DE1770591A1 - Linear, segmented polyurethane elastomers - Google Patents

Description

The invention relates to highly elastic, linear, segmented polyurethanes resulting from the use of certain Segmen resulting from semicarbazide diydrazides as chain extenders; e.

It is known that essentially linear, higher molecular weight NCO pre-adducts (hereinafter referred to as ICO or HCO prepolymers for short), produced from higher molecular weight polyhydroxy compounds (optionally with the addition of smaller ones Amounts of low molecular weight diols) and excess solar Amounts of organic diisocyanates ^ In highly polar, organic solvents such as dimethylformamide with essentially bifunctional chain extenders containing 2 active hydrogen atoms to react, viscous solutions of essentially linear polyurethane elastomers being obtained which can be deformed from the solution into elastic threads or films. As a chain extender in particular diamines, preferably of aliphatic or araliphatic structure, hydrazine or dihydrazide bonds used. Diamines and hydrazine have an »rather high reactivity *

105845/1764

Le A ii 532 * 1- _BATH

activity towards the WCO pre-adducts, which are preferred have aromatically bonded ffCO groups, which is why a. high risk of formation of inhomogeneous, cross-linked parts ("Jellyfish") exists within the elastomer solution * To reduce this crosslinking tendency, a number of chemical Modifications or complex technical devices required.

Hydrazide compounds as chain lengthening agents (cf. DBF 1 123 467), on the other hand, show a reactivity to ICO pre-adducts that is reduced to such an extent that their reaction can be conducted particularly well without undesired chemical crosslinking occurring with "swelling" of the solution. Such polyurethane-elastomer layers can be spun into highly elastic threads with high tear strength and low permanent elongation.

Such, old Dlhydrazlden chain-extended elastomer threads However, they also show downsides. Ea has z. B. divided up, that - despite z. T * good elastic properties at room temperature - the elastic behavior, especially of stretched threads

at elevated temperature, especially in hot water or in steam, is unsatisfactory. Such elastomer threads, which are subject to a small preload, are much longer in hot air than 1h air at room temperature and have a high reed elongation after relief. Even after hydrothermal treatment (* B in boiling water), in particular pretensioned Blae tomer threads (e.g. at 10O) K elongation) are the main stretch

109848/1764

^LtA11532 - ² - BATH ORIGINAL

high. This low resistance of such dihydrazide elongated elastomer threads to elongation under thermal or hydrothermal conditions is particular to equipment and Staining processes undesirable.

Furthermore, such Elsetomerfäden, z. B. when using of carbodihydrazide as a chain extender in the reaction with NCO pre-adducts, very sensitive to traces of heavy metals. Even when boiling with water, which z. B. Contains very small amounts of copper ions, a pinkish-red discoloration of the threads occurs, making them look less colored Tissue is reduced, although no influence on the strength properties can be observed. Is oxalic acid dihydrazide very sparingly soluble in dimethylformamide and, after reaction with HCO pre-adducts, results in elastomer threads which, like threads with malonic acid or succinic acid dihydrazide chain extension, are highly sensitive to hydrolysis and insufficiently resistant to stress Have hot water conditions.

Is used instead of the dihydrazide compounds for the implementation with the NCO pre-adducts Blseemicaxbazide as Kettenverlängerüngs- ■ ittel, z. B. ethylene-bissemlcarbazid or hexenethylene-bissemicarbazid, no spinnable elastomer solutions are obtained, since these change into a gel-like state during production or after a short period of time. Probably they will resulting polyurethane elastomers from the solvent only

- · ■ ■

insufficiently solvated and therefore separate as pasty

Gel that does not or very difficult to form threads or foils

deform IMt. 109845/1764.

BAD ORlGINAU

T. «A 11 532 -3-

The invention now relates to highly elastic, essentially linear, segmented polyurethanes made from higher molecular weight NCO pre-adducts and chain lengthening agents which have the characteristic chain lengthening segment -NH.NH.CO.NH. (CH ₂ ) ^ CO-NH-NH-, (x = 1 or 2) and by reacting the higher molecular weight NCO pre-adducts with essentially equivalent amounts of aliphatic semicarbazide _{hydrazides of the formula 'H 2} N.NH.CCNH. (CH ₂ ) _x .CO.NH.NH ₂ , (x = 1 or 2), in highly polar organic solvents and subsequent removal of the solvents by evaporation or coagulation. There are thus linear segmented polyurethane elastomers, consisting of reaction products of higher molecular weight diisocyanates with chain extenders, containing at least 55j6 - based on the total chain extension segments present - of a chain extension segment of the structure -NH.NH.CO.NH. (CH ₂ ) _X .CO.NH .NH-, (x = 1 or 2).

Knowing the properties of elastomers with dihydrazides as chain extenders and the behavior of the corresponding bisemicarbazides as chain extenders, it was extremely surprising that the aliphatic semicarbazide hydrazides of the formula H ₂ N-NH-CCNH. (CH ₂ ) _χ .CO.NH.NH ₂ , (χ = 1 or 2) elastomers with very good properties ^ result, the level of which is considerably higher than that of comparable elastomers with dihydrazide extensions.

Particularly excellent properties are shown by those with ß-semicarbazide-propionic acid hydrazide extended polyurethane elastomers (x = 2 in the above formula), which is why it is preferred as a bi-

109845/1764

Le A 11 552 -4-

functional compound containing 2 active Η atoms for chain extension of the NCO pre-adducts is used, especially when the polyurethanes are processed into elastomer threads. Such elastomers, after spinning the solution in conventional dry or wet spinning processes, result in high quality Elastoraerfäden with significantly improved thermal and hydrothermal properties and at the same time very good strength and elastic properties. B. copper ions, color-stable and show better resistance to hydrolysis than comparable dihydrazide compounds. The polyurethane elastomers are dariiberhinaus readily soluble in the customary% solvents such. B. dimethylformamide or di-ethylacetamide.

The advantageous property profile is explained in more detail in the examples by means of comparative experiments.

The compounds used as chain extenders: ot-semicarbazide-essifiric acid hydrazide and ß-Seüicarbazid-propionic acid hydrazide are new compounds. With only slight waste - -M conversion of the structure, eg. B. with progression in i ^ r homologs Row for y-semicarbazide butyric acid hydrazide (x = 3 in above Formula) aind the properties of the chain-lengthened elastomers with regard to the thermal and hydrothermal properties, for example for elastomer threads, are inadequate. Achieving high quality properties with aliphatic semicarbazide hydrazides is limited to the chain extenders listed (formula χ = 1 or 2 (preferably 2)).

109845/1764

Le A 11 532 _K - _5_

The following processes are to be mentioned for all the main embodiments of the production of elastomers with the -NH.NH.CO.NH. (CH ₂ ) _X .CO.NH.NH -Segmpnt (x = 1 or 2):

a,) reacting the NCO Yaraddukte from higher molecular weight Dibydroxyvprbindungen and excess molar quantities of diisocyanates (MCO-content in the pre-adduct as active between 1 i> and 6% NCO, based on the solid content) with equivalent approximately to amounts of bifunctional, 2 Low molecular weight chain extenders containing hydrogen atoms in the presence of highly polar, organic solvents, the chain extenders being aliphatic semicarbazide hydrazides of _{the formula H 2 N.NH.CO.} RH. (CH ₂ ) _X * CO «1IH.NH ₂ (x * ¹ or 2) can be used.

b) Implementation as a), but in addition to at least 55 Mol- #, of the claimed Semicarbaxidhydraiide up to 45 mol-56 Common, bifunctional compounds containing 2 activated hydrogen atoms with molecular weights from 18 to about? 00 (ζ. B. Waβ- | "Er, hydra" in, diaein, dihydrazide) as a chain extension

j -. . . 1 ■ ■

tel is also used.

I; i

0} Implementation of an ffCO pre-adduct, made from higher molecular weight

laren dihydroxy compounds en and niedermo

eecular diols with

Molecular weights from 62 to about 500, depending on 1 or 2 tertiary amino groups in the molecule, in amounts of about 0.05 to 1.0 mol per mol of higher molecular weight dihydroxy compound, and excess molar amounts of diisocyanates (ICO content between about 1 i> and 6 f> NCO in the solid NCO pre-adduct) with approximately equivalent moners on aliphatic semicarbazide hydrides

109845/1704

Le A 11 532 -6-

i7fO591

H ₂ LHH.GO.NH. (CH ₂ ) _{X .CO.HH.HH 2} (x = V or 2) as chain extenders in highly polar solvents.

d) Reaction of an NCO pre-adduct, prepared as described in process c), with approximately equivalent amounts of chain extension agents, with at least 55 mol # of the semicar.bazidhydrazide H ₂ N.NH.CO.NH. (CH ₂ ) _χ .CO .NH.NH ₂ (χ = 1 or 2) and up to 45 mol * of conventional chain lengthening agents can be used.

The products obtained by the process are linear, segmented polyurethane elastomers, consisting of intralinescent segments of the structure I -] (O «DOCO.HH.R.HH.CO.) _F > (O« -GO.CO • NH.R.NH .CO) J _m - | -NH.NH.CO.NH. (CH ₂ ) _x .CO.NH.NH.CO.NH.R.HH.CO.- | - _n obtained, where D is a long-chain, divalent, essentially aliphatic polymer radical without isocyanate-reactive substituents, with a molecular weight of 600 to 5000 and a melting point below 60 °, R is a divalent, organic radical of an aromatic, aliphatic, cycloaliphatic or araliphatic diisocyanate, G a divalent aliphatic cycloaliphatic or araliphatic radical of a dialcohol with molecular weights between 62 and 300, preferably containing one or more tertiary aliphatic amino groups, without the terminal hydroxyl groups, r = integer from 1 to 5, preferably 1 to J ' _f a = 0 or an integer from 1 to 5, preferably 1, χ = 1 or 2, a = 1 or an integer up to 5, preferably Γ up to 3 and η = 1 or an integer up to 5, preferably 1 or 2 .

TQ9845 / 1764

! • AH _λ 53 £ ν: Γ.Γ · -7- BAD ORIGINAL

These elastomers have an elongation at break in excess of $ 300 as well an inherent viscosity, (determined in a solution in hexamethylphosphoramide at 25 °) of at least 0.5 in order to produce sufficient elastic properties in the threads and foils.

In addition to structural segments of the formula I which is substantially linear, segmented polyurethane elastomers, up to a maximum of 45 wt * -. $ Of intralinear segments of the structure II are made which having by reaction of NCO prepolymers with known chain extenders such as water or two terminal NH ₂ groups Connections arise and the structure -I fö.
D.0.CO.NH.R.NH.CO) _r . (0.G.0.CO.NH.R.NH.CO) ₈ -I- _ffl .1 (NH.Z.NH.CO.) _p ,

-] ■■

NH.R.NH.CO-1-, where D, G ,. R, r, s, m and η are those given above Have meaning, ρ = 0 or 1 and Z is the remainder of a known chain extender with 2 terminal NHg groups HpN.Z.NHp »without these ΝΗ -, - groups. Z can be Zero or a divalent organic radical with 2 to 13 carbon atoms without substituents which react with isocyanates, e.g. B. a divalent aliphatic or cycloaliphatic radical with

at most 13 carbon atoms, preferably the -CH ₂ -CH-

R ¹ R ¹ = H, CH-,

.N- (CH ₂ -CH ₂ .N) _v . (CH _? ) ₅ - - (CH *).,. H ^ N. (CHg) ₃ - R ¹ = H, CH ₃

CH ₃ 'CH ₃ .ν = 0.1

^, CHp-CHp

cis / trans mixture CHg CH- residue, a divalent one

aromatic radical without condensed rings, preferably a radical; X = zero, -0-, -CHg-, -CH ₂ .CH ₂ -, CH-

1 09845 / T 76A

Le A 11 532 ". BAD ORIGINAL

a divalent araliphatic radical, preferably a 1,3 or 1,4 -CH ₅₁ (CHpUZ ^ - (CHp) -CH ₂ - radical, y = 0.1,

or a radical -HN.CO.R ^w .CO.NH-, -HN.CO.NH.R ".NH.CO.NH-, where R ^{w is} a divalent organic radical with up to 13 carbon atoms, e.g. B. an aliphatic, cycloaliphatic or aromatic radical, preferably one

-HN.CO. (CH ₂ ) _y .CH ₂ -N-CH ₂ .CH ₂ -JZCH _2. (CH ₂ ) y.CO.NH-

or, -HN-CO- (CH ₂ ) .CH ₂ -N ^ yN-CH _2. (CH. ^. CA., »» τ-! test is..

As higher molecular weight, essentially linear Polyhydroxylverr compounds with terminal hydroxyl groups (HO-D-OH) are such. B. polyesters, polyester amides, polyethers, polyacetals, polycarbonates or poly-N-alkyl urethanes, the above compounds optionally having further groups such as ester, ether, amide, urethane, N-alkyl urethane groups, with molecular weights between 600 and 5000 , preferably 800 to 3ooo and melting points of suitably less than 60 ⁰ C, preferably less than 45 ⁰ C. It can auca mixtures of the higher molecular weight polyhydroxy! used compounds.

Particular mention may be made of polyesters from adipic acid and optionally Mixtures of dialcohols, e.g. B. ethylene glycol, propylene glycol, Butanediol- (1,4), hexanediol- (2,5), 2,2-dimethyl-

109845/1764

Ie A 11 532 -9-

propandlol- (1,3) t hexanediol- (1,6), 2-methylhexanediol- (1,6), 2,2-dieethylhexanediol- (1,3) _f p-bis-hydroxylmethyl-cyclohexane, 3-methyl- Pentanediol (1,4), 2,2-diethylpropanediol (1,3), preferably those with diols or mixtures of diols of five or more carbon atoms, since such polyesters have a relatively good resistance to hydrolysis and especially when used of diols with pendant alkyl radicals also have good low-temperature elasticity in the end products. Polyesters, which are obtained by polymerizing caprolactone on diethylene glycol with a narrow molecular weight distribution, are also very suitable starting materials.

Excellent hydrolysis-resistant polyurethane elastomers can be used «Us polyalkylene ethers such as Polytriaethylenätherdiolen, polypropylene glycols obtained, preferably from Polytetraaethylenätherdiolen, which may also be used as mixed polyethers (by condensing in small amounts of epoxies such as propylene oxide or epichlorohydrin) or after end group modification, eg. B. Replacement of OH groups through the -O.CO.H (alkyl) .CHg ^ CH ^ OH grouping can be used. Are also suitable for flame retardant Process products polyepichlorohydrins with old terminal OH groups in the specified molecular weight range. Basic polyethers whose tert. Amino groups (if appropriate partially) quaternized are also suitable. Polycarbonates used in particular are those which 1,6-hexanediol are the only ones

1098A5 / 1764

BAD ORIGfNAL

17705H

. ^: . ^: '■■ ■■; ■■. μ '. . ; '■

or contain predominantly dialcohol in addition to other diols.

All diisocyanates (O = C = M = R-If = C = O) can, if necessary, in a mixture, aliphatic, cycloaliphatic, a-raliphatic, aromatic diisocyanates and heterocyclic diisocyanates. Particular mention may be made of aromatic diisocyanates with a symmetrical structure, e.g. B. Diphenylnethan-4,4 ^t -diisocyanate; Diphenyldinethyl »ethane-4,4'-diisocyanate; Phenylene diisocyanate-1,4; 2,2 ·, 6, ^ -'-tetranethyl-diphenylmethane - ^^ '-diocyanate; Diphenyl 4,4'-diisocyanate; Diphenyl ether 4,4'-diisocyanate or their 'alkyl, alkoxyl or halogen-substituted derivatives, also toluylene-2,4- or -2,6-diisocyanate, for example. their technical mixtures, 2 -, ^ diisopropylphenylen-iji-diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate and a ₍ a _f «* a ^t -tetranethyl.-p ^ xylylene diisocyanate, furthermore alkyl or halogen substitution products of the above diisocyanates, e.g. 2,5-dichloro-p-xylylene diisocyanate or tetrachloro-p-phenylene diisocyanate, dimeric toluene-2,4-diisocyanate or Bi8-3-methyl-4-isocyanatophenyl) urea, aliphatic diisocyanates such as hexane-1, etc. -diieocyanate ^ cyclohexane-1, 4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1-18ocyanato-3-iβocyanatomethyl-iSS-trimethylcyclohexane or 2,2,4-trimethylhexane-1,6-diisocyanate can, if appropriate in part, are used and produce very little discolouring products after exposure. Diocyanates such as WjW'-diisocyanatoethyl) benzene or 1,2,3,4,5,0-hexahydro-diphenylaiethan ^, 4'-diisocyanate give little discolouring products on exposure.

Because of their technical accessibility preferably diphenylmethane-4 _4'-t dii8ocyanat, diphenyl ether-4,4'-diisocyanate, the isomeric toluene diisocyanates and optionally partly hexane-1,6-diisocyanate, and dicyclohexylmethane-4,4'-used diisocynat.

To produce the essentially linear, higher molecular weight HCO pre-adducts, the higher molecular weight polyhydroxy compounds described are used ! compounds HO-D-OH with the diisocyanates in excess molar amounts, for example in a molar ratio of 1: 1.25 to 1: 4.0, preferably 1: 1.30 to 1: 2.5, optionally in stages Addition of the diisocyanates, in the melt or in solvents which are inert towards isocyanates such as tetrahydrofuran, Dioxane, ethyl acetate, butanone-2 or chlorobenzene, reacted at temperatures of about 40 to 130 °, preferably 70-100 °. With smaller molecular weights of the higher molecular weight polyhydroxy compounds, e.g. B. 650 to 1250, come preferably the diisocyanates with lower molar ratios, about 1: 1.25 to 1: 2.0 for reaction, at higher molecular weights, e.g. B. 1500 to 25ΟΟ, preferably with higher molar ratios, e.g. B. 1: 1.5 to 2.5.

If a polyhydroxyl compound OH.D.OH with a diisocyanate OCN.R.NCO converted in a molar ratio of 1: 2, an NCO pre-adduct is formed the structure 0 = C-N.R.NH.'C0.O.D.0.C0.NH. £ .N = C = 0. If the reaction takes place in a molar ratio of 1: 1.5 (= 2: 3), then forms an NCO pre-adduct of the general structure O = C = N.R.NH. CO.0.D.0.CO.NH.R.NH.CO.0.D.O.CO.NH.R.K = C = O.

1098A5 / 176A

ORIGINAL

Le A T 1

-12-

Formally, the same structure is formed when the polyhydroxy compounds are first converted in the OH / NCO ratio 2s1 takes place and the new "advanced" dihydroxy compound then - optionally with another diocyanate - is converted into the NCO pre-adduct in an OH / ICO ratio of 1: 2. With other molar ratios, statistical mixtures of corresponding KCO pre-adducts can occur.

Smaller quantities can be used in the production of the IfCO pre-adducts of low molecular weight diols OH-G-OH with molecular weights from 62 to about 300, especially those that have one or more tert. Have amino groups, in addition to the higher molecular weight polyhydroxyl compounds HO-D-OH in the reaction with the diisocyanates can also be used.

The diols can be added as a mixture with the higher molecular weight polyhydroxy compounds or at any point during or after the VCO pre-adduct formation from diisocyanate and higher molecular weight polyhydroxy compounds. As such diols, for example, ethylene glycol, 1,4-butanediol, Bia-HJi- (ßhydroxyäthyl) -methylamini Bie-M, H- (ß-hydroxypropyl) -methylamine} I, I ^t -dimethyl-H, i'-bis ( ß-hydroxyethyl) '- ethylenediamine; Ν, Η ^1- dimethyl-H, lp-bls (ß-hydroxypropyl) -äthylendlamine; », N'-Bisfßhydroxypropyl) -piperazinj M, M * -Bis- (fl-bydroxyäthyl) -piperazine or Hydrochinen-bisiss-hydroxy-ethylether) are used. The use of diols with tertiary amino groups especially increases the dyeability, improves the light resistance and gives the

Le A11 532

-13-

109845/1764

ORIGINAL

Point of attack for further follow-up treatments, e.g. B. Crosslinks with 4.4 ^l -dichlorometh, "l-'liphen.yläther.

In general, from 0.05 to 1.0 mol, preferably 0.05 to 0.5 mol, particularly preferably 0.07 to 0.25 mol low molecular weight diols per mole of polyhydroxyl compound in the HCO pre-adduct formation. It is expedient to increase the pin amount of diisocyanates in these cases over the boar specified molar ratios addition to the amount corresponding to the low molecular weight diols, z. B. around 0i05, up to 1.0 mol. It bi: - the NCO pre-adducts of the structure: O = C = N.R.NH.CO.0.D. 0.CO.HH.R.HH.CO.0.G.0.CO.NH.R.N = C = O or in the case of the "Prever lengthening "an NCO pre-adduct of the structure: O = C = N.R.NH.CO.0.D. 0.CO.HH.R.HH.CO ^ O.D.0.CO.HH.R.HH.CO.0.G.0.CO.NH.R.N = C = O.

The typical structural components of the NCO pre-adducts (which a »n can also be referred to as" higher molecular weight diisocyanates ") resulting from pre-extension ¹ or glycol incorporation arise in more or alnd statistical order and can, if necessary, occur more than once.

The content of NCO groups in the NCO pre-adducts (calculated as weight percent HCO in the solvent-free HCO pre-adduct) is of decisive importance for the properties of the polyurethane elastomers obtained therefrom. For reaction with the semicarbazide hydrazides to be used as chain lengthening agents according to the invention, essentially only those NCO pre-adducts are suitable whose HCO content in the metal is at least 1.0 + ,

I A Μ 532 .14.109846 / 1764

BATH ORIGINAL \

the NCO pre-adducts should preferably be 1.5 to about 6 wt .- ^ 9CO have. 1.75 to 3.5 NCO, calculated on the solids content of the NCO pre-adduct, are particularly preferred if the elastomers produced therefrom are to be used to produce elastomer threads.

Aliphatic semicarbazide hydrazides of the formula are used as bifunctional chain extenders having 2 active hydrogen atoms in approximately equivalent amounts, based on the NCO groups of the NCO pre-adduct

H ₂ H.IH.CO.NH. (CH ₂ ) _x .CO.! RH.NH ₂ (x = 1 or 2)

used, preferably as the sole chain extender. The use of Q-semicarbazid-proplonic acid hydrazide is preferred for the production of elastomer threads.

In addition to at least 55% of the aliphatic semicarbazide hydrazide up to 45 mol. B. water or compounds with 2 terminal NHp groups of the formula HgM.Z.NH ₂ , where Z is zero or a divalent, organic radical with 2 to 13 carbon atoms.

As usual chain extenders such. B. water or organic compounds with 2 terminal NH _? Groups are used, for example hydrazine (or hydrazine hydrate), aliphatic diamines, preferably ethylenediamine, 1,2-propylenediamine, cis and / or trans-1 ^ -Biaminocyclohexane, H, N-bis (γ-aminopropyl) methylamine; N ^ I-dimethyl-NiN'-bis (y-aminopropyl) -ethylene-

diamine; N, ir-bis (y-aminopropyl) -piperaf; in} N, N'-bis- (y-amino propyl) -2,5-dimethylpiperazine,

aromatic diamines, preferably 4,4'-diamino-diphenylmethane; 4 »4'-diaminodiphenyl ether, 4,4'-diamino-dipheriylethane, 4,4'-

Diaminodiphenyl-dimethyl-methane

or araliphatic diamines such as m- or p-xylylenediamine, 1,4-

Bis (ß-aminoethyl) benzene or

<x _f a, oc ', oi' -Tetramethyl-p-xylylenediamine,

or dihydrazides, bisemicarbazides or biscarbazine esters such as

Carbodihydrazide, terephthalic acid dihydrazide, hydroquinone

acetic acid dihydrazide, aminoacetic acid hydrazide, methylamino-

H, lf-bi8 (propionic acid hydrazide), H.H'-piperazine-bieipropion-

acid hydrazide), Ν, Η -dimethyl-ethylenediamine-Η, Κ ¹ -bie (propion acid hydrazide) are used.

To reduce the molecular weights or by despite a possible molecular branching that has occurred To obtain soluble polyurethane elastomers, monofunctional compounds can also lead to chain termination reactions in a minor amount, e.g. B. 0.01 to 10 Mol .- ^ (based on HCO content) can be used, for. B. butylamine, dibutylamine, acethydrazide, butyl semicarbazide, Ν, Ν-dimethylhydrazine.

The HCO pre-adducts are reacted with the chain extenders in approximately equivalent amounts (based on the NCO content), e.g. B. 100-120 %, preferably 100-110 Mol .- ^ of chain extenders, expediently at temperatures of about 0 to 130 °, preferably 20-80 ° in solvents. The higher the excess of chain extenders is chosen,

Le A11 532

109845/1764

BATH ORIGINAL

the lower the molecular weight of the polyurethane * By carefully adding further - preferably less reactive aliphatic di- or triisocyanates - one can set the desired molecular weight or the solution viscosity (according to German patent specification 1,137,386). After the desired viscosity has been reached, it can be used for stabilization of the as yet unreacted end groups by reaction with Mo- ' noisocyanates, such as. B. butyl isocyanate, anhydrides or other acylating substances such. B * acid chlorides or Carbamic acid chlorides ».

As the solvent, amide, urea or sulfide groups are having, strong for forming WaseerstoffbrUckenbindungen qualified, highly polar, organic, water soluble solvents, preferably having boiling points of about 140-225 ⁰ C, suitable, for example dimethylformamide, Diäthy! Formamide, Dimethy acetamide!, Formylmorpholine , Hexamethylphosphoramide, tetramethyl urea, dimethyl sulfoxide, dimethyl cyanamide or their mixtures. The technically preferred solvent is dimethylformamide or dimethylacetamide. Up to a certain proportion, which is about 33 percent by weight of the amount of solvent, less polar solvents, which alone cannot dissolve the polyurethanes or polyurethane ureas, can be added to the highly polar solvents, e.g. B. tetrahydrofuran, doxan, acetone, glycol monomethyl ether acetate or chlorobenzene. The concentration of the elastomer solutions should be about 5 to 43 percent by weight, expediently 10 to 33%, preferably 15 to 28 percent by weight, the viscosities being between 1 and 1000 poise, preferably between

Le A 11

-17-

109845/1764

see about 50 to 800 Poiae / 20 ° C should be. The molecular weight of the segmented elastomers according to the invention should

be so high that the inherent viscosity \ ^{= ln} * to measured at 25 ° G is at least 0.5 _f, preferably 0.70 to 1.9,

if you add 1.0 g of elastomer in 100 ml of hexamethylphosphoramide (Phosphoric acid tris-dimethylamide) has dissolved at 20 °. Here ^ means the relative quality (ratio of the flow time R.

the solution at the flow time of the solvent) and C the Concentration in g / 100 ml. The melting points of the elastomers should values above 200 ° when determined on the Kofler bench have, preferably above 230 °, if it is the starting material for elastomer threads.

The solutions of the polyurethanes or polyurethane ureas can organic or inorganic · pigments, dyes, optical brighteners, UV absorbers, phenolic antioxidants, special Light stabilizers such as 1,1-Dialkylaemicarbazide or I, H-Dialkylhydrazide and crosslinking substances such. B. paraformaldehyde, melamine hexamethylol ether or other formaldehyde derivatives such as dimethylol dihydroxyethylene urea, dimethylolethylene urea, trimethylolmelamine, dimethylol urea dimethyl ether, quaternizing! B. Di-chloromethyl-durol or polyaziridine urea, e.g. B. hexamethylene-w, w-bis-ethyleneimidurea, are added. Through a z. B. thermally triggered crosslinking reaction, the solution and source resistance to highly polar solvents is changed.

The elastomer solutions can be freed from the solvent by a wide variety of methods known per se by evaporation or coagulation, e.g. T. with simultaneous education

UK 11 532 -ie- 109846/1764

BATH ORIGINAL.

the desired moldings, such as threads or films. Films or covers are made by drying the elastomer solution on substrates, e. B. made of glass plates or textile structures. Filaments can be obtained by wet or dry spinning processes. Microporous coatings are created by spreading elastomer solutions on (possibly textile) substrates »exposure to moist air and subsequent coagulation in non-solvents for the polyurethane, e.g. B. water or aqueous solutions. Suitable additives such as finely divided salts, emulsifiers or soluble polyamides can further increase the microporosity of the films;

In the following examples, "parts" always mean parts by weight, unless otherwise stated.

The films or threads listed in the examples were after The following standard procedures are produced or eaten. Films: by spreading the elastomer solution on glass plates and Drying up (30 min at 70 ° + 45 min at 100 °) - final thickness approx 0.15 - 0.25 mm. .

Using a film cutting machine, e. T. Threads of about 250 to 800 the thickness cut and measured. Wet spinning process: A preferably 20 #ige Elästomerlösung is at a flow rate of about 1 ml / min through a nozzle with 20 holes of 0.12 mm diameter in an 80 ° - 85 ° hot coagulation bath comprising 90 wt .- $> water / 10 wt. -56 dimethylformamide (length about 3 m) spun in and afterwards at a take-off speed of 5 m / min

Le A11 532

-19-

109845/1764

_BA0

Passage of a Waechetrecke (Waeeer / 90 ^o ) wound. The coils are kept for 1 hour in hot water (5O ⁰ C) and then dried.

Dry spinning process: A preferably 24-26 ^ ige elastomer solution is through a nozzle with 16 holes of 0.20 mm diameter in a 5 m long, heated to 220-250 °, In the air is blown from about 210-280 °, spun. The threads are pulled off at a speed of approx. 100 m / min and, after preparation, with a talc suspension optionally with stretching, e.g. B. wound at a speed of 125-175 m / min. The threads can then be thermally on spools or in continuous form be treated afterwards.

The elongation at break is measured in a tearing machine under control of the clamping length by a light barrier and with compensation of the respective clamp bottom pluck.

To characterize the elastic values, the modulus 300 υ in the first expansion curve, the modulus 150 % (in the third return curve) and the permanent elongation (after 3 3t 300 Jt expansion, 30 seconds after unloading) are determined.

Determination of the heat distortion temperature (HDT) on elastomer threads:

On elastomer threads, which are tension-free for approx. 3 hours under standard

Le A 1 532 ^f - ₂₀ - 109845/176 4

ORIGINAL

>, 177Q591

which were placed on the table, the titer is determined (weighing a under a gate load of 0.05 ag / the 450 ma long thread pieces located).

An elastomer thread is hooked into a boring that contains air or is filled with nitrogen, with a preload of 2 mg / den at construction temperature. The Bohr is surrounded by a heating jacket, which is permeated by silicone oil heated by a thermostat. The tea temperature la Bohr is first increased to approx. 125 C in about 30 minutes. Further Teaperatursteigerung is old a speed of 3 ⁰ C per five minutes performed until a long change of elastomeric yarn on Aehr than 400 on occurred. The Meiwerte obtained are plotted in Onea Diagraaa such DAFL equivalent to 1 unit of length of a Teaperaturdifferenz 1O ⁰ C on the abscissa and on the ordinate By J λ 1 unit length of a length change of the Elastoaerfadens ▼ or "^ O aa is reproduced. Fora change temperature (HDT) denotes that tea temperature which

ProSection of the contact point · reads the 45 ° tangent to the temperature / length change curve on the abscissa.

The thermal resistance of the elastomers is generally higher, the higher the HDT value is found. For high-quality elastomer threads the value should be at least 145 °, Vt-sugsweiae * higher than 150 °. ■ "

A-.11: 532-21-10984S / 1784

Determination of the hot water tension drop (HWSA) of elastomer threads:

A thread stucco with 100 mm gauge length is stretched at 20 ⁰ C to 100 i * and the resulting after 2 minutes the yarn tension (mg / den) is measured (first value). The yarn stretched to 100 i 'held is then immersed in water of 95 ° C and after 3 minutes of residence time resulting voltage is determined (second value). After this measurement, the thread is taken out of the water bath and left for 2 minutes at room temperature. Then the thread, which is still pre-stretched in the tensioning clamp, is relieved of tension and the remaining stretch is immediately determined (3 x value).

Scheme of rendering in the examples (abbreviation HWSA):

1st value 2nd value 3rd value

Residual stretch after relief
(in air) at 20 °

The hydrothermal properties are all the higher evaluate, the greater the amount of the 2nd value (voltage in hot water, in mg / den) and the smaller the 3 value (the Residual stretch after treatment in the unloaded state) is * The tension value in water should be at least 15 mg / den, with high-quality elastomer threads an amount of <► 20 mg / den to be requested * The residual stretch after hydrothemical loading should be puttied

_ ₂₂ .

Voltage values in water in air at 95 ° at 20 ° (mg / den) (mg / den)

ner than 45 % _t better be less than 40 f .

Determination of the hot water length * (HWL) of elastomer threads:

A weight of 30 ag / den is attached to a 50 η long piece of thread using a Kleaaenvorrichtung and left to hang in the air for 25 minutes at the Rauteeperatur. After 25 minutes of exercise, the percentage elongation found is determined (i.'value). Then the so elongated thread ■ immersing it his Vorepanngewicht immediately in water at 95 ⁰ C and the elongation occurring in water is read after 25 minutes. The specification is made as a percentage elongation, based on the clamping length 50 u (2nd value). The loaded pad is then lifted out of the hot water bath and the remaining stretch is then determined by lifting the weight until it is tension-free (3 value).

Representation scheme in the examples (abbreviation HWL): 1st value 2nd value 3 «value

Elongation in air in water Residual elongation 20 °) 20 ° of 95 ° (after Entla W) " W) performance in air , (*)

The hydrothermal properties are to be rated higher, the smaller the 2nd value (elongation in hot water) and the higher

smaller 'the 3 · value (permanent elongation after unloading).

109845/1764

LeA 11 532 ₂ - ■ '

—C J

For quality Elaetomerfäden oolite the second value is less than 250 j> be eein and preferably less than 150 i »; the residual elongation (3 × value) should be smaller than 150 #, preferably smaller than 100 f> .

The melting point of the elastomer substance is measured on a strip of film after a run time of 2 minutes on the Kofler bench determined and should be above 200 °, better above 230 ° for elastomer threads.

To determine the inherent viscosity "V., samples of the elastomer substance (films) with a concentration of 1.0 g of elastomer substance per 100 ml are dissolved in hexamethylphosphoramide at room temperature and the relative viscosity 1 in an Ubbelohde viscometer at 20 °

η «= elapsed time of the solution

Solvent flow time

certainly. The inherent viscosity value is calculated from this η, -. In Jr (C = concentration in g / 100 ml.)

Manufacture of the new semicarbazides

IJCC semicarbazide acetic acid hydrazide:

140 parts of phenylchlorocarbonic acid ester are dissolved in 500 parts by volume of methylene chloride. The solution is off to 0-5 ⁰ C. cools and covered with 100 parts of water.

139.5 parts of glycine ethyl ether chlorohydrate are solid in proportions

Le A 1t 532

-24-

109845/1764

BATH ORIGINAL

entered, at the same time a solution of 56 parts of potassium hydroxide, 80 parts of potassium carbonate and 25 parts of potassium hydrogen carbonate in 300 parts of water * is added dropwise within 30 minutes. The two-phase reaction system then continues to stir for 2 1/2 hours without cooling, the phases are separated, the methylene chloride solution is dried over anhydrous sodium sulfate and finally the methylene chloride is distilled off. The carbethoxymethylene carbamide acid phenyl ether is obtained as an oil in 91% yield. After prolonged standing, the oil crystallizes, pp. 32 ⁰ O.

C ₁₁ H ₁₃ N ₄ calcd. 1 N 6.3 0 28.7

(Molecular weight 223) found: N 6.2 0 28.3

310 parts of phenyl carbethoxymethylene carbamate in 125 parts by volume of alcohol are added dropwise to a boiling solution of 280 parts of hydrazine hydrate in 250 parts by volume of ethanol, and the reaction solution is kept at the boil for 1 1/2 hours. After the reaction solution has cooled to ⁰ ° C., the white crystals which precipitate out in abundance are filtered off with suction, washed with alcohol and dried. The semicarbazide-acetic acid hydrazide is obtained in a crude yield of 91 Ί » d. Th. After recrystallization from alcohol (2 ml / g) and water (1.5 ml / g), pure, colored (yes, loose crystals) are obtained in a yield of 71 % pp: 167 ° C ₃ H ₉ N ₅ O ₂ calc .: N 47.6 *

(Molecular weight 147) found: N 47.5 +

II) ß-semioarbazid-propionic acid hydrazide

712 parts of ß-alanine are placed in 920 parts by volume of alcohol. Starting at 20 °, it is passed with rapid heating

109845/1764

Le A 11 532 -25-

to boiling (20 bins) 400 parts of hydrogen chloride; one thinks that Mixture boiled for 2 hours. After about 1 1/2 hours, the suspension has changed into a clear solution. After the reaction has ended 460 parts by volume of benzene are used for azeotropic distillation of the weather was added. Finally, the remaining alcohol is distilled off, finally in vacuo (15 torr). Man receives the ester-HCl salt as an oil in quantitative yield. To The oil crystallizes after standing for a long time or cooling down.

1180 parts of phenylchlorocarbonic acid ester are dissolved in 3800 parts by volume of methylene chloride, 700 parts of water are added and the mixture is cooled to 0-7 °. One drips with thorough mixing in the two-phase system 1228 parts of ß-alanine ethyl ester chlorohydrate (from a heated dropping funnel) and at the same time a solution of 450 parts of potassium hydroxide and 1090 parts of potassium carbonate in 2600 parts of water. The instillation time is approx. 60 min. The two-phase system is then stirred for a further 2 1/2 hours without cooling, the phases are separated, the methylene chloride solution is dried over anhydrous sodium sulfate and finally the methylene chloride is distilled off. The ß-Carbäthoxyäthylen-carbamidsäure-phenylester is an oil, which after long standing crystallized, pp 63 °; . Yield about 75 # (d.Th.).

The solution of is carried into the boiling solution of 1900 parts of hydrazine hydrate and 480 parts by volume of alcohol in about 30 minutes 1336 parts of ß-Carbäthoxyäthylencarbamidsäure-phenyl ester in 800 parts by volume of alcohol. Wake up 1 1/2 hour simmering the solution cooled to 0 °, the crystallized crude ß-semicarbazido-propionic acid hydrazide is sharply suctioned off, in alcohol

τ λ 11 "s", 109845/1764

Le A 11 532 _26-

BATH ORIGINAL

Slurried and again sharply suctioned off, after drying the raw yield is 872 parts (96.5 t of theory) after recrystallization from water (0.9 ml / g) and alcohol (2.0 ml / g) one 628 parts = 72 % d. Th. Pure ß-semicarbazido-propionic acid hydrazide, pp: 163-164 °.

^C 4 ^H M ^lf 5 ° 2 calc .: N 43.46 ^

(Molecular weight 161) found: N 43.45 #

example 1

1200 parts of a mixed polyester of adipic acid and the glycol mixture of 1,6-hexanediol / 2,2-dimethylpropanediol in a molar ratio of 65:35 (OH number 68.0, melting point 34-36 °) are mixed with 23.55 parts of N, N -Bie (ß-hydroxypropyl) -methyamine, 335.4 parts of diphenylmethane-4,4'-diisocyanate and 389 parts of chlorobenzene heated to 92-96 ° for 53 minutes and then cooled to room temperature. The NCO content of the NCO pre-adduct solution is 1.9 t (2.38 i> NCO in the solid substance).

400 parts of the above BTCÖ pre-adduct solution are stirred into a 70 ° hot solution of 14.85 parts of fl-semicarbazide-propionic acid hydrazide in 985 parts of dimethylformamide within a few minutes, a moderately viscous elastomer solution being formed, which is obtained by adding 12 parts of additional NCO - Pre-adduct becomes highly viscous. After pigmentation with 4 i TiOg, the viscosity is 855 poiee / 20 °.

The spinning of this solution by the dry spinning process (see general procedures) and - after dilution to 20 $ - by the wet spinning process gives elastomer threads, the properties of which are given in Table i; and the thread results from comparative tests.

109845/1764

LeA U 5.32. _ _2? _

imikv ¹ «at w.

be compared. The elastomer threads show at Lying for 1 hour or, if left to boil for a short time, in aramoniacal CuSO. Solution no discoloration.

The inherent viscosity in the Elaatomersubstanz is 1.27, the melting point (Kofler bank) is 230 ⁰ C

Comparative smoking;

Ee the structurally closest dihydrazide / or Bieeemicarbazid chain lengthening agent: -succinic acid dihydrazide (a) or Aethylenbissemicarbazid (b) as well as preferably as a chain extender for elastomer threads used carbodihydrazide (c) used for comparison, the same NCO pre-adduct being used as above used for extension with the ß-seaicarbazide propionic acid hydrazide became.

Comparative experiment a) Succinic acid dihydrazide

Λ00 parts of the NCO pre-adduct solution from Example 1 (1.9 1 ° NCO) are converted to a moderately viscous elastomer solution in an approx. 70 ° -hot solution of H, 2 parts of succinic acid dihydrazide in 922 parts of dimethylformamide, 5 parts of HCO pre-adduct is highly viscous. After pigmentation with 4 t TiO ₂ , the viscosity is 610 poiee / 20 ⁰ . The spinning of the elastomer threads was carried out as in the example above. (Results see Table 1). The melting point of the elastomer substance is 224 ^° C

108845/1764

A 11 532

-28-

BATH ORIGINAL

Comparative smoke b) -Aethylenbissemicarbazid 400 parts of the HCO-Vo rad product solution according to Example 1 (1.9 J * ^x HCO) are entered in a 70 ^o -hot solution of 16.24 parts of Aethylenbissemicarbazid in 928 parts of dimethylformamide, after adding about half the amount of pre-adduct an inhomogeneous solution is obtained, which turns into a stiff, crumbly mass upon further addition (insufficient solubility of the elastomers). The paste cannot be spun or deformed. When dimethylformamide was exchanged for Η-methyl-pyrrolidone, no solution could be obtained either, not even with greater dilution to 20 Ί »solids content . Spinning tests were not possible, and no homogeneous films could be obtained.

Comparative experiment c) - carbodihydrazide

400 parts of the HCO pre-adduct solution from Example 1 (1.9 % HCO) are introduced into a 70 ° -hot solution of 8.76 parts of carbodihydrazide in 907 parts of dimethylformamide, a moderately viscous elastomer solution being formed. laughing addition of further 25 parts of HCO-preadduct and pigmentation with 4 i "TiO ₂ is an elastomer solution is obtained having a viscosity of 645 poise / 20 ⁰ C. The spinning took place as indicated in Example 1). The measurement results can be found in the table.

When treated with ammoniacal CuSO. Solution, the Threads dark red-brown.

1Ö984S / 17S4

A 11 532-

-29-

he u. hydrothemi. Egg shafts

Β · 1 »? 1 · 1

Mr.

voltage rest in air in what-deh-

eration (jt) JO ⁰ 95 ° according to mg / den ng / hot

waaaerb · -

Features ίχΓ «—-» -

300 * eg / den

liter

the flexibility

g / denung

150

3 return to return 3x curve 3CKW ng / den + 50.2 / 20.9

500 177 481 219.532 130 48.1 / 22.9

"53? T04 469 IU 523 88

not terapinnable or see below

40.9 / 14.1

- »8ptl

aa * e "be called,

eeeen

-30-

Le A 1 '532

HWL

Elongation remaining length

in air in water after 20 ° 95 ° relief 5C i. (in air ^ 20 °)

54 68

186 148

80 58

92 800p, then ripped 106 800 ^, then torn

96

35Γ 406

200

The results in Table 1) show that the erfindungegemäfl threads produced have very good mechanical and elastic properties and that the thermal and hydrothermal Values are significantly improved. The "heat distortion temperature" (HDT) is much cheaper, and the hot water elongation (HWL) of threads loaded with weights is much lower and the tension around 100 pounds of stretched threads in hot water (HWSA) is at least twice as high as for the comparison threads. The residual elongation determined after this measurement is also very high much smaller than in comparison.

10ÖS45 / 1764

Le A 11 532 -31-

Tabel Resistance to hydrolysis of elastomer threads

(each dry spinning test, v »50) after 16 hours of treatment in a washing solution of 2g / liter soap and 5g / liter .toda at

Ripe oil - breakage. Remarks

ability elongation elongation g / den # j>

Thread according to example 1)

Original value

after 16 h hydrolysis

0.75 0.67

4Θ1 397

17 threads colorless 16 threads colorless

Comparative experiment (a)

Original value

after 16 h hydrolysis

0.63 469 16 threads colorless after 4 hours the threads cannot be measured Threads stuck together after 16 hours. Totally stuck together, no more mechanical strength.

Comparative experiment (c)

Original value

after 16 h hydrolysis

400 426

17 threads colorless

19 threads discolored reddish

The results of Table 2 show that elastomer threads according to the process according to the invention both eil have good hydrolysis stability as well as resistance to discoloration, while the reference threads are either hydrolytically degraded or result in severe discoloration.

Example 2

1200 parts of the mixed polyester described in Example 1), 15.9 parts of bis (β-hydroxypropyl) diethylamine, 283.4 parts of diphenylmetaane-4,4'-diisocyanate and 321 parts of chlorobenzene are heated to 95-98 ° for 35 minutes and the NCO pre-adduct solution formed is then cooled to room temperature. The NCO content of 2.01 Iiöeung is f> (equivalent to 2.5 Ί "NCO based on Festeubstanz).

In a solution of 16.5 parts of semicarbazide-propionic acid hydrazide in 932 parts of dimethylformamide, 400 parts of the above HCO pre-adduct solution are entered at 70 °, a viscous elastomer solution being formed which is pigmented old 4 $> Ti0 ₂ (based on pestle content) and then mixed with 0.33 parts of 1,6-hexanedieocyanate at room temperature, a final viscosity of the elastomer solution of 560 poises being reached. Aue of the elastomer solution is poured onto glass plates of Pilate approximately 0.2 in thickness and cut into threads with a titer of approximately 300 denier. After dilution with dimethylformamide to a concentration of 20 %, part of the elastomer solution is spun in the Hafl spinning process (for results, see Table 3).

Comparative example d) Reaction with hydrazine 400 parts of the NCO pre-adduct solution from Example 2) (2.01 # NCO) are stirred into a solution of 5.16 parts of hydrazine hydrate in 895 parts of dimethylformamide, a not entirely homogeneous elastomer solution containing a few jellyfish ( 116 poise / 20 C). After pigmentation with 4 1 » TIO« (based on solids

Le A 11 532 -33-

109845/1784

punch) 0.5 parts of 1,6-hexane diisocyanate are stirred into the solution at room temperature, whereupon the viscosity increases to 465 poise / 20 ^° C.

The yellowish discolored elastomer solution became partially too Films and cut threads processed from them, on the other hand in the form of a 20% solution. (Results 8. Table 3)

Example 3 Mixing extension with 55 MoI- ^ ß-semicarbazid-propionic acid-hy-

draeid and 45 mol- # hydrazine.

8.70 parts of B-semicarbazid-propionic acid bydrazide are dissolved in 800 parts of dimethylformamide and mixed at 45 ° with a solution of 2.45 parts of hydrasin hydrate in 116 parts of dimethylformamide. At low temperature, 430 parts of the NCO pre-adduct solution described in Example 2) are introduced, a very viscous, homogeneous elastomer solution being obtained which, after adding 320 parts of dimethylformamide and pigmenting with 4 H TiO _{2, has} a viscosity of 558 poise / 20 °. Results on films and threads see Table 3) · Melting point of the elastomer substance 234 ^° C *

BATH ORIGINAL

109846/1764

le A 1 '»532 -34-

Table elastic properties

Titer tearing fracture module module "stay, stigkeit elongation 300 $ 150 # elongation g / den 1» mg / den (3. RUCk- i »

reversal curve) mg / den (hydro) thermal properties

HWSA HflP in air in what- residual strain

eer

after hydrothermal shear loading

Example cut (2) threads

Wet spinning test

332 0.69

128

22nd

40/144/68 52.8 20.4 40

Compare cut matching threads

try wet spinning

290 0.67

110

22nd

70/336/154 37.2 14.7 45

example

3) cutting threads

Wet spinning test

323 0.81

123

23

58/236/104 47.3 17.5 43

The results show the advantageous mechanical properties and the improved hydrothermal properties Properties compared to the comparison with hydrazine extension. With mixed extension (example 3) the hydrothermal properties are improved accordingly compared to the comparative experiment. _, *

Le A11 532

-35-

Example 4

6500 divides a mixed polyester ■ described in Example 1) it the hydroxyl number 67.4 dewatered 1 h at 13O ^0/1 2 Torr and by the addition of 65 of a 30? 6igen solution of SO ₂ in dioxane ml deactivated. After brief heating in vacuo, the polyester is mixed with 129 parts of H ^ -bis (β-hydroxypropyl) -diethylamine and 1782 parts of diphenyl-ethane-4,4'-diocyanate at 45 ° and the temperature is then increased to 80-85 ° increased, and after 80 minutes of heating, the NCO pre-adduct with an NCO content of $ 2.24 NGO is formed.

In a solution of 297.5 parts of ß-semicarbazidpropionic acid hydrazide in 18,813 parts of dimethylformamide and, after suspending 267 parts of TiO ₂ pigment, 6360 parts of the NCO pre-adduct melt are introduced over the course of 15 minutes with intensive stirring and the viscous solution with 33.5 Parts of tris (3 »5-di-tert-butyl-4-hydroxy-benzyl) mesitylene and 1 part of 1,6-hexane diisocyanate are added. The highly viscous, homogeneous elastomer solution (770 poise) is spun after the dry spinning process through a nozzle with 40 bores of 0.2 mm diameter into a shaft heated to approx. 220 ° and after preparation with an aqueous falkum suspension at a speed of about 220 m / min wound onto bobbins with a pre-stretch of 0 *, 25 # and 50 * and thermally aftertreated in a cabinet for 1 hour at 130 °.

The properties of the threads, along with threads, are customary KaSspinnverfahren, listed in table no. 4 and leave the excellent recognize hydrothermal properties that

1 09845/1764

* A 11 532 -36-

Table 4

v = 0 Titer • Tear fracture module module stay * ■ 14th JDT I. in in 22.8 rest HWL in after ν = 2ί? the sturdiness strain $ 300 15096 strain 13th air water 25.4 deh Long us What Ent v = »50 365 g / den mg / den 3.Back- after 12th 20 ^a 95 ^δ 31.5 tion in ser burden
(in air Saßpinver- 277 turnaround 3χ3βΟ # mg / den mg / den after air 95 ⁶ 20 °) * search 238 ve mg / den stretch 14th 22.0 hydro % therm. 20 ° 296
i Bela * stung 74 ^ Dry pin 43.5 182 42 .ff euch 50.1 28 110 36 0.70 625 133 21st 59.9 26th 76 94 0.74 569 195 24 24 68 60 0.83 540 238 26th 52.2 60 162 163 29 0.59 461 246 23 48

O (D 430

cn

-j

ο cn co

differ slightly depending on the thread spinning and aftertreatment method. The melting point of the elastomer substance is 230 °.

Example 5

300 parts of one polytetramethylene ether diol (molecular weight 1020, melting point 33-35 °), and 6.45 parts of N ^ -Bis- (fl-hydroxypropyl) -methylamine are mixed with a solution of 114.1 parts of diphenylmethane-4.4 ^l - diisocyanate in 180.5 parts of chlorobenzene heated to 80-83 ° for 36 minutes. After cooling the NCO Voradduktlösung an NCO Gehalt'von 1.73 i "denotes (equivalent to 2.37 Ί * NCO in the solid substance).

17.1 parts of O-semicarbazide-propionic acid hydrazide are gelöet at 95 ⁰ C in 894 parts of dimethylformamide at 60 ° with 500 parts of the above NCO-Voradduktlösung stirred. The solution then reaches a viscosity of 372 poise. The addition of 0.29 part of Ptp'-diisocyanate-dicyclohexylmethane increases the viscosity to 556 poise. The solution is pigmented to a 4 + TiO ₂ content (based on solids) and cast into films in the usual form or spun in dry or NaS spinning processes. The elastomer substance has an inherent viscosity of 1.12. The thermal and hydrothermal properties are excellent. Under the usual hydrolysis conditions (cf. Example 1) the threads show no loss of strength. The melting point of the threads is 227-228 ° C.

109845/1764

Le A 11 532 -38-

f '» ¹ ;";:. ¹ :.; ¹ !! ¹ ! ¹ ! ¹ Λ ■',

Example 6

500 parts of a described in Example 5 NCO preadduct-LÖsun "(1.73 i> NGO) are stirred within 20 minutes in a 65 ° -Hot solution of 15.50 parts of semicarbazide eeaigsäurehydrazid in 891 parts of dimethylformamide. After cooling, a homogeneous, colorless elastomer solution with a viscosity of 189 poise is formed, which is brought to a pigment content of 4 % by adding TiOp. Subsequent addition of 15 parts of further NCO pre-adduct solution increases the viscosity to 561 poise. The inherent viscosity of the elastomer is 1.06.

The measurement results on films and elastomer threads are listed in the table. The thermal and hydrothermal properties of the threads are significantly more unfavorable than in the case of the similar elongation with the homologous β-semicarbazide-propionic acid hydrazide - see Example 5. The melting point of the threads is 223.degree.

Example 7

300 parts of a commercially available japrolactone polyester with a molecular weight of 830 and a melting point of 38-40 ° (commercial product of the Union Carbide Company under the name NIAX 520) are mixed with 6.55 parts of N, N-bis (ß-hydroxypropyl) diethylamine, 124.3 parts of diphenylmethane ^^ '- diisocyanate and 185 parts of chlorobenzene is heated 50 minutes to 94-95 ⁰ C. The NCO pre-adduct solution formed is then cooled to room temperature and then contains 1.21 # NCO (corresponds to 1 »725 $> NGO in the solid substance).

LeA 11 552 -59-

12.5 parts of β-semicarbazide propionic acid hydrazide are dissolved in 882 parts of hot dimethylformamide. 500 parts of the above WCO pre-adduct solution are stirred into this approx. 50 ° -hot solution over a period of 10 minutes, a highly viscous, homogeneous elastomer solution being obtained. After dilution with 51 parts of dimethylformamide and addition of 4 % TiO (based on elastomer substance) the viscosity is 660 poise. The inherent viscosity n ^ of the elastomer is 1.26.

The values listed in Table 5 are obtained by casting into films or by spinning the elastomer solution in dry and wet spinning tests. The threads have good hydrothermal properties. The hydrolysis resistance of these elastomer threads is excellent. After 16 stUndiger hydrolysis in a wash solution of 2 g / l of sodium carbonate and 5 g / l soap at 90 ⁰ C, no decrease in the tensile strength occurs.

Example 8

100 parts of a linear polycarbonate (OH number 122.5 molecular weight 915, melting point about 30-35 °) - produced by conventional thermal condensation of diphenyl carbonate and a mixture of the diols 1,6-hexanediol and ß-hydroxyethoxyl- (1) -hexanol -6 in a molar ratio of 3: 1 - are heated to 100 ° C. for 30 minutes after dehydration with 9.5 parts of tolylene diisocyanate (technical isomer mixture 65/35). After the polyhydroxy compound has been dissolved in 100 parts of chlorobenzene, the mixture is heated ^{to 100 ° C. with 23.2 parts of 4,4'-diphenylmethane diisocyanate for 30 minutes.} The NCO prepolymer oil has an NCO content of 1.40 % (NCO content of pest substance »2.46 %) « 5.60 parts of ß-semicarbazide-propionic acid hydraid

109845/1764

! • β Λ '' : * 2 _4Q_ " _BAD

in 400 parts of dimethylacetamide at 70 ° gelöst.'In this solution is allowed to 200 parts isocyanate prepolymer (/ 20 ⁰ 105 poise) incorporated with stirring. The 18.9 ^ ig? » Viscous elastomer solution is pigmented with rutile ($ 4 based on elastomer content) and cast into films or spun into elastic threads using the wet spinning process. For results on films and wet spinning tests see Table 5. The Graves tear strength, measured on films, is 30 kg / cm, the microhardness 65 · The melting point of the elastomer is 230 °.
Example 9 "

100 parts of the polycarbonate described above are extended with 9 »5 parts of toluylene diiso.cyanate and then reacted with 21.1 parts of 4.4 ^l -diphenylmeithanum diisocyanate after adding 100 parts of chlorobenzene to give the NCO-L prepolymer. The NCO content of the solution is 1.20 #. (NCO content calculated on solids = 2.18 i)

4.80 parts of ß-semicarbazid-propionic acid hydrazide are used in 400 Parts of dimethylformamide dissolved and as described above with 20Q Parts of the NCO prepolymer solution reacted and cast into films or spun into threads according to the wet spinning process (see Table 5)

Example 10 "

100 parts of a Mischjolyester from Herandiol- (i, 6) and 2,2-Dimethvlpropandiol-1,3 (molar ratio of the 'glycols 65:35) and adipic acid with the hydroxyl number. 66 (molecular weight 1700) are dehydrated after the addition of 0.1 part of a 33% solution of sulfur dioxide in dioxane. (110 ° / ln / ¹ 5 torr). After the addition of 2.0 parts of N, N-bis- (j!> - hydroxypropyl) -methylaoin and 5 parts of chlorobenzene, the hydroxy compounds with 28.t> parts of 4,4'-diphenylmethene-diocyanate become 45 minutes heated to 100 ° C. DIf

109845/1764

LeA 11 532 -4.I-.

HCO-Prepolyaerechaelee is dissolved in 95 parts of chlorobenzene. The HCO value of the solution is 1.40 4. (Corresponds to 2.47 1 » in the HCO prepolymer solid weight.)

200 parts of the NCO prepolymer solution are allowed to flow with thorough stirring at 80 ° C. to a solution of 5.70 parts of β-semicarbazidpropionic acid hydrazide in 300 parts of dimethyl sulfoxide and rinsed with 20 parts of dimethyl sulfoxide. The 22.5 # high viscosity elastomer solution is pigmented with 4 l > rutile (based on solids content) and cast into films and spun into elastic threads by a wet spinning process. For results, see Table 5 · The tear strength of films (according to Graves) is 55 kg / cm, the microhardness of films is 64 · Threads placed in ammoniacal copper sulfate solution (0.01 normal) remain white.

Comparison attempt e

100 parts of a mixed polyeter according to Example 1) (MO 1700), 2 * 0 parts of N, H-bis (ft-hydroxypropyl) - methylamine and 5 parts of chlorobenzene are added and 29.2 parts of 4, 4'-Diphenylmethane diisocyanate ^{heated to 100 °} C. for 50 minutes. The NCO prepolymer is diluted with 95 parts Calorbenzol, the NCO content of 55 $> solids containing solution is 1.38 # (equivalent to 2.51 NCO 96 in the solid NCO preadduct). 2.519 t of NCO in the solid NCO pre-adduct).

(. From CGH .0.CO.NH. (CH) ₃ .CO.OCH _'3 + hydrazine hydrate, mp 102 ⁰ C) 605 parts of y-semicarbazide-butyric acid aydrazid are dissolved in 300 parts of dimethylformamide at 120 ° . 200 parts of the NCO prepolymer solution are poured into this hot water.

109845/1764

le A 11 532 -42-

BATH ORIGINAL

pour in and rinse with 20 parts of dimethylformamide. the Elastomer solution is then rapidly cooled to room temperature. Films and threads (NaQ spinning process) are produced using conventional processes.

Example 11

150 parts of the mixed polyester described in Example 1) OH number, 68 and 37.2 parts of 4,4'-diisocyanatodiphenyl ether are boiled together with 47 parts of chlorobenzene for 45 minutes Water bath heated to temperatures between 90 and 98 °. After cooling to room temperature, the NGO pre-adduct solution has a

• i-

A HCO content of 0.816% .

104.5 parts of the NCO pre-adduct solution are introduced into a solution of 4.15 parts of δ-semicarbazla propionic acid hydrazide in 232 parts of dimethylformamide with vigorous stirring, a highly viscous elastomer solution being formed which, after dilution with dimethylformamide to a solids content of 20 i »has a viscosity of 206 poise / 20 ° C. After casting into films and cutting into threads, the elastic values are determined. According to the standard wet spinning method, elastomer threads are spun whose (hydro) thermal properties are very good (see Table 5). Melting point of the elastomers 244 ⁰ G.

Example 12

14.7 parts of α-semicarbazide-acetic acid hydrazide are dissolved in 1092 parts of dimethylformamide at 100 ° and mixed at 60 ° with 356 parts of the NCO pre-adduct melt from Example 4 and homogenized by stirring. The solution is with 4 # TiO _? (based on fixed

Le A 11 532 -43- 109845/176 4

substance) pigmented. The viscous solution is mixed with 1.02 parts of 1,6-Hexandiisocyamat and 80 farther file dimethylformamide to give a Viskositäteanstieg 874 poises / 20 ⁰ takes place.

“After the solution has been poured into films, the elastic properties of the films are measured on cut threads. As the results (see Table 5) show, good strength and elastic properties are achieved. However, the threads obtained after wet spinning tests (or dry spinning tests) show only moderate thermal and hydrothermal values (comparison and example 4) ammoniacal copper sulfate solution. The melting point of the elastomer substance is 213 ⁰ C.

Example 1?

800 parts of a copolyester from adipic acid and a mixture of ethylene glycol and 1,4-butanediol (molar ratio of glycols 1: 1), molecular weight 1980, melting point 33-37 ⁰ C, are reacted with 192 parts of diph'enylmethane-4,4'-diisocyanate and 174 parts of chlorobenzene for 100 minutes at 80 ° to give the KCO pre-adduct. NCO content of the solution = 2.56 i * (3.1 % NCO in the solid).

100 parts of the NCO pre-adduct solution are poured into a 70 ° hot Stirred solution of 4.92 parts of ß-semicarbazid-propionic acid hydrazide and 0.092 parts of Ν, Ν-dimethylhydrazine in 255 g parts of dimethylformamide, with a still viscous, slightly cloudy solution

109845/1764

Le A 11 532 ₄₄ . .

eung is obtained. After dilution with dimethylformamide to a concentration of 20 # (viscosity 480 poise), films and threads are produced in the usual way by a wet spinning process. The elastomeric substance shows an improved resistance to light and oxidation. The melting point of the elastomer substance is 234 ^° C.

Example U

100 parts of the NCO pre-adduct solution described in Example 13 above be with a solution of 4.23. Share ß-semicarbazid-propionic acid hydrazide and 0.96 parts of N, N-bis (γ-aminopropyl) diethylamine in 255 parts of dimethylformamide (molar ratio of chain extenders 80:20) stirred, one highly viscous elastomer solution is created. Threads or foils from this Elastomer substances show a significantly improved colorability and fastness when stained with acid dyes.

Example 15

3.97 parts of ß-semicarbazid-propionic acid hydrazide are dissolved in 255 parts of dimethylformamide at 70 ° and mixed with 1.12 parts of m-xylylenediamine (molar ratio of chain extenders 75/25 1>) _{. 103 t} 5 parts of those described in the example are added to this solution NCO pre-adduct solution entered within 4 minutes, a homogeneous, highly viscous solution (450 poise / 20) being obtained. The elastomer solution is converted into films or threads in the usual way (for results, see Table 5). Melting point of the elastomer substance 237 ⁰ C.

109845/1764

Le A 11 532 -45-

Example 16

In tin · solution of 3-7 parts of β-semicarbazide-propionic acid hydrazide and 1.98 parts of 4,4'-diaeinodiphenyl ether (molar ratio of chain lengthening agents 70 »30) in 259 parts of dimethylformamide, 107.5 parts of the HCO pre-adduct solution described in Example 13 are introduced. The resulting highly viscous elastomer solution is bit diaethylforaaaid to a concentration of Thinned 20 pounds (160 poise) and made into pilings and threads (For measurement results, see Table 5). Melting point of the elastomers 250 °, softening from 241 °.

Example 17

1000 parts of a mixed polyester of the composition described in Example 1) (hydroxyl number 67.4), 19.5 parts of 1 ^ i-Bie- (ß-hydroxypropyl) -eethylaein, 273 »2 parts of diphenylaethane-4,4'-diisocyanate and 327 Part of chlorobenzene is scratched to 90-99 ° C for 35 minutes. After cooling, the ICO pre-adduct solution has an ICO content of 1.93 t>

3.78 parts of S-seaicarbazide propionic acid hydrazide are dissolved in 230 parts of dieethylformamide and 0.075 parts of ethylenediaain are mixed in 32 g parts of dimethylformamide (ratio of chain extenders 9515). The solution is mixed with 104.5 parts of ICO pre-adduct solution with stirring, an elastomer solution with 315 poise / 20 ^{0 being} formed. Films are cast from the solution, or after dilution to 20 + (80 poise) are in the LASS

■ The pinning process produced threads. For results see table 5. Melting point 228 ^° C

109845/1764

^{Le A 11 532} -4b- 8ADORIGfNAL

Example 18

3.18 parts of ß-semicarbazid-propionic acid hydrazide are at 70 ° dissolved in 200 parts of dimethylformamide and with -1.00 parts Ν, Ν'-Bie (γ-Amino-propyl) -piperazine mixed in 32 parts of dimethylformamide (Molar ratio of chain extenders 80:20). 104.5 parts of the NCO pre-adduct solution from Example 17 are below Intensive with stirring, resulting in a homogeneous, colorless solution with a viscosity of 255 poises. Results on films or threads see Table 5

The substance can be dyed very well and easily with acid dyes.

Example 19

3.58 parts of β-semicarbazide-propionic acid hydrazide and 0.64 parts of piperazine-N, N'-bis- (propionic acid hydrazide) are dissolved in 232 parts of dimethylformamide (molar ratio of chain extenders 90:10). 104.5 parts of the NCO pre-adduct solution from Example 17 are introduced into this solution at 65 °. After diluting the viscous solution with dimethylformamide to 20 #, ^{films and threads are produced from the solution (50 poise / 20 0} ) as usual (wet spinning process) (see Table 5).

Example 20

1000 parts of the polyester (MW 1655) described in Example 1), 18.0 parts of N, N-BiS (0-hydroxypropyl) -aethylamine, 163.6 parts p-phenylene diisocyanate and 299 parts of chlorobenzene are 50 min heated to 96-99 ° and then cooled to room temperature (NCO content of the pre-adduct solution = 1.65 *).

109845/1764

Ie. A ■ 1 ι 532. ■■■.; · - ■■

-4.7-

In a solution of 13 »55 parts of ß-semicarbazidopropionic acid hydrazide in 917 parts of dimethylformamide are "at 70 ° 410 parts The above NCO pre-adduct solution is entered, the solution is pigmented with 4 # rutile (based on solid elastomer substance) and with.: 0.30 parts of 1,6-hexane diisocyanate are added. , -;

The elastomer solution (524 poise / 20 ⁰ ) is diluted with dimethylformamide to a concentration of 20 # Pestsubstanz and as _: usual wet spun. The threads have an extraordinarily high deformation temperature (HDT) of 171 ° and / a melting -

'. &' ■ · ■ \.

point of 246 ^0C .

Example 21 ;.

510 parts of the NCO pre-adduct solution described in Example 20 are placed in a 60 ° -warm solution of 15.25 parts of β-semicarbazidpropionic acid hydrazide and 0.53 part of hydrazine hydrate and then mixed with 0.89 parts of hexane diisocyanate. the The resulting viscous elastomer solution is cast into films or, ζά threads spun in the wet spinning process. The threads have a very high deformation temperature of 168 ° and a melting point of 238 °.

Example 22

800 parts of a mixed polyester of adipic acid and the diol mixture from 60 mol. # 1,6-hexanediol and 40 parts 2,2-dimethylpropanediol-1,3 (Molecular weight 2160) with 14.9 parts of N, N-bis (ß-hydroxypropyl) methylamine and a solution of 187.4 parts of diphenylmethane-4,4'-diisocyanate in 254 parts of chlorobenzene Heated to 85-88 ° for 50 minutes. The NCO content of the gebil

The deten NCO pre-adduct solution is then 1.87 #. ^{Le A 11 532} -48- -109845/1764

Table 5

example
Mr. L pad egg
after 1
Rubbing elastic properties
5rüoH- ~ Mödul ~ I <ödul stay. tion 300 * 150 * strain Curve 3x 300Jl 18th [the ralsche and hydrotheraiaohe
^{r S} HVBi Reetdeh β he 15.7 20.2 - 21.1 25.2 _ 13.4 18.3 - 17.7 _ Π, Ο -. 18.2 .hydro- • 42 properties in Thatch well - 72 ! • ■ sound i (hydro) thtr- • ■ · ■ I Ver consolidating- expanding 3 return to mg / den 20th tension in air in wa- nung naoh 95 ° 21.4 _- 20.5 therm Elongation IKn- Discharge 146 I. ■ leoh · own
• ohafteh , Xigenaehmf- 'Md en are fah speed mg / the sweeping. 18th 20 ° ι mg / the 8.7 17.5 ι. laatung 45 in • t Vaang Respect _ 182 worse ten for
ElastoeerfÄ- ru-fc ait RHn-- ren g / den 23 ' _ "·.. * LuJ •he (in 382 al · Btlipiel
5! the su e dyes • mg / den - 20 ^c 95 ⁶ air
20 °) 1 hydrolyaen- • ohleoht colorable 24 - * f reBiatent
Tad en ■ - U 13th 62 - 626 24 15th 26.6 • 32 46 - 74 (hydro) thermal 588 139 23 28 _ _ 128 158 ■ isohe own
stocks 5 I ¹ 0.60 583 159 20th 55.6 51 40 130 - 90 Tiel bad H 0.52 593 130 18th 175 46 _ - 204 t «r ala Bei 6th P. 0.75 142 22nd 25th -. 48.5 38 248 - 104: game 4! '- N 0.70 25th 159 56 80 250 476 20 ι 38 76 - 460 ' 121 20th 48 _ 7th Ϊ 0.58 400 190 20th 16 _ ■ 47.0 186 66 H 0.78 480 243 15th 20th 163 57.6 39 56 138 tears 70 8th P. 0.75 555 209 16 165 36 42 - not eatable 8th* 9 P. 0.87 406 128 17th 159 53.0 60 36 140 174 94 10 H 0.54 ■ ■ » 76 168 36 50 Pad 204 Ver P. 0.50 - 20th _- 33.5 104 234 same
attempt H - 25th 130 74 e) 524 22nd 23 436 125 21st - 72 11 P. 0.54 488 179 13th - 61.5 TI 0.53 470 118 15th 166 12th P. 0.68 157 15th _ 43.1 H 0.60 22nd 15th 149 - 14th * 58 680 20th 14th - 143 22nd 56 13th F. 0.60 755 - 16 15th - 49.5 H - 610 89 20th 164 64 15th P. 0.76 745 127 22nd 15th - 43, β H 0.69 666 78 21st 11 162 16 P. 0.62 542 117 16 - 40.6, H 0.68 554 109 22nd i 17th P. 0.75 95 52 18th P. 0.66 57β 22nd 52 68 110 20th 60 19th P. 0.73 559 19th ■ 59 76 7H 138 »3.9 20th If 0.64 567 105 71 13.0 21st N , 65 126 68 } 8.2 22nd H , 59 59

P = Heßergebnlese on cut threads from films, which by Aufatreiohen the solution on glass plates and ab-

vapors dea solvent at 100 were obtained *

N = standard KaQspinnprozeQi spinning in 20 weight-weight elastomer solutions in a bath of 90 ° (water + 10 ° C Diiie-

, thylformamide

The elastomer threads listed in Example 5-19 show no discoloration when treated with dilute solutions of bohwermetallsalaen (e.g. CuSOa).

The inherent viscosity of the elastomers in Example 5-22 is within the range of values 0.7 - 1.9. ie A Π i> 32 -49-

109845/1764

COPY

410 parts of the above NCO pre-adduct solution are added to a solution of 15.45 parts of ß-semicarbazidpropionic acid hydrazide in 925 parts of dimethylformamide, the viscosity of the solution increasing to 735 poise / 20 °. After pigmentation with 4 wt .- # TiO ₂ (based on elastomer solids content), the solution is spun in the usual form or cast into films.

109845/1764

Claims (8)

Claims; 1. Linear, segmented "polyurethane _{elastomers /} consisting of transfer products" of higher molecular weight diisocyanates with chain extenders, containing at least 55 $> - based on the total chain extension segments present - of a chain extension segment of the structure -NH.NH.GO.NH. (CH _? ) -CO .NH.NH- (x = 1 or 2). _ 2. Linear, segmented polyurethane elastomers with an elongation at break of more than $ 300 and an inherent viscosity of at least 0.5, determined in a solution in hexamethylphosphoramide at 25 °, consist1 of intralinear segments of the structure. - (ODOCO.NH.R.NH.CO) _r . (OrG.O.CO.NH.R.NH.CO.) _S -L --NH.NH.CO.NH. (CH ₂ ) _x .CO .NH.NH.CO.NH.R.NH.CO.- | - _n where D is a long chain, divalent aliphatic polymer residue with a molecular weight of 600 to 5000 and a melting point below 60 °, R is a divalent, organic residue of an aromatic, aliphatic, cycloaliphatic or araliphatic diisocyanates, G is a divalent, aliphatic, cycloaliphatic or araliphatic radical of a dialcohol with molecular weights between 62 and 300, optionally one or more Containing tertiary aliphatic amino groups, r an integer from 1 to 5, s zero or an integer from 1 to 5, x -1 or 2, m is an integer from 1 to 5 and η is an integer from 1 to 5 means. . 10 9 8 4 5/1764 Le A 11 532 _ ₅₁ _ 3 / Process for the production of essentially linear, segmented ter polyurethane elastomer by converting a 1.0 to 6.0 Ge ^ - weight ^ NCO containing NCÖ pre-adducts from higher molecular weight Dihydroxy compounds and excess, molar amounts of diisocyanates with approximately equivalent amounts of bifunctional, Low molecular weight chain extenders containing 2 active hydrogen atoms in the presence of highly polar, organic solvents and subsequent removal of the solvents, characterized in that the chain lengthening agent is aliphatic Semicarbazide hydrazides of the formula H ₂ N.NH.CO.NH. (CH ₂ ) _χ .00.NH.NH ₂ (x = 1 or 2) can be used. 4. The method according to claim 3)> characterized in that in addition to at least 55 Mol .- # of the aliphatic semicarbazide hydrazide up to 45 Mol. -I » customary, bifunctional, 2 active hydrogen atoms containing compounds with molecular weights from 18 to about 300 used as chain extenders will. 5. Process for producing substantially linear, segmented Polyurethane elastomers by reacting an NCO pre-adduct containing 1.0 to 6.0% by weight # NCO from higher molecular weight dihydroxy compounds and lower molecular weight diols with molecular weights of 62 to about 300, preferably with tertiary amino groups in the molecule, in amounts of approx. 0.05 to 1.0 mol per mol of higher molecular weight dihydroxy compound, and over- 1ÜB845 / 1764 -32- Schüssigen molar amounts of diisocyanates with approximately equivalents Quantities of bifunctional chain extenders containing 2 active hydrogen atoms in highly polar, organic solvents and subsequent removal of the solvent, characterized in that aliphatic semicarbazide hydrazides H ₂ N.NH.C0.NH. (CH ₂ ) _x .C0.NH.liH ₂ (x = 1 or 2) can be used. 6. The method according to claim 5), characterized in that in addition to at least 55 Mol .- # of the aliphatic semicarbazide hydrazides up to 45 Mol .- # customary chain extenders are used m . . 7. The high-elastic polyurethane elastomer yarns old an elongation at break of at least 300 # and a strain temperature of above 145, consisting of linear, segmented polyurethane elastomer having an inherent viscosity (measured in 1 wt. Solution in hexamethylphosphoramide at 25 ⁰ G) of at least 0.5 wt . #, containing intralinear segments of the structure (OD0.C0.NH.R.NH.CO) _r . (0.GOCÖ.lfH.R.NH.CO) _| - -HH.NH.CO.NH. (0Η ₂ ) _χ .0Ο.ΝΗ.ΝΗ.0Ο.ΝΗ.Η.ΝΗ.0Ο.-ί · _η where D is a long chain divalent aliphatic roxymer radical with a molecular weight of 600 to 5000 and a melting point below 60 °, R is a divalent, organic radical of a aromatic, aliphatic, cycloaliphatic or araliphatic Diisocyanates, G a divalent, aliphatic, cyclo » aliphatic or araliphatic radical of a dialcohol with Molecular weights between 62 and 300, optionally containing one or more tertiary aliphatic amino groups 10 9845/1764 Le A 11 532 -53- Number from 1 "to 5 _t s zero or an integer from 1 to 5, m an integer from 1 to 5, preferably 1-3 and η an integer from 1 to 5. 8. Solutions of polyurethane elastomers, containing in highly polar, aliphatic solvents with amide, urea or sulfoxide groups and boiling points up to 225 ⁰ C 10 to 33 weight ^ essentially linear, segmented polyurethanes with intralinear structural segments according to claim 1). 109845/1764 Le A11 532