DE1669412C3 - - Google Patents

Description

such as in the wrapped or wrapped "^,

State to be used. The main areas of application 60 ²

are corsetry, sportswear fabrics, support stockings and the manufacture of elastic waistbands on ¹ ^
Lingerie and stockings. The basis for making the

elastic threads and fibers are mostly high- _{molar, in which R 1} and R _{2 are} lower alkyl radicals or R ₁ and R ₂ are segmented polymers with urethane and urine- 65 together with the carbon atom form a cycloaliphatic substance group which, according to the isocyanate polyaddition The remainder mean, in a molar ratio of 50:50 to 85:15, process from hydroxyl-containing polyesters to high-molecular-weight polyurethane-polyurea-poly or polyethers, diisocyanates and diamines, and extend the highly viscous spinning solution

then after the wet or dry spinning process at least, however, only 80 to 150 mVal of tertiary embroidery elastic Threads twisted. Examples of such di- material per kilogram of Elastojnerubstan = available, Amines are 2,2-bis- (4'-aminophenyl) -propane and for the production of pglyoretban-poryhamstoff, l-bis- (4'-aminophenyl) -cyclohexane. Solutions are those obtained in the melt

To carry out the process, essentially linear hydroxyl 35 ° C., preferably below 25 ° C., are slowly converted into grtippenhaltige polyester with an average mol of a solution of ethylenediamine and the additional weight from 1600 to 2600, preferably 1700 to 210G, diamine in a polyacrylonitrile solvent in the melt or in inert solvents, as metered. The amount of solvent is usually methylene chloride, tetrahydrofuran, dioxane, benzene, such that after the end of the extension reaction chlorobenzene, optionally mixed with lower, the desired final concentration of the polymolecular diols with one or more teruretban polyurea solution is present . The Verlängetiären nitrogen atoms, addition reaction with diphenylmethane-4,4'-di- is a rapid viscosity increase isocyanate reacted below 130 ⁰ C. The connected ratio, with viscosities between 150 and the OH to NCO groups, should be ^{achieved at 20 0} C at the 15 600 poise used. The setting for components is only 1: 1.5 to 1: 1.95, so that a desired higher final viscosity then results in pre-adducts with free NCO groups. often by adding a small amount of hexamethylene

The starting material used linear poly-1,6-diisocyanate, tetramethylene-1,4-diisocyanate or

esters with terminal hydroxyl groups can be biuret triisocyanate, which by reaction of 3 mol

by condensation of dicarboxylic acids and diols ao hexamethylene-1,6-diisocyanate and 1 mol of water

is recovered in a known manner at elevated temperature. Most of the time, however, the isocyanates

put. The acid numbers should generally be below 8, added diluted with a little solvent,

preferably from 0 to 3. The melting point of the solids content of the finished elastomer solution

Polyester should expediently be less than 60 ° C. and can be 18 to 30 percent by weight. The Ver-

otherwise the elastic properties of the final 95 turned polyacrylonitrile solvents, such as N, N-Di-

products especially at low temperatures- methylformamide, Ν, Ν-dimethylacetamide and N-Me-

go and also the tendency of the polymers to gel in thylpyrrolidone, must be free of such constituents

Solution is adversely affected. Be as dicarboxylic acids capable of reacting with diisocyanates;

for these polyester z. B. succinic acid, adipine- however, these solvents can be technically

acid. Contain pimelic acid, azelaic acid, sebacic acid, thio- 30 usual small amounts of water,

called dibutyric acid and sulfonyldibutyric acid. As the molar ratio of the applied extender

Diols can e.g. B. Ethylene glycol, diethylene glycol, mixture of ethylene diamine and the additional

1,2-propanediol, 1,3-butanediol, 1,4-butanediol, hexane-diamine can be varied from 50:50 to 85:15,

diol-1,6, hexahydro-p-xylylene glycol, 2,2-dimethyl is preferably 75:25 to 80:20.

1,3-propanediol, 2,2-diethyl-propanediol-1,3 and their ratio of the extender mixture is partially

Alkoxylation products are used. Even through that in the production of the NCO-containing

Polyesters from lactones, e.g. B. r-caprolactone, pre-adducts used ratio of OH- to NCO-

Starting materials to be used advantageously. Groups specified. Generally this is how it works

Since it is with the in this way produced poly before that with a relatively low NCO content in the pre

esters are very reactive components, 40 adduct also a low proportion of additional di-

it is quite common to apply the polyester in the extender mixture before the further amine,

Reaction with diphenylmethane-4,4'-diisocyanate while, conversely, a higher NCO content before

by adding small amounts of dioxane-SO ₂ adduct, a higher proportion of additional di-

Benzoyl chloride or traces of hydrogen chloride to amine for the production of non-gel-forming polyurethane

deactivate. 45 polyurea solutions required. The at the

The amount of the diamine mixture used optionally in admixture with the poly-lengthening of the low molecular weight diols with one or more tertiary nitrogen atoms, depending on the pre-adduct or more tertiary nitrogen atoms, is the given OH to NCO ratio and the desired one is bisalkoxylation products more primary and the final viscosity 90 to 140 mol percent, based on the secondary amines with ethylene oxide, propylene oxide and 50 free NCO groups present in the pre-adduct.
Biitylene oxide with a molecular weight below 500. For the production of the polyurethane-polyurea, N-methyl-diethanolamine may be mentioned, for example, but it is not absolutely necessary to use the N-butyl-diethanolamine, N-cyclohexyl-diethanol melt of the NCO-containing pre-adduct to meter into the amine, N, N '- di - (ß - hydroxyethyl) - N ₁ N' - diethyl solution of the extender mixture. According to hexahydro - ρ - phenylenediamine, Ν, Ν '- di - (β - hy- 55 of another embodiment, it is definitely possibleroxyethyl) -N, N'-dimethyl-ethylenediamine and bis- borrowed, the pre-adduct melt in part of the polyj8- hydroxyethyl piperazine. However, acrylonitrile-solvent are preferred to dissolve and rapidly to about N-methyl-diisopropanolamine and Ν, Ν'-Di - (. Β hydrogencarbonates cool 25 to 30 ⁰ C. This solution is then as droxypropyl) -N, N'- dimethyl-ethylenediamine used. previously described in the solution of the extender but also low molecular weight basic polyethers with 60 mixture. However, if the pre-adduct is in tertiary nitrogen atoms, which is produced by condensation of one of the aforementioned inert solvents in the presence of, then it is generally advisable that solution phosphoric acid are accessible and can be mixed with the agent by distillation to form polyester before the extension reaction. Remove the amount of diols, but the process will in no way contain one or more tertiary nitrogen atoms. However, the presence of these inert solvents should always be such that the content of is impaired, provided that their proportion is based on the tertiary nitrogen atoms on the finished total amount of solvent, not exceeding 20 percent by weight of elastomer substance 200 meq / kg, mei-. Of course it is possible to do this

To add titanium dioxide, talc or other pigments to elastomer solutions before further processing, or even to add these pigmentation agents to use the extension reaction.

In compliance with the specified conditions p Polyurethane-Polybarnstoff-Polymers obtainable in solution are because of their good solubility and the Resistance of your solutions to gel formation and degradation at room or slightly elevated temperatures for the technical processing of special bexo interpretation. The production of the elastic threads or fibers takes place according to the known methods of Dry spinning technique, i.e. by spinning the elastomer solution in air or inert gases at increased Temperature, or wet, d. H. by injecting the elastomer solution into coagulation baths and winding the obtained threads, with a surface treatment to prevent the thread winding from sticking together done with talc or oily preparations. The spun threads show excellent physical ao Properties such as high elongation at break and strength, low permanent elongation and high modulus of elasticity.

example 1

250 parts of a polyester of adipic acid, 1,6-hexanediol and 2,2-dimethyl-l, 3 (weight ratio of diols 65:35; OH number 55.5; acid number 0.8) 1 hour at 120 ⁰ C and dehydrated under a pressure of 12 torr and then reacted with 50 parts of diphenylmethane-4,4'-diisocyanate at 90 to 95 ° C. for 1 hour. The melt of the polyester-diisocyanate adduct is dissolved in 400 parts of Ν, Ν-dimethylformamide and cooled to 20 to 25 ° C in about 10 minutes.

This solution is poured into a solution of 3.8 parts of ethylenediamine, 3.6 parts of 2,2-bis- (4'-aminophenyl) -propane and 432 parts of N, N- in about 5 minutes at 15 to 2O ^{0 C with stirring.} Entered dimethylformamide, the viscosity of the solution increasing rapidly.

The spinning solution containing about 27% solids has a viscosity of about 390 poise / 20 ° C. she will in compliance with the spinning conditions described below according to the wet spinning process into threads processed with the following properties:

Titer
(the) strength
(g / den) fracture
strain
CW Permanent ones
T \ »t» «... ■■! ■
I, -iffnni In P,
(VJ Ε module
(mg / den) 700 0.31 650 18th 62

Example 3

250 parts of the polyester described in Example 1 ^ are mixed with 3 parts of a 36% SOJ-dioxane solution, stirred for 4 hours at 100 ⁰ C and then in about 1 hour at 100 ° C and a pressure of 12 Torr of dioxane and Freed traces of water. S parts of N-methyldiisopropanolamine are stirred into the polyester melt; and in 1 hour by further reaction with 63.6 parts of diphenylmethane-4,4'-diisocyanate at 80 to 85 ° C, an NCO-containing pre-adduct is produced, which in about 10 minutes in 400 parts of Ν, Ν-dimethylformamide (H _s O content 0.01%) and at the same time cooled to 25 ° C.

The solution of the pre-adduct is stirred at 16 to 22 ° C in 25 minutes in a mixture of 4.95 parts of ethylenediamine, 7.28 parts of 1,1-bis- <4'-aminophenyQ-cyclohexane, 8.3 parts of titanium dioxide and 517 parts of Ν, Ν-dimethylformamide entered. Viscosity of the solution 237 poise / 20 ^o C

The solids content of the solution is 27 percent by weight. The elastomer substance contains 100 mVal of tertiary nitrogen per kilogram.

The processing of the spinning solution into threads takes place under the conditions of the wet spinning process described below, whereby the following thread properties are achieved:

Titer
(the) strength
(g / den) fracture
strain
CW Permanent ones
strain
C « Modulus of elasticity
(mg / den) 500 0.44 540 21 90

Titer
(the) strength
(g / den) Book
strain
C /.,) Permanent ones
strain
(V.) Modulus of elasticity
(mg / den) 700 0.40 610 19th 70

Example 2

250 parts of the dehydrated polyester described in Example 1 are ^{reacted at 90 to 100 °} C. in 130 parts of anhydrous chlorobenzene with 50 parts of diphenylmethane-4,4'-diisocyanate in the course of 1 hour. The solution of the polyester-diisocyanate adduct is then cooled to about 25 ° C and at 15 to 20 ° C in a solution of 3.6 parts of ethylene amine, 3.4 parts of 2,2-bis (4'-aminophenyl) - propane and 702 parts of NN-dimethylformamide entered. The spinning solution with about 27% solids, which is created by the rapid increase in viscosity to about 300 poise / 20 ⁰ C, is shaped into threads with the following properties according to the wet spinning process explained below:

Example 4

250 parts of the polyester described in Example 1 are deactivated and dehydrated in the same way as in Example 3, 5 parts of N-methyldiisopropanolamine are stirred in and reacted with 71.5 parts of diphenylmethane-4,4'-diisocyanate at 80 to 85 ° C. in 1 hour NCO-containing pre-adduct produced. The pre-adduct is dissolved in 400 parts of Ν, Ν-dimethylformamide (HO content 0.01%) in 15 minutes, at the same time cooled to 25 ° C and by introducing the NCO-containing solution into a stirred mixture of 6.28 parts of ethylenediamine, 9.3 parts of l, l-bis (4'-aminophenyl) cyclohexane, 8.6 parts of titanium dioxide and 548 parts of N ₁ N-dimethylformamide at 20 to 27 ° C extended. Then 1 part of hexamethylene 1,6-diisocyanate is stirred into 5 parts of NN-dimethylformamide. After 4 hours the viscosity is about 340 poise / 20 ° C.

The proportion of elastomer substance in the spinning solution is 27 percent by weight and the tertiary nitrogen content is 97 meq / kg solids. The solution is processed according to the wet spinning process described below, whereby threads with the following Properties are obtained:

Titer
(the) strength
(g / den) fracture
strain
(V.) Permanent ones
strain
(V.) Modulus of elasticity
(mg / den) 600 0.53 510 20th 102

Example S.

250 parts of the polyester described in Example 1 are _{mixed with 2 parts of a 39% SO 2} -dioxane solution, stirred for 2 hours at 10O ⁰ G and then in about 1 hour at 100 ⁰ C and a pressure of 12 Torr of dioxane and Freed traces of water. By reaction with 56.25 parts diphenylmethane-4,4'-diisocyanate is produced a pre-adduct containing NCO in 1 hour at 85 to 90 ⁰ C, which it in 400 parts of N, N-dimethylformamide (H _E O content 0.02% ) is dissolved and cooled to 25 ° C in about 15 minutes.

a) The pre-adduct solution is introduced into a solution of 4.4 parts of ethylenediamine and 8.25 parts of 2,2-bis (4'-aminophenyl) propane in 473 parts of N, N-dimethylformamide at room temperature with stirring. The final viscosity of the solution is about 180 poise / 20 ⁰ C. After the following instructions for the wet spinning process are obtained from this dope filaments having the following properties:

Titer
(the) strength
(g / den) fracture
strain
(· /.) Permanent ones
strain
(° / o) Modulus of elasticity
(mg / den) 290 0.23 390 9 110

b) The pre-adduct solution is converted into a solution of 5.2 parts in 15 minutes at 18 to 24 ° C. with stirring Ethylenediamine and 6.5 parts of 2,2-bis (4'-aminophenyl) propane in 459 parts of Ν, Ν-dimethylformamide registered. The final viscosity of the solution is about 230 poise / 20 ° C. According to the following instructions For the wet spinning process, this spinning solution is processed into threads with the following Characteristics:

Titer (the)

strength (g / dcn)

Elongation at break

Permanent ones strain

Modulus of elasticity (mg / den)

40

0.36

440

19th

145

Example 6

Titer
(the) strength
(g / den) fracture
strain
(· /.) Permanent ones
strain
C /.) Modulus of elasticity
(mg den) 210 0.77 510 19th 126

3750 parts of the dehydrated described in Example 1 Polyesters are stirred at 82 to 87 ^ C with 844 parts of diphenylmethane-4,4'-diisocyanate Brought to reaction for 1 hour, then dissolved in 6000 parts of Ν, Ν-dimethylformamide and dissolved in 25 minutes Chilled to 25 C. This NCO-containing pre-adduct solution is converted into a solution of 69 parts at 20 to 25 ° C Ethylenediamine and 129 parts of 2,2-bis (4'-aroinophenyl) propane in 7280 parts Ν, Ν-dimethylformanwd, which also contains 120 parts of titanium dioxide (rutile) dispersed, entered. The spinning solution obtained has with a solids content of 27%, a viscosity of 620 poise / 20 ° C. According to the below described In the dry spinning process, the spinning solution is processed into threads with the following properties:

85 ⁰ C brought to reaction with 750 parts of diphenylmethane-4,4'-diisocyanate for 1 hour, then dissolved in 6000 parts of Ν, Ν-dimethylformamide and cooled to 25 ° C in 20 minutes. This N CO-haUige pre-adduct solution is at 18 to 24 ° C in a stirred mixture of 53.1 parts of ethylenediamine, 67.5 parts of 2,2'-Bi ^ (4'-aminophenyl) propane, 7000 parts of NN ^ and dimethylfbnnamid 185 parts of titanium dioxide (rutile) injected 3 parts of hexamethylene-1,6-iditsocyanate in 27 parts of Ν, Ν-dimethylformamide are then added dropwise. To obtain a spinning solution having a solids content of 27 '' and a viscosity of 690 poise / 2O ⁰ C. In the following given for the dry spinning method, spinning conditions could be produced from this solution filaments having the following properties:

Titer strength
(g / den) fracture
strain
C / ") Permanent ones
strain
C /.) Modulus of elasticity
(mg / den) 150 0.66 490 14th 128

Example 7

3750 parts of the dehydrated polyester described in Example 1 are stirred at 80 to
described spinning solutions into endless threads

Before spinning, the solutions are well filtered through a filter press and then until they are free of bubbles degassed in a vacuum.

The solutions listed can be spun wet as well as dry.

I) wet spinning process

The filtered and degassed solution is spun using a spinning pump through a multi-hole nozzle with nozzle diameters of 50 to 200 μ into a 2 to 10 m long water bath heated ^{to 20 to 80 c} C, primarily 40 to 70 ^{r C, which is 2 to 10%} Contains Ν, Ν-dimethylformamide. The emerging threads are drawn off at a speed of 5 to 50 m / min with a delay of 0.5 to 5. After subsequent drying at 60 ° C., the threads are wound up. The physical properties given in the examples are then determined according to the known methods.

U) dry spinning process

The filtered and degassed solution is fed via a spinning pump to the spinning head, depending on the viscosity at a temperature of 15 to 90 ⁰ C. The solution is injected into a heated shaft through a multi-hole nozzle with nozzle diameters of 80 to 250 μ. The temperature of the blowing air must be chosen so that the air temperature at the spinneret is 130 to 230 ° C. The air entering the shaft from above, meanwhile loaded with the solvent, is sucked off in front of the shaft end. The threads emerging at the end of the shaft are withdrawn at withdrawal speeds of 200 to 600 ml min, preferably 200 to 400 m / min. The Ν, Ν-dimethylformamide content of the threads is less than 1 "". Before the threads are wound up, a preparation to reduce adhesion is applied. The thread ends are then checked using known methods.

Explanations for thread testing

1. All dynamic tests were carried out with a deformation speed of the thread of 400% performed per minute.

2. The permanent elongation becomes 300% of the original length after the thread has been elongated three times and determined after a recovery time of 30 seconds.

3. The modulus is determined when the thread is stretched by 300% of the original length.

Example 8

21000 parts of hexanediol-l, 6 / 2,2-dimethyl-1,3 / adipic acid polyester mixed (molar ratio of diols 65:35; OH number 63.9; acid number 1.45) 1 hour at 120 ⁰ C in vacuo dehydrated, at 70 ⁰ C with 445 parts of N-methyl-diisopropanoIamin and 6300 parts of diphenylmethane - 4,4 '- diisocyanate and mixed unteir stirring 50 minutes to 90 ° C heated. 23,800 parts of the above NCO-containing pre-adduct melt are poured into a cold solution of 480 parts of ethylenediamine and 600 parts of 2,2 - bis (4 '- aminophenyl) propane in 70,000 parts of Ν, Ν-dimethylformamide, with vigorous stirring

Contains 1035 parts of titanium dioxide (rutile) in dispersed form, entered. A spinning solution with 27% solids and a viscosity of 610 poise / 20 ° C. is obtained

a) The solution is briefly ^{heated to 90 °} C. and immediately thereafter dry-spun from a 48-hole spinneret at a shaft ^{temperature of 200 ° C.} After leaving the spinning chute, a preparation agent which reduces adhesion] is applied to the threads. The threads are wound up at a speed of 300 m / min.

Killer (the)

strength (g / den)

Fracture·

strain

Ch)

450

0.68

480

Permanent ones

strain

Cl.)

20.5

B module (mg / den)

134

b) The solution is spun briefly heated to 65 ⁰ C unc immediately thereafter from a 12-hole spinneret at a Schachtcemperatur of 170 "C dry. The take-off speed amount 450 m / min.

Titer
(the)

strength (g / den)

84

1.05

Book

strain

OY.)

Permanent ones

strain

Ch)

365

11.4

Modulus of elasticity (mg / den)

580

Claims (4)

y 1 can be established According to a process known as "chemical patent claims: spinning", the pre-adducts are extruded through spinnerets into a coagulation bath, 1. A process for the production of rubber elastic that as a reaction component to obtain the see threads by spinning solutions 5 threads with high molecular segmented polyurethane (Segmented polyurethane-polyurea polymers, polyurea structure, ethylenediamine and possibly in polar organic solvents, which also contains small amounts of polyamines. The size characterized in that one Lö- reactivity of the pre-adducts with free Isosungen spun from polymers, which are caused by cyanate groups and the resulting: low Implementation of linear polyesters with a final shelf life of the pre-adducts made it possible to reduce the risk Hydroxyl groups and mean molecular weights appear worthy of soluble high molecular weight segmented from 1600 to 2600, optionally mixed with polyurethane-polyurea adducts in low molecular weight solvents To produce diols with one or more parts and these solutions after the wet tertiary Nitrogen atoms, with diphenylmethane or dry spinning processes into threads and fibers 4,4'-diisocyanate to be processed into an NCO-containing precursor. adduct and further implementation of the pre-adduct in From Belgian patent specification 672 046 it is a polar organic solvent with kannt, a prepolymer containing NCO groups a mixture of ethylenediamine and a di- with p-menthane-l, 8-diamine to extend. solutions amine of the formula of this polyurethane show only slight pasting 20 tendencies, however, are made from such solutions Threads in their hydrothermal and thermal properties according to the process of this - Invention made inferior. Furthermore, it is known to contain hydroxy proteins 25 to convert polyesters and diisocyanates at elevated temperature to NCO-containing pre-adducts and these wherein R ₁ and IR ₂ lower alkyl radicals or R ₁ and R ₂ then in polyacrylonitrile solvents at Tempe- together with the carbon atom a cycloaliphatic raturen below 20 ⁰ C with ethylenediamine to high mol- mean remainder have been obtained. cular polyurethane-polyurea adducts 2. The method according to claim 1, characterized thereby set 30. Those made from these solutions by spinning draws that one uses polymers, the available threads show good physical and Manufacture the molar ratio of ethylenediamine to elastic properties. Particularly a hindrance for them additional diamine in the range of 50:50 to the production of threads on an industrial scale is the 85:15 was chosen. relatively short time in which these solutions 3. The method according to claim 1, characterized in that they are subject to formation so that spinning is impossible draws that one uses polymers with which is. This is particularly disadvantageous in the production of a solution the ratio of the hydroxyl groups with viscosities from 600 to 1000 poise at 20 "C noticeable to the isocyanate groups of diphenylmethane. For the production of threads according to the 4,4'-diisocyanate in the range of 1: 1.5 to 1: 1.95, however, dry spinning processes are solutions with the was chosen. 40 of the aforementioned viscosities are required, while other 4. The method according to claim 1, characterized in that it is marked with a bearing in the normal operating sequence, that polymers are used whose times are longer than a week for the production of the spinning solutions the NCO-containing pre-adduct must be taken into account. Ethylenediamine and 2,2-bis (4'-aminophenyl) -pro- It has now been a process for the production of rubber pan was implemented. 45 elastic threads found if one were essentially linear polyesters with terminal hydroxyl groups with an average molecular weight of 1600 to 2600, given if in the presence of small amounts of low molecular weight Diols with one or more tertiary nitrogen-50 atoms, with diphenylmethane ^ '- diisocyanate, where The present invention relates to a method for the ratio of OH to NCO groups used Production of rubber elastic threads and fibers from only 1: 1.5 to 1.95 may be, to an NCO -haltigut soluble and against gel formation in polyacrylonitrile pre-adduct and converts the reaction product Solvents besröndigen segmented polyurethane in a polyacrylonitrile solvent with a mi-polyurea elastomer. 55 schung from ethylenediamine and a diamine of There are a number of known methods of elastic formula
Polyurethane-based threads and fibers for a multitude of r number of textile purposes, whereby they are both 1 *