DE1570241A1 - Process for the production of synthetic elastomers - Google Patents

Description

Description sur patent aaamelclung of

BUIiISH ITCLON SPIMERS LIHITlSD, Ppntypool, Monmouthshire,

Grass Britain

concerning
"Process for the preparation of synthetic lactomers ¹¹ "

The priority of the application dated February 20, 1964 in £ rcy33t> UK is claimed.

The invention relates to the production of new synthetic elastomers and in particular to those elastomers which consist of subdivided polyether urethanes with aliphatic urethane segments and which can be sock-spun into threads o

Synthetic rubbers have been manufactured for many years »including polyester urethane aerators. Se is

909 887 / U 8 8

However difficult or impossible these elastomers aind cross-linked (cured) to solve without degradation and such solutions as are obtained könnnen, can not be solution-spun into threads "One more can be produced by melt spinning of elastomers threads ₀ Elastic threads could only it can be produced by mechanically cutting thin sheets into narrow strips, such a method having disadvantages. In particular, it is not possible to produce threads with a low denier, ie.

In the last decade a lot of development of synthetic on developing elastomers that can be löeungsgesponnen to elastic threads with gewünsohten Textlleigensohaften has been spent "Such elastic threads have an elongation of over 100 fi, a low initial modulus and a high percentage of elastic Sr * HOLUNG »The terms" extensibility "," initial modulus "and" elastic recovery "are defined below» A rope of development work was also directed to the improvement of elastomers that were polyester urethanes. For example, US Pat. No. 3,079,192 describes the manufacture of Polyesterurethanhametoffen from a «polyester, a molar excess of an aromatic diisocyanate and a diaminej the polyester urethane-8toffβ can become elastic threads by moist or

909887 / U88 " _ba d ORIGINAL

Dry spinning can be solution spun · Such polymers contain fractions »which consist of a low molecular weight polymer which - when fully polymerized so that it is a fiber-forming homopolymer - has a relatively high melting point, along with fractions that can be regarded as similar to that of a fully polymerized homopolymer descending with a relatively low melting point. The first. Fractions are often called hard segments and the latter soft segments, for example Xn the article by VoH. Gharch and JC Shiverβ, titled "Elastomeric Condensation Block Copolymers" from Textile.Research 'Journal, July 1959 ·

Attempts have been made to use synthetic To produce elastomers that can be spun into textile threads, since melt spinning is known has numerous advantages over solution spinning »For example, Belgian patent 619 994 proposed to produce melt-spinnable polyurethanes by reacting a polyester or mixed polyester with Hydroxyl endgroup (i.e., a diol) having a thermoset molecular weight not more than 1400, with a organic diisocyanate and a chain spreading agent, preferably a dihydric alcohol, e.g. 1,4-butanediol where the molar excess of diisooyanate to total diol

-9 0 9 8.8 7 / U 8 8

between 1.14: 1 and 1.02: 1 »The Belgian patent specification mentions alicyclic and aliphatic Diisocyanates, such as tetramethylene diisocyanate or Ilexamfithylendiiaocyanat, however, there are no examples of their application ,, In fact, procedures are described, wherein a molar excess of diisocyanate is heated with a polyester with hydroxyl groups; is it impossible to do such a process with an aliphatic To carry out diisocyanate, since gelation takes place under these conditions "

It has now been found that new, melt-spinnable polyester-urethanes with improved properties can be prepared from a foißohpolyeeter with hydroxyl end groups with a molecular weight of over 1500, a dihydric alcohol and an aliphatic or cycloaliphatic diisocyanate, provided that the diisooyanate is neither molar Excess is applied _{9 is} still in a molar excess at any point during the reaction *. Although the above Belgian patent states that the use of high molecular weight polyester yields filaments of inferior quality, it has been found that by increasing the molecular weight of the polyester, better values for the gain in performance (work recovery) and stress decay (as defined below) can be obtained.

~ 5 -909887 / U88

BAD ORfGiNAL

After all, the elastic threads made from polyester urethanes, derived from aliphatic diisocyanates, differ from the elastic threads based on aromatic diisocyanates by virtue of their advantageous properties. The former had polyester urethane threads. their elastic properties and manner return to a greater extent when exposed ₉ than the latter; finally, the latter yellow when subjected to bleaching by hot aqueous sodium chloride, and also when they age, in contrast to the former ”. The "degree of resistance to light and bleaching is determined in tests that can be explained in the following way"

Exposure resistance

Jie threads are wound on a frame and with a Xenon arc exposed for 500 hours = the elastic ones Properties and the color of the threads are determined before and after exposure «

Lead resistance

The threads are 45 min in an aqueous solution with 0.1 Percentage by weight of sodium chlorite and 0.5 oom per liter of glacial acetic acid immersed, which is kept at B5 ° C. The color the threads are determined before and after bleaching.

909887 / U88

~ 6

With regard to the polyester urethanes of the Belgian In patent specification 619 994, the present polyester-urethanes differ not only in terms of their molecular weight the polyester used and the proportion and chemical constitution of the diisocyanate used, but rather the elastic threads obtained by melt spinning the polyester urethanes according to the invention superior textile properties o

Definitions of the thread properties extensibility ·.

The extensibility of the threads is understood to be the length to which they can be drawn out before they break, expressed as a percentage of their original length _{or the like}

The load of the threads expressed in grams per denier,

Initial module

The initial modulus of the threads is understood to be the quotient that is obtained by dividing the specific load by the elongation, if the elongation is an extension of 1 # of the original length "(The specific load is on page 138 of" Textile Terms and Definitions ", 4 * edition, published on

9 0 9 8 8 7 / U 8 8 - 7 -

Teetile Institutes Manchester., Defined and can be expressed in grams per denier) Ό

ΕΊ.μ ΰ flat recovery;

The elasticity of the threads is expressed by the Break made by dividing the length, in which the threads be sucked out when applying a load, durah is the length ρ of which they are after removal of the load pull together «. The fraction is commonly referred to as a percentage

salary expressed ..

The power recovery of the threads is expressed ale halt "to consider when dividing the energy or" the power that is consumed in stretching the filaments by applying a load _s by the energy or "power to win _r when the threads to their original size retract while removing the load «The fraction is commonly expressed as a percentage

Square Babfal. L

The tension drop of the threads is expressed by the Fraction that <π3.η by dividing the necessary load to stretch the threads to a selected percentage of their original length by <? who eats necessary, ura the same stretch at the end of a

9 Ö ■ 9 8 8 7 / U 8 8

BATH ORIGINAL

a certain time, with the elongation being kept constant over the entire time. The break will generally expressed as a percentage "

Sticks temperature

The lowest temperature »at which the threads get hot Glue on the smooth surface if they are brought into contact with it ο

Internal viscosity

The intrinsic viscosity is defined as twice the natural logarithm of the viscosity at 25 ° O _{9 of} a solution of 1/2 part by weight of polyester-urethane dissolved in 100 parts by volume of m-cresol, divided by the viscosity of the m-kreeol at the same temperature .

Vlcat augmentation point

The mentioned Vicat softening point is by one Fenetrometer similar to that of Edgar and Ellery on page 2638 of the Journal of the Chemical Society 1952, described apparatus has been determined.

Accordingly, the invention relates to a method sur Manufacture of synthetic polyester urethane elastomers, which can be spun into threads, v. whereby nan duroh heating carries out a conversion between 1) a Diöl, the a linear:. * is a mixed polyester with hydroxyl end groups,

909887 / U88 ~ ⁹ ~

BAD ORfGlNAL

that of one or more aliphatic or cyeloaliphatic Glycols having 2 to 20 carbon atoms and adipic acid, optionally with one or more others «Female acids from the group of saturated aliphatic and aromatic aweibasic acids derived iat »and that have an average molecular weight of 150Q to 3500, 2) 2 bio 20 moles per mole of the 'above Polyestars diol of an aliphatic diol, optionally with arylene groups or an cycloaliphatic diol, wherein the diol has no more than 20 carbon atoms, and 3) from 96 to 100 per 100 moles of total weight of the above diols of an aliphatic or cycloaliphatic .Diisocyanates with 4 to 24 carbon atoms, which optionally may contain aromatic nucleus »provided that the latter of the isocyanate groups through at least one Methylene group are separated »

Examples of participants in the reaction who enjoy the invention Procedures that can be applied are the following:

Linear mixed polyesters with hydroxyl end groups Mixed polyesters derived from the added glycols and dibasic acids in the specified weight ratio and the specified molecular weight (MoVZ ₀ ),

BATH ORIGINAL 909887/1488

Glycols

ZweiTaa-

RatioJBohe ratio Acids never

Ethylene Glycol Propylene GlycoX

Ethylene Glyeol 23Bi

7: 3

Ethylene glycol 1,3-butanediol

Äthylengly c oil 1,3-dihydroxy «2, methylpropane

Ethylene glycol ethylene glycol

Ethylene glycol 1,3-Dihydroxy-2, 2- diäthylpropan

Ethylene glycol 1,4-butanedio!

Ethylene glycol) 2.5 ~ hexanediol)

Ethylene glycol) 1,3-dihydroxy-2,2,4-) trimethylpentane)

Ethylene glycol propylene glycol

Ethylene glycol trimethylene glycol

7: 3 ] 7: 3

7: 3

7: 3

7: 3 7: 3

7: 3

7: 3 7: 3

7: 3 Adipine adipine adipine

Adipine

Adipine-Bernstoin-

Adipine «Phthal

Adipine

jidipin-adipin-

iidipine

Sebacin adipin

1640 1550 1550

1540

3: 1 1560 3: 1 1550 - 1550 - 1600 - 1550 ... 2490 1650 - 1550 1630

11 -

909887/1488 ORIGINAL BATHROOM

The linear copolyesters having hydroxyl terminal groups ^ can be prepared in manner known per se from the desired glycol and the dibasic acid, d, ho by using a moderate excess ZOB _f "$ 10> of the glycol. Instead of the acid, the acid chloride can be used four den ο it is also possible to use the methyl ester of the dibasic acid au _e do ho to produce the polyester by an Ea terauseh., Bieee method requires the use of a catalyst j qb is preferred not to use a catalyst, in the preparation of the copolyester gsmäes as Reaktioneteilnehmer the present invention, _t can be used. " Bite therefore ,, Sa üle presence of even small ICatal2rsatormengen ₉ aekwer or not be removed "kunnsn * a Hiss- 'coloration of polyester ^ ürethans trenar- ■ gently obtained at Bnde, such Mies colorations sisad by! Aandeietibliolieii Tesitilfäden unacceptable ea' case d @ nn ₅ dasat letstts ¹ © should be deeply colored ,, Bs ± Bt
lichj polyester su v © rw © 2idea _?
Catalyst used what is »

the ge ^ eb ^ neafaXlB

en and cycloaliphatiaehe 'Hiole

1,4-butanediol

1 _P 6-hexanediol

Di { 2 »-hydroxyethyl) -1erephthalate

DI \ 4 -hdbil5thth

909887/1488. - 12

trans-Ί _f 4 ~ dihydroxyeycloh8; run

cia-1.4 ml hydroxycyelohexun

2 , 2 , <! j 4 tetraraethyl-cyclotutane-1,4-diol

1.4 "di (hydroxyinethyl) benzene

1, 4 ~ di ( ? ~ Hydroxy-n-propyl) -benzene

trans-2,5-di (hydroxyraetnyl) 1,4-dioxane

cie-1,4 * Dl (hydroxyraethyl) cyclohexane

trane-1,4-di (hydroxymethyl} cyclohexane

ι, 4-Üi-betß ~ hyiroxyethoxybenBOl

2.2 IIis-4-beta-hydroxy-ethoxyiUenylpropane

Alij3hat. _i iaohe _i and cycloaliphatic Dliaooyarmte: uexamethylene diisocyanate

trane-1,4-diocyanate cy alohexane

Tetramethylene diisocyanate

n-xylylene diocyanate

P-xylene diisocyanate Fentamethylene dieooyanate

trans-1,4-Üi8-iocyanate-methyl-olyolohexane

Deoamethylene diieooyanate;

2,2-Di (4'-ie ooyanat-oyöloher / 1) propane

Di- (4-booyanate-cyclonexyl) ma than

In making the present synthetic elastomers, the diols and diisooyanate can be brought together in any conventional manner. ¹ ; » there is no molar excess of diocyanate, which takes place under reaction conditions compared to the total weight of the diols present, that is, for example, at a temperature high enough for the decomposition to occur. One method to be carried out is to "mix the methylene ether diol with the low molecular weight diol, heat the mixture, for example, to 100 ° C and add dioxyanoate while the temperature is further increased so that the polyester-urethune formed does not solidify"

909887/1488 " ¹ L"

BAD ORiGiNAL

Mo reaction is preferably carried out in an inert atmosphere carried out j. for example under nitrogen to a To prevent oxidation of the .Polymer ,, Effective mechanical Guarding the reaction participants is very welcome »A another method of implementation is ea, part of the Putting asocyanates on the milk polyester diol »That Diiaocyanate can be 2.Bo half or two thirds moles per mole of mixed polyester, the low molecular weight Diol is then added followed by the remainder of the diisocyanate

The low molecular weight diol that makes up the hard parts in the polyester urethanes according to the invention «Yiie already mentioned - used in a molar excess compared to the mixed polyester diol, which the soft Parts, where the molar ratio of the two diols is from 2: t to 20: 1 «x) ie from the polyamide methane However, spun filaments have the most desirable textile properties when the above-mentioned molar ratio from 3: 1 to 9: 1 is-

Catalysts such as the following, can be optionally included in the reaction mixture _for the environmental setaung of diisocyanates su promote.

909887 / U 8 8 BAD ORIGINAL

Mbutyltin IV dilaurate

DiLmethylcyclohexylamine

Sodium ethoxide

Triumphant

Ferric acetylaoetonate

Finally, the manufacture of polyester urethane be carried out in solution - Suitable solvents for this are:

ΪΪ t K-dimethylacetamide

Pyridine

Dinethyl sulfoxide mixed with a like

Volume of methyl isobutyl ketone

lI, N ~ dimethylformamide

Hexamethylphosphoramide

Tetramethylene sulfone.

The polyether urethanes according to the invention can be used in Solution can be produced and the latter directly into threads according to the "known dry or wet pinna" method are spun »The solutions of polyethers ^ urethanes can also be poured into films. As already stated? however, the textile threads are preferably melted spinning, in which case no solvent is necessary »The threads can be in a solid state drawn (a process often referred to as cold drawing), although this is not essential; if the maximum extensibility is needed, there should be no pulling.

- 15 -909887 / U88

BATH ORIGINAL

Under the conditions used for preparing the present polyester urethanes Reactio ball taker, pigments, plasticizers * matting agents and stabilizers may be _o

The polyester urethanes according to the invention preferably have a molecular weight corresponding to an intrinsic viscosity of 0.5 to 1.5.

pie invention includes the melt-spinning of the above-mentioned new synthetic polyester-urethanes into threads and the threads thus obtained ain · The latter have excellent elasticity and do not discolour if they are etched out in a xenon arc or treated with sodium chlorite as mentioned above Exposure resistance and bleach resistance tests. The threads also have good elastic recovery and good performance gain; they often exhibit an elastic Brholung at 50 i> elongation of mindeetens 95 # and a Leiatungsrlickgewinn aei 50 ^ Deliming of at least 75 / £ c Bie threads of a hot Peuchtbehandlung be üblichervreise subjected sB "with boiling Y / asaer during dyeing or ßntschlichtens before the economic application; for this reason iatf i η the following. Examples of boiling water treatment have been carried out before the physical properties have been agreed, in order to obtain better comparable results.

909887 / U88 ¹⁶

The present polyester-urethanes are advantageously distinguished from other synthetic elastomers by the ease with which they can be spun into threads that have no tendency to stick together and therefore do not need to be dusted with Tsicum powder * These new polyesters also bind Urethane threads are superior to the known elastomer threads with similar physical properties, since they do not discolor when they are subjected to the lightening and bleaching resistance tests. The filaments are suitable for so-called corselettes as corsets, in elastic outerwear, such as sweaters, ski pants, also in surgical-elastic hosiery and B ndagen _ft. Other uses are woven or knitted swimsuits, hosiery, brassieres, and pajamas. The present threads are also suitable for similar widespread use in the form of staple fibers, especially mixed zJ. With wool, cotton, Polyhexamethylenadipinsäureainida You new polyester-urethane threads according to the invention can be processed into composite elastic yarns by forming them as continuous threads together with one or more rovings of staple fibers, polyethylene terephthalate, wool or cotton fibers, in the usual way Introduces spinning or knitting frames. In the form of the fibers, the polyether urethanes obtained according to the invention can be used in the production of nonwoven fabrics or

909887 / U88 ^BAD ° FHGIWAL ~

mixed with wool for search, for men's suits, used v / earth.

In the following examples, which are given for illustration but not to limit the invention, parts are parts by weight _o

example 1

54.7 parts of a fciischpolyestera with hydroxyl end groups,

K derived from ethylene and propylene glycols in an alcohol ratio of 7: 3 and adipic acid and a molecular weight of 1640 are mixed with 14.0 parts of 1,4-butanediol Stirring heated «

Add to the above mixture of diols with stirring 15.7 parts of hexamethylene diisooyanate were added over the course of 5 minutes. " A further addition of 15 # 7 parts of hexamethylene diocyanate is then carried out for 70 minutes while the temperature is gradually increased to 200 ° C and the reaction mixture is constantly stirred »The Mixing will last 25 minutes at the same temperature stirred and then cooled under a nitrogen atmosphere.

The polyether urethane obtained has an inherent viscosity of 0.59 and a Vicat softening point of 150 ° C

- 18 -

909 8 87 / U

The polyester urethane is at a temperature of 190 to 195 ° C in 10 J threads of a total of 319 denier schmelzge spönnen «, the 10-ply yarn has after the Treatment with boiling water has the following properties:

Tenacity 0.43 grams per denier Initial modulus 0.24 g ^M " Voltage drop at 24. " Stretching 25 _f 2 i> (15 minutes]

37.6 f (16 hours)

Ullastic recovery

50 Joiger stretch 98 5 *

Performance gain at

50 £ strength J ₆ hnung - 75 9t

iteisplei 2

The description of polyether described in Example 1

urethane is repeated with the assumption that the there

58.8 parts Used / kieohpolyester by 5ü, 8 parts a «liisch polyether with hydroxyl end groups derived from Ethylene glycol and 1,4-butanediol in a moly content of 7t3 and adipic acid and a molecular weight of 1600 be replaced, the weight of 1.4 - üutanediol of 14.0 has been reduced to 12.2 parts and the total weight of hexamethylene diisocyanate 28.3 instead of 31.4 parts cheats.

The iSigensohaf-tn of the polyether urethane are as follows Intrinsic viscosity 0.88 Vioat boiling point 164 ° 0

909887/1 488 -

BATH ORIGINAL

15702A1

The yarn, which is definitely aehmelzgeoponnen and cold-drawn to three times its original length (at 15 ⁰ C) is then treated with boiling Yfaseer and has the properties given below!

Voltage drop at 25

34.5 "/ ο (16 hours)

Elongation 22.2 # (15 minutes)

345 ", Ό (16

Clastic recovery at

50 pointer expansion 9B #

performance recovery te!

50 ^ extension 94 pounds

Example 3

Example 1 is repeated with the exception that the reactants used are replaced by the following will: ..

The mixed polyester is derived from ethylene glycol auaamaen with adipic acid and succinic acid in a molar ratio from 3: 1 and has a molecular weight of 1560; it of which 58.7 ϊβίΐβ are taken and 12.2 parts .-. 1,4-butanediol geoiched; 29.1 parts of hexamethylene diisocyanate are used (in two equal proportions)

! The properties of the obtained polyester urethane are:

Intrinsic viscosity 1.14 Vicat softening point 160 ° 0

- 20 - 909887 / U88 _BAD OR! ®

The yarn made from it has melt-spun after treatment with boiling water has the following properties:

Waste of energy at 25 5 »iger

23.4 (1st

6 hours)

Expansion ~ 23.4 (15 minutes)

37.4 (1 '~ ~'

Elastic recovery at

50 # expansion 94

Performance recovery at

50th cowardly extension $ 93>

Example 4

Example 3 is repeated with the excludes that the mixing polyester by 5UE> 4 parts of a üichpolyesters is replaced, the of ethylene glycol and 1,3 dihydroxy ~ ~ 2 _f 2-dimethylpropane in a Holverhältnis of 7: 3 and adipic acid is derived, and a molecular weight from 1540 «

They properties of polyester urethane are: Intrinsic viscosity 0.60 Vicat softening point - 165 ° C.

The polyester-urethane is melt-spun in the process described in Example 1 and the resulting Threads sucked to four times their original length and treated with boiling water ο

909887 / U88

- 21 ORIGINAL BATHROOM

~ 21 ~ SiO have the following properties:

Toughness. . Initial module ..- Delinability Sticking temperature

Shrink in boiling water before pulling

Voltage drop at 25% expansion

Elastic recovery at 50% expansion _{; power recovery at 50% expansion;}

0.67 g per denier 0.4 g per denier 230 & tO2 ° 0 35.9 # 2.2 fo

16.7

30 Ji

97? I

[15 minutes), 16 hours)

A polyester urethane elastomer with greater elasticity can be obtained by Jirhöhön the molecular weight of the Miechpolyesteirjund change in the proportions of the reaction participants as follows: . .

Mixed polyester

üutandiol

Diisocyanate

84.0 parts 12.9 TeUe 32 «2 parts

The polyester "urethane obtained has an inner Vzskosität of 0 _ff 85 and a Vicat Erweichun / jspunkt of H0 ^(l C. Its Delmbarkeit is 460 #»

9 0 9 8 8 7 / U 8

_Bm

- * ■ 22 · -

Example 5

A polyester-urethane is produced in the manner described in Example 1 with the exception that the mixed polyester is made up of 58.9 parts of a liisohpolyester derived from ethylene glycol and Sritnethyj.englycol in a molar reserve of 7: 3 and adipic acid and with a molecular weight of 1631 _{f is} replaced «. 29 »7 parts of Ilexamethylendiißooyanat v / erden used» The polyester urethane has an intrinsic viscosity of 1.03 and a Vicat softening point of 159 ° C ° - the polymer is melt-spun into threads and the latter is drawn to three times its original length » Me threads show, when stretched to 50 "/», an elastic recovery of 99 / * and a return gain of 79 9 »«

.-Example 6

57.6 parts of dos iiischpolyeater of Example 2 are on 100 ° 0 heated under a nitrogen atmosphere and 2.6 parts Hexamethylene diocyanut added over the course of 15 minutes. " Effective stirring is continuously maintained during the production of the mixed polyeter urethane * The reaction mixture is heated to 120 ° C and held there for 30 minutes » The temperature is then lowered to 60 ° 0 and 12.2 parts of 1,4-butanediol are added over the course of 10 minutes The mixture is heated to 100 ° G over the course of 15 minutes and 25.2 parts of hexamethylene diocyanate are added batchwise over the course of 60 minutes

,,, -.- ■ 90 9887 / U88 - 23 -

6ad original

Minutes added, while the temperature is further increased to 180 ° C, bo that the ResktionGmischiog remains melted ο The temperature is 30 minutes?.; H? .l held 10 ° C and the polyester urethane cooled άειηη «, Eo has an intrinsic viscosity of 0.65 and a. Vicat softening point of 171.

The polymer is spun at 169 ° C and yields Mden, which after undressing to three times their original length and treating in boiling water Features:

Voltage drop at

25 # extension 25 »0 # (15 minutes)

36.2 fo (16 hours)

Clastic recovery at

50? * Iger expansion 99 i *

liGiGiTy bridging profit at

50 Joiger iiusdelinung ÖO $>

Example 7

Example 6 is repeated except that ₉ the first batch of hexamethylene diisocyanate 2.6 parts to 3.6 T _e ile increased and the second batch of 25.2 parts 22ρ8 part; The polyester urethane obtained has an internal viscosity of 0.85 and a Vicat softening point of 178 ° C =

Those spun from the above polyester-urethane 3clir £: elzspun i .- 'äden- benitKon a good elasticity.

909887 / U 8 8 BATH

Example 8

57 parts of a polyester having hydroxyl iSndgruppen derived from Älitylenglycol and 1,3 ^ 2,2-ihydroxy- diraethylpropan in a liolverhäl ¹ JnIs of 7.3 and adipic acid and having a molecular weight of 1540 are, with 18.95 parts of 1 , 40l (ü4iydroxyäthoxy) benzene mixed at 110 ° in a nitrogen atmosphere and stirred for 30 minutes.

15 parts are then added to the above Diola odor with stirring llexamethylene diisocyanate added over 15 minutes, while the temperature is raised to 1b0 ° C. V / pus 8.18 parts of uexamethylene dileocyanate are used for 60

Added in a few minutes while the temperature gradually increases

at

200 C is increased. The mixture is stirred at the same temperature for a further 40 minutes and then cooled under a nitrogen atmosphere «,

The polyether urethane obtained has an intrinsic viscosity of 0.16 and a Vicat softening point of 179 °

The polyester urethane is pinned at 215 ° and After treatment with boiling water, the yarn has the following Characteristics:

■ - 25

909887 / U88 BAD ORIGINAL

! Voltage drop at

25 long stretch 18 $ (15 minutes)

Elastic recovery at

100 younger stretching $ 93

Performance gain at

100 5 »i (each elongation 62 i *

13 egg game 9

70 ropes of polyester according to example ΰ and ü, 23 parts ciss / trun8-1,4 ~ dihydroxyoyclohexane are mixed together and 2? Share Hexanethylendiieooyunut with it as in above Example heated «

The polyester urethane obtained has an inherent viscosity of 1.0 and a Vioat JSrweiouunga point of 145 ° · Bas Polyester-urethane is sohmeltspun at 210 ° 0 and after Treatment with boiling water, the yarn has the following properties:

Voltage drop at 25 Ϊ * Elongation 47 i » (after 15 minutes) Elastic recovery at

100 * /> iger elongation 95 #

LeietungsrUokgewina at

100) tiger elongation 75 i

Example TO · ■.

60 parts of a polyester containing hydroxyl end groups derived from ethylene glycol and 1,3-dihydroxy-2,2-dimethylpropane

90 988 7 / U88 - 26 -

BATH ORIGINAL

in a molar ratio of 7: 3 and adipic acid and with a molecular weight of 1656 are with 15 »3 parts p-xylylene glycol at 110 ° in a nitrogen atmosphere mixture'!; and stirred continuously for 30 minutes

The mixture of diols is then added to the above mixture with stirring 12 ropes of hexamethylene diisocyanate added over 15 minutes, while the temperature is increased to 180 ° C. A further 11.7 parts of llexamethylene diisocyanate are added over 60 minutes while the temperature is increased to 200 ° o you mixture is then stirred at the same temperature for 30 minutes longer and then cooled under a nitrogen atmosphere

The polyester urethane obtained has an intrinsic viscosity of 0.56 and a Vicat softening point of 180. D _B s polymer is melt spun at 203 ° to a yarn which, after treatment with boiling water, has the following properties:

Voltage drop at

25 # extension 31 # (about 15 minutes)

Elastic inheritance

100; & iger elongation 87 lbs

Line recovery at

100 # expansion 50 $>

9 0 9 8 8 7 / U 8 8

■ = · 27 - '

Example 11

D _a s p-xylylene glycol of Example 10 is replaced by 15.7 parts of cis / Trane-1,4-di (hydroxyraethyl) oyclohexäno The AOlyester urethane obtained has an inherent viscosity of 0.59 and a Vicat of 151 ° ßrweiclmngspunkt . A yarn with good elastic properties is sniffed at 102 ° C

12th

36 parts of a hydroxyl terminal group-containing polyester of ethylene glycol and 1,3- ^ ihydroxy-2,2-dimethyjpropane in a molar ratio of 1: 3 and adipic acid and with a molecular weight of 2028 are mixed with 4.95 parts of 1,4-butane -1HoI mixed at 110 ° C in a nitrogen gas atmosphere and stirred together for 30 minutes ο

Then add the above mixture of diols with stirring 191.05 parts of trans, tims-di (4-isocyana1reycloiiexyl) methane over 75 canoeists are added while the temperature is gradually increased to 200 ° C. The mixture is further at 200 ° G Stirred for 40 minutes and then cooled ο.

The i ^ olyester urethane obtained has an inherent viscosity of 0.96 and a Vicat softening point of t93 ° C,

-.28 90988 77U88

BATH ORIGINAL

Example 15

The Beginning of the Reaction Participants of Example 12

are changed as follows:. '

Polyester '35 parts

Jiut £ .ndiol 12.32 parts

l) i (isooyanatooyclolxexyl)

methone 12.32 parts

The polyester urethane obtained has an inherent viscosity of 0.64 and a Vieat softening point of 172 ° C. It is melt-spun at 205 ° to give a yarn with. following Characteristics:

Elastic recovery at

100> stretch 96

leiotuiigsreck gain at

100 toger stretch 78

Example 14

35 parts of a polyester containing hydroxyl end groups and made from ethylene glycol and 1,3-dihydroxy-2 _f 2 -dimethylpropane with an iiol ratio of 7: 3 and adipic acid and with a molecular weight of 2028 are mixed with 4.95 parts of 1,4-butane mixed diol at 110 ° C in a nitrogen atmosphere and stirred together for 30 minutes »

* P. 29 ~

90 988 7 / U88

BATH ORIGINAL

To the above mixture of di-oils, 19.05 Part di (4-ioocyanato-oyclohexyl) methane (a mixture steric isomers) added over 75 minutes while the temperature is gradually increased to 200 ° C. The mixture is kept at this temperature for a further 40 minutes stirred and. then chilled «

The obtained polyester urethane has an inherent viscosity of 0.50 and a Vioat turning point of .141 ° 0.

The polymer becomes a yarn with the following properties at 188 ° C melted:

Elastic recovery at

100 # elongation 89 ⁰ A

Performance gain at

100 elongation 56 pounds

Example 15

Example 14 is repeated except DASA 36 Hydroayl end groups-containing polyester obtained in place of 35 parts are used, the butanediol is ersetut by 6.7 parts of P-Xylylenglyool and Meng · on Diieooyanaten of 19 "05 to 17" 3 ropes is diminished,

Jas Polyeeter urethane has an inherent viscosity of 0.67 and a softening point of 161 Vieat ₀ ° C The at 220 ° 0 deraue

90 98 87/1488 - 30 ~

- 30 -diespun yarn has the following properties

Clastic recovery at

100 # stretch 90

Performance gain hot

100 # stretch 55

Example 16

Example 15 is repeated with the exception that the 17.3 ropes of Si (4 "isocyanate ~ Gyolohexyl) methane (mixed steric isomers) by replacing the same amount of m-xylylendl isoyanate. The polyether urethane obtained has an intrinsic viscosity of 0.66 and a Vicat expansion point clay 127 ° 0.

Example 17

Example 14 is repeated with the exception that the reduced to .dutane-1,4-diol from 4.95 8Uf 3.6 ropes and the di (isocyanatooyü.ohexyl) Bothan duroh 11.2 part " p-xylylene diocyanate is replaced, the polyether urethane obtained has an intrinsic viscosity of 0.44 and a vioate expansion point of 174 ° U.

Claims t

909887/1488 ORIGINAL BATHROOM

Claims (1)

“31 patents say 1e method aur production of synthetic polyester urethane elastomers can be melt-spun aeden to J?, In dom, 1 ") a diol ,, the hydroxyl-Endgruj penhaltiger linear Iviiochpolyester _f derived from one or more aliphatic or cycloaliphatic ßlyoolen 2 up to 20 carbon atoms and adipic acid, optionally together with one or more other saturated aliphatic or aromatic aliphatic acids, 2.) a diol with not more than 20 carbon atoms, which is aliphatic, optionally with arylene groups, or cycloaliphatic and 3.) an organic diocyanate heated together with 4 to 24 carbon atoms, characterized in that a mixed polyester is used with an average molecular weight between 1500 and 3500, of 2 to 20 mol of the aliphatic or cycloaliphatic diol per mole of polyester diol, as the diisocyanate an aliphatic or cycloaliphatic _t the optionally aromatic nucleus contains, vo provided that the latter are separated from the diisocyanate groups by at least one methylene group, and from 96 "to 100 moles of diisocyanate are used per 100 moles of total weight of the preceding biols. 9098 8 7 / U88 2 «. Process according to Claim 1, characterized in that from 3 to 9 mol of aliphatic or cycloaliphatic mol per mol of polyester diol are used. 3e method according to claim 2, characterized in that one verwandet a Polyeaterdiol eating derived from Athylenijlycol-1,3-Dih3rdrox3 ^r -2,2-dimethylpropane and adipic acid, and ala Diioocyanat Hexamethylendiiaocyanat 4. Elactoraeror Paden aua a polyester-urethane mach claim 1, characterized by an elastomeric recovery at 50 5aiger elongation of at least 95 ^c J> _t a lieiatungarrückgewinn at 50 ^ iger expansion of at least 75 V »and not discolored on exposure to a Xenon arc or bleaching with sodium chloride after exposure to exposure and fatigue strength tests » BATH ORIGINAL 909887/1488