DE1570844B2 - PROCESS FOR PRODUCING HIGH POLYMERS BY POLYCONDENSATION - Google Patents

Description

The invention relates to a process for being subjected to polycondensation.
Manufacture of high polymers through polycondens - When using spheres, cubes, cylinders,

The product of the polycondensate to be produced after a diffusion path is advantageously 0.05 to 5 mm, in the case of foil deformation on particles of a defined shape and size, flakes and fibers 0.001 up to 0.5 mm.
is further condensed in the solid state, given- The particle mixtures are produced by

if in a continuous manner. Mixing before polycondensation. But you can

It was found that the course of the poly- also by separating off certain particle size condensation of the diffusion of the 60 fractions during the reaction over sieves after the end of the polycondensation in each case The compound split off from the sation controls the molecular weight distribution precondensate formed particles and thus achieve from the lung. The execution of this operation depends on the shortest route to the surface. For a short time in the technical framework, the usual and a uniform path to the surface creates small aggregates.

Products with a narrow molecular weight distribution. 65 The molecular weight of deformed particles lung. If the diffusion path is long and inconsistent, preliminary products can fluctuate within wide limits, products are created that are widely distributed. Because it depends on the effects to be achieved in the end defined shaping succeeds the diffusion product as well as according to the reaction conditions and

3 4

apparatus-related conditions. Can be added in the case of poly- sation. The addition of suitable mono-

Ester condensation from terephthalic acid and ethylene mers is also conceivable, provided that the polycondensation

Glycol cannot interfere with the molecular weight of the precondensation. These monomers can

sates are between 200 and 10,000 or higher. even parallel to the condensation reaction for itself

While there are no upper limits, 5 will polymerize or onto the polycondensate formed

the lower molecular range through the enamel in the particle graft.

point of the preliminary product. For the given one, however, the Case should be the particularly favorable appearing molar polycondensation of mixtures of different partial weights can be determined by preliminary tests. chen, such as from polyamide and polyester die Further condensation of the particles of defined preliminary products, with a specific molecular weight distribution and size is at temperatures below the same as under the conditions of the polycondensation Melting point of the respective product through- sation in the melt is not possible, guided. The temperature is therefore different from case to case in contrast to previous polycondensation methods. The process permits the choice of the most favorable reactions in melt or powder temperature also has the special relationship to the production of polycondensates factors, such as, among other things, the stability of the starting material with a targeted and defined molecular weight distribution and end products and the reactivity of the system, lung and great uniformity. While there so far To take into account. The reaction can also be used when it was not possible to control the increasing reaction Temperatures are carried out. Are these conditions and equipment the end products are crystalline, it is advantageous to achieve the 20 uniformly reproducible, this is after condensing particles for a longer time at temperature by choosing the method according to the invention in which the polycondensates too critical a suitable diffusion path over the shape of the start installing. By doing this, particles can be easily accomplished. You can too sticking of the particles and crusting increases the breadth of molecular weight distribution easily on the wall of the apparatus. 25 by changing the mixing ratio of the

The further condensation will affect particle sizes in a temperature. ' range between the melting temperature and about 100 ° C, preferably 50 ° C below, the production is carried out quickly and without difficulty. In practical experiments it has been found to be unfortunate that polycondensate types with the different It has been shown to be expedient to convert the further widths of molecular weight distribution to be carried out in a temperature range, what exactly depends on the application-related face of the as close as possible below the melting point from is very desirable. Since you are in such lies, but it is to be chosen so that the individual cases through lengthy experiments to the recipe particles do not stick together. This area of manufacture of products with desired changes e.g. at 13 to 10 ° C below the melting molecular weight distribution must go temperature. For further condensation, such production changes will be made with the previous to achieve the desired molecular weight distribution polycondensation methods at the expense of the host takes a certain amount of time, depending on the uniformity. The functioning of the procedure replaced However, the product and the temperature used allow a quick changeover, since fluctuates within wide limits. In general, 40 is due to the defined particle size and targeted fraction of this Time between a few minutes to several particle size distribution, the setting of the new per hour, For example, 10 minutes to 10 hours can be done immediately and reproducibly, or more. In the practice of the method is also applied to the manufacture of Process times have been applicable for carrying out block copolycondensates, polycondensation from about 30 minutes to about 45 minutes. 4 hours proved to be particularly useful. example 1

The process according to the invention can be carried out in vacuo, in a heatable, thermometer, column and at normal pressure. The stirrer vessel, which is equipped with a connected cooler, can, but does not have to, require a mixture of 6000 parts by weight of dimethyl. Understandably, it is indispensable for oxy terephthalate, 4800 parts by weight of ethylene glycol and products sensitive to dation. The 1.38 parts by weight of zinc acetate (· 2H ₂ O) within the process is gradually heated to 220 ° C. for 190 minutes, very versatile and is carried out in the usual apparatus suitable for 1975 parts by weight of distilling for this purpose . With methanol from. After adding 1.5 parts by weight of the use of appropriate aggregates, 55 triphenyl phosphite and 1.8 parts by weight of antimony can also be carried out continuously. The trioxide is the excess glycol within the movement of the particles during the reaction is expedient - from 30 minutes at slowly increasing to 270 ° C, moderate, but not necessary. Temperature and continuously falling to 1.8 Torr. The polycondensation is driven off after the pressure according to the invention in the vessel. Thereafter, the Ge process can also be heated in the presence of other substances that are not involved in the actual reaction for 60 mixing 30 minutes at 1.8 Torr vacuum to 275 ° C., a precondensate being formed. The spezistattfinden, the fish to form after the processing viscosity of the precondensate, measured in the fabric special effects, such as, for example, as anti-Ubbelohde viscometer than l ° / ^e oig solution in a statikum, plasticizer, stabilizer, pigments jeg- mixture phenol Tetrachloroethane, of the type of mixture, fillers, modification and foam 65 nis 60:40) at 25 ⁰ C, calculated according to the formula medium and crosslinker, should cause. Self- ^ course, also mixtures of these substandard γ, ^λ _ti ~~ ° zen before the particles or during the polycondensates * ^v 'T ₁

(T ₁ = flow time of the solution, T ₀ = flow time of the solvent) is 0.3.

This preliminary product was ground and the ground material was divided into not too small a number of fractions divided according to the particle size, in the selected example into 8 particle fractions, which in the following Table 1 in column 1 (order of the fractions) and column 3 (particle diameter) are.

When grinding was carried out, those in column 2 of the table were found for the 8 particle fractions 1 specified percentages by weight of the intermediate product. Depending on the duration and intensity of the carried out grinding, the proportional participation of the 8 particle fractions in the ground Move preliminary product.

The 8 particle fractions were each subjected to polycondensation for a period of 50 minutes by heating with stirring in a vacuum vessel at 250 ^{° C. and 0.4 Torr vacuum.} This gave 1 to 8 polycondensates from the individual particle fractions with the values for their specific viscosities and the average molecular weights calculated therefrom, given in columns 4 and 5 of Table 1 and determined by the method described above.

Condensed a mixture, which is again composed of the 8 particle fractions of the milled precursor (precondensate) as indicated in Table 1 by subjecting the mixture in a vacuum vessel at 0.4 torr vacuum for 50 minutes at a temperature of 250 ⁰ C. was stirred, a polycondensate was obtained, the specific viscosity of which was determined by the method given above to be 0.748. This gives an average molecular weight (number average) of 16,700.

• By mixing several particle fractions of the preliminary product with one another in the same or different The quantities and polycondensation of these mixtures are entirely up to you, the properties to design the polycondensates produced largely as desired, d. H. the specific viscosity and thus to control their molecular weight distribution according to the invention at will.

Table 1

Particle
fraction
No. Weight
percent By
knife
in mm η spec. *) MJ -IQ ³ **) 1 30th 1.00 to 2.20 0.689 15.3 2 20th 0.75 to 1.00 0.740 16.5 3 15th 0.60 to 0.75 0.833 18.6 4th 10 0.50 to 0.60 0.890 20.0 5 10 0.40 to 0.50 0.969 21.9 6th 8th 0.30 to 0.40 1.014 23.0 7th 5 0.20 to 0.30 1.070 24.3 8th 2 <0.20 1.088 24.5

Example 2

If the particle fractions (grain size fractions) specified in Example 1 and formed from the preliminary product are each polycondensed for 120 minutes with stirring at 250 ° C. and 0.4 ton vacuum, polycondensates are obtained; their specific viscosity and mean; -Molecular weight according to C o η i χ from Table 2 can be seen. - ■ · ■ ·. ··· '-

Table 2. η spec. M7-W ³ - particles
fraction
No. diameter
in mm 0.972 21.9 1 1.00 to 2.20 1.101 22.9. 2 0.75 to 1.00 1,313 30.0 3 0.60 to 0.75 1.437 33.0 2O 4 0.50 to 0.60 1.476 33.8 5 0.40 to 0.50 1,589 36.5 6th 0.30 to 0.40 1.623 37.2 7th 0.20 to 0.30 1.665 38.8 8th <0.2

*) Because of the high crystallinity of the polyesters obtained in this way In contrast to the precursor described above, which is dissolved at 80 ° C., these can only be achieved at temperatures be brought into solution above 120 ° C, additional stirring or shaking accelerates the dissolution process.

**) IvTn is the average molecular weight (number average), calculated according to C ο η ix, "Makromolekulare Chemie" 26, (1958), p. 22.

For a mixture of the 8 particle fractions in

the mean specific viscosity determined according to the weight percentage ratio given in Example 1 is 1.023, from which a number average molecular weight of 23,000 is calculated.

Example3

The approach described in Example 1 for the preparation of polyalkylene terephthalate is polycondensed to a precondensate by heating for 45 minutes at 275 ° C. and a vacuum of 1.8 Torr. The intermediate product obtained in this way is processed in a known manner into strips 0.7 mm or 1.5 mm in diameter. The ribbons are then cut into cubic particles in the ribbon granulator. Each of the two types of granulate is heated individually in a heated rotary tube from 130 to 250 ^° C. within 2 hours and then polycondensed at 0.4 Torr vacuum and 250 ^° C. for 3 hours. A mixture of 70 parts by weight of granules 0.7 mm in diameter and 30 parts by weight of 1.5 mm thick granules is heated in the same way as indicated above for the types of granules, and then polycondensed. Table 3 shows the influence of the particle diameter and the proportionate participation of particles with different particle diameters in a mixture on the molecular weight distribution.

Table 3

No. Diameter in mm η spec. M7-10 ³ . 1 0.7 0.92 20.8 2 1.5 0.73 16.3 3 Mixture of 0.86 19.43 70 weight percent No. 1 30 weight percent No. 2

Claims (5)

1 2 ■■■ Patent claims · how to make the particles short or long and you have it in your hand by heating them together 1. Process for producing high poly of particles with a long diffusion path or with merging by polycondensation, resulting in a short diffusion path, or by mixing them indicates that a precursor of the 5 particle with a long or short diffusion path, to be produced polycondensates after shaping the molecular weight distribution as desired on particles of defined shape and size in the control. solid state is further condensed, given- As a preliminary product is a if in a continuous "manner. low molecular weight reaction product of the 2. The method according to claim 1, characterized in that ίο production of the polycondensates required, that the form and size gang connections with a defined melting range defined particles in the forms of cubes or designated In the manufacture of polyethylene cylinders be applied. terephthalate, it is usually the terephthalic acid 3. The method according to claim 1 and 2, characterized in bisoxyäthylester or precondensed polyethylene that the shape and size 15 terephthalate. In the case of polyamide made from adipic acid and defined particles of precursors from hexamethylenediamine can make the precursor adipine Polyesters or polyamides or acidic hexamethylenediamine or a precondensate polyimides in the solid state can be further condensed with a low molecular weight. will. Under polycondensation productions the 4. The method according to claim 1 to 3, thereby understood reactions in which under cleavage characterized in that the further condensation in a volatile high molecular compound Vacuum or normal pressure is carried out. Polymers are formed. The inventive 5. The method according to claim 1 to 4, characterized in that the method can be identified for the production of polycondens that the further condensation in seeds, such as high-polymer carboxylic acid anhydrides, Presence of reaction-inert, optionally 25 hydrazides, triazoles, aminotriazoles, tetrazines, carried out in gaseous substances. Ureids, thioureids, thioamids, imides, chinwird. oxalines, quinazolines, oxdiazoles, in particular but use of polyamides and polyesters. the Use of more than bifunctional starting It is known that in the case of polycondensation reactions 3 ° connections are also possible, but leads tions polymers with a molecular weight distribution to branched and crosslinked polymers. The Auslung the so-called "Flory transitional components can of course be classified" correspond to (P. J. F 1 ο r y, J. Am e r Chem. or be multiply substituted or hetero-atoms Soc. 58 [1936] p. 1877). Included depending on the choice. the reaction conditions and the apparatus are for the poly one obtains products with different condensation particles to be used in which the wide chain distribution. So far, however, it has been able to take the diffusion path from the shortest spatial axis there is no exact connection between reaction and is as uniform as possible in the particle, since this is conditions and molecular weight distribution - way the evenness and the degree of breadth be averaged. Determined because of the undefined and only 4 ° of the molecular weight distribution. When difficult evenly to be designed proportions of desired broad distribution, it is therefore possible During the reaction, the usual polycondensation leads to defined mixtures of particles of different proportions in the melt and in the powder always condense only to a molecular diffusion path. For the uneven and the production of the particles, which are difficult to reproduce, are available in many processes. This lower reproducibility has a reason that allow it to be deformed from the melt great influence on the evenness of production or pressing of powders, particles in the form of tion, so that therefore the economy considerably balls, cubes, cylinders, tablets, platelets and is affected. As the quality of finished products manufacture film filters. But you can also get through The distribution of grains depends essentially on the breadth of the molecular weight spraying from solution or melt is influenced, there is a need to testify 50, after classification according to particle size to control these in a targeted manner. in the individual fractions or defined mixtures