DE1694767A1 - Process for making elastomeric products - Google Patents

Description

Plenzenauerstraße 28 Patent attorney Telephone 483225 and 486415

Telegrams: Chemindus Munich

19 IUi J97o W26 / F H 323

Hay documents

P 16 9 * 767. * - * 3

EI DU POHT DE HEMORS AND COMPANY
10th and Harket Streets, Wilmington, Delaware 19898, V.St,

Process for the manufacture of elastomeric products

The invention relates to elastomeric products made by reaction of organic diisocyanates with compounds containing hydrogen that react with Ieocyanate groups can be produced »It particularly affects the Her« · Positioning of linear, segmented polyurethanes (Spandex) by converting ¥ on polyether glycols, organic Diisocyanates and organic diamines.

There are numerous elastomeric materials known from aue.

" ¹ ""009849/1988

Segaenten existing polyurethanes are made. Even though 4it ·· substances many desirable phyaiicalitohen £ igen * oh * ften beaitsen,! "" stands for the need for improvement. in eolohen properties like Lusllohkelt in Lusungeaategories sur Production of spinning solutions, retention of whiteness and greater ret2 »akulonekr & £ fc with repeated expansions at the aa most commonly applied tendons in use. The need for improved physical properties can be expressed in

^To a large extent, it is attributed to the desire of the textile industry to extend the application of these synthetic elastic fibers to new and widely diverse fields of application.

The invention creates a process for the production of superior 3pand® £ «»? Oiym @ risat®n, which can be spun into elastic threads at technical spinning speeds. The invention also provides spandex threads which ) have a high resistance to discoloration, while at the same time they have the property of great strength at low elongations. The invention also creates linear segments consisting of segments. Polyurethanes which have improved solubility in spinning solutions, the solutions being stable for longer periods of time.

The polyurethanes according to the invention are particularly advantageous "because this polymer can be used to produce solutions in solvents known for this class of polymers" which contain polymerizate dissolved as 50% of the polymer. . _Ä .

009849/1986

L-126 }

Erfindungegenüiee a method sur Here division created a "linear" of segments existing polyurethanes "wherein a polyether glycol with a" Molekülargtwioht above about 600 and a Sehmelepunlct below about 50 ⁰ C bit oyanat an organic Dileocyanat in a MftlTerhältnie Diis ©: Giykol larger than 1: 1 to form βineβ polymer i · ate with Ieocyanatendgruppen and low molecular weight umgeeetst u d dae check resultant polymer with Ieooyanatendgruppen aneohliefteend sit a substantially ■ töehiometrieonen Jtenge "ine" ergaaleohen Bieeine uageeetst is wherein dae lHieooyanet m & Aa "Si aia 'inender gttncende monomers eind, did sin ltmtares ■ at with a melting point dboroalb 200 ⁰ C and tintm molecular weight in fi »erbildtiia« n tesäek biiata characterized thereby by 8 mm

(1) ale Folyf @ y

Glycol with a single Moljilnsl «rge% iio & t i * range from 1200 to 200O ₉

(2) on off

miä Ät ^ ris ^ & tltiiititeii «a £ tsi R3jsg # n trfegsPi £, mgVK7X * Am orgsniistesgi Miso» p where ^ m we & m $ MtikB Mtsou ^ ass & t äa «Sats fell«

3 -

1-126 is

1.85: 1 is used »and

(3) an organic dieunin is used which contains at least 60 moles of P from ithylenediaain.

In the DurohfUhrung the present invention, the starting material is a special polyether glycol, nMalioh polytetraethylene ether glycol. Dae Polytetramethylenätherglykol has a molecular weight bit a Zahlenduroheohnltt i 'range from 1200 to 2000 «preferably la range from 1500 to 1950 · These materials all have a Sohaelspunkt below 50 ⁰ C. Se can Mieohungen used by Polytetraaethylenätherglykolen if these mixtures durchsohnittliohes molecular weight la own specified area.

The polytetraethylene ether glycol is bit in the usual way A disruptive overcoat of a suitable organic diisocyanate is used to produce the foliarizate of isocyanate end groups The greatness of this etuohioBetrisohen überohueses matters; Expressed as the molar ratio Jileooyeitatsslykol "oll" r in Range from 1.5 * 1 to 1.85s1 · As a precaution, this ratio is la range from 1.6t1 to »1.75» 1 ·

The suitable organic diisocyanates are ρ, ρ'-methylene

Q0S849 / 1986

diphenyldilsocyanate, ρ, ρ -isopropylidendiphenyldiieocyanat, ρ, ρ'-Oxydiphenyldiisooyanat _f ρ, ρ'-Thhlodiphsnyldiisoeyanat and the homologues of these diisocyanates, which contain methyl and / or ethyl substituents in the rings, for example 4 , 3-methylphenyl) diiseeyanate, 4,4 · -methylene bis (2,5-diraethylphenyl) diisocyanate and 4,4 * -methylene-bis- (2s, 6-dimethylphenyl) -diiaocyanato The use of other than those of the The above definition encompassed Diisocyana-Sen should be avoided »apart from small amounts, ie it binds up to about 10 mol % of other diisocyanates known in the polyurethane sector *: permissible p-2ylylendlisooyanat in amounts up to about 10 moles of 1 »of Inageeaat diisocyanates present seinο Bs used 1st clear that the diisocyanates of substituents should be free, which are reactive with a Ibocyanatgruppe · M Mixtures of diisocyanates can be used

The polymer is then old with Isooyanatendgruppen a substantially Btoohiometrischen containing amount of the organic diamine containing 60 to 100 mol ethylene * i, us & gesetst (chain extended). Other diamines can be used in small amounts together with the ethylene dial and

i-126 6

For superior solution stability, other blanint are preferably used in low Menken susanaen with dta Athylendiaain. NEN to for this purpose suitable organic diamino include diprimary and disskundären organic diamines, for example Triraethylendiamin, m-xylylenediamine, 1 "3-Cyoloüezylendlaffiin and Piperasin" The preferred © operation gemäee the present invention comprises the application

"of polytetramethylene ether glycol with a molecular weight of 1800» reaction with p, p'-methylenediphenyl diisocyanate in a molar ratio Dilsooyanatzulykol of 1.7 «1 and acechlleeeende chain extension with a mixture of organic diamines, the 80 mol ϊ ethylenediamine and 20 mol% 1 _s 3 ~ Cyclohexylsndiaaiii comprises "to regulate the molecular weight of the segmented polyurethane can also during chain extension ein® small amount of an agent kettenabsohliesatnden _r ispiele% #% @ ise Diäthylasdn

) or Cyclbhezylamin, are added. Haoh termination of Kettenverlängerungssohrittes can Susätse as Antioxytiantien, matting ₉ PhotostaMliaatoren and · "same be mixed into the product"

The method according to the invention can be used in a more conventional manner Polymerizat! Setaäiö the preferred me the de the LoemigBiiOlyiaerisatidH are the Reaction partneliaer, ö, h "the polymer with terminal

V ■

L-126 Γ

Ieocyanate groups and the organic diajain can be dissolved in separate portions of a suitable solvent which also serves as a solvent for the resulting polyurethane, which consists of segments. Two solutions are then dissolved. aann mixed; t una a period in Dereich vcn üis few minutes to several hours at a temperature between ⁰ ° C unc about 100 ⁰ C stirred. During this time, the viscosity increases and the polymer can be obtained and purified by customary methods. Suitable solvents for the Polymerieationareaktion include N _r N-Dimethylf orctamld't Ν, Ν-Dlinethylacetamid, N-Methy! Pyrrolidon, Hexamethylirhosphoraaid, methyl sulfoxide and tetra-diethylene sulfone. Alternatively, other polymerization methods can also be used, for example those in the ÜSA patent application 2 3Π 8 '. 2 described bind, be applied

The advantage of producing the polyurethanes consisting of the outer segments in a solvent is that the solution can be used directly for the production of films, threads, coatings and the like. The coatings Filme.oder can be prepared by the solution ⁴ is poured or otherwise applied, with könnej by evaporation of the solvent, a thin film bildeti threads! from these solutions obtained by conventional methods

009849/1986

169A767

which include dry spinning and wet spinning. The stability of such polymer solutions is of obvious importance in technical Irookenepr.nn and wet spinning processes. The process according to the invention is therefore particularly advantageous if the polymer is produced in a solvent, from which threads are spun. Shaping and polymerisation can also be combined in a single step according to the process described in US patent specification ⁽ Reissue) 246ü (), commonly known as Chemicoh-Spinneri.

After the spinning process, the threads can be drawn to a length in the range from 1.2 times to 1.8 times and then drawn relaxed before they are wound up. This treatment is easily achieved by in the usual way the pad loading rolls and those below the spinning cell The applied roll-up reels are run in a suitable manner will. ίο the second feed roller is driven faster than the erete feed roller and the The rewind is run at a slower speed than the: wide feed roller, the tension ("Strength") of the weights during the subsequent stretching The elastic threads produced according to the invention are particularly useful in medical applications Strupfen »! Corsetry, bathing suits, sock laces and

BATH 0 984 9/198 6

elastic garments of all kinds.

The segmented polyurethanes described herein and made according to the invention, which are most useful for making films and threads, have an intrinsic viscosity in the range of 0.9 to 1.1. The intrinsic viscosity is based on the limit value of the printout.

H -To

when the concentration approaches 0, where η is the viscosity a dilute solution of the segmented polyurethane, η is the viscosity of the solvent in the

Io

the same units and at the same temperature and c is the concentration in grams of polyurethane per 100 ml of solution. The details given herein Intrinaic-yiskosität values are measured in hexamethylphosphoramide at -25 ⁰ O. The products ₉ obtained according to the invention, which have an intrinsic viscosity in the range from 0.9 to 1.3, provide particularly valuable elastic threads.

The following examples are intended to further illustrate the invention

9.

00 9849/1986

sohauliohen without restricting them. Unless otherwise stated, the parts and proportions are weighted. The expressions P- ₀₀ and P ₂ OO ^refer to tension values ( ⁿ St ^; irkewerte ⁿ ) without load in the fifth cycle for the respective elongations given as indices, according to the following cycle, yarn is stretched five times between 0 and 300% with a constant elongation / a speed of 1000 % per minute in the cycle. The sample is held at the maximum extension for 30 seconds after the fifth cycle to allow a voltage drop. Then the voltage is measured upon release from this last cycle "At the end dee fifth cycle, the Garnlitoge is measured and (" set ") in determining dor described below deformation used · A Aligleiten the yarn sample xu the holders of the test instrument is to be avoided" by "providing for a non-gliding spawning of the tea prototypes". . . ■ "... ^: _."; .. '

The own liability »measured as in the above Absata are important in evaluating an elastomeric yarn for use in bare or bare clothing State. The circulatory limit 300 5 "Dehnung et" lit die normal mazimal extension represents a yarn during the Clothing manufacture and the use of cladding

10

00984-9 / 1986 <

L-126 H

will. ! The wirkeane strength in KX)? '> 200 ο from ί Uni th cycle of unbelloteten curve simulates the Elaatomerdehnungen that occur during dee wearing a fabric "Since the carrier beita these fibers use only bie about 100 he stretches, lies the importance Tina dee P _1ÜO -Vrertes on, the hand. The greater this value is for the elastic fiber, the greater the "holding power" that the finished item of clothing has. Ui. P ₁₀₀ and P ₂ OO ^e * ^{n <} * * ^{n values of the i} examples are expressed in units of grams per effective denier obtained by dividing the tension in grams by the denier of the yarn at the indicated elongation.

The term "deformation" refers to the increase in the length of the sample as a result of the five-cycle tests described above and is expressed as a percentage of the original length. A low value of the deformation is desirable because it results in a higher retraction force when the load is removed, especially when the elongation is low.

The term "elongation at break" refers to the percentage elongation at break in the sixth cycle. In the fiber test, three oarn strands are tested at the same time. The elongation at break will have been when the first strand breaks.

009849/1986

1-126 W-

which gives a value lower than the average for the three strands. In the film test, only one sample is examined at a time. The elongation at break is determined for each

Rehearsal be & tlmat. Examples 1 bla 4

A stream of polytetramethylene ether glycol, which has been carefully predried by treatment with a molecular sieve and has a molecular weight as shown in Table 1, and a stream of liquid p, p ^f -methylene diphenyl diisocyanate are fed into a mixer kept at about 50.degree The reagents are intimately mixed for about 1 minute and continuously emptied into a jacketed line which is kept at a temperature of 75 to 95 ^° C. In the line (average residence time 90 to 100 minutes) the reagents combine to form a polyether with isocyanate end groups. The isocyanate-terminated polyether is fed to a high shear mixer containing a rotating log and an 11, N-dimethylacetamide solution is added to make a mixture of about 45 % solids. The mixture is stirred thoroughly for about 15 minutes and then transferred to a container ₉ in

009849/1986

L-126 13

an approximately stoohiometric amount of the chain-lengthening diamine, which contains a mixture of ethylene diamine and a co-diamine, as indicated in Table 1, together with 0.12 to 0.16 moles of diethylauain per mole of diamine and with further diraethylaoetamide as one stream is given with vigorous stirring. The molar amount of diathylaaina per mol of chain extender is measured in such a way that the Löaungaviacoaität given in Table 1 is obtained. The mixture is zt a reaction chamber conducted, wherein it is held by 20 · ⁰ to 100 C for about 2 bia 3 Minuten.auf a temperature. To the Polymerieatlb'eung a slurry of titanium dioxide in Diaethylaoetamid and a solution of Polydiethylaminoäthylnethaerylat, 2- (2 ^f -Hydroxy-3'-t-buty 1-5'-methylpheny 1) -5-chloro.benjstriaeol, 1, 3 '-. $ 5-Trimethyl-2,4,6-tria- (3,5 ^ di-t-butyl-4rhydroxybenByl) -benBol and ultramarine blue pigment given in üimethylaoetamid, eo that the enemia odor 4,7 #, 3 5 · , 0.5? Ί, 1 Φ or ■. Contains 12.5 ppm of the respective additive, based on the polyurethane consisting of segments. When the turbid Auetreten Polymerisatlöaung has at 40 ⁰ C a Viscous did!, As indicated in Table (measured within several hours), and contains the indicated in Table 1 the percentages of solids from existing Segaenten einaohlleaalloh polyurethane additives. The intrinsic viscosity of the segmented polyurethane is in the range of 1.1 to 1.2.

- 13 -

009849/1986

L-126

t «H

«4

A O «A

! 4 »η 4» « WJ-H ff ft

"2 3 p.

11-r «

«« 49 Ή

• Η Ο JOl O

> O 4 * (U

I Vi 4 "Vi" O

Jf

ouch

iiiiif

KV

KV

S S

ο uv rl

oo KV

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O O

KV KV

car rt

J!

se ». *. «· Sr · - M« β

8 S g

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f I l

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003141/1986

iS

The Miachung is βrhitet to a temperature of about 65 ⁰ C and trockengeeponnen in a conventional manner, wherein a koaleeBiertee varied spandex Oarn is obtained with 420 denier. Daa yarn is treated with a silicone-based finish and is stretched 1.06 times between two rollers below the spider cell. The yarn is then relaxed and wound up in the usual way. The properties of the yarn are shown in Table 2.

00-98-49 / 1986

Table 2

example deformation ^P 100 ^P 200 fracture
strain 1 19.5 0.033 0.075 480 2 19.3 0.036 0.076 471 3 26.2 0.030 0.065 575 4th 27.4 0.031 0.071 509

Unlike ien shown in Table 2 "results products with significantly lower values for PI ₀₀ higher Verformuig from Polytetramethylenätherglykol with a Molekularg3wicht outside dea inventive range and / ODSR at a molar ratio diisocyanate: get Po \ y ether outside the erf indungsgenrieaen area

The yarns of Examples 1 to 4 are examined for discoloration when exposed to an artificial atmosphere, which simulates smog, and it is found. " dasss they show a relatively low discoloration "Other samples of these yarns werien ^v respect tested chlorine discoloration by si · * are immersed at 70 ⁰ C for two 20 minute periods in an aqueous solution, 1500 ρρα sktv.-it keeps chlorine en "In comparison a with commercially available a iJpar.-lex-Jarn, Cd by chain lengthening with" hydrazine

0 09 849/19 8 6

"AD ORIGINAL

has been held, the yarns of Examples 1 to 4 show a much lower level of aluminum discoloration »

Examples 5 till 8

Polytetramethyle: lätherglykol marked with a molecular weight, as shown in Table 3, for two hours under nitrogen with ppp'-MethyleiLdiphenyldiisocyanat in the shown in Table 3 Mo ratio Dii8Ocyanat: Polyä.therglykol heated to 85 ⁰ C, "10 x) parts of the thus Polyethers produced with isocyanate groups are dissolved in 100 parts of diethyl acetamide. To this solution a stöehiometrisohe amount of a mixture of Diarainen that unt of 80 mole i "ethylenediamine. 20 mol $> of the given in Table 3 Kettenmitverlängiirers consists, together with 207 parts of whore thy Iac et am i d ui.d sufficiently diethylamine, to control the intrinsic viscosity of the formed segmented polyurethane so that a value within the range * tos, 1.2 to 1.8 is obtained . The polyurethanes made from segments in this way have the intrinsic quality values given in Table 3 »

16 -

009849/1986

169A767

L-126

Tabel

MoI-

For polyether ratio play Mol.Gew. SÜBocyanat /

Polyether

ν 7

1780

1780

V680

1680

1.8

1.8

1.65 1.65

Chain extender

Intrinsic Viscoeitat

1,3-Cy ₀ IO-1,77 hexylenediamine

4,4'-methylene. 1.41 dicyclohexylene- « diamine

1,3-Cyolohexylenedlamine 1,26

N-methylimino-1.34 bis- (3-propylamine)

The solution of the polyurethane covering the segments is cast in a film about 0.432 stroke (17 miles) thick. The elastic film is cut and dried ir thin strips overnight at 5O ⁰ C, which are dried in a relaxed condition for 10 minutes at 130 ⁰ C on. The strips are boiled for 5 minutes in a relaxed state, dried and measured as individual strips for deformation and elongation at break. The values obtained are given in Table 4 *

17th

009849/1986

L -126

Table 4

Example deformation
= ■ -i · fracture
strain
* » 27.8 572 b 26.7 534 7th 24.7 536 a 26.0 585

■ 8

009849/198

Claims (1)

P 16 9 * T6T. * - * 3 19th IUd 1970 L-126 / P * 1 323 P t t ι ρ t a κ β ρ r ϋ ο in % 1. A process for the production of a linear polyurethane consisting of segments by reacting a polyether glycol with a molecular weight above about 600 and a melting point below about 50 ⁰ G with an organic biisooyanate in a molar ratio Diieooyanat: ßlykol greater than 1 * 1 with the formation of a polymer with Isooyanatfndgmppen and low molecular weight and aneohlieeeeiicie ümentzimg of the resulting polymers with I8ooyanatendi; 'groups with a stoichiometric in substantial amount of an organic diamine, wherein the Diisooyanat and daci diamine are complementary monomers that a linear Harnstoffpolymerisat having a melting point above 2CiO ⁰ C and a molecular weight can form in the fan-forming area, characterized in that one (1) as a polyether glycol component, polytetramethylene ether glycol with a molecular weight in the range of 1200 until 2000, (2) a from p, p ^f ~ methylenediphenyl diisocyanate, ρ, ρ'-Ιβο-propylidendiphenyldiieocyanat, ρ, ρ'-OxydiphenyldÜBooy'anat, p, p ^f -thiodiphenyldi8ocyanat and homologous di- Q09849 / 1986 isocyanates, the methyl and ethyl substituents on the Rings contain selected organic diisocyanate, the organic diisocyanate in a molar ratio DiisooyanatsSlykol in the bar range from 1.5 * 1 to 1.85 * 1 used will, and (3) an organic diamine that is made up of at least 60 moles Ethylenediamine is used. 2ο The method according to claim 1, characterized in that the tetramethylene ether glycol has a molecular weight of 1500 until 1950 hatο 3. Process according to claim 1 or 2, characterized in that the diisocyanate: glycol ratio is in the range from 1.6: 1 to 1.75: 1. 4 «The method according to any one of the preceding claims, characterized in that the organic diamine from ethylenediamine together with at least one of the compounds triethylenediamine, m-xylylenediamine, 1 _P 3 ~ cyclohexylene. diamine, piperazine, 4 »4 '~ A * ethylene-dicyclohexylenediamine and N ~ methylimino-bis (3 ~ propylamine). . 50 method according to one of the preceding claims. ila ■ ■ 20 / ' - 0 0'9 8 49/1 9 8 # ^ ® '"" characterized in that the polytetramethylene ether glycol has a molecular weight of 1800, the bioyanate is p, p'-methylenediphenyldiisooyanate, the molar ratio of diisocyanate glycol is 1.7 * 1 and the organic diamine is composed of 80 mol $> ethylenediamine and 20 mol # 1 _f 3- Cyolohexylenediamine consists. 6, * Linear polyurethane consisting of segments, characterized in that it consists of stoichiometric quantities from (a) an organic diaoin, of which at least 60 mol % are ethylene diaaine, and (b) a macromolecular intermediate with isocyanate end groups, wherein polyether residues of the formula O- with aromatic radicals of the formula -Ar-X-Ar- via links of the formula OH Ii ι ' -C-N- alternate in which the free valence of nitrogen on Ar gebußde 'is: i, η is an integer that gives a molecular weight between 1182 and 1982, Ar p-phenylene or on the ring with methyl and / or ethyl groups su> atituated homologues thereof and I ? ^H 3
'one of the groups CH ₂ , C, ο and S means formed CH " ²¹ " 009849/1986 willι where the ratio of aroaatisohen residues eu the Polyätterreeten la range of 1.5: 1 I) Is 1.85t1 and the organic diaraine and the dioxyanoate OCH-Ar-X-Ar-RCO are complementary monomers that make a linear urea polymer may form a Sohmelapunkt above 200 ⁰ C and a fiber-forming molecular weight in the range. ?. Linear polyurethane consisting of segments according to Anepruoh 6, characterized in that Ar is p-phenylene and X is the CH ₂ group _β 8, Shaped objects made of a linear, segmented polyethane, the duroh conversion of a FoIyätherglykole with a molecular weight above about and a melting point below about 50 ⁰ C with an organic diisocyanate in a molar ratio diisocyanate glycol greater than 1t1 to form a polymer with low molecular weight and terminal isocyanate groups and ansokliessende reacting the resulting polymer with isocyanate end groups with a substantially etöchiometrischen amount of an organic diamine, wherein the Diieocyanat and that diamine complementary 'monomers bind to a linear Harnetoffpolymerisat having a melting point above 200 ⁰ C and a molecular weight in fiber-forming 009849/1986 Can form area «1st, daduroh marked that nan (1) ale polyether glycol component polytetramethylene ether * glycol with a molecular weight in the range of 1200 until 2000, (2) one of ρ, ρ'-methylenediphenyldiieooyanate, ρ, ρ'-isopropylidenedipheayldiisooyanate, p, p'-oxydiphenyl diisocyanate, ρ, ρ'-thiodiphenyldiieooyanate and homologous diisooyanates, the methyl and ethyl substituents Rings contain selected organic diisocyanate, the organic diisocyanate in a molar ratio Diieooyenati31ykol in the range from 1.5: 1 to 1.85: 1 is used, and (3) an orguniacaee diamine that is at least 60 moles> made of ethylene diaaii is used. Shaped objects according to claim 8, characterized in that the polytetraethylene ether glycol has a molecular weight of 1500 to 1950. 10. Shaped articles according to claim 8 or 9 »thereby labeled, let the molar ratio diisocyanate: glycol is in the range from 1.6x1 to 1.75: 1 » 00984971986 11. Shaped objects according to one of claims 8 "to 10, characterized in that the organic diaraine from ethylenediamine together with at least one of the compounds trimethylenediamin * m-xylylenediarain, 1,3-cyclohexylenediamine, piperasi.n, 4 _P 4 '•» methylenedicyclohexylenediamine and N-methylimino-l): iB (3 ^ propylamine) consists » 12. Shaped articles according to any one of claims 8 to 11, characterized in that the polytetramethylene ether glycol has a molecular weight of 1800 »the dubocyanate ρ, ρ'-Mettylenediphenyl diisocyanate is »the molar ratio Diissccytnat: glycol 1.7: 1 and the organic Diamiii from 80 moles of ethylenediamine and 20 moles of 1,3-CyOIohexylenediamine consists, 13. Shaped objects according to one of claims 8 to in the form of threads « 14o Shaped counter bands according to one of Claims 8 to in the form of a Pi Ims _c BATH 24 009849/1386