DE1495832A1 - Polyamide-polyester block copolymers - Google Patents

Description

Polyamide-polyester block copolymers ο

The present invention relates to a process for the production of block copolymers from polyamides and polyesters, fibers produced from these copolymers and their use in tires.

Polyamides are used today for many purposes, but also have certain disadvantages in overcoming them the area of application for polyamides could be increased. For example, polyamides are used for tire fabrics despite the so-called "Flattening", which is a very unpleasant property, is quite suitable. Under "Flatten" the Property understood that a tire is pressed in at the point where it rests on the road surface, if the vehicle has to stand for several hours, so that the tire for some time after the restart as a result the flat at one point while driving. The "flattening" is largely reduced when in tires Fabrics made from fibers are used which have been produced from the copolymers according to the present invention are.

Spun polyamide fibers "creep" and "shrink" ^11, especially at elevated temperatures, even after heat treatment. This unpleasant property is also reduced to a considerable extent in the case of the copolymers according to the present invention.

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Polyester fibers have a high modulus of elasticity and are essentially free from the property of "flattening". In relation to this, polyamide fibers have a low modulus of elasticity and - as already stated above - are subject to the so-called "flattening" to a considerable extent. The fibers of the present invention are made from these two polymers. Blends of these polymers are generally incompatible and result in inferior fibers. It is Airch the method according to the present invention, however, possible to react the two polymers to such an extent with one another that they are compatible and can be, for fibers with good properties, which moreover are free from the characteristic of the "flattening ¹¹ process. If the reaction to produce the copolymer from these two polymers is carried too far, only low-melting fibers can be obtained from the product obtained, which are subject to a high degree of "flattening" good strength and the other good properties required for textile applications which, moreover, do not cause the tires to flatten when used in tire cord.As will be explained in more detail below, the copolymer according to the invention is a block polymer Ation led too far, an equilibrium is formed and a mixed polymer with random distribution is produced, which has a low melting point and can only be processed into fibers which have the property of "flattening".

For making the polyesters according to the present invention are used, various aromatic dicarboxylic acids can be used. The ones used according to the invention Polyesters conform to the formula

(1) HO (CH ₂ ) _a - [p-CO-aryl * CO-O (CH ₂ ) _b -3 _x OH 209815/1576

Polyester is used in particular for tire cord, which are derived from terephthalic acid and the formula

(1-a) HO (CH ₂ ) _a - [b-CO / "S-CO-O- (CH ₂ ) _b "] _x OH

correspond.

The polyamides used according to the invention can be derived from a cyclic lactam or the reaction product of a dibasic Acid and a diamine. Both the cyclic lactam and the reaction product of dicarboxylic acid and diamine can be reacted with an alkylene diamine to form polyamides which are in excess of $ 50 Contain amino end groups. The polyamides can either made from a polylactam from Formfei

(2) H [HN (CH ₂ ) _c CO-J _m OH

or a reaction product of an aliphatic dibasic Acid and an aliphatic diamine of the formula

(3) HO [CO _(CH2) ^ CO-IMH- (CH _{2) e} NH-] _y H

or reaction products of one of the abovementioned compounds with an alkylenediamine that have the formulas

(4) H IhN (CH ₂ J ₀ CoJ _1n -IIH (CH ₂ ) ^ ₂

(5) H ₂ N- (CH ₂ ) _f -Nh [cO- (CH ₂ ) ^ CONH- (CH ₂ ) _e -NH-] H

correspond.

"Aryl" means a divalent aromatic radical which is preferably symmetrical. In the formulas a, b, d, e, and f numbers ranging from 2 to 10; a, b, d, e and f can be the same or different in the formulas? c is a number from 3 to 10; m is a number from 10 to 300, preferably 80 to 200 for tire cord; χ is a number from 10 up to 150, preferably 25 to 100 for tire cord; y is a number from 10 to 200, preferably 20 to 125 for tire cord.

..the sum of the molecular weights of the polyester of formula (1) and the polyamide according to one of the formulas (2), (3), (4) or (5) should be in the fiber-forming range, i.e. at least at

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about 10,000 lie. The polyamides can also be a mixture of the substances mentioned above, e.g. a mixture, in which an alkylenediamine with only part of the polylactam or the reaction product from the dibasic acid and the diamine has been reacted.

The polyester used is derived from an aryldicarboxylic acid. To produce the polyester, the acid is mixed with a diol, e.g. ethylene glycol, 1,4-butanediol, 1,3-propanediol etc. implemented. The diol can have up to 8 or more carbon atoms contain. The polyester must have a melting point of at least 200 ° C, preferably even higher, e.g. 225 to 250 ° C, even better 275 ° C and more. For tire cords a polyester with a melting point of at least 200 ° C. is required, and terephthalic acid esters are generally used used for this purpose. The aryldicarboxylic acids should preferably be symmetrical, although this requirement only applies to further processing on tire cord fabric absolutely must be fulfilled. The following acids can be used, for example: terephthalic acid, isophthalic acid, symmetrical biphenyldicarboxylic acid, diphenylmethanedicarboxylic acid (preferably the 4,4 * isomer), diphenylsulfonedicarboxylic acid (preferably the 4,4'-isomer), diphenyl-1,2-ethanedicarboxylic acid, the naphthalenecarboxylic and anthracenedicarboxylic acids and mixtures of the aforementioned compounds. These acids contain 8 to 16 or more carbon atoms. The polyesters that can be used include, for example, polyethylene terephthalate, Polytetramethylene terephthalate, mixed. polymers of ethylene glycol with terephthalic and isojithalic acid etc.

As already stated above, the polyamides must have a melting point of at least 175 to 200.degree. C., preferably even higher, for example 225 to 240.degree. C. or even 250 to 275.degree. For fibers to be used as cord in loops, the melting point must be at least 200 °. Polyamides that can be used according to the invention can be derived from the following dicarboxylic acids: succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid or sebacic acid, these acids are reacted with diamines to produce the polyamides, which are 2 to 10

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contain. Such diamines are, for example, ethylenediamine, Tetramethylenediamine, hexamethylenediamine, octamethylenediamine, 1,4-di (methylamino) cyclohexane - e.g. in nylon or nylon 610 -. Nylon can also be derived from omega-aminocarboxylic acids, e.g. omega-aminobutyric acid, onega-minopimelic acid, Umega-aminocaproic acid, etc. or of the lactams of these acids. The plastic material can e.g. Made using nylon 4, 5, 6, 7 and 8 and 11 "The polyamide can, as can be seen from the above formulas, consist of a lactam, or of a Lactam to which an alkylenediamine has been added during the polymerization, or which has been post-treated a carboxyl group-containing polyamide has been produced. The polyamide can also be made so that a Dicarboxylic acid reacted with a diamine w ± d, with a small excess of an aliphatic diamine during production, e.g. ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc. is used or where the reaction material is treated accordingly

In the usual large-scale production, no diamines are used in the adjustment of polylactams; the Polymers have about 50 ^ amino end groups. Pure production of the polyamide-polyester copolymers according to the invention the polyamides made with the addition of diamine contain more than 50 $ and sometimes up to 1000 amino end groups.

Polyester and polyamide can be reacted in any proportions, so that the ratio of the hydroxyl end groups in the polyester to the amino end groups in the polyamide in a ratio of 2: 1 to 1: 2, preferably 0.8: 1 to 1.7 r 1. The higher the percentage of polyester, the greater the reduction in "flattening", although this disadvantage is already significant even with high percentages of polyamide in the copolymer is reduced «,

The polymerization is carried out so that a physical mixture is in an inert atmosphere until it melts is heated, for which temperatures of 260 to 290 ° C, preferably 275 to 280 ° C are generally necessary. As soon

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the mixture is in a molten state, a Vacuum applied to remove the volatile reaction products. After removing these volatile products the remaining reaction product is essentially insoluble in boiling o-diclilobenzene. ^ he solubility in o-Dichlorobenzene is referred to below in percentages on the weight of the "reaction product, which can be extracted with 100 g of boiling o-dichlorobenzene. A Product is considered essentially insoluble if no more than $ 5 of material is extracted in this way can. The vacuum is then released and the polymer is removed from the charging zone before the melting point of the product falls below that of the lowest melting component. For use as a "tire cord, the product must have a Have a melting point of at least about 200 ° C. For the purposes of the present invention, the melting point is Understood the lowest temperature at which the disappearance of the crystallinity is observed under a hot-stage microscope will.

The present invention relates to the resulting higher melting block copolymer. Repeated heating of the block polymer causes a reduction in the melting point, which is probably related to the fact that the formation of a copolymer with random distribution occurs as an opposing reaction. Consequently the higher melting point can be regarded as evidence of the presence of a block copolymer. The diminution the melting point cannot be completely avoided; the high melting point product is therefore essentially a Block copolymer with the good properties mentioned at the beginning, which characterize the polyamide-polyester block copolymer of the present invention.

Within the possible variations already explained above resins with properties which are particularly favorable for the production of tire cord can be used in particular Win the use of polyethylene terephthalate as a polyester resin. A polycaprolactam is preferably used as the polyamide resin used, which is produced in the presence of a diamine

* expressed

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represents or has subsequently been reacted with a diamine, so that a larger proportion of amino end groups, for example as in formula (4) ι about 70 ^c / o or more, is present in the product. The proportion by weight of the polyamide entering the copolymer should be in the range of $ 55-85, preferably $ 60-70, based on the total weight of polyamide and polyester in the copolymer. The ratio of gram equivalents of hydroxyl end groups in the polyester to gram equivalents of amine end groups in the polyamide should be between 0.8: 1 and 1.7: 1. Components are preferably melted separately and the two melts are mixed. However, the solid constituents can also be melted under anaerobic conditions, for example under a nitrogen blanket. The molten mixture of the two components must be heated under vacuum in the reaction zone in order to remove the glycol formed as quickly as possible; as soon as free glycol remains in the reaction zone, a rearrangement and an equilibrium formation occurs in the copolymer, The reaction is continued until not more than 5% of the copolymer with 100 g of boiling o-dichlorobenzene per gram of copolymer can be extracted. The undesired formation of equilibrium also takes place to a certain extent For this reason, as soon as the desired degree of o-dichlorobenzene insolubility is reached, the reaction should be terminated before the melting point (which becomes lower with the formation of the mixed polymer with random distribution) below the value of the lowest melting constituent (polyester or polyamide The reaction should preferably end before the melting point has dropped below a Y / ert of about 225 ° C. This can be achieved by rapid cooling of the heatsink> on tree perimeter, for example by direct extrusion of the mass into threads.

Under the reaction conditions used according to the invention, a block copolymer is formed from the two polymers,

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which under conditions that the development of an equilibrium promote, the structure of a copolymer assumes with an arbitrary distribution.

The reaction product in the molten state can be solidified by cooling and until the time of use be stored. The production of the mixed polymer and the production of the fibers can be carried out continuously, preferably with a screw extruder with connected to a vacuum pump, works. The copolymer can as it comes out of the reaction vessel, continuously are hot spun, the usual methods and devices for melt spinning are used. The product can also initially cooled and then processed further in a manner known per se, e.g. by melt spinning or dry spinning will. The polymer should not be preheated for a long time or for a long time at reaction temperatures be held, as this promotes the formation of equilibrium, which leads to a lowering of the melting point and to a Recurrence of the "flattening" of tires made with such filaments has resulted.

About the degree of flattening in a tire made with a cord or a multifilament yarn of a certain structure has been produced, the cord or multifilament yarn an after-effects sensitivity cresporise lag) test as follows subject to ι

After-effects sensitivity test

The investigation is carried out with a 1680 denier cord or multifilament yarn at a temperature of 24 ° C and a relative humidity of $ 55.

A piece of the test material of 50 cm length is hung at one end and loaded with a weight of 1.36 kg at the other end for 4 hours. After that, the

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Length measured and recorded. The value gained in this way corresponds to the inflation pressure of a tire.

After that, the load is reduced by 0.9 "tg; the remaining one A load of 0.45 kg is applied for 16 hours. This value corresponds to the pressure of the tire in the road area.

Then the 0.91 kg load is reattached. This corresponds to the return to the tension created by the Inflation pressure is generated as the material in the aid leaves the area of the road surface. That Test material does not return to its original length in 12 seconds and the length at the end of this Time is measured.

The difference between (a) the length of the test material after 4 hours under the 1.36 kg load and (b) the Length of the test material 12 seconds after the 1.36 kg load was restored in the manner described An impact is referred to as aftereffect sensitivity and is expressed in millimeters.

This? / Ert is found to do the flattening pretty well of tires again. The lower the sensitivity to after-effects the more complete the flattening elimination is. A jach effect sensitivity of 2.54 mm or less was measured on garbage cans, shows a considerable reduction in flattening

example 1

4 tests were carried out. The results are compiled in the following table:

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Table 1

Attempt no. 2 2 3 4th Nylon 6, parts 65 65 65 65 PÄT *, parts 35 35 35 35 Ratio of 0H / NH ₂ 1.3 / 1 1.3 / 1 1.3 / 1 1.3 / 1 Reaction time: Melting time, min. 15th 20th 30th 30th Vacuum duration, min. , 30 40 60 120 Melting point, ⁰ C > 200 > 200 170 Solubility in o-dichloro
benzene, $ <C1 <1 2.4 5.2 Sensitive to aftereffects
speed, mm: commercial Nylon 6 4.34 4.34 - - Copolymer according to 1.91 2.28 ——

the invention
♦ polyethylene terephthalate

Manufacture of the polyamide

A nylon 6 was prepared by reacting 100 parts of caprolactam and 1.20 parts of 50 aqueous hexamethylenediamine for 16 hours at 256 ° C. in a closed reaction vessel. The purpose of this reaction is to increase the amine end group content for the reaction with the polyester. The polymer obtained was ground in a Wiley mill, washed for 16 hours at 7O ⁰ C with deionized water for 16 hours at 8O ⁰ C in a vacuum dryer dried. The total yield of polymer was 90%. The relative viscosity of the polyamide, as determined in a one volume percent solution in concentrated sulfuric acid, was 2.01, indicating a molecular weight of approximately 12,500. The amine end group content in the copolymer was calculated as follows, using 100 g of the starting material as the basis:

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Grams of the polymer obtained = 100 0.90 = 90 grams

Mol of the polymer obtained 90 = 0.0072 mol.

12 _# 500

Equivalents of NHp of caprolactam = moles of polymer = 0.0072 eq.

Under the assumption that all of the hexamethylenediamine is Polymer was introduced:

Equivalents of NH ₉ of diamine = moles of diamine = 1.2 χ 0.50 = 0.0052 eq. ^ά 116

Total equivalents of NH ₂ groups = 0.0072 + 0.0052 = 0.0124.

Total equivalents of end groups = 2x moles of polymer = 2x 0.0072 =

0.0144.

Percent NH _{P end} groups = 0.0124 x 100 = $ 86. * 0.0144

Manufacture of the polyester.

A polyester was made by reacting 194 parts of dimethyl terephthalate, 124 parts of ethylene glycol, 0.06 parts of antimony trioxide and 0.10 ropes of manganese acetate were produced. The reaction was placed in a three-necked round bottom flask fitted with a stirrer, nitrogen inlet tube, and detachable condenser was carried out. The reaction mixture was heated with a "Glascol" heating mantle heated to 156 ° C; at this temperature the methanol formed began to distill off. The reaction temperature was then increased to 249 ° C. for 3 hours; after this time all the methanol was removed. A vacuum of 4-5 mm was then slowly applied, simultaneously the temperature was increased to a maximum of 280C. The reaction was continued for 5 hours under a vacuum of 4-5 mm. This gave a polyester with a viscosity number of 0.26, measured at 25 ° C. in a solution of phenol and Tetrachloroethane (50/50), which indicates a molecular weight of 5800.

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The above approach includes:

Equivalent hydroxyl groups =

2 χ moles of polyester = 2x35 = 0.012 eq.

5800

Equivalent FHp groups =

2 χ moles of polyamide χ £ NH _{Q end} groups = 2x65x0.86 = 0.009

^ά 12 _f 5OO

Ratio 0H / NH ₂ = 0.012 / 0.009 = 1.3s 1

The values for the amine end group contents and did OH / FH ratios, which are given in the examples below are on the same basis as given above, has been calculated.

Production of the polyamide polyester block copolymer

The interpolymerization was carried out by adding 65 g Nylon 6 was placed in a 500 cm round bottom flask fitted with a stirrer, nitrogen inlet tube and removable condenser, was equipped. The flask, with the contents under a blanket of dry nitrogen, was placed in a metal bath immersed so that the temperature of the contents rose to 275-280 C. After the polyamide had melted, they were under Stir added 35 g of polyester until the reaction mass melted. (The time it took to melt the polyester is given as "melting time" in Table 1 given above). The reaction mixture is then placed under vacuum of less iata 5 mm until the inasse became very viscous. The vacuum must be sufficient to withstand the interpolymerization reaction to remove formed glycol, which, if it is not removed, by reaction with the polyamide and the polyester causes an equilibrium to be established, whereby products with lower melting points and higher extractability are obtained than with reduction an equilibrium adjustment.

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The copolymer was then under a blanket of dry Nitrogen cooled, the flask broken, and the polymer ground in a Wiley mill. The solubility in boiling o-dichlorobenzene and the crystal melting point (hot stage polarization microscope) were determined and given in the table. The copolymer was dried in vacuo and turned into a Miltifilgam spun. After that, the after-effects became more sensitive certainly.

The melting time and the duration of the vacuum treatment were changed in the various tests. Prolonged heating dee Polymers at melting temperatures favored the establishment of equilibrium. This resulted in products with lower Melting points and higher solubility in boiling o-dichlorobenzene, as indicated in the table. For further processing on tire cord fabric, the solubility in o-dichlorobenzene Do not exceed $ 5. It follows that in the experiments and 4 pasers were obtained which are not suitable for further processing on tire cord fabric.

The OH / NH ₂ ratio relates to the ratio of the OH- end groups in the polyester units to the NHp end groups in the polyamide units. When this ratio approaches 1, there is no limit to the possible interpolymer chain length.

Example 2

4 tests were carried out, the polyamide used and the polyester used were prepared as described in Example 1; otherwise the same became general Working method applied. The molecular weight of the polyamide was the same in all experiments (12,500), while the molecular weight the polyester has been changed; the results were observed and recorded.

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The production of the polyethylene terephthalate was carried out in such a way that different degrees of polymerization were obtained and the ratio of polyamide to polyethylene terephthalate was adjusted so that the ratio of hydroxyl groups to amino groups was as shown in Table 2.

In general, the higher the polyester age, the higher the sensitivity to the effects of the after-effects of the polymer decreased; a comparison of experiments 2 and 4 shows that the An increase in the molecular weight of the polyester causes a reduction in the sensitivity to after-effects.

Table II

Trial No. 1 2 3 4th Nylon 6, parts 65 68 65 59 PAT, parts 35 32 37 41 OH / NH ₂ ratio 1.3 / 1 1/1 1/1 0.9 / 1 PÄT, viscosity number 0.26 0.31 0.37 0.43 PÄT, molecular weight 5800 7100 9000 11,000 Reaction time: Melting time, min » 25th 17th 40 15th Vacuum duration, min. 60 30th 30th 15th Viscosity number of the mix
polymerizates 1.02 0.95 0.82 0.95 Crystal melting point > 200 ^ 200 7200 > 200 solubility in o-dichloro
benzene 3 * 1.6 * 3.1 * 2.2 * After-effects sensitivity,
mm: Nylon 6 * (control) 4.08 4.08 4.34 4.19 Copolymer according to
the invention 1.86 1.93 1.45 1.40

* In this and the following examples, the control experiments carried out with commercially available nylon on the same day as the tests with the polymers to be tested.

Mixed

These fluctuate somewhat depending on the environment and machine conditions

from day to day.

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Each of the 4 products is for further processing on tire cord fabric suitable. The melting points are over 200 G, and the solubilities are low. The equilibrium formation was minimal.

Example 3

This example shows that both the molecular weight of the polyamide as well as that of the polyester can be changed within a larger range, with nevertheless a considerable improvement the after-effects sensitivity is reached. In general, the sensitivity to after-effects decreases with it increasing molecular weights of the two components. During the preparation of the copolymer in Experiment 2, the Temperature during melting below 260 ° G for a long time, so that there is an extended melting period for the polymer revealed. Otherwise, the procedure was as indicated in Example 1; Variations and deviations are given in the following table.

Table III Trial No. 1 63 2 Nylon 6, parts 60 12,500 64 Nylon 6, mole weight 8,000 $ 86 17,700 Nylon 6, i » NH ₂ end groups $ 95 37 $ 88 PAT, parts 40 9,000 36 PATT, mole weight 41500 1/1 11,100 0H / NH ₂ ratio 1.2 / 1 1/1 Response time: 40 Melting time, min. 11 30th 17th Vacuum duration, min. 29 > 200 25th Crystal melting point, ⁰ C > 200 * 200 Solubility in o-dichloro 3.1 / » benzene $ 1 $ 2.4 Viscosity index: il des 0.82 Mixed polymer - 1.08 Sensitive to aftereffects speed, mm: 4.34 Nylon 6 3.12 * 4.29 Ilischpolymerisat according to 1, 45 the invention. 2.39 * 1.45 * Monofilament yarn 2 0 981 5/1 B 7 6

Example 4

Commercial nylon 66 was used. It could be inclined that when using the method according to the invention, pasers with reduced sensitivity to after-effects can be obtained. Nylon 66 corresponds to the formula (3) given at the beginning and contains 50 amine end groups. Otherwise, as in Example 1 indicated worked; Deviations and changes are indicated in the following table:

Table IV

Nylon 66, parts 68 PAT, parts 32 OH / ITC ^ ratio 1/1 Molar weight of nylon 66 24,000 Mole weight of PÄT 11,000 Reaction time: Melting time, min. 17th Vacuum duration, Hin. 17th Crystal melting point C. > 240 Solubility in o-diclilor-
benzene 1.8 # After-effects
possibility, mm: Nylon 66 2.72 Copolymer according to
the invention 2.18 Example 5

A polyamide was used which was produced by polymerizing caprolactam at 256 ° C. in the presence of water and consequently contained equal amounts of amine and carboxy1 end groups.

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Otherwise, the procedure was as indicated in Example 1; the The results are compiled in the table below.

This example shows that the usual hydrolytic Polymerization available nylon to produce the

wij.suxipuj.ymerj.sauB geinau uex JE1xx.tiJ.11uj Attempt no. ag vejrweiiue υ we IU eil XLtLlIIi » Table Y Nylon 6, parts PuT, parts ₁ CMl OH / NH ₂ ratio 67 67 Nylon 6, mole weight 33 33 PÄT, moi-weight 1.7 / 1 1.45 / 1 KristallschmelzDunkt. C. 18,500 15,900 10,700 10,700 > 200 > 200

Solubility in o-dichloro

benzene 1 # 1.7 $

Reaction time r

Melting time, min. 65 72

Vacuum duration, min. 22 23

Aftermath sensitivity, mm:

Nylon 66 (control) 4.06 4.06

Copolymer according to

of the invention 1.65 1.83

Example 6

This example serves to illustrate that a polycaprolactam with more than 50 $ end groups, which in the presence of / ethylenediamine had been polymerized "for the production of the copolymers can be used in accordance with the present invention

can. - '■'

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Tabel Attempt no. VI 1 2 Nylon 6, parts 60 65 PAT, parts 40 35 CH / NH ₂ ratio " 1.41 / 1 1/1 Nylon 6, mole weight 9,000 13,000 PÄT, mole weight 4,500 8,200 Crystal melting point, C. > 200 > 200 Solubility in o-dichloro benzene 3.2 i>

The copolymers had the same excellent properties, which also the products of the other examples from zeicimen.

The present invention will be explained with reference to the accompanying drawings explained in more detail in which

FIG. 1 shows a flow diagram which shows the sequence of the procedure, and

Figure 2 is a cross-section through a tire with the new polyamide-polyester copolymer fibers.

Fibers to be used in tires are stretched during spinning and then twisted into cord The cord yarn obtained is processed into tire cord fabric, welchqg serves as an insert for the tire. All previously known tires with nylon fiber inserts have the disadvantage of flat printing on. A tire of any construction containing 4 cords (see FIG. 2) made from fibers of the invention Polyamide-polyester copolymers have been produced, has the disadvantage of bottle printing hardly or not at all. The fibers have an unusual dimensional stability.

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The tire fabric can, for example, made of fibers from a Polyamide-polyester polymer according to the present invention, which has a melting point of over 200 C or even of 225 to 250 or 275 Mg at 300 ° C. The polymer is preferably produced by continuous reaction made in an extruder under vacuum and the extruded molten polymer is preferably direct spun in a device illustrated in FIG. 1.

209815/1576

Claims (1)

U95832 Claims ι 1. Blockpisohpolyaerisat, consisting of (1) a polyester hit a melting point τοη least « 200 ° C and the formula H0 (CH ₂ ) _a -Q) -CO- aryl-CO- ₂ ) _a and (2) a polyamide having a melting point of at least 175 ° Cf whichever of the formula (A) lfmi (CH ₂ ) _c GO-] _ffl OH (1) Ho [CO- (CH _{2) d} -CO-LTH (CHg) _e MH] JJ (C) H [HN (CH ₂ CO ₀ J - ^ - NH (CH _{2) 2} JIiH or O)) H ₂ N- ( CH ₂ ) | -Nh {cO- (CH ₂ ) _d -C (JiH- (CH ₂ ) ^ iTH-] yfl corresponds to, in which a, b, d, e and f are each small Numbers in the range from 2 to 10 mean » c 3 to 10, * 10 to 300, χ 10 to 150 and y 10 to 200 mean the ratio of the hydroxyl groups i «PoIy esters eu the amine groups ia polyamide ia Bereioh ron 2 t 1 to 1 * 2, which is essentially unl ^ sliah In boiling o-T> ichlorbenBol is and a squint 20Ö ⁹ C display *. 2. Blookniechpolymerieat according to claim 1, characterized that ■ 80 to 200, χ 25 to 100 and y 20 to 125 mean. 5. Copolymer according to -'mepruch 1, characterized in ^ (the polyamide corresponds to the formula (B) , d = 4, e = 6 and y ₍ greater than 150 1st. - 21 - U95832 4. Copolymer according to claim 1, characterized in that the polyamide corresponds to the formula (A), ο = 5 and m is not greater than 250. 5. Blockmisehpolymerisat according to claim 2, characterized in that that the polyester is a terephthalate. 6. Block copolymer according to claim 1 in the form of a fiber. 7. Fiber product according to claim 1 for use in ieifen, at which m is 30 to 200, χ is 25 to 100 and y is 20 to 125. 8. Fiber product according to claim 7, characterized in that the polyester is a terephthalate, the ratio of the hydroxyl diene groups in the polyester to the amine end groups in the polyamide in the range from 0.8 t 1 to 1.7: 1 and the fiber in the form of / ultifil yarn is sensitive to light effects when tested of no more than 2.4-5 mm (100 nils). 9. i ^ in mature, which contains the fibers according to claim 5. 10. £ in teifen, the carcass threads of which are essentially complete consist of iaser according to Anspruoh θ. 11. ^ in mature, which contains fibers according to claim 7, in which the polyamide is a lactam. 12. A tire which contains fibers according to claim 7, in which the polyamide is an ITmetzungpeodukt from a ° olylactam and is an alkylenediamine. 13. Sine tires containing fibers according to claim θ, in which the polyamide is polycaprolaotam. 14. Process for the production of a block polymerizate from (1) a polyester having a melting point of at least 200 ° C and the formula, HO (CH ₂ ) - £ o - CO - aryl - GO - O - (OH ₂ ) ^ _x OH and (2) a polyamide with a melting point of at least 175 ° C, which of the formula (A) K [im (CH ₂ ) _o (B) Ho [CO- (CH ₂₎ a-CO-ITH- (DH _{2) 0} ^ NH (C) h [hh (ch ₂ J ₀ 20 9815/1576 -22. H95832 or (D) H ₂ N- (CH ₂ ) _f -NH ^ CO- (CH ₃ ) ^ COlJH- (CH ₂ ) _e ~ NH ^ JH corresponds to in which a, b, d, e and f are small numbers in the range from 2 to 10, c 3 to 10, m 10 to 300, χ 10 to 130 and y 10 to 200 mean, characterized in that the polyester and the polyamide at a ratio of the hydroxyl end groups in the polyester to the amino end groups in melts the polyamide in the range of 2: 1 to 1: 2, the melted material in a Tleaktionezone under left under reduced pressure in order to remove the volatile substances formed during the copolymerization until the resulting product is essentially insoluble in boiling o-dichlorobenzene and the melted product removed from the reaction zone before the melting point falls below the higher of the following two temperatures: 1. 200 ° C and 2. the melting point of the lowest melting point of the two polymers used. 13 · The method according to claim 14 »characterized in that the polyamide is a lactam. 16. The method according to inspruoh 14, characterized in that dafl the polyamide is the reaction product from a Laοta «and is an alkylenediamine. 17 · The method according to claim 14, characterized in that the material directly from the "reaction zone / to be piped Bponnen is 209815/1576 BADORJGINAL