DE1595081A1 - Adhesive mixture - Google Patents

Description

DR.-ING. WALTER ABITZ DR. DIETER F.'MOR F DR. HANS-A. BROWN

Patent attorneys

Munich,

Postal address 8 München 86, PO Box 860109

Pienzenauerstraße 28 Tel. 483225 and 486415 Telegrams: Chemindus Munich

September 29, 1969 FED-I204 (P 35 4o8)

P 15 95 08I. 9-44 New documents

E. I. IU PONT DE NEMORS AND COMPANY 10th and Market Streets, Wilmington ", Del. 19898, V.St.A,

Adhesive mixture

For the invention, polymers are used which through the recurring structural units:

009813/1654

BAD OBSGiMAL

1204

H ₂ N-

R ₃ -:

η η

AA

■ Η H ₁ N-

η η O O

O 0 H η C G

^4th Α

η
O

denote in which R ₁ , H ₂ , H ₅ , H ₄ and R _{5 are} identical or different, with the exceptions given below; the best can be aliphatic, aromatic, carbocyclic or heterocyclic radicals, or they can contain one or more such radicals. At least one of the radicals R ₁ , R ₂ , R ,, R, and Rc must contain an aromatic keto carbon atom (-C-) which is directly connected to a = N * -Rg-Hs = ~ group, whereby the group ο ^ -Ηβ ^ = ^{5 is} formed »
The carbon atom in the latter group connects an aromatic ring directly to another carbon atom »The unsaturated nitrogen bonds indicated in the latter group are with an adjacent unit in
connected to the polymer, for example by binding to
another aromatic keto carbon atom in another

009813/1654

595081

FFE-1204

Ε, ^ κ-Resir or did a carbonyl couple eat one? neighboring unit of the polymer with the formation of: 'a Bstdringes _e (corresponding to the pairs % - ₉ Z and?. _e 8 · Rg'Ist'gleich or Yer-

divorced from Hg R * mud, H ₁ -. . -

Ib des * - © Mg®ε St ^ xfcturfpxtsel slad the beds Hj and E «orga-'iaie" ehe "Äeete ρ wel; il _: ^ S @ OsrlioiE ^ IgrappeR 1 ₉ 2 ^ 5 _S 45 S» 6 tuad 1 _? S direct aa-'beaftefel> Bfft® E® & l «EBt © ffatome are bound«

are- <l £ e Reete S ^ ₉ Hg ₉ H ^ ₈ E ^ uni Ες aromatida these "eefej? -nöeliejpweloÄende Solyaerisate lieia-t ftii * '© iB @ tt -Rsebaaafe * -nearby that the on».

the one in - Slesiaie? !! - standing Blieitee te der WqtwsX iegelmäseig © i @ r - can be irregular, what the Blgeaschsft ^ si; the fisalctionstsilneluBer depended on the _: production''d ^; ee-Polymerisates aet "Bie Btzeich- - Z izMi j © iftcl gssse sequins which reflect the / number of the genes: dett -elBagiltlBBBtertett S &nnelt" ts. The values-magea ^ © n "d @ 3? -Amount of the inventions implemented

from _c the .den structural units inneraianeni correspond «.- Ssr value x. lot geifSbJtIi (At "gross; -y is usually min- -feann than theoretically O be · .'Tom.-practical

χ ala auehi! .y- _: tt! »ldLo.berweise.-grosss-

5 - 'bAD ORIGINAL

β ©, whole numbers. 3) recommend © lg © iamfasst @ ia® simple implementation only swei Sealrtioneteilnettoer »for example Sas Dianhydrid äer 5.3% ^^ '' - BeBEopfeenoatetracarbeasaiir © and 4» 4 ^f -0sydi-

aniline. . "." "·..

uad "Eg have the formula

etc.

Bie @ingt! SlaiBii @ rt © Ölngeklasii @ rt © lla in this case moderately easy

ö 22 Mm®, i

© q © 1s like ii ©

y ₉ if-enough Biaaia the folyisid di «following® yerhftltsiis

t $

00981371654

H ₂ H - -

⁰ X (2)

in which the unsaturated bonds of the nitrogen atoms serve to crosslink the structure shown with another unit of the polymer by becoming with implement or link one or more Carbony! groups »

It is noted that in formula (Z-) 'every linear' recurring unit (within the brackets) is replaced by the

009 813/1654

-5 -

BATHROOM ORIGlNAt

PPD-1204

is networked. Normally, some of these embeddings are not crosslinked, but instead simply contain an "= 0" group instead of the crosslinking group. The amount of diamine in the reaction mixture naturally determines the degree of crosslinking, and it is important that a molar excess of at least 15 ° diamine , based on the dianhyarides used, is present in the reaction mixture »The diamine is preferably present in a 20 to 50 molar excess, and there is no advantage if the diamine excess is greater than 100 mol.

The term "aromatic keto carbon atom" used here refers to a keto carbon atom (-C-) ₉ which is bonded directly to an aromatic carbon atom and to another carbon atom, as is the case with benzophenone and acetophenone. The carbon atoms of the carbonyl groups in the heterocyclic imide or anhydride rings of the above formulas are not aromatic keto carbon atoms. The terms "aromatic ring" and ^B aromatic radical "refer to rings and radicals that are aromatically unsaturated.

009813/1654 " ⁶ "

«R / r \ m, ·

^ .. _v ; ¹ IJi y; } j

add “Eestes

^ 1

009813/1654

BAD ORiGJNAL

FPD-1204

In the above radicals, Y means the radical “0,“ N-Rg-N ”or“ N-Rg-NHg? Rg denotes alkylene, arylene, a heterocyclic or carbocyclic groupei R ^ is preferably alkylene or arylene; R _Q is an alkyl radical and Rn can be any non-harmful, divalent radical, for example alkylene, arylene,

O alkyl alkyl alkyl

- 0 -, - S - _f - S -, - Si -, - O - Si «0 _Γ , - 0 - P * 0 - and O alkyl alkyl 8

Alkyl
P -

The alkyl groups listed in the latter residues can be replaced by aryl, for example phenyl. As is expressed by the above formulas, the la J> eri positions remaining carbon atoms of terbonds like naphthalene and aattoacene Im Balnea, neighboring the invention Carbon atom®

The by R ^ ₃ E ^ ₅ E ^ mai Ig äarg®at®llt © ia Beste ® ± M

i © lestSjj # i © ziw Bilimag © iss © Bisii

SS13 / 1654

PFD-1204

are capable and can be aliphatic, aromatic, carbocyclic or heterocyclic. Typical such radicals are two valent radicals which _{correspond to the radicals R 1} and R ₂ mentioned above} however, preferred reets are illustrated by the following formulas:

-R ₇ -

and rq the

In the above radicals, the radicals Y _{0 have the} same meaning as above; the designation H within a ring means that the ring is saturated.

As used herein, the terms "alkyl" and "alkylene" are

BAD ORiGiNAL

009813/1654

-12C4

preferably the best with fewer than 7 carbon atoms, but larger groups can be used if the associated difficulty is not decisive »Accordingly, phenyl or * phenylene are preferred as aryl and arylene groups, but larger groups can also be used * Also alkyl-substituted aryl and arylene groups and ary-leubstituierte alkyl and alkylene groups may be used "Efeesso, each of the radicals R j η various non-harmful Sufeetituenten include, for example, fluoride, chloride, bromide, Nu ₂₉ Gooh, COOZ ₉ wherein Z is alkyl, aryl, alkaryl, aralkyl, etc. ₀ ,

The polyimides according to the invention are crosslinked and are made from polyamic acids, which in turn are made by reaction of a diamine with a dianhydride of a tetracarboxylic acid. The dianhydride has the structural formula

0 0

ti

AA

Vv

0 0
in which A represents the radicals R ₁ or R ₂ defined above, where Y is equal to 0, ie _n in the radicals B _f and

009813/16 54 " ₁₀

FFD-1204

are instead-of-any amino-substituted keto carbon atoms (-C-) carboxyl groups (-CK The diamine has ate formula HgN-M-IiH ₂₉ in which M represents a divalent organic -best like the radicals R3..5 defined above, where! is equal to = 0, ie in the radicals R, _ ■ "there are (-C-) carbonyl groups (-C-) instead of any amine-substituted keto carbon atoms. At least one of the radicals A or K contains one aromatic keto group, pas diamine is present in the mixture in an at least 15 molar excess, based on the dianhydride present.

This reaction is carried out in an organic solvent, that for at least one of the reactants Is solvent, preferably for both; the solvent is inert to the reactants and is preferred anhydrous. The reaction is carried out by calling the reactants "If heated to a temperature below 175 ° C." The reaction temperature and reaction time change with the combinations used in each case of the reaction part "aehiner and the solvent used in each case,"

009813/1654. "_ Bad or," Äl

FFD-1204

Reduction is exothermic and therefore, it selects the Umsetzungetemperatur so that it is sufficiently tractable to give a polymeric composition of at least 50 percent by _e # of structural, tureinheiten possess the specified polyamic acid structure, that is less than 50 $ of the Units have been converted into the polyimide. Although the reaction time can be as short as a minute, the reaction conditions are generally chosen so that a polymeric composition with the desired. Properties is created; this usually requires a reaction time in the range of about 30 to about 500 minutes. To achieve maximum internal viscosity, it is usually necessary to operate at a reaction temperature below 60 ° C, preferably not above about 50 ° C.

The proportion of the organic solvent need only be sufficient to dissolve a reactant, preferably the diamine, sufficient to stimulate the reaction of the diamine and the dianhydride. When shaping the polyamic acid masses to form shaped structures, the best results are obtained when the solvent component forms at least 40% of the finished polymer solution, ie the solution can contain 0.05 to 60% of the polymer component. For coating purposes, the content is polyamic acid

009813/1654

. _12th

■ "FHM204

usually in the range of 5 to 40%. If desired, the polyamic acid can be isolated in a stable form by precipitating it from the polymer solution by adding a solvent in which the polyamic acids do not dissolve, for example cyclohexanone, dioxane or benzenes

Solvents that can be used for the synthesis of the polyamic acid masses by solution polymerization are essentially inert, organic liquids that do not belong to the polymer-forming reactants or their homologues. Primary or secondary amino groups and no monofunctional dicarboxylic acid anhydride groups are - The solvent is preferably characterized in that it is a solvent for both reactants and is preferably also a solvent for the polyamic acid reaction product. A particularly useful Klas & e of solvents are the normally liquid N, N-dialkylcarboxylamides, one of which will prefer lower molecular weight, ζ.B "$, N-Dimethy! Formamide and N, N-dimethylacetamide. Other solvents which can be used according to the invention are: NjU-diethylformamide.

009813/1654 ORIGINAL BATHROOM

■ «13 -

PFD-1204

N, N-diethy! Acetamide, Ν, Ν-dimethylmethoxyaeetamiä, N-methyleaprolactam, dimethyl sulfoxide, N-methyl-2-pyrrolidone, 3? © tra- !! »ethylene urea, pyridine, dimethyl sulfone, hexamethylphosphoramide, tetramethylene sulfone, formamide, N- Methylformamide, butyrolactone and H-Acety1-2-pyrrolidone, ketones, for example _a methyl ethyl ketone, nitroalkanes, ss.B. Nitroethane and kitropropane. The solvents can be used alone, in solvent combinations or in conjunction with poorer solvents or non-solvents, for example benzene, benzonitrile, dioxane, xylene, toluene and cyclohexane.

The tetracarboxylic dianliydrides, which expediently as a starting material for the production of the invention Polyimides used have the general formula

0 0

It Il

(5)

in which A has the above meaning. Some dianhydrides suitable according to the invention include: 3.3% 4 _t 4'-Senso-

0 0 9 81 37 1 6 5 4 ^B ^ o * iqinai *

- 14 -

IS

FPD-1204

phenon-tetracarbonic acid _{dianhydride f} pyromellitic acid dianhydride, 3,3 ', 4,4 * -diphenyltetfacarfeoiiBäurediaahyäria, 1,2,5,6-naphthalenetetracarbonic acid dianhyärid, 2,2 ·, 3,3'-diphenyltetracarboxylic acid dieahydride, 4,4 * -leopropylidic acid dieahydride, 4,4 * -leopropylidianhydride ? MifQ! Nyl-diphfhalsäiir anhydrid, 3,4t9,10- * peryleate tetraoarboxylic acid dianhydride, 4,4'-oxide! Phthalic anhydride, 1,2,4,5-naphthalenetetracarbonic acid ^{dianhydride, 1} »41-5, e-naphthalene tetracarboxylic acid dianhydride , 7 ~ naphthalenetetraearboxylic acid dianhydride, 3,3'-iBopropylidene diphthalic anhydride, 3,3'-ethylidene-diphthalic anhydride, 4,4 ^l -ethylidene-diphthalic anhydride, 3,3 ¹ -methylene-diphthalic anhydride, 4,4'-methylene-diphthalic anhydride, lophanoic dianhydride, 2,3,5,6-pyrazine tetracarboxylic acid dianhydride, 2,3,4,5-thiophenedetracarboxylic dianhydride, 4,4'-biphthalic anhydride, ^^ '- biphthalic anhydride, 2,3,4,5-pyrrolidone tetracarboxylic dianhydride, 1,4-Dimethyl-7,8-diphenylbicyclo- (2,2,2) -oct-7-en-2,3,5,6-tetracarbonic acid dianhy drid, 1,4,7,8-tetrachlorobicyclo- (2,2,2) -oct-7-ea-2,39 5,6-tetracarboxylic acid dianhydride, 7,8-diphenylbicyclo - = (2,2,2) - oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 1,8 ~ dimethyldicyolo- »(2 _f 2,2) -oct-7-en-2,3,5,6-tetracarboxylic acid dianhydride, 1,2 _f 3,4-cyclopentanetetracarboxylic acid dianhydride c

0 0981 3/165 A © AD

PfD-1204

Other useful dianhydrides include, in addition to the 3.3 ' _t 4 _t 4 ^> -benzophenonetetracarboxylic acid dianhydride and its positional isomers, the following:

Il

C = O

wherein Ro and E ₈ are as defined above, and the positional isomers of these compounds as well as other obvious equivalents thereof, for example those which do not contain harmful substituents.

- 16 -

+49 9 813/1654

1595Q81

FFD-1204 »

The organic diamines that are used as the starting material for Production of the products according to the invention used the general structural formula

· »M -

in which M has the meaning given above. Particularly preferred diamines include: 4,4'-leopropylidene-dianiline, 4.4 ^l »methylene-aianiline _t benzidine, 3,3 * -dihlorobenzidine, 4,4'-ϊ1ι1οαΐ8ηϊϋη, 3.5 ^f -sulfonyldianiline , 4,4 ¹ ^ SuIfonyΙα! Aniline, 4,4 * -Qxydianiline _t 1,5-naphthalenediamine, 4,4 * - (liäthylBilylen) -dianiline, 4,4 '- (diphenylsilylen) -dianiline, 4, 4 - (Ethylphoephinyliden) -dianiline, 4,4 '- (Fhenylphosphinyliden) -dianiline, 4,4 * - (H-methylamine) -dianiline, 4,4' - (! T-phenylamine) -dianiline and mixtures thereof, m-phenylenediamine, p-phenylenediamine, 2,6-Diaminopyrid in, 4,4'-methylenedicyclohexylamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, N.onamethylendiamin, decamethylene and 1 ₉ 4 ~ Cyclohexandiamino

The positional isomers of these compounds, for example the corresponding 2,2'-diamino, 3,3'-diamino and 3,4'-diamino compounds can also be used as starting material »

0 0 9 81 _{3/1 6 5 A ^ 17} , BAD

FFD-1204

In a similar way one can use diamines which have the following formulas:

HH ₂ H ₂ H

These can carry non-harmful substituents, for example halogen, hydrocarbon, alkoxy and nitrile groups.

When carrying out the process according to the invention, it is important that one of the dianhydrides or one of the diamines or both contain an aromatic keto group, which means a keto group (-C-) which, on the one hand, is directly attached to an aromatic ring carbon atom and, on the other hand, to an an-

009 813/1654

- 18 -

PHM2Q4

The carbon atom can be bound ₍ as in the case of bensophenone-tetracarbonic acid dianhydride or acetophenone. In addition, the dianhydride and / or diamine containing the aromatic keto group and / or diamine in the reaction should be in a range of at least about 30 mol9 (of the total of 40 common dianhydrides present) Up to 100% of all dianhydrides and / or diamines which contain the aromatic ketone groups are present if polymers are desired which have the very useful properties, in a reaction agemiaoh in which both the dianhydride and the diamine contain aromatic keto groups If the total amount of the components which contain the groups is present in an amount of at least 30 mol, based on all dianhydrides present, so that at least 20 of the residues _{1-5 are} cross-linked.

The polyamic acid iJaaaen, which are herge-βbe part according to the invention, are in a two-dimensional form for Applied as an adhesive or wire covering or for manufacture of molded articles for which high softening points, rigidity and high dielectric properties are required. Whatever the application or whatever geometric shape is used, the polyamic acid paste becomes

0 09 * 13/1 «S4 ^; _ ₁₉ _ sad

FFD-1204

In two ways converted into the polyimides according to the invention by turning them for about 200 to 10 minutes at about 50 burns up to 200 ° C. To receive products of higher value, after shaping, the solution is heated for about 120 to 30 minutes at about 80 to 150 ° C. or until essentially all of the solvent has been removed and the mixture solidifies and solidifies. This "pre-burning" helps to one large part of reducing the brittleness and cracking in the final polymer to a minimum, then the temperature is increased from 1000 to 1 min. to about 150 to 500 ° C, preferably about 500 to 2 minutes at 200 to 400 ° C, or until substantially all of the diamine reacted is; the lower temperatures correspond to a longer time.,

It is noted that the polyamic acid compositions according to. the Invention can be modified by adding other monomeric or polymeric materials before or even after shaping in a desired shape before heating. In some cases you can get as much as $ 50 or more modifiers add. Of course, you can also use inert materials, such as pigments, dyes, organic and inorganic Add fillers before or after shaping.

009813/1654 ■ - '20 -

FFIM2Ö4

Adhesive materials based on the polyimides according to the invention are normally used as liquid adhesives, unsupported films or film strips, the latter preferably being on a woven or nonwoven fiberglass carrier *. Suitable types of glass cloth include those commonly referred to as Type 112 or. These fabrics should preferably be heat-cleaned before use or have a methacrylate chromyl chloride finish. After a strip has been impregnated with the liquid adhesive composition, the solvent removal system is pre-cured for about 120 to 30 minutes at 50 to 200 ° C., preferably 60 minutes at 100 ° C., a strip which is easy to handle is obtained and is shelf stable for extended periods of time. If you want a maximum shelf life, the strip can be stored in a cool place (0 to 10 ° C) _n Other carriers that can be used include metal screens, refrasil fabric (fabric made of quartz glass silk), graphite fabric, asbestos fabric, paper, foils and cloth-like fabrics from high-melting synthetic polymers, for example from fully aromatic polyamides, from polytetrafluoroethylene and the like,

Adhesive maasen from the polyimides according to the invention can

0 098 13/16 54 '.-.... 21- - ■ ■ ^ - ■ .-— *

. '- BAD ORIGINAL

one compoundierη with suitable reinforcing fillers, for example aluminum _{dust t} powdered asbestos, aluminum oxide powder, elsen powder, glass flakes, tin dust, zinc dust, zinc tetraoxide and chromium oxide. It can be desirable for special purposes. To use mixtures of polyimides with other resins, for example with phenolic resins, epoxy resins, silicone resins and fabric resins. It is desirable that the resins be compatible with the particular crosslinked polyimides used; but they can also form a chemical bond with the reactive groups of the polyimide. Suitable compatible materials include bisphenol type epoxies such as "Epon 828", "Epon 1007" and other types of epoxies such as the resin having the formula

OCH9.CH-CH «

■ v

OCH ₂ .CH-CH ₂ OCH ₂ .CH-CH ₂

that has an average molecular weight of about 500 and one

009813/1654

FFB-1204 -

Epoj ^ däquival <enir of about 150 has. Other suitable Materials include Biephenol-A, Epoiynovolacke, Polyphenyle ^ oxydo, benzoguanamine-pornaldehyde resins, polyphenylenes, aliphatic polyamides, e.B. Nylon resins, aromatic polyamides, e.g. m-phenylene isophthalamide and terephthalamide, polyester, e.g. hexamethylene-i80phthalBt, cyanurate-containing polyesters, polyvinyl formal, polyacetal and tiutyral resins, coumarone indene resins, polyacrylonitrile and acrylonitrile copolymers.

Ee can also be desirable for special end-use purposes, since aa loan ssu adds heat stabilizers to the glue mix. Beiepiele of such materials are Arsenthioarsenat, copper-8-ohinolinolat, Eieen chelate of 8-ltydroxychinolin _f copper diäthylentriamindibromid, tris (chloroethyl) phosphite, and Phenylphoephinsäure Arsenpentoxyd.

These adhesive mats are used for a variety of Substrates. In general, the metals such as aluminum alloys, stainless steel are more cold rolled Steel, magnesium, titanium, copper, brass, galvanized iron, as well as glass, ceramics, quartz, silicone resins, phenolic resins and polytetrafluoroethylene. You can also use it to glass fabric and laminates of glass fabric, as well as

009813/1654

₂₃

FFB-1204 ■ -._. ·

Tereohiedene organic polymers in the form of shaped articles, e.g., films, filaments or coatings to bond · Examples of such polymers are polyimides, Polyaeideäuren, polyamides, Polybenzimidetoie, Polybenethia-ISQIe ₉ polyoxadiazoles, polyphenylene ether and Folyeater. Dia metals can "ache" surface treatments required and in certain cases primer coatings can be used.

Typical adhesives are

Polyamic acid aluminum dust Arsenthioarsenet DiBethylaoetamid

110 parts 100 parts 20 parts 440

PolyamideSurt Aluminum oxide powder Copper-e ^ quinolinolate

CII)

110 60 parts 1.0 part

00981 3 / 16SA

PKD-1204

Dimethylacetanide xylene

220! File 220! Parts

(III)

Polyamic acid zinc dust ^imi ~ ■ arsenic pentoxide N-methylpyrrolidone xylene

110 parts 100 parts 20! Peile 330 parts 110 parts

These masses are pre-hardened for 60 minutes at 100 ° C. The connection point is then made with the. Adhesive cured for 120 to 30 minutes at 250 to 350 ° C, preferably 60 minutes at 300 ° C. Pressure, from touch up to 176 kg / cm, can be used at this stage * Pure For optimal behavior, post-curing for about 64 hours at 260 ° C is desirable.

If special properties are desired, the polyimides prepared according to the invention can be mixed with other polymers Cover materials, e.g. with epoxy resins, silicone resins, Phenolic resins, polyvinyl formal, -aceta] -. or butyral resins,

BATH ORIGINAL

009813/1654

- 25 -

FFD-1204

with polyurethanes, alkyd resins, polyamide resins, polyester resins, nitrogen resins, e.g. melamine formaldehyde, urea formaldehyde, benzoguanamine formaldehyde, and with polytetrafluoroethylene and copolymers.

The invention is illustrated in more detail by the following examples. Unless otherwise stated, all parts of the information relate indicated on the weight.

Example i

Production of polyamic acid from 3.3 *. 4.fl'-Benzophenontetracarboxylic acid planhydride and 4.4'-OxYdJBnJlJn

A flask is charged with a stirrer and a The reflux condenser is provided with 25 parts of 4,4'-oxydianlin, which is dissolved in 173 parts of N-methylpyrrolidone and 86 parts of N, N-dimethylacetamide. 40.7 parts of 3,3 ', 4,4'-Benzophenontetracarbonsäuredja.nhydrid are added in portions Add stirring. The temperature of the mixture is kept between 20 and 25 ° C. by means of an ice bath. Stirring is stopped continued for 30 minutes to allow the dianhydride to dissolve to complete. The viscosity of the polyamic acid solution

009813/1654

- 26 -

1695081

fiD-1204

2§ ^a * C) bftrMgt 124 F.Di · inner Viecoaität let

1.1 (measured at 0.5 g / 100 al in dimethylaqetamide at 25 ° O ₉ 50 'with relative temperature). The solution is converted to a polyimide and exhibited its idle properties as shown below.

B e 1 ■ _: p 1 tbsp Ija)

tttgaba one 20 "oUtigen tlberaohueseB an 4.4 '-" Oxyd! aniline

IQO parts of the ventilation from example t are diluted to a Feetetoffhalt τοπ 12 Jt by adding τοη 46 parts of toluene. 0.935 parts of 4,4'-oxide / aniline are added to 1Q parts of this solution and the solution is converted into a clear solution in a closed container by moving it on rollers for 2 hours. The polyamic acid solution is converted into a polyimide and evaluated as described below. , ".. ', ..," ... ■. -

Be la ρ 1 el Kb)

Addition of various excesses of 4,4'-oxydianiline

0098 13/1 6S4 sad ^

FPD-1204. ""'

Following the procedure of Example 1 (a), a Range of blends that have a (1) 33, (2) 50, (3) 6? and (4) contain 100 molar excess of oxydianiline, using in each case 10 parts. These solutions are converted into polyimides and used as adhesives assessed as described below.

Example Ue) Addition of a 33 molar excess of 4.4 ^t -methylenedianp.in

100 parts of the solution of Example 1, diluted to a content of 10 Peststoff i "by adding 75 parts toluenes To 100 parts of this solution are 1.25 parts to 4.4 ^f -Methylend! Aniline and converts the mixture by stirring for 30 minutiges in a flask to a clear solution. This solution is converted into a polyimide and assessed as an adhesive as described below »

Example 2

Production of polyamic acid from 3.3 *. 4.4'-Benzophenonetetracarboxylic acid dianhydride and a 50 molar excess of 4.4'-O3cyflianiline

009813/1654 -28- Bad Ori _GiNal

JW3M2O4

A flask equipped with a stirrer and a reflux condenser is charged with 30 parts of 4.4 ^f- oxydianlline which is dissolved in 95 parts of IT methylene pyrrolidone and 47 parts of N, N-dimethyl acetamide. 32.2 parts of 3,3 ', 4,4 ^f -benzophenontetraearboxylic acid dianhydride are slowly added with stirring, and then a mixture of 43 parts of N-methylpyrrolidone and 22 parts of ϊί, Ν-dimethylaeetamld, the mixture is stirred for one hour; the product, a clear red-brown solution, has a viscosity of 1.5 P (Brookfield 25 ° C) / This solution is converted into a polyimide and assessed as an adhesive as described below »

Example 3

Production of polyamic acid from 3.3 *. 4.4 * -Β6ηζορη6ηοη- totra oarboxylic acid dianhydride and 4.4 ^{t -Methylendianilln}

A flask is charged with a stirrer, a Nitrogen inlet tube and a powder belt attached eats, with 198 parts of 4,4 * -methylene dianiline together with 1956 Parts of N, N-dimethyl acetamide (dried over molecular sieves). The mixture is stirred until the 4,4'-methylenedianiline has solved. 328 parts 3,3 ', 4,4' ~ benzophenone tetracarboxylic acid

009813/1654 - ~

FFD-1204

dianhydride is added in portions over a period of 15 minutes while maintaining the temperature of the mixture at 27 ° C. Another 106 parts of N, N-dimethyl acetamide are used to rinse and then add them to the reaction mixture. The mixture is stirred for 2 hours to remove all solid material to dissolve and to make a clear amber solution that has 20 # solids and a viscosity (25 ° C Brookfield) of 53 P. This solution is converted into a polyimide and assessed as an adhesive as shown below,

Example 3 (a)

Use of various excesses of 4 * 4'-methylenedianiline

100 parts of the solution from Example 3 are diluted to one Solids content of 15 # by adding 33 parts of toluene.

Each 10 parts of this solution are used to make a series of mixtures, one of which is) 20, (2) 33, (3) 50, (4) 67 and (5) Contains 100 molar excess of 4,4 * -methylene dianiline, to be prepared according to the method of Example i (a) » These solutions are converted into polyimides and used as

-30-009813 / 16 54

FFD-1204

Adhesives assessed as shown below.

For β ρ i el 4 .

Production of polyamic acid from 3 «3 *» 4.4 ^> -Benzophenon ~ tetraearboneäuredianfaydrid and a 50 molar excess of 4.4 ^t -methyleadianiline

29.7 parts of 4 _{t of} 4'-methylenedianiline are dissolved in 94.95 parts of N-methylpyrroliaeone in a 3-neck round bottom flask equipped with a stirrer, nitrogen inlet tube and reflux condenser. 33.6 parts of 3,3 '^^' - benzophenone tetracarboxylic dianhydride are added with stirring added _f while the temperature of the mixture from ambient temperature to 50 to 55 ° C increased. The mixture is kept at this temperature for 30 minutes. The end product is a clear orange-brown solution with a viscosity of 510 P (Brookfield 25 ° C.) ₀

The orange-brown solution is diluted with 63.9 parts of xylene and 21.3 parts of N-methylpyrrolidone to a pesticide content from 26 jC. Pie viscosity is then 4.5 P.

Copper wire (1.024 naa), which is connected to a commercially available poly-

.009813 / 1654 * 31 - ~~ /

· _SsAD ORIGINAL

JZ

FFD-1204 '

is coated with imide wire enamel, it is formed into a spiral With the help of a 6.35 mm mandrel «, this spiral is cut into 10.2 cm long spirals and preheated them in an oven at 150 ° C for one hour. Then you immerse the spirals into the solution prepared above, soak it in for 5 minutes, slowly pull it out vertically and leave it for 20 minutes drain. Then they are baked at 150 ° C for 1 hour. After removing them from the oven and placing them on the surrounding area, If the temperature has cooled down, the process is repeated, but so that the spiral is immersed in the opposite direction. To the second firing at 150 ° C is followed by a final 16-hour firing Firing at 200 ° C. The average uptake of converted resin (per spiral) is 0.36 g. The spiral one then tests for bond strength according to Dow-Dexter. at This experiment brings the spirals individually in a horizontal position in a special device, which is in the clamping clamps of a tensile strength tester of the type Instron is built in. This keeps them in the form of a simple axis and until a knife edge breaks exposed, moving at a speed of 5.1 mm / min, emotional. The tensile load under which the spiral breaks is recorded. The following results are an average of 10 determinations.

- 32 -009813/1654

FFD-1204

Average bond strength (25 ° C) * 33.43 kg - 1.45 kg Bond strength ■ 93.67 kg / g resin

The solution is converted into a polyimide and as below shown as adhesive "judged.

Example 5

Production of polyamic acid from 4 _f 4 * -methylenediphthalic anhydride and 4 «4 ^? ~ I) iainino "benzophenone

A reaction vessel equipped with a stirrer, thermometer and nitrogen inlet tube is charged with 6.93 parts of 4,4'-diaminobenzophenone together with 84 parts of N, N-dimethyl acetamide. The mixture is stirred until it is removed, the entire Peststoff and are added 10.06 parts of 4,4 ~ ^f -Methylenäi phthalic anhydride. The mixture is then stirred under nitrogen at ambient temperature for one hour? During this time the temperature increases to 25.5 ° C, at most up to 28.5 ° C. The solution has a viscosity of 8.84 P (Brookfield 25 ° O) and an internal viscosity of 0.79 (conc " a 0.5 g / 100 ml in dimethylacetamide at 25 ⁰ O). This solution is converted to a polyimide and shown as below

BATH ORIGINAL 009813/1654 - 53 -

FFD-1204

judged as an adhesive,

Example 5 (a)

Addition of a whey excess of 4,4'-methylenedianiline

0.216 parts of 4,4'-methylenedianiline are added to 10 ropes of the solution from Example 5 and mixed vigorously by moving the container on to Hollen for 2 hours until the sown pesticide is dissolved. This solution is converted to a polyimide and judged to be an adhesive as shown below *

Example 5 (b)

Addition of a 33 molar excess of 4 «4 ^> -diaminobenzo-> phenone

0.234 parts of 4,4'-diaminobenzophenone are added to 10 parts of the Solution of Example 5. This solution is converted into a polyimide and judged as adhesive as shown below.

- 34 -009813/1654

«HM2.04

Bel el le 1 Λ

Production of polyamic acid from 4,4'-methylenediphthalic acid anhydride and 4 «4'-oxide / aniline

A reaction vessel equipped with a stirrer and a nitrogen inlet tube is bombarded with 10 parts of 4,4'-oxide / aniline together with 79 parts of Ν, Ν-dimethylacetamide. The mixture is stirred until all of the solid is dissolved and 15 »4 parts of 4.4 ^l -methylenediphthalic anhydride together with 50 parts of Ν, Ν-dimethylacetamide are added. The mixture is stirred under nitrogen for one hour until all of the solid has dissolved. Me solution has a viscosity of 4.15 P and an internal viscosity of 1.1 (conc. * 0.5 g / 100 ml in Dlmethylacetamld at 25 ° C). This solution is converted to a polyimide and judged to be an adhesive as shown below. -

B ei s ρ i e 1 6 (.a)

Addition of various excesses of 4.4'-0xydianiline 100 part? the solution from Example 6 is diluted by adding it

. 35 _ ORIGINAL BATHROOM

009813 / 1B5.A

FFD-1204

of 10 parts of toluene to a Peatatoffhalt of 15 # ♦ 10 parts each of this solution are used to prepare samples which contain a (1) 20 and (2) 50 molar excess of 4,4'-oxydianiline, according to the method of Example 1 (a) to manufacture. These solutions are converted to polyimides and evaluated as adhesives as shown below.

B e i 8 ρ le I 7

A glass fabric is impregnated (the type is in the table shown) with the solutions of Examples 1, 1 (a), 1 (b), 1 (t>) - 1, 1 (b) ~ 2, 3 (a) -2 and 4 and burn them for 15 minutes 150 ° C. Laminates are made from this fabric and tests them for flexural strength at different temperatures. The results are summarized in the following table:

009813/16 54

Resin glass number Min./°O/kg/om ² Flexural strength holds _ weave of the lamination conditions- kg / cm ² x 1O _n

Layers around 25 ° C 288 ° C 371 C

3O, 5 ¹ (A) 2 49.2 ¹ (A) 6th 36.0 ¹ (B) 14th 30.0 ¹ (C) 14th 37.8 ² (A) 6th 31.1 ' (A) 6th 32.4 ³ (A) 14th 25.7 ³ (B) 14th 31.2 ⁴ (A) 6th 35.7 ⁵ (A) 6th 27.0 ⁵ (A) 2 30 ₉ 6 ⁶ (A) 6th

20x371x14.1 2.78 1.26 1.07

3. Ox 371 χ 14.1 2.76 - 1.02

60 χ 371 χ 14.1 2.25 1.73

60 χ 371 χ 14.1 2.95 2.40

30 χ 371 χ 14.1 2.12 - 0.68

30 χ 371 χ 14.1 · 3.30 - 0.39

60 x 371 x 14.1 2.53 1.12

60 x 371 χ 14.1 2.84 1.09 -

60 χ 371 χ 14.1 1.84 - 0.76

60 χ 371 χ 14.1 1.87 - 0.97

20 x 371 χ 14.1 2.35 1.40 0.71

30 x 371 χ 14.1 1.91 - 0.80

[A) Type 181-B; A-1100 finish B) Type 181-S 994? HTS finish _k C) Type 181-Ej heat-cleaned

1 ο solution according to example 4 2, solution according to example 3 (a) -2 3ο Solution according to example 1 4 »Solution according to Example-Ha) 5« Solution according to Example 1 (b) -1 6, solution according to example i (b) -2

00981 3/16 5 A bad

"* 37 '-

FFD-1204

Example 8 Assessment of adhesives on aluminum substrates

Coated aluminum alloy strip (2024-T3; 10.2 cm χ 2.5 cm ac 1.6 mm) is degreased with trichlorethylene vapor, dry them and etch them in a chromic acid solution to a line 1 inch from one end 10 minutes at 66 to 71 ° 0, rinsing them with deionized Water off and dry them in an air oven at 60 ° 0, the adhesive solution is spread on one side of the Etched ends of the aluminum strips with a camel hair brush and dry the strips for 1 hour at 100 ° C in one Air oven. The dried strips are placed in pairs on top of each other, so that the coated sides are aligned with one another Touch the overlap of 1.3 cm and harden it in a press, which is equipped with electrically heated plates, 1 hour at 300 ° C and under a pressure of 14.1 kg / cm.

The adhesive bonds are tested in a · tensile strength Instron type testing device for shear strength at 0.5 mm / toin., 25 ° C, 50 # relative humidity or at 1.3 mm / win, at 300 ° C.

00981 3./16 54 - 38 -

Results

Bonding fairness in k «/ em sample Checks etroera door 23.48 25 ° C 69.47 Example 1 (control) 66.95 75.37 Example i (b) -1 74.53 Aluminum ver
said Example 1 (c) 71.01 Example 5 (e) -3 124.72

B e i β ρ i e 1 9

Assessment of adhesives on stainless steel substrates

Several strips of stainless steel (10.2 cm 2.5 am χ 0.13 cm 17-7PH; Condition A) are degreased with trichlorethylene vapor, dried and immersed in an alkaline detergent solution at 75 ° C for 10 minutes , εpult them along
Water off and dry them in a convection oven at 93 ° C. Then they are etched up to a line that extends
2.5 cm from one end by immersing it in a sulfuric acid solution at 68 ° C for 10 minutes and then

00981371654 -39- '© AD

PFD-I204

At the end of 10 minutes in a pluorwaöseretoif-nitric acid solution immersed at skin temperature. You can rinse them in distilled water and dry them in an air oven at 93 ° C.

You cover the etched ends on one side with the solutions given below by painting them with a camel hair brush. The coated strips are dried 30 minutes at 100 ° C, lay two strips on top of each other so that that they overlap each other 1.3 cm and harden in a press 1 hour at 300 C and a pressure of 14.1 kg / cm »Then they are cured for 64 hours at 260 ° 0 naked

The adhesive bonds are verified by shear effects in a test apparatus of the type Instron at 1.3 mm / min, and at! Temperatures of 25 ° C, 300 ° C and 371 ° C ₀

BATH ORIGINAL

O09813 / 1 & 54 - 40 -

-I204

Results

BJndungafeatigkeit / kg / cml /

sample

Test temperature £ 2oofL 371 ° C 25 ° C 16.6 13.0 132.6 70.3 49.2 122.0 96 ₉ 3 71.7 109 ₉ 3 98.5 52.3 116.4 91.0 64.0 101.9 93.1 85.5 111.3 93.1 51.7 107.5 6.3 0 54.3 118.1 38.0 159.6 122.7 52.3 131.2 115.5 67.2 123.2 92.5 72.5 123.3 82.1 64.1 126.9 103.4 60.5 130.4 13.4 - 119.5 73.1 - 141.3 49.9 - 144.8

Example 1 (control)

Example Ka)

Example Kb) -I Example Kb) -2 Example i (b) -3 Example 1 (b) ~ 4

Example 2

Example 3 (control) Example 3 (a) ~ 1 Example 3 (a) -2 _ Example 3 (a) -3 Example 3 (a) -4 Example 3 (a) -5

Example 4

Example 5 (control)

Example 5 (a) Example 5 (b)

0 098 13/1664. ₄₁ \.

BATH

-I204

25 ° C. 39 ° ⁰ C 571 ⁰ C 79 , 4 7th , 0 159 , 6 16 , 2 5 , 6 115 , 3 18th , 3 0

Example 6 (control)

Example 6 (a) -1 (control) 159.6

Example 6 (a) «2 (control) 115.3

Example 10

A polyamic acid composition containing 33 mol of excess diamine is prepared by adding 20% by weight of an equimolar mixture of 3,3 ', 4,4'-benzophenone-tetracarboxylic dianhydride and 4,4'-methylenedianiline in dimethylacetamide at room temperature stirs in. 6.26 parts of a 20 # strength solution of 4,4'-methylenedianiline in dimethylacetamide are added to 50 parts of this solution. 25 parts of the solution thus obtained are then placed in a cylindrical reaction vessel together with 15 parts of xylene, 1 part of arsenic thioarsenate and small glass beads. The vessel is then moved on rollers for about 20 hours in order to form a fine dispersion of the arsenic thioarsenate. Then 5 parts of aluminum dust are added and dispersed by moving the cylindrical vessel on rollers for a further 30 minutes; the reaction mixture is then filtered ο

0 0981 3/1 6 5A - 42 -

JFD-12Ö4

A heat-cleaned glass fabric (commercially available as 112-112 E glass fabric) is stretched over a metal frame and coated with the filtered slide by brushing 3 coatings on each side of the fabric. After each coating process, the coated fabric is baked for 12 minutes at 93.3 ° C and after the last coating process T hour at 93.3 ° C. The coated fabric obtained is evenly coated, fairly stiff and non-sticky when loaded ( * ¹⁰ °) ™ ⁵⁴ *

A strip of the fabric covered above (19 »4 cm 1.6 cm) is used to make 2 cut sheets of stainless steel Steel (17-7PH) hot-hardened under condition TH 1050, to laminate · The laminate bond cures for 1 hour at a Temperature of 301.7 C and under a pressure of 14.1 kg / cm; post-curing takes place in a convection oven for 64 hours 260 ° G. The plates are cut into 7 individual pieces; the average adhesive thickness of the bonds is 0.102 mm. The bonds are tested for shear strength using an Instron tester a cross head speed of 0.508 mm per minute, wherein the following results are obtained:

00 98 13/1 6 5Λ " ^ bad original

PPD-1204

Temperature Average shear force

25 ° C _t 216.6

288 ° C 93.5

371 ° C 38.7

Example 11

186 parts of the solution according to Example 3 are treated with

29.5 parts of a 20% strength by weight solution of 4,4'-methylenedianiline in N, N-dimethyl acetamide and uses them both for experiments (a) and (b) below.

(a) To 7 parts of this solution add 3 parts of a 20 # length Solution of a butylated phenolic resin in N, N-Dimethylaeet ~ amide. This mixture is spread on a glass fabric (112-112E) and dries it by baking at 93.3 ° C for 60 minutes. The resin uptake as described in Example 10 is

49.6 %. Aluminum strips of the type described in Example 8 are used to make bonds with an overlap of 1.3 cm and are cured in a press for 1 hour at a temperature of 300 ° C. and under a pressure of

009813/1654

PFD-1204

1-4 * 1 kg / cm. The adhesive bonds are checked in a testing device of the Xnstron type at 1.27 mm / tain, and at one temperature from 25 ° C and 288 ° C.

Average Shear Strength Obtained:

95.8 kg / cm ² at 25 ° C. 64.4 kg / cm ² at 288 ° 0.

(Jb) 3 parts of a 20 # strength solution of novolac resin in N, N «-dimethylacetamide are added to 7 parts of the solution. This mixture is then spread on a glass fabric (112-112E) and dried by firing for 60 minutes at 93.3 ° C? the resin uptake as described in Example 10 is $ 41.8>. Aluminum strips of the type described in Example 8 are used to produce bonds with an overlap of 1.3 cm and are cured in a press for 1 hour at a temperature of 300 ° C. and under a pressure of 14.1 kg / cm. The adhesive bonds are tested in an Instron type tester at 1.27 mm / min, at a temperature of 25 ° C and a temperature of 288 ° C.

Average shear strength obtained: 125.8 kg / cm ² at 25 ° C

85.8 kg / cm ² at 288 ° C ₁

00 9813/16 5Λ

⁴⁵ "BAD ORSGlNAL

Claims (1)

E. I. du Pont de Nemours and Company. FPD-1204 (P 35 4o8) Pat entans check oh e 1 · Adhesive mixture »containing (1) a polyamic acid with at least 30 aromatic ketc-carbonyl groups / 100 amic acid structures. and (2) an organic diaaine in an amount of at least Mol / 100 amldelure structural units and optionally an organic solvent. 2 · Adhesive mixture according to claim I _9, characterized in that it is applied to a substrate, e.g. B. applied to glass fiber wool 1st. 3. Process for the preparation of an adhesive mixture according to Claim 1 «characterized in that a Tetracarbonsliuredianhydrid of the general formula 0 0 η η Π C VN η η 0 0 09813/1654 PPD-1204 with a diamine of the Forael H ^ N-M-NH «, in which A is a tetravalent organic radical with two carbonyl « gnippenpaaran and H a divalentex organic And where A or H is aliphatic, aromatic » carbocyclic heterocyclic or combinations thereof, and where at least one of the radicals A or M contains an aromatic keto group, the compounds containing this group are present in an amount of at least 30 mol # of the dianhydride present, and the mixture in an amount of at least 15 mol Excess over the dianhydride is present. 13/16 54. '-' - * - 2 - ORIGINAL BATHROOM