DE1494606C - High molecular weight linear polycarbonate threads and processes for their manufacture - Google Patents

Description

3 4

b) drive the residual content remaining after thread formation, the solution being fed through multi-hole nozzles into the non-or. Bad solvent may be spun into a shaft heated to about 200 to 250 ⁰ C in an inert atmosphere with no plasticizer effect on the polymer and the continuous thread freed from loosening, ie the non-solvent or solvent to be used, at the speed of bad solvent, in addition to its low 5, should be from 100 to 500 m / min, drawn off via godets and only a low affinity for dissolving and swelling is wound on.

did to own high molecular body. Those produced by the method according to the invention

Fabrics are mainly chlorinated aliphatic and made threads that fibers possess at an elevated level

aromatic hydrocarbons; Sufficient crystallinity. Solvent resistant

c) a boiling point that is not too high or too low, excellent uniformity according to the point of the, according to the invention at 60 to 180 ° C, stretching and a substantially increased temperature preferably should be at 80 to 150 ° C; resistance with increased crystallite melting point so-

d) low flammability. . like improved technological properties.

The following examples are intended to illustrate the invention

These non-solvers or bad solvers are characterized by 15 procedures that explain, but in no way limit, a certain value of the cohesive energy density,. · ·.,

which is defined as' ''. example 1

Polycarbonate with a molecular weight of

_{e =} internal heat of evaporation ₌ Li 83,000, that from 4,4'-dihydroxydiphenyl-2,2-propane

Molar volume V mol ^{20 was produced} by the phosgenation process,

in methylene chloride to a 24 ° / ₀ solution

and commonly discussed in the form of] Te is dissolved, pushed through a filter press and a and supplied for the non-mixing device to be used according to the invention. In this mixing organ is now or poor solver] / ~ e = 8 - 10. Such additionally 1,2-dichloropropane as a bad solvent in Nonsolvent or poor dissolver who injected the above 25 in such an amount that when leaving To meet the requirements, both mixing elements are, among other things, an 18% polycarbonate solution for example dichloropropane and chlorobenzene. . results.

From this point of view, the intensively mixed with the additional component have proven to be

A particularly suitable bad solvent for the solution according to the invention is immediately thereafter in a solution process 1,2-dichloropropane at a temperature of 75 ° C. through a multi-hole nozzle with an energy density of 8,8 with a boiling hole diameter of 100 μ into a duct that is heated to 220 ° C and is pressed at 96 ° C and chlorobenzcl with a cohesion-heated duct, which is blown at the nozzle with a pre-negy density of ] / ~ e = 9.5 at a boiling point of heated air of 110 ° C. The threads proved to be ^{132 0 C.} are about godets at a speed of

Spinning solutions are produced which are drawn off and wound up as much as 35 180 m / min. The one above Bad solvents contain that a gelled solution becomes viscous with the freezing temperature in a ratio of 1: 6.8 Properties contained in the homogeneous phase Stretched threads have the following properties: and thus remains spinnable. This spinning obtained in this way.

solution is briefly heated before spinning, titer 50/20 den

at temperatures between +70 and +150 ⁰ C, so 40 strength 3.7 g / den

that the previously gelled solution to a clear through- breaking elongation 26 ° / ₀

visible real solution of the polymers. Due to the uniformity of the thread ± 2.5%

the addition of these bad solvers is already used in the

Solution a precrystallization of the high polymers

that are maintained at the 45 X-ray interference ^{widths C 1} ) .... 1.15 ° spun according to the invention

Threads due to a uniform stretchability and crystalline content ( ² ) 20.5 ° / ₀

Dyeability is particularly beneficial. . Crystallite melting point 269 ^° C.

Polycarbonates are especially those based on (according to Differential-Thermovon Dimonohydroxy-diaryl-alkanes-, -sulphones, sul- analysis) foxides, -sulphides or -ethers or a mixture of these 50. Shrinkage in trichlorethylene Dihydroxy compounds with one another use. Room temperature 10 minutes Their molecular weight should generally be between and above 14%

about 50,000 and about _{95,000, corresponding to a / <ΝΛ} . ".. _x . _xr ■ _ ·. j · * ■ · 1, "* ■ · j ·

,,. , .., ...... . _o,. ~ _1C / (1) The X-ray interference width serves as a measure of the

relative viscosity of η _Μ = 1.48 to 2.15 (measured crystallinity. The interference width here is the width of 0.5% in methylene chloride at 20 ^° C.). Molecular weights around 85,000 selected X-ray scattering curves of polycarbonate are referred to as the preferred 55 main maximums recorded with CuK α radiation. Sie / γ, _ j 82) 'is measured halfway up the main maximum and * ■' * £ -? \ ..., j ■ ,, c ι. · Jj π 1 in the angular measure of the glancing angle (half the scattering angle) in To carry out the procedure, the poly angular degree is expressed. Carbonate because of the polycarbonate which solvent residues often in the form of a powder-grain initially contained is the Mes mixture is present, in methylene chloride to a 15 to 60 of the interference width solution safer than 25 ° / _o solution of the crystalline, preferably 20 to 24 ° / _o solution, fraction.

■ dissolved, filtered and preferably continuous with the solution (2) The crystalline portion was determined according to Hermans (Makromol,

^{the chemistry 64} ^ ¹⁹⁶³ I- ^{s 135 to l39} > determined precisely and immediately before the deformation,

bad solvent according to the invention in such an amount. ...

mixed in that the resulting spinning concentration 65 e 1 s ρ 1 e

14 to 24%, preferably 17.5 to 19.5%. Proceed as in Example 1, but jet into that

In addition to the mixing device, such a quantity of monochlorobenzene is suitable for the production of threads

Wet spinning process preferably the dry spinning association that the resulting spinning solution is 18.5%

Polycarbonate will. The threads drawn above the ETa in a ratio of 1: 6.8 have the following properties:

Titer 80/39 den

Tensile strength 3.4 g / den

Elongation at break 31%

Yarn uniformity ± 2.2 ° / ₀ mass fluctuation

X-ray interference latitude 1.05 °

Crystalline content 18.8%:

Crystallite melting point 265 ° C

Shrinkage 14%

Comparative Example A:.

The procedure is as in Example 1, but instead of the jet Add non-solvent or poor solvent methylene chloride as solvent, so that a pure 18% polycarbonate solution results. The threads drawn above the ET at a ratio of 1: 6.8 have the following properties: ■

Titer 50/20 den

Tear strength 3.2 g / den

Elongation at break 22%

Yarn uniformity ± 25% mass fluctuation

X-ray interference width 2.45 °

Crystalline content 3%

Crystallite melting point cannot be determined After one minute in trichloro

. ethylene decay

Comparative example B:

The procedure is as in Example 1, but jets a mixture of methyl glycol acetate into the ίο mixing element Methylene chloride in such a ratio and amount that a 17.5% polycarbonate solution with a methyl glycol acetate content of 42%, based on polycarbonate, results. The one after the stretching in a ratio of 1: 6.8 Threads obtained above the ET have the following properties:

Titer 80/39 den

ao tear strength 3.15 g / den

Elongation at break 27%

'' Thread uniformity ± 3.5% mass fluctuation

X-ray interference width 1.32 °

Crystalline content 17.5%

Crystallite melting point. ¹²⁴² ° C

Shrinkage 18%

Claims (3)

1 2 These non-dissolvers or poor dissolvers were used in quantities of 10 to 100%, preferably 25 to 50%, based on polycarbonate. 1. Threads made of high molecular weight, linear poly In addition to their crystallization-promoting effect on carbonates, characterized in that 5 high molecular weight linear polycarbonates have that the stretched structures. an X-ray previously mentioned connections but also interference width in the range from 1.05 to 1.15 °, disadvantages. In the production of threads from such a crystalline proportion of 18.8 to 20.5% b. ^e - Polycarbonate solutions occur as a result of phase separation, sit and the crystallite melting point is not below 260 ° C in the case of thread changes in viscosity or as a result of decomposition of shaped structures. io of the additions faults, so that it is difficult 2. A process for the production of threads from any threads from such solutions to obtain linear, high molecular weight polycarbonates, so that, for example, when using the good effect characterized in that the solutions seed polyhydroxy compounds in the thread linear high molecular weight polycarbonates with a position according to the known Process of the dry content of 15 to 25 percent by weight of poly- 15 spinning a relatively high residual content of carbonate so much of a bad or nonsolvent called polyhydroxy compounds in the threads, or mixtures thereof, that the result, which due to its softening effect, has a negative effect Solution causes a content of 14 to 24 controlled post-crystallization and also has a weight percentage of high molecular weight linear poly- in general the technological properties, carbonate, with chlorinated hydrocarbons 20 such as tensile strength and elongation at break, as well as the Temals bad or Nic be used htlöser, ^N peraturbeständigkeit as a result of Kristallitschmelzderen value of the cohesive energy density] / ~ e = 8 point depression adversely affected. For the Herbis 10 and whose boiling points are between 60 and position of crystalline polycarbonate threads after 180 ° C, the gelled solutions are suitable for a short dry spinning process, the esters of phos heated to temperatures between 70 and 150 ⁰ C, 25 phosphoric acid due to decomposition, then these solutions only spun into threads at the required spinning temperatures and the spun threads are drawn. limited. In addition, many find well-suited ones 3. The method as claimed in claim 2, characterized in that non-solvers or poor solvers mark a limit of their application, that, as a non-solvent or poor solvent, dichloromability due to its easy flammability or inflammable propane or chlorobenzene is used. 30 availability. The present invention relates to threads made of high molecular weight, linear polycarbonates, which there- ______ are characterized by that the stretched Gebil de an X-ray interference width in the range of 1.05 35 to 1.15 °, a crystalline proportion of 18.8 to 20.5% and the crystallite melting point at thread- It is known that high molecular weight linear poly-shaped structures are not below 260 ° C,
carbonates based on bisphenols according to another object of the invention is a different process for threads, films, foils and drive for the production of threads from linear, highly similar structures from the melt or from the general 40 molecular polycarbonates, which are marked thereby Methylene chloride solution are deformable net that the solutions are more linear hochmolesind. In addition to some very valuable polycarbonates with a content of 15 to full properties, in particular good light weight percentages of polycarbonate, these structures have as much resistance, excellent electrical insulation properties, poor or nonsolvent or. Mixtures of the same quality and low flammability, one of which adds to the fact that the resulting solution has an insufficient solvent resistance content of 14 to 24 percent by weight of high molecular weight due to its inadequate crystalline linear polycarbonate, with chlorinated carbon content of <5% . Hydrogen used as a poor solvent or non-solvent has a particularly disadvantageous effect. Too low a crystalline content in threads or fibers, whose value for the cohesive energy density results in a very strong titre unevenness 50 "fi = 8 to 10 and their boiling point are between 60 and ± 25% of the stretched filamentary structures ■ 180 ⁰ C, which is profiled solutions briefly to noticeable. temperatures between 10 and 150 ⁰ C heated Toggle It is furthermore, according to the published, these solutions are spun into threads and the Documents of Belgian patents 646 153, 646 154 drawn spun threads. Preferably will and 646 155 known that threads or fibers or 55 here as non-or. Bad solvent dichloropropane or Foils or films made from high molecular weight linear polychlorobenzene are used. , carbonates based on bisphenols with increased such non- or poor solvent or non- or crystalline portion and, associated with it, with a bad solvent mixtures have under normal conditions improved solvent resistance and improved the following properties: Let uniformity be established by 60 · - " the solutions in methylene chloride before deformation a) they must be determined by the polycarbonate to be used Non-solvers or bad solvers mixed in. As a solution, exert a gelling effect, whereby suitable non-dissolvers or poor dissolvers are, according to their own, the gelled solution even after a long standing time older proposals mono-, di- and / or poly-, up to 500 hours even when used relatively Hydroxy compounds or their esters and / or high amounts of the additive (e.g. 100% ether, Esters of phosphorous acid as well as alkyl, attracted to the polymer) must not harden and Alkylene and / or aryl carbonates used must have predominantly viscous properties been. and therefore remains spinnable;