DE1520616A1 - Polymer masses - Google Patents

Description

Patent attorneys DR.-ING. WALTER ABITZ DR. DIETER MORF

Munich

June 16, 1964 P-1367-R / 1433

B. I. DU POHT 3XS HEMOURS AHD 00MPAHY 10th and Market streets, Wilmington 98, Delaware, V.St.A *

Polymeric masses

The invention relates to new polymeric materials, particularly the preparation of a new group of polyimides. Other goals emerge from the following description ^: '

The new group of polyimides is characterized by one recurring unit of the structural formula

Il

Il

It

/ ^c \

Il

ο ·

NR ₁

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where E denotes a tetravalent, aromatic best, which preferably contains at least one six-membered carbon ring which is aromatically unsaturated, and in which the four carbonyl groups are located directly on different ring carbon atoms and each pair of carbonyl groups are bonded to adjacent carbon atoms in a ring of the radical R, f and where R _{1 is} a divalent aromatic radical of the formula

represents in which Rg is fluorine and R ~ is chlorine or fluorine.

Each ring can also be substituted with halogen or lower alkyl.

The polyimides produced according to the invention show excellent physical and chemical properties _; This is why they are of high value as molded structures such as films, fibers, threads, foams, powders and the like. The Öebilde are characterized by good tensile strength, strength properties, desirable electrical properties and a surprising resistance to

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Heat and water. Mainly they are weakly colored, sometimes even colorless.

A particularly useful polyimide among the inventive methods manufactured polyimides, is the polyimide made from diamine and dianhydride, which contain hexafluoropropylidene BrUokene. Lake Folyinid eliminates recurring units of the Pormel:

CF,

This polyimide has very unusual solubility properties, a moderately low softening temperature and good thermal resistance. This is in contrast to the workability and insolubility of the most polyimides. Of course you can use other dianhydrides and diamines together with 4,4 '- (hexafluoropropylidene) dianiline (also called 2,2-Bie «(4-aminophenyl) -hexafluoropropane) and 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydxide use to form copolyimides as long as they do not have the machinability or solubility and solubility destroy this useful polyimide.

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The polyimides are made by mixing at least « of an organic diamine of the structural formula

H ₂ NH ₁ -HH ₂ , in which R _{1 is} a divalent, aromatic radical of the formula

R ₃

^H 3.

denotes in which R _{2 represents} fluorine and R ~ represents chlorine or fluorine, and at least one tetracarboxylic acid dianhydrideB of the structural formula

0 0

0 0

in which ft means a tetravalent, aromatic radical, which preferably contains at least one carbon six ring which is aromatically unsaturated, and on which the four Carbonylgruppeη directly on different Ringkohlenetoffatomern are bonded and each pair of carbonyl groups on adjacent carbon atoms (ortho or peri) in a ring of the

The rest was sitting

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In the preferred process for preparing the polyimides of this invention, one first prepares a polyamic acid _t ago an inner Viseosität of at least 0.1, preferably from 0.3 to 5, has, by reacting the diamine and the dianhydride in an organic solvent is a solvent for at least one of the reaction participants, and weloises is inert towards the reactants, the reaction preferably being carried out under substantially anhydrous conditions and at a temperature below 175 ° C. for a sufficient time to obtain in most cases at least 50 # of the corresponding polyamic acid , and then converts the polyamic acid into the imide, which also has an internal viscosity of at least ^ 0.1, preferably from 0.3 to 5

The internal viscosity of the polyimide is determined at 30 ° on a 0.5 # solution, the polyimide in a suitable Solvent is dissolved. For many of the invention

Concentrated (96 #) sulfuric acid is a suitable solvent for the polyimides produced. However, you can select ^one from a group smittel the solution of concentrated sulfuric acid, fuming nitric acid, the Monohjdret of synKDichlortetrafluoraceton and the hydrate of mono chloropentafluoroacetone is <>

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Also, one preferably, but not necessarily, poses a molded Sebilde from the polyamic acid mass before Conversion of the polyamic acid into the polyimide. In any case, the conversion of the polyamic acid into the polyimide can be carried out by a heat treatment or any chemical treatment or by combinations of treatments such as they are described below, reach »

One purpose of the preferred method is to provide a composition that contains enough polyamic acid that one can mold that composition into useful articles prior to converting the polyamic acid to the polyimide. The polymers can also be modified with inert materials before or after shaping. These modifiers can be selected from a large number of types, for example from pigments, dyes, inorganic and organic fillers

In addition, a certain time and a certain temperature for the formation of the polyamic acid are determined of a given diamine and a given dianhydride several factors have to be considered. The maximum permissible temperature depends on the diamine used, the Dianhydride used, the respective solvent, the desired percentage of polyamide in the finished mass

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acid and the minimum time required for implementation away. With most combinations of diamines and dianhydrides Within the framework of "the above definitions, masses with a polyamic acid content of £ 100 can be formed" by adding the Implementation below 100 ° C. Deform while achieving " However, temperatures of up to 175 ° C can be permissible for the bulk masses be. The special temperature below 175 ° 0, which must not be exceeded for a given combination of clay, diamine, dianhydride, solvent and reaction time, to obtain a reaction product eu that of enough polyamide acid is formed in order to be deformable varies, but can be determined in a simple experiment *

In practicing a preferred procedure, equimolar amounts of the diamine and the dianhydride are used premixed as dry solids, after which the mixture, in small portions and with agitation, becomes an organic Adding solvent. Premixing the ingredients and then adding them in small portions to the solvent is a relatively simple Mixtel to control the reaction temperature and the reaction rate » You. uie reaction is exothermic and becomes very strong Speeding up, it is important to use the additives that way too regulate, daae the reaction temperature on the desired Higher, viirö. However, the order of addition can

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to be changed. You can naoh the Vormiaohan dee Diamine * and the dianhydrideβ the solvent agent under the Oeaisoh Add movement. Ee is also possible because * diamine is in the to dissolve organic solvent with agitation, to preheat the solution and then to add the dianhydride slowly enough to control the reaction temperature. Will be habitual In the last-mentioned mode of operation, the last case is that Dian- ^ hydrides are set with a rope of the organic solvent. Another possible way of working will be dia Reaction participants to the solvent in small proportions eetat, but not .ala Vorgemlaoh, but in the order Diamine, then dianhydride, again diamine, etc. In every vaIl let it is advisable to terminate the LUeungepolyaeriaationseystern neon * Move the additive until it reaches a maximum level, which indicates maximum polymerisation Other methods dissolve the diamine in one portion of one solvent and the dianhydride in another portion the same or some other solvent and fail then the two solutions.

The degree of polymerization of the polyamic acid can be controlled arbitrarily Participants under the stated conditions results Polyamic acids with a very high molecular weight. The use of a large excess of the two reaction participants limits the degree of polymerization. Except for the use of an excess of a reactant

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Limiting the molecular weights of the polyaide acid can

sen a Kettenabbxeoher, such as phthalic anhydride, dim

' Use to tilt the bonds of the polymer chain iu.

In the production of polyamic acid products, a single molecular weight is essential, since the internal number of the "polymers" is at least 0 * 1, preferably 0.3 or 5.0. The internal viability of the polyamide acid is determined at 30 ° with a polyamide cone entxation to 0.5% by weight in a suitable medium, B. aoetamide. To calculate the inner Yieooeität the viscosity is the in Polymexiaatlöeung Be "ug to that dee Löeungsmittele aelbet determined:

Viflooeity of the LCt

Inner Viecoeität * In Yiecoaltät deä £ ueunfce »ittele

Here, C is the concentration expressed in örama Polymer to 100 ml of solution »Xn the PolymeriBatlonefaohmann As is well known, the internal viacoativity is directly related to the molecular weight of the polymer atea. -

The amount of organic LösungBiaittele used in the preferred operation only needs to be sufficient, u »sufficient to stimulate the reaction of the diamines and of the amount of a Dlanhydrides Reaktionsteilnehmerβ, preferably

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dee diamine, su löeen. Both; Deformation of the Maeee su shaped structures has shown eioh, dase obtained the best Brgebniese when the Löeungeaittel forms at least 60 Jf the finished Polymerieatlöeung, ie the solution is 0.05 bie $ 40> the polymer component included. The viscous solution of the polymer breath, which contains polyamic acid in the polymer component, which is dissolved in the solvent, can be poured in as such for forming shaped structures. They are then converted into the corresponding molded body from the molded Poiyimid Oebilde, which are formed by a substantial amount, at least 50 gewöhnlioh i "acid of polyamide.

Instead of being shaped into the usual structures, the polyamic acid mass in the solvent can also be used as a liquid coating agent. Such coating agents can be pigmented with compounds in the form of titanium dioxide in amounts of 5 to 200 wt. They can be applied to a variety of substrates, e.g. B. on metals, e.g. B. copper, brass, aluminum, steel, etc., the metals in the form of sheets, threads, wires, nets and sieves udw. are present, on glass in the form of sheets, fibers and threads, foams, fabrics, etc., on polymeric materials, e.g. B. cellulose materials such as cell glass, wood, paper, etc., on · polyolefins such as polyethylene, polypropylene, polystyrene, etc. ₉

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on Polynia ·, polyester, wit polyethylene terephthalate etc., • of Perfluorkohlenetoffpolymeriaate, via Polytetrafluoroethylene, Llieohpolymerieate tob Tetrafluoroethylene ait Hexafluorpropylen, υ · «.» on polyurethanes, alia being polymers MatarlalltD la torn too plates and pollen, fibers and threads, Sonatiaatoffen, Oevabac and non-woven Paaeratoffen, letsen aaw. TorllegeOf on leather plates, etc. You then ground a polyamide acid overafic or here Tarfahren la PoljlMldUberaUee ueeewandalt.

laoh a working group become polyaidatures, welohe dia repeating units represent structural formula

HOOO .COOB

(where the arrow—> Iaoaerle means)

- - »-0 TJ-II ₁ - -

HO OH

aattapltett, converted by Braltiaa above 50 ° 0. The heating serves aur Tkniaadlung tob pairs tob Amid- ναΛ Oar boηetturegruppeη la laidgruppent ale can last a few seconds blue au several hours.

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The conversion of the Polyamidaäuremaaae in daa Polylaid on chemically high sweeping »meanwhile all with a dehydrating agent alone or in Combination with a tertiary amine, a. B. Baaiga acid anhydride or a Beelgeäureanhydrld-Pyrldln-aemlaoh treated. Mao can daa molded structures from the polyamide acid in a bath Treat as far as the Eeelgeäureanhydrid-Pyrldln-Oaalaoh contains. The ratio of alcoholic anhydride to pyridine can be used Tone just above 0 bla au infinitely rows Ba is assumed that pyridine is a catalyst for the effect of dea Cyollaierungamlttele, of the Baalgic anhydride, works »2a other possible dehydrating agents to use can include proplonic anhydride, butteric anhydride and Similar Petta Acid Anhydrides, as well as Aromatic Anhydrides · To other tertiary Amlo catalysts include examples frläthylamine, leoohiuolln, α-, 8- or γ-Piοollη and 2,5-lutidine. The above conversion bands are closer

in the VSA patent ahrift. (U8A registration 8th vo.

169 106 and the German Atialegeaohrift (patent application P> 1 005 IVd / 39 o) beechrleben.

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A third conversion method, a combination treatment, can be used. You can use the polyamic acid duroh ohamiaohe treatment partly in the polyimide conversion and then through aneohlieeaende heat treatment the oyolization lead to the polyimide at the end. When the Maeae is deformed is to be, aoll the conversion of the polyamic acid into the Polyimide in the first stage still a malleable Maaae resulted in After the deformation, the oyolization of the polyimide / polyamide acid can be carried out to the end.

The presence of the polyimides also makes them unlikely in cold similar reagents (compared with the raaohan Solubility of polyamic acid). Your presence shows eloh also when examining the polyamic acids during the conversion to the polyimide with ultrared. They show spectra initially a predominant absorption band with the above 3.1 Micron, which is based on the NII bond. This bond is gradually disappearing; and as the reaction progresses, the Polyimide absorption bands, a sublet, at oa. 5,64 and 5.89 microns and a peak at 13.85 microns. When the transformation is complete, the oharacterial one predominates Polyimide band.

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The starting materials for the manufacture of the products according to the invention are special organic diamines and tetraoarbonic acid dianhydrides. The organic diamines are characterized by the formula R ₂ NR ₁ -RH ₂ , in which B _{1 is} a divalent aromatic beat of the formal

H ₂ -OH ₃

is in which R _{2 is} fluorine and R _{5 is} chlorine or fluorine.

One can prepare these diamines by mixing two moles of an aromatic amine with a fluoroketone in the presence of Condensed aluminum chloride. Each ring can also be duroh Halogen or lower alkyl may be substituted. Diamines suitable for the purpose of the invention include for example

4,4 ^> -> (hexafluoroisopropylidene) dianiline,

4,4 * - (hexafluoroisopropylidene) -bis- (2,6-dibromaniline),

4,4 ^f - (hexafluoroisopropylidene) ~ bie ~ (2,6-dimethylaniline),

4,4 '- (hexafluoroisopropylidene) -bis- (2-bromaniline),

4,4 '- (hexafluoroisopropylidene) -bis- (2-methylaniline),

4,4 '- (hexafluoroisopropylidene) -bis- (2-chloroaniline),

4 _i 4 ^I - (hexafluoroisopropylidene) -bis- (2,6H3iohloraniline),

4,4 '- (chloropentafluorieopropylidene) dianiline,

4,4 '- (chloropentafluoroisopropylidene) -bis- (2,6 ~ dibromaniline),

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fS

F-1367-R / 1433

4 »4 - (chloropentafluorieopropylidene) -bis- (2-aminotoluene),

4,4 '- (1,3-Diohlortetrafluorieoprop ^ liden) -dianiline and

4f4 '- (1 _t 3-Dlohlortetr8 / luorieopropyliden) -bie- (2-aminotoluene)

The letracarbonBaure diaahydrlde are characterized by the

formula

OO η η

η η OO

where R is a fully valent organic radical which has at least six carbon atoms and is aromatically unsaturated, the four carbonyl groups of the dianhydride each sit on separate carbon atoms and each Pair of carbonyl groups directly on adjacent carbon atoms bound in group R 1st and a five-membered ring in the form τοη

0 0 0

ti w ην

0-0-C 'or C-O-C

I I

= 0 - C - -C-C-

llefert.

Examples of suitable dianhydrides for use in processes according to the invention include pyromellitic acid dianhydride, 2,3,6,7-naphthalene-tetraarboxylic acid dianhydride, 3 "3 ^> " 4,4 ¹ -diphenyl tetracarbic acid dianhydride, 1,2,5, 6-iaphthalene

■ f '■■ ·.'. ·

■ · ■■ - ■ '* ^1§ "" 909881/1498 BAD ORJGINAJ ,,,

IM367-R / 1433

tetraoarboxylic acid dianhydride, 2,2 ', 3,3'-diphenyl-tetracerbonic acid dianhydride, 2,2-BiB- (3,4-dicaxboxyphenyl) -propane-dianhydride, bis (3,4-dioarboxyphenyl) -sulfor.-dianliyaride , ~ Pexylen 3,4-9f10-tetxaoaxb6neftuxe _dianhydxld-f bis (3 '4-dicarboxyphenyl) ether dianhydride, naphthalene-1,2,4,5-tetraoarboneäure dianhydride, 2, 2-bis- (2, 3-dioarboxyphenyl) propane dianhydride, 1,1-Bie- (2,3-dicarboxyphenyl) -ethane-dianh ^ dxide, 1,1-Bie- (3,4-dicarboxyphenyl) -ethane-dianhydride, Bia- ( 2,3-dicarboxyphenyl) methane anhydride, Biß- (3i4-dioarboxyphenyl) methane dianhydride, Beneol-1,2,3 »4-tetra- _t carboxylic acid dianhydride, PyraBin-2,3,5,6- tetracarbonic anhydride, thiophene-2 _f 3f4 ₉ 5-tetxaoaxbon8a; uxe-dianhydxid ^ 3,4,3 ', 4'-benaophenon-tetraoarboxylic acid dianhydxide, 2,2-bee (3,4-dicarboxyphenyl) -hexafluoropropane- dianhydride and similar dianhydrides with dex formula

O? 3 O

R ₂ -CR ₃

in which each pair of carbonyl groups each anhydride moiety B. directly to adjacent carbon atoms each aromatic

Restee is bonded, and in which R _{2 is} fluorine and E, fluorine or chlorine (hex position takes place according to the above-mentioned US patent applications).

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The sieving of one or more diamines or dianhjdride which do not belong to the disclosed, for example of aliphatic diamines or aliphatic dianhydrides, or, Multiple Aromatic Reactants All Htakiioiate participants in the process can contain one or more desired Impair the properties of the polymeric products. Jedooh the inclusion of such materials can be to such an extent that

that they received the reaction participants with the listed * The desired results essentially do not adversely affect the formation of the corresponding copolymers in brief to be pulled·

As a solvent for the synthesis of the polyamide acid masses by polymerization in solution in the preferred method the organic ones are suitable for the production of the polyimides Solvents whose functional groups do not combine with any of the reactants (the diamines or dianhydrides) react to a noticeable degree. Except for the bigenso adherence to be inert to the system and preferably a solvent for the polyamic acid, the organic solvent must have the property of being a solvent for at least one of the reactants and preferably for both reactants * In other words the organic solvent is an organic liquid that neither of the reactants and no

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HornQIogeβ same is the tin solvent for at least forms a reactant and the. functional · has groups »where the functional groups do not represent · monofunctional primary and secondary amino groups and not from the monofunctional dicarboxyl anhydro groups · Appropriate solvents for the process According to the invention, the normally liquid, organic solvents are of the !!, N-dialkylcarboxylamide class. Preferred solvents are the low molecular weight members of this class, in particular H, N-dimethylformamide and H, H-diraethylaoetamide. They are easily shaped by the Formed from polyamic acid and / or the polyamic acid remove by evaporation, displacement or diffusion. Other typical compounds in this valuable class of solvents are », N-diethylformamide, N, N-diethy! acetamide, H, H-dimethylmethoxyd-acetamide, N-methyl-oaprolaotam, etc. Other solvents which are used in the process according to the invention can find are dimethyl sulfoxide, N-methyl-2-pyrrolidone, Tetramethylene urea, pyridine, dimethyl sulfone, hexamethyl phosphoramide, tetramethylene sulfone, formamide, N-MathyIformamid, Butyrolactone and H-Aoetyl-2-pyrrolidon ^ The Solvents can be used alone, in solvent combinations or in combinations with poor solvents such as benzene, Benzonitrile, dioxane, xylene, toluene and cyolohexane can be used.

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The following examples serve to provide a global explanation and a better understanding of the invention. These examples explain special embodiments of the invention without however, to mark the same exhaustively.

example 1

Pyromellitic dianhydride is added at room temperature with movement of an equimolar amount of 4,4 '- (hexafluoroisopropylidene) dianiline or 2,2-ble- (4-aminophenyl) hexafluoropropane, which in about 10 parts by weight of 11,1-dimethylaoetamide is resolved. Baohdea one up to an internal viscosity of 0.6 (determined at 0.5? C in H, H-Dimeth ^ laoetamid) polymerized has, Ban cools the solution and adds a disturbance Excess (based on the number of free carboxyl groups) Add acidic anhydride, using O-Piodine as a conversion catalyst. The UfceetBungegemlsoh is poured on an old steam-heated plate. The chemical conversion into the polyimide film and the removal of solvent, excess conversion agents and the resulting lifting products take place after about two hours of heating at 270 to 300 ° 0 ended. The polyaldfoll obtained is clear, tough and very faintly colored.

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Be i β pie 1 e 2 to 6

Its entepreohende polyimide film is obtained by the The procedure of Example 1 is repeated with the modification that the pyromellitic acid dianhydride is used in each case replaced one of the following diarihydrides:

2 _v 2-Bie- (3,4-dicarboxyphenyl) -propane-dianhydride Ble- (3f4 ~ dicarboxyphenyl) -methane-dianhydride Ble- (3,4-diearboxyphenyl) -eulfon-dianhydride Bie- (3,4-dioarboxyphenyl) -ether-dianhydride and 3,4,3 ·, 4 · -ben-bophenone-tetraoarboxylic acid-dianhydride

In all five cases one does not get the casting through casting modified polyamide acid β solution and β heating for several hours to about 300 ° C pollen of the same quality as the dee examples 1. '

Examples 7 to 9

Haoh the procedure of the example 1 are entepreohtnde High quality polyimide films made by .2,2-Bie- (4-aoinophenyl) -hexafluoropropane duroh one at a time of the following diamines are ereetati

4.4 ^f - (Hexafluorieopropyliden) -bie- (2-methylaniline) 4,4 '- (Chlorpentafluorisopropyliden) -dianilin and 4,4' - (1,3-Dichlortetrafluorisopropyliden) -dianilin.

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Example 10

2.18 g (0.01 mol) of pyromellitic acid dianhydride are added in portions to a stirred solution of 3.34 g (0.01 mol) of 2 | 2-BL8- (4-aminophenyl) -1 in a nitrogen atmosphere at about room temperature , 1,1,3,3 »3-hexafluoropropane or 4,4 '- (hexafluoroisopropylidene) dianiline in 35 ml of anhydrous pyridine. Another 50 ml of anhydrous pyridine is added after the anhydride addition has ended. The somewhat viscous solution is then heated quickly to 125 ° C. and kept at this temperature for 15 minutes. After cooling, the mixture is filtered to be formed, fine, yellow precipitate off, washed thoroughly with acetone and dried two stun the vacuum oven at 60 ° C. That powder then heated for 15 hours in a nitrogen atmosphere at 300 ° G ₀ A portion dies3s Pulvera is converted into a cylindrical shape with a diameter of 3.18 cm and subjecting it to a pressure of 1406 kg / cm ² at about 385 ° C. The StUoI obtained: is atark and tough, showing that as "powder eiiiaii homogeneous piece coalesced iat and that Ver ~ arbeitiing of useful mechanical goods under conditions gleiuhen possible.

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Example 11

10Og (0.275 Hol) hexafluorieopropylidenebi- (o-xylene) and 720 g (4 mol) of 35 # strength nitric acid are heated together two Hours in an autoclave at 160 ° C. The precipitated Bis (phthalic acid) is separated off by filtration. It weighs 111.5 g and melts at about 223 ° C after melting it solidifies when it transforms into the dianhydride »which melts again at 243» 5 to 247.5 ° C. The hate of tetra-acid can be converted by heating for 16 to 18 hours in one Vacuum oven at 160 to 170 ° C in 2,2-bis- (3,4-dicarboxyphenyl) -hexafluoropropane dianhydride around. After recrystallization from a mixture of 700 ml of glacial acetic acid and 150 ml of acetic anhydride the dianhydride melts at 252 to 253 ° C.

0.001 mol (0.4442 g) of this dianhydride and 0.001 mol (0.3343 g) bis- (4-arainophenyl) 4iexafluoropropane are stirred together in 7 ml of dioxane for about 18 hours at room temperature. A sample diluted with N, N-dimethylacetaraid to O ₉ 5 $> pesticides shows an internal viscosity of 0.52 at 30 ° C.

To the bulk of the polyamic acid solution was added 0 ₉ 8 ml Ssöigsäureanhydrid and 0.08 ml of beta-picoline "After 15 minutes stirring without cooling, poured into the mixture onto a glass plate. The plate on which the gel film is located is heated in an oven for 12 hours at 120.degree. C. and then for two hours at 250.degree

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> lei clear and colorless. It's in chloroform, benzene, dioxane and in AoetonlösHöh. Your freezing temperature is included about 340 ° C. It is infusible up to 400 ° C, the thermal breakdown in the air begins at about 479 ° C A solution of this polyimide in Aoeton is used to coat a film made from the polypyromellitimide from bis (4-aninophenyl) ether.

The polyimides obtained according to the invention are used by many Applications used in a variety of spatial forms. The most significant of these forms include foils and Threads or fibers. The valuable combination more desirable the physical and chemical properties that this polymer possesses is unique. Foils and threads from this Polymers don't just have excellent physical properties Properties and appearance (eohwaohe coloration) at room temperature, but also retain their strength and their excellent response to stress in use at elevated levels Temperatures for long periods of time at · Sin such behavior leads to a high technical value for diverse End purposes. The polyide polymers produced according to the invention combine excellent resistance to corrosive atmospheres with exceptional resistance against degradation due to the action of high-energy particles and gamma rays. Because of the unusual and surprising

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tJi367-R / 1433

Lbaliohkeit daa Polymer-Voxliuftre at dtf betorauftan ^ Ott- V β division, can aan dltttn Petoat? -Torilufat ntohMrkfc * llehtn Working methods au gefpnateo ι webUven, like foils tend ftWB building. raatrn process and invented in aftu In daa & | 0 £ vaäte

■ ■ · ■ ■ ■ »· ■

and convert manufactured polylaid polymers.

Title dieaar Polyimide trwtlthtn with sufficiently low ftaperaturen, eo daee ele ala Utbatoffe or ala atlbatklebtndt Structure bxauohbar aind. Aueetrftea can aan alt ala Polfialdt ▼ trforaen. also eiad tinlft tone dltttn folylaidta äo löa-

■ ■ ''. '■. ■ »■ Iioh, daaa aan alt ala transferrable · or aua foratn atta XttfaungtB

Can turn

great aaa dea invention-based polymettn laeeen alth use everywhere there, 4w «has used before folitn. You can find great old Torteil at tlntr wide Titlfalt ▼ on llahttll-, Ttrpatkunga- BBd lttadtlttBfaarbet% tB TtMtBfBBg. One can further daa ftlymere and filaMldtndtn Polyaereo ale in verschiedeaen foratB ftrketoff for dlt Inatadeokenrerkleldung of fcraftfahratijin and flogaeugea for Zltrbtaata and SlerbesohlHg "FttF hoohttnpertturfaata tlektriao] eolation! TUEX, Botor-sohlltaattakleidungen and Httar-faaaeB-laolation, Fux Tranaforaatortn, tlix Capacitors, filt coils and cables (fora-wound coils! Eolation fttr motors), aur packaging of products that are in the Paokung

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BATH ORIGINAL

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4th

high temperature or energierelohti radiation auagttttit "Should be grounded for corrosive drilled holes, for lohraue cladding and pipes, for containers and container messages and for lamination of wood and composite materials,"

. ■ ■ '' ■ ·:. / 'ftf'' ¹

whereby the pollen is bound to other foils will. That can be laminated «at Bit Epoxjhara-Kltbetoffeii reach. -

♦ ■.>

The foil can also be used as a base for printed storage. Electrical circuits can be produced by covering the polyimide foil with a thin copper or aluminum layer, either by overlooking the metal with the polyamic acid and converting it into polyamide, or by coating a polyimide foil or by evaporating the metal onto the foil in a vacuum . One covers the Sohaltaohema with a protective upper suction; the metal lying on the outside continues to etch and waxes aneohlieeeend to stop the etching. ι

The foil can also be used for all outer layers of flat wire or cables, in which flaoh wires or metal strips are laminated between the ends of polyimide foils. The laminated structures can be made aneohlieeeend au ·, - i: t .: position of flat wire strip length

- 25 -BAD ORIGINAL 909Ö81 / U98

«Earth, each isolated by the fact that they are connected to each other two polylmidsohiohten is embedded, with the exception of dlt bands. Oil wrappings can be versatile, i. H. alternating layers of solid and metal a. Alternatively know the wire as described in the examples must be oversized, uv have a polyimide coating. The tibersogen wire can then be superposed with another polymer, for example with silicones, polyamides, polyesters, Tetrafluoroethylene and its copolymers with hexafluoropropylene, polyvinyl acetals, for example polyvinyl butyral and epoxy resins »

In thread or Paserforro sioh offer the invention manufactured polymers for high temperature resistant electrical Insulation, protective clothing and curtains, piltration media, for diohtung and storage materials, brake linings and clutch linings.

In summary, it shows that the polymer can be used for a variety of purposes, for example as a surface coating for the interior of ovens, as a lining for dryers, as a silencer cover, as a lining for high-temperature manufacturing equipment, as a lining for hot water heaters, as a splitter Coating in the form of very thin films, for glass that is exposed to high temperatures (lamps with high wattage, Bratschüaaelr »made of 'Pyrex etc.}»

" ²⁶ - 90S881 / U38 BAD ORIGINAL

1-W7-B / 1455

tit | i »t * tt *» # ratarittt «r ettlffUe ait gtrlngtx Rtltmng, • I · ria ^ MMBiMBMBdta AAttflohMltttl, la 8tl> tl0Btnitn _f dlt du ob Blntrbalttojl« attaltdUoh §% tttadtU tob Bttaltttr? # 0 odti ltltoadtt OteitiUgtB dtt ^e ahtatltt «" r-ffpt htx _t ittttlU ajatdtB, la flUal «ni · dlt fttx Bo6nttnpt * atur» f0vdtx-

▼ tnMBiti vtttea, alt AuakltlduB «for faxing Awfnafa won eonatlata, ala Uattzlaet for

koaltaaltrtadt, Ttxaaltala » aolmaoh fttfixM fulvtr uad la tlalgtn Pillta ala

- 27 -

BATHROOM OFMQINAL 909881 / U98

Claims (1)

F-1367-B / H33 Claims 1. Linear polyimide, containing essentially the repeating units Il I-R «- - it O wherein R is a tetravalent aromatic group in which the four carbonyl groups directly connected to different carbon atoms of at least one of the ring, R Resteβ are bonded, and where R _{1 is} a divalent aromatic radical of the formula represents in which mean. Fluorine and H, fluorine or chlorine - 28 - 909881 / U98 BAD ORIGINAL F-1367-R / 1433 ?. Linear polyimide according to claim 1, characterized in that the radical R represents the aromatic radical of pyromellitic acid dianhydride, 2,3 _f 6,7-naphthalene-tetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenyl-tetraarboxylic acid -dianhydride, 1,2,5,6-naphthalene-tetraoarboxylic acid dianhydride, 2,2 ', 3,3'-diphenyl-tetraoarboxylic acid dianhydride, 2,2-BiB- (3,4-dicarboxyphenyl) propane dianhydride, BLe- (3 »4-dioarboxyphenyl) methane dianhydride, Me- (3,4-dioarboxyphenyl) sulfonic dianhydride, 3» 4 _t 9,10-perylene-tetraarboxylic acid dianhydride, bis- (3,4-dioarboxyphenyl ) ether dianhydride, 3 _t 4,3 ', 4 ^f -Benzophenon-tetraoarboxylic acid-dlanhydride and 2,2-bis- (3,4-dioarboxyphenyl) -hexafluoropxopane dianhydride. 3. Linear polyimide naoh Claim 1, characterized in that the radical R _{1 represents} the aromatic radical from 2,2-bis- (4-aminophenyl) -hexafluoropropane , 4,4 '- (hexafluoroisopropylidene) -bie- (2-methylaniline), 4 _t 4 "- (Ohlorpentafluorisoprop, v: 3.iden) -dianiline or 4, 4 '- (1,3-Diohlortetrafluoroisopropylidene) dianiline. 4. Linear polyimide naoh claim 1 in the form of a self-supporting film. 5. Linear polyimide according to Claim 1, in the form of a powder. 58 ^ / 14 9 8 BAD ORtGlNAk so P-1367-R / 1433 6. Linear polyamic acid consisting essentially of the recurring units HOOO J300H NC TJ-NR ₁ - - I It Il I ' , .HO 0 H in which B denotes a tetravalent aromatic radical in which the four carbonyl groups are bonded directly to different carbon atoms of at least one ring of the radical R, and in which R _{1 is} a divalent aromatic radical of the formula means in which R _{2 is} fluorine and R »is fluorine or chlorine. 7 · Linear polyamic acid according to claim 6, characterized in that the radical R represents the aromatic radical from pyromellitic acid dianhydride, 2,3,6,7-naphthalene-tetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenyl-tetraocarbon " -30- 909881 / U98 BAD ORiÖINAl Acid dianhydride, 1,2,5,6-naphthalene-tetracerbonic dianhydride, 2,2 ^^ '- Diphenyl-tetraoarboxylic acid dianhydride, 2,2-Bie- (3, 4-dioarboxyphenyl) -propane-dianlihydride, Bie- (3,4-dicarboxyphenyl) -nethan ~ dianliydrid, bending (J, 4-d ioarboxyphenyl) -eulfon dianhydride, 3,4,9 '10 Perylentetraoarbonaaure dianhydride _t Bl8- (3,4-dicarboxyphenyl) -Ktlier dianhydride, 3,4,3 * »4 '-benuophenone-tetracarl> oneäuredianliydrid or 2,2-Bie- (3,4-dicarboxyplienyl) -hexafluoropropane dianhydrido 8. Linear poly aiii d acid similar to Anepxuoh 6, which means that the Heat R _{1 represents} an aromatic beat as well as 2,2-Bie- (4-aninophenyl) -hexafluoropropane, 4,4 • - (Hexafluorieopropylidene) - biB- (2-methylaniline), 4 »4 ^f - (CblorpentafluoriBOpropyliden) -dianiline or 4,4 · - (1,3-Diohlortetrafluoriaopropyliden) -dianiline. 9 · Mouldable dimensions, containing in general the polyamide grade according to requirement 6 in a solvent for this · 10. Techniques for producing malleable polymeric hairs, characterized in that one nindeatene a Diainin the structural formula in which R _{1 is} a bivalent aromatic beat of Porael 909881 / U - 31 ORJGlNAk F-1367-B / 1433 ? 3 R "-c-: 2-0-K, B ₃ represents, in which B _{2 is} fluorine and R _{5 is} chlorine or fluorine, with at least one aromatic Tetraöarbönsäuxe-dianhydxid, in which the four Oar bony lgruppen of the dianhydride bonded directly to an aromatic ring dee dianhydridβ, in an organic solvent that at least one · Solvent for Biaain, the solvent being inert towards the Syβtee, the temperature being kept sufficiently below 175 ° O during the heattion to form a polymeric mass which is a polyamic acid of the formula Il H-O-O 0-0-H , Vh CHH ₁ H
i contains, in which the arrow means laomerism, H represents an aromatic tetravalent organic radical, H ₁ breaks the meaning given above and η is an integer which is high enough to give a film-forming polymer. 90988 ^ 1498 BATH ORIGINAL 1520615 S3 P-1-367-S / 1433 11 _O A process for preparing einee molded body, characterized in that the "converting the composition produced according to claim 10 in a molded body and heating the structure at a temperature of at least 50 ° C for sufficient time to the polyamic acid of the structure in polyimide convert. 12. The method according to claim 11, characterized in that a self-supporting film is produced as a shaped structure 13. A method for producing a molded structure, characterized in that the polymeric composition produced according to claim 10 is converted into a molded structure and this structure is treated with the anhydride of a monocarboxylic acid in order to convert the polyamic acid of the structure into polyimide _o Ho method naoh claim 13 * characterized in that a self-supporting film is produced as a shaped structure. 909881/1498 ORIGINAL BATHROOM