DE1620932A1 - Process for the production of heterocyclic, nitrogen-containing thermostable resins - Google Patents

Description

DR. F. ZUMSTEIN - DR. E. ASSMANN I O / U 3 J ^ DR. R. KOENIGSBERGER - DIPL.-PHYS. R. HOLZBAUER

TELEPHONE: 2234 76 and 221911

TELEGRAMS: ZUMPAT SMONCHEN ₂ ,

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80 / zö ^{| There}

Affair 527

INSTITUT FRANOAIS DU P & TROLE, DES CARBURAJiTS-ET LUBRIFIANTS »

Eueil-Malmaisong Soe _a 0 _Qy Frantaeieh

Process for the production of heterocyclic ^, nitrogen-containing

thermostable resins

The invention relates to the production of substances with thermally stable, nitrogen-containing resins are impregnated, which have excellent mechanical properties combined with good have thermal stability »

The process according to the invention relates to the reaction of a diester of the formula (A)

ROOO - Ar -

Ap- OOOR

(A)

with an aromatic tetraamine of formula (B)

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(B)

whereby polymers are obtained which alternate the imide groups and Benzimidezolringe contain «, These polymers have following elementary unit

CO -OO - Ar • N ^

• N ^ - ^ N - Ar - <T Nf Λ> - (C)

In the above formulas, the radicals Ar, which can be the same or different, mean homocyclic aromatic radicals (arylenes) or heterocyclic aromatic radicals, each of which has two free valences, X .. and X ₂ mean aromatic nuclei or groups of aromatic nuclei which are optionally separated by heteroatoms or linking groups and have 4 free valences, two of which are always in the ortho position, and R denotes a monovalent hydrocarbon radical, preferably an aryl radical, in particular phenyl.

Even if the degree of polymerization cannot be determined with certainty, it is assumed ₉ that it is greater in the case of polymers which have good mechanical and thermal properties.

00 9 820/1636

is greater than 10 «. The polymers are very easy by their inherent viscosity, measured at a concentration of 0.5 wt _o - # identified in dimethylsulfoxide at 30 ⁰ C. ₉

The inventive method is characterized in that one carries out the reaction between the reactants A and B at a temperature below 250 ° C and preferably between 100 and 200 ⁰ C until a resin having a Eigenviekosität, determined as indicated above, between O ₉ OJ and 0.15 »preferably between 0.05 and 09 O ₉ having a softening point below 300 ⁰ C, preferably between 200 and 29o C ^0, receives in that said resin iner'js substances with this prepolymer impregnated and that which to give compositions resulting a temperature above 250 ⁰ C, for example between 275 tsnd 400 ⁰ Q, exposing in this way the reaction to complete and the products obtained have a softening point above 300 ⁰ C. "

This process allows the preparation of compositions especially of laminates, which are also excellent *, mechanical properties and good thermal stability own. This is an unexpected result as it does the other methods of making the resins, for example by converting a dianhydride "such as pyromellitic anhydride, with a bis (aminophenylbenzimidazole), such as Μβ-2,2 * ~ (ρ ~ Απι1ηο-pheayl ^ iS'-äibenzimidazole, do not allow. Laminates

009820/163 6 baths

with satisfactory mechanical properties *

In the above formulas, the Reate Ar are generally identical _p although the identity is not mandatory »

Examples of the radicals Ar can be mentioned phenylene, tolylene ₉ xylylene, naphthylene »oxydiphenylene ₈ oxodiphenylene, methylenediphenylene ₉ thiodiphenylene _s biphenylene ₉ sulfonyldiphenylene, sulfoxydiphenylene ₉ pyridylene ₉ thienylene» furylene, 1,3-oxazolylene- (2.5) t 2 , 4-Ohinolylen, iy3,4 ~ Shiadiazolylen ~ (2 ₉ 5K These radicals usually each contain 6 to 20 carbon atoms and 0 to 3 heteroatoms (0, S and / or H) _n

X- and X "can be exemplified among the following aromatic nuclei or systems being chosen

Benzene, toluene, XyIoI ₉ naphthalene ,, Diphenyl, Mphenyloxyd, Diphe ° nylmethan _P Diphenylsulfoxyd, Diphenylsulfon, Diphenylketon, Diphenylsulfid o Each of the groups X 1 and X ₂ preferably contains 6 to 20 carbon atoms

The cores or systems must have four free valences * of which two are in the ortho position ₀ It is clear that _s the free valences of the radicals Ar are located in any positions relative to each other ^ as well as the two groups of free

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«. 5 =
ortho valences of the best X ₁ and X ₀ *

The preparation of the polymers is preferably carried out in the following Conditions carried out:

The diester of the formula (A) is condensed with an aromatic etramine (B) _9, which is preferably used in an equimolar manner. The reaction is preferably carried out in a polar solvent, for example dimethyl sulfoxide, methylpyrrolidone, pyridine or others below carried out solvents described

The diester of the formula (A) can be prepared, for example, as follows will:

The mixture is allowed, preferably in a polar organic! ^ Beschrieoen solvent such as below ₉ a Tßtracerbonsäuredianhydrid with an ester ,, a phenoliechen ester is preferably an aromatic amino acid to react "The reaction proceeds at ambient temperature to form a Amidsäur & zwischenprodukteso

Cyclization to Xmid throughput is heating to a temperature above 100 ° G _s preferably carried out between 120 and 180 ° ö _P "Formation of the amic acid and its cyclization can be carried out virtually simultaneously / if at the beginning of the reaction

BAD ORfGINAt

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works above 100 ° O,

One can either directly use the solution of the beast obtained in this way use or the diester beforehand by precipitation with a non » solvent, for example water, ethanol or ether, isolate and use a different solvent «

The following starting materials can be used in the reactions » the:

A) Dianhydrides:

The dianhydrides of tetracarboxylic acids can be used, the acid groups of which are in the second ortho position and among these can be mentioned: pyromellitic dianhydride, 313 · # 4,4 * -diphenyltetracarboxylic dianhydride, 2,3, δ, 7-baphthalenetetracarboxylic dianhydride, 3,4 »9» 1Ö ~ Perylenetetracarboxylic acid dianhydride, 3 ₁ 3 '· 4 * 4' ■ »Benzophenone tetracarboxylic acid dianhydride, bis- (3,4-dicarboxyphenyl) -sulfondianhydricl," bis- (3 »4 *» Diearboxyphenyl} ether dianhydride and the like »»

B) Esters of aryl amino acids

You can use all homooyclic or heterocyclic esters of aromatic amino acids »preferably phenol esters, and in particular the phenol esters of p-aminobenzoic acid, m-aminobenzoic acid, of 3-aminonaphthalenecarboxylic acid, of 5-aminonaphthalenecarboxylic

009820/1636 ° '

acid ρ dee 6 ~ Amlno-3- = use carboxyp _£ yridins and dglog,

You can also use the esters of aromatic amino acids, their amino group and their carboxyl group are located on separate aromatic nuclei, these nuclei being one below the other through a carbon / carbon intermediate bond ,, a. Ethereal

* Dung, a methyl group or other analog binding. "Group are connected, for example, the Phenolester of 4 '~ amino-2-carboxydiphenyls, the 4 ⁱ ~ Amina- = 4 ~> carboxydiphenyläthers, the 4 * amino Sf-carboxydiphenylsulfids , 4'-amino-4-carboxybenzophenone and the like ».

C) tetraamines:

The aromatic tetraamino compounds are selected from those compounds which contain two reactive ortho-diainino centers. These compounds can have the two reactive centers on a single aromatic nucleus , which consists either of a ring or of several condensed rings _f as 1,2 ρ 4 9 5-Te traaminobenzene ₉ 2 _s 3 ₉ 6 ₁ 7 ^ e traaminona ph thalin and the like ".

The tetramines can have each ortho-diamino center on two different rings in the same way, whereby the rings are separated by a carbon / carbon bond or by a bonding group such as O, S, SO, SO ₂ , CO, CH ₂ ", Under these terms

0 0 9 8 2 0/1636 bad original

Bonds can be mentioned who lens 3,3'-diaminobenzidine, 3,3 '»4,4'-tetraaminodiphenyl ether, 3 _S 3% 4,)' -Tetragminodiphenylmethan, 3,3 '» - 4,4' - (Petraaminodiphenylsulfid, 3 »3 ', 4,4'-Tetraaminodiphenylsulfon and the like ..

D) diesters of formula ( ₁

The following can be mentioned as examples:

Ms-Ef ₉ N '- (4 = Phenoxycai "' honylpheny? _> .) - pyromellitimid, Me-N ₉ N · - (3-Pnenoxycarbonylphenyl) -pyromellitimid, liis-Ν, Ν · - (4 · -Hienoxycarböi ^ ^r l-4-diphenylyl) pyromellitimide, 4,4 * -oxo-bis- (3 = * plithaliinidophenylben2.öspt} 4 _f 4 ^a -Oxy = -Ms <= (3 = phthalimidophenyl3enzoate), 4 _t 4 ⁹ -methylene bis- (4-phthalimidophenylbenzoate) and 4,4'-Sul; Vonyl "= bis- (3 = -phthalimidophenylbenzoate) e

E) Solvent:

The working methods use organic polar solvents, i.e. solvents which contain at least one oxygen, sulfur, nitrogen or phosphorus aiom whose functional groups do not react with the compounds that are reacted. Among these solvents can Dimothy! Formamide, dimethylacetamide, dimethyl sulfoxide, N-methyl _t pyridine, dimethyl sulfone, hexamethylphosphoramide, Tetramethylensuli'on and "are called" like

F) Inert substances:

These substances can be of any kind provided that _{t 9} that they are stable between O and at least 350 ⁰ C "For example,

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! • asei'n, Wä & e & $ fabric or substances made of (lias, metals, asbestos, carbon ρ graphite ₉ high polymers and the like "are mentioned",

Mr 100 GeWo ropes of dry 'impregnated material are preferred 10 to 60 parts of resin and the rest of the inert substances are used ("dry" material means without solvents

However, then one can to facilitate the impregnation of the resin by one of the abovementioned solvents dilute the _s before the final heating or ferlauf vaporized thereof is.

The following examples are intended to further illustrate the present invention without restricting it. Unless otherwise indicated, ropes are parts by weight. The intrinsic viscosities corresponding to a concentration of 0 "5 wt% polymer in _e ~ Dimethylsulfoxydo

example 1

In a 100 ml flask equipped with a stirrer, ascending condenser and an inlet for an inert gas, 40 ml of dimethyl sulfoxide and 6 _s 08 g (0.01 Hol) of up to N ₉ I ³ - (3-phenoxyearbonylphenyl) pyromellitimide are added . the diester is completely dissolved, 2. T4 g (10 " ² mol) 3 ₉ 3 ^S -diaminobenzidine are added and the solution is refluxed for two hours. 30 ml of the solvent are then quickly evaporated to obtain a suitable

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to achieve the prepolymer concentration «The inherent viscosity of the prepolymer is Q _p 053ο

To prepare the Biestere S88 part of pyromellitic dianhydride is dissolved in 100 parts of dimethylformamide »To this solution are added 8.52 parts of m-Aminobenzoesäuiephenylester and stirred for 1 hour at ambient temperature and reflux for 5 hours ₀ Haoh cooling, the 3I depositing gold yellow crystals are isolated by filtration , washed with ither and dried. F. m ⁰

Example 2

Under the same conditions as described in Example 1, 60 ml of dimethyl sulfoxide, 12.16 g (0.02 mol) of the diester of Example 1 and 4.28 g (0.02 mol) of 3 _f 3 · -diaminobenzidine react The prepolymer obtained after a reflux time of 2 hours 15 minutes has an intrinsic viscosity of 0.060 °

Example 3

a) Sas bie-N _f N ^t - (4-Phenoxycarbonylphenyl) «pyromellitimide is prepared under the same conditions as in Example 1 by reacting the pyromellitic dianhydride with the p-aminobenzoic acid phenyl ester»

b) Under an inert gas, 5 parts of bis-N ₉ N · «^ (4-phenoxycarbony! phenyl) -pyromellitimide and 1.57 parts 3.3 ^l - 3> iaminobenzidih

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-limit 30 parts Dimetaylsulfoxyd 135 minutes refluxed «The prepolymer obtained has an inherent viscosity of O ₈ 070»

Example 4

A prepolymer with an inherent viscosity of 0.066 is prepared by adding 2 moles of diaminobenzidine with 1 mole of Ms = H ₉ IP - (3-pheno2ycarbonylphenyl) pyromellitimide and 1 mole of Μβ-Η, Η ¹ · = ^ =

PhenoxycarbonylphenyD-pyromellitimide in 500 ml of dimethylsulfoxide implements *

Example 5

si

a) Bach, the procedure of Example 1, the 4.4 ^t -0xO "= bis- (3-phthalimidophenylbenzoate) is prepared by adding 3 mol of the dianhydride of 3 * 3 V _P 4,4'-benzophenone tetra carboxylic acid with 6 mol m -Phenyl aminobenzoate be converted ·.

b) Under the working conditions of Bcäispiel 1 to 7 sets "12 g (0.01 mol) of the above obtained Die3ters 2 _r 14 g (O OI ₉ mol) of 3,3 ~ ^f 3> iaminobenzidin in 40 ml Dimethylsuifoxyd to _o Uach 25 ml of solvent are rapidly evaporated for 1 hour at reflux. The prepolyraerisate obtained in this reaction has an inherent viscosity of O ₉ 052 o

Example 6

a) The 4 ₉ 4 '~ oxybis (3 »phthalimidophenylbenzoate) is prepared according to the working conditions of Example 1 by the

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m ~ aminobenzoic acid phenyl ester reacts with the dianhydride of 3 * 3 ⁸ »4 ₈ 4 ^I ~ diphenyl ether tracarboxylic acid.

b) The same as in the previous example with the 3 »3'-diaminobenzidine converted diester results in a prepolymer with an inherent viscosity of 0 * 057 *

Example 7

a) According to the working conditions of Example 1, the 4.4 ^f '= 0xybie- (4 ~ phthalimidophenylbenzoat) prepared by the p-Aminobenzoesäurephenylester with the dianhydride of the 3' * 3'ί4 "4 - Diphenyläthertetracarbonsäure reacting _β

b) This diester is condensed with the 3,3'-diarainobenzidine a prepolymer with an inherent viscosity of 0.061 ο

Example 8

Bs are the Vorpolymerisatlösungen of the above examples for the impregnation of glass cloth used _ö After evaporation of the solvent is the Gewiehtskonzentration of dry prepolymer on the impregnated fabric, in general, between 20 and 50 $><The pre-impregnated fabric sheets are layered to a S in this manner chi old material with the desired thickness, and are placed in a press, the plates of which were preheated to the softening temperature of the resin.

009820/1636 ⁰

These are (cf. Table I) ο Sa a pressure of 15 kg / cm is applied and then the temperature of the press is increased up to 350 ⁰ C at a rate of 2 ° C / Mln _o “The laminate is hot 35O ⁰ C kept under pressure for 3 hours and removed after cooling. The mechanical characteristics of the material are given in the table below.

Softening point Tabel Mechanical properties 47-49 50-53
62 Bare v ο of the resin Type of test- bending restlg-
conditions _t . kg / aar 49-51
49
46 . 47-48 example 265 ° C Glasge
webes Ambient
temperature 49-50 1 268 ⁰ C DET ⁺ Surrounding stem » 51 cm 275 ⁰ C DET Surrounding stem
temperature 51-52 3 263 ° C DET Surrounding stem
temperature 250 ö 50
300 ⁰ C ** 45
after 50 hours, bfei
30O ⁰ C in air <5 <5 4th 250 ⁰ C DET Ambient tem- Surrounding stem
temperature
Surrounding stem
temperature 5 DET Ambient temperature
rature 225 ⁰ C 6th 240 ° C DET
A ItOO ⁺ ++ 7th DET

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BATH

+ DET: Glass fabric with double satin weave, without finish »

++.: The experiment was carried out after 30 minutes at the specified temperature _o

+++ A 1100: Glass fabric designated as BET, but with a

Finishing of γ-Aminopropyitriäthoxysilan has been treated ο

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Claims (1)

Claims SS = S S3 1 _Q Process for the production of impregnated substances, characterized in that nan a) a ester of the formula 00 00 - HOOO -Ar-H. Xl H-Ar-COOB with a tetralin of the formula wherein Ar 'is constantly a divalent aromatic radical, X and X "eroma- radicals having 4 free valencies _5, the ortho two by two, and H is a monovalent hydrocarbon radical be" indicate "hot a temperature below 250 C reacting, until a technique called Yorpolyaerisat resin having an inherent viscosity at 30 ° C in an _O-9 5 wt _e "= 5igen solution in B & methylfonaamid 0.03 to 0.15 and having a softening point below 300 ⁰ C is obtained, 009820/1636 BATH b) the inert substances are impregnated with this prepolymer and o) brings the impregnated substances to a temperature above 250 ^{0 O.} 2ο method according to claim 1, characterized in that R a phenyl radical iBt © 3 «Method according to claim 1, characterized in that« an works in a solvent during stages a) and b) * 4ο Impregnated hates, characterized in that they 10 up to 60 wt .- # of a polymer prepared according to claim 1 and contain residual inert substances " 009820/1636