DE1570241B2 - METHOD FOR MANUFACTURING POLYESTERURETHANE ELASTOMERS - Google Patents

Description

3. an aliphatic or cycloaliphatic diisocyanate with 4 to 24 carbon atoms or m- or p-xylylene diisocyanate.
The method is characterized in that the diisocyanate is used in an amount of 96 to 100 moles per 100 moles of the total hydroxyl group-containing compounds.

The elastic threads produced from the polyester urethane elastomers produced according to the invention Can be different from the elastic threads, which are used to make aromatic Diisocyanates were used due to advantageous properties. So the former keep their elastic ones Properties and their white appearance to a greater extent when exposed to im Contrast to the latter; eventually the latter turn yellow, both when treated with hot aqueous sodium chlorite as well as aging in contrast to the former. The resilience to light and bleaching is determined by the following tests.

Exposure stability

The threads are wound on a frame and exposed to a xenon arc for 300 hours. The elastic properties and the color of the threads are determined before and after exposure.

Bleach resistance

The threads are immersed 45 minutes in an aqueous solution containing 0.1 weight percent sodium chlorite and 0.5 cc per liter of glacial acetic acid which is maintained at 85 ⁰ C. The color of the threads is determined before and after bleaching.

With regard to the polyester urethanes of Belgian patent 619 994, the invention differ produced polyester urethane elastomers not only in terms of the molecular weight of the polyester used and the proportion and chemical constitution of the diisocyanate used, but also through superior textile properties of the elastic ones obtained therefrom by melt spinning Threads.

Definitions of thread properties
Extensibility

The stretchability of the threads is understood to mean the length to which they can be drawn out before they break, expressed as a percentage of their original length.

tensile strenght

The breaking load of the threads, expressed in grams per denier.

Initial module

The initial modulus of the threads is understood as the quotient of the specific load and elongation, where the elongation is an expansion of 1% of the original length.

(The specific load is on p. 138 of "Textile Terms and Definitions", 4th edition, published by the Textile Institutes, Manchester, and can be expressed in grams per denier.)

Elastic recovery

The elastic recovery of the threads is expressed by the quotient of the length to which the threads when applying a load, ίο and the length to which they are extended after removing the Contract load. The quotient is given in percent.

Power recovery

The power recovery of the threads is expressed as the quotient of the energy or the power, which is consumed when stretching the threads by applying a load, and the energy or Performance gained when the filaments return to their original dimensions when the load is removed withdraw. The quotient is expressed as a percentage.

² S voltage drop

The tension drop of the threads is expressed by the quotient from the necessary load, to stretch the threads to a certain percentage of their original length, and the Load that is necessary to obtain the same expansion at the end of a certain time, the elongation being kept constant throughout the drawing. The quotient is in percent th expressed.

Sticking temperature

The sticking temperature is the lowest temperature at which the threads on a hot smooth surface stick on.

Internal viscosity

The intrinsic viscosity is defined as twice the natural logarithm of the viscosity, measured at 25 ° C., of a solution of 0.5 parts by weight of polyester urethane dissolved in 100 parts by volume of m-cresol, divided by the viscosity of the m-cresol at the same temperature.
50

Vicat softening point

The Vicat softening point is determined by a penetrometer, similar to that of Edgar and E 11 e r y in the Journal of the Chemical Society, 1952, p. 2638.

Examples of reactants that can be used in the process of the invention are as follows:
60

Linear mixed polyesters with hydroxyl end groups

Suitable mixed polyesters are those mentioned in the table below, composed of adipic acid and optionally other saturated aliphatic or aromatic dicarboxylic acids and the diols mentioned Polyester produced in the specified weight ratios.

5 Diols Weight
relationship Dicarboxylic acids 6th Weight
relationship Molecular
weight of
Mixed polyester Ethylene glycol
Propylene glycol
Ethylene glycol
2,3-butanediol
Ethylene glycol
1,3-butanediol
Ethylene glycol
1,3-dihydroxy-2,2-dimethylpropane
Ethylene glycol
Ethylene glycol
Ethylene glycol
1,3-dihydroxy-2,2-diethylpropane
Ethylene glycol
1,4-butanediol
Ethylene glycol
2,5 hexanediol
Ethylene glycol
1,3-dihydroxy-2,2,4-trimethylpentane
Ethylene glycol
Propylene glycol
Ethylene glycol
Propylene glycol
Ethylene glycol
Trimethylene glycol ) -
} -
} ™
} "
} '='
} ^{7: 3}
} "
} '='
} ^{7: 3}
} ^{7: 3}
} ^{7: 3} Adipic acid
Adipic acid
Adipic acid
Adipic acid
Adipic acid
Succinic acid
Adipic acid
Phthalic acid
Adipic acid
Adipic acid
Adipic acid
Adipic acid
Glutaric acid
Sebacic acid
Adipic acid 1640
1550
1550
1540
1560
1550
1550
1600
1550
2490
1650
1550
1630

The linear mixed polyesters with terminal hydroxyl groups can be known per se Way are prepared from the desired diol and the dicarboxylic acid, the diol being im moderate excess, e.g. B. 10%. used. It is preferred in the manufacture of the mixed polyesters do not use a catalyst, since the presence of even small amounts of catalyst, which is difficult or cannot be removed at all, causing discoloration of the polyester urethane elastomer. Such discoloration is unacceptable in commercial textile thread unless it is dark should be colored.

Aliphatic diols, which may contain arylene groups, and cycloaliphatic diols

1,4-butanediol

1,6-hexanediol

Di- (2-hydroxyethyl) terephthalate

Di (4-hydroxy-n-butyl) terephthalate

trans-1,4-dihydroxycyclohexane

cis-1,4-dihydroxycyclohexane

2,2,4,4-tetramethyl-cyclobutane-1,4-diol

1,4-di (hydroxymethyl) benzene

1,4-di (2-hydroxy-n-propyl) benzene

cis-1,4-di (hydroxymethyl) cyclohexane

trans-1,4-di (hydroxymethyl) cyclohexane

1,4-di - /? - hydroxyethoxybenzene

2,2-bis-4 - /? - hydroxyethoxyphenylpropane

Aliphatic and cyclic diisocyanates

Hexamethylene diisocyanate

trans-l ^ diisocyanato-cyclohexane

Tetramethylene diisocyanate

Pentamethylene diisocyanate
trans-l ^ -Bis-isocyanato-methyl-cyclohexane
Decamethylene diisocyanate

2,2-di- (4-isocyanato-cyclohexyl) propane
Di- (4-isocyanato-cyclohexyl) methane

as

m-xylylene diisocyanate or
p-xylylene diisocyanate

In the process according to the invention, the mixed polyester and the diol can be brought together with the diisocyanate in any conventional manner, but there must not be a molar excess of diisocyanate over the hydroxyl-containing compounds. A variant of the process is to mix the mixed ^{polyesters with the aliphatic or cycloaliphatic diol, heat the mixture to 100 °} C., for example, and add the diisocyanate while the temperature is increased further so that the polyester urethane elastomer formed does not solidify.

The reaction is preferably carried out in an inert atmosphere, for example under nitrogen to prevent oxidation of the polymer. There is effective mechanical mixing of the reactants very welcome. According to another variant of the process, part of the diisocyanate is first used added to the mixed polyester, the amount of diisocyanate z. B. one-half or two-thirds moles can be per mole of mixed polyester, then added the aliphatic or cycloaliphatic diol and finally the remainder of the diisocyanate is added.

The aliphatic or cycloaliphatic diol that

provides the hard parts in the polyester urethane elastomers produced according to the invention, is in one

7 8

molar excess compared to the mixed polyester, sticking together and therefore do not have to which provides the soft parts, is used, whereby the talcum powder is dusted. The threads are Moiverratio of diol to mixed polyester 2: 1 up to suitable for the manufacture of underwear, such as Is 20: 1. The corsets spun from polyester urethane elastomers, from elastic outerwear, for example However, threads possess the best 5 wise sweaters and ski pants, and from surgical, Textile properties when the molar ratio 3: 1 to elastic hosiery and bandages. Other 9: 1. Uses are woven or knitted Badean catalysts, Such as the following, can be given suits, hosiery, brassieres, and pajamas. the if added to the reaction mixture, threads can also be in the form of staple fibers, insdie Promote implementation of the diisocyanate. io special mixed z. B. with wool, cotton and

Polyhexamethylene adipamide, can be used.

Dibutyltin (IV) dilaurate, I _n the form of the fibers may according to the invention

Dimethylcyclohexylamine obtained polyester urethane elastomers in the manufacture

Sodium ethoxide position of nonwovens or, mixed with wool,

Sodium phenolate i _{5 can be used} for cloths for men's suits.

Iron (III) acetylacetonate I _n the following examples, which are illustrative

,,. ",. ,, .. _TT ", _, serve the invention, parts are parts by weight.

Finally, the production of the polyester urethane elastomers can be carried out in solution. . -I ₁
Suitable solvents for this are: ₂₀ Example I

Ν, Ν-dimethylacetamide 54.7 parts of a mixed polyester with terminal ends

Pyridine hydroxyl groups from ethylene and propylene glycol

Dimethyl sulfoxide mixed with an equal in a molar ratio of 7: 3 and adipic acid and

Volume of methyl isobutyl ketone with a molecular weight of 1640 are used

Ν, Ν-dimethylformamide ² 5 14.0 parts of 1,4-butanediol mixed. The mixture

Hexamethylphosphoramid is 30 minutes at 100 ⁰ C in a nitrogen atmo-

Tetramethylene sulfone sphere heated with continuous stirring.

. If the polyester urethane elastomer is prepared in solution for 5 minutes, then the solutions can be added directly to this mixture. A further addition of 15.7 parts of hexa threads according to the known dry or wet spinning methylene diisocyanate is then carried out over a period of time. The solutions can be poured into films of 70 minutes, with the temperature gradually increasing. Preferably increased to 200 ^° C. and the reaction mixture becomes the same, but the textile thread is moderately stirred by melt spinning. The mixture is prepared at the same time, whereby no solvent is necessary. 35 chen temperature stirred for another 25 minutes and then the threads can be stretched in the solid state cooled under a nitrogen atmosphere,
by a process which calls for cold stretching, although this is not essential. inherent viscosity of 0.59 and a Vicat-Erwei If the maximum extensibility is required, should monitoring point of 150 ⁰ C.

no cold stretching take place. 40 The polyester urethane elastomer is at a

During the production of the polyester urethane elastomers temperature from 190 to 195 ° C in ten threads of

Pigments, plasticizers, matting agents can also be melt-spun - a total of 319 denier. The lOfädige

agents and stabilizers are also used. Yarn possesses after treatment with boiling

The polyester urethane water produced according to the invention has the following properties:

elastomers preferably have a molecular 45 τ .... _n , - ^.

weight corresponding to an intrinsic viscosity of tensile strength 0.43 g. per denier

0 5 to 1 5 initial modulus 0.24 grams per denier

'The inventively produced from the polyester ?? ^{"a, n. now} ff? ^ ^{1 bd} ",.,""..

urethane elastomers produced threads a 247 ₀ strength elongation have 25.2 _"0 15 minutes)

excellent elasticity and does not discolour, 50. ",,,. '' ° ^ hours)

if they achieve the above-mentioned exposure resistance - elastic recovery

and subjected to bleach resistance tests. 50 / _o hydrochloric elongation ... _98/0

The threads also have good elastic recovery and power gain

and good performance recovery. Most is her / o'ger strain _75/0

elastic recovery at 50% elongation at least 55.

95% and its power recovery at 50% elongation Example 2

at least 75% · Since the threads before their processing The production of

usually a treatment, e.g. B. with boiling polyester urethane elastomers is repeated with the

Water, during dyeing or desizing, exception that the 54.7 parts used there

In the following examples, 60 mixed polyester was replaced by 58.8 parts of a mixed polyester

a treatment with boiling water carried out, with terminal hydroxyl groups from ethylene

before the physical properties are determined glycol and 1,4-butanediol in a molar ratio of

were to get better comparable results to 7: 3 and adipic acid and a molecular weight

obtain. from 1600 and the weight of the assigned

The polyester urethane 65 prepared according to the invention mixed 1,4-butanediols from 14.0 to 12.2 parts

elastomers advantageously differ from is reduced and the total weight of hexa-

other synthetic elastomers by their light methylene diisocyanate 28.3 instead of 31.4 parts

Melt spinnability. They show no tendency towards amounts.

ίο

The properties of the polyester urethane elastomer are as follows:

Intrinsic viscosity 0.88

Vicat softening point 164 ° C

The resulting melt-spun and at three times its original length cold stretched yarn (at 15 ⁰ C) is then treated with boiling water, and has the properties indicated below:

Voltage drop at

25% elongation 22.2% (15 minutes)

34.5% (16 hours) elastic recovery at

50% elongation 98%

Performance recovery at
50% elongation 94%

Example 3

Example 1 is repeated with the exception that the reactants used thereby the following are replaced:

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

The properties of the polyester urethane elastomer obtained are:

Intrinsic viscosity 1.14

Vicat softening point 16O ⁰ C

The yarn melt-spun therefrom after treatment with boiling water has the following Characteristics:

Voltage drop at

25% elongation 23.4% (15 minutes)

37.4% (16 hours) elastic recovery at

50% elongation 94%

Performance recovery at
50% elongation 93%

Example 4

Example 3 is repeated with the exception that the mixed polyester used there by 58.4 parts a mixed polyester is replaced by ethylene glycol and l, 3-dihydroxy-2,2-dimethylpropane in one 7: 3 molar ratio and adipic acid and has a molecular weight of 1540.

The properties of the polyester urethane elastomer are:

Intrinsic viscosity 0.60

Vicat softening point 165 ° C

They have the following properties:

Tensile strength 0.67 grams per denier

Initial modulus 0.4 grams per denier

Extensibility 230%

Gluing temperature 102 ° C

Shrinkage in boiling

Water 35.9%

Shrinkage before pulling at 2.2% voltage drop

25% elongation 16.7% (15 minutes)

30% (16 hours) elastic recovery at

50% elongation 97%

Performance recovery at
50% elongation 96%

A polyester urethane elastomer of greater extensibility can be obtained by increasing the Molecular weight of the mixed polyester and change in the proportions of the reactants as follows:

Mixed polyester of ethylene glycol and 1,3-dihydroxy-2,2-dimethylpropane (Molecular weight 1540) 84.0 parts

1,4-butanediol 12.9 parts

Hexamethylene diisocyanate 32.2 parts

The polyester urethane elastomer obtained has an intrinsic viscosity of 0.85 and a Vicat softening point of 140 ^° C. Its extensibility is 460%.

Example 5

57.6 parts of the mixed polyester from Example 2 are ^{heated to 100 °} C. under a nitrogen atmosphere and 2.6 parts of hexamethylene diisocyanate are added over the course of 15 minutes. Effective agitation is continuously maintained during the preparation of the mixed polyester urethane. The reaction mixture is ^{heated to 120 °} C. and kept at this temperature for 30 minutes. The temperature is then lowered to 6O ⁰ C and 12.2 parts of 1,4-butanediol added during minutes. The mixture is heated to 100 ° C. for minutes and 25.2 parts of hexamethylene diisocyanate are added in portions over 60 minutes, while the temperature is increased further to 180 ° C. so that the reaction mixture remains molten. The temperature is held at 180 ° C. for 30 minutes and the polyester urethane elastomer is then cooled. It has an inherent viscosity of 0.65 and a Vicat softening point of 171 ° C.

The polymer is melt spun at 169 ° C and provides threads that, after drawing, onto the Three times their original length and treatment in boiling water have the following properties:

Voltage drop at

25% elongation 25.0% (15 minutes)

36.2% (16 hours) elastic recovery at

50% elongation 99%

Performance recovery at
50% elongation 80%

The polyester urethane elastomer is in the B e 1 s ρ 1 e 1 6

Example 1 described manner melt-spun 65 60 parts of a terminal hydroxyl group-

and the. obtained threads to four times their holding mixed polyester of ethylene glycol and

original length and with boiling l, 3-dihydroxy-2,2-dimethylpropane in a molar

Treated water. ' ratio of 7: 3 and adipic acid and with one

11 12

Molecular weight of 1656 with 15.3 parts inherent viscosity of O ^ o and a Vicat softening

p-Xylylene glycol at HO ⁰ C in a nitrogen atmosphere of 193 ⁰ C.

Sphere mixed and poured continuously for 30 minutes. .

stirs. At _P1 el 9

5 35 parts of a terminal hydroxyl group to 12 parts of hexamethylene diisocyanate are then added to this mixture over a period of 15 minutes for a period of 15 minutes, while the 1,3-dihydroxy-2,2-dimethylpropane with a mol- Temperature to 180 ⁰ C is increased. Further 11.7 parts ratio of 7: 3 and adipic acid and having a hexamethylene diisocyanate be with 4.95 parts utes added while maintaining the temperature to 200 ⁰ C io 1,4-butanediol at 110 ⁰ in 60 micro molecular weight of 2028 C is increased in a nitrogen atmosphere. The mixture is mixed at this temperature and stirred together for 30 minutes,
Stirred for a further 30 minutes and then under nitrogen. 19.05 parts of the atmosphere are cooled to this mixture with stirring. Di (4-isocyanatocyclohexyl) methane (a mixture Polyesterurethanelastomere The obtained has a of stereoisomers) passed within 75 minutes hinzugeinnereViskositätvonO ^ oundeinenVicat-softening-15, while the temperature gradually to 200 ⁰ C point of 180 ⁰ C. The polymer is at 203 ° C is increased. The mixture is melt-spun at this temperature to form a yarn which, after handling, is stirred for a further 40 minutes and then cooled with boiling water. The polyester urethane elastomer obtained has the following properties: intrinsic viscosity of 0.50 and a Vicat-Erwei voltage drop at ²⁰ point of 141 ⁰ C.

25% stretch 31% (15 minutes) elastic recovery at 100% stretch

Elastic recovery at 89%

100 ° / _o strength at break 87% power recovery at 100 ⁰ / cent

Power recovery when stretching 56 ° / ₀

100 ° / ₀ stretch 50% ²⁵

Example 10

Example 7 Example 9 is repeated with the exception that

The p-xylylene glycol from Example 6 is replaced with 36 parts of the mixed polyester used there

by 15.7 parts of cis, trans-1,4-di- (hydroxymethyl) - 3 ° point of 35 parts are used, the 1,4-butane

cyclohexane. The polyester urethane elastomer diol obtained is replaced by 6.7 parts of p-xylylene glycol and

has an inherent viscosity of 0.59 and a Vicat the amount of diisocyanate of 19.05 to 17.3 parts

Softening point of 151 ° C. It is decreased at 182 ° C.

to a yarn with good elastic properties The polyester urethane elastomer has an inner

melt spun. 35 viscosity of 0.67 and a Vicat softening point

_. -ίο from 161 ⁰ C. The melt-spun ^{from it} at 220 ° C

^{ü e! sp! e 1 8} yarn has the following properties:

36 parts of a terminal hydroxyl group on elastic recovery at 100% stretch

pointing mixed polyester made of ethylene glycol and mine 90 ° /

l, _3-dihydroxy-2 2-dimethylpropane in a molar 40 power recovery at '^

ratio of 7: 3 and adipic acid and with a stretch

Molecular weight of 2028 will be 4.95 parts ^ c "mmg

1,4-butanediol at HO ⁰ C in a nitrogen atmosphere. .

mixed and stirred together for 30 minutes. example

45 Example 9 is repeated with the exception that

19.05 parts of trans, trans-di- (4-isocyanatocyclohexyl) - the amount of 1,4-butanediol from 4.95 to 3.8 parts

methane added over a period of 75 minutes, reduced and the di- (isocyanatocyclohexyl) methane

while the temperature is gradually increased to 200 ° C is replaced by 11.2 parts of p-xylylene diisocyanate,

will. The mixture is kept at 200 ° C. for a further 40 minutes. The polyester urethane elastomer obtained has a

stirred and then cooled. 5 ° intrinsic viscosity of 0.44 and a Vicat extension

The polyester urethane elastomer obtained has a breaking point of 174 ° C.

Claims (3)

1 2 it would be completely polymerized, so that it represents a patent claim · fiber-forming homopolymer - has a relatively high melting point, together with proportions which - when viewed similarly as a completely process for the production of polyester urethane 5 polymerized homopolymer - a relatively low elastomer by heating them together to have a melting point. The former proportions of the mixture are often called hard segments and the latter soft segments, for example in the article by 1. 1 mole of a two terminal hydroxyl group W. H. Charch and J. C. Shivers, titled containing linear mixed polyester with an io »Elastomeric Condensation Block Copolymers« average molecular weight from 1500 Textile Research Journal, July 1959. to 3500, which consists of aliphatic or cycloali- There have been attempts to synthesize them Glycols with 2 to 20 carbon- tables produce elastomers that lead to textile thread atoms and adipic acid, if necessary, can be melt-spun, since the melt-together Spinning with other saturated aliphatic 15 is known to have numerous advantages over it or aromatic dicarboxylic acids prepared by solution spinning. So after the Belgian patent 619 994 melt spinnable 2. 2 to 20 moles of an aliphatic diol, the polyurethanes produced by reacting a poly, if necessary, arylene groups, or an ester or mixed polyesters with hydroxyl end groups of cycloaliphatic diol with not more than ²⁰ with an average molecular weight of not 20 carbon atoms and ^{more than 1400} ' ^{with an} organic Diisocyanate and a chain extender, preferably one 3. an aliphatic or cycloaliphatic dihydric alcohol, e.g. B. 1,4-butanediol, wherein the diisocyanate having 4 to 24 carbon atoms _mo lar excess of diisocyanate to Gesamtdiol or m- or p-xylylene diisocyanate, ₂₅ between 1.14: is 1: 1 to 1.02. The Belgian Patent mentions alicyclic and aliphatic characterized in that the diisocyanate, such as tetramethylene diisocyanate or Diisocyanate in an amount of 96 to 100 moles of hexamethylene diisocyanate, however, gives no examples per mole of the total hydroxyl groups contained for their use. Indeed, procedures trending connections is applied. 30 described, with a molar excess of diisocyanate heating with a hydroxyl-terminated polyester; it is impossible to use such procedure to carry out an aliphatic diisocyanate, since gelation takes place under these conditions. 35 From the published documents of the Belgian Synthetic rubbers have been known for many years in patent 638,215 to make polyesters, including polyester urethane urethanes, which are elastomeric from the melt. However, it is difficult or impossible to be extruded and which, by reacting, can dissolve these elastomers which are crosslinked without degrading a hydroxyl-terminated polyester. Such solutions cannot be solution spun into 40 or mixed polyesters with a molecular weight of filaments, nor can organic diisocyanate and chain lengthening filaments be produced by melt spinning the elastomeric filaments with a molar excess. Elastic threads could only be produced from these elastomeric agents containing active hydrogen atoms in the form of thin hydroxyl and amino groups, especially foils, into narrow strips, one of which is dihydroxyl compounds such as 1,4-butanediol , he method has disadvantages. In particular, it is not going to hold up. In this description, it is possible to manufacture threads with a low titer, that is to say high, among other things, the use of aliphatic half 500 denier. Diisocyanates are mentioned, but in the last decade there has been a lot of development work only on aromatic diisocyanates in the development of synthetic elastomers, ie those in which the diisocyanate group is bound directly to the aromatic core to form elastic threads with desired textile properties.
The invention relates to a method of manufacture. Such elastic threads of polyester urethane elastomers have a combined extensibility of over 100%. low heating of a mixture
Initial modulus and a high percentage of 55 elastic recovery. The terms "extensibility" mean 1. 1 mole of a two terminal hydroxyl group "Initial modulus" and "elastic recovery" are linear mixed polyester with a containing defined below. Part of the development work was 1500 average molecular weight also on the improvement of elastomers made up to 3500, made from aliphatic or cycloali polyester urethanes were directed. The USA. Patent 60 Phatic Glycols with 2 to 20 carbon characters 3,079,192, for example, describes the heratomes and adipic acid, possibly a combination of polyester urethane ureas from a men with other saturated aliphatic or Polyester, a molar excess of an aromatic aromatic dicarboxylic acid Diisocyanate and a diamine; which is polyester, urethane ureas can become elastic threads through 65 2. 2 to 20 moles of an aliphatic diol, the Wet or dry spinning processes are spun. optionally contains arylene groups, or one Such polymers contain fractions that consist of a cycloaliphatic diol with no more than low molecular weight polymers exist that - if 20 carbon atoms and