sufficient viscosity is obtained. This viscosity, referred to as inherent viscosity, can be, for example, _f 0i2 to 2 dl / g; by adding benzene, toluene or cyclohexane, the water formed during the reaction can be eliminated more easily.

It has also been found that the polyimides of the present supplementary application can also be obtained by reacting an N ₁ M ¹ -diacyclated biprimary diamine with the paraphenylene-bis-ihydroxymethylene ^^ phthalic acid instead of the biprimary diamine itself.

The ones from the

manufactured polyimides can, as ut » i» ## »· H» «fiiPtent described polyimides of the MfteplifnyJ ^ it ^ biiwiltfiiifficirpmliifitii * '^ · phthalic acid), especially in the production of composite

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d ORiQINAL. ^?

th bodies, adhesives, insulating varnishes, cast bodies, Films - »the fibers are used.

They can also be used to manufacture porous materials such as foams.

The following examples serve to illustrate the present invention.

For example £ ielJ_

Production of a polyimide from the hemiester of para-phenylenebis (hydroxymethylene-if-phthalic acid) and diphenyl ether

Enter a reaction vessel with a capacity of 250 cm Mixture of

10.00 g tetra acid obtained according to Example 5,

'4 »05 g' bV -di-aminodiphenyl ether and
80 g of distilled N-methyl pyrrolidone.

The / mixture is stirred under a nitrogen atmosphere and for ^ hours long heated to 220 G by means of a metal alloy bath. The intrinsic viscosity of the collodium finally obtained is 0.7 dl / g (measured at 25 ° C. at a concentration of 0.5. g in 100 g of N-methylpyrrolidone).

The polymer is separated from its solution by precipitation in toluene with stirring using a turbine stirrer.

The infrared spectrum shows the presence of the characteristic bands of the imide function at 5> 62 and 5 | 82 / u and the characteristic Bands of the alcohol function at 2.9 and 9.6 / u.

309850/1084

This polymer is also obtained by applying the collodium obtained on a glass plate and drying it at 120.degree and then obtained at 300 ° C in the form of a film.

Example 2. .

Production of a polyimide from Eara-Phenylen-bis ^ h ^ droxyjneth ^ len / + - phthalic acid) and 'fi ^' idi

The the following substances:

9.328 g para-phenylene-bis (hydroxymethylene / f-phthalic acid),

if, OO6 g 4 »V-di-aminodiphenyl ether and 70.00 g m-cresol

and the mixture heated for 5 hours with stirring to 130 ⁰ C. The measured at 25 ° C at a concentration of 0.5 S on tOO cnr intrinsic viscosity is 0.22 dl / g.

Vs is further heated to 160 ° C. for 1 mouth, as a result of which the intrinsic viscosity reaches 0.75 dl / g.

The infrared spectrum of the precipitated in toluene (under strong Stirring by means of a turbine stirrer) shows the characteristics of the imide and alcohol functions.

Example j

The collodion produced according to Example 2 is used for bonding Stainless steel is used in accordance with the ASTM D 1OO2-6 * t standard.

Metal plates 100 mm long and 25 mm wide and a thickness of 2 mm are made with acetone and then with tricbloroethylene degreased in the vapor phase. They are then stripped by soaking them in a bath of hydrochloric acid for 10 minutes, Phosphoric acid and hydrofluoric acid are submerged and then carefully rinsed with distilled water and dried at 70 ° C in a drying cabinet.

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BATH ORIGINAL

The platelets treated in this way are coated with two layers of the collodium from Example 7 over a length of about 20 mm and dried in the meantime at 100 ° C in a drying cabinet. After the last layer has been applied, these platelets will last 1 1/2 hours dried for a long time at 100 ° C.

I) Lo bon-coated tiles are placed in a mold, namely r, o that jo two platelets are on an area of 25 x 12.5 mm ti curbs.

Be j. G never 1 ^ "

Production of a polyimide from para-phenylene-bis- (hydroxymethyleneif-phthalic acid ") and the i +, if'-di-aminodiphenylmethane in m-cresol

The the following reaction components:

9.328 g para-phenylene-bis- (hydroxymethylene / f-phthalic acid)

3.966 g / f, V-di-aminodiphenylmethane and 70.00 g m-cresol.

The mixture is heated to 130 ° C. for 2 hours with stirring; the intrinsic viscosity is then 0.37 dl / g.

The heating is carried out for 1 hour up to a temperature of 165 ° C continued; the intrinsic viscosity then reaches 1.29 dl / g.

By pouring the solution onto a glass plate with subsequent heating:
Film.

Heat first to 180 ° C and then to 300 ° C one sets

Raiejri.ol 5

Division of a polyimide from the para-phenylene-bis-oijfdroxy-

methyl acetamide

3 09 8BO / 1084

Put into a reaction vessel

9.528 g para-phenylene-bis- (hydroxymethylene-V-phthalic acid) if, OO6 g / fi ^ '- di-aminodiphenyl ether and 70.00 c dimethylacetamide.

The mixture is heated to 130 ° C. for 21/2 hours with stirring and then at 160 ° C for 2 hours (viscosity: 0.23 dl / g).

The polymer separated off by precipitation in the toluene by means of a turbine stirrer has the same infrared spectrum as the polymer produced according to Example 2.

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BATH ORIGINAL

Claims (6)

Claims CIIOlI in which M is a divalent aliphatic alicyclic, aromatic or alkyl aromatic, homocyclic or heterocyclic Rest is. 2. Ancestors for making an aromatic polyimide according to Claim 1, characterized in that at least one diester of the general formula ROOC HOOC J-L-CHOH CHOH COOR COOH in which R is a monovalent aliphatic or aromatic, homocyclic or heterocyclic radical, with at least a biprimary diamine of the general formula NEL, - M - NHg » in which the divalent radical M has the same meaning as in claim 1. 3 0 "9BSO / 1.0 8 3, method for producing an aromatic polyimide according to Claim 1, characterized in that at least one tetraester of the general formula CHOH- r ^ Π ^ X ^ COOR CHOH 1- COOR * in which R and R · each represent a monovalent aliphatic or aromatic, homocyclic or heterocyclic radical, with at least one biprimary diamine of the general formula NH ₂ - M - NH ₂ , in which the divalent radical M has the same meaning as in claim. implements » 4 _# Process for the preparation of an aromatic polyimide according to Claim 1, characterized in that the para-phenylene-bis (hydroxymethylene / f-phthalic acid) is reacted in a polar solvent with at least one compound which is a biprimary diamine of the general formula NH ^ - M - NHo * ^ ^{n we} l ~ rather the divalent radical M has the same meaning as in claim 1, or is a Ν, Ν'-diacyclated derivative of the biprimary diamines mentioned, 5. A solution of an aromatic polyimide with a carbinol chain link according to claim 1 in a polar organic solvent. 6. The use of an aromatic polyimide with a carbinol chain linkage in the manufacture of composite bodies, adhesives, lacquers, cast bodies, films, fibers or porous substances. 309850/1084