DE1570659A1 - Polyamide acid resins and processes for their manufacture - Google Patents

Description

Polyamic acid resins and processes for their preparation

OD O U)

The present invention relates to polyamide resins made by repeating Units of the formula

II

Il

H -N-C C-N-R'—

RZ ₂ Si-OC 'CO-SiZ ₃

'o' o

are characterized in which Z is a monovalent hydrocarbon rest, R is a tetravalent radical with at least six carbon atoms in a ring with benzene unsaturation Grouping means and the four carbonyl groups on separate Carbon atoms of said tetravalent radical are bonded in the ring and each pair of carbonyl groups to adjacent ones Carbon atoms in the R radical or bonded to those which are separated from each other by at most one carbon atom, where furthermore in the aforementioned formula R · a divalent aromatic Remainder with at least six carbon atoms and χ represents an integer greater than 1, and a method for their preparation.

In particular, the invention relates to a method of manufacture polyamide resins containing both solid and liquid organosilyl groups, which are both useful per se and which can be converted into polyamide resins after heating, the repeating units of the formula:

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ir

C ir

it

Il

1S 7.06 5 9

■ R ¹

own, which method consists in that a reaction of a mixture of ingredients is carried out, which

consists of (1) a triorganosilylamine of the formula

HH
II Z, Si - N - R '- : ϊ - SiZ,

(2) from at least one tetracarboxylic acid dianhydride (im hereinafter referred to as "Dianhydrio") with the structural formula

III

If

and (3) a solvent which is non-reactive with the functional groups of (1) and (2), where χ is an integer of less than 1, zE Io to loo, ooo and beyond, Z is a monovalent hydrocarbon radical, R a tetravalent radical which contains at least 6 carbon atoms in a ring which has benzolically unsaturated grouping, furthermore the four carbonyl groups of said dianhydride being bonded to separate (single) carbon atoms of said tetravalent radical in the ring and each a pair are bonded to carbonyl groups to adjacent ^Tj carbon atoms in the R radical or at most through a

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Carbon atom are separated ^{therefrom and R 1 represents} a divalent aromatic radical with at least 6 carbon atoms, with the formation of a new polyamic acid resin containing silyl groups of the formula:

IV

O \ / O / H R ¹ - H 11 R.
S \ It - N - - N- C. C. \
C. M. SiZ ₃ O -O- ί-Ο- C. π O

in which χ, Z, R and R ^{1 have} the meaning given above.

If so desired, the polyamide can be acidic resin of the formula IV heated to remove the triorganosilyl radicals To effect (Z, Si-) and the solvent, with formation of the polyimide resin of the formula I.

In the British patent ° o? 271 and in Australian patent 58 424 iüx the preparation of lujyimidharzen which correspond to the formula I (where R ^{1 is} a divalent aromatic radical, for example a benzene radical of the formulas

represents in which R "carbon, oxygen, silicon or Can be sulfur); these polyimide resins have viscosity

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of at least 0.1 measured at 30 C in a 0.5 weight percent solution of the polyimide in sulfuric acid.

The polyimides, which according to the aforementioned British and Australian patents are obtainable by a reaction between a diamine of the Structural formula

- I? ¹ - NH

in which R ^{1 is} a divalent aromatic radical containing at least 6 carbon atoms, the two amino groups of this diamine each being bonded to separate carbon atoms of said divalent radical, uno at least one tetracarboxylic acid dianhydride with the structural formula III, in which R has the meaning given above, causes. When the first reaction is carried out, a polyamic acid resin is obtained which is composed of repeating units of the formula

Il

-NH-C

Il

C -NH-R'-

HO-C

Il

C-OH

Il

composed. After further heating, this becomes the latter Pol ;, ..er converted into the polyimide structure of formula I.

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Unfortunately, however, the polyamic acid resin produced according to the method of the British patent is only of limited solubility in a limited number of polar organic solvents which have boiling points of more than 5 125 ° C, with some of these solvents the boiling points are even 2OC ⁰ G or about that. Lower boiling solvents cannot keep the reactants or the polyamide mural resin formed in solution. If one tries to dilute the reaction mixture with less expensive solvents, the polyamide urine resin will fill out.

It worr. e now surprisingly been found that instead of using i.jr silyl diamines ACCORDING-rS formula II have the no silyl group-containing diamines of the formula IV, may employ the simultaneous preparation of the new sil3 ^r lgruppenhaltigen polyamic acid resins, solvents that significantly lower boiling points, and that by using these lower boiling solvents one is now able to avoid the problem of the urolubility of the polyamic acid resin and the need for unusually high temperatures to remove the solvent after the resin solution has been applied to surfaces.

It has also been found that by using these silyl groups Diamines one is now able to use the expensive higher boiling solvents mentioned above in larger proportions with larger amounts of cheaper and lower to dilute boiling solvents, such as with the above-mentioned aromatic hydrocarbons, tetrahydrofuran or dioxane, so that this also reduces the cost of manufacture of these polyimide resins are degraded without being in in any way adversely affects the properties of the intermediate polyamic acid resin or the polyamide resin

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were.

If one uses pyroniellitic anhydride and the derivative of ρ, τ; ¹ -Oianiriodiphenylathers selected as examples of the Roaktanten for producing -.es Folyamidsäureharzes, it can be assumed that i ie tgemäss reaction of the following equation uabalancierten ^veri: air, wherein the lower boiling solvent (s expensive or ueißische of such solvents with higher boiling) , of which, according to the present invention -eTunlen, that they can be used viii advantage, are used:

Il

Il

0 + n (CH3) 3Si-

NH-Si (CH ₃ )

Pyrone11itic dianhyoride

SiIyl-containing diamino diphenyl ether

(CH ₃ ) ^ SiO-C ^J 3 π

^ C-OSi

Il

0 (CH ₃ )

NH -

Acid-resistant polyamide

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_V W2n (CH ₃ ) ₃ SiOH

Polyimide resin.

It may be emphasized that the polyamide acid resin is the first to be emphasized is formed with the triorganosilyl groups on the carboxylic acid group and that then by applying heat the bil dung deu polyimide takes place, with the simultaneous formation of Triorganosilanol, which generally condenses to form hexamethyldisiloxane.

In the above equation, χ has the meaning given above, η is used to indicate the molar equivalence relationship of the reactants. Both the solvents and numerous triorganosilanols e are low-boiling enough to be easily evaporated.

The diaminoaryl compounds containing two silyl groups of formula

- R

H - NSiZ

(in which Z and R 'are as defined above) are detailed in terms of their properties and processes for production in the parallel patent application of the same applicant with the same old patent application entitled "Organosilicon Associations and processes for their production "described.

The iriorganosilyldiamines of the formula II can be prepared in this way be that a diamine of the formula V with a hydrolyzing

suitable triorganosilane of the formula: "<*

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Z ₃ SiX

is reacted, where Z has the meaning given above and X is halogen, for example chlorine, bromine or fluorine.

In the preparation of the triorganosilylamines of the formula II, at least two, but also more, up to eu 6 or slightly more, moles of hydrolyzable silane of the formula Z-SiX substituted with three hydrocarbon radicals are reacted with one mole of diamino compound of the formula V, preferably in the presence of a non-polar solvent such as benzene, toluene, xylene, 'dioxane, etc., under anhydrous conditions and at temperatures up to the boiling of the mass (at reflux conditions), ie in the range from slightly above room temperature, about 125 ⁰ C , lie. The hydrolyzable triorganosilane, for example trimethylchlorailane, generally causes an exothermic reaction when it is added to a diamino compound in the presence of a hydrogen halide acceptor such as ityridine, triethylamine or other tertiary amines, the temperature increasing to a value of about 40 to 70 ⁰ C increases. The mixture of ingredients is preferably stirred for half an hour to two hours and then heated for a further 15 minutes to 1 hour under reflux conditions to the boiling point of the reaction mass, then the hydrogen halide salt of the hydrogen halide acceptor is filtered off and the reaction product is used to isolate the desired triorganosilylamine of the formula II subjected to fractional distillation.

The tetracarboxylic anhydrides, which in the case of the present Invention are useful by the following formula

909884/1603

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Il Il

A A \ A /

c c

H Il

0 0

characterized in which R is a tetravalent radical, e.g. one that is formed by an aromatic group containing at least six carbon atoms and by a benzene group unsaturated moiety is characterized, derived from or contains, each of the four carbonyl groups of the dianhydride is bonded to a separate carbon atom in the tetravalent radical and the carbonyl groups in each case in such a way present in pairs that each pair are bonded to adjacent carbon atoms of the R radical or to carbon atoms in the R radicals that are separated from one another by at most one carbon atom, so that five-membered or six-membered ring systems of the following types:

O 0

Il U

C-O-C,

t ι or

O
Il O O
Il or 0
ii - Ö 0
Il C - ■ Wed
■ Wed - C
I. C.
I. m C
I. - C C = s C -

Examples of dianhydrides which can be used in accordance with the present invention are given below, the abbreviations used in this description also being given in brackets: pyromellitic dianhydride (PMDA); 2,3,6,7-naphthalene tetracarboxylic acid dianhydride; 3 , 3 ', 4,4 ^f -diphenyltetracarboxylic dianhydride j 1,2,5,6-naphthalenetetracarboxylic dianhydride, * 2,2 ■ ♦, 3,5 · -diphenyltetracarboxylic dianhydride j 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride ;

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bis (3,4-di carboxyphenyl) sulfone anhydride; Benzophenone tetracarboxylic acid dianhydride (BPDA); Perylene-1 ^^ jS-tetraoarboxylic muredianhydride; bis (3,4-arboxyphenyl) '4therdianhydride; bis (3,4-dicarboxyphenyl) methane dianhydride; Perylene-3f4,9 »lo-tetracarboxyl-3jured ianhydride of Porrael

, and

1,8,4,5-naphthalenetetracarboxylic acid dianhydride of the formula:

The solvents which are useful in the preparation of the silyl Polyamidsäureharze3 and which have boiling points of generally below 150 ⁰ C at atmosphärera pressure, which are also easily procured and not expensive, examples include

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for example dioxane, tetrahydrofuran and tetrahydropyran. In general, the solvents which are useful for the preparation of the polyamide resin containing silyl groups are characterized in that their functional groups, if any, do not react with any of the reactants. In addition to the requirement that these solvents be inert to the reaction system and must also be a solvent for the polyamic acid resin containing silyl groups, these solvents must also be able to dissolve at least one of the reaction participants, preferably both. Therefore, not only, for example, the aforementioned compounds are used as the sole solvent, but they are optionally mixed with other solvents to be used at the same time which boil above 150 ° C., of which the following may be mentioned, for example: N ₁ N-dimethylformamide, Ν, Ν- dimethylacetamide, N, N-diethylformamide, N, N-diethy! acetamide, Ν, Ν-dimethylmethoxyacetamide, N-methylcaprolactam, dimethylsulfoxide, N-methyl-2-pyrrolilon (NMP), tetra-. methylene urea, pyridine, dimethyl sulfon, iie ^ aruathylphosphoramid, tetramethylene sulfone, formamide, N-methylformamide and N-acetyl-2-pyrrolidone.

to reduce the cost of higher-boiling solvents, one can dilute the latter with such solvents, which generally only weak solution properties with regard to one or both reactants or with regard to the one containing silyl groups have polyamic acid resin. From such dilution solutionSr Agents may be mentioned, for example: benzene, benzonitrile, acetonitrile, butyrolactone, xylene, toluene, cyclohexane, mixtures of alkylated benzenes (e.g. xylenes, mesitylenes and durens).

In general, when carrying out the inventive Process from about Io to about 6o percent by weight or something there-

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In addition, weaker solvents together with the more common ones higher boiling solvents which use βi & d indicated in the aforementioned British and Australian patents.

The reaction between the dianhydride and the diamine containing silyl groups for the purpose of producing the polyamide acid resin containing silyl groups is preferably carried out under essentially anhydrous conditions (this means in particular that moisture-free solvents must be used), with a temperature between room temperature (about 25%) during the entire reaction ⁰ C.) and a maximum of 6O ⁰ O is observed. Higher temperatures are generally unnecessary, since mixing the ingredients in the correct solvent starts the desired addition reaction even at room temperature.

In general, according to a preferred embodiment According to the present invention, equimolar amounts of sllyl groups Diarain and dianhydride premixed and then the solvent was added with stirring. On the other hand, it is also possible dissolve the silyl group-containing diamine in the solvent and add the dianhydride while stirring effectively, having control over the reaction temperature. Stirring the reaction mixture after all of the addition is complete Reactants and the solvent is continued until the maximum viscosity of the polyamic acid containing eilyl groups reached 1st, which also indicates the maximum degree of polymerization.

Given the equimolar concentration of the reactants given above under the conditions described above

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changes significantly, then - as has been found - the degree of polymerization is significantly weaker and products with a lower molecular weight (and lower intrinsic viscosity) are obtained. In general, up to about a 10 % molar excess of a reactant can be employed without fear of serious difficulty. In some cases it may even be desirable to use a larger molar excess of either silyl-containing diamine or dianhydride.

By the process described above, it is possible to obtain polymers whose intrinsic viscosity is tetrahydrofuran between o, l and 5 dl./g. or more, the molecular weights of the polyamide resins containing silyl groups is in the order of magnitude from about 1,000,000 to 500,000 and beyond.

All of the end groups present in the polyamic acid resin containing silyl groups exist, consist of or anhydride groups -SiZ, groups, where Z has the meaning given above.

The amount of organic solvent used in the manufacture of the polyamic acid resin containing silyl groups is such that it is ensured that the silyl group-containing diamine is dissolved and also the dissolution of the finally formed polyamic acid resin containing silyl groups completely occurs to form a product with the solvent of adequate viscosity. Also should Amount of solvent used be sufficient, in view of the intended application, for example in view to the production of films for coatings, or with a view to on fiber production using extrusion technology,

909884/1603 β "OBM".

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in each case, a suitable viscosity can be achieved through the choice of the amount of solvent.

In general, the solvents should be in such a concentration be used that the content of the pesticide formed silyl group-containing polyamic acid resin in the solution in the range from about 5 to 35 percent by weight, based on the total weight of solvent and polyamic acid resin containing silyl groups.

With regard to the requirements set out above, it has been found that in the production of the polyamic acid resin containing silyl groups it is advantageous to use amounts of solvent or solvent mixtures which are about 65 to 95 percent by weight or more, based on the total weight of solvent and the resulting silyl group Polyamids.iureharz amount. After forming the solution of the silyl group-containing polyamic acid resin, it is only necessary to heat it to temperatures of about 150 to 300 ⁰ C, to effect the conversion to the polyimide mold of the resin repeat units has, in accordance with the above formula I. During the formation of the polyimide resin, triorganosilanols are released from the polyamic acid resin containing silyl groups, which in turn are generally converted into hexaorganodisiloxane. As a result of the low boiling point of many of these hexaorganodisiloxanes, there are hardly any difficulties in the evaporation or evaporation of these disiloxanes just mentioned at temperatures at which the solvent can be removed and the polyimide resin is formed.

One of the advantages of the method of the invention for manufacture of polyimide resins is that none of the other customary or necessary additives is required, such as it for example Mixtures of Bssigaäureanhydrid and pyridine, JGprbödiiiaide,

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such as dicyclohexylcarbodiimide or others so far required additives. The application of heat alone is sufficient to change the state or form of the silyl group-containing Polyamide murine resin in the state of the polyimide resin.

In order to give those of ordinary skill in the art an even better understanding of the practical implementation of the present invention, the following are given by way of explanation, but not limitation Examples listed «All parts are parts by weight, unless otherwise specified. At all stages of the manufacturing process of polyamide acid resins containing or not containing silyl groups are anhydrous conditions and anhydrous and pure reactants and solvents have been used.

The silyl group-containing diamines used in the following examples are used, were, as initially stated, produced:

Production of NjN'-bisftrimethylsilyl) -p, ρ '-d iaminodipheny lather

The compound N ^ '- bisCtrimethylsilylJ-pjp'-diaminodiphenyl ether with the formula:

Si (CH ₃ ) 3

was made by taking 164 grams of ρ, ρ'-diaminodiphenyl ether in a mixture of 1.5 liters of dry benzene and 250 grams of triethylamine, which acts as a hydrogen halide acceptor serving, have been suspended. W while the mixture was stirred, were Ιθο grams of trimethylchlorosilane added under anhydrous conditions. The temperature of the mixture rose after the addition of the

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Found theory 63, ο % 62.7 % 8.0 % 8.2 % θ, ο % 8.1 % 16.3 % 16.3 Ji

Chlorosilane to about 60 ⁰ C. After two hours of stirring, the mixture was heated under reflux conditions for a further otund ram pressure was obtained; after recrystallization from dry η-hexane, this compound had a melting point of 72 to 73 ^° C. The analysis showed that it was the desired compound.

The analysis data are:

H
N
Si

This compound is hereinafter referred to as "containing silyl groups Oxydianiline ".

Preparation of N, N'-bis (trimethylsilyl) -m-phenylenediamine

N, N ¹ -bis (trimethylsilyl) -m-phenylenediamine was prepared by dissolving Io8 grams (1 mole) of m-phenylenediamine and 300 grams of triethylamine (hydrogen halide acceptor) in one liter of dry toluene and the mixture of the contents stci 'te was then heated to the boiling point of the mass (under reflux conditions). After this temperature was reached, 23o grams (2.0 mol) of trimethylchlorosilane were slowly added over a period of 30 minutes under anhydrous conditions and then the mixture was kept boiling for a further 2 hours under reflux conditions. The precipitated triethyl araine hydrochloride was removed by filtration and the

909884/1603

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resulting product subjected to fractional distillation, a silyl-containing amine of the formula

Si (CH ₃ ) ₃ Si (CH ₃ ) ₃

was obtained which possessed at 13O ⁰ C./3, boiled 5 mm and a refractive index η ^{fJ 3} 1.5266. This compound is referred to ^{below as D} "m-phenylenediamine containing silyl groups".

Manufacture; from NN ¹ -bis (trimethylsilyl) -p-phen.vlenediamine.

The compound N ₁ N ¹ -bis (trimethylsilyl) -p-phenylenediamine having the formula

Si (CH ₃ ) 3

was produced similarly to the silyl group-containing ra-phenylenediamine with the modification that instead of the meta-phenylenediamine this time an equivalent amount of para-phenylenediamine was used became. The expected diamine, after being recrystallized from dry η-hexane, had a melting point of I03 to Io5 ° 0; the analytical values are given below, where the values in brackets are the theoretical values:

"Si 0: 57.3 (57.1)? % Hi9.7 (9.6) | % ItIl ₁ I (11.1); % Si: 22.2 (22.3).

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This compound is hereinafter referred to as "containing silyl groups p-phenylenediamine ".

Preparation of N ₁ N ¹ -bisitrimethylsilylj-p ^ '- diaminodi rheny! Methane.

The compound N, N'-bis (trimeth, ylsilyl) -p, p'-diaminodiphenylmethane was prepared similarly to the silyl group-containing oxide! Aniline described above, with the one modification that instead of the diaminodiphenyl ether this time 196 grams, p, p'- Diaminodiphenyl line than and instead of 180 grams of trimethylchlorosilane this time 22o grams of this compound were used. The reaction product was isolated, it had a melting point of 52 to 54 ⁰ C and corresponds to the formula:

H (CH ₃ ) ₃ Si - N- ^

as is ensured by the analytical data, which are as follows:

% C: 66.5 (66.3); % H: 8.9 (8.9); % H: 8.5 (8.3); ■% Si: 16.8 (16.6).

This compound is referred to below as "containing silyl groups Methylend! Aniline ".

Example It

A solution of 7.18 parts of PKDA and 11.48 parts of oxydianiline containing silyl groups in 5.7 parts of tetrahydrofuran was obtained manufactured. After the reaction mix for about 10 minutes was stirred at room temperature, a complete was obtained homogeneous solution with about 15 percent by weight Pesticide content of polyamic acid containing silyl groups, which repeating units of the formula ^

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H N

- O

* fi - O - S 1 (CH ₃ ) 3 O

composed, in which χ has the meaning given above.

From this solution it was easy to pull threads or piping. When these threads were drawn in a dry atmosphere, the tetrahydrofuran solvent evaporated very quickly at room temperature to give clear threads which could be stretched and then had a high rate of passage of polarized light, indicating a high degree of orientation. If the solvent was allowed to evaporate from the drawn fiber in air (containing moisture), an opaque, strong fiber structure was obtained, which is also ¹ to. an oriented J: ^ »är could be stretched.

If one gives the above "solution of the silyl group-containing polyamic acid resin described on a base surface and can evaporate the solvent in an atmosphere of dry nitrogen, thin films of this silyl polyamic acid resin can be obtained. When heated, these films 13o minutes to a temperature of 150 ⁰ C. , they are converted to a polyimide resin structure that is completely free of silyl groups, v.-see has no difference in properties compared to the same polyimide resin structure, which is derived from polyamide acid resin that does not contain silyl groups.

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Comparative example It

When example 1 is repeated with the modification that this time a squimolar amount of non-silyl group-containing oxydianiline instead of the oxydianiline containing silyl groups was reacted with IMDA, using tetrahydrofuran as sole solvent, an insoluble mixture was obtained which does not show any sign of gum formation; out of this it can be concluded that the use of oxydianiline containing silyl groups in the reaction with the PMDA using Tetrahydrofuran is absolutely necessary as the only solvent. An adequate solution of the reactants and the formation to achieve a clear solution of polyamic acid resin at least 3o percent by weight of tetrahydrofuran by N-methylpyrrolidone (NMP) to be replaced.

Example 2;

According to this example, 24.87 parts were PMDA and 28.6 parts Parts of m-phenylenediamine containing silyl groups with 3o2.8 Parts of tetrahydrofuran, similar to that described in Example 1, reacted, with a clear solution of a polyamic acid resin containing silyl groups in tetrahydrofuran arose, which is made up of repeating units of the formula

O
ti O
Il -NH- % (QH ₃ ) ₃ Si-O- C.
Il
O Q
C.
Il
O

-O- S1 (CH ₃ ) ₃

-Jx

BATHROOM OFMGINAL

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composed in which χ had the meaning given above and the solids content of the solution was 15 percent by weight. The heating of surfaces which were covered with this solution, to a temperature of 150 to 200 ⁰ G within time periods of several minutes up to a .Stunde gave the expected polyimide resin of the formula I.

Example 3:

According to this example, a solution of 2519 parts BPDA and 27.5 parts of oxydianiline containing silyl groups in 3o3.6 parts of tetrahydrofuran for about 50 minutes at room temperature stirred, resulting in a polyamic acid resin containing silyl groups in an approximately 15 percent by weight solution, which resin is made up of repeating units of the formula

NH-

-Jx

in which χ has the meaning given above. The casting the tetrahydrofuran solution of this polyamic acid resin containing silyl groups onto a surface and subsequent heating within about 15 minutes to a temperature of 150 ° C. yielded a polyimide resin which is different from the use of the BPDA residue.

The following examples explain the possibility of using larger amounts of more expensive, weaker solvents,

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i.e. of those that in themselves have little or no Solution property with respect to the participants in the reaction and with respect to of the reaction product3, together with a more expensive and better solvent of a higher oil point, the results of using such mixed solvents in the reaction of silyl group containing disaine with Dianhydride is described.

Comparative Example 2;

About 5. oil parts of WiT) A and 4.61 parts of p, p'-diaminodiphenyl ether were mixed with 70, S2 parts of toluene, resulting in a mixture which contained about 12 % pest bodies. When matt stirred this mixture for about 30 minutes at room temperature, virtually no reaction was observed. In order to achieve a complete dissolution of the reactants and also a complete reaction for the purpose of the formation of a polyamide acid resin or its solution with a pesticide content of 7.8 % , it was necessary to combine NMP (N-2-methylpyrrolidone) in a Meage sufficient to ensure a weight ratio.

Comparative example 4t

There were implemented 11.94 parts _r to silylgruppenhaltigem Oxydiandlin together with 7.53 parts of PMDA in 185.6 parts of toluene untrer addition of 45.2 parts of NMP? it was possible to obtain a homogeneous solution and an equivalent amount of silylgruppenhaltigem polyamide acid resin (7.8 wt -% Pestkörper.) to obtain; the weight ratio toluene / NMP was 81/19 “it was there to ensure that it is possible to use more toluene with NMP, if one uses oxydianiline containing silyl groups instead of oxydianiline not containing silyl groups.

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Comparative example 3 '

According to this example, equivalent molar concentrations of m-phenylenediamine and PMDA were reacted with one another, a combination of toluene and NKP being used as the solvent. As a result of the use of m-phenylenediamine which did not contain silyl groups, it turned out that it was necessary to maintain a weight ratio of toluene to NMP of 46/54 in order to achieve a pesticide content of 5.9 % . However, Venn is used an equivalent amount of silylgruppenhaltigem m-phenylenediamine instead, it was found that it is possible to comply with toluene and NMP in a weight ratio of 93/7.

example 5 '>

Equimolar amounts of BPDA and m-phenylenediamine containing silyl groups were easily obtained in a mixture of toluene and NKP dissolved in a weight ratio of 84/16. After a reaction similar to Example 4 had taken place, a polyamic acid resin containing silyl groups was obtained, which is made up of repeating structural units of the formula

- NH-C

(CH ₃ ) ₃ SiO-C O

composed, where χ has the meaning given above; this resin was found to be completely miscible in the solvent mixture with a solids content of 10 percent by weight.

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If, on the other hand, you use a non-silyl group-containing m-phenylenediamine is used instead of the silyl group-containing diamine, the amount of toluene which is used together with the HMP could, at most 60 wt .- # of the two solvents when a homogeneous solution of the polyamic acid resin with the same Solids content as stated above, wanted to achieve.

Example 6;

If you have equimolar amounts of p-phenylenediamine containing silyl groups and PMDA dissolved in a mixed solvent of toluene and NMP was found to dissolve completely and formation of a homogeneous solution of the silyl group-containing polyamic acid resin could be obtained at a weight ratio of 81/19 of toluene / UMP with a pesticide content of about 8.7 percent by weight. If, on the other hand, p-phenylenediamine does not contain silyl groups, instead of deo silyl groups When diamines began, the toluene / NMP weight ratio was found to be 6O / 40, eliminating the need the use of considerably higher amounts of MP has been indicated, provided that a suitable solution of the reactants and des Wants to achieve polyamic acid resin.

example 1'.

According to this example, equimolar proportions of BPDA and of p-phenylenediamine containing silyl groups were easily dissolved in a solution of toluene and NMP, the weight ratio of the last two bodies mentioned being 85/15. After the reactants had been stirred into the solvent, a homogeneous solution of a polymeric polyamic acid resin containing silyl groups was formed with about 9.3 % solids, this resin being composed of the same repeating units as described in Example 8, with the one modification that

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parts of the m-phenylenediamine residue, this time a p-phenylenediamine residue stands.

If you use equivalent amounts of non-silyl group-containing p-phenylenediamine instead of the silyl group-containing diamine and otherwise the same conditions prevail, it has been found that an amount of HMP is necessary in order to achieve equivalent solutions or the equivalent proportion of pesticides, which is approximately 4o $> the total weight of the two solutions.

Comparative example 4i

If an attempt was made to dissolve m-phenylenediamine and PMDA in equimolar amounts in tetrahydrofuran, it was found that before an adequate solution of the reactants could arise and before a clear homogeneous solution of the resin, which was formed according to Comparative Example 2, could be achieved , it was necessary to add NMP in such an amount that the weight ratio of tetrahydrofuran / MMP was 56/44, and then a polyamide resin or its solution with a pesticide content of Q.4 % could be obtained. This result should be compared with Example 2, where tetrahydrofuran could successfully be used as the only solvent when the silyl group-containing m-phenylenediamine was used »

Example 8:

When mixing p-phenylenediamine containing silyl groups with PMDA in equimolar proportions in a mixture of HMP and tetrahydrofuran it was found that adequate dissolution of the reactants and formation of the silyl group-containing polyamic acid resin could then be achieved when the tetrahydrofuran to the HMP was in a weight ratio of 91/9.

When using p-phenylenediamine that does not contain silyl groups were at least equal parts by weight of HMP and tetrahydrofuran

9 0 98 8A- / 16 0.3

BATH

- sheet 26 -

required to provide an adequate solution of the reactances w & ä the formation of a polyamide resin with a solid clay. To achieve 13.8 %.

Example 9?

According to this example, equimolar proportions of silyl group-containing oxydianiline and ItlDA were dissolved in a "solution consisting of acetonitrile and NMP, the ratio of acetonitrile / NMF to achieve complete solubility being 74/26; if, on the other hand, non-silyl group-containing oxydianiline was used, this was required amount of MP, 41 how old the acetonitrile was used together, considerably more solid, ä »<a, the ratio of the two aforementioned substances is 62 / 3Θ with a pesticide content of about lo, 7 % *

Example lo:

If equimolar amounts of PMDA and oxydianiline containing silyl groups are added to dioxane, it is found that it is possible to dissolve the reactants and bring about a difference between these reactants, with the result that: a laser liquid solution of the polyamide containing silyl groups is obtained ^ if the dioxane and the NMP are present in a weight ratio of iron 9? »β / 7.2, the pesticide content of polymer being 8.1 % .

If , on the other hand, one uses non-silyl group-containing oxydianiline instead of the silyl group-containing oxydianiline, while otherwise the same conditions can prevail, a ratio of dioxane to IiMP of 76/24 is necessary to ensure that the reactants and a homogeneous solution of the polymer with the to achieve the same pesticide content as above.

BAD OfUGlNAL 909884/1603

Example II;

According to this example, tetrahydropyran was used as the solvent for equimolar proportionate amounts of PMDA and those containing silyl groups Oxydianiline used. In order to achieve the necessary solubility for optimally achieving a homogeneous solution of the polyamic acid resin containing silyl groups To achieve this, only a very small amount of NMP was necessary, so that the weight ratio of tetrahydropyran to NMP was 96.1 / 3.9. It is evident that this is tetrahydropyran is at least as good a solvent as tetrahydrofuran.

Example 12:

Samples of polyamic acid resin containing silyl groups (according to Example 3) were cast into films from BPDA and oxydianiline containing silyl groups using tetrahydrofuran as solvent, the solvent was evaporated and the films were then heated ^{to a temperature of 200 ° C. for about 1 hour.} The pilms, which were initially clear, became opaque and somewhat stiff. However, the pilms were mechanically strong and did not show any crystallization when examined by X-rays. A cross-section of such a film under the electron microscope showed that the opaque appearance is evidently a consequence of the fact that particles are embedded in the matrix of the film. It is therefore clear that a "self-filled" film was produced in accordance with the present method, in which particles of polymer are suspended as filler in the matrix of the same polymer, the polymer apparently being in two different physical manifestations or states.

Example 13s

To 12.9 parts of BPDA and 13.7 parts of methylenedianiline containing silyl groups 6.9 parts of tetrahydrofuran were added thereto. the

9098 8 A / 1603

- sheet 28 -

Reactants dissolved easily and after stirring for about two hours at room temperature, a homogeneous viscous polymer solution was formed, in which the polymer consists of repeating units of the formula

- NH - C.

(CH ₃ ) ₃ S tO- C
O

Il

and the solids content of the polyamic acid resin containing silyl groups was about 20 % .

If you tried a methylenedianiline that did not contain silyl groups to dissolve together with BPDA in tetrahydrofuran, it is found that the reactants are insoluble and not satisfactory soluble resinous reaction product can be obtained under these conditions. -

Comparative example 5 '

About the effect of using a methylenedianiline that does not contain silyl groups To show, 15.8 parts of BPDA and 9.7 parts of non-silyl group-containing methylenedianiline with 92.1 parts of NMP and 32 parts Mixed tetrahydrofuran. After about 3 hours of stirring, a viscous and completely homogeneous solution of the polyamic acid resin was obtained. Tetrahydrofuran was then added in portions with stirring until the onset of turbidity indicated that this was the result Due to the insufficient solubility of the polyamide acid resin, a precipitation set in. After adding a drop of NMP, the solution was clear again and completely homogeneous. The mixed solids corresponded to this point Ιοο, Ι parts NMP and “197.4 parts tetrahydrofuran what a weight ratio of NMP to tetrahydrofuran of 33.6 / 66.4

909884/1603

BAD OFMGiNAi

-Leaf- "70659

corresponds, while the polymer concentration was 7.9 % solids.

to match the details of this example with example 1? compares, it is clear that by using a silyl group-containing diamine not only solvents with lower Boiling point, which are also cheaper, such as tetrahydrofuran, can use, but that you can also achieve higher solids content (in the solution).

Example Uf

This example illustrates the ability to use larger amounts of mixtures of alkylated aromatic compounds with higher boiling solvents as described in the aforementioned British and Australian patents, as a consequence of the use of silylated diamine. The mixture of alkylated aromatics which reached for use is commercially available under the registered trademark "Solvesso loo" and consists chemically of a öchnitt aromatic compounds which boil between 159 ° and 172 ⁰ C; The following are the individual ingredients of Solvesso loo:

⁺ Ingredient Weight percent Cg aromatics 3.4 Cq aromatics 78.8 C- £ aromatics 13.5 Cn, aromatics o, 5 Indans 1.8 Total 98.0 #.

= Mainly methyl and ethyl substituted benzenes. - Balance of higher-boiling aromatics.

909884/160 3rd ^BA °

- sheet 3o -

In particular, the Example 1 8.51 parts PHDA were prepared following the procedure ₁ 4.o7 parts mixed at not silylgruppenhaltigem oxydianiline and 6.62 parts silylgruppenheltigem oxydianiline together and mixed with 6.72 dividers Solvesso loo and 3o, 53 parts of HKP.

After stirring for about 2 hours, a viscous box made of a partially insoluble polymer was obtained. NKP was then added in small proportions until the solution became clear and all of the polymer dissolved was; then further shares in Solvesso loo were added, to reprecipitate the polymer; eventually became a a further amount of NMP is added in individual portions until the polymer is again dissolved and the solution itself was clear.

In this way, a number of solubility levels were related to a range of pesticide concentrations of the polymer was found in relation to the increase in the total amount of solvent.

The accompanying Figure 1 is a graphical representation of FIG various individual additions of solvents and shows the Solubility limits when using silyl group-containing Oxydianiline can be achieved instead of non-silyl group-containing oxydianiline.

The filled circles in the accompanying graph indicate the incipient insolubility of the polymer, while the open circles indicate complete solubility of the View Polymers in Solvent System. The lines which are drawn between the points, therefore show the solubility

BAD OFUGiNAL 909884/1603

- sheet 31 -

adjoin.

The attached figure shows that when using a molar ratio of silyl-containing oxydianiline and non-silyl-containing oxydianiline of 50/50 together with PMDA, larger Amounts of Solvesso loo can be used together with NMP. If, on the other hand, oxydianiline not containing silyl groups is used alone PMDA is used, only small amounts of Solvesso loo can be tolerated in order to obtain clear and homogeneous solutions.

It should be emphasized that in addition to or in addition to the use of a diamine containing two oilyl groups, a diamine with a silyl group of the formula H ₂ N "- R '- NH - SiZ can be used with the diamine containing two SiIy groups, whereby in the formula R 'and Z just mentioned have the meanings given above.

Under these circumstances, the silyl group-containing polyamic acid resin becomes have some carboxyl groups without silyl substituents, which is a consequence of the reaction participation of the diamino compound, which contains only partial, i.e. semi-silyl groups.

On the other hand, one can use mixtures of fully silylated and non-silylated (not containing silicon groups) diamino compounds use, taking advantage of the increased solubility due to the presence of silylated diamine, which was described in detail above, can perceive.

_in those cases in which both a silyl group-containing Diamine as well as a diamine which does not contain silicon groups sam is reacted with the dianhydride, it is clear that repeating units of the formula

909884/1603 bathroom ORIGINAL

- sheet 32 -

Il

Il

Z ₃ Si

C C

V /

H ►Ν

It

- Ο — SiZ ₃

as well as units of the formula

Il

Il

-NH-C / C-NH-R ¹ -

HO-C

Il

X-OH

Il

Jx

arise in which x, Z, R and R 'have the meaning given above.

In general, it is preferable that at least 75 % of the units are derived from the completely silyl group-containing amine type in order to ensure optimum solubility in solvents which are either no solvents per se or only weak solvents for one or both reactants, namely for the diamine containing no silyl groups and the dianhydride and also for the polyamide acid resin, as well as in mixtures of bad and good solvents for the reactants of the diamine type containing no silyl groups and the dianhydride, as well as for the polyamide acid resin, if the advantage is desired is cheaper. Solvents that also boil lower should be used together with more expensive and rarer solvents such as N-methylpyrrolidone.

In all the examples in which a poly-

909884/1603

BATH

amic acid resin was obtained, the latter could be made to the required elevated temperatures are heated to achieve cleavage of the triorganosiloxy group, which is in the form of the TriorganosHanois or Hexaorganodisiloxane is free, under simultaneous formation of the polyimide resin.

Both the sllylgruppenhaltige Polyamidsäureharζ and that polyimide resin formed therefrom has numerous uses .

Solutions of these resins can be cast into films that can be used, for example, as a slot chuck in (electric) motors. Furthermore, these films can be used in all of the Cases where wood-resistant products are used or body are required, for example in packaging or packaging operations, for example for the production of coatings or coverings for a wide variety of surfaces etc.

Furthermore, solutions of the polyamide acid resin on electric conductors, for example copper, aluminum, etc. are applied and then the thus covered conductor by a heat tower, where temperatures of 150 ⁰ C. to 300 ° C. within periods of time, which can be about 1 minute to 30 minutes, in order to bring about the formation of the polyimide resin with simultaneous evaporation of both the solvent and the triorganosHanois *

Finally, solutions of the polyamic acid resin containing silyl groups can be used can also be used for spinning fibers, either spinning organs containing the polyamic acid containing silyl groups

". ' ·* BATH

90 9884/160 3.

- sheet 34 -

resin in the dry air or in nonsolvent for the Spinning resin and these fibers, if necessary, oriented and further treated at an elevated temperature to achieve a certain Achieve formation of the polyimide resin structure.

If desired, the pasers can be stretched and oriented as long as they are still from the siIylgruppenhaltigeη Polyamide resin and then converted into the polyimide form in this stretched and oriented state by heating will.

In the polyimide resin form, these fibers have a special one good heat resistance and can be used to produce heat-resistant Textile products, filters, brake linings, etc.

The polyimide polymers, which are derived from the polyamic acid resin containing ailyl groups, also show good resistance to a wide variety of chemicals and, due to the large number of aromatic nuclei in the polyimide resin structure, also good resistance to radiation from high-energy particles and to gamma -beams. If you have these polyimide resins elevated temperatures in the truss. If the order of 300 to 40O ⁰ C is exposed, these resins are not adversely affected by this.

Films or other moldings made from the polyamide resin containing silyl groups can be irradiated with rays of high energy, for example with electron beams, useful products being obtained, for example capacitor films.

Other uses for the polyimide resins are

909884/1603

- sheet 35 -

for example, their use for the production of capacitors, for sheathing cables or for sheathing pipes in order to make them corrosion-resistant. Laminated body made from these
Polyimide resin films can also be produced; these have good heat resistance and desirable electrical properties at elevated temperatures.

/ Claims:

BATH
909884/1603

Claims (1)

Claims 1.) Polyamic acid resin characterized by recurring Units of the formula , 00 H "" H _N — C CNR ¹ - R.
Z ₃ Si-OC CO-SiZ ₃ in which Z is a monovalent hydrocarbon radical, R is a tetravalent radical with at least six carbon atoms in a ring with a benzolically unsaturated group and the four Oarl: ony! groups are bonded to separate carbon atoms of said tetravalent radical in King and each pair of carbonyl groups to adjacent carbon atoms is bonded in the R radical or on "oolche", which are separated from one another by at most one carbon atom, wherein R ^{1 is also} a divalent aromatic radical with at least six carbon atoms and χ is an integer greater than 1 in the aforementioned formula. 9G9884 / 1603 ^BATH ORIGINAL - patent claims - 2.) Polyamic acid resin characterized by recurring Units of the formula Il Il (CH ₃ ) ₃ SjL-OC where χ is an integer greater than 1. 3.) Polyamic acid resin characterized by recurring Units of the formula -NH (CH ₃ ) ₃ Si-O Il - C Il .C -NK CO-Si (CH ₃ ) ₃ 0 where χ is an integer greater than 1. k.) Polyamic acid resin characterized by repeating units of the formula C-OSi- (CH,) - 0 BAD ORi (SiMAL 9098 84/160 3 « Claims - in which χ is a value greater than 1. 5 ·) Polyamic acid resin characterized by repeating Units of the formula (CH ₃ ) ₃ Si0 - C-OSi (CH) It where χ is an integer greater than 1. 6.) Polyamic acid resin characterized by repeating units of the formula It NH-C (CH ₃ ) ₃ Si0 - C - OSi (CH _{3) 3} 0 where χ is an integer greater than I. 7.) Polyamic acid resin characterized by recurring Units of the formula 0 ii —NH — C (CH ₃ ) ₃ SiO -C 0 c -NH - // \ C-OSi (CH ₂ ) 3 bath 909884/160 Claims - where χ is an integer greater than 1. 8.) Polyaraidsäurehaltige homogeneous solution, marked by a polyamic acid resin containing silyl groups of the formula O O H ■ "" H - NC - C — Ν — R ¹ - " R ' —Ο - C C — 0 — SiZ- Il Il in the. '■ a monovalent column hydrogen radical, Iv a tetravalent:.; en radical with at least six Kolilenstoffatomen in a ring with benzolically unsaturated G-ruOpierung denoted and the four carbonyl groups to separate I-hlenstoffatone of said tetravalent radical in the iline _; r are bonded and each pair of carbonyl groups to r-cnaclibarfe carbon atoms in the R radical or to those r; cl -undes which are separated from one another by at most one carbon atom, furthermore in the aforementioned formula R 'being a divalent aromatic radical with at least six Carbon atoms and χ represents an integer greater than 1. BAD QR2GSNAL - patent claims - 9 ··) Process for the production of polyamide acid resins, characterized in that silyl group-containing polyamide acid resins, the repeating units of the formula O \ R. / / O H —R'— H It It —N - N-C \ C. - ^SiZ 3 -O C.
It O Z ₃ Si-OC
Il O are composed, in which Z is a monovalent hydrocarbon radical, R is a tetravalent radical with at least six carbon atoms in a ring with benzene unsaturation Grouping, means and the four carbonyl groups to separate carbon atoms of said tetravalent radical are bound in the ring and each pair is attached to carbonyl groups to adjacent carbon atoms in the R radical or to such which are separated from one another by at most one carbon atom, wherebyj. also in the aforementioned formula R 'is a divalent aromatic radical with at least six carbon atoms and χ is an integer greater than 1 symbolizes, being obtained by being in a solvent for at least one of the reactants and for that by the Polyamic acid resin containing silyl groups formed in the reaction a reaction is caused in a mixture of ingredients consisting of a silyl group-containing diamine of the formula HH
-KR '-K- 909884/1603 BAD Of = MGfNAL and of at least one tetracarboxylic acid dianhydride with the structural formula QO consists, where the symbols R, R ¹ and Z have the meaning given above. TO.) Method according to claim 9, characterized in that the silyl-grouped diamine is composed of N, U'-bis (trimethylsilyl) ρ, ρ'-d! Aminodiphenyl ether, N, N'-bis (trimethylsilyl) -mphenylenediamine or N ₁ If ¹ -bis (trimethylsilyl) -p-phenylenediamine consists, ¹ i ·) Process according to claim 9 or 10, characterized in that the dianhydride consists of ityromellitic dianhydride or of benzophenone tetracarboxylic dianhydride .. ^12. ) Method according to claim 9 bisi1, characterized in that the reaction is carried out in a solvent which consists of tetrahydrofuran. T3.) Method according to claim 9 to TJ ?, characterized in that that the reaction is carried out in a solvent which is composed of (1) N-methylpyrrolidone and (2) toluene, tetrahydropyran, Dioxane or a mixture of alkylated benzenes. BAD OFUGlNAL 909884/1603. / - patent claims - 1U.) Method for producing a polyimide resin, thereby characterized that a 3 ily lgruppenhaltiges Polyaieidsäureharζ produced according to the method of claims 9 Fels13 and then the silyl groups by the action of heat are split off from the polyamic acid resin. 15.) A method for coating an electrical conductor with a polyimide resin, characterized in that a solution of polyamide resin containing silyl groups produced according to the method ier claims 9 to 13 and this is then applied to the wire and the latter then subjected to heat for the purpose of removal of the solvent and for desilylation (= removal of silyl groups) of the resin. ORIGINAL 909884/1603