DE1769662A1 - Synthetic polyamides - Google Patents

Description

Folder 21687 - Dr.K.
Case PCο20330

Description of the patent application of

Imperial Chemical Industries Ltd., London, Great Britain

regarding synthetic polyamides

Priority: 26 _β June 1967 - United Kingdom

The invention relates to synthetic polyamide and MiochpolyainidzusaiiTmensetzungen for the production of molded articles, such as "filaments, bristles, yarns, films, and the like _Of possess improved resistance to deformation, and made therefrom objects,

The invention is particularly made with reference to threads, yarns and fabrics having improved durability

009849/1998

described against deformation; but this is not supposed to Restriction can be understood.

Aesthetic polyamides such as Mylon-6 or Bylon-66 have long been used in the manufacture of yarns and fabrics because of their desirable properties such as good wear resistance and high strength. Solo yarns and lextiles usually have a slack, foldable handle and easy rapier, and in some cases »like ζ „ Β. in the case of curtains, this slight deformation or foldability is an advantage. In other cases, especially in the clothing sector, yarns and textiles that are more resistant to deformation than are available with normal vylon yarns are an advantage Wear-resistant and inherent in the high strength of Hylon.

üin a well-known veg sur increase the resistance to deformation of the threads from which a nylon textile is made is »is the tanning. Either the finished textile material or the yarn used here can be treated for this purpose in a bath, which contains a tanning agent such as a.B. Gerbetture, contains. However, the effect obtained in this way can normally easily almost completely by heiflee Nasser or

009849/1998

Dastpf be eliminated, if there is no further fixation treatment, like ε.B. a TVrtmiKVhmg with metal salads, carried out will.

In the manufacture of synthetic polyamide or mixed polyamide yarns if the molten polymer is extruded through Löoher, to provide threads, which threads are then usually stretched in order to orientate the molecules lying therein and improve the properties au.

The treatment of twisted or undrawn threads, or of yarns containing them, in a top bath is not only an undesirable process, but it is also almost unnecessary, if these threads or yarns are in the form of a wound oarowel, to combine this treatment execute tanning bath in a practical manner, "the Qerbmittels was _β into your yarn package due to a difficult and uneven Sindringung

It is of course desirable that synthetic polyamide or polyamide threads can spin in the normal way, which threads after a possibly subsequently carried out Yeretreokung an improved resistance to deformation during cold surgery. Bs is also desirable that a

009849/1998

BATH

such improved resistance to deformation not by hot water or by steam treatment to a large extent Will get removed.

The resistance of a thread to deformation can be in resistance to stretching or bending. This resistance can for example with the help of dea Modules like to become BBQn. The modulus of elongation can be defined by the force per unit area which is required »a thread and a given percentage of its original Stretch length. The flexural modulus or flexural rigidity can be defined with the help of the force pair that is required to move a thread of given dimensions around one another to bend given angle. In the case of synthetic polyamide or polyamide threads, the bending element is in one positive connection with the elongation modulus, and for this reason this latter property usually becomes eur definition the entire resistance of such threads to deformation is used.

The elongation modulus can be adjusted with the help of a suitable elongation percentage be expressed. In this description the nominal module of £ 1 is commonly referred to as the initial module. The starting module will be for a thread or a yarn like is measured as follows:

0 09849/199 8 * ² * ^{6 / f} "^; - ^:

Sin 50 cm long piece of thread or twine will be diner with

its original length
Speed of 10 $ 6 / min on an Instron theater in a building atmosphere of approximately 67S * relative humidity and 22 ⁰ C
stretched, The tension in the yarn changes depending on the degree of
Elongation, and the two variables, length and tension, are automatically plotted by a device. The axial stress / elongation a gradient at the point where the elongation is approximately i £ is multiplied by 100 and divided by the original yarn denier. The resulting "number is designated as the initial module"

An object of the present invention is to provide a combination su create one or more synthetic polyamides or Hisohpolyaiaide contains, which composition sohaelsgeeponnen or otherwise deformed and, if necessary, pre-stretched to provide threads, bristles, yarns, filae and the like in an improved manner Share out resistance to perforation "

Bb is of course desirable that such threads, game and the like
duroh the gewöbnliah methods used for this purpose can be deformed, such as * .B, puckered or puckered.

The fnifiwMinttinncm dtr present charge contain a

»YntbetUöh ·
or aenrera / polyaeidt or Miechpolyaiiid · «with a etatietchen or eit a Kooknature.

009849/1998

The three important criteria for the polyaidsusosuinsetungen of the present invention are of course the following:

1) You should wor des Scheela pins at elevated temperatures or deform be stable;

2) They should be spun or deformed and possibly burned away will know

3) The other properties of the objects made from it, such as B. Strength, should at least be B. satisfactory, and preferably even improved be"

Since many of the tools used in watery louvers, are phenolic compounds, these compounds were fttr den 2usats «u feschaolsenen Polyaaldan, In tMrtraokt sjMMtgfn. furthermore, phenol-free compounds are htarfl £ in small ones

su g »sohaol — nsn Polvaeiden sugeeetst, especially oxfdatl degradation advise.

8 " iMi jedooh mn & miA know that" some phials, "ssj", are metMtst in considerable quantities, su one "shared (firing""r geeohaoT aenen Poly wide (as is the case with belsvielaveise bein simple pbenol), AnUI Ba wa $ " also revered that the addition of pbsnolisehea Terbtndus""au feeohaol — nen Poljnaiaan Ib quantities up to 400 A" n iaTsjss

009849/1998

The objects are more resilient. Increased compliance iet an effect in the present pail is exactly the opposite of the desired effect.

Bb, however, has now been found to be a class of phenolic There are compounds which, when mixed with molten polyamides or miooh polyamides, are those made therefrom Do not give objects an increased resilience, but surprisingly their resistance increase compared to deformation.

The phenolic compounds according to the present invention also have the surprising advantage that mixtures of the » same «with polyamides or mixed polyamides la melted State sufficiently thermally stable that normal melt spinning or deformation can be carried out, too if these mixtures contain a relatively high proportion of the Contain phenols. Articles made from it can be stretched in the usual manner to make usable to manufacture pre-stretched articles with improved resistance to deformation.

The phenolic compounds for use in the present Invention are essentially pure, well-defined chemical compounds with a characteristic molecular structure

009849/1998

important that practically agrees with the ohemiechen formula " and are not impure oligomers or mixtures of oligomers or polymers or hareses. Si * «earth continues never follows defined *

a) They contain one or more Benaol rings Ib molecule »

b) There is no more than one hydroxyl group on each bond bound"

o) at least one solenoid is a hydroxyl group bound)

d) if the molecule contains fewer than four bensol rings " then let the Rlngwaeeerstoffatoa in one or both Orthodontics had one for each hydroxyl group secondary or tertiary alkyl groups, elneohlleilioh Cycloalkyl, aryl or aralkyl group, substituted,

e) each connection should be a Auanaß of 1-40 percent _a - £ in Miechung with one or nebreren Polyaaiden or Mieohpoly · "aadden löelioh be.

The size and nature of the Substitution groups or the Ansah! the oil rings Ib molecule beetlBaen, are the solubility of the compound in the polyamide or Kiechpolyamid and the formation of a ZueaanaeetBung, which is extremely thermally stable, so that it is sohmels-spun or can be deformed and possibly deformed »über Oegonstän ·

0098A9 / 1998

~ Q M.

to produce de with an increased resistance to defibrillation »

The length of the phenol molecule can be modified by any suitable Group or chain linked »a, for example duroh methylene groups or chains, or by SuIf on or Amide groups and the like that meet the above requirements to be met.

One or more such phenolic compounds should be im Polyamidgemiach be present »that the objectives of the present Invention to be achieved · Overall should be a total between 2 and 20 hydroxyl equivalents per 100 anid equivalents and preferably between 3 and 10 equal equivalents be"

By the term "hydroxyl equivalent" is molecular weight in grams of the phenolic compound divided by the number the hydroxyl groups in the molecule.

With the expression "100 amide equivalents" let the molecular weight in Öraam an assumed polyamides or mixed polyamides, which contains 100 carbonamide groups, means

009849/1998

- ίο -

Although practicing phenolic compounds old one or twelfth struggle in the molecule with regard to the enhancement of resistance to deformation one effect as "the preferred phenols contain three or more bensol rings in their molecule,

The subject of the invention eats a Zuaaansnsetsung a or contains several synthetic polyamides or mixed polyamides, which additive sohmelsgeeponnen or deformed and possibly can be pre-stretched around thread, bristle, yarn, film and other things to produce with an improved resistance to de-oreation » This is because the Zuoapnensetung contains a phenol, which is essentially pure, well-defined chemistry see connection with a “characteristic molecule” is * which can be derived from its chemical formula, and which is not an impure oligomer or an oemisoh of oligomers or a Is polymer or a bare and which is further defined as follows

a) «s contains one or more bensol rings in the molecule,

b) no more than one hydroxyl group is bound to each bensol ring »

c) at least one bensol ring is a monohydric hydroxyl * group bound »

d) if the molecule contains fewer than four Benaol rings, then the hydrogen atom is in one or both

009849/1998

BATH

Orthoetellungen mn each hydroxyl group by a secondary or tertiary * alkyl group, a noMieilloh cyoloalkyl, aryl or arcdkylgruppe, substituted, e) it should be in an amount of 1-40 wt .- ^ i in a mixture with one or more polyamides or misohypolyamides be"

with one or more such phenols in an amount «wiping 2 rad tO hydroxyl equivalents per 100 aml equivalents is, whereby the Hydroxylöquiraletite ale dme NolekulArgewioht in Oraian of the phenolicobes connection divides by the Anaohl of the hydroxyl groups in the molecule is defined and where the named laidUlquivalente duroh da · molecular weight in Qraaa a common polyamide or polyamide, welohei Contains 100 carbon amide groups, defines let »

The pbenoliaohen connections apply to the PoQLJfMBiA with everyone stage dead the Sonael plans or deformations can be specified. For example, they can be used in the manufacture of the polyamides be given "and" was Toraye-like corsage before this is poured, around granules, which are then used in the sebum spinning · Alternatively, they can be mixed with the granules mentioned or mixed with the polyamide in the Sohmelsepinn- or Yerrmngevorriohtung can be suggested.

009849/1998 construction

~ 12 -

In another ewooka-like procedure, the addition of Prepare granules that have a suitable mixture of one or more polyamides or mixed polyamides !! contain and a high prosentaats to one or more of the above Have connections. Such consolidated anticipated ones Granules can then be bit in a suitable ratio Polyamides or Mieohpolyasiden, which for the Sohmelssplnnen or Deform to be used »to be mixed»

Examples of compounds used in the manufacture of the * dungagem8 & en compositions are used in table roped

The charge will now be explained in more detail using the following examples « The examples are not to be construed in a restrictive sense.

example 1 Sins each of the compounds shown in Table 1 was used in Ijrlon-66 by stirring continuously for 15 bin at 2BO ⁰ O in a stiok-

stoffatHOsphare dissolved. The Oesdsons, which contained 4 parts of the compound, were cooled, and the products were spun, from the spun pleasure to manufacture, the csfan

endless Ρφβη. of each about 9 contained. These (were then camouflaged under the conditions shown in Table 2

009849/1998

BATH ORIGINAL

cold and hot Yerstreäkt; Both the nutshell and the spreading were good. The treetop games were then immersed for 15 min in low-temperature water , dried in air with approximately 67 relative humidity and 22 ⁰ C 24 at, whereupon their initial modulus, their elasticity and their tear strength were measured.

The tear strength is the tear load of the yarn, expressed in g / den. The elasticity is the length of the yarn by which the yarn can be stretched before breaking, expressed as a percentage of its original length · The initial modulus is as defined above. The results obtained are in Table 2 as a function of the number of phenolic sols Hydroxyl groups in the molecule of the phenolic additives β decreased Ss it can be seen that none of the stated compounds have a unacceptable change in elongation or tearability and that in general the initial modulus increased with the number of hydroxyl groups in the molecule »

Folyamide to banana compositions containing various amounts of the compound III <Table i) , which compound had been prepared as described in Example 1, were spun and extended to produce games which were tested as described above

009849/1998

The results obtained are shown in Table 3 * From these results it can be seen that the initial modulus, with the amount of additive increases, without the other properties being seriously changed. In all cases, of course also in the absence of the additive, decreased Cooking changed the initial modulus and aaoh other properties, but if 10 * Zueats was present »then the initial modulus after boiling was as high or almost as high as the value for the normal yarn before Äeja boiling ·

Example 3

A mixture of 92 ropes of Bylon-66 and 8 parts of compound HI (Table 1) was produced according to the procedure of Example 1 and was spun as a cream before production. This yarn was drawn with different draw ratios in order to produce yarn with different extensibility glides. The connection swteohen dem ^ ^ ^ ff PCftntodTii uxkL der D oib ^^ B ^^ (Ar * \ * _{t for} both the cooked and the uncooked 0am ₉ is inclined in fig. I. Bs can be seen that the module increases the effect of the Zueates is available for all disabled persons

Examples 4-28

More polyamide and misoh polyasLldmisamiBeneetsangen were produced, the different quantities of different Stwnale according to the invention revealed that the compositions were spun

0098A9 / 1998

BATH ORIGINAL

and reretreolrt, among other things, yarns made of 5 threads of approximately 50 those, which stretch such as approximately JO and Taeeaflen.

The additional yarns were boiled and their initial module measured as described above its extensibility decreases and the initial modulus takes on, inter alia, the increased modules of the Oarna, which were produced from the inventive Sueamniensetungen roa Table 4, show these modules with the modules that correspond to the same elasticity of the polymer does not contain any phenolic ingredient * (see examples as in n «. 1).

0098A9 / 1998

Table 1

Connectionp-
Mr. Ohemiaoher Kant 1 2,4-dimethyl-6-t-
butylphenol II 2,2'-methylene-bi »-
(4-ethyl-6-t-butyl-
phenol) III 1 _t 1,3-Irl [(2H »tlvl-
4-hytoxy-5-tl * rtyl-)
phenyl] butane IV 1 ή _f 5,5-Ietraß2-Mtnyl-
4rhydroxy-5-t-Vatyl) -
ph «nyljp« ntan

009849/1998

Table 2

pheöli— ee groups in the molecule of Zuöata toffee

Connection] jdung in
[Hyloa-66

▼ inherited 5.0

staple
after d <
Boil

Stretching at
Rough temperature

pile S, 5

Stretchable—
speed %

Maturity / it

14.8

36.7

5.41

1β, 9

33.2

5.39

20.1

30.0

5.39

25.3

30.6

5.01

25.2

30.5

5.18

de »

21.2 26.0

speed

EissfQbility g / den

6.70

25.1

22.4

7.10

27.7

24.5

6.33

31.6

■■■: ■■ ■ ri

009849/1998 ORIGINAL INSPECTED

module
g / den 100 each 0 1.3 2.6 3.9 5.4 6.9 Stretching 0 2 4th 6th 8th 10 Bydroxylaquivaxvxree
Afflldäaulvalente Äelöfe-
etig-
speed
g / den before the 29.7 37.6 56.3 41.6 43.9 43.4 % Connection IH Start- 14.8 21.1 25.3 25.8 27.5 32.4 Stretched
kung at
Room temperature
temperature
▼ he
atreok-
beh & l-
never 5.0 module
g / den well that
Cook 19.3 16.9 16.6 20.1 20.2 20.2 Veretrefc-
kong over
one
hel0 «a
Blaffe
180 ⁰ C
Yer-
etreok-
never 5.5
(• 5.25) Dehnf &> ■
% ·. before the
Cook 36.7 28.2 50.6 37.9 37.0 40.9 Celt
g / den well that
Π nifrCUVH 5.79 6.04 6.55 6.05 5.80 5.72 5.41 5.01 5rO1 5.22 5.01 5.23 before the 40.8 42.9 51.3 * 61.4 62.4 well that 21.2 23.7 27.7 24.3 28.8 34.5 * 13.3 12.2 2.2 11.9 11.0 12.9 * before the 25.6 26.1 4.6 26.0 » 24.2 26.7 * 7.80 ■ ** ■ 8 * 26 7.30 · 7.61 7.46 * well that 6.71 6.33 7.30 » before the
Koohm well that
Cook before the well that.

0098A9 / 1998

example
Ir.

Polytunid
or
Mieoh »
polyaadd

phenolic

eohtr

Zueate

Zuaat * - properties dee Contentration correct

lente U A «ld-

In the*·

■ module

Hylon-66

Dleethyl-bie-

7.7

pen in

den ^ ydroxyl-41

18th

Wylon-66

l A 6.9

pen In
long sa den yroxyl ^ groppen)

5B

21

2,2-di- (4-

bydroxy »?" ■ ethylphenyl)

7.7

41.1

17.8

Ρτ1οη-66

tocay-3,5-

6.9

57.7

«1.3

feyloa-66

fdroiy ^ 3.5-

5.5

phenyl) -pro « 36.7

23.0

009849/1998

Nylon 66 XaMlIe 4 (I. \ - & r
phenyl) * Ler Ua-
nriecaen
tttaren 6.3 ietsunf) 37.3 31.9 9 Nylon 66 1,1,3-dr
dimethyl 2,2,5,5-tetra
dimethylphenyl) -
hexane 5.9 5.4 37.0 26.2 10 Nylon 66 putan tert · -btf 8.3 5.0 38.7 24.8 11th Nylon 66 nyuroxy-i
phenyl; »
benaol 8th 5.5 38 29 12th Nylon-6 byl-4 ^
2-o »ethyl
rthyl) 0 5.43 45 10 13th Hylon-6 metoyl-4-hydro-
butyl) phenyl)
butane 8th 0 45 13th 14th Nylon-11 It tt 0 5.4 44 22nd 15th Nylon-11 It It 8th 0 44 32 16 MXD /
Hylon-6 It H 0 8.7 30th 56 17th M. It N 8th 0 31 61 18th N It 7.7 5.9 Iylon-6e It 1 » 41.3 19th Product (
setAuug ι 5.0 • llffAhwn Ϊ and DiiuBJ peHoli fleas
Store
2-hydro
xy-p ^ to- re

009849/1998

3 * abe! LLa A

20th Nyion-66 2-HydroJty-
p-toluene
acid ha-pheny-
U.-
diamine hydroxy
»Ethyl« ·
pheoyl} -
valerian
acid
(Tetraiw-
thyldiphe-
nolefture) P-PheooylenJ
T ¹ I £ itn * i.Vi I Γ 5.0 39.7 24.2 21 Nylon 66 η p «· Amino—
oyolo-
heyyl-
jnethan S-
r ' . - 9.6 5.0 33.8 28.0 22nd Nylon 66 3,3-Di-
phenyl)
Telerlan
acid
(Diphenol
acid) p-pheny-
lendia-
min te. 6.7 5.0 31.8 28.4 23 Nylon 66 If o-pheny-
lendla-
min « .*O 29.2 32 _# 6 24 Nylon 66 7.5 5.0 34.1 26, T. 2 * Nylon 66 diphenyl 6.9 5.0 44.8 26th Nylon 66
'-Μ 7.7 V, W- 40.6 25.1
j * ■ 27 «Ylon- <| 5.0 43.1 28 ΠΙ f 33.6

009849/1998

ORIGINAL INSPECTED

Claims (1)

Claim ZueaBttenoetsunf, dl · one or more synthetic polyanides or mixed polyamides, which additive nnTwrrti spun or deformed and possibly veretreokt «earth katm, ov Thread, bristles »flame, Fllae and the like old of an improved Defornationsbeetändiekeit create, thereby marked that the door is set Contains phenol, which unites in the purely · »well defined · Unique compound with a "character!" and high molecular weight is different from your unique Voxnel is, tttkä which is not an impure Ollgoeer or an öemleoh aue OUeTOMeren or a polymer or a resin and which one is further defined as follows: α) «s contains. one or more bensol rings la molecule, b) at every bensol ring is not very much considered a droxy group bound" o) a single hydroxyl group on at least one surface bound, d) mention that the molecule contains fewer bensol rings than animals then let the Ringwaeseretoffatea in either or both 009849/1998 Ortho positions on each hydroxyl group by a eecondary or tertiary alkyl group, a little different Cycloalkyl, aryl or aralkyl group, substituted, e) it should be in an Ausaafl of 1-40 Gerr, - ^ In Hieofanng with one or more polyamides or Mieohpolyajdden soluble eein, wherein one or more such phenols in an amount swisohen 2 to 10 hydroxyl & quiralenten 100 Aaidäqnivalenten is present, the hydroxyl vobei than the molecular weight in Grtunm the phenol laughing compound divided by the hydroxyl groups of ten genann-ix molecule defined let and vobei the / Amidäquivalente diiroh the molecular structure in Grame of an approximate polyaide or Hieohpolya «ide, contains almost 100 carbonaaid groups, defines it. Dt.-INO.H.HNCtt.Oin -INO H «Λ.ΙΝΟ.S STAIGfI 009849/1998 ti Blank page