DE1301909B - Process for making linear polyamides - Google Patents

Description

The invention relates to a method for producing linear polyamides from diprimary diamines with aliphatic or cycloaliphatic dicarboxylic acids with 2 to 20 carbon atoms, terephthalic acid, isophthalic acid or their chlorides or esters by thermal condensation or by boundary phase condensation in Presence of solvents.

The production of polyamides from diprimary, aliphatic diamines and dicarboxylic acids, such as. B. terephthalic acid and isophthalic acid, with increased Temperature, possibly in the presence of solvents, is already known, likewise the production of polyamides with the help of the so-called boundary phase condensation.

The method according to the invention is now characterized in that diprimary diamines are those diamines which are formed by dimerization of monomeric fatty acids with 8 to 24 carbon atoms, subsequent conversion into the dinitriles and hydrogenation have been prepared, or their mixtures with diamines of the general formula H2N-R-NH2, in which R is an aliphatic which may be interrupted by oxygen atoms or an aromatic radical having 2 to 20 carbon atoms is used.

The diamines used according to the invention to produce the polyamides are made from dimerized fatty acids. These dimerized fatty acids are reacted with ammonia to form the corresponding dimerized fatty acid nitriles, which are then hydrogenated. Relatively pure dimerized fatty acids can be obtained from commercially available polymeric fatty acid mixtures are distilled off. The term "fatty acid" like as it is applied here, it refers to the naturally occurring and synthetic ones monobasic, aliphatic monomeric acids that have a hydrocarbon chain Have 8 to 24 carbon atoms. The term "fatty acids" thus includes saturated ones as well as acids with a double bond and a triple bond.

The dimerization takes place in a known manner. To suitable saturated Fatty acids include caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, Palmitic acid, isopalmitic acid, stearic acid, arachidic acid, behenic acid and Lignoceric acid.

Suitable unsaturated fatty acids include 3-octenonic acid, 11-dodecenonic acid, Linderic acid, lauroleic acid, myristoleic acid, tsuzuic acid, palmitoleic acid, Petroselinic acid, oleic acid, elaidic acid, vaccenic acid, galoleic acid, cetoleic acid, Nervonic acid, linoleic acid, linolenic acid, eleostearic acid, hiragonic acid, moroctic acid, Timnodonic acid, eicosatetraenonic acid, nisinic acid, scoliodonic acid and chaulmugric acid.

Suitable examples of fatty acids with a triple bond are 10-undecanoic acid, Tariric acid, stearolic acid, behenolic acid and isamic acid.

Oleic acid and linolenic acid are the preferred starting materials for the production of dimerized fatty acids.

The dimerized fatty acids are converted into the corresponding dinitriles converted by reacting the dimerized fatty acid with ammonia. The details this implementation is described in Chapter 2 of the publication “Fatty Acids and Their Derivatives "by A. W. Ralston, John Wiley and Sons, Inc., New York (1948). It is essential that the diamine has a high degree of purity.

As aliphatic, cycloaliphatic or aromatic dicarboxylic acids with 2 to 20 carbon atoms come into question: Adipin-, Sebacin-, Terephthal- and Isoterephthalic acids and their chlorides and esters.

The esters can be alkyl or aryl esters, such as dimethyl adipate or sebacate, diethyl adipate or sebacate, diphenyl adipate and sebacate, dimethyl terephthalate and diphenyl terephthalate.

A part of the diamine used according to the invention can be by one or several additional diamines can be replaced, which have the following general formula: H2N-R "-NH2 in the R" is optionally interrupted by oxygen atoms or means aromatic radical with 2 to 20 carbon atoms. Examples of such Compounds are: ethylenediamine, propylenediamine, 1,2-diaminobutane, 1,3-diaminobutane, Trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, Decamethylene diamine, octadecamethylene diamine, m-xylene diamine, p-xylene diamine, cyclohexylene diamine, Bis-aminoalkyl ethers.

The equivalent ratio of the dimeric diamine to that given above second or further diamine can range from 95: 5 to 5:95.

Ratios from 25:75 to 75:25 are preferred.

The polyamides are made by reacting practically equivalent amounts of the starting compounds. A relatively small excess of either acidic reactants or the diamine can also be used.

The polyamides can be made from the diamines and an acyl chloride an interfacial polycondensation. So are the diamine and the chloride separated in a suitable solvent such as a hydrocarbon, z. B.

Benzene, dissolved. These solutions are then separated into an aqueous one Solution of a suitable emulsifier added. The aqueous phase should also contain a basic compound, such as sodium carbonate, so that in freedom to neutralize hydrochloric acid. The hydrocarbon solutions and the aqueous Phase are vigorously stirred to form an emulsion and then the solvent peeled off, which breaks the emulsion and granulates the polyamide.

The granules are removed by filtration, then washed and dried.

The polyamides can be made from the dibasic esters and acids will. This reaction is carried out by heating the products to such a temperature carried out that quickly a polyaminolysis of the ester or dehydration the polyamine salts of the acid occurs. Generally it is at the beginning of the implementation expedient, temperatures above 120 "C and preferably from about 150 to 180 "C. The final temperature will usually be and can be above 200" C range from 280 to 290 "C.

The working temperatures and the conversion time vary depending on the situation on the type of starting products and the properties desired in the end products. The reaction is usually carried out at normal pressure or elevated pressure, although towards the end of the reaction it is advantageous to apply under reduced pressure work. This working method supports the bringing into contact of the conversion products as well as the removal of the by-products and thus enables a quantitative as possible Yield. The condensation can optionally be carried out in the presence of suitable solvents or dispersion media are carried out with the proviso that such Media does not interact to any noticeable extent with the other components of the mixture implement and have the same boiling points that are sufficiently high so that the temperature can be kept at the desired level. As the amines and esters or acids have noticeable and generally different volatilities, it may be necessary to take it on the reflux cooler or in a closed vessel Pressure to work to reduce the loss of implementation participants. the more volatile products, such as alcohol, phenol or water, can also be used as mediators Passing the distillate through a fractionation column and recycling the less volatile products are removed in the reaction vessel. Through this The implementation will be completed more quickly.

The invention is described below on the basis of exemplary embodiments explained. The diamines used in the following working examples are distilled Diamines which have been obtained from dimerized fatty acids and which are essentially consist of mixtures of dimerized linolenic and oleic acids. It can be dimerized Fatty acids with practically any content of dimeric fatty acids are used, however, the content of dimeric fatty acids should preferably be in the order of magnitude of 80 ° / o or more.

Example 1 In a metal laboratory vessel are the following Ingredients introduced: 271 g (1.99 moles) of 85.4% aqueous hexamethylenediamine, 126 g (0.2205 mol) of distilled dimeric diamine, 326.5 g (2.23 mol, 1% molar Excess) adipic acid.

The metallic reaction vessel is then purged with nitrogen and sealed under nitrogen.

It is then gradually brought to a temperature over 1.5 hours heated from 150 to 250 "C.

The reaction will run for the next 1.5 hours at 250-270 "C kept under gradual depressurization so as to slowly relieve the pressure exerted by the water present in the hexamethylenediamine and developed by the reaction caused. At the end of this period, the reaction vessel becomes 1 hour long at a negative pressure (20 mm) formed by a water jet pump and then below Treated high vacuum for 0.5 hours. Then the reaction product from the Reaction vessel under a nitrogen atmosphere put in water. The product shows an inherent viscosity of 0.789 in m-cresol at 30 "C.

Example 2 To 400 ml of distilled water containing 0.5 g of emulsifier which Mainly composed of sodium lauryl sulphate, are placed in a mixer With a capacity of 1000 ml 200 ml benzene, which is 1.37 g (0.005 equivalents) contains distilled dimeric diamine, which is derived from dimerized fatty acids with a Dimer fatty acid content of 950 / o has been obtained, and 14.30 ml of a 20% Solution (0.045 equivalents) hexamethylenediamine (10:90 equivalence ratio) given. The mixture is stirred and 5.30 g (0.055 equivalents) Na2CO3 (10% excess over the total amine equivalents used) given with additional stirring.

A solution becomes practically in one pour to the dispersion obtained of 4.57 g (0.05 equivalents) of distilled adipyl chloride in 150 ml of benzene.

This mixture is stirred rapidly for 2 to 3 minutes and then the benzene is drawn off, breaking the emulsion and granulating the polyamide will. The granules are removed by filtration while using hot water washed until the washing water is free of chloride ions, and then under the negative pressure a water jet pump at 75 "C until constant weight is reached. The white, granular polyamide obtained has an intrinsic viscosity in m-cresol of 0.783 at 30 "C and a capillary melting point greater than 255" C.

The close correspondence of the inherent viscosities between the products according to Examples 1 and 2 proves the equivalence of the two production processes.

The product according to Example 1 is applied with a pressure of 13,600 kg of punch force (10.16 cm stamp) deformed at a temperature of 260 "C. This gives a deformed piece that is hard and rigid, and white and translucent quality owns.

Various polyamides are prepared according to the procedure of Example 2, various ratios of the dimeric diamine and hexamethylene diamine (HMDA) being reacted with adipyl chloride and sebacoyl chloride. The properties of the polyamides are shown in Table I below: Table I Equivalent to- Acid ratio own rapmar At- compound of dimer viscosity melt game point (Chloride) diamines (30 ° C) to HMDA ° C 3 Adipyl 5: 95 0.816 254-258 4 Adipyl 10:90 0.815 245 5 Adipyl 25:75 0.381 244-254 6 Adipyl 25:75 0.475 240 7 Sebacoyl 5:95 0.779 213-214 8 Sebacoyl 10:90 0.881 213-214 9 Sebacoyl 10:90 0.775 215 10 Sebacoyl 25:75 0.606 200-214 11 Sebacoyl 25:75 0.488 214 12 Sebacoyl 50:50 0.404 194 to 210 13 Sebacoyl 100: 0.434 156-170 Various polyamides are made using the acids or esters in place of the chloride, as in the following. Embodiments is shown.

In these embodiments, the mechanical properties deserve of the products manufactured according to the invention, such as the tensile strength and elongation, special attention. These properties are measured according to ASTM D-1248-58 T.

Tensile strength = - load in 0.454 kg at break cross-sectional area (6.45 cm2) The percent elongation is calculated as follows: Test length at break # Test length at 0 load% elongation = ## 100.

Test length at 0 load In addition to the breaking length and elongation most of the polymers produced have the following properties measured: 1. Ball and ring melting point -ASTM E 28-58 T.

2. Amine and Acid Numbers - conventional analytical titration methods. These are commonly referred to as the milligrams of potassium hydroxide equivalents per 1 g Amine or acids defined.

3. Intrinsic viscosity - defined by the equation: EIV island C where C = concentration of the polymer, expressed in grams per 100 ml of solvent, in rel = natural logarithm of the relative viscosity of the diluted polymer Solution.

In the following examples, all viscosities are in m-cresol measured at 30 "C, usually at a concentration of 1.0 / 100 ml.

4. Tensile modulus - as defined by ASTM D 638-60T.

5. Toughness (see Carswell and Nason, Symposium on Plastics, ASTM Philadelphia, February 1944, p. 23).

Example 14 In one with a stirrer, thermocouple and distillation head If the reaction vessel is provided, 276 g (0.97 equivalents) of distilled dimeric are obtained Diamine brought from the polymeric fatty acids of tall oil of the following analytical Composition has been prepared:% Monomer (M) ......... 0.2% Dimer (D) .......... ... 98.4% trimer (T) ......... 1.4 and 74.6 g (1.0 equivalent) of adipic acid given.

The mixture is left at 150 to 170 ° C for 1.5 hours, then 0.25 hours for a long time at 250 ° C and finally for 3 hours under reduced pressure (about < 0.1 mm Hg) heated to 250 ° C. The polyamide obtained has the following properties on: Amine number (mAq / kg) ................................ 0 Acid number (mAq / kg) ... ............................. 110 Ball and ring melting point (° C) 120 Intrinsic viscosity ................................ 0.37 elongation (%) ................................ 550 tensile strength (kg / cm2) .... ............................ 189 Example 15 In one equipped with a stirrer, thermocouple and distillation head The reaction vessel is 285 g (1.0 equivalent) of the distilled dimeric diamine given according to Example 14 and 74.6 g (1.0 equivalent) of adipic acid. The mixture will For 13/4 hours at 250 ° C, then for 2l / 2 hours at 250 ° C and finally Heated at 250 ° C for 13/4 hours under reduced pressure (about <0.1 mm Hg). The polyamide obtained has the following properties: Amine number (mAq / kg) 24 Acid number (mAq / kg) 29 Ball and ring melting point (° C) 155 Intrinsic viscosity ................................ 0.58 elongation (%) ................................ 500 tensile strength (kg / cm2) .... ............................ 280 Example 16 In one equipped with a stirrer, thermocouple and distillation head The reaction vessel is 285 g (1.0 equivalent) of the distilled dimeric diamine given according to Example 14 and 101.1 g (1.0 equivalent) of sebacic acid.

The mixture is heated to 150 ° C. for 0.5 hours, then 2 1/2 hours at 200 "C for 1 1/2 hours at 150 to 250 ° C and finally for 13/4 hours heated to 250 ° C under reduced pressure (about <10 mm Hg). The polyamide obtained has the following properties: Amine number (mAq / kg) ................................ 45 Acid number (mAq / kg) ................................ 16 Ball and ring melting point (° C) 154 Intrinsic viscosity ....... ........... 0.57 Elongation (%) ................... ............. 470 Tensile strength (kg / cm2) 287 Example 17 In a with stirrer, thermocouple and a reaction vessel provided with a distillation head, 285 g (1.0 equivalent) of the distilled dimeric diamine according to Example 14 and 99.5 g (1.0 equivalent) of dimethyl-1 , 4-cyclohexanedicarboxylate given.

The mixture is heated to 0 to 150 ° C. for 0.7 hours, then 1.5 hours for a long time at 150 to 250 ° C, then for 1.3 hours at 250 ° C and finally 2.1 Hours under reduced pressure (approx <0.1 mm Hg) Heated to 250 ° C. The polymer obtained has the following properties: Amine number (mAq / kg) .. ........ 218 Acid number (mAq / kg) ............................ .... 57 spherical and ring melting point ("C) .. 169 inherent viscosity ................ ... .. 0.29 elongation (%) ................................ 125 tensile strength (kg / cm2). 126 example 18 In a reaction vessel equipped with a stirrer, thermocouple and distillation head 285 g (1.0 equivalent) of the distilled dimeric diamine of Example 14 and 90.4 g (1.0 equivalent) of suberic acid.

The mixture is heated to 150 to 250 ° C. for 1 hour, then 2 hours to 250 ° C for a long time and finally to 250 ° C for 3 hours under reduced pressure heated. The polyamide obtained has the following properties: amine number (mAq / kg). .... 25 acid number (mAq / kg) ................................ 99 spherical and ring melting point (° C) 157 Intrinsic viscosity ....... ..... .... 0.61 elongation (%) ......... ... 500 tensile strength (kg / cm2) ... 280 Example 19 In a with stirrer, thermocouple and a reaction vessel provided with a distillation head, 285 g (1.0 equivalent) of the distilled dimeric diamine according to Example 14 and 99.5 g (1.0 equivalent) of dimethyl 1,4-cyclohexanedicarboxylate given.

The mixture is heated to 210 "C for 0.8 hours, then 1.5 hours to 210 to 270 ° C and finally for 3 hours under reduced pressure (approx <0.1 mm Hg) heated to 270 ° C. The polymer obtained has the following properties on: amine number (mAq / kg) ................................ 192 acid number (mAq / kg) ... ............................. 29 Ball and ring melting point (° C) 167 Intrinsic viscosity ................................ 0.30 elongation (%) ................................ 260 tensile strength (kg / cm2) .... .............. 119 Example 20 In one equipped with a stirrer, thermocouple and distillation head 285 g (1.0 equivalent) of distilled dimeric diamine are added to the reaction vessel, that of polymeric fatty acids of tall oil with the following composition:% M = 0.3 ° / 0 D = 97.1% T T = 2.6 and 74.7 g (1.0 equivalent) of adipic acid prepared has been.

The mixture is heated to 0-200 "C for 1.5 hours, then 0.5 hours for 200 to 250 "C, then for 0.75 hours at 250 ° C and finally 1 hour long under reduced pressure (about 0.2 mm Hg) heated to 250 ° C. The polyamide obtained has the following properties: amine number (mAq / kg) 60 acid number (mAq / kg) ............................... . 37 Ball and ring melting point (° C) .. 125 Intrinsic viscosity ................................ ...... 0.58 elongation (%) ................................ 540 tensile strength (kg / cm2) 280 Example 21 In one provided with a stirrer, thermocouple and distillation head The reaction vessel is 279 g (1.0 equivalent) of the distilled dimeric diamine given, that of polymeric fatty acids of tall oil with the following composition: % M M 0.6% D = 99.4% T = 0 and 74.7 grams (1.0 equivalent) of adipic acid prepared has been.

The mixture is heated to 100 to 250 "C for 2 hours, then 1 1/2 hours to 250 ° C and finally 2½ hours to 250 ° C under reduced pressure (about < 0.1 mm Hg). The polyamide obtained has the following properties: Amine number (mAq / kg) ................................ 25 Acid number (mAq / kg) ..... ........................... 28 Ball and ring melting point ("C) .. 146 Intrinsic viscosity. ..... .. .... 0.56 Elongation (%) .............. 470 to 540 tensile strength (kg / cm2). 224 to 245 example 22 In a reaction vessel equipped with a stirrer, thermocouple and distillation head are 279 g (1.0 equivalent) of distilled dimeric diamine of Example 21 and 86.3 g (1.0 equivalent) 1,4-cyclohexanedicarboxylic acid were added.

The mixture is heated to 100 to 250 "C for 1 1/2 hours, then 1 1/2 hours to 250 ° C and finally 3 hours under reduced pressure (about <0.1 mm Hg) heated to 2500 C. The polyamide obtained has the following properties on: amine number (mAq / kg) ................................ 67 acid number (mAq / kg) ... ............................ 32 Ball and ring melting point ("C) .. 200 Intrinsic viscosity.. ............. 0.49 Elongation (%) ................................ 290 Tensile strength (kg / cm2) 230 Example 23 In a reaction vessel equipped with a stirrer, thermocouple and distillation head are 276 g (1.0 equivalent) of distilled dimeric diamine of Example 21 and 73.1 g (1.0 equivalent) diethyloxalate given.

The mixture is heated to 150 to 250 "C for 1 1/2 hours, then up to 1 hour 250 ° C and finally 4 hours under reduced pressure (approx. <0.1 mm Hg) heated to 2500 C. The polyamide obtained has the following properties: Amine number (mAq / kg) ................................ 46 Acid number (mAq / kg) ..... ........................... 1.3 ball and ring melting point (° C) .. 100 inherent viscosity. . ...... 0.375 elongation (° / 0). 600 Tensile strength (kg / cm2) ....................... 105 Example 24 In a reaction vessel equipped with a stirrer, thermocouple and distillation head 276 grams (1.0 equivalent) of the distilled dimeric diamine of Examples 21 and 86.3 g (1.0 equivalent) 1,4-cyclohexanedicarboxylic acid added.

The mixture is heated to 100 to 250 ° C. for 11/4 hours, then 13/4 hours to 250 ° C and finally under reduced pressure (about <0.2 mm Hg) for 3 hours heated to 250 ° C for a long time. The polyamide obtained has the following properties on: amine number (mAq / kg) ................................ 19 acid number (mAq / k) ... ............................. 42 Ball and ring melting point (° C) ................. 191 Intrinsic viscosity. 0.53 Elongation (%) ................................ 320 Tensile strength (kg / cm2) ....... ................. 252 Tests were also carried out with regard to water absorption at room temperature carried out.

The results of the tests are given in Table II below.

Table II example 18 21 24 24 hours ......... 0.15 0.15 0.13 1 week ............. 0.34 0.37 0.28 2 weeks .......... - - 0.35 3 weeks ......... . $ 0.50 0.59 0.37 4 weeks 0, 54 0.54 0.68 68 5 weeks .............. 0.57 0.76 - 6 weeks .............. 0.61 0.84 - 7 weeks 0, ...... 0.61 0.84 - 8 weeks .............. - 0.95 - EXAMPLE 25 To 400 ml of distilled water containing 1 g of emulsifier consisting essentially of sodium lauryl sulfate, 200 ml of benzene containing 13.7 g (0.05 equivalents) of distilled dimeric diamine are added in a mixer having a capacity of 1000 ml which has been obtained from dimerized fatty acids. The mixture is stirred and then 5.3 g (0.05 mol) Na2CO3 are added with additional stirring. A solution of 5.08 g (0.05 livalents) of terephthalyl chloride in 150 ml of benzene is added to the resulting dispersion in one pour. This mixture is stirred rapidly for 2 to 3 minutes and the benzene evaporated. This breaks the emulsion and grains the polyamide. The grains are filtered off, washed with hot water until the washing water is free of chloride ions, and then dried to constant weight at 75 ° C. under a vacuum built up by a water jet pump. The white, granular polyamide obtained has an intrinsic viscosity in m-cresol of 0.434 and a capillary melting point of 156 to 170.degree.

Example 26 The procedure of Example 25 is repeated, however, isophthalyl chloride is used instead of terephthalyl chloride. The white, granular polyamide obtained has an inherent viscosity of 0.314 and a capillary melting point of 90 to 123 "C.

Example 27 Distilled mixtures obtained from dimerized fatty acids dimeric diamines and hexametitylenediamines are made with terephthalyl chloride using the same procedure and conversion ratios as described in Example 25 are implemented. The diamine ratios, intrinsic viscosities and capillary melting points of the white, granular opaque products are shown in Table III below specified.

Table III Equivalence- ratio of intrinsic capillary melting point HMDA Zll viscosity Equivalent to @@@@@@@@@ dimeric diamine ° C 5:95 0.39 168 to 212 10:90 0.40 170 to 214 25:75 0.39 charred at 263 75:25 insoluble 263 (change in color)

Claims (1)

Claim: Process for producing linear polyamides by Reaction of diprimary diamines with aliphatic or cycloaliphatic dicarboxylic acids with 2 to 20 carbon atoms, terephthalic acid, isophthalic acid or their chlorides respectively. Esters by thermal condensation or by boundary phase condensation in the presence of solvents, characterized in that one is called diprimary Diamines those diamines that are formed by the dimerization of monomeric fatty acids with 8 to 24 Carbon atoms, subsequent conversion into the dinitrile and hydrogenation or their mixtures with diamines of the general formula H2N-R-NH2, in R an aliphatic which is optionally interrupted by oxygen atoms or an aromatic radical having 2 to 20 carbon atoms is used.