DD270549A1 - METHOD FOR STABILIZING FIBROUS, FLUORES, AND OTHER POLYOXADIAZOLE FORM BODIES - Google Patents

Abstract

The invention relates to a method for stabilizing fibrous materials, surface structures and other moldings of polyoxadiazole. The stabilization process is used in the polymer manufacturing industry, the chemical industry, and the polymer processing industry, light industry, for improving the light stability, the oxidation stability, and the weathering stability. This is achieved by the use of stabilizer combinations which are added to the polymer immediately after preparation or during further processing. Depending on the stabilization process, the stabilization can take place in or on the polymer. With this stability improvement of the polymer or products made therefrom, a greater range of application and a higher utility value is achieved on the textile and technical field of application.

Description

Field of application of the invention

The invention relates to the stabilization of Polyoxadiazolmassen in the original or in a finished composition against the degradation by light, oxidation and weathering during manufacture, processing and application, to advantageous properties of the polyoxadiazoles or treatment states thereof for the technical and textile. To obtain and improve implements for longer and more extensive care.

Characteristic of the known state of the art

Polyoxadiazole lasers, fabrics produced therefrom or other shaped articles have a low stability on exposure to light and acid with or without further agents such as water and other environmental factors. It is known polyoxadiazole against degradation by light or by light and heat or by weathering with low molecular weight organic compounds, eg. Example, with hydrazine (JP-PS 019348), with salicylic acid derivatives (JP-PS 003603), with amides or cyanides (JP-PS 120735) to stabilize. However, this type of stabilization does not result in sufficient effects in some cases by partial migration of the low molecular weight stabilizers, e.g. in case of possible washouts. It is also a stabilization of the polyoxadiazoles with staining known (JP-PS 000164). However, under application conditions, an undesirable change in coloration is accepted, which ultimately does not only lead to a deterioration in the appearance of the polymer.

Object of the invention

The aim of the invention is the development of a method for the stabilization of Polyoxadiazolmassen, such as granules, fibers, fabrics or other shaped articles in the unrefined or partially finished state and / or applied to their partial refinement or applied adjuvants and / or dyes against degradation by light, oxidation and weathering to obtain advantageous properties of the polyoxadiazole, for. B. strength, and its finishing states, z. As dyeings, to obtain longer, to increase the use cases, to increase its utility value.

Explanation of the essence of the invention

The object of the invention is the development of a process for the stabilization of polyoxadiazole in the crude composition and / or after incorporation of low molecular weight auxiliaries and / or dyes by application of polymeric stabilizers in combination with further organic compounds in or on polyoxadiazole granules or fiber materials or

Formed bodies in states of formation, in processing states, in moist, in swollen or in dried form against the damaging effect of light and oxygen and weathering. A further object of the invention is to use stabilizer combinations which, at low and elevated temperature in the dry and moist state during storage or when used in air under the action of light, give the polyoxadiazole pulps or molded articles increased light, oxidation and weathering stability. This is reflected in a lower discoloration, a more stable surface texture, a stabilization of the strength level j and thus a higher utility value or the reduction of material losses.

According to the invention, the object is achieved by combining substance combinations of the substances polyester resin, cyclohexanone peroxide, cobalt octoate, vinylbenzene and mono- and / or polyhydric alkylaryl hydroxy compounds and / or mono- or dihydroxydiarylcarbonyl compounds substituted or unsubstituted with the alkoxy group, and / or aliphatic or aromatic phosphates used as stabilizers.

Dihydroxydiarylcarbonyl compounds can be used as a unitary compound or as a mixture of differently substituted compounds.

When d "'stabilization is carried out in homogeneous mixtures.

Taking into account the technological conditions and the required field of use, it may be appropriate in organic medium, in the dipping, padding, film, orifice application or spraying method, at temperatures of 293-393 K for stabilizer application, at 298K during stabilizer application and at 299 to 293 K for homogenization and solidification without or with other processing aids to stabilize undyed or previously dyed Polyoxadiavol.

Advantageously, according to the invention, such reactive monomeric and / or polymeric organic compounds are used as constituents of the stabilizer combinations which, after their application and solidification, form a transparent film which has high water resistance and surface quality for preventing migration and degradation.

The composition of the stabilizer combinations and the amount of substance to be added in the stabilizer mixture depend on the application, the condition and the processing conditions of the polyoxadiazoles.

The use concentration of the stabilizers in the combinations vary between 0.1 and 100 parts by mass in%, in particular between 0.5 and 97 parts by mass in%, based on their homogeneous mixture.

With the stabilization a coloring can be carried out at the same time.

embodiments

The invention will be explained in more detail by exemplary embodiments.

Example 1:

Unprepared polyoxadiazole silk 100 tex f 1000 is prepared in a homogeneous mixture of the composition

58 parts by weight polyester resin in%

2 parts by weight of cyclohexanone peroxide in%

1% by weight of cobalt octoate in%

1 part by weight of mixture of alkylarylhydroxy compound> n%

1% by weight Mixture of mono- and dihydroxydiarylcarbonyl compounds in%

i? Mass proportions vinylbenzene in%

heated continuously at a temperature of 298 K for a short time and then through a pinhole for the purpose of further; Setting and homogenization of the coating led. The soaked or coated silk is solidified at 313 K in air. This creates a transparent, solid film on the silk. The light resistance of the silk is tested in a Xenotest device at 303 K and 67% relative humidity. Table 1 shows the exposure tearing force ratio (ratio of the tearing strength of the unexposed silk to that of the exposed silk) of the unstabilized compared to the stabilized silk after 20 hours of exposure.

Table 1 Polyoxadiazole silk, unprepared f _B in%

without stabilizer 17

with o.g. Mixture treats 66

Example 2: Polyoxadiazole silk 100 tex f 1000 is prepared in a homogeneous mixture of the composition

62 parts by weight polyester resin in%

2 parts by mass of cyclohexanone peroxide in%

1% by weight of cobalt octoatin%

1 mass fraction Mixture of alkylarylhydroxy compounds in%

1 mass fraction Mixture of mono- and dihydroxydiarylcarbonyl compounds in%

33% by weight of vinyl benzene%

at a temperature of 298K short time continuously wetted and then passed through a pinhole 'for the purpose of further network and homogenization of the coating. The soaked or coated silk is solidified and tested as in Example 1. Table 2 shows the corresponding exposure tearing force ratios f _B after 20 hours of exposure.

Table 2 Polyoxadiazole silk f _B in%

without stabilizer 30

with o.g. Mixture treats 61

Example 3: Yarn 50 "x 4" made from polyoxadiazole is placed in a homogeneous mixture of the composition

60% by weight of polyester resin in%

2 parts by weight of cyclohexanone peroxide in%

1% by weight of cobalt octoatin%

1 fair share Mixture of alkylarylhydroxybindings in%

1 mass fraction Mixture of monohydroxyrr.jnoalkoxy and dihydroxydiarylcarbonyl compounds in%

0, S mass fractions triphenyl phosphite in%

34.5% by weight of vinylbenzene in%

soaked for a short time at a temperature of 303K and then passed through a pinhole for further network and homogenization of the coating. The soaked or coated yarn is as described in Example 1 and solidified and tested. Table 3 shows the corresponding exposure tearing force fo after 20 hours of exposure.

Table 3 Yarn made of polyoxadiazole fiber f _B in%

without stabilizer 14

with o.g. Mixture treats 87

with o. g. Mixture treated and stored for 20 days in aqueous washing solution 87

Example 4:

Made of polyoxadiazole and dyed blue fiber 0.17tex / 38mm is laid to a surface and with a homogeneous mixture of the composition

58 parts by weight polyester resin in%

2 parts by weight of cyclohexanone peroxide in%

1% by weight of cobalt octoatin%

0.5 parts by weight of a mixture of alkyl & rylhydroxyverbindungentn in%

2 parts by mass Mixture of monohydroxy- and dihydroxydialkoxydiarylcarbony! Compounds in% 36.5 parts by weight of vinylbenzo! in %

coated at a temperature of 288 K and then solidified at 308 K in the air. Subsequently, the coated bevel; Illuminated behind window glass for 100 hours. Table 4 shows the visually assessed color of the uncoated compared to the coated fiber after exposure.

TABLE 4 Colored polyoxadiazole fiber color

without stabilizer very weak blue

with o.g. Mixture treats blue

example:

Slightly yellow colored polyoxadiazole silk 100 tex f 1000 is obtained in a homogeneous mixture of the composition

69% by weight of polyester resin in%

2 parts by weight of cyclohexanone peroxide in%

1% by weight of cobalt octnate in%

1.5 parts by weight of mixture of alkylarylhydroxy compounds in%

1.5 parts by weight of dihydroxydialkoxydiarylcarbonyl compounds in%

36 parts by weight Vinylbenzo! in %

at a temperature of 298K short time as in Example 1 and 2 wetted or coated, solidified and exposed for 100 hours left window glass.

Table 5 shows the visually assessed color of the uncoated compared to the coated silk after exposure.

TABLE 5 Colored Polyoxadiazole Silk Color

without stabilizer yellow

with o. g. Mixture treats slightly yellowish

Claims (13)

1. A process for stabilizing fibrous materials, fabrics and other moldings of polyoxadiazole against degradation by light and oxidation, characterized in that are applied to stabilize this polymer in the unrefined or refined, dried or moist preparation or processing state substance combinations consisting of the substances polyester resin, cyclohexanone peroxide, cobalt octoate, vinylbenzene and mono- and / or polyhydric Alkylarylhydroxyverbindungen and / or ί / lono- or Dihydroxydiarylcarbonylverbindungen, substituted or not t-vibstituiert with the alkoxy group, and / or aliphatic or aromatic phosphates. 2. The method according to claim 1, characterized in that the Dihydroxydiarylcarbonylverbindungen be used as a unitary compound or as a mixture of different substituted compounds. 3. The method according to claim 1 and 2, characterized in that one works in homogeneous mixtures. 4. Process according to claims 1 to 3, characterized in that is stabilized in the dipping process. 5. Process according to claims 1 to 3, characterized in that is stabilized in the spray process. 6. Process according to claims 1 to 3, characterized in that is stabilized by the padding process. 7. Process according to claims 1 to 3, characterized in that it is carried out according to the film coating method or pinhole application method. 8. Process according to claims 1 to 7, characterized in that is stabilized at 293 to 393 K. 9. Process according to claims 1 to 8, characterized in that the stabilizer combination at 298 K or introduced and uniformized at 299 to 393 K and solidified. 10. The method according to claims 1 to 9, characterized in that dyed fibers and / or fabrics and / or moldings are used. 11. The method according to claims 1 to 10, gekannzeichnet in that the stabilizer combinations are used simultaneously with antistatic agents and / or complexing agents and / or quenchers and / or lubricants or lubricants. 12. The method according to claims 1 to 11, characterized in that the use concentrations of the stabilizers and other additives 0.1 to 100 parts by weight in%, in particular 0.5 to 97 parts by mass in%, based on their homogeneous mixture amount. 13. The method according to claims 1 to 9,11,12, characterized in that a dyeing is carried out simultaneously with the stabilization.