DE1770485A1 - Phosphorus, thiophosphorus and silicate containing polyimides and methods for making these polyimides - Google Patents

Description

BpL-iiMj. Hcns-HeUiki ' Baiin-DcWem, PodbidbW

20 450 Berlin «May 2, 1968

SOCIETE RHCDIACETA PARIS (France)

Ph ft p pho r ~ _u tibJophojgphx r and allika1; l> altlfc polyimide process y.tif manufacture dleaer

Addition to patent or iPatentana clothing S 10% 497 IVd / 39o)

The present invention inspects on phosphorus-, tbiophosphor- and / or eilikathaltlg "Kit polyimides a structure analogous to the structure of those polyimides is that 1« Patent *, r,, - (S Patent Application 104,497 IVd / 39c) are described and the - compare old the latter - have better properties

The foly alde described in the pntnnt include two-valued radicals "B" dl "contain at least one group of carbon atoms and at least one group" selected from the following: aliphatic ", aromatic", cycloaliphatic heterocyclic radical "; the at least "Ιηέβ dsr Atoai" N, 0 and S, wherein said Oruppen simple or g <~ _r can form mlsohte chains in which they are linked directly or by one of the following free radical ";

~ S0 ₂ ~ _v -0- ₅ -CO-

0 Y

-P-, -C- -KY-CO- X-CO NY-. -CO-NY-X-NY-CO- "

Y Y

-co-oxo-co- 10 0: ϋ Ul 1720

-U-Ci) -X-CO 0- and -CO-NY-NY-CO- 2-

where X em divalent aicoylene, dicxya: .., ylen-j Cyel & nylidQn- or arylene hadical sisfc and Y and Y ^{1 are} alcoyl, aryl or cyclanyl radicals} these awe :! worthless η Hadicals H are bound by groups of the formula:

β · ⁿ m-

where H ^{s represents} a tetravalent hadical that at least ? iCoh ™ contains W lenstoffatome and otherwise corresponds to the same definition as R, and where the valency of these divalent hadicals R is given by G groups of the formulas

CO -N = G = O and -IT

are saturated.

The corresponding to the above definition linear polyimides cell excellent mechanical and thermal liigenschaften, but they do not have enough Widerstandsfähigst; ι §β £ βη the attack of certain chemical products, especially the acids un.ld <"al kaiischen ilydroxyden to their use in certain applications ? areas to allow.

The polyimides according to the present invention now have better ones .Properties, both in terms of mechanical and thermal properties and in terms of resistance to chemical attack, compared to those of the linear Polyimide de «main patents?

BAD ORIGINAL 1 098 <U / 1 720

They are characterized by the fact that they are also n-valued Radical K ?! containing at least η -uohlenstcffatoraen, where η is an integer at least equal to 2, and at least two Groups contain; selected from the following ϊ aliphatic «, aromatic, cycloaliphatic; the heterocyclic Ead.iica.le contain at least one of the atoms N, 0 and S, and the said groups form simple or mixed chains, that contain at least one of the following compound radicals!

O S S S

* ι it ι

O- P ~ 0- ϊ -0- 1 »-0"; -P = -; -0- P -0-

6 OY Y

- ■. ■ '■■■ γ ■.

0 0 0 p

1 I: - .. I »

0- P -0-; -O-Si -0-; -P-; -0- P

Ii i

Y 0 0

and -0 »Ρ -0

0
Ο- P -0 d 0 Ρ

1 '

These radicals H ^SI are bound by the same groups'"■ μ radicals H bond, and the remaining free valences of this Kadikaie H ^{1 {will} be saturated by the same groups that absHttigen the free valences of the radicals H _o

The polyimides forming the subject matter of the present invention, which can be linearly or crosslinked, depending on whether one uses polyisocyanates in which n = 2 or greater than 2, contain phosphorus, as binding radicals in their molecule, groups containing thiophospnor or s US zium, the nature of which gives them a particularly good thermal and chemical stability,

used, 1088 4 W 172 0

BATH ORIGINAL

1770A85

Ale v & fiante know the Polyieide according to the present invention uee * "r the above-defined radicals R and R ^'4, the radicals R" ^f "include; dlt correspond to the same definition as Im HftUftpatatt , ie that the radicals B "'n-valent · Had I kai β Bind, which contain at least n-carbon atoms» where η is an integer of at least = 3, and the at least one, , Ό group contain ₉ which is to be selected from the following: Aliphatic, aromatic, cycloaliphatic j the heterocyclic radicals contain at least one of the atoms N, 0 and S, and the strung groups can form simple or mixed chains in which they are directly or through at least one of the following radicals are bound:

- SO ₂ -, -0-, - CO-,

ι ι

0 0

-0-öi -0-, 0 ■ P - 0 and -CH

9 4

These radicals H " ¹ are bound by the same groups that ^{bind the radicals H and R 1} ', and the valencies of these radicals R ^{1. 1} ' that have remained free are saturated by the same groups that ^{bind the free valencies of the radicals R and H 11} saturate.

The present invention also relates to a method for Production of the aforementioned phosphorus, thiophosphorus and / or silicon-containing polyimides.

This process, according to which in the presence of an inert polar organic solvent in a MoJ.ratio 1: 1 at least a LUieocyaiiat according to the general formula

O = C = W-E-HsC-O

1 0 9 8 k U i 1 7 ν '■> . »J

in the H the'above indicated. Has meaning _? can react with at least one carbonyl compound which can form an internal diimide, which contains swel vaare carbonyl groups, * each of these groups being bonded to a carbon atom of the same tetravalent kadikais on the one hand and to on the other an oxygen atom; and where the carbonyl groups belonging to the same pair are separated by at most three carbon atoms ρ is characterized in that, either before the reaction or in general, the Raak'Cion the - * di: isocyanate and the carbonyl compound one "Adds mixture that contains the same carbon compound and at least one polyisocyanate of the general formula:

contains, in which η is an integer at least «2, H '' die has the meaning given above, the amounts of the compounds of these mixtures are such that it is in the Heaktiohsmi-SChung half a mole of carbonyl compound for each isocyanate group

Diisocyanates in particular are used as iOlysisooyanate _3, which are added as a mixture with the carlonyl compound, namely the following:

Diisocyanato-4 «4 'triphenyl phosphate

Diisocyanato- 4 »4 ^f -triphenylthioitosphate

Diisocyanato-. 4 »4'-triphenylphosphine sulfur

Diisocyanato 4 ₉ 4 ⁵ triphenyl phosphonate

Diisocyanato-4,4'-triphenylthiophosphonate

üiisocyanato-4,4'-tetraphenylsilicate

and 'J) riisocyanates, in particular;

109844/1720

BATH 6 -—ζ

Triisocyanato-4.4% 4 · ¹ '-triphenylthiophosphate Triisocyanato-4,4', 4 ' ¹ -triphanylpJiosphine-Oxyd Triisocyanato-4t4 ·', 4 "-triphenylthiophosphonate

The Carbonylverbitidungen used eind diejenlgen are described in the main patent _a, ie ^ anhydrides of TetracarDoxyisäuxen, the tetracarboxylic acids or a mixture of a dianhydride and an acid, the general formulas:

OO QO

ff ti 1 I

HO O. J3 OH

) and
-Q ^ HO Qf ^ ^ C

correspond to «in which h 'has the meaning given above.

The heat is in the presence of an inert polar organic Solvent at a temperature between 40 and 350 ° 0 and depending on the Aüsgangsproriulcten used and the desired molecular weight to be achieved varies, carried out: The ingredients are dissolved in the inert solvent; the solution obtained is immediately or gradually reduced to the ^ ewnnsohfce Brought to temperature, under normal pressure or under an appropriate vacuum, depending on whether the polyimide is in the form of a Wish to obtain powder through precipitation or in the form of a film through evaporation of the solvent «

The solvents preferably used are: N-dimethylaoetamide, N-dimethylformamide, W ~ methyl ~ 2- £ # rrolidone,

■■■■ - \ G ^ ' and dimethyl sulfoxide.

1 0 2 S A £ / 1 7 *> 0

One can also use a mixture of these solvents and others use inert solvents such as xylene, acetone and dimethyl * ether of Dl- or Triethylea-aiykol.

As a variant, it is also possible to add -XtSgHoIi, au · terde «dtr mixture for carbonyl compound and polyleocyanate binding tints dtr polyisocyanates mentioned in the main patent, ie, a polyisocyanate which has the general form

E ¹ "(-H = C = O) _n ' ^:

in which n * and H ^H 'have the meaning given above, with the required amount of carbonyl compound also being added so that in the adhesion ratio tinj (<half a mole of carbonyl compound coats for each eocyanate group.

As for these latter polyisocyanates, one will preferentially use those mentioned in the above-mentioned patent, i.e.:

Triioocyanato - 4,4Ί 4 "- triphenylmethane Triisocyanato - 2,4f4 ^f -diphenyl ether Triisooyanato - 4,4 *, 4 "- triphenyl phosphate Triisocyanatec-2,4f6-methyl-1-fienzol

iCrii8ocyanato - 2,4 »6 - trimeithyl - 1,3,5-benzene

Iriisocyanato - I »3t7 - naphalin Triisocyanato - 2 _t 4 »4 * - diphenyl

Triisocyanato - 2,4,4 '- m§thyl-3-diph§ny; laetiian Tetraisocyaxiatö- 2,2 ^f _f 5,5' - dimethyl-4,4 ¹ -diphenylmethaa i-olyisocyanato - polyphfenylÄn - JÜymethyltn J ^ lyiKticyp .P'ito - ooJyoxyDh & iiylAn

example 1

I4ö Diisocyanate ·· 4 »4 ^; - Diphe.nyläther and 12, 11g dianhydride of pyromellitic acid are dissolved 140 cm JN-dimethylacetamide, and the resulting solution is poured into a vessel with a flat bottom surface of 1300 cm, which is in an oven for 2 hours "to 40 long ⁰ G holds »The solution is then placed in a glass flask and kept at ambient temperature for about 12 hours. The solution is then ^{heated to 70 °} C. under a pressure of 15 ram Hg in order to increase the viscosity»

To 70g of this viscous solution was added under Hühren and simultaneous heating to 80 ⁰ G, a solution of l »^ 2g Triisocy gft 4,4 ', 4 * -triphenylthiophospat and 0,845g of pyromellitic dianhydride in 20 cflor N-dimethylacetamide hinfeu * The mixture these two solutions are heated for 30 minutes. Then the solution is poured into the same flat-bottomed vessel, as mentioned above, and the container is placed in an oven in which the pressure is reduced to 100 mm. s- heated and the temperature held in the various stages according to the program;
1 hour at 60 ⁰ G, 20 hours at 70 ⁰ G and 2 hours at 80 ⁰ C,

From the bottom of the container is then releases the film formed and gradually increased over the period of 8 hours, the temperature to 140 ⁰ G after the other hand dex pressure has been further decreased to 50 atm Hg "Then v / ill be in the furnace, the pressure on again atmospheric temperature and the heating continued for 6 hours, gradually increasing the temperature to 250 ° G. Then the temperature is increased to 300 ° 0 and held at this value for 3 hours. ^BAD ORiGiNAL

109844/1720 ~ T

Man. receives a transparent, flexible film that can also be used against repeated buckling is resistant and insoluble in organic solvents,

Dynamometric measurements carried out on several samples of the film produced according to the above example have given the following results:

at 22 ⁰ C

Resistance (kg / mra ² ) 9.55

Elongation (in $) 13> 1

Module (kg / mm ² ) "26Θ. Β

Example 2

■ A mixture of 1'5 g diisocyanate - 4,4 '- dipnenyl methane and 11 »349 £ dianhydride of pyromellitic acid is dissolved in 130 carbons of N-dimethylacetamide and the solution obtained is placed in a cylinder 500 cm long and 5 cm in diameter poured.

The solution is stirred using a vibrating mixer while a nitrogen atom is bubbled through at a rate of ι liters per minute and the temperature is kept at 40 ° C. for 5 hours. The solution is then transferred to a glass flask and kept on for 15 hours Maintained ambient temperature * Wan then heats the solution to TO ⁰ O under a pressure of 15 mm Hg for as long as is necessary to increase the viscosity of the solution.

To 70 g of this viscous solution is then added with stirring and heating to 80 ⁰ O a solution of a mixture of 1 g triisocyanate - 4,4 ', 4 "- tripiienyl-tlilophosphat and 0.7 g of the dianhydride

10 9844/1720 " ¹⁰ " ■

ίο

Add J-pyromellitic acid in 17 cm "JN-dimethylacetamide. The mixture these two solutions are further heated and stirred for 20 minutes.

Then proceed as indicated in the previous example, so that a transparent, flexible Yi Im is obtained, which is resistant to repeated kinking and insoluble in organic solvents, and which shows the following mechanical properties:

at 22 ° C

Resistance (kg / mm-) 8.9

Elongation (in ^) 17.6

Module (kg / mm ² ) 227

Example 5

A mixture of 0.7 g of triisocyanate - · 4,4 ', 4 "- triphenyl thiophosphate and 6.55 g of pyromellitic acid - diannydri.d is dissolved in 70 car U-dimethyac et amide, and the obtained is kept. Lösun; at 40 ⁰ C for 4 hours, then additional 15 minutes a'jf 70 "C. then adding it to the solution? Add g diisocyanate 4,4 - Q * phenyl ether and pour the solution into a container * with a flat bottom with a surface of 525 cm, in which this solution is kept at 40 ° C for 2 hours and then at ambient temperature for 15 hours ο

Then, the solution was heated to 60 ⁰ C under a pressure of 15 mm Hg for a period of time, the emergency to the viscosity ürhöhung

11

109844/172 0

■■ - ii ■■■ .-

For the rest, the procedure is as in the two preceding examples given for the production of a film. The film obtained in this way is transparent, flexible, resistant to repeated kinking and not soluble in organic solvents »

Example ,, .4

5.04 g of diisocyanate-4,4 * -diphenyl ether, 12.25 g. Diisocyanate 4,4 '- tripiienyl phosphate, 2,54 &■'. JPyromellitic acid and
8.72 β dianhydride of pyroaellitic acid are dissolved in 140 N-dimethylacetamide and the solution is placed in a vessel

poured flat bottom of 1300 cm surface, which is maintained for 2 hours in an oven at 4O ⁰ C * Then the pressure is reduced to 100 mm Hg. The mixture is heated gradually and the temperature at different levels to the following program entsprechendi,
1 hour at 60 ° G; 20 hours at 70 ⁰ C and 2 hours at 80 ⁰ G.

Is then dissolved from the bottom of the formed film and brings Behnlters during 8 hours a? .Lmählich the temperature to 140 ⁰ C after -den'Druck hat0 even "reduced .uf a value of 50 mm Hg then placed in the oven aen . Pressure back to atmospheric pressure and heated for a further 6 hours, gradually increasing the temperature to ^ 50 ⁰ G. Finally, the temperature is increased to 300 ^° C. and this temperature is kept upright for 3 hours

You get a transparent, pliable and repetitive Wrinkle Resistant Films T

example

5 »04 g diisocyanate - 4,4 '- diphenyl ether,

12.25 g of diisocyanate - 4 »4 ^f - triphenyl phosphate,

2.54 g of pyromeliitic acid and

8.72 g of dianhydride of pyromellitic acid will be

dissolved in 140 cm fl-Dimethylaeetamid and the solution in a vessel

ρ
poured with a flat bottom with a surface of 1500 cm, which can be 2

Can stand for hours at 40 ⁰ G in the oven "It then directs the solution into a u-laslcolben and keep it at about 12 hours W to ambient temperature.

One then proceeds as specified in Example 1, ie, one Fogt the same amounts of the same solution of triisocyanate 4,4 ', 4 ^W - triphenyl thiophosphate and Pyromeliitsaure dianhydride of the N-Diaethylaeetamid at and provides a film in the manner described here.

The film obtained shows the properties analogous to those of the example 1.

Example 6

A mix of

7.5 g diisocyanate - 4 * 4 * - dipaenylmethane,

5.04 a diisocyanate - 4.4 * - triphenyl phosphate, 2.2 g of triisocyanate -. 4,4 '~ 4 ^M triphenylmethane, 5.08 g tyromellitic acid and

8.5 g of dianhydride of pyromellitic acid is

dissolved in 130 car ft. dimethylacetamide, and the resulting solution is poured into a cylinder 500 cm high and 5 cm in diameter. ,,

109844/1720

.-. 13. ■ - · ■. ■. ■■■ "

The solution is stirred by means of a Vibr-o-mixer while a jjuft stream with a throughput of -1 jjiter per minute is bubbled through and the temperature is allowed to stand at 40 ° C. for 5 hours. The solution is then. transferred to a glass jar and kept at ambient temperature for 15 hours. The solution is then heated to? 0 ° G under a pressure of 15 mm Hg for a period of time to evaporate part of the solvent and to increase the temperature Viscosity of the .solution is required »

The viscous solution is then spread .auf.einer.Glasplatte which one provides the la _f the pressure is reduced to 100 mm Hg in an oven "is heated gradually and the temperature of the various stages geiaäss the following program; 5 hours at -60 ^° O; 3 hours at 70 ⁰ Oι 3 hours at 80 ⁰ G.

The film formed is then detached from the glass plate and the temperature is gradually brought to 140 ° C. over ⁶ hours after the pressure has been reduced to a value of 50 mm Hg

* ■

then brings the pressure on the furnace to the outer-spherical pressure and drives

■■■■■: ■■ '■

Heat continued for 6 hours isu, Indians can progressively the temperature to 25O ⁰ G steioSrt "aan Finally, increasing the temperature" TIAR to 300 ⁰ C and kept at this temperature 3'Stunden long upright.

You get a transparent, flexible, against repeated Film resistant to bending and insoluble in organic solvents,

/ ■; ■ './, ■■■ ^: '

Tbr / Ho claims

109844/1720.

BATH

Claims (12)

Claims 1) Polyinide, the divalent hadikala ä contain and at least in turn contain at least two carbon atoms, one under the following selected Jruppe: simple aliphatic, aromatic, cycloaliphatic, wherein the heterocyclic Kadikaie contain at least one of the atoms N, 0 and S, and said groups and can form mixed chains in which they are linked directly or through at least one of the following Hadikaiβs -ÖOp- »" 0-, -CO- 0 Y
-jL, - (L _f -NY-CO-X-CO-NY-, -CO-NY-X-NY-CO-, Y Y -CO-O-X-O-CO- -0-CO-X-CO-O- and -CO-NY-NY-CO- wherein ί a divalent alooylene, dioxyalooylene, cyclanjjL-liden- or arylene radical, where Y and γ · are alcoyl, aryl or cyclanyl hadicals and these are divalent Kadikai6 R by groups of the formula CO CO
-N ^ H 'N- - Jl- 10 9844/1720 CO No BAD ·?, - ■■■■ JS are bound «= where H 'represents a tetravalent hadical that Contains at least two carbon atoms and the rest of the corresponds to the same definition as R; the ones left free Valences of these divalent radicals H are saturated by groups of the formula: co co -H-C = O and CO CO according to """^ ₀₀ (Fstentanaeldung S 104 * 97 IVd / 39c), characterized in that it further comprises _f or n-valent radicals R ^H comprise at least η Üohlenstoffatome.- wherein n is an integer of at least 2 and which contain at least two groups selected from the following: aliphatic aromatic, cycloaliphatic; wherein the heterocyclic radicals contain at least one of the atoms N, 0 and δ and said groups form simple or mixed chains which comprise at least one of the following connecting radicals: 0 S ■ '£ S -Q- p -0-; -0- P '-O-; ■ - I- ; H -'- f -O-; O 0; Y i i Y. ο ο ρ s s -0- P -0- ί -0 - Si-O-; -Ρ—; - P -; «-0- P-O-; ο s -0- P -0- and -0- I -ΟΙ I - these radicals R ^H are in turn bound by the same groups as the radicals R, and the values that remain free 109844/1720 - % . 1T70485 These radicals H "are saturated by the same groups as the free valencies of the liariical K, 2) Polyimides according to claim 1, characterized in that they also comprise n? -Valent radicals H "'which at least n'-carbon atoms - where n 'is an integer equal to at least 3 is - and contains at least one group selected from the following: aliphatic, aromatic, cycloaliphatic; whereby the heterocyclic radicals contain at least one of the atoms N, 0 and S and the said groups are simple or can form mixed chains in which they are bound directly or through one of the following hadicals: -SO ₂ - j -0- j -CO-, · 0 0 -0- ii -0- j -0- ί -0- and -CH-, these radicals E " ¹ are bonded by the same groups as the radicals H and H ^M , and the valencies remaining free of these radicals B" f are saturated by the same groups as the free valencies of the hadicals H and H ". 3) polyimides according to claim 1 or claim 2, characterized in that that the radical H * is a Hest benzene, because in the positions 2,3 and 5,6 is substituted. 10984A / 1720 4) Polyimides according to one of claims 1, 2 or 5, with a molecular weight between 1,000 and 10,000, as a solution in at least one polar organic solvent selected from the group consisting of -H-, ^{M 1 -pearethyl acetamide, N-} Dimethylformamxd, U -methyl-2-pyrrolidone and Dimethylsulfoxld includes » 5) Process for the preparation of polyimides, in which one in the molar ratio IiI in the presence of an inert polar organic ^ Solvent at least one diisocyanate of the general Formula: '■ .. 0 «C« »-E-H« 0'h-Ö- in which R has the meaning given in claim 1, subjected to an action with at least one carbonyl compound which can provide an internal diimide which contains two pairs of carbonyl groups, each of these groups having an identical carbonyl atom tetravalent Hadikal 5 on the one hand and with an oxygen atom on the other hand M and the carbine groups belonging to the same pair are separated by at most three carbon atoms, which characterizes that either before the reaction or in the course of the reaction, the diisocyanate and adding a mixture to the carbonyl compound which contains the same carbonyl compound and at least one polyisocyanate of the general formula:, contains, in which η is an integer equal to at least 2, E "has the meaning given in claim 1 and the amounts 10 9844/1720 " ⁵ ■." BAD ORiGSNAL M. the constituents of these mixtures are such »that in the Heaktionsmiechung half a pint of the carbonyl compound each I so cyanate r uijp e is available. 6) Method ^ ernäse claim 5, characterized in that the mixture of the carbonyl compound and the polyisocyanate at least one polyisocyanate of the general pre-oil: H "'(-K» C * O) _n , in which n ^{1 is} an integer number at least equal to 3 and R "has the meaning given in claim 2, adding the amount of carbonyl compound which is necessary to add 1/2 mol of the carbonyl compound per isocyanate group in the reaction mixture obtain. 7) A method genäss claims 5 and 6, characterized in that said Polyisooyanat and the carbonyl compound to a temperature between 40 and 35O ⁰ C heated. 8) Method ^ emass claim 5, characterized in that said polyisocyanate is a diisocyanate 9) Method ^ emass claim 8, characterized in that said diisocyanate is one of the following: Diisocyanate - 4 »4 * - triphenylphoephate Diitooyanato - 4,4 * - trlphenylthiophotphate Diiiocyanato - 4,4 '- trlphenylphoephine-sulfur Diiiooyanmto - 4,4 * - triphenylphofphonmt t0 9844 / t72Q. _6th 177-85 Diisocyanates - 4.4 ^! - triphenylthiophosphonate diisocyanate «· 4,4 '" tetraphenyl silicate 10) Method o ^em ^ ss claim 5, characterized in that said tolyisocyanate is a triisocyanate. 11) The method according to claim 10, characterized in that said triisocyanate is one of the following: Triisocyanato - 4,4 '»4 ^H ■■ - triphenylthiophosphate Triisocyanato .- 4,4 ', 4 "- triphenylphosphine oxide Triisocyanates - 4 »4 ^f , 4" - triphenylphosphine-sulfur Triisocyanato - 4,4 ', 4 ^W - triphenylphosphonate Triieocyanato - 4 »4'f 4" - triphenyfpnüiphonat 12) Method. ^ Em according to claim 6, characterized in that said polyisocyanate is one of the following Triisocyanato - 4 _t 4 * t 4 ". R triphenylmethane Triisocyanato - 2,4» 4 ^f - diphenylather Triisocyanato -4,4 ', 4 ^M - triphenylphosphii * i Triisocyanato - 2,4,6 - methyl-1-benzene Triisocyanato - 2,4VS - trimethyl - 1,3,5-benzene triisocyanato - 1,5 * 7 - naphthalene triisocyanato -2,4,4 '- diphenyl triisocyanato - 2,4 _V 4' - methyl-3-diphenylmethane 10984Λ / 1720 Tetraisocyanato - 2,2 ', 5,5' -dinethy1-4,4 ' -d iphenylmethane lOlyfcisocyanato - rolyphenylene - polymethylene Polyisocyanato - polyoxyphenylene. Tbr / Ho 109844/1720