DE2317472A1 - FIBERS WITH HIGH TEAR STRENGTH - Google Patents

Description

The present invention relates to the manufacture of yarns by melt spinning poly (ethylene-1,2-diphenoxyethane-4,4-dicarboxylate).

The present invention provides a method for producing a yarn from poly (ethylene-1,2-diphenoxyethane-4, V-dicarboxylate) or its mixed polyester proposed, with poly (ethylene-1 ^ -diphenoxyethane- ^ j ^ '- dicarboxylate) or a mixed polyester thereof is pressed under such conditions to thereby become a spun Yarn with a birefringence greater than 60 χ 10 ""%, however does not have a value to be determined by the equation

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Δ - 7 χ 10 " ^δ W + 50 χ ΙΟ" ⁵

is expressed in which & ■ is the birefringence of the spun yarn and W is the winding speed of the same, which is then followed by an orientation of the threads by stretching.

The birefringence of the spun yarn should preferably be above 110 χ 10b and the value that is determined by the equation

Δ * 5.4 χ 1Q ~ ⁶ W + 50 χ 10 ~ ^{5 is} expressed, do not exceed «

A mixed polyester of poly (ethylene-1,2-diphenoxyethane-4,4'-dicarboxylate) is understood to mean a mixed polyester in which at least 90 % of the structural units of the formula

- CO - ff y- O - CH ₂ - C & 2 - Q -ff ^ - CO - O GH ₂ -CH ₂ - O X = / V = /

correspond. Such mixed polyesters can be in the chain contain small amounts of other structural units, which are derived from glycols, and swsr arideren than ethylene glycol and / or of dicarboxylic acids, and av / ar other than Bis-1,2- (parecarboxypb.enoxy) -äthsn and / ode? from one Hydroxycarboxylic acid.

The poly (äthy len-1,2-diphenoxjätEsn »'! -., ^ - ⁸ or its mixed polyester, which can be used according to the invention, can be produced by known processes and it can contain finer or multiple additives,

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for example anti-glare agents; Pigments, optical brighteners or contain stabilizers.

The yarns made according to the invention are special Value if the poly (ethylene-1,2-diphenoxyethane-4-, V-dicarboxylate) or its mixed polyester of which they are made, an intrinsic viscosity greater than 2.0, measured in orthochlorophenol at a concentration of 1 g per 100 ecm of solvent and at a temperature of 25 ° C,

It has been found that it is advantageous to carry out the working process according to the invention in such a way that that the spun yarn is amorphous, while it still has a high spin birefringence. The advantage for one amorphous yarn is based on the fact that the crystallinity in the spun yarn results in lower extensibility in the drawn product. "Amorphous" means that when tested by X-ray refraction none Crystallinity is established.

The crystallinity of the spun yarn can be regulated by appropriate selection of the intrinsic viscosity of the poly (ethylene-1,2-diphenoxyethane-4,4 ^l -dicarboxylate) and by the parameters of the melt spinning. So the crystallinity is favored by increasing the tension, which in turn is increased by increasing the intrinsic viscosity, by increasing the spinning hole diameter for a certain spun denier value, by reducing the temperature of the poly (ethylene-1,2-diphenoxyethene - ^^ '- dicarboxylate ) when squeezing out, by increasing the cooling rate in the melted area of the paden line and by increasing the amount of draw-off when spinning.

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The ease of peeling in the formation of the spun yarn is inversely related to that The viscosity of the extrudate is constant and the two-dimensional spinning temperature will vary with the limiting viscosity of the yarn enlarge. It has been found that for intrinsic viscosities of 2.0 to 2.3 the appropriate spinning temperature is within of the range from 295 to 335 ° C. If higher intrinsic viscosities are present, it can be advantageous to use the Reduce the rate of cooling of the thread, for example by using a heated sheath like them is described in British patent specification 1,052,067, and this is more advantageous than using impractically high Auspresstemperaturen.

Spun yarns made from poly (ethylene-1,2-diphenoxyethane-4-, 4'-dicarboxylate) have the property that when heated under little or no tension, either shrink or spontaneously increase their length, which is due to the initial birefringence of the spun yarn and depends on the heating temperature. It was found, that if it is preferred to draw yarns with high birefringence, in this case less risk of undesirable spontaneous expansion before stretching exists when the value of the birefringence is at or above 110 χ 1o lies. Below this value, the spontaneous expansion of the product makes it difficult to control the tension of the spun Maintaining yarn when running over heated surfaces. ,

When the spun yarn spontaneously expands under zero tension as noted above, it also crystallizes and possesses the crystalline form (referred to as β-crystallinity) a monoclinic habitus,

The crystallization, which occurs under tension during the

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Spinning occurs, is of different crystalline form and has an orthorhombic habit (as 0 (-form designated). It has been found that during the crystallization under tension the C (-form arises. which under the spinning tension and during the drawing using only one drawing pin takes place, for example as described in British Patent Specification 1 04-7 978, in the (Χ form.

It has been found that in the production of high intrinsic viscosity yarns with high tensile strength a modification of the drawing conditions in such a way that the drawn yarns have a certain β-crystallinity is advantageous provided that the intrinsic viscosity is above about 2.00.

If the molten threadline is cooled by contact with the ambient air at room temperature, then it is in this case the ratio between the intrinsic viscosity of the spun yarn and the extrusion temperature is around to obtain optimal tensile strength properties of the yarn after drawing, given by the following equation:

Pressing temperature ■ (89 x intrinsic viscosity + 128) ° C.

One advantage of the method forming the subject of the invention is that it produces drawn yarns which have a tensile strength of more than 9 »5 g per denier and an elongation at break of own more than 7 #. Such yarns are particularly useful for the production of ropes and cords. The cords are particularly useful for making tires and V-bands where high modulus means good hydrolytic

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Stability and low shrinkage properties are desirable are. When using these cords to make The good lightfastness of the threads is a special feature of ropes Advantage.

Orientation by stretching, i.e. stretching, can be achieved by known methods can be carried out. Heated feed rollers or heated slide pins can be used here will. It has been found that the use of the sliding pins is particularly advantageous »

The invention is explained in more detail in the following examples.

Examples 1-20

Poly (ethylene-1, £ -diphenoxy-% 4 ^! «Dicarboxylate) with the intrinsic viscosity given in Table 1; (UV), measured in a 1% strength by weight solution of ortho-chlorophenol at 25 ° C., was melt-spun at the temperature entered in Table 1 are also listed in Table 1.

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Tabel

co ο co

Ex. number
the
Threads Spinning hole
diameter
in mm Limit
viscous
act d.
Yarn Extru-
sion
temp.
⁰ C Wrapping
temperature
⁰ C Winding
speed
age
m / min Birefringence
spun Yarn shape 1 5 0.9 2.04 280 no 152 8 χ 10 " ³ Amorphous 2 304 21 χ 10 " ⁵ η 5 457 58 χ 10 ~ ³ ti 4th 609 88 χ 10 ~ ³ CX-Po rm 5 762 98 χ 10 " ³ η 6th 1067 115x10 " ⁵ η 7th 5 0.5 2.00 501 305 304 3.2 χ 10 " ⁵ Amorphous 8th 609 11 χ 1O ~ ³ Il 9 914 22 χ 10 " ⁵ π 10 1219 55x10 " ⁵ η 11 1524 112 χ 10 ~ ⁵ η 12th 1828 145 x 10 ~ ⁵ η 15th 5 0.23 2.07 292 no 1372 152 χ 10 " ⁵ Of-Form 1* 5 0.23 2.05 505 no 1372 118 χ 10 " ⁵ Amorphous 15th 48 0.38 2.15 312 no 1372 155x10 " ⁵ CX form 16 48 0.58 2.07 311 no 1372 125 x 10 ~ ⁵ Amorphous

Table 1 (port setting)

co

(O OO

to

Ex. number
the
Threads Spinning hole
diameter
in mm Limit
viscous
act d.
Yarn Extru-
sion
temp.
⁰ C Wrapping
temperature
⁰ C Winding
speed
age
m / mm Birefringence
spun Yarn shape 17th 3 0.5 2.00 302 no 1219 139 x 10 ~ ⁵ Ö (-Porm 18th 3 0.5 2.00 310 305 1828 145 x 10 "^ Amorphous 19th 3 0.9 ■ 1.96 290 no 1524 150 χ 10 "" * D [form 20th 3 0.23 1.96 290 no 1828 146 χ 1O ~ ⁵ Amorphous

00
I.

Examples 1 to 10 do not correspond to the invention.

K3 CO

Examples 21 to 27

These examples show the poorer drawn yarns can be obtained from Oi crystalline spun yarn.

48-ply yarns with intrinsic viscosities of 2.07 and 2.13 were ^{extruded at a temperature of about 31O 0} G and then wound up to give spun yarns with a birefringence of about 130 χ 10 -4.

The X-ray refraction revealed that the yarn, which had a lower intrinsic viscosity, was amorphous while the higher intrinsic viscosity yarn has a remarkable proportion of Of-crystalline material contains.

Despite the higher molecular weight, the yarn possessed mitä higher intrinsic viscosity after stretching, poorer ductility. The results are shown in Table 2.

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Tabel

Ex. Limit
viscosity
d.Garnes Yarn form Birefringence
spun Maximum
Strength
d. ver
stretched
Yarn
g / den Strength properties of the
Single thread strain 2 # module g / den /
100 # stretch 21
22nd
23
24 '
25th
26th
2? 2.07
2.13 Amorphous
Head
neutrally 125 χ 10 "" ^
133 χ 10 "" ⁵
.!in 8.9
8.4
8.0
7.1 *
8.7
8.0
7.2 Tensile strength
speed
g / den 8.2
3.5
8.9
11.0
6.6
7.5
9.1 198
197
194
170
219
184
158 9.8
9.2
8.8
9.6
8.8
7.9

Examples 28 to 33

The following examples show that without external heating, for example by a threadline coating, the spinning extrusion temperature door changes with the intrinsic viscosity and that the methods have the best tensile properties at a given intrinsic viscosity can be obtained.

The results are compiled in Table 3.

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Table 3

(O OO

Ex. Limit
viscosity
d. Yarn Birefringence
spun Extrusion
tempera door
⁰ C Maximum strength properties
of the yarn strain
% 2 f * module g / den /
100 # stretch number
the
Threads 28
29
30th
31
32
35 1.53
1.79
1.84
2.02
2.08
2.32 5.5 x 10 ~ ⁵
106 χ 10 "" ⁵
99 χ 1O ~ ⁵
130 χ 4O " ⁵
95 χ 10 ~ ⁵
153 x 10 ~ ⁵ 265
290
290
312
312
330 Tensile strength
speed
g / den 3.8
4.6
6.3
7.1
7.7
7.0 174
220
203
197
183
183 5
5 "
5
3
24
24 5.4
9.3
9.5
9.6
9.2
9.4

ro ro

Ca)

-j ro

Example 28 does not correspond to the present invention.

A certain trend line can be seen from the values in table 3 the optimal spinning temperature door compared to the limiting viscosity of the yarn can be removed. This relationship makes a good straight curve that corresponds to the equation:

Optimal spinning temperature - 89 x intrinsic viscosity in 1 #

Solution corresponds to + 128 ^{0 C.}

Example 34

This example shows how the dimensional stability of amorphous spun yarn changes as Puncture of the birefringence of the yarn and the temperature of the heat treatment.

Yarns were spun whose birefringence varied from 4 χ 10 ^ to 173 x 10. Strands of these yarns were then ^{hung in a 10O 0} O steam bath for 15 minutes and their change in length was measured. Further samples of these yarns were then suspended in an air oven at 160 ⁰ O 15 minutes and also their length changes were measured. The values for the various changes in length with initial birefringence of the spun yarn at 100 and 160 ^° C. are compiled in Table 7. From these values it can be seen that below a birefringence of about 110 χ 10 the G8rn has a remarkable tendency to expand spontaneously. It was found that at the start of the drawing treatment in which no slippage was allowed on the heated drawing rolls, the spontaneous expansion resulted in considerable difficulties which were remarkably reduced, at values above 110 10 "" ^. The results are shown in Table 4.

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At 100 C the change in length was measured by measuring the Loop lengths determined.

At 160 ⁰ O the change in length was calculated from the change in the garnishing value.

Table 4

Change in dimensional stability of amorphous spun yarn at 100 and 160 ⁰ C.

10 ~ ⁵ % Lengths 160 ^c 10 " ⁵ % Lengths 100 ° < Il modification Il modification Birefringence Il -1.0 Birefringence ti spun Il -1.6 spun η +6 3.4 χ Il -1.6 ti +4 3.9 left -1.4 '3.9 x It . + 11 6.0 ft +0.5 '6.0 ti +24 7.6 It +4.2 7.6 It +14.2 10.4 If +6.8 11.8 ti +29 13.0 Il +16.3 13.0 It +26 13.9 Il +19.6 27.0 ! I +23 24.0 Il +19.2 32.0 Il +18 27.0 N +19.0 46.0 Il +15 32.0 n +16.8 60.0 +5 38.0 Il +12.5 * "69.0 +4 46.0 It +12.6 112.0 +3 61.0 It +9.2 121.0 68.0 ti +5.4 136.0 81.0 Il +2.1 95.0 Il +0.7 113.0 +0.3 125.0 -1.5 135.0 160.0

The minus sign shows a shrinkage and the plus sign an elongation.

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Examples 35 to 37

These examples can be seen in which way affect both Streckstift- and plate temperatures, the relative amounts of & r and beta crystalline forms in the drawn product.

A 24-filamentous yarn as spun in a similar manner in the Pall II to an intrinsic viscosity of 2.08 at 312 ⁰ C and at a speed of 1067 m per minute wound to a emorphes spun yarn having a birefringence of 7 ^ * x 10 "" ^ to yield. It was found that the yarn can be drawn under optimal conditions to give a product with a thread strength of more than 10.0 g per denier.

The spun yarn was drawn at a draw ratio of 2.9: 1 at the drawing pin and plate temperatures shown in the table, and the relative proportions of ( and ß-crystalline form in the product were measured by X-ray diffraction. The results are summarized in Table 5. They recognize blank that the pen temperature fixes a limit of the content of ß-form, and this limit will be reduced with increasing pin temperature. the table also shows that this limit increases rapidly at temperatures above ⁰ plate

The results are compiled in Table 5 below.

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Table 5

Ex. Plate temperatures Relative ^ content of mono-
clinical ß-form in the crystal
linen areas of the stretched
ten yarn 17O ⁰ C 19O ⁰ C 210 ° C Pen temperatures 10O ⁰ C
¹¹ 125 ⁰ C
¹¹ 150 ° C 150 ⁰ C 9
11
11 45
30th
18th 46
31
22nd 35
36
37 O
7th
4th

Examples 38 to 43

These examples show that when the yarn is drawn in this manner, the drawn product predominates is crystalline in the of portn, the tensile strength properties get worse, i.e. that, within certain limits, an increased proportion of B-form is beneficial for the tensile strength properties is.

Yarns having an intrinsic viscosity of 2.07 was extruded through a spinneret having 48 holes at 312 ⁰ C and at speeds of 1372 m 6o9 and wound per minute to spun yarns having birefringence of 17 and 125 x

- ■ 5

10 ^ to yield. It was found that the yarn was spun in State were amorphous.

The yarns were drawn over a heated pin and plate at a speed of 107 meters per minute, at the appropriate maximum draw ratio using the optimal plate temperature, where the pin temperature was changed. The results of these investigations are summarized in Table 6 below

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and the results indicate that at a pen temperature from 125 ° C a reduction in elasticity occurs.

The results are shown in Table 6 below.

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Tabel

co ο co

Ex. Birefringence
spun Stretch
behaves Pen-
temp. Plat-
ten- Strength properties
of the thread strain 2 # module
g / the /
100 % deh
tion # ß-form in
crystalline 17 χ 10 ~ ⁵ nis ⁰ C temp.
⁰ C train
firm
speed
g / den 7.7 194 Areas 38 5.8 105 196 8.8 7.5 200 39 5.8 125 196 9.2 6.3 196 8th 40 125 x 10 " ³ 5.8 150 196 8.9 8.2 200 - 41 3.2 105 196 9.8 7.9 203 - 42 3.2 125 196 9.8 6.8 205 13th 43 3.2 150 196 9.5

Examples 38, 39 and 40 do not correspond to the subject matter of the invention,

Examples 44 to 57

In a manner similar to Examples 38 to 43 were made spun yarn made, namely

(a) a 24-ply yarn with an intrinsic viscosity of 2.08 was extruded at 312 ° C and wound at a winding speed of 1067 m per minute, a spun amorphous pleasure with a

- ~ * i birefringence of 74 χ 10 -'zu result;

(b) a 24-ply yarn with an intrinsic viscosity of 2.32 was extruded at 32 5 ° C and wound at a speed of 1351 m per minute, to give a spun yarn that was partially of crystalline and birefringence of

92 χ 10 "'* owned.

These two spun yarns were spun at a speed of 107 meters per minute using a drawing pin and over stretched on a plate, with the appropriate maximum stretch ratio, with a fixed pin temperature and a changing plate temperature. The effects of the plate temperature on the tensile strength properties and the percentage of ß-crystalline form in the crystalline areas of the drawn yarn can be seen from Table 7.

The results are compiled in Table 7 below.

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Table 7

ο co co

Ex. Double
refraction arenz-
visco- Extru-
sion - Stretch
ver Pen-
temp. Plat-
ten- Strength properties of the ver
stretched thread train
firm
speed
g / den strain 2 % module
g / the /
100 % deh
tion IOOOC
Schrum
exam 44 spon
nen sity
of
Yarn temp.
⁰ C ratio ⁰ C temp.
° C ß-
shape
* 8.5 6.0 188 4.2 45 74 χ 10 ~ ⁵ 2.08 312 4.0 115 175 2 10.1 7.0 230 2.7 46 4.0 120 188 12 " 9.9 7.3 222 2.5 47 4.0 115 198 22nd 9.6 7.3 225 2.6 48 4.0 120 205 18th 8.1 7.6 216. 2.2 49 4.0 115 212 29 8.4 6.4 173 4.0 50 92 χ 10 "" ⁵ 2.32 325 3.5 125 176 4th 8.9 7.9 170 4.0 51 3.5 125 196 7th 9.7 8.0 194 4.0 52 3.5 125 208 12th 9.0 8.2 177 3.8 3.5 125 215 13th

For both values of the intrinsic viscosity, the proportion. '. An ß-shape larger with the flattening temperature while the tensile strength properties can be improved with a higher plate temperature and then above a certain temperature sink again.

At an intrinsic viscosity of 2.08, the falling trend at 205 ° C is noteworthy, however, no change takes place at an intrinsic viscosity of 2.32, is achieved until a temperature of 215 ⁰ C. It can therefore be established that the optimum flattening temperature increases with the intrinsic viscosity up to a value of the intrinsic viscosity of at least 2.32.

Patent claims:

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Claims (6)

1. A process for the production of a yarn from poly (ethylene-1 ₎ 2-diphenoxyethane-4j4 ^l »aicarboxylate) or its mixed polyester, characterized in that poly (ethylen-1 ^ -diphenoxyethane - ^^ '- dicarbc-xylate) ^{odex 1} a mixed polyester of the same is pressed out under such conditions that a spun yarn with a? Birefringence of more than 60 χ 10 "" * arises, this value, however, not being higher than that of the a & r equation ^ - 7 x 10 " ⁶ V / + 50 s: 10""^ corresponds to, where <£ » &.? Birefringence d®3 spun yarn and W dia Auf ^ lukel ^ eEChwindigksit is in m / min, whereupon the yarn is oriented by drawing. 2. A method for producing a yarn according to claim 1, characterized in that the birefringence of the spun Yarn is over 110 χ 10 "^, but not larger is than the value of that of the equation »5.4 χ 10 ~ ⁶ W + 50 χ 10 ~ ³ is equivalent to. 3. A method for producing a yarn according to claim 1 or 2, characterized in that the relative viscosity of poly- (ethylene-1 ^ -diphenoxyethane- ^ j ^ '- dicarboxy lat) or a mixed polyester of the same greater than 2.0 is. 4. A method for producing a yarn according to a of claims 1, 2 or 3, characterized in that the 309842/1113 Extrusion conditions are chosen so that a spun The result is yarn that is amorphous, as determined by X-ray refraction. 5. A method for producing a yarn according to one of claims 1, 2, 3 or 4, characterized in that the intrinsic viscosity of the poly (ethylene-1,2-diphenoxyethane-4-, 4'-dicarboxylate) or the mixed polyester is not less than 2.0 and not larger than 2.3, and the extrusion temperature door is not less than 295 ° C and not larger than 335 ⁰ C. 6. A method for producing a yarn according to one of claims 1, 2, 3 «4- or 51, characterized in that the cooling of the melted threadline takes place by contact with the surrounding air at NormeItemperetür and the ratio between the intrinsic viscosity of the spun yarn and the Extrusion temperature corresponds to the following formula: Extrusion temperature - (89 x intrinsic viscosity + 128) ° C. PAUNTANtWlTt Nt-ING H. FINCKE, DIN.-INS. H. BOHt 309842/1113