DE1929155A1 - Process for the production of synthetic elastomers - Google Patents

Description

DESCRIPTION for the patent application of Pixma IMPERIAL CHEMICAL INDUSTRIES LIMITED, London SW t / Großbr _e

concerning

Process for the production of synthetic Elastomers

Priority; Great Britain from 7 »

1968 * Hr ₃ 27264/68

You invention relates to the production of new synthetic elastomer "and especially iron such Blast Omaren * consisting of segmented en polyet © r» urethanes with aliphatic Ursthansegmesiten and in PM @ q scbmel & gQspömen werdäii Kings' nen _o It already rnordsa attempts made synthetic elastomers manufacture which can be in schmelsgesponnen Textilfädeji, as is known, the method of the Schsaelssspiimens daö has advantages over the LSsuogsspimien, which is the current conventional method of processing synthetic elastomers "

It is well known to implement polyether urethanes of a hydroxyl-capped polyalkylene oxide with a diisocyanate and with a chain extender, preferably a double

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8AD

high-quality alcohol, which is referred to as diol in the following, to produce.

The properties of the elastomers naturally depend on the starting materials used and on the reaction conditions, in particular on the ratios of the reactants to one another. Important properties of synthetic elastomers are the tensile strength, the "elastic regression", the formation of the working gap and the Vikat softening point ₉ which are defined in the following.

Definitions .dey Elg angghasffEagi whom J

Safely wrapped

Hit BehufUhigkeit of the threads is the Luenga gemoiatg about which it can be stretched before si © r © ies®? _S i expressed as Prozentsatss the original

Tear resistance

The tear strength is the breaking load of the threads, expressed in Gv & sm / den of the original. Thread «,

Light resistance test

The threads are on one. Frame wound with light from a xenon arc lamp 300 Stiaadea Ismg exposed to the elastic properties, and the color of the threads are determined before and after exposure,

Bleach resistance ateate

The threads are Langr immersed 45 minutes in an aqueous solution containing 0.1 parts by weight 96 includes Hatriumohlorit and 0.5 ml / 1 of glacial acetic acid and which is maintained at 85 ⁰ C. The color of the threads

9 0 9 8 5 0/1623 && original

is determined before and after the bleaching treatment

Elastic recovery

The elastic regression of the threads is expressed by the breakage which is obtained when the length by which the threads are stretched when tension is applied is divided into the length by which they contract when tension is removed "The fraction is usually" expressed "as a paragraph (U ₀ Bf. The speed of" stretching or Sufiomra toe is 500? ", Ie minute),

Work recovery

The work of recovery of the threads is expressed in terms of breakage? obtained _s when one is obtained said filaments while stretching is the energy or work ,, by applying a voltage, hineindividiortp in the energy or work the back is obtained when said filaments on the ur ~ nprünglichen dimensions upon release of the voltage · contract, by breakage .gewöhnlich air Prozsntsate ausg6drückt _t and it will genoxranen the average of four consecutive Beeti-m "·" Ungen with the same test sample "

ViBkoaltät number

The ViskositatBgfilil is defined as twice the natural logarithm of the viscosity of a solution of Y2 VoI ₀ -% dea polyether urethane _f dissolved divided in ortho-chlorophenol at 25 ° C _f of the ortho '= Ghlorophenols by the viscosity at the same Temperature

Vicat Erwei chun gepunkt mentioned here Vicat Erweichungspunlcte were using

6 2 3

8AD ORIGINAL

of a penetrometer determined by that of Edgar and Ellery 1952, page 2638 of the Journal of the Chemical Society is similar «. The degree of penetration is against the temperature automatically applied to all graphic representations

Annealing

The yarn was wound up without tension onto a Hulbe, and the yarn package was heated for 30 minutes at 11O ⁰ C. All shrimp properties mentioned here in this description (with the exception of ZST) were determined with this annealed yarn.

Shell strength temperature (ZSI)

A loop of elastomer having a weight of approximately O ₉ 1 g / den carries, ⁰ C immersed in a liquid paraffin bath of 1Op The temperature is gradually raised "to the yarn completely tears" The temperature at break is as feBtigkeitstemperatur "(ZST ) designated,,

Growth in water of 6ofc

A loop of approximately 200 denier of yarn is made by clipping in place a split lead ball _{weighing O 9} 17 g and the length is determined while the lead ball hangs freely _o The loop is stretched 100 # on a frame, which is then 5 minutes is immersed in water of 60 ^° G for a long time. The loop is then removed from the straw and left hanging in the air for 1 hour, after which its length is measured. The increase in length, expressed as a percentage of the original length, is referred to as "growth".

Growth in air from 200 % strain

Sine yarn clusters are made by cutting a split lead

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ball is clipped on, the weight being 0.45 g for yarns from 150 to 210 den »

The garnish is hung up to relax for 24 hours while it is gently tensioned by the lead weight. The length of the sling is then determined. The sling is stretched 200 # and held at the stretched length for 24 hours. The stretching is then removed and the loop is allowed to relax, while bearing the weight of lead ₀ the length is determined after 1 minute and after a 24-hour relaxation. The increase in length as a percentage of the original length, expressed as growth in air at 200% elongation _o

Oemäfi of the invention is a process for the production of a synthetic polyether-urethane elastomer which can be melt-spun into threads proposed, which process is carried out by using heat (1) a diol, which is a hydroxyl-terminated linear Polyether or mixed polyether having an average molecular weight between 1000 and 6000, preferably 2000 and 460Of, (2) 0.1 to 20 moles, preferably 0.1 to 1.9 moles, of an aliphatic, cycloaliphatic or arylaliphatic diol per mole of the above Polyätherdiols, and (3) 96 to! 06 mol of an aliphatic or cycloaliphatic diisocyanate, preferably p-Iylylene diisocyanate or transtrans-4 »4 ⁱ -diisocyanatodioyclohexylmethane, per 100 mol total weight of the above diols converts»

It is extremely preferred that the ratio of the aliphatic, cycloaliphatic or arylaliphatic diol to JPolyätherdiol is 0.2 to 1.0, ■ - ■

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Suitable diols are, for example:

Ethylene glycol

1 »4-butanediol

1,10-decanediol

trana-oyelohexanediol

trans -cyclohexanediiflethanol

1,4-bis (hydroxyethoacy) benzene

Ble (hydroxymethyl) durol

Examples of suitable polyether should be mentioned: poly (tetra "ethylene oxide) glycol and poly (propylene oxide) glycol _e

In the preparation of the present synthetic elastomers, the diols and the Dilsoeyanat may An advantageous method are brought together * for this is to mix the Hiechpolyätherdiol with the entire Dlieocyanat to heat the mixture to, for example white 120 ⁰ G and react for about 1 hour in any zweekmäasigen White to let *, After cooling to 98 HO bit ⁰ G the nledrigmolekulare diol, DOH, the aliphatic ^, cycloaliphatic or arylaliphatißche diol is added and the iüemperatur is 150 bit 21O ⁰ C increases, and heating for 5 minutes fortgesetato Alternatively been can daa polyether diol 2uerst at 170 to 210 ⁰ C erhitat, and the low molecular weight diol and the diisocyanate may then be added and the heating may Werdan continued, for example, about 1 hour _o e ^ findungegemässe manufacturing process can also be carried out continuously by the polyether diol, the low molecular weight diol and that Diisocyanate can be passed in a mixture through a hex'conventional reactor, which in an expedient manner has a screw forward movement direction ₃ In this case, on-

8AD ORIGINAL

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grand the shorter VerweilEelt the temperature slightly higher than the temperatures given above, for example, 200 to 25O ⁰ C. The reaction is preferably carried out under an inert atmosphere, for example nitrogen, to prevent oxidation of the polymer "An effective mechanical mixing of the reactants is very welcome. Another method is to add part of the diisocyanate to the polyether diol. The amount of diisocyanate can be, for example, Ϋ2 to 2/3 mol per mol of polyether. The low molecular weight diol is then added, followed by the addition of the remainder of the diisocyanate. The reaction temperature should be high enough to ensure a clear melt «,

If desired, catalysts such as the following can be added to the reaction mixture can be added to support the reaction of the diisocyanate:

Triethylamine

Dibutylainndllaurate

Dimethylcyclohezylamine

Sodium ethoxide -

Sodium phenate

Eiaen (III) -aGetylac * ton * t

In addition, k is the Serstellung m dee polyether-urethanes in solution run "Suitable solvents for this purpose sindi

■ - * ■ -Ν, Ν-dimethylacetamide

Dimethyl sulfoxide mixed in an equal volume Methyl isobutyl ketone

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Ν, ϊί-Dijaethylformamld

Hexaethylphosphoramide

Tetramethylene sulfone

The örfindungsgeaiäseen polyether urethane can be produced in solution. can be put, and the latter can be done directly by a conventional ! rock or hate spinning processes are spun into threads. The solutions of the polyether urethane can also be used in films be poured «. However, as already stated, the textile thread preferably produced by melt spinning »in which case no solvent is required»

The used in the manufacture of the present polyether * urethanes The reagents used can also contain pigments, plasticizers, Matting agents or stabilizers can be added.

According to the invention there is also a. synthetic polyether urethane elaetomer suggested which one VlekoaitätsaaJal from 0.5 to 1.5, and which is obtained thereby, that using Vane (1) a diol which is a hydroxy lab-closed linear polyether or mixed polyether sit an average molecular weight between 1000 and 6000, preferably 2000 and 460Q, 18t, (2) 0.1 Me 20 mol an · »aliphatic, cycloaliohatiechen or araliphatic diols per mole of the "above-mentioned polyether" diol, and (3) 96 to 106 moles of an aliphatic or cycloaliphatic Diisocyanates, preferably p-xylylene diisocyanate or trans, trane-AtA'-Diisocyanatodioyclohe ^ loö ^ haa per 100 mol Total weight of the above Dlole implements «

The invention also encompasses melt spinning of the above novel

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synthetic polyether urethane in threads and the threads obtained from them * The latter have excellent elasticity. and do not discolor when exposed to a xenon arc lamp or bleached with sodium chloride, according to the light resistance and lead resistance tests defined above i & Lgen elongation at least 95 % and the work recovery from 100 & Lger elongation at least 75% »The threads are subjected to a heat treatment (tempering) in order to achieve the best elastic properties. For this reason, in Examples 1 to 3, they were heated to 110 ° C. for 30 minutes before the physical properties were determined «.

The present polyether urethanes differ in an advantageous manner from other synthetic elastomers, namely by the ease with which they can be melt-spun into threads, whereby the threads show no tendency to stick together and therefore do not have to be dusted with talc powder These new polyether urethane threads work better than known elastomeric threads with similar physical properties because they do not discolor when subjected to the above mentioned light and bleach resistance conditions elan tables outwear such _o B _o sweater, ski pants, "and also for medical elastic stockings and bandages ,, Change uses are woven and knitted Sohwimmkleldungen, 'ladies' hosiery, bras and pajamas" These threads are also suitable for similar broad applications in the form of Staple fibers, in particular dere

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if they are mixed with, for example, wool, cotton or polyhexamethylene adipamide «. The novel polyether-urethane-filament of the present invention can be processed into composite elastic yarns by ALB endless thread together with one or more rovings of staple fibers such as _o B "PoIyäthylenterephthalat-, wool or cotton fibers, in a conventional spinning or pulling frames are stirred in »The present polyether-urethanes can be used in the form of fibers in the manufacture of non-woven fabrics, or mixed with wool, they can be used to weave tiles that are suitable for men's suits»

The invention is explained in more detail in the following examples «, Organic examples are not to be construed in a limiting sense. Parts are parts by weight.

example 1

70 parts of a hydroxy-separated poly (tetramethylene oxide) glycol with a molecular weight of 2095 to which 0.1 % of an antioxidant (Nonox WSL) had been added are ^{mixed with 13.14 parts of 4,4 1} -diisocyanatodicyclohexylmethane (trans · - trans Isomer) and vacuum-flushed with dry nitrogen. The mixture is ^{heated to 120 °} C. for 2 hours with rapid stirring. It is cooled to 93 ° C. and 3.31 parts of p-bia- (β-hydroxyethoxy) benzene are added. The mixture is vacuum purged with nitrogen. Eü is stirred vigorously for 10 minutes, "The temperature is then raised rapidly to 190 C, and at this temperature is stirred for 10 minutes" After removing the stirrer, the melt is vulkanisert 2 hours at 190 ⁰ G *

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Daa resulting polyether "urethane has a Polyätheraegmentgehalt of 81 G €> w _e - #, a diol / Polyätfeer-Molverhär & never of 0.5 and an isocyanate / diol proportion of 1.0 ₀ Bas polymer" has a viscosity number of 1.33 and has a Vicat softening point of 167 ⁰ C. It is spun at 222 ⁰ C in a 5 fädigee yarn with a total denier of 269, which has the following properties after IeBiperung at 110 ⁰ C:

HullfeBtigkeltstemperatur 167.5 ⁰ C

Tear strength g / den 0.675

Able to Döhner # 527

Blastic regression %) 97

. . ,. ., _Λ . , _α % from 100 # elongation "" Sleeve recovery% ί 87

Waistum in air at 200 % elongation

24 hours 1 minute relaxed TA $>

24 hours relaxed 2.4 ^

Growth in water at 60 ⁰ C from 100 % elongation 3.4 %

Example 2

70 ropes of a hydroxy-terminated poly (tetramethyleneoxy) glycol with a molecular weight of 2934 »ifelchee 0.1 wt vacuum purged with dry nitrogen _o Groittieoh is heated to 12O ⁰ C with rapid stirring for 2 hours. Ss is then cooled to 95 ° C and 2.36 ropes p-bending (ß-hydrozyäth03Ey} ~ benzene are added The mixture is vacuum purged with nitrogen and gerüart vigorously for 10 Hinuten long. The temperature is then rapidly raised to 190 ⁰ C , and the stirring at this tapering temperature is continued for 10 minutes. After the stirrer has been removed from the melt, it is vulcanized for 2 hours at 190 ° O

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The resulting polyether urethane has a Polyätherweichsegmentgehalt of 85 ₁ 7 wt _o - #, a diol / polyether Äolverhältnis of 0.5 and a DüBOcyanat / Geaamtdlol-Molverhältnie of 1, O ₀ has the polymer has a Viekositätszahl τοη 1.58 and a Vikat softening point of 170 ⁰ Oo Ea is ^{spun at 220 0} C a 5-ply yarn with a total titre of 272 »which after annealing at 110 ⁰ C has the following properties:

Zero strength temperature 174 »5 ° C Tear strength g / den 1.188

Extensibility% 561 Elastic recovery i> from 100 % elongation 98

% Gain from 100% elongation 81 Waohstun in air at 200 j6 stretching during

24 hours 1 minute relaxed 26.4 ^

Relaxed 24 hours. 13.2 ^

Growth in water at 6O ⁰ C from 100 Jt elongation snail

70 ropes of the polyether from Example 1, which contains the antioxidant, are mixed with 13.78 parts 4,4'-diisocyanatodioyclohexylmethane (tranatrane-Isoaier) and vacuum-flushed with dry nitrogen. The mixture is stirred for 2 hours with rapid stirring 12O ⁰ C heated. Ee is then cooled to 98 ⁰ C and 2.04 feile trans-cyclohexane-1,4-diol are added Bas mixture wixu vakuumgeapült with nitrogen and stirred vigorously for 5 Hinuten. The temperature is then rapidly increased to 190% urd the stirring at this Teaperatur is 10 minutes, "continued" Hachdem the stirrer mm U t Schmelee been entnotaoen ows, these two Stunien is% u - i00 ^ 0 ^ ^{vulkanisiertp;}

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The resulting polyether urefchau besitst a Polyäthej ^ weiehe.egmentgehalt of 81 wt .- $ _f 6, a diol / polyether Molverhältnla. of 0.5 and a diisocyanate / total diol molar ratio of 1 ₃ 0 “The polymer has a viscosity number of 1.12 and a Vikat = softening point of 240 ⁰ G ₀ Bs at 251 ⁰ C in a 5-ply yarn with a total denier of 123 melt spönnen, which after tempering at 110 ⁰ G has the following properties:

Hull strength temporabur Tear strength g / the elongation #

Elastic recovery % from 100% elongation Work recovery% from 100% elongation Growth in air at 200 % elongation for 24 hours relaxed for 1 minute

Relaxed 24 hours
Wakutum in water at 60 ⁰ O from 100 # elongation

Example _n 4 .

70 parts of the polyether of Example 1, containing the Antioxydationsmibhei are mixed with 11.48 parts of 4 »4 ^I diisocyanato-di ~ cyclohe ^ rlmethan (trana-trans-isomer) and vacuum purged with dry nitrogen. The reaction is carried out as in Example 3 , with the intersection that instead of 2 * 04 parts, 1.02 parts of trans-cyclohexane-1,4-dol are added «

The resulting Poiyäther-urethane has a Polyätherwelchsegmentgeiialt 84.8 5 ", a diol / polyether Molverhaltnia of 0.264 and a diisocyanate / Gesaratdiol-MolveriiältniB of 1 ₈ 03" The polymer has a Viscous! Bätsaahl of 1.10 and a Vikat- Softening point of 159 ⁰ Oo Ea is under a AufspulgeBchwin-

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199 ⁰ C O , 550 957 95 79 15th , 4 # 9 , 8 5 * 10

85 768 9 fi ο, 401 96 79 5 # 9, 3.5 % 6,

- 14 -

speed of 30.5 m / min at 226 ⁰ C in a 5-filamentous yarn melt-spun Yarn C has after annealing during Y2 hour at 110 ⁰ the following properties;

Shell strength temperature 164 ° G

Denier tear strength g / den extensibility &

Elastic recovery JSS 100 f> Strain job recovery% 100% elongation growth in air at 200% elongation during

Unaptvnnt 24 hours 1 minute

24 hours "relaxed
Growth in water at 60 ⁰ C from 100 $> elongation

Example 5

70 parts of elnas hydroxyabgeaehlosaenen poly (tetramethylene oxide) glycol with a molecular weight of 2095 are mixed with 14.05 parts of 4s 4 ⁵ -dilsooyanato-dicyclohexylmethane (trans-tranfl'-isomor) and vacuum-flushed with dry nitrogen Heated for 3 'to 120 ⁰ G and ^{cooled to 96 0} O, whereupon 3.47 parts of p-Ble ~ (β-hydroxyethoxy) -benzene are added. This will be with nitrogen vakuumgespülto The mixture is _β stirred vigorously for 10 minutes and the temperature is then raised rapidly to 190 ⁰ C, and the RUiiren is continued for 10 minutes at this temperature, Urd, although for 5 minutes under dry nitrogen, and 5 minutes under vacuum, the vacuum is then replaced by dry nitrogen and _B has been removed naohdem the agitator, the melt "90 ⁰ C for 2 hours! vulcanized,

BATH ORIGINAL

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The resulting polyether urethane a besitat Polyätherweioheegmentgehalt of 80.0 wt .-? S ₀ a diol / polyether molar ratio of 0.524 and a diisocyanate / öeaamtdiol molar ratio of 1.05 · The polymer has a reduced viscosity of 1.43 and a Vicat Softening point of 195 ⁰ C ₀ Dae polymer is melt-spun at a winding speed of 45.7 m / min at 232 ⁰ C into a 5-ply yarn which, after tempering at 110 ⁰ C, has the following properties:

Bullet resistance temperature 178 ⁰ C

Denier 128 tear strength g / den 0 * 897

Elongation # 448

Elastic recovery from 100 for stretching 96

Work recovery% «us 100% elongation 76 growth in air at 200 i» elongation for 24 hours 1 day relaxed 5 * 8 %

Relaxed 24 hours 1 _f 9 i>

Growth in Vaeser at 60 ⁰ C, 100% strain 2.0 Ji

Example 6

70 files of a hydroxy-sealed poly (tetramethylene oxide) -glycol with a molecular weight of 1000, to which 0.1% of an antioxidant agent (Nonox WSL) has been added, will be 26.1% in a hurry mixed ^ lstöthan (trans-trana-Ißomer) and vacuum purged with dry nitrogen * The mixture is erhitat% Yz hours under rapid 'stirring at 120 ° C and at 94 ° G cooled 5,5t tejö-ö jHBis- (ß-hydroxyätlioxy ) «- beiiaöl are added, and the gtettiacli is stirred with drinking stickstoft ir ^ kutimgeiiplia ^ Mq nird" Äefi ^ gf for a few minutes, tmd the ipempöraturirirddanti to t9Ö ° G angöiotien * be

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te ~

this temperature is stirred for 5 minutes Raiter vacuum "The vacuum is replaced by dry nitrogen, and is after the agitator removed, has been that melt is two hours" at 19O ⁰ C vulcanized "

.The resulting Polyätlier-urethane has a Polyätherweichsegmentgehalt vo '68 _P 9 GeWo- $ £ _t a diol / polyether ~ Molver »· ratio of 0.4 and a Biißocyanat / Geeamtdiol-MolTerhältnis of 1,015ο The polymer has a Viiskositätezahl of 1, 24 and a Vlkat softening point of W ⁰ C. It is spun at 225 ° Q at a winding speed of 61.0 m / min into a 5-ply yarn.

Zero strength temperature 178 ⁰ C

Denier 160 tensile strength g / den 0 _P 44Ö

Extensibility & 743

Elastic regression i \ ftue 100 ^e / o elongation 95

% Recovery from 100% elongation BO Growth in air at "? 00 $ while stretching

24 hours 1 minute relaxed "32 * 53 %

24 hours relaxed 19 »04 ^

Growth in water at 60 ° C from 100 ^ elongation 14 * 6 $>

Example 7

70 parts of a hydroxy-sealed poly (tetramethylene oxide) "glycol with a molecular weight of 2000 _p, which contains 0.1% of an antioxidant (Nonox WSL), are mixed with 18-34 parts of 4 _f 4 ^l -Diißoeyanatodicyclohexyliaethan (trans-tranß isomer) and 6 _s O9 parts 1 _s 10-Decan.dlol geioieoht and with dryö- =

_{Λ Λ Λ A,.} 8AD ORIGINAL

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! 7

nem nitrogen Trakiarans'sspülto The mixture is under raseto.era RLüiren 30 minutes 110 ⁰ C erkLtsst and the! daam temperature for 40 minutes atif 190 G angehobeiia In this Semperator for 5 minutes nut ex ¹ Vacuum stirred. The vacuum is replaced by dry nitrogen, "and after the stirrer has been removed, the melt is vulcanized for ^{2 hours at 190 ° C."}

The resulting Polyätlier-tirethaa "possesses a polyether * - * soft segment content x ^r on 74 ₈ 1 (row * - = ^ a DioX / Polyäth & r --- Hol'Ver '-> hilltnia iron 1 _s 0 and a Diisooyanat / Geflasitdiol -MolYerhaltnifj iron I ₉ OOo The polymer has a viscosity of τοη 1.40 and «inen

k'ä 144 ⁰ Ce It is hot 222 ⁰ G under one roof * - ·

6I ₉ O m / iain in a 5Madiges G-arii rmoh one! © npersiiig "bsi Ή 0 ö die f

140 ⁰ O 220

645

HUcJrbildusag $> from 100 i * Dehamag 98

% from 100 % elongation S6 in üöft hai 200 $ ^J S Deimmiag during

24 S'öifficleEL 1 Mtoutö: öa-tispfnurfc JT ₂ SS ^>

24 S'feunden eatapaimt 8 ₃ 35 i «

ixt water Ijgl € 0 ° Ö from 100 fS Defeaasg 1O ₅ 4 Si

with a Molekiila ^ gswioiit tos 2000 »weXahsa. 0,, t

ι ". ^; f""ii · 'i. ■ - _K , -."

098 SO / 162-3 ßAD ORJGlNAt

25 _t 68 parts 4 "4 '~ Dlisocyanato = ^ ixcyololiexyl3iiethan (traiie-trans" · Iaomer) and 1O ₉ 98 ropes 1 ₉ \ O "Decanediol gsmiaakt ίλϊιΛ with dry nitrogen x ^r battery-flushed ₀ Da3 mixture becomes tmtex" rapid stirring, 1} 2 hours then heated rapidly avf IMD the temperature to 110 ⁰ C. 190 ⁰ G angeho "beno The mixture IIIrd less than 3 minutes stirring, and dat? Talcuuin is then ers.vfc55fe by -fer nitrogen, ilaohdem the stirrer has been entnoaaaija that Sohtnalse is 2 Stacdeii at ISO * C viilkani £ IOERT! _O

The resulting polyeth ';u' --- urethfrJi bes.! tzt a oegaientgehalii you 65 ₃ ö G & jo ^ h © i ^ - I) iol / I ^J olyäfcJier-41ölTe £ iiälta: i3 of 1 j8 and eia Dj.ioocyanat / iriiSQin'tdiol'-ÜIül'vcärMiltiaiö of "I ₉ QQo Das Polymer be.aiiiSG ejiia 7: Lr »3cosltätB2; ahl vpa i _? 2; i iiml yikat-Brwtilclmng« i> wi] iki; voa 179 ⁰ O ,, Ea becomes "at 225 ° G uuhsr

t; you 6i _B 0 m / kin in 8: 1k 5 ^ 2ää ± gßn fes-ii

schmeliigeß £) oimi.ii: after a Semperung oei 11OC 'b & Bi: hy / ü the yarn die

tmpei'ci tar 162

Denier 1 ^ rf

lceil; g / the 0

Elastic IttieJcbiXihmg rf hus sOO> έ Dehnmi ^ 9;>

Worker recovery% ms 100 1 stretching 68 faehstuia in l / mft at $ 200 »D-ilimmg during

24 Stimduii 1 minute relaxed 28, ö> i

Relaxed 24 hours SS ₅ 3 f>

Waohstiffi ia water at 60 ° 0 aas 100 fo Dehmmg 24 ₀ 0 vS

Example ft

70! Rush of a hydro3Ey shot down

BATH ORIGINAL

_Λ . ,, _: 909850/1623

glycols with a molecular weight of 2000, which contains 0.1 of an antioxidant (Nonox WSL), is mixed with 18.36 parts of 4,4 '»DiiaooyanatQ-dicyclohexylmethane (trans-trane isomer) and 2.1 parts of ÄtltylenglyJrol and with dry nitrogen vakimingoptilto The mixture is ^{heated to 110 0} O for 30 minutes with rapid stirring, the temperature is raised to 90 ° C over 25 minutes, and the GremissCh is heated for 3 minutes under dry nitrogen and 5 minutes under Takuina at this temperature », The vacuum is replaced by dry nitrogen, the stirrer is removed and the Sohraelse is turned on for 2 hours. 190 ⁰ G vulcanized

The resulting polyether urethane has a polyether soft segment content of 77.4 oew _e ^ _t . a diol / polyether Molver ^ nältnis of 1 "and a 0 Dilsooyanat / Gesamtdiol-iiolverhältniß of 1,0O ₃ The polymer has a Viekositätszahl of 1.21 and a Vicat of 203 ° C Enreichungspunkt Ee is at 220 ⁰ C and a . Winding speed of 3O _t 5 m / min in a 5-fädigee yarn geßponnen _a lisch a temp <
following properties:

ßponnen _a lisch annealing at 110 ⁰ C besitat the yarn, the

Ultimate strength temperature 176.5 ° C

Denier 193 tear strength g / den ΐ ^ ΐΟ

Extensibility f * 393. Elastic regression, % from 100 % elongation 99 Arbeiteradtgeuinnung%, from 100% elongation 8t growth in air at 200 pounds elongation for 24 hours, 1 minute relaxed $ 10.55

24 hours relaxed 4.48 ^

Growth iji water at 60 ⁰ C from 100 $ elongation 6.85 1 »

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Example 10

"70 parts of a hydroxyabgeschlosoenen poly (tetraxaethylenoxya) ~ glycols having a molecular weight of 2,000, containing 0.1 wt ','#'of an antioxidant (Nonox WSL) are t8,34 with ropes 4 _J 4 ^l -DÜsocyanato" -dicyclohex3rlEiethar (Trane trana ^ Ieomer) and 3 s 15 parts of 1 ₉ geraiaeht 4-Butandioi and dry stick * · material vakuwngespülto Dae Greraiach 45 minutes on TiO heated ⁰ O with rapid stirring, the temperature is währed "* S minutes The temperature is raised to 90 ° 0, and the stirring is continued under vacuum for 5 minutes at this temperature. The vacuum is replaced by dry nitrogen, the stirrer is removed, and the melt is hardened at 190 ° C for 2 hours

The polyether urethane obtained has a Polyätherweicheogmentgehalt of 76 ₉ 5 percent, - ^, a diol / polyether Molverhältnls of 1.0 and a Diieocyanat / Geeamtdiol-Molverhältnie of 1.00 "The polymer has a Viskoeitätazahl of 1.33 and a Vikat worship puTiki; from 163 ° G _e Eb is melt-spun at a winding speed of 30.5 m / min at 232 ⁰ G into a 5-ply yarn. A temp <
Yarn the following own soft clay;

enamel spun. After tempering at 110 0 this has

Zero strength temperature 167.5 ° O

Denier 242

Tear strength g / den 0.643

Extensibility % 794

Elastic regression f * from 100 ^ elongation 99

Worker recovery% from 100% elongation 82 awake in air at 200 % elongation during

24 hours 1 minute relaxed 22.16

24 hours relaxed 12.92

909850/1623

.Growth in water at 60 ° C from 100 "A elongation 27 _f 40 ^a ß> Example 11

70 parts of a hydroxyäbgeßchlossenen poly (tetramethylenoxyd) ~ glycols having a molecular weight of 4600, which 0 _F 1 wt ,, «# contains an antioxidant (Nonox WSL) are, with 7» ropes 97 4 4 ¹ _{f-diisocyanato} dicyclohexylinethan (trans trans-isomer) 3.02 parts of p-IMD or bite (J3-hydroxyäthoiy) -l) ensoi mixed with dry nitrogen vakuumgesptilto the mixture is heated with rapid stirring for 1 hour at 90 C, the temperature is then slowly to 190 ⁰ G and the mixture is stirred under vacuum for 5 minutes. The vacuum is increased by dry; Nitrogen ear "= · setst, the fiührer is taken out, and the melt is cured 2 hours at 190 ⁰ C,"

The resulting polyether urethane "has a Polyätherweiohsegmentgehalt τοη 86.4 οβν · -§6, a diol / Polyaiher molar ratio of 1.0 and a Diißocyanat / Sesamtcliol-liolverhältniB of I ₁ OO ₀ The polymer has a Viskosltätszahl of O ₈ 95 "and a Vicat softening point of 162 ⁰ ₀ G Ss is at 208 ⁰ G under a winding speed to 6%, 0 m / min schmelagesponnen in a 5 * filamentous yarn ₀ ifach a Temp"
Yarn the following. Properties

Schmelsgesponneno STach a Temperong of HO ⁰ G that sits there

Shell strength temperature 165 ⁰ G

Denier 278

Ice resistance g / äen 0.593

Extensibility % 998 _f 7

Elastic regression ^ from 100 %> elongation 97

Laboratory gain *% from 100% stretching, 85 growth in water at 60 ° C from 100 & Behnuog 16.8 56

9GS85Ö / 1623

BADOFUGINÄt

«, 22 -

Example 12

70 parts of a hydroxyabgeschloss enes PolyCtetramethylenoxyd) * - _p glycol which having a molecular weight of 2000 C l _s wt _o - ^ contains an antioxidant (Nonox WSL) are with 13.76 parts of 4,4 ^ä -DiisocyajQato ° dicyelohö3: ylmethane (trans -trans-Ißomer) and 2.52 parts 1,4 ~ trans ^ yclohexand: LmethanQl mixed and vacuxirogespüTbο with dry nitrogen that mixture is heated for 1 hour with rapid stirring to 120 0, the temperature is then raised rapidly to 190 ⁰ C, and the mixture is stirred for 10 minutes under vacuum at this temperature. The vacuum is replaced by dry nitrogen, the stirrer is removed, and the melt was vulcanized at 190 ° C. for 2 hours.

The resulting polyether urethane has a polyethylene segment content of 81.1 (Jew, -ftf. A diol / polyether molar ratio of 0.5 and a diisocyanate / total diol ratio of 1.000. The polymer has a viscosity number of 1.07 and a Vikat softening point of 170 ⁰ G ₀ It is at 196 ⁰ C and a winding speed of 61.0 m / min in a 5 ° filament yarn aehmelagesponneno After a
the following properties;

aehmelagesponneno After tempering at 110 ⁰ G, the

Shell strength temperature 172 ⁰ G

Denier 21 0 tear strength g / een 0 * 895

Dehnfahigkelt? & 668 Elastic regression 5 & from 100% elongation 96 Worker recovery% from 100% elongation 90 Growth in air at 200 # elongation for 24 hours 1 minute relaxed 8? 4 §

Relaxed 24 hours S _{5 OfS}

9 0 9.850 / 1623

8A0 ORIGINAL

Growth in water at 6O ⁰ O from 100 pounds elongation 8.73

example

"Comprising 60 parts deo polyether of Example 7 has a molecular weight of 2000 and 0.1 wt _o ~ 9 £ of an antioxidant (Nonor WSI) which are charged with 11.0 parts of 4,4'-Diisocyanatodioyclohexylmethan (tranB-trans isomer ) and 2 drops of triethylamine mixed the mixture is rakuumgespült with dry nitrogen and one hour with vigorous stirring to 120 ⁰ G heated ITO After cooling to ⁰ G 2.33 parts of 3 »6-bis- (hydroxymethyl) -durol sugegeben, and the polymerization is continued as in Example 5

The resulting polyether urethane has a Polyätherweiehsegmentgehalt from 81-, 7 wt _o - ^ _s a diol / polyether molar ratio of 0.4 and a diisocyanate / Gesamtdiol molar ratio of 1 _t 0o The polymer has a viscosity number of 2 "97 and a Vicat BiTfeichungspunkt of 17t ⁰ C ₀ is at 225 ° C with an up winding speed of 30 _s to 5 m / min in a 5 ~ filamentous yarn schmelzgesponneno Hach annealing at 110 ⁰ C for V2 stun ~ de has the yarn, the following run properties

Zero strength temperature 164 ° C

381 denier tear strength g / den 0.352

Extensibility % 1009 Elastic recovery % from 100% elongation 95 Worker gain% from 100% elongation 80

909850/1623

BATH ORIGINAL

- 2Ί -

'' .O parts of a hydroxy iib gea chlossi .rien poly (propylcnoxyd) cjyjcol "nd: _s einerm molecular weight of 2000 which 0- 25 wt« -% of a ■ Äi: contains lioKydationsEiiltel "Ülonox WSL) are 7 ₉ 52 Divide p-xylyl on diisocyanate and mixed 2 drops of triethylamine. The GcwHch is vacuum purging with dry nitrogen: _s under-1: ';: er; i stirring for 1 l / H -hours u if 120 ⁰ C and then a further 2 Hours to IBO ⁰ C. * The mixture is ^{cooled to 90 0} C. ;. S, 3t Tcilii vi-bis (ß "h.ydro3iyäthoxy)" benzene are given and Φ "?; polymerization vSvd as in Beiöpissl 5 foi-tgssetiit.

Dar? obtained PoÄyätheϊ ^ -υχethan beoitst Eirien PolyätherwcichsrgBientgehsXt of 77 _s Γ ₁ wt "% _s is a diol / Po ^ ^ S'ütho.r Molver'hAltnis".'on I ₅ O and a diisocyanate / Gesaffifcdiol-Molvo ^ ■ ratio of i _s C. The polymer has a viscosity number. of 2 _s and an ^r 02 icate 'softening point of 3G7 ⁰ C ₄ is at 227 ° C a Aifcpul riit "gfischvjindigkeit of 15 _s 2 m / min in a 5" fädigei, yarn schirielzge- "siionneru Dns just _p;" ~ -'- ^ ormene yarn bssitst a zero strength system: a re tu:? of 171 ⁰ C v.ad good elasi-ischo properties ,.

6ADORlGtMAL

909850/1623

Claims (1)

PA TENT CLAIMS! (iloj process for the production of a synthetic polyether urethane elastomer which can be melt-spun into threads, characterized in that the application of heat (1) produces a dial which is a hydroxy-terminated linear polyether or mixed polyether with an average molecular weight between 1000 and 6000 »(2) 0.1 to 20 mol of its aliphatic, cydoaliphatic or arylaliphatic diol per mol of the above-mentioned polyether diol, and (3) 96 to 106 mol of an aliphatic or cycloaliphatic diisocyanate per 100 mol total weight of the above diols, 2. The method according to claim l _s, characterized in that the average molecular weight of the polyether is between 2000 and 4600. and the ratio of the moles of the aliphatic, cycloaliphatic or ary! aliphatic diol to the moles of the polyether diol is 0.1 to 1.9. 3. The method according to claim 1 or 2, characterized in that the diisocyanate p-xylylene diisocyanate or trans-trans-4,4 * - DÜBocyanato-dicyolohexylaethane is. f. Method according to one of the preceding claims, characterized in that the polyether is poly (tetramethylene oxide> glycol or poly (propylene oxide) glycol * 5, A method according to any one of the preceding claims, characterized in that the polyether diol is heated with the whole diisocyanate and is cooled to 90 to 110 ⁰ C, the aliphatic or cycloaliphatic diol ¹ arylaliphatic added and is heated to 150 to 210 ⁰ C. 3098 50/182 3 BAB 6. The method according to any one of claims 1 bx3 U, characterized in that the aliphatic, cycloaliphatic or arylaliphatic diol and the diisocyanate ^{are added to the polyether diol previously heated to 17 0 to 210 0} C and heating is continued, 7. Polyether-urethane elastomer, characterized in that it has aine viscosity range from 0.5 to 1 _ä 5 and that as has been obtained by »that one. under the action of heat (1) a diol, which is a hydroxy-capped linear polyether or mixed polyethers having an average molecular weight is between 1000 and 6000, preferably 2000 and 460Q, (2) 1.0 to 20 mol of an aliphatic, eyoloaliphatic or ¹ »arylaliphatic diol per half of the above-mentioned polyether diol and (a) 96 to 106 mol of an aliphatic or cycloaliphatic diisocyanate per 100 mol total weight of 4 of the above diols . 8. polyethers-urethane elastomer according to claim 7 »characterized, ά * Α the average molecular weight of the polyether is between 2000 and H600, and in that the ratio of moles of the aliphatic, cycloaliphatic" !! or arylaliphatic diol to the moles of the polyether diol is 0.1 to 1.9 » 9. Polyether-urethane elastomer according to one of claims 7 or 8, characterized in that the diisocyanate is p-xylylene diisocyanate or tranö-trane-HjU'-diisocyanato-dicyclohexylmethane, 10 _; Polyäthar-urethan-elafitomer according to one of claims 7 to 9, characterized _9, that the polyether is poly (tetrame thy lenoiiyd) glycol or poly (propylene oxide) glycol » 8AD ORIGiNAL
9 09850/1623 PATENT ADVOCATE - »MG H. FIHCKC, DSPl.-IMG. H.