NL8603318A - Heat resistant adhesive - comprises polymer e.g. polyamic acid prepd. by reacting ether di:amine and tetra;carboxylic di:anhydride(s) - Google Patents

Abstract

A heat resistant adhesive comprises a polymer with a repeating unit of formula (I): X is (II) and/or (III) and R is tetravalent gp. selected from 2C aliphatic, alicyclic, monocyclic aromatic, condensed polycyclic aromatic gps. and non-condensed gps. where aromatic gps. are mutually connected directly or by crosslinking member. Pref. polymer is e.g. polyamic acids or polyimides. The polyamic acid is prepd. by reacting an ether diamine ingredient of formula (IV), i.e., 6,6'-bis(3-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spirobiindane and tetracarboxylic dianhydride(s). Acid is dehydration cyclised to give a polyimide.

Description

-1-26 130 / Vk / mvl

Short designation: Polyimide, process for the preparation of a polyimide and high temperature adhesive based on such a polyimide.

5

The invention relates to a new polyimide and to a process for its preparation. The invention further relates to adhesives which can be used at high temperatures on the basis of this polyimide. In particular, the invention relates to adhesives with excellent adhesive strength and high temperature stability.

Various adhesives based on synthetic / organic high polymers are known. Polybenzimidazole and polyimide-containing adhesives have been developed because they have excellent stability at high temperatures. In addition, other adhesives have also been developed based on fluorine-containing polymers, polyamideimide, silicone, epoxy novolac, epoxy acrylic, nitrile rubber-phenolic resins and based on polyesters. However, the properties of these adhesives are not yet sufficient because good high temperature stability decreases the adhesive strength, while high adhesive strength results in less high temperature stability.

An object of this invention, therefore, is to obtain a new polyimide that can be used for adhesives with excellent bond strength and durability at high temperatures over a long period of time.

Another object according to the invention is to obtain a process for preparing such a polyimide and for obtaining a process in which the adhesion is carried out using this polyimide.

Within the scope of this invention, intensive research has been conducted to improve the adhesive strength of high temperature adhesives, and new polyimides derived from indan derivatives have been found.

The polyimide according to the invention is therefore characterized in that it is a polymer with repeating units of formula 1, wherein Y is a divalent radical represented by formula 2 or formula 3, which is an indan derivative with two oxy radicals and Y is 8 0 v ~ »1 *“ r ί, V * - · fv ft «* -2- 26130 / Vk / mvl bound to two phenyl radicals in the meta or in the para position and R is a tetravalent radical selected from the group consisting of from an aliphatic radical with not less than 2 carbon atoms, cycloaliphatic radical / mono-aromatic radical / condensed polyaromatic radical 5 and an uncondensed polyaromatic radical, the aromatic radicals being mutually connected with a bond or cross-linking function.

The process for the preparation of the polyimide with repeating units of formula 1, wherein Y has the above-mentioned meaning, consists in that a diamine of formula 4, wherein Y has the same meaning as previously indicated, is reacted with a tetracarboxylic dianhydride of formula 5, stated on the formula sheet, wherein R has the same meaning as mentioned above, in an organic solvent and thermally or chemically imidizing the obtained polyamic acid with repeating units, corresponding to formula 6, stated on the formula sheet.

Thus, an adhesive can be obtained resistant to high temperature based on a polyimide with repeating units, corresponding to formula 1, stated on the formula sheet, wherein Y and R 20 have the same meaning as indicated above. The adhesion using this polyimide according to the invention consists in that this polyimide is applied to a substrate, on the surface on which the agent is applied an untreated surface of another substrate is applied and a heating under pressure takes place above the glass transition point of the polyimide. Adhesion can also be carried out by applying polyamic acid with repeating units represented by formula 6, indicated on the formula sheet, which is a precursor of a polyimide, imidizing on a substrate to obtain the polyimide with the repeating units, represented by formula 1, mentioned on the formula sheet and on the treated surface, to apply a substrate with an untreated surface or another substrate, after which the whole is heated under pressure to above the glass transition point of the polyimide.

The invention is further elucidated on the basis of the following description, reference being made to the appended drawing, in which: f - r - r. -7 - 4 Λ - .V ..? 1, 2 and 3 IR absorption spectra are of the polyimides obtained according to three examples of the present invention.

The novel polyimide of this invention with repeating units of formula 1 can be prepared by reacting a diamine with tetracarboxylic dianhydride in organic solvents and further cyclizing the resulting polyamic acid by dehydration.

The diamine used according to this invention is the ether diamine having an industrial structure. The ether diamine of formula 7, reported on the formula sheet, includes 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) -10 phenyl] -1,1,3-trimethylindan and 5- (3 "aminophenoxy> -3- [4- (3-aminophenoxy) -phenyl] -1,1,3-trimethylindan.

Another ether diamine of formula 8, listed on the formula sheet, includes 6.6 * bis (4-aminophenoxy) -3,3,3,3,3 "tetramethyl-1,1'-spirobiindan and 6.6" bis (3-aminophenoxy) -3,3,3,3,3-tetramethyl-1,1'-spirobi-15 indan.

These ether diamines can be used singly or as a mixture.

Tetracarboxylic dianhydride that can be used according to this method corresponds to formula 5, stated on the formula sheet, wherein R is a tetravalent radical selected from the group consisting of an aliphatic radical with not less than two carbon atoms, cycloaliphatic radical, monoaromatic radical condensed polyaromatic radical and non-condensed polyaromatic radical wherein the aromatic radicals are mutually linked by a bond or a cross-linking function.

Tetracarboxylic dianhydride used in this method includes, for example, ethylene tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromelitinic dianhydride, 3,3,4,4'-benzo-phenonetracarboxylic dianhydride, 2,2 ', 3,3, benzophenontetracarboxylic di-3,3-anhydride 4'-biphenyltetracarboxylic dianhydride, 2,2 ^ 3,3 ^ 01-phenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenylpropanedianhydride, 2,2-bis-2,3-dicarboxyphenyl) propanedianhydride, bisC3,4-dicarboxyphenyl > anhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis-C2,3-dicarboxyphenyl) ethanedianhydride, bis (2,3-dicarboxyphenyl) methanedi-35 anhydride, bis (3,4-dicarboxyphenyl ) methane dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,2,3,4-benzene tetracarboxyl f tt r · Τ 7 T- L- .., i.

* 4-26130 / Vk / mvl of acid dianhydride, 3,4,9,1O-perylene-tetracarboxylic dianhydride, 2,3,6,7-anthracene-tetracarboxylic dianhydride and 1,2,7,8-phenanthrene-tetracarboxylic dianhydride.

Of these dianhydrides, pyromellitic acid dianhydridide and 3,3,4,4'-benzophenone tetracarboxylic dianhydride are preferred.

Tetracarboxylic dianhydride can be used singly or in mixtures of two or more of these substances.

The polymer can normally be prepared by reacting ether diamine with tetracarboxylic dianhydride in organic solvents. The organic solvents used in this reaction include, for example, Ν, Ν-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, N-methyl-2-pyrroli-don, 1,3-dimethyl -2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, 15 bis [2- (2-methoxyethoxy) ethyl] ether , tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethyl urea and hexamethylphosphoramide. These solvents can be used singly or in mixtures of two or more of these.

The reaction temperature is 60 ° C or less, preferably 50 ° C or less. The reaction pressure is not particularly limited and atmospheric pressure is sufficient to conduct the reaction. The reaction time depends on the type of solvent, the reaction temperature and the starting materials such as diamines and tetracarboxylic dianhydrides and is usually sufficient to stop the formation of polyamic acid represented by the compound of formula 6. The reaction for 4 to 24 hours is usually sufficient at about 60 ° C or less.

Such a reaction gives polyamic acid with repeating units of formula 6 shown on the formula sheet.

In the next step, the thermal dehydration takes place of the polyamic acid in solution at 100 to 300 ° C or the chemical dehydration by treatment with an imidizing agent such as acetic anhydride to obtain the corresponding polyimide with repeating units of formula 1 shown on the formula sheet.

The method of applying the thus obtained polymer for adhesives can be divided into two operations: (1) the polymer is used as an adhesive-containing solution containing the polyamic acid precursor as the main component and the imidization takes place before the adhesion is carried out.

B o i) ΰ ó I ö § -5- 26130 / Vk / mvl C2) The polymer is used in the form of the polyimide.

In the method mentioned under (1), the solution of the adhesive is a solution in an organic solvent of the polyamic acid. The resulting polyamic acid reaction mixture may be obtained by reacting ether diamine with tetracarboxylic dianhydride in the organic solvents. It may also be that the solution contains the polyamic acid as main component and polyimide, which is a cyclized product of polyamic acid. Thus, the solution with the adhesive containing polyamic acid can be the solution or suspension containing polyimide as an auxiliary.

When the adhesive containing such a polyamic acid is applied, a thin layer of polyamic acid is formed on the articles to be adhered, after which preheating of the coated articles in air takes place for a certain period of time at a temperature of 180-350 ° C, preferably 200-300 ° C. The excess solvent is removed and the polyamic acid is converted into a more stable polyimide. The objects to be bonded are then strongly bonded together by applying a pressure of 1-1000 kg / cin at a temperature of 50-400 ° C, followed by curing at a temperature of 100-400 ° C.

In method (2) in which the polyimide is used as an adhesive, this method is roughly divided into three possibilities.

(a) The polyimide is simply used as a powder.

Cb> The polyimide is dissolved in the solvents or used in the form of the obtained solution at the end of the imidation.

(c) The polyimide is first formed into films before it is used.

In these cases, the polyamic acid can be present in the polyimide.

In possibility (a), the objects to be joined together can be strongly bonded by applying the powder therebetween, applying a pressure of 1-1000 kg / cm 2 at a temperature of 50-400 ° C and curing at a temperature of 10Q-400 ° C.

In possibility (b), a thin layer of polyimide is formed containing the solution of the adhesive on the 6603318 -6- 26130 / Vk / mvl * articles to be joined, followed by preheating the articles in air for a period of time at about 30-200 ° C to remove the solvents. The objects to be joined are brought together, 2 a pressure is applied of 1-1000 kg / cm at a temperature of 50-400 ° C and hardened at a temperature of 100-400 ° C to obtain strongly connected objects .

The invention is further illustrated by the following examples.

Synthesis 10 5- (4-Aminophenoxy) -3- [4- (4-aminophenoxy) phenyl] -1,1,3-trimethylindane used in the present invention was prepared as follows.

A reaction vessel equipped with a thermometer and a stirrer was charged with 67.1 g (0.25 mol) 5-hydroxy-3- (4-hydroxyphenyl) -1,1,3-tri-15 methylindan, 86.7 g ( 0.55 mol) 4-chloronitrobenzene and 250 ml dimethyl sulfoxide. The temperature of the mixture was raised while passing nitrogen and kept at 100-110 ° C.

Then, 49 g (0.55 mol) of 45% aqueous sodium hydroxide as a solution were added dropwise over 1 hour. After the addition, the reaction was run for two hours. After the completion of the reaction, the resulting mixture was filtered to remove the inorganic salt and evaporated under reduced pressure in an evaporator.

The residue thus obtained was mixed with 500 ml of water.

The crystals formed were filtered, washed with water and dried to give 126.7 g (99.3% yield) of 5- (4-nitrophenoxy) -3- [4- (4-nitrophenoxy) -phenyl] - 1,1,3-trimethylindan. The crystals were recrystallized from ethanol to obtain a pure product of white needles, mp 214.5-215.5 ° C.

The elemental analysis for the compound of formula 30 C3qH26N2 ° 6 was: C (%) H (%) N (%) calculated: 70.58 5.13 5.49 found: 70.60 5.05 5.51.

In the next step, a closed reduction vessel fitted with a stirrer and thermometer was charged with 10.21 g (0.02 mol) of the above 5- (4-nitrophenoxy) -3- [4- (4-nitrophenoxy) phenyl] -1,1,3-trimethylindan, 0.3 g of Pd / C catalyst and 30 ml of ethanol and gaseous hydrogen

6 0 G 'j 1 S

3 * -7- 26130 / Vk / mvl fed under strong stirring. The reaction was stopped after taking 2760 ml of hydrogen at 62-68 ° C for 4 hours. After completion of the reaction, the resulting mixture was filtered to remove the catalyst and evaporated in the evaporator to recover the solvent.

The evaporated residue was then mixed with 6.5 g of concentrated hydrochloric acid and 50 ml of a 20% aqueous isopropyl alcohol solution and dissolved by heating. The resulting mixture was slowly cooled and the crystals of 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl] -10 1,1,3-trimethylindan hydrochloride separated. The crystals were filtered off and neutralized with aqueous ammonia in 50 ml of 70¾ aqueous solution of isopropyl alcohol. White needles were separated after they were cooled and stored. The needles were filtered, washed and dried to give 7.9 g (87.6% yield) 5- (4-aminophenoxy) -15 3- [4- (4-aminophenoxy) phenyl] -1,1,3- trimethylindan with a melting point of 135-136.5 ° C.

The data from the elemental analysis for the compound of formula £ 30 ^ 39 ^ 2 ^ 2 were: C (%) H (%> N (%)) calculated: 79.97 6.71 6.22 found: 80. 02 6.73 6.17.

NMR spectrum, solvent: acetone-D ^, at room temperature 1.05 ppm C3H singlet), 1.35 ppm (3H singlet), 1.65 ppm (3H singlet), 2.25-2.75 ppm (2H multiplet ), 3.2-4.2 ppm (4H singlet), 6.6-7.35 ppm (C15H multiplet).

MS spectrum (M / e): M + = 450, 435, 312, 250, 217, 108.

Synthesis 2

The 5- (3-aminophenoxy> -3 [4- (3-aminophenoxy) phenyl] -1,1,3-trimethylindan to be used according to the invention was prepared as follows.

A reaction vessel equipped with a stirrer and thermometer was charged with 67.1 g (0.25 mol) 5-hydroxy-3- (4-hydroxyphenyl) -1,1,3-trimethylindan, 10.09 g (0.6 mol) m-dinitrobenzene, 69.1 g (0.5 mol) anhydrous potassium carbonate and 650 ml Ν, Ν-dimethylformamide. The reaction was carried out at 150-153 ° C for 7 hours with stirring while passing nitrogen.

After the completion of the reaction, the resulting mixture was filtered to remove organic salt and evaporated under evaporation.

V vj -J v v "ί O

£ * -8- 26130 / Vk / mvl low pressure in an evaporator. The evaporated residue was a brown oil.

The residue was mixed with 280 ml of 2-methoxyethanol and 20 ml of water and dissolved by heating. The crystals were formed by cooling which were then filtered, washed and dried to give 112.5 g of 5 (88.1% yield) 5- (3-nitrophenoxy) -3- [4- (3-nitrophenoxy) phenyl] - 1,1,3-trimethylindan.

The crystals were recrystallized from ethanol to obtain a pure product of light yellow needles, mp 90 ° 92 ° C.

The data from the elemental analysis for the compound of formula were: C (%) H (%) N (%) calculated: 70.58 5.13 5.49 found: 70.62 5.18 5.43.

In a next step, a sealed reduction vessel was provided with a stirrer and thermometer, filled with 10.21 g (0.02 mol) 5- (3 "nitrophenoxy) -3- [4- (3-nitrophenoxy) phenyl] - 1,1,3-trimethylindan, 0.3 g of 5% Pd / C catalyst and 30 ml of ethanol and hydrogen gas were added with vigorous stirring.

The reaction was stopped after absorbing 2760 ml of hydrogen at 62-68 ° C for 4 hours.

After the completion of the reaction, the resulting mixture was filtered to remove the catalyst and evaporated in the evaporator to recover the solvent.

The evaporated residue was then mixed with 6.5 g of concentrated hydrochloric acid and 50 ml of 20% aqueous isopropyl alcohol solution, dissolved by heating and filtered off after addition of activated carbon.

The filtrate was added dropwise to a dilute aqueous ammonia solution to separate precipitate. The precipitate was filtered off, washed and dried to give 8.5 g (94.3% yield) 5- (3-aminophenoxy) -3- [4- (3-aminophenoxy) phenyl] -1,1,3-trimethylindan with a melting point of 70-72 ° C.

The data from the elemental analysis for the compound 35 of formula C3qH3qN2 ° 2 were: C (%) H (%) N (%) calculated: 79.97 6.71 6.22 found: 80.12 6.76 6 , 20.

fi 6 ft / * i H

** '· - "». * Λ · .r V' $ -9- 26130 / Vk / mvl NMR spectrum, solvent: acetone-D ^, temperature: room temperature: 1.05 ppm (3H singlet), 1, 35 ppm (3H singlet), 1.65 ppm (3H singlet), 2.3-2.5 ppm (2H multiplet), 3.6-4.2 ppm (4H singlet), 6.0-7.3 ppm (15H multiplet).

HS spectrum CH / e): M + = 450, 435, 312, 250, 218.

Synthesis 3

The 6,6'-bis (4-aminophenoxy) -3,3,3 ', 3'-tetramethyl-1,1,1'-spirobiindane used according to the invention was prepared as follows.

A reaction vessel equipped with a stirrer, thermometer and reflux condenser was charged with 77.1 g (0.25 mol) of 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'-spirobiindan, 86.7 g (0.55 mol) 4-chloronitrobenzene, 41.4 g (0.3 mol) anhydrous potassium carbonate and 350 ml N, N-dimethylformamide.

The reaction was carried out at 150-153 ° C for 8 hours while stirring and passing nitrogen.

After the completion of the reaction, the resulting mixture was diluted with 350 ml of water. The separated pale yellow precipitates were filtered, washed successively with isopropyl alcohol and water and dried to give 133.5 g (97% yield) of 3,3,3 ', 3'-tetra-methyl-6,61-bis (4-ni rofenoxy) -1,1'-spi robinin.

Pure 3,3,3,3,3-tetramethyl-6,6'-bis (4-nitrophenoxy) -1,1'-spirobiindan, mp 200.5-201.5 ° C, was obtained in the form of white needles by recrystallization from 2-methoxyethanol.

The data from the elemental analysis for the compound of formula were: 25 C (%) H (%) N (%) calculated: 72.0 5.49 5.09 found: 71.92 5.39 5.11.

In the next step, a sealed reduction vessel was equipped with a stirrer and thermometer, filled with 11 g (0.02 mol) of the above-mentioned 3,3,3 ', 3'-tetramethyl-6,6'-bis (4- nitrophenoxy) -1,1'-spirobiindan, 0.3 g Pd / C catalyst and 40 ml 2-methoxyethanol and gaseous hydrogen were added with vigorous stirring. The reaction was stopped after absorbing 2650 ml of water at 70-80 ° C for 8 hours.

After the completion of the reaction, the resulting mixture was filtered hot to remove the catalyst and cooled. The separated crystals were filtered off, washed with isopropyl alcohol and dried. Thus, white, flake-like crystals f50 331 8 t: -10-26130 / Vk / mvl were obtained in an amount of 8.5 g (86.6% yield) consisting of 6.6 bis (4-aminophenoxy) -3 3,3 ', 3,3-tetramethyl-1,1 * -spioboindan, mp 214-215 ° C.

The results of the elementalr analysis and the MS spectrum 5 were as follows: the elementalr analysis of Ο ,, Η ,, Ν-, Ο- .: 33 34 ci C ('%) H (%) N ( %) calculated: 80.77 6.98 5.71 found: 80.62 7.05 5.70.

MS spectrum (M / e): M + = 490, 475, 238, 65.

Synthesis_4

The 6,6'-bis (3-amino-phenoxy) -3,3,3 ', 3'-tetramethyl-1,1'-spirobiindan to be used according to the invention was prepared as follows.

A reaction vessel equipped with a stirrer, thermometer and reflux condenser was charged with 77.1 g (0.25 mol) of 6.6-dihydroxy-3,3,3,3,3-tetramethyl-1,1'-spirobiindan, 100.9 g (0.6 mole) m-dinitrobenzene, 69.1 g (0.5 mole) anhydrous potassium carbonate and 650 ml Ν, Ν-dimethylformamide. The reaction was carried out at 150-153 ° C for 12 hours with stirring with nitrogen passage.

After the completion of the reaction, the resulting mixture was diluted with 650 ml of water. The separated light brown precipitates were filtered off, washed with isopropyl alcohol and dried to give 116.5 g (84.6% yield) of 3,3,3,3,3-tetramethyl-6,6'-bis (3-nitrophenoxy) -1,1'-spi robi indan.

Pure 3,3,3,3,3-tetramethyl-6,6, bis (3-nitrophenoxy) -1,1'-spirobiindan with a melting point of 173.5-175 ° C was obtained in the form of light brown needles by recrystallization from ethanol.

The data from the elemental analysis for the compound of formula ^ 33 ^ 30 ^ 2 ^ 6 were: 30 C (%) H (%) N (%) calculated: 72.0 5.49 5.09 found: 71, 83 5.39 5.10.

In a next step, a sealed reducer was fitted with a stirrer and thermometer, filled with 11 g (0.02 mol) of the above-mentioned 3,3,3 ', 3'-tetramethyl-6,6, bis (3- nitrophenoxy) -1,1'-spirobiindan, 0.3 g of Pd / C catalyst and 40 ml of 2-methoxyethanol and gaseous hydrogen were added with vigorous stirring. The reaction was stopped after C £n "C T 1 ft * * -11-26 130 / Vk / mvl absorption of 2650 ml hydrogen at 70-80 ° C for 8 hours.

After the completion of the reaction, the resulting mixture was filtered hot to remove the catalyst and diluted with 50 ml of isopropyl alcohol. The separated crystals were filtered / washed with isopropyl alcohol and dried. The white needles obtained were 7/5 g (76 / 4¾ yield) and were ó / ó'-bisO-aminophenoxy) -S / S / S '/ S'-tetramethyl-1 / l-spirobiindan, melting point 206 ° C.

The results from the elemental analysis, NMR spectrum and HS spectrum were as follows.

Elemental Analysis for the Compound of Formula C, H, N 4 O: C (X) H (%) N (%) Calculated: 80.77 6.98 5.71 Found: 80.62 7.05 5.70.

NMR spectrum, solvent: acetone-D ^, temperature: chamber-15 temperature: 1.4 ppm (12H doublet), 2.2-2.5 ppm C4.H multiplet), 6.0-6.5 ppm ( 8H multiplet), 6.7-7.3 ppm (6H multiplet).

MS spectrum (M / e): M + = 490, 475, 238, 65.

Example I

A reaction vessel equipped with a stirrer, reflux cow 20 and nitrogen supply tube was charged with 4.5 g (0.01 mol) of 5- (4-aminophenoxy) - 3- [4- (4-aminophenoxy) phenyl] -1.1 , 3-trimethylindan and 20.0 g N, N-dimethyl acetamide and to this was added 2.18 g (0.01 mol) pyromellitic dianhydride in portions at room temperature under nitrogen atmosphere, which was carefully performed so that the temperature of the solution was not exceeded 30 ° C. The reaction mixture was further stirred at room temperature for 20 hours.

The polyamic acid thus obtained had an inherent viscosity of 2.04 dl / g at 35 ° C in 0.5% N, N-dimethylacetamide solution.

Part of the polyamic acid in solution was poured onto a glass plate and heated for 1 hour, which was carried out at 100 ° C, 200 ° C and 300 ° C.

The polyimide film thus obtained had a glass transition point of 297 ° C in accordance with the TMA penetration method and a temperature at which a 5% weight reduction occurred in air of 515 ° C in accordance with DTA-TG.

The polyimide film was placed between cold-rolled, «T ί Ö» i- i · r · '·

vJ V V v- t V

1 »

V

-12- 26 130 / Vk / mvl

steel plates CJIS, G3141, spcc / SD, 25 x 100 x 1.6 mm) which were preheated at 130 ° C and compressed for 5 minutes at 340 ° C

2 under a pressure of 20 kg / cm. The interconnected objects had a shear strength of 260 kg / cm at room temperature and 205 kg / cm 5 at 240 ° C in accordance with JIS-K6848 and K6850.

Example II

The reaction vessel used in Example I was now charged with 4.5 g (0.01 mol) of 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl] -1,1,3-trimethylindane and 20.0 g Ν, Ν-dimethylacetamide and 2.18 g (0.01 mol) of pyromellitic dianhydride were added in portions at room temperature under nitrogen atmosphere, which was carefully done so as not to raise the temperature of the solution above 30 ° C . The reaction mixture was further stirred at room temperature for 20 hours.

The polyamic acid thus obtained had an inherent viscosity of 2.04 dl / g.

The polyamic acid solution was applied to a cold-rolled steel plate which had been previously washed with trichlorethylene and dried for 1 hour each at 100 and 220 ° C. The polyamic acid was converted to polyimide. The coated sheet was covered with another cold-rolled steel sheet and pressed for 5 minutes at 340 ° C under a pressure of 20 kg / cm 2.

The plates thus joined together had a shear strength of 270 kg / cm2 at room temperature and 210 kg / cm2 at 240 ° C.

Example III

A reaction vessel as in Example 1 was charged with 4.5 g (0.01 mol) of 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl] -1,1,3 "tri- methylindan and 20.0 g of Ν, Ν-dimethylacetamide and to this was added 2.10 g (0.096 mol) of pyromellitic dianhydride in portions at room temperature under a nitrogen atmosphere which was carefully performed so as not to raise the temperature of the solution above 30 ° C. The reaction mixture was further stirred at room temperature for 20 hours.

The polyamic acid thus obtained had an inherent viscosity of 0.82 dl / g.

After diluting the polyamic acid solution by adding 39.4 g of Ν, Ν-dimethylacetamide, 2.02 g (0.02 mole) of triethylamine and 4.08 g (0.04 mole) of acetic anhydride were added and stirring was carried out 8603318 ft m -13- 26130 / Vk / mvl continued at room temperature under nitrogen atmosphere.

Yellow powdered polyimide started to precipitate after about 1 hour after the addition and stirring was continued for 12 hours.

The precipitated polyimide powder was filtered off, washed with methanol and acetone and dried at 180 ° C for 5 hours under reduced pressure.

Fig. 1 shows the IR absorption spectrum of the polyimide powder thus obtained. The spectrum gives a remarkable absorption of 1 -1 10 at about 1780 cm and 1720 cm, which are the characteristic absorption bands of the imide.

The polyimide powder thus obtained was suspended in methanol, applied to a cold-rolled steel plate and dried at 100 ° C for 30 minutes.

The coated sheet was covered with another cold-rolled steel sheet and pressed at 340 ° C for 2 minutes under a pressure of 20 kg / cm.

The superimposed plates had a shear strength of 2 kg of 275 kg / απ at room temperature and 213 kg / cm at 240 ° C.

Example XV

A reaction vessel equipped with a stirrer, reflux condenser and nitrogen supply tube was charged with 45.0 g (0.1 mol) 5- (4-aminophenoxy) -3 [4- (4-aminophenoxy) phenyl] -1,1,3- trimethylindan and 231.6 g of Ν, Ν-dimethyl-acetamide and to which was added 32.2 g (0.1 mole) of 3,3,4,4-benzophenone-tetracarboxylic acid dianhydride in portions at room temperature under a nitrogen atmosphere. care should be taken not to raise the temperature of the solution above 30 ° C. The reaction mixture was further stirred at room temperature for 20 hours.

The polyamic acid thus obtained had an inherent viscosity of 1.45 dl / g.

Part of the polyamic acid solution was poured onto a glass plate and heated for 1 hour at the following temperatures: T00 ° C, 200 ° C and 300 ° C.

The polyimide film thus obtained had a glass transition temperature of 262 ° C and at a temperature of 508 ° C the weight dropped 5% in air. The film also had a tensile strength of 13.2 kg / mm and an elongation of 10¾ in accordance with ASTM D-882.

% f f- 3 3 1 6 -14- 26130 / Vk / mvl

The polyimide film was placed between cold-rolled steel plates preheated at 130 ° C and compressed for 5 minutes at 340 ° C under a pressure of 20 kg / cm 2. The bound samples had a shear strength of 254 kg / cm2 at room temperature and 5 201 kg / cm2 at 240 ° C.

Example V

The reaction vessel mentioned in Example IV was charged with 45.0 g (0.1 mol) 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl] -1,1,3-trimethylindan and 231.6 g Ν, Ν-dimethylacetamide and to this was added 32.2 g of 10 (0.1 mol) 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride in portions at room temperature under a nitrogen atmosphere, which was carefully performed so as not to affect rise above 30 ° C. The reaction mixture was further stirred at room temperature for 20 hours.

The polyamic acid thus obtained had an inherent viscosity of 1.45 dl / g.

The polyamic acid solution was applied to two cold-rolled steel plates first washed with trichlorethylene and dried for 1 hour at 100 and 220 ° C each. The coated sheets were superimposed and compressed for 5 minutes at 340 ° C under a pressure of 20 kg / cm.

The plates thus joined together had a shear strength of 260 kg / cm2 at room temperature and of 195 kg / cm2 at 240 ° C.

Example VI

The reaction vessel mentioned in Example IV was now charged with 45.0 g (0.1 mol) 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl] -1,1,3-trimethylindan and 231.6 g Ν, Ν-dimethylacetamide and to this was added 32.2 g (0.1 mol) 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride in portions at room temperature under nitrogen atmosphere, which was carefully performed to Do not raise the temperature of the solution above 30 ° C. The reaction mixture was further stirred at room temperature for 20 hours.

The polyamic acid thus obtained had an inherent viscosity of 1.45 dl / g.

After diluting 100 g of a polyamic acid solution by adding 150 g of Ν, Ν-dimethylacetamide, 6.54 g (0.065 mol) of triethylamine and 13.2 g (0.13 mol) of acetic anhydride were added and the Hf 'U 1 · * r: ... c -15-26130 / Vk / mvl stirring was continued at room temperature under nitrogen atmosphere. Stirring was continued for 12 hours.

The separated polyimide powder was filtered off, washed with methanol and acetone and dried at 180 ° C for 5 hours under reduced pressure.

The polyimide powder thus obtained was applied to a cold-rolled steel plate.

The coated plate was covered with another one

cold rolled states plate and compression was performed at 340 ° C

2 10 for 5 minutes under a pressure of 20 kg / cm.

The joined plates had a shear strength of 255 kg / cm 2 at room temperature and 201 kg / cm 2 at 240 ° C.

Example VII

The reaction vessel mentioned in Example I was now filled with 4.5 g (0.01 mol) of 5- (3-aminophenoxy) -3- [4- (3-aminophenoxy) phenyl] -1,3,3-tri- methylindan and 20 g N, N-dimethylacetamide and to this was added 2.18 g (0.01 mol) pyromellitic dianhydride in portions at room temperature under nitrogen atmosphere, which was carefully performed so as not to raise the temperature of the solution above 30 ° C.

The reaction mixture was further stirred for 20 hours at room temperature.

The polyamic acid thus obtained had an inherent viscosity of 1.90 dl / g.

Part of the polyamic acid solution was poured onto a glass plate and heated for 1 hour each at 100 ° C, 200 ° C and 300 ° C.

The polyimide film thus obtained had a glass transition temperature of 237 ° C and a drop of 5% by weight occurred in the air at a temperature of 503 ° C. The film thus obtained had a tensile strength of 8.9 kg / mm and an elongation of 6%.

The polyimide film was placed between cold-rolled steel plates preheated at 130 ° C and compressed for 5 minutes at 340 ° C under a pressure of 20 kg / cm 2. The plates thus joined together had a shear strength of 320 kg / cm @ 2 at room temperature and of 225 kg / cm @ 2 at 220 ° C.

8 H '3 5 1 8 -16- 26130 / Vk / mvl

Example VIII

The reaction vessel mentioned in Example I was charged with 4.5 g (0.01 mol) of 5- (3-aminophenoxy) -3- [4- (3-aminophenoxy) phenyl] -1,1,3-trimethyl-indan and 20.0 g Ν, Ν-dimethylacetamide and 2.1 g (0.096 mol) of 5-pyromellitic dianhydride were added in portions at room temperature under a nitrogen atmosphere, which was carefully done so as not to raise the temperature of the solution above 30 ° C. The reaction mixture was further stirred at room temperature for 20 hours.

The polyamic acid thus obtained had an inherent viscosity of 0.78 dl / g.

After diluting the polyamic acid solution by adding 39.4 g Ν, Ν-dimethylacetamide, 2.02 g (0.02 mole) triethylamine and 3.06 g (0.03 mole) acetic anhydride were added and the stirring was carried out at room temperature continued under nitrogen atmosphere. Stirring was continued for 12 hours.

The separated polyimide powder was filtered off, washed with methanol and acetone and dried at 180 ° C for 5 hours under reduced pressure. The polyimide powder thus obtained was applied to a cold-rolled steel plate.

The coated sheet was covered with another cold-rolled steel sheet and compressed therewith at 340 ° C for 5 minutes under a pressure of 20 kg / cm.

The interconnected plates had a shear strength 2 2 o of 310 kg / cm @ 1 at room temperature and of 215 kg / cm -1 at 220 ° C.

Example IX

The reaction vessel mentioned in Example I was charged with 4.5 g (0.01 mol) of 5- (3-aminophenoxy) -3- [4- (3-aminophenoxy) phenyl] -1,1,3-trimethyl-indan and 23.2 g Ν, Ν-dimethylacetamide and to this was added 3.22 g (0.01 mol) of 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride in portions at room temperature under nitrogen atmosphere, which was carefully performed to maintain the temperature of not to raise the solution above 30 ° C. The reaction mixture was further stirred at room temperature for 20 hours.

The polyamic acid thus obtained had an inherent viscosity of 1.25 dl / g.

Part of the polyamine solution was poured onto a glass plate and heated for 1 hour at both 100 ° C, 200 ° C and 300 ° C.

6 S 0 3 3 1 8 -17- 26130 / Vk / mvl

The polyimide film thus obtained had a glass transition temperature of 214 ° C and a drop of 5% by weight occurred in air at a temperature of 507 ° C. The film also had a shear strength of 14.8 kg / mm 2 and an elongation of 9%.

The polyimide film was placed between cold-rolled steel plates preheated at 130 ° C and compressed for 5 minutes at 340 ° C at a pressure of 20 kg / cm 2. The 2 joined plates had a shear strength of 300 kg / cm at room temperature and 218 kg / cin at 200 ° C.

10 Example X

The reaction vessel mentioned in Example I was charged with 4.5 g (0.01 mol) of 5- (3-aminophenoxy) -3- [4- (3-aminophenoxy) phenyl] -1,1,3-trimethylindane and 23, 2 g of N> N-dimethylacetamide and to this was added 3.22 g (0.01 mol) of 3,3,4,4'-benzophenone tetracarboxylic dianhydride in portions at room temperature under nitrogen atmosphere, which was carefully done so as not to alter the temperature of the solution rise above 30 ° C. The reaction mixture was further stirred at room temperature for 20 hours.

The polyamic acid thus obtained had an inherent viscosity of 1.25 dl / g,

The polyamine solution was applied to a cold-rolled steel plate that had been previously washed with trichlorethylene and dried for 1 hour at both 100 ° C and 220 ° C. The coated sheet was covered with another cold-rolled steel sheet and pressed for 5 minutes at 340 ° C under a pressure of 20 kg / cm.

The interconnected plates thus obtained had a shear strength of 310 kg / cm at room temperature and of 220 kg / cm at 200 ° C.

Example XI

A reaction vessel equipped with a stirrer, reflux condenser and nitrogen supply tube was charged with 49.0 g (0.10 mol) 6.6 bis (4-amino-phenoxy) -3 / 3.3,3,3-tetramethyl- 1,1'-spirobiindan and 211.1 g of N, N-dimethyl-acetamide and to this was added 21.36 g (0.098 mol) of pyromellitic dianhydride in portions at room temperature under nitrogen atmosphere, which was carefully performed to maintain the temperature of the do not raise the solution above 30 ° C. The reaction mixture was further stirred at room temperature for 20 hours.

I f; V ~ 1 δ η »-18- 26130 / Vk / mvl

The polyamic acid thus obtained had an inherent viscosity of 0/58 dl / g.

After diluting the polyamic acid solution by adding 422.1 g of Ν, Ν-dimethylacetamide, 20.2 g (0.2 mole) of triethyl-5 amine and 30.6 g (0.3 mole) of acetic anhydride were added and the stirring was continued at room temperature under nitrogen atmosphere. Yellow powdered polyimide started to precipitate at about 2 hours after the addition and stirring was continued for 12 hours.

The separated polyimide powder was filtered off, washed with methanol and acetone and dried at 180 ° C for 5 hours under reduced pressure.

Fig. 2 shows the IR absorption spectrum of the polyimide powder thus obtained. The spectrum represents the remarkable absorbance -1 -1 at approximately 1780 cm and 1720 cm, which are the characteristic absorption bands of the imide. The polyimide powder thus obtained was applied to a cold-rolled steel plate and dried at 100 ° C for 30 minutes.

The coated plate was covered with another cold-rolled steel plate and compressed at 340 ° C for 2 minutes under a pressure of 20 kg / cm.

The joined plates had a shear strength of 130 kg / cm @ room temperature and 100 kg / cm @ 240 ° C.

Example XII

The reaction vessel mentioned in Example XI was charged with 49.0 g (0.10 mol) / /''-bisG-aminophenoxy-S / S / S '/ S'-tetramethyl-1/1' - spirobiindan and 211, 1 g of Ν, Ν-dimethylacetamide and 21.36 g (0.098 mol) of pyromellitic dianhydride were added in portions at room temperature under nitrogen atmosphere carefully so as not to raise the temperature of the solution above 30 ° C. The reaction mixture was further stirred at room temperature for 20 hours.

The polyamic acid thus obtained had an inherent viscosity of 0.79 dl / g.

The polyamic acid solution was applied to a cold-rolled steel plate which had first been washed with trichlorethylene and dried for 1 hour at both 100 ° C and 220 ° C. The coated sheet was covered with another cold-rolled steel sheet and pressed for 5 minutes at 340 ° C under a pressure of 20 kg / cm 2.

81-0 3 3 1 8 5 -19- 26130 / Vk / mvl

The pooled sample thus obtained had a shear strength of 250 kg / ctn at room temperature and of 180 kg / cm -at 240 ° C-

Example XIII

The reaction vessel mentioned in Example XI was charged with 49.0 g (0.10 mole) of bis-aminophenoxy] -Si2-tetramethyl-1. -spiro-biindan and 211.1 g Ν, Ν-dimethylacetamide and 21.36 g (0.098 mol) of pyromellitic dianhydride were added in portions at room temperature under a nitrogen atmosphere, which was carefully done so as not to raise the temperature of the solution above 30 ° C. The reaction mixture was further stirred at room temperature for 20 minutes.

The polyamic acid thus obtained had an inherent viscosity of 0.79 dl / g.

Part of the polyamic acid solution was poured onto a glass plate and heated at 100 ° C, 200 ° C and 300 ° C for 1 hour.

The polyimide film thus obtained had a glass transition point of 253 ° C and a reduction of 5% by weight at a temperature of 501 ° C in air.

The polyimide film was placed between cold-rolled steel plates preheated at 130 ° C and compressed for 5 minutes at 340 ° C under a pressure of 20 kg / cm.

The compressed sample had a shear strength of 2 260 kg / cin at room temperature and 185 kg / cr at 240 ° C.

Example XIV

The reaction vessel mentioned in Example XI was charged with 49.0 g (0.10 mol) 6.6, bis (3-aminophenoxy) -3,3,3, 3,3-tetramethyl-1,1 spirobiindan and 211 1 g Ν, Ν-dimethylacetamide and to this was added 21.36 g (0.098 mol) of pyromellitic dianhydride in portions at ambient temperature under nitrogen atmosphere, which was carefully performed so as not to raise the temperature of the solution above 30 ° C. The reaction mixture was further stirred at room temperature for 20 hours.

The polyamic acid thus obtained had an inherent viscosity of 0.79 dl / g.

After diluting 100 g of the polyamic acid solution by adding 150 g of Ν, Ν-dimethylacetamide, 7.13 g (0.07 mole) of triethylamine and 14.4 g (0.14 mole) of acetic anhydride were added and the 30303318 -20 - 26130 / Vk / mvl stirring was further continued at room temperature for 12 hours under nitrogen atmosphere. The reddish brown solution of the polyimide thus obtained was added to 1000 g of methanol.

The separated polyimide powder was filtered / washed with methanol and acetone and dried at 180 ° C for five hours under reduced pressure.

Fig. 3 shows the IR absorption spectrum of the polyimide powder thus obtained. The spectrum shows the remarkable absorbance -1-1 at about 1780 cm and 1720 cm, which are the characteristic absorption bands of the imide.

The polyimide powder thus obtained was applied to a cold-rolled steel plate and dried at 100 ° C for 30 minutes.

The coated plate was covered with another cold-rolled steel plate and pressed at 340 ° C for five minutes under a pressure of 20 kg / cm.

The compressed sample thus obtained had a shear strength of 263 kg / cm at room temperature and of 190 kg / cm 2 at 240 ° C.

Example XV

The reaction vessel mentioned in Example XI was charged with 49.0 g (0.1 mol) 6.6, bis (3-aminophenoxy) -3,3,3 ', 3,1-tetramethyl-1,1 spirobiindan and 241 .7 g Ν, Ν-dimethylacetamide and 31.56 g (0.098 mol) of 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride were carefully added in portions at room temperature under nitrogen atmosphere so as not to raise the temperature of the solution above 30 ° C. The reaction mixture was further stirred at room temperature for 20 hours.

The polyamic acid thus obtained had an inherent viscosity of 0.66 dl / g.

Part of the polyamic acid solution thus obtained was poured onto a glass plate and heated for 1 hour at 100 ° C, 200 ° C and 300 ° C.

The light yellow transparent polyimide film thus obtained had a glass transition temperature of 226 ° C and a reduction of 5% by weight of air at 503 ° C. The film also had a tensile strength of 8.9 kg / mrn and an elongation of 6%.

The polyimide film was placed between cold-rolled steel plates preheated at 130 ° C and compressed for 5 minutes at 340 ° C under a pressure of 20 kg / cm. The compressed S 50 3 3 1 8 thus obtained

-21- 26130 / Vk / mvL

2 sample had a shear strength of 260 kg / cm at room temperature and 180 kg / cm2 at 200 ° C.

Example XVI

The reaction vessel mentioned in Example XI was charged with 5 49.0 g (0.1 mol) 6.6, bis (3-aminophenoxy) -3,3,3 ', 3,1-tetramethyl-1,1 spirobiindan and 241 1.7 g Ν, Ν-dimethylacetamide and to this was added 31.56 g (0.098 mol) 3.3, 4.4, -benzophenone tetracarboxylic dianhydride in portions at room temperature under nitrogen atmosphere which was carefully performed so as not to alter the temperature of the solution 10 rise above 30 ° C. The reaction mixture was further stirred at room temperature for 20 hours.

The polyamic acid thus obtained had an inherent viscosity of 0.66 dl / g.

After diluting 100 g of the polyamic acid solution with 150 g of Ν, Ν-dimethylacetamide, 6.54 g (0.065 mol) of triethylamine and 13.2 g (0.13 mol) of acetic anhydride were added and stirring was continued at room temperature under nitrogen atmosphere. Stirring was continued for 12 hours.

The separated polyimide powder was filtered, washed with methanol and acetone and dried at 180 ° C for 5 hours under reduced pressure.

The polyimide powder thus obtained was applied to a cold-rolled steel plate and dried at 100 ° C for 30 minutes.

The coated sheet was covered with another cold-rolled steel sheet and pressed at 340 ° C for 2 minutes under a pressure of 20 kg / cm.

The compressed sample had a shear strength of p 2 265 kg / cm at room temperature and 181 kg / cm at 200 ° C.

In summary, the invention relates to a new polyimide and to its preparation, polyimide-based adhesives and to a process for the application.

The polyimide has repeating units of formula 1 represented on the formula sheet, wherein Y is a radical of formula 2 or 3 and wherein R is a tetravalent radical selected from the group consisting of an aliphatic radical of not less than 2 carbon atoms, cyclo- aliphatic radical, mono-aromatic radical, condensed polyaromatic radical and non-condensed polyaromatic radical, the € v 0 3 3 1 6 * -22- 26130 / Vk / mvl aromatic radicals being linked by a bond or a cross-linking function.

The polyimide can be prepared by reacting diamine with tetracarboxylic dianhydride in organic solvents and the imidization gives the polyamic acid.

The diamine used is an ether diamine having an industrial structure and includes 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl] -1,1,3-trimethylindan, 5- (3-aminophenoxy) - 3- [4- (3-aminophenoxy) phenyl] -1,1,3-trimethylindan, 6,6 * bis (4-aminophenoxy) -3,3,31,3'-tetramethyl-1,1'-spiro -10 biindan and 6,6-bis (3-aminophenoxy) -3,3,3,3,3-tetramethyl-1-1'-spirobiindan.

Various tetracarboxylic dianhydrides can be used, and especially preferred are the pyromellitic dianhydride and 3,4,4'-benzophenone tetracarboxylic dianhydride.

8603318

Claims (10)

Polyimide, characterized in that it is a polymer with repeating units of formula 1, wherein Y is a divalent radical represented by formula 2 or 3, which is an indan derivative with two oxy radicals and Y is bonded to two phenyl radicals in meta or in para positions and R is a tetravalent radical selected from the group consisting of aliphatic radical of not less than 2 carbon atoms, cycloaliphatic radical, mono-aromatic radical, condensed poly-10 aromatic radical and non-condensed polyaromatic radical in which the aromatic radicals are mutually linked with a bond or crosslinking function. Polyimide according to claim 1, characterized in that R is a tetravalent radical of formula 9 or 10. A process for preparing polyimide with repeating units of formula 1, wherein Y is a divalent radical represented by formula 2 or 3, which is an indan derivative with two oxy radicals and Y is bonded to two phenyl radicals in the meta or the para positions and R has the same meaning as defined in claim 1, characterized in that a diamine of formula 4, wherein Y has the same meaning as indicated above, is reacted with a tetracarboxylic acid anhydride of formula 5, wherein R has the same has meaning as indicated above, in an organic solvent and thermally or chemically imidizing the obtained polyamic acid with repeating units of formula 6, wherein Y and R have the same meaning as indicated above. 4. Process according to claim 3, characterized in that R is a tetravalent radical of formula 9 or 10. 5. «foodstuff based on a polyimide resistant to high temperature with repeating units of formula 1, wherein Y is a divalent radical represented by formula 2 or 3, which is an indan derivative with two oxy radicals and Y and R have the same meaning as stated in claim 1. 6. «High temperature resistant foodstuff according to claim 5, characterized in that R is a tetravalent radical of formula 9 or 10. 8303318 P ft -24- 26130 / Vk / mvl 7. A method of carrying out a bonding, by a polyimide with repeating units of the formula 1, wherein Y is a divalent radical represented by the formula 2 or 3, which is an indan derivative with two oxy radicals and Y is bonded to both phenyl radicals in the 5 meta or the para positions and R has the same meaning as indicated in the main claim, on a substrate, applying the coated surface to a substrate with an untreated surface or a surface coated with another substrate and heating under pressure above the glass transition point of the polyimide. The method of bonding according to claim 7, characterized in that the polyimide is prepared by applying a polyamic acid with repeating units of formula 6, which is a precursor of the polyimide, on a substrate and then imidizing it of the polyamic acid. Process according to claim 7 or 8, characterized in that R is a tetravalent radical of formula 9 or 10. Eindhoven, December 1986 6603318