DE909861C - Process for the production of clear, transparent plastics from polyamide, polyurea or polyurethane-forming compounds - Google Patents

Description

Process for the production of clear, transparent plastics made of polyamide, polyurea or polyurethane-forming compounds To plastics, by virtue of their good firmness and high toughness, their coloring and their thread-forming properties a special class of valuable high polymers represent, include the substances that are made of polyamide, polyurea or polyurethane forming Compounds made by polycondensation or polyaddition or by both can be. All of these high polymers that only consist of one of these condensable Connections are formed, are opaque and cloudy and in thicker layers, e.g. B. already in a layer z cm thick, completely opaque.

To the condensable polyamide, polyurea or polyurethane forming Compounds are mainly to be included in the following body classes Z. aminocarboxylic acids, such as 6-aminohexanoic acid, g-aminonanoic acid, r-aminoundecanoic acid; 2. Lactams of amino acids, like e-caprolactam; 3. Diamines + dicarboxylic acids in the form of their salts or of the individual Components, e.g. B. Ethylenediamine -f- adipic acid, hexamethylenediamine + adipic acid, Octamethylenediamine + sebacic acid, ß, 3'-diaminodiethyl sulfide - sebacic acid; q .. Urethane carboxylic acids, e.g. B. Urethylan-N-19-pelargonic acid; 5. diurethanes + dicarboxylic acids, e.g. octamethylene diurethylane or tetramethylene diurethane -f- sebacic acid or Adipic acid.

Furthermore are. useful, especially in connection with the substances of classes z to 5: 6. Diurethanes, such as octamethylene, tetramethylene, ethylene diurethylane or -diurethane; 7. Diurethanes + diols, e.g. B. Substances of class 6 -i glycol or i, 6-hexanediol; B. Diurethane -f- diamines, e.g. B. Substances of class 6 - octa-, hexamethylene-, ethylene-diamine; 9. Diurethanes + dihalohydrocarbons, e.g. B. Substances of class 6 -: - Ethylene bromide, i, 6-dibromohexane; ok Urethane carboxylic acids + diamines.

It has now been found that liischpolymers are composed of two or three compounds of the classes mentioned then clear and still in layers of one or more centimeters Thick transparent plastics result from using two or three starting materials polycondensed together and the melts obtained by cooling to deep Deterring temperatures. The common polycondensation of two or three starting materials of the type mentioned above and the subsequent rapid cooling of the melt in any case to clearer condensates than the merging of two or three Resins, each of which condenses on its own from a single starting material or has been polymerized, even if this melt is cooled rapidly. this applies in particular to groups i to 5, whereas one applies to groups 6 to io Concomitant use of compounds from groups i to 5 is advantageous.

To carry out the process, two or three different Starting materials of each of the above ten groups are used, indifferently whether the starting materials come from the same group or from different groups be taken. The prerequisite for the transparency of the resin mass is of course the absolute purity of the materials used. Additives such as zinc chloride, zinc acetate, Sodium acetate to the mixed resin groups favor the formation of clear end products, however, the resins often lose some of their good properties through such additives, such as elasticity and water resistance, so it is preferable in many cases is to work without such additives.

The rapid cooling of the molten products can be achieved by either Immersion in cold water, ice water, cold mixture, ether-carbonic acid mixture Or achieved by using carbon dioxide snow, preferably by squeezing it out the melt from the vessel into the quenchant.

Give the masses that have solidified once transparent and almost free of turbidity transparent again and again even with repeated melting and rapid cooling and completely or almost cloud-free polymers, which are more advantageous for many purposes are than the like cloudy products. Examples i. io g e-caprolactanx and 10 g of 9 aminonanoic acid are grounded in a steam atmosphere and heated at 250 ° for 6 hours. Then the melt is cooled by immersion in cold water and the mass received in crystal clear form. -2. 10 g of 9-aminonanoic acid and 10 g of urethylane-N, t9-pelargonic acid are heated at 2io 'for 45 hours. By cooling the melt in a carbonic acid-acetone mixture at -70 'a glassy, clear condensate is obtained.

3. 4 g of 9-aminonanoic acid and 4. g of hexamethylenediamine adipic acid salt are condensed for 16 hours at 200 'and then for 4 hours at 30o'. By Immersing the melt in cold water creates a glass-like, hard resin.

4. 4 g e-caprolactam and 5 g urethylan-N-O-pelargonic acid are 6 Heated at 25o 'for hours. Rapid cooling results in a clear condensate.

5. io g e-caprolactam and io g hexamethylenediamine sebacic acid salt are heated at 2io 'for 17 hours. This is done by quenching the melt in ice water the condensate obtained is crystal clear.

6. 4 g of a precondensed product from hexamethylenediamine-adipic acid of viscosity 1.7 (measured in an i-volume percent sulfuric acid) and 4. g e-caprolactam are heated for 16 hours at Zoo ', then 3 hours at 300'. Quenching the melt creates a clear, translucent resin.

7. 3 g of 9-amino acid, 3 g of e-caprolactam and 0.3 g of sodium acetate are heated for 4 hours at 22o 'and 1, hour at 26o'. The slowly cooling melt remains crystal clear.

B. 3 g of 9-aminonanoic acid, 3 g of hexamethylenediamine sebacic acid salt and 2.8 g of octamethylene diurethylane -; - 2 g of sebacic acid are 17 hours at 2io ' heated and cooled at - 6o '. The result is a haze-free, transparent one Resin that softens at about i3o '.

d. Crystal clear polyamides are made from 5 g of hexamethylene ketone isoxime (= E-caprolactam), 10 g hexamethylenediamine sebacic acid salt and 10 g hexamethylenediamine adipic acid salt, by heating these substances for 17 hours at zio 'and then cooling them in ice-water.

ok 10 g hexamethylenediamine sebacic acid salt, 10 g hexamethylenediamine adipic acid salt and 5 g of urethylan-O-pelargonic acid are heated for 16 hours at 220 '. By cooling down of the condensation vessel in an ice-salt mixture at - 20- a glassy, clear resin.

11. 5 g of 9-aminonanoic acid, 5 g of i, 6-hexamethylenediamine adipic acid salt and 5 g of urethylan-N-0-pelargonic acid are heated at 22o 'for 5 hours. By quenching of the condensation vessel at - ho ', a glass-like condensate is formed.

12. 5 g of 9-aminonanoic acid, 5 g of urethylane-N-0-pelargonic acid and 5 g e-caprolactam are heated at 22o 'for 17 hours. By cooling the vessel in Ice-salt mixture at - 20 'creates a clear resin.

13. 3 g of 9-aminonanoic acid, 3 g of hexamethylenediamine sebacic acid salt and 2 g of octamethylene diurethylane are heated at 2io 'for 17 hours. By quenching the melt at -15 'produces a transparent resin with a glassy appearance.

14. 3 g of 9-aminonanoic acid, 3 g of hexamethylenediamine sebacic acid salt and 2.6 g of i, 8-octamethylene diurethylane + i, i g of hexamethylene diamine are used for i7 hours at 21o- heated. By cooling the melt at --- io ', a hard, almost clear resin.

1y. 39 9-aminonanoic acid, 39 hexamethylenediamine-SebaClnS, "iure salt and 2.6g octamethylenediurethylan -rigi, 6-hexanediol" are heated for 17 hours at 21o ". After cooling in ice water, a hard, crystal-clear condensate is formed.

Claims (1)

PATENT CLAIM: Process for the production of clear, translucent Plastics made of polyamide, polyurea or poly, urethane-forming compounds, characterized in that two or three different resin-forming `compounds condensed together and the melted masses by cooling to low "temperatures be deterred.