DE1815192B2 - Process for the production of polyxylylene adipina midfäden - Google Patents

Description

The invention relates to a process for the preparation - where X is the content of p-xylylenediamine in the di-

Development of polyxylylene adipamide threads by melting amine mixture m mol percent means and that the

spinning of a condensation polymer from adipine- freshly spun thread by means of a cooling gas-

acid and m-xylylenediamine or m- / p-xylylenediamine are cooled, which with a flow velocity

with a p-xylylenediamine content in the diamine medium of less than 1 m / s
research of less than 30 mole percent at Spinntem- By observing the three pa-

temperatures below 290 ^ C, cooling the freshly spon-

nenen threads and stretching the threads on more hydroxyl compound in the specified amount and /

than three times its length at 70 to 90 = C, or water, setting the spinning temperature as well

while the water content of the threads is less than 30 cooling the freshly spun thread by means of a

4%> if cooling gas is kept under the specified conditions,

The above-described polyxylylene adipine in melt spinning of polyxylylene adipine

amides are already known, and amides of the specified type are likewise known, for example from

knows, from these fibers, which are known as "MXD-6" fibers in the above-mentioned US Pat

are designated to produce (see. The US-PS 35 obtained a high degree of whiteness. The strength of the

29 87 506, 29 97 463 and 32 00 183). Since this thread produced according to the invention amounts to more

However, polymers have a relatively low thermal stale than 5 g / den. The threads obtained are at the

have stability and are difficult to handle, compliance with the stated conditions completely

could not do it in a satisfactory manner to evenly.

The technical production of MXD-6 fibers is preferably used to carry out the are, according to the method, a highly pure polymer

The object of the invention is therefore used in the sat. For example, a polymer

Creation of a process for the production of poly- used that meets the following conditions: xylylene adipamide fiber by melt spinning

its implementation no thermal decomposition 45 1 7n << * ~ (2)

of the melted material takes place, threads with Mw = '/ "/ = i_o, 984r" "

a high degree of whiteness as well as a high mechanical strength can be obtained.

This object is achieved in a process of the one where η _{η1 means} a relative viscosity, which type described above is achieved in that the 5 <> at 25 ° C using a solution of 1 g of melt, a non-volatile hydroxyl compound is dissolved in the polymer in 100 ml of a 96% in an amount of 0.05 to 0.7 mol per kg of polymer is sulfuric acid, and r contains the ratio of the number of moles and / or water that the spinning temperature T of the polyamide salt constituents, as in the following equation met: ment of the polymer used to the sum

55 of the number of moles of said polyamide salt constituents

265 + 0.33 X <; T ° C <Ξ 290, (1) and the viscosity stabilizers

/ _ Number of moles of the polyamide salt components \.

\ ~ Number of moles of polyamide salt constituents + number of moles of viscosity stabilizers / '

In equation (2), the right side shows the range that can be selected. If r = 1, are

the desired polymers are those with y _r ei ⁼ IJ

/ 1.11 - 1.052r \ to 3.6. On the other hand, if r becomes smaller, then the becomes

^ 1 - 0.984 r / ⁶ 5 range for y _reh which to gain before

added polymers can be selected, narrower, and

indicates that when the size »r« approaches 1 (where no if r is not greater than 0.95, the left side, stabilizer, can be used) r \ _rel in another η _ηΙ = 1.7 of the formula (2 ) are not satisfied.

The relationship between relative cobalt salts was also mentioned. The added amount of 10

Viscosity (η ,, Ο and the amount of end groups of up to 1000 ppm is used as hypophosphorous acid

Investigated "MXD-6" polymers and found that, calculates. The addition is preferably carried out before or

if the extent of the polymerization reaction during the polycondensation stage is

is formed substantially at 0.988 ± 0.03, a pounding of the polymer during the reaction

can receive lymerisat, which avoid the sliding and ensure an even distribution

chung (2) satisfied. to deliver. However, it is also possible to use the above

It was also stated that to obtain a compound during the melting and the

to add satisfactory polymers by discontinuing these spinning.

'in terms of the extent of ^the reaction, a process in which the non-volatile

to which the condensation polymerisation by producing hydroxyl compounds are said to be aliphatic alcohol

heat the reaction mixture under high vacuum, for example propyl, butyl or octyl alcohol

(as is usually the case with the polymerisation of polyethylene, ethylene glycol, glycerine, pentaerythritol, neo-

amides, polyesters, etc.), pentylglycol, pyrogallol or cyclohexyl alcohol

must avoid throwing. For example, the 15 saccharides, for example glucose or cellobiose,

Desired setting not mentioned with the conventional or mixtures thereof The addition of these

Process for the production of "MXD-6" -Folyme- connections takes place in an amount of 0.05 to

ren, as in the exemplary embodiments of US-PS 0.7 mol / kg of the polymer, since when using

27 66 221 and 29 97 463, an amount outside of this range causes a

· ^the can occur as gelling.

It was found that the desired setting- The water content can be used, for example, when

development can be effected in a process in spinning a polymer with a relative viscosity

which the polycondensation reaction in the presence of "?", of about 2.0 at 275 ° C 0.14 mol / kg des

unity of steam or water vapor in contact with polymers.

the molten polymer is carried out, as the undrawn threads throw after the Ver-In this case can be atmospheric pressure or a spinning and cooling to 3 to 5 times the length Pressure stretched slightly above or below atmospheric at 70 to 90 ° C, while the water pressure are present. In this way, the extent of the content can be kept below 4 °, preferably in the case of a non-polycondensation reaction almost theoretically from around 3%. If desired, they can be stretched Throw the water equilibrium curve between the steam 30 threads fixed in a conventional manner. if phase and the molten polymer in the re-the water content in the threads exceeds 4%, treaktionsapparat and undesired hyperextension phenomena often arise from the kinetics of the polycons. Density rate with reversible reaction If the humidity increases further, crystallizes (G. V. Schulz: Z. Physik Chem., A 182, 127, 1938) the thread and becomes difficult to stretch. the set throw. 35 Stretching and heat setting can be done on

Throw an aqueous solution of adipic xylylene- carried out the usual way (for example-

diamine salt was introduced into an autoclave. The way as in US-PS 32 00 183).

Water was gradually removed during the in- The quality of the polymer and the quality of the

nere pressure below 4 to 10 kg / cm ² at 120 to melt spinning can be determined by the number of knots

180 ⁰ C was held. After completion of the printing 40 in the drawn threads and also through the

The autoclave was closed and the stretchability was assessed. The most important fact

Temperature increased to 260 to 280 ° C, and the re- tor forms the absolute amount of contained in the threads

Action took place at an internal pressure of 20 to ten, degraded polymer. This can also be done by

0 kg / cm ² completed. The molecular weight of the amount of insoluble polymer can be assessed

resulting »MXD-6« polymers {n, _el = 1.70) 45 den, when the thread is dissolved in formic acid,

was about 10,000. This is a polymer of The relative measurement can be made by measuring the fluo-

lowest molecular weight, which satisfies the rescence intensity of the polymer solution (in Amei-

representing to threads spun according to the invention (sensacid) carried out throw,

can throw. The part which is insoluble in formic acid is a gel

In order to set the values of r and η _{Γ <! Ϊ́} (i.e. in the 50 polymerizate that is produced when one second

essentially the extent of the reaction) it is an unavoidable or side reaction to a certain extent

particularly important, depending on the absolute value of η _Τί1. Even those soluble in formic acid

tig, a substantial equilibrium amount of water in polymers also occurs when a

hold the molten polymer. Side reaction has taken place. It is assumed

If the polymerization reaction continues 55 men that the fluorescence is due to the presence of until the extent of the reaction is higher than 0.992 heterogeneous dopwiiJ formed by the side reaction, ν ürden side reactions cause complicated chap- pel bonds. It throws found Rakters occur in the molten polymer, that of the addition of hypophosphorous acid Not only thread produced before gelation and / or discoloration of the polymer to polymer melt cause. Such side reactions are also excellent with regard to the degree of whiteness, but fail with the melt viscosity of the molten dem also a low fluorescence intensity in the ver-primary in connection. equal to polymers without the additive mentioned

Preferably throw the polymer melt points. Therefore, it is believed that this addition

Hypophosphorous acid or metal salts of the under- also have a positive effect in preventing the

has phosphorous acid in an amount of 10 to 65 secondary reactions occur.

1000 ppm to improve the whiteness draw- The knots observed in the drawn threads

puts. The sodium salts are of the metal salts, and cats represent a local, thick part with a vain un-

Hum, calcium, zinc, aluminum, manganese or 1.5 to 2 times the diameter compared to the

normal part of the threads and are less than a few mm in length. It is known that such nodes occur in polyamide threads and other synthetic threads, but m in a Größenoidnung of just 0 to 5 knots per 10 ^s. In the case of PoJyxylyJenadipinamitfj However, there is a strong tendency that gelation during desSchmelzspinnens occurs, so that it was customary , the conventional "MXD-6" threads have knots on the order of a few hundred or a few thousand knots per 10 * m. In order to prevent the formation of knots, the presence and amount of the hydroxyl compound in the molten state is very important. According to the method according to the invention, it is possible to produce "MXD-6" threads with a number of knots below 15 per 10 ^e i.

Claims (2)

ι 2 from 0.05 to 0.7 mol per kg of polymer and / claims: or contains water that the spinning temperature T satisfies the following equation: 1. Process for the production of polyxylylene-265 + 0.33 X ^ T ° C <Ξ 290,
adipinamide threads by melt spinning a 5 .. ", / - v" i, """".YwiuiflnHiamin; « a
Condensation polymer from adipic acid and where X is the content of p-xyly ¹ ^ P *** " m-xylylenediamine or m- / p-xylylenediamine with diamine coating m mol percent, and a p-xylylenediamine content in the diamine that the freshly 8 ?? ° ™haben ^ ". ™ £ g»? Mixture of less than 30 mole percent with cooling gas is cooled ^ that with an Stto spinning temperature below 290 ⁰ C, cooling the xo mung speed of less than 1 m / s of freshly spun threads and drawing of the flows. . . , J _Ai _.
Thread II is more than three times its length 2. Process according to ^^^^ g- 70 to 90 ° C, while the water content of the Fä- indicates that the polymer atschnielze and earth is kept less than 4 ° / ", characterized by phosphonic acid or metal sake or untergekinTleichnet that the melt a 15 phosphonic acid in an amount of 10 to non-volatile hydroxyl compound in an amount of 1000 ppm can be added.