DE1931808A1 - Process for the production of synthetic elastomers - Google Patents

Description

Process for the production of synthetic elastomers

Priority: 2t June 1968 - Great Britain

Addition to patent application 17 20 987ο9

The invention relates to the production of new synthetic. Elastomers, and especially those of those blastoins, which consist of segmented polyester-urethanes with aliphatic urethane blends, and which can be melt-spun in t ^ aden

nen C

Attempts have already been made to heart synthetic elastomers which can be melt- spun into textile thread, since it is generally known that the melt-spinning process has numerous advantages over spinning

cream * / - 1

BATH ORIGINAL

Belgian patent 619 994 describes the production of melt-spinnable polyurethanes, wherein a hydroxy-terminated polyester or mixed polyester (d, h ₀ a diol) with an average molecular weight not more than 1400 with an organic diisocyanate and a chain extender, preferably a dihydric alcohol, for example butanediol-1, 4ρ is implemented "In the Belgian patent, alicyclic" and aliphatic diisocyanates, such as Z ₀ B ₀ tetramethylene diisocyanate or hexamethylene diisocyanate, are mentioned, but no examples of their use are given

The properties of the resulting elastomer naturally depend on the particular starting material used and the reaction conditions used, and in particular on the relative proportions of the participants in the reaction. »Important properties are the tensile strength _? the elastic recovery, the work recovery and the Vicat softening point, all of which are defined below,

In the German patent application P 17 20 987ο9 a process for the production of polyester urethanes with excellent properties is described, in which {1) a hydroxyl-terminated linear polyester with (2) butane-1,4-diol _F p-xylylene diol or p -BisCs-hydroxy-athQxyJbenzoldioi and reacted with (3) P-xylylene diisocyanate or trana, trans- ^ V ^ '^ Düsocyanato-dieyclohexylmethan ₀

Bb has now been found that the method described above can be modified and that similar polyester urethanes can be prepared _s when other aliphatic carboxylic acids, used as adipic acid in the preparation of Polyesterdiol3 and werua to diols other than butane ~ 1 _P 4 ~ Dioli> p -Xylylene glycol or p «B ± s (ß» hydro: xyätiioxy) benzene used _ö

According to the present invention, a modification of the process described in German patent application P 17 20 987 »9, which relates to the production of synthetic polyester urethane elastomers which can be sohmelzspönnen in threads, proposed, which is carried out by using Heat converts the following substances with one another (1) a linear misoh polyester diol, which is composed of one or more aliphatic or cycloaliphatic glycols with 2-20 carbon atoms and one or more dibasic acids, dte of saturated aliphatic dibasic acids and mixed aliphatic / aromatic dibasic acids in the ratio of 3 * 1 are selected _? and has an average molecular weight between 1500 and 6000 and a melting point below 60 ⁰ C or a glass transition temperature below 20 ⁰ C, (2) 0.1 to 1.9 mol (preferably 0.2 to 1.0 mol) of an aliphatic, cycloaliphatic or arylaliphatic diol chain extender per mole of the above-mentioned polyether diol, and (3) 96 here 1OC moles of p-xylylene diisocyanate or tear »trans-4,4 '^ iisoayanato-dicyelühe: Kylmethane per 100 moles of the total weight of the above diols, except that, if the divalent acid is adipic acid, the Dlol not butane-1,4-diol _f p-xylylene glycol or p-BiB (ß-hydroxyethoxy) benzene isο

Preferably the average molecular weight of the interpolyester diol is. between 1900 and 440O ₀

Preferably the aliphatic dibasic acids, which are used in the production of the mixed polyester oil, have no more than 36 carbon atoms in the molecule

'Are examples of hydroxyl-capped linear interpolyesters Mixed polyesters consisting of the glycols specified below and sweibasic acids in the specified molar ratios ο

193180 $

ßlycole Relationship I Jl dibasic Relationship J nis Acids nis } 3-1 Ethylene glycol
Propylene glycol ] ^7s5 Adipic acid Ethylene glycol
2,3-butanediol ) ^{7: 5} Adipic acid Ethylene glycol
1,3-butanediol ] ^{T: 5} ] 7: 3 Adipic acid Tr-.t \ y · I Ethylene glycol ) ) 1,3-dihydroxy-2,2- ) 7: 3 ) 7: 3 Adipic acid dimethylpropane ) ) C! J Ethylene glycol ] 7: 5 Adipic acid Succinic acid «Μ Ethylene glycol 5 1: 1 Adipic acid ) Phthalic acid - Ethylene glycol ) Adipic acid ) 7: 5 Terephthalic acid “Ethylene glycol ) Adipic acid ) Isophthalic acid Ethylene glycol
2 _{tons of} 5-hexanediol ) 7: 5 Adipic acid Ethylene glycol ⁾ 1,3 ~ dihydroxy-2,2,4- Adipic acid trimethylpentane Ethylene Glyc Oil
Trimethylene glycol Adipic acid 1,4-butanediol 2,2-dimethyl-1,3- Suberic acid propanediol Ethylene glycol 2,2-dimethyl-1,3- Azelaic acid propsindiol Ethylene glycol 2,2-dimethyl-1,3- Sebacic acid propanediol

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The hydroxy-terminated linear copolyesters may consist of the desired glycol and the desired zweibasisohen acid are prepared by conventional procedures ^ for example, a moderate excess is used of from about 10 fetch $ of the glycol ο Ansteile of the acid, the acid chloride may be used ,, it is also possible «To use the dibasic acid methyl ester, i.e. _{, Q} " to produce the polyester by an ester interchange process, but this process requires the use of a catalyst and it is preferred that no catalyst be used in the production of the interpolyesters, to be used as Heagenaien according to the invention. the reason for this is that by the presence of even small amounts of catalyst which are difficult or impossible zii remove discoloration of the finally obtained Folyester "urethane. occur _a such a discoloration is at commercial textile thread unanne hmbar _{9 as} long as they are not later dyed in a deep color *, it is therefore normally essential to use polyester in the production for which no catalyst has been used, _etc.

Suitable acids other than adipic acid are the aliphatic iiwe! Basic acids ₉ which contain 4--2O carbon atoms, such as a ο B r, 3 ebac ins aure _o

Suitable chain extenders are ZoB _o i

a) freradkettige. or branched-chain aliphatic © glycols with 2-12 carbon atoms? like S ₀ B ₀ ethylene glycol, 1 _? 4-butanediol and 1,1CM) ecandiol;

b) Cycloaliphatic Glycoie _s like a «B, trans-Cyclob.exan-1 A ^ diol and trans« -Cyolohexan.-1 y ^ dimethanolj

ö} arylal.ipbabisoho glycols _p tile s _o B, p-xylylene glycolp 3 ₉ 6 ~ bis- {hydroxymethyl) duröl and p-bis (ß-hydrosyäthoxy) bensol,

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19318Oi

j. «Q ttm

Definitions of

Extensibility

The stretchability of the threads means the length by which they can be stretched "before they break, expressed as a percentage of the original length _{or the like}

Eeißfegtigkelt

The tensile strength is the breaking load of the threads, expressed in grams / that of the original thread _Q

Light resistance test

The threads are wound onto a frame and exposed to the light from a xenon arc lamp for 300 hours. The elastic properties and the color of the threads are determined before and after exposure " _a

Bleach resistanceatesb

The threads are immersed in an aqueous solution for 45 minutes ₉ the Og 1 wt, ~: # 'sodium chloride and ü _? 5 mL / l glacial acetic acid -

and which is kept at 85 ⁰ O. The color of the threads is determined before and after the bleaching treatment ₃

Elastic regression

The elastic recovery of the threads is expressed by the. Fractions that are received? if one divides the length by which the threads are stretched when a tension is applied, by the length _t . by which they are ausamaenaieheno the break is usually expressed as a percentage ο The harmlessness of animal successive determinations on the same sample is determined (NoBo the speed of stretching or contraction -s "is 500 $ per minute)» ■ . ■

Arbeitsruokjgewirmung. '.

- »Ill ■ !! > l— ■ !! ■ »BtMiIIIIlIIlI! ■ Hl ill I f I Il 1 Γ Γ 'I Il III III 1 T'hl *. - '

The work recovery of the threads is expressed by the -

009808/1639

Fraction that is obtained when one has the energy or work that when stretching the named threads by applying tension is divided into the energy or work that is obtained back when the said threads contract to the original dimensions when the tension is removed, The fraction is usually expressed as a percentage, and es the average value is taken from four consecutive determinations with the same test sample

VlskoBltätszahl

The viscosity number is defined as twice the natural logarithm of the viscosity of a solution of V2 VoI ₀ -JS of the polyester urethane, dissolved in ortho-chlorophenol, at 25 °, divided by the viscosity of the ortho-chlorophenol at the same temperature

The VißBt calibration values mentioned here were determined with the aid of a penetrometer similar to those described by Edgar and Ellery on page 2638 of the "Journal of the Chemical Society" 1952, _etc.

Annealing

The yarn was wound up without tension to a HülBe, and the yarn package was then heated 50 minutes to 1 \ 0 ⁰ C "All counters in this description yarn mentioned (with the exception of ZST) bestimmtο were-with this heat-treated yarn

Main strength temperature (ZSg)

A loop of the elastomer, of approximately 0 _P 1 g / carries a weight which is einge- in a liquid paraffin bath of 100 ⁰ C.

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. dips »The temperature is gradually raised until the yarn tears completely "The temperature when tearing is called the" zero strength temperature " (ZST).

Growth in water yon 6O ⁰ C.

A loop of approximately 200 denier of yarn is made by clamping a split lead ball weighing 0.17 grams and the length is determined * while the lead ball hangs freely. «The loop is stretched by $ 100 on a frame, which then Is immersed in water at 60 C for 5 minutes »The loop is then removed from the frame and suspended in air for 1 hour; ge - leave what their length is measured on. The increase in length, expressed as a percentage of the original length, is referred to as "growth"

Growth in air from 200 # elongation

A loop of yarn is made by clipping a split lead ball, the weight 0.45 g for yarns of 150 to 210 den is «

The thread loop is hung up to relax for 24 hours while it is slightly tensioned by the lead weight. The length of the ■ soles is then determined. The sling is stretched $ 200 and held at the stretched length for 24 hours. The stretch is then released and the sling is allowed to relax while it carries the lead weight '. The length is determined pa.ch 1 minute and after a 24-hour relaxation ° The increase in length, as a percentage of the original length, is expressed as growth in air at $ 200 elongation »

In preparing the synthetic elastomers of the present invention, the diols and the diisocyanate can be used in any convenient form Way to be brought together. An advantageous process

009808/1639

"ordered that Mischpolyesterdiol with the entire diisopropyl" oyanat to mix * to heat, for example, 12O ⁰ C and allow to react for 1 to 2 hours ο After the mixture to 80 the mixture, "has cooled .110 ⁰ _C? the low molecular weight diol is added, and the ^ temperature is raised to 15Ο ~ 2TO ⁰ C and held at this value for 2 to 5 hours ₀ Alternatively, the polyester ^{diol can first be heated to 170-210 0} G, then the low molecular weight bio and the diisocyanate can be added and heating is continued for 1 hour. The manufacturing process according to the invention can also be carried out continuously by passing the polyester diol, the low molecular weight diol and the diisocyanate in a mixture through a conventional reactor, which is more expedient as also having a screw forward movement means * In this case, the Tempe "kamx due to the shorter residence time temperature slightly higher than it was mentioned above, for example, they may be 200-250 ⁰ C. The reaction is preferably carried out under an inert atmosphere for example under nitrogen _t, in order to prevent oxidation of the polymer A ^ aasreichendes mechanical mixing of the reagents is extremely erwii'ischto Bin Another method is to ,, add a portion of the diisocyanates Mischpolyesterdiol * The diisocyanate · example, one-half to 3.2 moles per mole of mixed polyester amount "That low molecular weight diol is then added, the addition of the rest of diisocyanates woraif connects <> the temperature of the reaction should be sufficiently high to ensure so äa.3 sine clear Sohmelze is,·,

Catalysts, such as Z ₀ B ₀ the following ₈ can, if necessary, ο be incorporated into the reaction mixture in order to promote the reaction of the Diiao oyan-ri s;

BATH ORIGINAL

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Bibutyl ainn dilaurate

Dimethyloyclohexylamine

Sodium ethoxide.

Sodium phenate

EisenCIII) ~ acetylaeetonat

Furthermore, the production of the polyester urethane can be carried out in solution * Suitable solvents for this purpose are:

^ N, H-Dimethylacetamide

Dimethyl sulfoxide mixed with an equal volume of methyl isobtityl ketone IT f IT-DimethyJLformamide
Hexamethylphosphoramide tetramethylene sulfone

The present polyesterurefehanes can be prepared in a solution and the latter can be made into threads directly by conventional dry or wet spinning processes. The solutions of the polyester urethanes can also be poured into filines. As already mentioned, the textile yarn but are preferably prepared by melt spinning does not require a solvent, in which case _t "is ₀

Among other things, together with the reagents for production Dar polyester - urethane also pigments, plasticizers, matting agents or stabilizers can be used

According to the invention, a synthetic polyester " urethane, which can be melt-spun in threads and has a viscosity range of 05.5-1 »5, and which has been obtained by converting the following substance:

009808/1639 ^ßAD original

(i) a linear Miechpolyesterdiol, which is selected from one or more aliphatic or cycloaliphatic glycols with 2-20 carbon atoms and one or more dibasic acids, which are selected from saturated aliphatic dibasic acids and mixed aliphatic / aromatic dibasic acids in the ratio of 3: 1 , and has an average molecular weight between 1500 and 6000 and a melting point below 60 ⁰ C or a glass transition temperature tmteraalb 20 ⁰ C, (2) 0.1 to 1.9 mol

. :. "■; j ,: '-'.} Of an aliphatic, cycloaliphatic or arylaliphatic / m diol Se KoI of the above-mentioned polyether diol, and (3) 96 to 106 mol of p-xylylene diisocyanate or trans, trans-4,4t-diisocyanato -dicyclohexylmethane per 100 ha of the total weight of the above board, except that when the dibasic acid is adipic acid, the biol is not butane-1,4-diol, p-aylylene glycol or p-bie (ß-hydroxyethoxy) bensol is ₀

The invention also encompasses the melt-spinning of the above new synthetic polyester-urethanes in filaments and also the filaments thus obtained. The latter have excellent elasticity and do not discolour if they are exposed to a xenon arc lamp or bleached with sodium chlorite according to the light and lead resistance test defined above good work recovery. They often show an elastic regression from 100% elongation of at least $ 5 and a recovery from 100% elongation of at least ^ 75 ^. The threads are usually subjected to a heat treatment (annealing) in order to achieve the best elastic properties. _{In the examples,} they were therefore subjected to a heat treatment at HO ⁰ C for 30 minutes before the physical properties were determined, - ...;

ORtQINM. INSPECTED

OQSSOB / 1β39

The present polyester-urethanes differ in an advantageous manner from other synthetic elastomers in the ease with which they can be melt-spun into threads that show no tendency to stick together and therefore do not have to be dusted with TaXcum powder. These new polyester-urethane threads are also used Known elastomeric threads with similar physical properties are superior to _p because they do not discolor when they are d & n. The threads are suitable for so-called basic garments, such as ZeB ₀ corsets, for elastic outerwear, such as z _e B ₀ sweaters, ski pants, and also for medical elastic stockings and bandages »Other uses are woven or knitted» Swimwear, hosiery ₉ bras and pajamas “ Ί) ± ψ the threads present are also suitable for a wide range of applications in the form of staple fibers, especially when srgle are mixed with wool, cotton or polyhexamethylene _{adipamide o} The new polyester urethane threads according to the invention can be made into composite elastic Yarns are processed by being introduced into a conventional spinning or drawing frame as endless threads together with one or more staple fiber rovings, such as Z ₀ B _{0 polyethylene terephthalate, wool or cotton fibers} the manufacture of non-woven fabrics or in a mixture with wool for weaving cloths that are suitable for men's suits "used"

The invention is explained in more detail in the following examples. The examples are not to be interpreted in a restrictive sense. _O The parts are expressed in parts by weight.

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"· 1331808

example 1

70 parts of a hydrosy-closed mixed polyester, which has been obtained from ethylene and neopentylene glycol in a molar ratio of 7 * 3 and adipic acid and which has a molecular weight of 1940, are _{mixed with 16.1 parts of 4 P} 4 "-Düsooyanatodicyclohexylmethan (trans-trans isomer ) mixed The mixture is heated under a nitrogen atmosphere for 2 hours with continuous stirring to 120 ⁰ C <,

The above mixture is cooled ^{to 90 °} _{C. t} 1 _? 56 parts of ethylene glycol are added? and the mixture is then stirred for 10 minutes "to thoroughly mix the glycol" The temperature is raised to 190 C over a period of 10-15 minutes _? and the mixture is stirred for 5 minutes at this temperature. After the stirrer has been removed ^ the melt is allowed to polymerize for ^{2 hours at 190 ° C. *}

The resulting polyester-urethane has a mixed polyester segment content of 79 »9 wt ₀ - ^ ₉ is a diol / polyester" molar ratio of O ₅ 70 and a diisocyanate / Gesamtdiol molar ratio of 1 _s 0 _o The polymer has a Yiskositätszahl of 1.30 and a Yicat-Enreiöhungspunkt of 151 ⁰ C and at 206 ⁰ C in a 5 ~ filamentous yarn with a total denier of 529 to spun _o After the yarn has been heat-treated at 110 ⁰ C 72 hours _ff it has the following properties:

.Hull strength fcemperatuTj, ° G tensile strength _s g / den extensibility » $ elastic regression from 100 % elongation,% ' energy recovery from 100% elongation» growth in air at 200 ^ elongation for 24 hours ,, $

i minute relaxed 24 hours relaxed

Growth in water of 60 ^° C. at 100 $ elongation » fo

0098Oi / 1639

170 (before tempering) O ₉ 554 547 98 84 16, 7, , o - Λ

1931008

- ■ 14 ■■ .--.

Example 2 '■

70 parts of the mixed polyester from Example 1, which has a molecular weight of 2870, are mixed with 12.02 parts of 4,4'-diisocyanatodicyciohexylmethane (trans-trans isomer). The mixture is heated to 120 for 2 hours with rapid stirring and under a nitrogen atmosphere ⁰ C. It is then ^{cooled to 87 0} O, and 1.36 parts of ethylene glycol are added. The mixture is stirred for 15 minutes, and the temperature is then quickly raised to 190 ° 0. Stirring at this temperature

»Temperature continues for 10 minutes. After the stirrer ο has been removed, the melt is 2 hours at 190 G

allowed to polymerize "

The resulting polyester urethane has a mixed polyester segment content of 83.7% by weight, a diisocyanate / polyester molar ratio of 0.90 and a diisocyanate / total diol molar ratio of 0.99 a Vicat softening point of 147 ^ ⁰ C. Bs is at 228 ⁰ C in a 5-filamentous yarn with a total denier of 389 to woven, the yarn has after it has been annealed at 110 ⁰ C V'2 hour, the following properties :

^ Zero strength temperature, C tear strength, g / den Extensibility, $

elastic regression "from 100 $ elongation,

Labor recovery from $ 100 stretch, $

Growth in air at $ 200 elongation during 24 hours, $

Relaxed for 1 minute, relaxed for 24 hours

Growth in water of 60 ⁰ C at 100 $ elongation, $

176 (before tempering) O ₈ 568 821 98 88 18 8th, , 0. , 2

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Example 5

70 parts of the mixed polyester from Example 1 are mixed with 11.8 parts of 414'-diisocyanato-dieyclohexyl-methane (trans-trans isomer). Bas mixture is heated under continuous stirring and under a nitrogen atmosphere iy2 hours at 120 ⁰ C. Bs is then cooled to 91 ⁰ C, 1 "05 parts of trans-cyclohexane-1,4-diol are added, and the mixture is stirred for 15 minutes ο The temperature is then rapidly raised to 19O ⁰ C, and was taken after the agitator is, the melt is allowed to ^{polymerize at 19O 0} C for 2 hours.

The resulting polyester-urethane has a mixed polyester segment content of 84.5 wt <> - #, a diol / polyester molar ratio of 0.25 and a Diisoeyanat / Gesamtdiol molar ratio of 1 _s 00 _o The polymer has a TTiskositätszahl of 1.18 and a Vicat ErwSichungspunkt of 211 ⁰ C. it is spun at 23O ⁰ C in a 5-filamentous yarn with a total denier of 594 ,, the yarn has after it has been annealed YZ hour at 110 ^0C, the following properties:

Hullfestigkeitstemperatur, ⁰ C>> 200

Tear Strength, g / den 0.225

Extensibility, & 1015

elastic recovery from 100% elongation, f> 95

Work recovery from IOO56 elongation ,, % 83

Growth in air at 200 # elongation for 24 hours, %

1 minute * relaxed 28 _P 4

Relaxed 24 hours 12 _P 4

Example 4

70 parts of the mixed polyester from Example 2 are mixed with 7.59 parts of 4 _f 4'-diisocyanatodicyclohexylmethane (trans-trans isomer). The mixture is under a nitrogen atmosphere

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»16 - ■. -

heated with rapid stirring for 2 hours at 120 C "It is then cooled to 85 ⁰ C O _F 56 parts of trans-cyclohexane-1,4-Äiol be added ;, and the mixture stirred for 10 minutes _o The temperature is quickly to 19O ⁰ C is raised, and after the stirrer has been removed, the melt is polymerized at 190 C for 2 hours

The resulting polyester-urethane has a mixed polyester segment content of 89.5% by weight, a diol / polyester molar ratio of Os.20 and a diisocyanate / total diol molar ratio of 0.99. The polymer has a viscosity number of 1.39 and a Vicat softening point of 147 ° C, is at 218 ⁰ C in a 5-filamentous yarn with a total denier of 461 to melt-spun "the yarn has after it has been annealed at 11O ⁰ C Ϋ2 hour, the following properties:

Zero strength temperature, ⁰ C 174

Tear strength, g / den. 0.363

Extensibility, $ 711

elastic regression from $ 100 stretch, $ 97

Work recovery from $ 100 stretch, $ 83

Growth in air at $ 200 elongation
during 24 hours, $

1 minute relaxed 21 _p 1

Nothing relaxes 24 hours

Growth in 60 ⁰ C water at $ 100 elongation, $ 6.5

Example 5

70 parts of a hydroxy-terminated mixed polyester made from 1,4-butanediol and 2 _? 2-dimethyl-1 _? 3-propanediol has been obtained in a molar ratio of 1: 1 and from suberic acid and which has a molecular weight of 3540, are mixed with 7.77 parts of 4,4'-diisocyanatodicyclohexylmethane (trans-trans isomer). The mixture is 2 hours under a nitrogen atmosphere

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phere heated with continued stirring to 120 ⁰ C ,, Bs is at 9O ⁰ G cooled _{9 1?} 96 parts of p-bis (ß-hydroxy-ethoxy) benzene are ziugegeben, and the mixture is 5 minutes _or stirred, the temperature is then raised to 200 ⁰ G for a period of 15 minutes, ^ and the melt is stirred for 15 minutes at this temperature Of the. Agitator is then removed, and the melt is 2 hours at 190 ⁰ C allowed to polymerize "The resulting mixed polyester-urethane has a mixed polyester segment content of 87» 8 Gewo- $ _r a diol / polyester molar ratio of 0.5 and a diisocyanate / Gesamtdiol Molar ratio of 1 | j0 _o The polymer has a viscosity number of 1.61 and a Vicat softening point of 156 ⁰ C ₀ It is melt-spun at 214 C into a 5-ply yarn with a total denier of 356 0 The yarn, after it has Y2 Hour has been annealed ^{at 11O 0} _C? the following properties:

Hull's strength temperature, ⁰ C 165 (before

Tempering)

Tensile strength, g / den 0.14

Extensibility, %. 774

elastic regression from $ 100 stretch, $ 95

Labor recovery from $ 100 stretch, $ 85

Growth in air at $ 200 elongation for 24 hours, $

Relaxed for 1 minute. 25.8

Relaxed 24 hours 8 ₈ 0

Growth in water of 60 ⁰ C at 100 $ elongation ₉ $ 9 _S 4

Example 6 _r

50 parts of the hydroxyabgeschlossenen copolyester of example 1 are mixed with 9 »04 parts of 4 _P 4 ^l diisocyanato-dicyclohexylmethane (trans-trans isomer) The mixture is heated 174 hours -under an atmosphere of nitrogen with vigorous stirring to 120 ⁰ C ο It is then allowed to cool ^{to 110 0 C ,, 1.50}

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Parts of 3> 6-bis (hydroxymethyl) durol are added and the mixture is flushed with a nitrogen vacuum. The mixture is stirred vigorously for 5 minutes and the temperature is then raised rapidly to 190 ^° C. over a period of 15 minutes, leaving a viscous melt The melt is freed of gas bubbles by applying a vacuum for 5 minutes. Stirring is stopped, nitrogen is let in, the stirrer is removed, and the melt is polymerized for a further 2 hours at 190.degree

^ The resulting polyester-urethane has a mixed polyester soft segment content of 82.5 & ewo ~ $, a diol / misoh polyester molar ratio of O ₉ 3 and a diisocyanate / total _{diol molar ratio of 1.0 ^ 0.} The polymer has a viscosity number of 1.0 and a Vicat Brweichungspunkt of 196 ° C _a it is spun at 220 ⁰ C at a winding speed of 60.69 m / min in a 5-filamentous yarn. The yarn has after it has been / long two hours annealed at 110 ⁰ C ^1, the following properties:

Zero strength temperature tp ⁰ C 189

Titer? the 393

Hot strength, g / den 0.242

Elongation ₉ % 904

elastic recovery from 100 $ elongation, % 97

"Labor recovery from $ 100 stretch» % 90

Growth in air at 20O7 & elongation for 24 hours, %

1 minute relaxed 25 »1

24 hours relaxed 13.2

Growth in water of 6O ⁰ C at 100? & Elongation _s & 1O _S 6

Example 7

T10 parts of the mixed polyester from Example 1 "which, however, has a molecular weight of 2700, are 19» 05 parts 4 ₉ 4 ""

00 9808/1639

Diisocyanato-dieyclohesylmethan (trans ~ trans isomer) mixed ₀ The mixture is then heated for 2 hours under a nitrogen atmosphere and under vigorous stirring to 120 ⁰ C. Then it is left to cool to 100 ⁰ G, 8.15 parts of 1,10-decanediol are added and the polymerization is carried out as in Example 6. FIG.

The resulting polyester-urethane has a mixed polyester soft segment content of 72% by weight, a diol / polyester molar ratio of 1.8 and a diisocyanate / total diol molar ratio of 1.00. The polymer has a reduced viscosity of 1.22 and a Vicat softening point of 179 ⁰ C is at 220 ⁰ C at a winding speed of 60.69 m / min in a 5-filamentous yarn schmelzgesponneno the yarn has after it at V2 hour 11O ⁰ C has been tempered, the following properties:

Zero strength temperature, ⁰ G Siter, den

Tear strength, g / den debnability, $>

elastic recovery from 100% strain, ^a / ° Working recovery from lOOfo elongation f °

Growth in air at $ 200 elongation for 24 hours, %

entspännt i Minute
Relaxed 24 hours
Growth in water of 60 ⁰ C at 100% elongation, %

Example 8

70 parts of the copolyester of Example 7 "having a molecular weight of 2700, are mixed with 10.2 parts of 4,4'-dicyclohexylmethane-Düsocyanato (trans-trans isomer) The mixture is iy2 with vigorous stirring hours to 120 ⁰ C. heated and then cooled to 100 ° C 1.85 parts of 1 _f 4-trans-cyclohexane

OBIQIM INSPECTED

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155 4th 248 3 4th 0.480 721 99 75 33, Ht 20,

193180 «

dimethanol are added, and the polymerization is carried out as carried out in Example 6. The composition of the resulting Polyester-urethane, the properties of the polymer and the properties of the yarn made from it and annealed are compared in Table 1 with the properties of the polyester urethane of Example 9

Example 9

70 parts of the copolyester of Example 7 »the weight of 2700 has a molecular * are mixed with 11» 90 parts of 4? 4'-diisocyanato-dicyclohexylmethane (trans-trans isomer) The mixture is \ Y2 hours with vigorous Bühren to 120 ⁰ C heated and ^{cooled to 100 0} C ρ 2.80 parts of 1 _p 4-trans-cyclohexanedimethanol are added, and the polymerization is continued as in Example 6. The composition of the resulting polyester urethane, its properties and the properties of the produced from it and annealed yarn are compared in the table with those of the polyester urethane from Example 8 »

ORIGINAL INSPECTED

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!Table 1

Mixed polyether urethanes containing various concentrations of diol (1,4-trans-Cvdohexanedimethanol)

Ratios of the reaction part Example 8 Example 9 taker, properties of the poly mers and yarn Mixed polyester soft segment content, 85.5 82.6 Diol / mixed polyester molar ratio 0.5 0.75 Diisoeyanate / total diol molar ratio 1.00 1.00 Viscosity number 1.14 1.16 Vicat softening point ⁰ ^ 126 185 Melt spinning temperature G 225 226 Winding speed, m / min 60.96 60.96 Yarn properties Titer den 518 247 if full strength temperature ⁰ G 150 184 Tear strength g / den 0.274 0.540 Extensibility , $ 695 748 elastic regression from $ 100 Elongation, $ 98 98 Labor recovery from $ 100 Deh tion, $ 94 90 Y growth in air at $ 200 elongation during 24 hours, $ Relaxed for 1 minute 55.1 51.7 Relaxed 24 hours 11.5 15.5 . Growth in water of 60 ⁰ G at $ 100 elongation, $ 29.0 22nd

0 0 S 8 OS / 16 3 9

ORIGINAL INSPECTED

1931 «Of

The main effect of changing the hard segment content (diol / polyester molar ratio) is substantial Change in the softening point of the polymer and the zero strength temperature of the yarn "

Example 10

70 parts of a hydroxy-terminated mixed polyester, which has been obtained from ethylene glycol and a mixture of adipic acid and phthalic anhydride in a molar ratio of 3: 1 and which has a molecular weight of 2450, are _{13-64 parts of 4 i} 4 ⁱ -diisocyanato-dicyclohe2? Ylffiethan (trans-trans-isomer) and 1.42 parts of ethylene glycol _o mixed, and the mixture is vacuum purged with dry nitrogen "the polymerization vessel containing the mixture is immersed in an oil bath at 200 ⁰ C and 8 minutes vigorously stirred There is a viscous Melt obtained, which is freed from bubbles by a vacuum lasting 5 minutes. "Dry nitrogen is let in, the stirrer is removed, and the melt is ^{vulcanized at 190 °} C. for 2 hours"

The resulting polyester-urethane has a Misehpolyesterweichsegmentgehalt of 82.2 wt _o - ^ _p is a diol / polyester mixed molar ratio of 0.8 and a diisocyanate / Gesamtdiol molar ratio of 1.01 _o The polymer has a reduced viscosity of 1.16 and a Vicat softening point of 122 ⁰ C _0, it is spun at 208 ⁰ C at a winding speed of 60.96 m / min in a 5-filamentous yarn which, after being annealed Ϊ2 hour at 110 ⁰ G, has the following properties s

OBIQINALiNSPECTED

009808/1639

193180 »

Zero strength temperature, ⁰ C- 151

Titer, the 270

Tear strength, g / den. 0.344

Extensibility, # 656

elastic back formation from 100 $ elongation * $ 97

Labor recovery from $ 100 stretch, $ 87

Growth in air at $ 200 elongation for 24 hours, $ '

1 minute relaxed 52.4

24 hours relaxed 21.9

Growth in barrels of 60 ⁰ C at 100 $ strain, # 36.2

Example 11

70 parts of the mixed polyester from Example 10 are 13.23 Share 4,4'-diisooyanato-dioyclohexylmethane (trans-trans isomer) and 3.1 parts of 1 ^ -trans-Cyclohexandimethanoi mixed “The Polymerization is carried out as described in Example 12

The resulting polyester urethane has a mixed polyester white segment content of 81% by weight, a diol / mixed polyester molar ratio of 0.75 and a diisocyanate / total diol molar ratio of 1.01 o The polymer has a viscosity number of 1.03 and a Vicat softening point of 161 ⁰ C, Bs is melt-spun at 218 ° 0 with a winding-up speed of 60.96 m / min in a 5-filamentous yarn which after it has been annealed for Y2 hour at 110 C, has the following characteristics:

JMSPECTBD

009808/1639

193180 «

Zero strength temperature, ⁰ C 142

Titer, the 263

Tensile strength ρ g / den 0.247

Extensibility, $ 943

elastic recovery from 100 $ elongation ,% 97

Work recovery from $ 100 stretch, $ 86

Growth in air at $ 200 elongation
"during 24 hours, $

1 minute relaxed 46.6

24 hours relaxed 20 _t 8

Growth in water of 6O ⁰ G at $ 100 elongation, $ 54.4

Example. 12

70 parts of a hydroxy-terminated polyester, which has been obtained from ethylene glycol and Empol 1010 dimer acid (from Unilever-Emery) and has a molecular weight of 2900, are combined with 9f68 parts of 4,4 '- »diisocyanatodicyclohexylmethane (transtrans isomer) and 2 _f 39 parts of mixed p-bis (iB-hydroxyethoxy) benzene The mixture is polymerized as in Example 12 "

The resulting polyester-urethane has a polyester soft segment content of 85 3 wt "- $ _r a diol / polyester molar ratio of 0.5 and a diisocyanate-Gesamtdiol molar ratio of 1.02 _t, the polymer has a viscosity number of O _8, 52 and a Vicat reaching point of 175 ⁰ C-. It is melt-spun at 193 ° 0 with a winding speed of 60 _s 96 m / min in a 5-fädi- ~ ges yarn .. The yarn has after it has been annealed for V2 hour at 110 ⁰ C, the following properties:

ORiQlNALINSPECTED

009.008 / 1639 "

Eull strength temperature _ff ° ö 155

Titer, the 263

Extensibility ₉ $ 315

elastic regression from $ 100 stretching »$ 97

Labor recovery from $ 100 stretch, $ 84

Example 15

50 parts of the copolyester ^ hydroxyabgeschlossenen be ig of Example which, however, has a molecular weight of 1900 "with 7.43 parts of p-xylylene diisocyanate tind _P 1 53 parts of trans cyclohexane-1 ~ j4-diol mixed as the mixture is to. Example 12 polymerized _o

The resulting polyester-urethane has a polyester soft segment content of 84ρ8 weight _a - $ p is a diol / polyester molar ratio of O ₉ 5 and a diisocyanate / Gesamtdiol molar ratio of I ₈ O ₁₅ The polymer has a viscosity of 1 ₉ 18 and of 3.O ₉ 48 m / min schmelzgespönne at 223 ° C in a 5-filamentous yarn n _a The yarn has a Vicat softening point of 207 ~ C, is winding speed with an up after at

ο
_S has been annealed 110 C the following properties:

Zero strength temperatures, ⁰ G 177.5

Tit he _s the% 5

Tear strength ,, g / den 0 * 112

Elongation ρ $ 606

elastic regression from $ 100 stretch, $ 98

Work recovery from $ 100 stretching »$ 87

However, 70 parts of the hydroxy-terminated mixed polyester of Example I ρ has a molecular weight. 4400 has to be 7 "29 parts of 4» 4 "-Diisocyariato-dicyclohexylmethane (trans-ti'ans isomer) _o The mixed Geraisch is under hefti-

0 0 9 8 0 8/1 639 ° ^miHAL

gem stirring and dry nitrogen atmosphere under a 1JM-hour heated to 120 ⁰ C and 98 ⁰ G cooled 1.72 parts of 1,4-trans-cyclohexane are added and the polymerization is continued as in Example 6. "

The polyester urethane obtained has a polyester soft segment content of 88.5% by weight, a diol / polyester molar ratio of 0.75 and a diisocyanate / total diol molar ratio of 1.0. The polymer has a viscosity number of 1, 15 and a Vicat softening point of 159 C ^O "Bs is a Aufspulge speed of 60.96 m / min at 214 ° C in a 5-filamentous spun yarn" the yarn has in the state immediately after spinning the following properties:

Zero Strength Temperature, C. 166

Titer, the 213

Tear Strength, g / den 0.278

Extensibility, $ 702

elastic regression from 100? » Elongation, % 98

Work recovery from 10OfS stretching, f ° 89

Growth in air at 200? '> Elongation
during 24 hours, %

1 minute relaxed 34.8

Relaxed 24 hours 14 »2

Growth in water of 60 ⁰ C at 100 ^ elongation, fo 22.2

.ORIGINALICSPECtED

009808/1639

Claims (1)

193 TBDl Pat enta η. sayings “Process for the production of synthetic polyester urethane elastomers, which can be melt-spun into threads, according to patent P 17 20 987» 9, thereby geke η η show that the following substances are reacted with one another with the application of heat? (1) a linear mixed polyester diol, * which is made up of one or more aliphatic or cycloaliphatic glycols with 2-20 carbon atoms and one or more dibasic acids, selected from saturated aliphatic dibasic acids and mixed aliphatic / aromatic dibasic acids in a ratio of 3M, and has a relative molecular weight between 1500 and 6000 and a melting point below 60 C or a glass transition temperature below 20 ⁰ C ,, (2) 0.1 to 1 _P 9 mol of an aliphatic, cycloaliphatic or arylaliphatic diol chain extender per mole of the above Polyesterdiols, and (5) 96 to 106 mol of p-xylylene diisocyanate or trans, trans-4,4'-diisocyanato-dicyclohexylmethane per 100 ha of the total weight of the above diols _? except that _s if the dibasic acid is adipic acid _f 'the diol butane-1 _F 4-diol, p-xylylene glycol or p-bis (ß »hydro3yäthoxy) benzene is not = ο A method according to claim 1 characterized _v gekennze ichne t t that the number of moles of the aliphatic, cycloaliphatic or arylaliphatxschen diol per mole of polyester diol 0.2-1 _P O is ο CJRIQINAL INSPECTED 009808/1639 1931800 Process according to claim 1 or 2, characterized in that the average molecular weight = ¹ weight of the mixed polyester diol is between 1900 and 4400 " _F Method according to one of claims 1 to 3 »characterized in that the copolyester is derived from an aliphatic dibasic acid, which not more than 36 carbon atoms in the molecule" ο procedure according to. Claim 4, characterized in that the acid contains 4-20 carbon atoms " ο method according to claim 5 »characterized that the acid succinic acid, adipic acid "sebacic acid "Succic acid or azelaic acid is". 7. The method according to any one of claims 1 to 4 _f, characterized in that the polyester is derived from a mixture of saturated aliphatic and aromatic dibasic acids in a molar ratio of 3 s 1, the mixture of adipic acid and phthalic acid, adipic acid and terephthalic acid or adipic acid and isophthalic acid is selected " 8s Synthetic polyester urethane, which is melt-spun in threads can be and a viscosity number of O "5-1» 5 characterized in that it has been obtained from the following substances: (1) a linear one Mixed polyester diol which is derived from one or more aliphatic or cycloaliphatic glycols with 2-20 carbon atoms and one or more dibasic acids »those selected from saturated aliphatic dibasic acids and • mixed aliphatic / aromatic dibasic acids 0 0 9 8 0 8/1; 6 3 9 originally inspected 193180 ».. - • 29 - _{n is} selected in the ratio of 3i1 and has an average molecular weight between 1500 and 6000 and a melting point below 6O ⁰ G or a glass transition temperature below 20 ⁰ C, (2) 0.1 to 1.9 mol of an aliphatic “cycloaliphatic or arylaliphatic diol chain extender per mole of the above-mentioned polyester diol, and (3) 96 to 106 moles of p-xylylene diisocyanate or trans "trans ^^" - diisocyanatodieyclohexylmethane per 100 moles of the total weight of the above diols _? except that when the dibasic acid is adipic acid "the diol is not butane" 1 ".4-diol ,, p-xylylene glycol or p ~ bis (ß-hydroxyethoxy) benzene ο ο polyester «urethane according to claim 8 _P, characterized in that the number of moles of the aliphatic, cycloaliphatic or arylaliphatic diol per mole of the polyester diol is 0.2-1 ₉ 0 «, OK, polyester urethane according to one of claims 8 or 9 * characterized in that the average Molecular weight of the mixed polyester diol is between 1900 and 4400, ί ο polyester urethane according to one of claims 8, 9 or 10 "characterized" that the mixed polyester from an aliphatic dibasic acid containing no more than J6 carbon atoms in the molecule has ο \ 2> Polyester-urethane according to claim 11, characterized in that the acid contains 4-20 carbon atoms ο,. ■ ■. 00 9808/163 9 13 ° polyester urethane according to claim 12 »characterized in that the acid succinic acid, adipic acid, Is sebacic acid, eorkic acid or azelaic acid, Ho use of the polyester-urethanes produced according to one of claims 1 to 7 for melt-spinning Taää which. Have an elastic recovery of at least $ 95 and a work recovery of at least $ 75 * 15o method of use according to claim 14? thereby g e k e η η shows that the threads after manufacture 30 Minutes can be annealed at 110 G * FATBSTANWXtTE D £ rtt * K3-H.RNCfCe.D Pt-ING.H.BOHl DifL-lNG. S. STAEGER 009808/16 39 originally inspected