DE2045770A1 - New polyamides and methods of making them - Google Patents

Description

DIpL-Ing. Karl Kiefcebm 2 O A 5 7 7

Godfather η ta η wal t 1 Berlin 1O ₁ Kaiaerdaaw 2S

September 11, 1970 P.5128

Asalii Kasei Kogyo Kabushilri Kaisha in Osaka City (Japan).

New polyamides and methods of making them.

The invention relates to new linear polyamides as well as a method for producing the same.

In particular, it relates to new linear polyamides which are at least 10 percent haul of periodic repeating structural units of the formula

-HN - CH - CH ₉ CH ₉ - CH - NH - C - R - C -

/ \ / \ H Il

CH ₂ CH - CH CH ₂ OO

CHp- CHp CHp "■ CHp

en
contains / wherein R is a divalent organic group selected from the group consisting of an alkylene group having 4 to 10 carbon atoms, 1,3-phenylene and

- 2 109617/2038

1,4-phenylene.

It also relates to a process for making the linear polyamides defined above.

Various methods for producing polyamides have heretofore been proposed, which are excellent Have light permeability (! Transparency). One of these methods is polycondensation an aromatic diamine or an aliphatic diamine and an unsymmetrical dibasic acid such as trimethyladipic acid. Usually this method gives a polyamide with a low glass transition point.

In addition, it has been proposed to produce a transparent polyamide by forming a copolymer by incorporating therein the raw materials of known polyamides such as polycapramide, polyhexamethylene adipamide, polyhexamethylene sebacamide and the like. However, these polyamides have the disadvantage that they have a glass transition point of only 2O ⁰ C and they are soluble in organic solvents such as alcohol and the like in a.

It has also been proposed that the amounts of the geometric isomers, for example bis (4-aminocyclohexyl) methane, which are used as the raw material of a polyamide to control or separate to the To decrease the amount of trans-trans-Ieomer, and thereby to improve the transparency of the polyamide. In this case, however, the separation operation is complicated and hence the process is not very useful from an economic point of view.

It is therefore a primary goal of the present Invention of showing a polyamide that has an excellent

- 3 109817/2030

excellent transparency as well as a high glass transition point.

As a result of extensive studies, it has now been found that new linear polyamides can be prepared by polycondensation of a dibasic acid and / or an amide-forming derivative thereof and a mixture of isomeric 3, -3'-diaminodicyclohexane and / or an amide-forming derivative thereof, and, if desired, another diamine, a lactam and / or an aminocarboxylic acid, this polyamide having at least 10 mole percent of a diamine component derived from a mixture of isomeric 3,3'-diaminodicyclohexane, and that these polyamides have excellent transparency and one have a high glass transition point of above 10O ⁰ C and are soluble in an organic polar solvent.

The present invention is based on this new finding.

In one aspect, a transparent, soluble in an organic polar solvent, linear polyamide is demonstrated by the present invention which, as measured, was in m-cresol, an inherent viscosity above 0.5 and a glass transition point above 100 ⁰ C and at least 10 mole percent periodically recurring structural units of the formula

- HN - CH - CH ₉ GHp - CH - NH - C - R - C -

y \ ^d / \ H II CH ₂ CH - CH CH ₂ OO ^N CH ₂ - CH ₂ ^X CH ₂ - CH ₂

St. 9817/2038

wherein R is a divalent organic group selected from the group consisting of an alkylene group having 4 to 10 carbon atoms, 1,3-phenylene and 1,4-phenylene is.

You invention polyamides have in addition to their excellent transparency and a high glass transition point, a high heat resistance and when they are melted at about 32O ⁰ C and shaped to have a good whiteness.

In contrast to the conventional aliphatic polyamides have a glass transition temperature of only about 50 ⁰ C and are crystalline, has the polyamide according to the invention, which has been obtained by polycondensation of adipic acid and 3,3'-Diaminodicyclohexan, a high glass transition point of 155 ⁰ C, and the present polyamide which obtained by polycondensation of dodecanedioic acid and 3,3'-Diaminodicyclohexan has a high glass transition point of 110 ⁰ C. In addition, has the polyamide obtained by polycondensation of an aromatic dibasic acid, for example isophthalic acid and 3,3'-Diaminodicyclohexan a high glass transition point of 245 ⁰ C Moreover, it should be noted that all of the aforementioned polyamides according to the invention have excellent transparency.

In connection with this, it should also be taken into account that if the polyamide according to the invention is at least 80 mol percent the diamine component derived from 3,3 · -diaminodicyclohexane the polyamide has a remarkably high post-transition temperature or glass transition temperature Has.

In another aspect of the invention, the present polyamide as defined above can be made

- 5 10 9817/2038

by, a method which is characterized by that Heating a substantially equimolar salt of a mixture of isomeric 3,3'-diaminodicyclohexane and / or an amide-forming derivative thereof and a dibasic acid represented by the following formula

HOOO - R - COOH

wherein R is an alkylene group having 4 to 10 carbon atoms, 1,3-phenylene or 1,4-phenylene and / or an amide-forming derivative thereof, the mixture of isomeric 3,3'-diaminodicyclohexane and / or said amide forming derivative thereof can be used alone or in a mixture, and the dibasic acid and / or the amide-forming derivative thereof can be used alone or in mixture, "to a temperature of 200 to 300 ⁰ C under normal pressure or under excess pressure, with subsequent heating the obtained polymer of low molecular weight on a! temperature of 250 to 35O ⁰ C under a pressure of 0.1 mm Hg to 760 mm Hg.

As an amide-forming derivative of 3,3'-diaminodicyclohexane For example, the diacetyl amide thereof and the dibenzoyl amide thereof can be used.

As mentioned above, the polyamide of the present invention has at least 10 mole percent of a diamine component derived from 3,3 '- ^ diaminodicyclohexane is derived. In the inventive Processes can therefore use diamine components other than those derived from 3,3'-diaminodicyclohexane are to be introduced. At most 90 mole percent of the mixture of isomeric 3,3'-diaminodicyclohexane can be used for this purpose and / or the amide-forming derivative thereof can be replaced by another diamine, a lactam

- 6 109817/2 0 38

and / or an aminocarboxylic acid, which can be used alone or in admixture. Suitable examples of such diamines include bis - ^ - aminocyclohexyl) methane, bis (4-aminocyclohexyl) ethane, hexamethylenediamine, m- or p-xylylenediamine or a mixture thereof, 1,4-diaminomethylcyclohexane, 1,4-diaminoethylcyclohexane, 4,4'-diaminodicyclohexane and 3,4'-diaminodicyclohexane, which is a by-product in the production of 3,3'-diaminodicyclohexane, which will be explained in more detail later. Suitable examples of such lactams include ε caprolactam, CQ -enantholactam and sodecanolactam. Suitable examples of such aminocarboxylic acids include E -aminocaproic acid, CO -aminopelargonic acid, cJ -aminoenanthic acid and ώ -aminolauric acid.

Dibasic acids which can be used in the process according to the invention are, for example, dibasic acids having 6 to 12 carbon atoms, such as adipic acid, pimelic acid, suberic acid, sebacic acid, azelaic acid, undecanedicarboxylic acid, bodecanedicarboxylic acid and od , oO -'-dimethyladipic acid; and aromatic dibasic acids such as isophthalic acid and terephthalic acid. Examples of the amide-forming derivatives of such dibasic acids include dimethyl ester, diphenyl ester, cyclohexyl ester and acid halides thereof.

The method to be used in the inventive 3 _t 3 'Diaminodicyclohexan is a novel compound which is represented by the formula

HgN - CH - CHg CHg - CH - NHg CHg CH - CH CHj ^X CHg- CHg ^X CHg - CHg

- 7 10981 7/2038

The mixture of isomeric 3,3'-diaminodicyclohexane can are prepared by hydrogenating 3,3'-dinitrodiphenyl or 3,3'-diaminodiphenyl in the presence of a rhodium catalyst, a ruthenium catalyst or a cobalt oxide or nickel oxide catalyst at elevated temperature and under high pressure.

The rhodium catalyst is defined as a catalyst which, as a catalytically active component, contains metallic rhodium, a rhodium oxide or an associated compound thereof, rhodium halide or a salt thereof, or a rhodium complex compound such as Rh — Al ₂ O 1, Rh — C, Rh -SiO _2, Rh ₂ O _3, Rh ₂ O ₅ -H ₂ O, Rh _£ 0, RhO, RhO ₂ · Η _£ 0, RhCl _5, RhF _5, RhCl ₅ · HgO, Rh (CN) ₅ · HgO, [Rh (NH ₅ ) ₆ ) Cl ₅ , [Rh (NH ₅ J ₅ Cl) Cl ₂ , (Rh (NH ₅ J ₅ (H ₂ O)] C1 ₅ , Na ₅ [Rh Cl ₆ ) or K ₂ [ Rh Al ₅ ).

The ruthenium catalyst is defined as a catalyst which acts as a catalytically active component contains metallic ruthenium, a ruthenium oxide, a ruthenium salt in which ruthenium is present as an anion or a ruthenium salt in which ruthenium is present as a cation and an anion does not polymerize is. Examples of such ruthenium catalysts include ruthenium oxide such as ruthenium sesquioxide, ruthenium dioxide and ruthenium tetraoxide; Ruthenium hydroxide; Salts of Perruthenite such as barium perruthenite and sodium perruthenite; Salts of ruthenic acid, such as potassium, sodium, Barium, strontium, calcium, magnesium and silver ruthenates; Perruthenate salts, such as potassium perruthenate and sodium perruthenate; Ruthenium halides, such as ruthenium pentafluoride, Ruthenium dichloride, ruthenium trichloride and Ruthenium tetrachloride; and salts of chloropruthenic acid, like potassium chloropruthenate.

109817/2038

Of these catalysts, preference is given to using catalysts such as ruthenium dioxide, potassium ruthenic acid, ruthenium carbon, ruthenium aluminum oxide, ruthenium silicon oxide, ruthenium hydroxide carbon or ruthenium hydroxide aluminum oxide, and ruthenium hydroxide (or Ru ₂ O ₃ · H ₂ O) - carbon.

If necessary, rhodium or ruthenium can be carried along by a carrier substance, such as active charcoal, Silica gel or alumina. Such catalysts carried by a carrier substance can be prepared by melting rhodium or an oxide thereof with sodium peroxide, dissolving it in water, soaking the carrier substance with the solution thus obtained and drying the impregnated mass, or by another known method.

The cobalt oxide or nickel oxide catalyst can be prepared, for example, by the method described in "PB Report" pages 13 to 742 (1941) or in Dutch Patent No. 17150 (1968). The catalyst is characterized in that it contains cobalt oxide or nickel oxide. For this catalyst system, one or more alkali metals and alkaline earth metals can be added, as well as from activating the carbonates, hydroxides and oxides of the catalyst and to improve the yield of the desired 3,3 ^I -Diaminodicyclohexans.

In the process for the production of 3,3'-diaminodicyclohexane becomes a rhodium catalyst, a ruthenium catalyst or a cobalt oxide or nickel oxide catalyst in an amount from 0.005 to about 10 percent by weight, preferably from 0.2 to 1.0 percent by weight,

- 9 1 ü 9 B 1 7/2038

drew on the amount of starting material used.

3? For the hydrogenation in this process becomes liquid Ammonia or aqueous ammonia is used. The liquid ammonia or the aqueous ammonia is in a Amount of 0.01 Ms 10 parts by weight per 100 parts by weight of the starting material is used. Liquid ammonia or Although aqueous ammonia can be used in an amount greater than that specified above, it will result there are no corresponding specific effects.

Hydrogenation in this method is usually effected until a benzene nucleus is completely saturated. The reaction time of 0.5 to 10 hours is sufficient for such a benzene nucleus to be saturated.

The solvent used in this method is generally an organic solvent, which under is not subject to hydrogenation under the conditions of this method, or water. Suitable examples of such organic Solvents include any of the saturated aliphatic hydrocarbons or cyclic hydrocarbons, such as η-hexane, cyclohexane, dioxane, ethyl ether, isopropyl ether, n-propyl ether, n-butyl ether, isobutyl ether, Amyl ethers, tetrahydrofuran and dicyclohexyl ethers. Methyl alcohol or ethyl alcohol can also be used will.

The solvent, if used, is generally used in an amount of from 0.2 to 2000 parts by weight, preferably used from 50 to 150 parts by weight per 100 parts by weight of the starting material.

The hydrogenation reaction is performed at elevated temperature under high pressure, nähmlich at a temperature of 100 ⁰ C to 300 ⁰ O, preferably from 120 ⁰ C to 23O ⁰ O, under a hydrogen partial pressure of more than 2 kg / cm,

- 10 -

10 9 8 17/2038

2 2

preferably from 50 kg / cm to 150 kg / cm. A reaction ^ emperature below 100 ⁰ C reduces the reaction rate, and a temperature above 23O ⁰ C the formation of a considerable amount of resinous substances for!, Which leads to a reduction in yield of the desired diamine. On the other hand, although the reaction can be carried out under a hydrogen partial pressure above 150 µg / cm, the practical advantages are reduced.

The preparation of the mixture of isomeric 3,3 ^I -diaminodicyclohexane is explained below, all parts and percentages being parts by weight and percentages by weight.

1. Production of 5.3'-Dinitrodiphenyl (a starting material for the production of 3t3'-I) iaminodicyclohexane) from Mtrobenzene and production of 3 _> 3 ^I -Diaminodiphenyl (another starting material for the production of 3.3 ^I -Diaminodicyclohe3can)

0.1 part of palladium chloride, 0.2 part of lead chloride and 0.1 part of potassium chloride were dissolved in dilute hydrochloric acid. To the resulting solution, 10 parts of granular silica gel was added, followed by evaporation Dry, which is made easier by adding alkali hydrazine hydrate, washed with water, and then dried. 10 parts of the obtained was placed in 0.2 part of an aqueous solution of potassium acetate, which was subject to evaporation

11 -

1 Ü9817 / 2038

was subjected to dryness, and then to manufacture of the catalyst further dried.

10 parts of nitrobenzene, 10 parts of acetic acid, 1 part of sulfuric acid (98 56) and 20 parts of the catalyst prepared in the above manner were introduced into a high-pressure vessel, and the whole thing was at 150 ^° C. under a

2 hydrogen partial pressure of 40 kg / cm was stirred for 10 hours.

The catalyst was removed from the resulting reaction mixture, and water was added to crystallize 3,3'-dinitrodiphenyl, which was washed with methanol to obtain 8 parts of the remaining unreacted nitrobenzene. 1.9 parts of 3,3'-dinitrodiphenyl with a melting point of 193 ^° C. were obtained.

3,3'-Diaminodiphenyl is easily obtained by reducing of 3,3'-dinitrodiphenyl in the presence of a Raney nickel catalyst according to the known method.

2. Preparation of 3 «3'-diaminodicyclohexane by hydrogenating 3 «3'-dinitrodiphenyl

An aqueous solution of RhCl ₅ ^ HpO was neutralized with 1 η aqueous KOH solution to a pH of 9 to form a precipitate, which was ^{dried at 80 °} C. for 5 hours to produce a catalyst.

In a pressure vessel were placed 20 parts of dioxane, 12.3 parts of 3,3 * -dinitrodiphenyl and 0.4 part of the above-prepared catalyst under a hydrogen partial pressure of 190 kg / cm, and the hydrogenation of 3.3 ^f -dinitrodiphenyl was carried out carried out at 130 ⁰ C for 2 hours. The reaction mixture obtained in this way was filtered to completely remove the catalyst.

- 12 -

1 0 9 8 1 7/2 Π 3 8

constantly removed, and then subjected to distillation, around the solvent and the water too. remove.

3.3 x -Diaminodicyclohexan with fully saturated by hydrogenating benzene nuclei having a boiling point of 12O ⁰ C to 127 ° C / 1mm Hg was withdrawn from the top of the column. 8 parts of 3,3'-diaminodicyclohexane were obtained, which is liquid at normal temperature and, based on an analytical result, was found to be 3,3'-diaminodicyclohexane.

?. Preparation of 3i3 ^f -diaminodicyclohexane by hydrogenating 3,3'-diaminodiphenyl

Into a pressure vessel were placed 12.5 parts of 3,3'-diaminodiphenyl, 3 parts of liquid ammonia and 5 $> Rh-alumina under a hydrogen partial pressure of 150 kg / cm, and the hydrogenation of 3,3'-dinitrodiphenyl was carried out in 1 hour at 200 ⁰ C causes. The reaction mixture thus obtained was filtered to completely remove the catalyst and then subjected to distillation. 12 parts of 3,3'-diaminodicyclohexane with benzene crystallization nuclei which are completely saturated as a result of the hydrogenation were obtained.

4 »Production of 3,3'-diaminodicyclohexane by hydrogenating 3,3'-dinitrodiphenyl

An aqueous solution of RuCl · HgO was neutralized with 0.1 η aqueous KOH solution to a pH of 8.5 to form a precipitate of 5 hours at 16O ⁰ C was dried.

- 13 -

1 09817/2038

20 parts of dioxane and 12.3 parts of 3 »3'-dinitrodiphenyl were placed in a pressure vessel

Hydrogen partial pressure of 150 kg / cm in the presence of 0.4 part of the ruthenium catalyst prepared in the above manner, and the hydrogenation of 3 $ 3'-dinitrodiphenyl was carried out ^{at 130 ° C. for 3 hours.} The reaction mixture thus obtained was filtered to completely remove the catalyst and then subjected to distillation to remove the solvent and water. 3,3'-Diaminodicyclohexane with benzene crystallization nuclei completely saturated by hydrogenation and with a boiling point of 120 to 127 ° C./1 mm Hg was withdrawn from the top of the column. 9 parts of 3 »3'-diaminodicyclohexane were obtained, which is liquid at normal temperature and, on the basis of an analytical result, was found to be 3>3'-diaminodicyclohexane. Yield: 87 fi *

5. Preparation of 3t3'-diaminodicyclohexane ■ by hydrogenating 3'3'-diaminodiphenyl

Into a pressure vessel were placed 12.5 parts of 3,3'-diaminodiphenyl, 3 parts of liquid ammonia and 0.4 part of RuO ₀ under a hydrogen partial pressure of 150 kg / cm, and hydrogenation of 3,3'-diaminodiphenyl was carried out during 1 Hour at 200 ^° C. The reaction mixture obtained in this way was filtered in order to remove the catalyst completely and then subjected to distillation. 3,3'-Diaminodicyclohexane with benzene crystallization nuclei which are completely saturated by hydrogenation and with a boiling point of 120 to 125 ° C / 1mm Hg

- 14 -

109817/2 0 38

was withdrawn from the top of the column. 12 parts of 3,3'-diaminodicyclohexane were obtained, which at normal Temperature is fluid.

6. Preparation of 3 »3'-diaminodicyclohexane by hydrogenating 3> 3'-dinitrodiphenyl

In a pressure vessel were placed 100 parts of dioxane, 100 parts of 3,3'-dinitrodiphenyl and 10 parts of a Cobalt oxide catalyst prepared by the method described in »P.B. Report "page 742 (1941) and which contained 10 parts of cobalt oxide, 15 parts of calcium oxide and 6.5 parts of sodium carbonate anhydride

under a hydrogen partial pressure of 150 kg / cm, and the hydrogenation of 3 »3'-dinitrophenyl was carried out ^{at 200 ° C. for 5 hours.} The reaction mixture thus obtained was filtered to completely remove the catalyst and then subjected to distillation to remove the solvent and water. 3,3'-Diaminodicyclohexane with benzene crystallization nuclei completely saturated by hydrogenation and with a boiling point of 120 to 127 ° C./1 mm Hg was withdrawn from the top of the column. 70 parts of 3 »3'-diaminodicyclohexane were obtained, which is liquid at normal temperature and is based on an analytical result, for example grass chromatography,

gyaphs
a mass spectrum of infrared absorption spectrum

proved to be 3,3'-diaminodicyclohexane.

7. Preparation of 3i3 ^f -diaminodicyclohexane by hydrogenating 3 ♦ 3'-diaminodicyclohexyl

- 15 -

10 98 17/2038

20 kg of pumice stone were treated with a 10% aqueous g ^ solution by boiling for 15 minutes and treated further with a 50% aqueous gluoxal solution. To the thus treated pumice were added followed by heating to dryness at 120 ⁰ O for 10 hours and further heating to 45O ⁰ C for 6 hours, 24 kg of nickel. The nickel oxide catalyst obtained in this way was introduced into a 10 J & Lge solution and then dried at 110 ° C. for 10 hours.

100 parts 3.3 ^! -Diaminodiphenyl, 5 parts of liquid ammonia, and 5 parts of the catalyst prepared in the above manner under a hydrogen partial pressure of 150 kg / cm, and the hydrogenation clay 3.3 ^f -Diaminodiphenyl was effected for 1 hour at 200 ⁰ G. The reaction mixture thus obtained was filtered to completely remove the catalyst and then subjected to distillation. 3,3'-Diaminodicyclohexane with benzene crystallization nuclei completely saturated by hydrogenation and a boiling point of 120 to 127 ° C / 1 mm Hg was withdrawn from the top of the column. 3,3'-Diaminodicyelohexane, which is liquid at normal temperature, was obtained in a yield of 90%.

When carrying out the process according to the invention, the polycondensation reaction can be effected without Limitation by some critical condition, rather under conditions that are customary for the production of polyamides are used. The polycondensation is, however, expedient / essentially by heating a equimolar salt of a mixture of isomeric 3,3'-di-

- 16 -

109817/2 0 38

aminodicyclohexane and / or an amide-forming derivative thereof and a dibasic acid of the formula

HOOC -R- COOH,

where R has the meaning described above, and / or an amide-forming derivative thereof in the presence or absence of water at a temperature of 200 to 300 ⁰ C under normal pressure or under increased pressure, and then heating the resulting polymer with low molecular weight at a temperature of 200 to 35O ⁰ C under a pressure of 0.1 to 760 mm Hg. the presence of water is advantageous because it dissolves the salt contained therein. Water is used in an amount of 5 to weight percent based on the amount of salt. In the case of polymerization, it is advantageous to carry out the polymerization until the intrinsic viscosity or intrinsic viscosity of the polyamide formed, measured in m-cresol at 35 ° C., is at least 0.5.

Especially when a halide of dibasic acid is used as an amide-forming derivative of dibasic acid, the polycondensation of the present invention can be carried out in an organic polar solvent such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrolidone or the like. The solvent is preferably used in an anhydrous state. The reaction can be brought about at a low temperature, preferably in the range from ⁰ ° C. to 100 ^° C., because it is a solution polymerization. The reaction is complete within 1 to 10 hours. The hydrogen halide formed in the reaction is expediently removed by neutralization. For this purpose, an epoxy compound such as phenylglycidyl ether, epichloro can be added to the reaction system

- 17 -

1Ü9817 / 2038

hydrin, ethylene oxide, propylene oxide; a tertiary amine, such as trimethylamine, triethylamine, tributylamine, pyridine, quinoline * N, H ^f -DiiDethylaniline; or an alkali or alkaline earth metal hydroxide such as sodium hydroxide, potassium hydroxide and calcium hydroxide.

When carrying out the method according to the invention, an additive, a stabilizer, a pigment, such as Titanium white, carbon black., Or the like, and / or one of the gloss removing agents commonly used for polyamides be added, namely during the course of the polymerization or after the end of the polymerization.

The novel polyamides according to the invention have a glass transition point of above 10O ⁰ O, and they are excellent in terms of their transparency and soluble in an organic polar solvent such as dimethylformamide, Dimethy lace tamid, dimethyl sulfoxide, If-methylpyrrolidone and the like. These polyamides have a wider range of uses such as fibers, coating materials, compressible materials, and castable materials.

Embodiments are given below for purposes of detailed explanation, but without limitation of the invention here.

The "glass transition point ¹¹ , which is used in the description and in the following examples, was measured by the following method:

A sample is placed in a cuvette for various thermal analyzes, which has ^{melted at 320 0} O in a stream of nitrogen and then rapidly cooled. Thereafter

- 18 -

109817/2038

the temperature is increased at a rate of 16 ⁰ C per minute in a nitrogen stream troclmen. The center of a part in which the base line changes is defined as a glass transition point.

example 1

146 parts of adipic acid were added to 196 parts of 3,3'-diaminodicyclohexane, a mixture of isomers which ^{is liquid at 25 °} C. and which was introduced into a reaction vessel, and the reaction vessel was opened under a pressure of 25 at for 1 hour 200 ⁰ C heated. Then, the heating was continued for 1 more hour at 25O ⁰ C under a pressure of 1 mm Hg to remove the water. This gave a transparent polyamide having an inherent viscosity and intrinsic viscosity of 1.23, a glass transition point of 155 ⁰ C and a flow temperature of 200 ⁰ C.

Example 2

The procedure described in Example 1 was repeated with the exception that 174 parts of at , oL '-dimethyladipic acid were used in place of adipic acid. This gave a transparent polyamide having an inherent viscosity of 1.25, a glass transition point of 157 ⁰ C and a flow temperature of 20O ⁰ C.

- 19 -

10 9 8 17/2038

Example 3

The procedure described in Example 1 was repeated except that 160 parts of pimelic acid were used in place of adipic acid. A transparent polyamide was obtained having an inherent viscosity of 1.30, a G-lasumwandlungspunlct of 150 ⁰ C and a flow temperature of 195 ⁰ C.

Example 4

The procedure described in Example 1 was repeated except that 174 parts of suberic acid (suberic acid) were used in place of adipic acid. A transparent polyamide was obtained having an inherent viscosity of 1.27, a glass transition point of 148 ⁰ O and a flow temperature of 193 ⁰ O.

Example 5

The procedure described in Example 1 was repeated except that 188 parts of azelaic acid were used in place of adipic acid. A transparent polyamide was obtained having an inherent viscosity of 1.28, a Giasumwandlungspunkt of 145 ° C and a flow temperature of 182 ⁰ C.

Example 6

To 196 parts of 3,3 ^I -diaminodicyclohexane, a

- 20 -

109817/2038

mixture of isomers, which is liquid at 25 ⁰ C, and which was placed in a reaction vessel, 250 parts of dodecanedioic acid were added, and the reaction vessel was charged under nitrogen with a pressure of 1 atm for 1 hour at 20O ⁰ C heated. The heating was then continued for 5 hours at 260 ^° C. under atmospheric pressure. This gave a transparent polyamide having an inherent viscosity of 1.05, a glass transition point of 110 ⁰ C and a flow temperature of 150 ⁰ C.

Example 7

The procedure described in Example 6 was repeated except that 202 parts of sebacic acid were used in place of dodecanedicarboxylic acid. This gave a transparent polyamide having an inherent viscosity of 1.29, a glass transition point of 120 ⁰ C and a flow temperature of 160 ⁰ C.

Example 8

The procedure described in Example 6 was repeated except that 216 parts of undecanedicarboxylic acid were used in place of dodecanedicarboxylic acid. A transparent polyamide was obtained having an inherent viscosity of 1.30, a glass transition point of 115 ⁰ C and a flow temperature of 155 ⁰ C.

- 21 -

10981 7/2038

Example 9

To 98 parts 3.3 ^! -Diaminodicyclohexane, a mixture of isomers, which ^{is liquid at 25 0} C, and which was introduced into a Realrfcionsgefaß, 83 parts of isophthalic acid and 10 parts of water were added, and the reaction vessel was heated under nitrogen with a pressure of 25 atm. Then heating was continued for 1 hour at 20O ⁰ G under a pressure of 1 mm Hg. A transparent polyamide was obtained having an inherent viscosity of 1.21, a glass transition point of 245 ⁰ C and a flow temperature of 29o C. ⁰

Example 10

The procedure described in Example 9 was repeated except that 83 parts of terephthalic acid were used in place of isophthalic acid. A transparent polyamide was obtained having an inherent viscosity of 1.25, a glass transition temperature of 34O ⁰ C and a flow temperature of 260 ⁰ C.

Example 11

To 98 parts of 3.3 ^I -Diaminodicyclohexan, a mixture of isomers, which is liquid at 25 ⁰ C and which was introduced into a reaction vessel were added 41 parts of terephthalic acid and 35 parts of adipic acid, and the reaction vessel was charged under nitrogen with a pressure from 25 at 1 hour to 240 ⁰ C heated. Then the

- 22 -

1098 17/2038

continued heating at 30O ⁰ O under a pressure of 1 mm Hg for 1 hour to cause polymerization. A transparent polyamide was obtained having an inherent viscosity of 1.15, a glass transition point of 253 ° C and a flow temperature of 291 ⁰ C.

Example 12

36 parts of hexamethylenediamine, 83 parts of isophthalic acid and 5 parts of water were added to 65 parts of 3,3'-diaminodicyclohexane, a mixture of isomers which ^{is liquid at 25 ° C. and which was introduced into a reaction vessel.} The reaction vessel was charged under nitrogen with a pressure of 25 at 1 hour at 23O ⁰ C heated. Then heating was continued for 1 hour at 300 ^° C. under a pressure of 1 mm Hg. A transparent polyamide was obtained having an inherent viscosity of 1.23, a glass transition point of 200 ⁰ C and a flow temperature of 275 ° C.

Examples 13 to 16 and Comparative Example 1

merized

Series of polymerizations carried out in the same manner as described in Example 12 with the exception that in each case the molar ratio of 3,3 * -diaminodicyclohexane to Parajtylylenediamine is changed, which can be seen from Table 1 can be seen. The results of the polymerizations thus effected are shown in the same table.

- 23 -

109817/2038

The polymerization realrfions were each effected using isophthalic acid, the moles of which were equal to the sum of the moles of S ^ ' and paraxylylenediamine

- 24 -

109817/2038

ro
I. example Molar ratio
from 3,3'-Di-
aminodicyclo-
hexane to para
xylylenediamine Tabel 1 Sansparenz Glass wall
settlement point
( ⁸ C) Flow temperature
rature
( ⁰ C) t
ro NJ -Λ
CD 13th 3: 1 out
draws 230 285 ¹ O 7 /? ( 14th 3: 2 Own vis
kosity out
draws 180 265 co
cc 15th 3: 3 1.26 out
draws 120 255 16 1: 2 1.32 Well 108 260 Comparative
example 1 *
1: 3 1.61 bad 75 270 1.25 1.23

2,577

Example 17

33 parts of 4,4'-diaminodicyclohexane and 83 parts of isophthalic acid were added to 65 parts of 3,3'-diaminodicyclohexane, a mixture of isomers which ^{is liquid at 25 °} C. and which was placed in a reaction vessel, and the reaction vessel was added ^{heated to 240 0} O for 1 hour under nitrogen with a pressure of 26 at. Then heating was continued for 1 hour at 300 ⁰ G under a pressure of 1 mm Hg. A transparent polyamide was obtained having an inherent viscosity of 1.31, a glass transition point of 260 ⁰ C and a flow temperature of 33O ⁰ C.

Example 18

65 parts of 3,3'-Maininodicyclohexan, a mixture of isomers, which is liquid at 25 ⁰ C, 33 parts of 3,4'-Diaminodicyclohexan and 83 parts of isophthalic acid were polymerized in the same manner as in Example 17th The eopolyinerisierte polyamide thus obtained was a transparent resin having an inherent viscosity of 1.21, a GIaBumwandlungspunkt of 240 ⁰ C and a flow temperature of 289 ⁰ C.

196 Tel ie 3,3 '-Di am i nod i cyelohexan, a Gera iacii τοπ isomers, which α. at 25 ⁰ C liquid ink, and 203 'i.'oLlö terephthaloyl chloride were in Gegenwarb of 184 parts

1 0 9 8 17/2 0 3 B.

2 η / {s 7 7 ο

Pyridiri brought under stirring in 2000 parts of dimethylformamide at 25 ⁰ C for 5 hours aur reaction. A polyamide was thus obtained in the form of a solution of dimethylformamide. The intrinsic viscosity of the polyamide was 2.03 and a glass wall limit point was 34O ⁰ G,

Example 20

196 parts of ^^ '- DLamüiodicyclohexan, a mixture of isomers, which is liquid at 25 ⁰ C, and 203 parts of isophthaloylechloride were brought to reaction in 2000 parts of dimethylacetamide for 5 hours at 25 ° 0 with stirring. After the reaction, 148 parts of calcium hydroxide were made added to the obtained reaction according to L s cn; to neutralize the hydrochloric acid gas formed. There was thus obtained a polyamide in the form of a solution of dimethylformamide, The intrinsic viscosity of the polyamide was 1.82 and its glass transition point of 245 ⁰ C.

Patent claims:

1 i) ⁽ A i)} 7 / ? ι)! J

Claims (1)

- 27 claims: 11.7 A transparent, soluble in an organic polar solvent, linear polyamide having a measured in m-cresol inherent viscosity of above 0.5 and a glass transition point above 100 ⁰ C and with a content of at least 10 mole percent of recurring structural units of the formula - HN - CH - CH ₀ CH ₀ - OH - BH - C - R - 0 - / \ ^2/2 \ Il -II CH ₀ CH - CH CH ₀ 0 0 CH ₂ - CHg CH ₂ - CHg wherein R is a divalent organic group from the group consisting of an alkylene group having 4 to 10 carbon atoms, 1,3-phenylene and 1,4-phenylene jet. 2. A transparent, in an organic polar solvent soluble, linear polyamide according to claim 1, characterized in that it is at most 90 mole percent one of - HN - CH - CH ₀ CH ₀ - CH - NH - / \ ^2/2 \ CH ₉ CH-CH 'CH ₉ CH ₂ - CHg CHg - CHg contains different diamine component, which is derived - 28 - 1 night 9 8 1 7/2 0 3 8 of a diamine, a lactam and / or an aminocarboxylic acid, the diamine component being incorporated therein alone or in admixture. 3. A transparent, in an organic polar solvent soluble, linear polyamide according to claim 2, characterized in that the diamine is selected from the group consisting of bis (4-aminocyclohexyl) methane, Bis- (4-aminocyclohexyl) -ethane, hexamethylenediamine, m- or p-xylylenediamine or a mixture thereof, 1,4-diaminomethylcyclohexane, 1,4-diaminoethylcyclohexane, 4,4'-diaminodicyclohexane and 3,4'-diaminodicyclohexane. 4. A transparent, in an organic polar solvent soluble, linear polyamide according to claim 2, characterized in that the lactam is selected from the group consisting of £ -caprolactam, £ J-enantholactam and dodecanolactam. 5. A transparent, soluble in an organic polar solvent, linear polyamide according to claim 2, characterized in that the aminocarboxylic acid is selected from the group consisting of du- amino enanthic acid, 60-aminopelargonic acid, ^ ü-aminododecanoic acid and S- aminocaproic acid. 6. A process for preparing transparent one, soluble in an organic polar solvent, linear polyamide having a measured in m-cresol inherent viscosity of above 0.5 and a glass transition point above 100 ⁰ C, characterized by heating a substantially equimolar salt of a mixture of isomeric 3,3'-diaminodicyclohexane and / or an amide-forming derivative thereof and a dibasic acid of the following formula HOOC - R - COOH - 29 - 109817/2038 wherein R is an alkylene group having 4 "to 10 carbon atoms, 1,3-phenylene or 1,4-phenylene and / or an amide-forming derivative thereof, the mixture of isomeric 3,3'-diaminodicyclohexane and / or said amide -forming derivative thereof can be used alone or in a mixture, and the dibasic acid and / or the amide-forming derivative thereof can be used alone or in a mixture, to a temperature of 200 to 300 ⁰ C under normal pressure or under excess pressure, with subsequent heating the obtained polymer of low molecular weight to a temperature of 250 to 35O ⁰ C under a pressure of 0.1 mm Hg to 760 mm Hg. 7. The method according to claim 6, characterized in that the heating to a temperature of 200 ⁰ C to 300 ⁰ C in the presence of 5 to 50 percent by weight of water, based on the amount of salt, is carried out. 8. The method according to any one of claims 6 or 7, characterized in that at most 90 mole percent of the mixture of isomeric 3,3'-diaminodicyclohexane and / or the amide-forming derivative thereof are replaced by one of 3,3'-diaminodicyclohexane different diamine, a lactam and / or an aminocarboxylic acid. 9. The method according to claim 8, characterized in that that the diamine is selected from the group consisting of bis (4 ^ amiöocyclohexyl) methane, bis (4-aminocyclohexyl) ethane, Hexamethylenediamine, m- or p-xylylenediamine or a mixture thereof, 1,4-diaminomethylcyclohexane, 1,4-diaminoethylcyclohexane, 4,4'-diaminodicyclohexane and 3 »4'-diaminodicyclohexane. 10. The method according to claim 8, characterized in that the diamine is selected from the group consisting of 109817/2038 from £ -caprolactam, CO -ÖnantliolactaiD and dodeeanolactam. 11. The method according to claim 8, characterized in that the iminocarboxylic acid is selected from the group "consisting of £ -aminocaproic acid, 6J -aminopelargonic acid, CO -aminoonanthic acid and ώ -aminododecanoic acid. 12. The method according to any one of claims 6 or 7, characterized in that the mixture of isomeric 3,3'-diaminodicyclohexane is prepared by a process which "consists in the hydrogenation of 3,3'-dinitrodiphenyl or 3,3'- Diaminodiphenyl "at a temperature of 100 to 300 ⁰ C under a hydrogen partial pressure of 2 2 2 kg / cm "to 150 kg / cm in the presence of a catalyst, such as rhodium, a rhodium compound, ruthenium, a Ruthenium compound, cobalt oxide or nickel oxide. 13. A method for producing a transparent in an organic polar Lösungemittel soluble, linear polyamide having a measured in m-cresol inherent viscosity of above 0.5 and a glass transition point above 100 ⁰ C, characterized by the reaction of a mixture of isomeric 3,3 ' -Diaminodicyclohexane with a halide of a dibasic acid of the formula XOOC - R - COOX wherein R is an alkylene group having 4 to 10 carbon atoms, the 1,3-phenylene or 1,4-phenylene group and X is a halogen atom, in an organic polar solvent at a temperature of 0 to 100 ^° C. 14. The method according to claim 13, characterized in that the reaction mixture is treated with a member, selected from the group consisting of epoxy compounds, tertiary amines, alkali metal hydroxides and alkaline earth metal hydroxides . 109817/2038