CS245097B1 - Dyeable polypropylene for production of fibres, foils and other shaped products - Google Patents

Description

(54) Polythene polypropylene for the manufacture of fibers, sheets and other shaped articles

The present invention relates to the preparation of dyeable polypropylene for the production of fibers, films, nonwovens, fiber layers and the like.

It is known that isotactic polypropylene has some advantageous properties such as specific gravity, acid resistance, high strength, and others.

Due to its low production cost it becomes a material of interest for the production of textile fibers, foils and other shaped products.

Since its chain has an olefinic character in the absence of atoms or groups to bind dye molecules, the polypropylene fibers cannot be colored with conventional dyes. Attempts to color untreated fiber resulted in failure. The dyes were washed, resulting in a very light color. A further disadvantage is the relatively high content of crystalline fraction, which is not colored at all, since the penetration of the dye into the crystalline regions is virtually eliminated.

The methods for overcoming this major deficiency of polypropylene are mostly based on the principle of incorporating such compounds into polypropylene containing atoms or groups capable of forming bonds with dye molecules, for example by mixing polypropylene with other polymers or low molecular weight additives or complex compounds.

When the compounds containing basic nitrogen atoms are incorporated into the polypropylene, a blend is obtained from which the prepared fibers have an affinity for acid, direct, chromium, metallized and other types of anionic dyes commonly used in dyeing wool and polyamide. However, some additions such as styrene- (3-dimethylamino) propylamaleimide (1: 1) or polyvinylpyridine copolymers are poorly miscible with polyolefins, and such a mixture is not sufficiently homogeneous. In addition, when the fiber is subjected to frictional force during ducting and further processing, the additive is released from the polyolefinic phase and may fall out of the fiber and contaminate portions of the fiber. In addition, it has been found that increasing the molecular weight of the additive reduces the cohesiveness of the polymer blend Some processes utilize system cohesion agents obtained by copolymerizing ethylene or by grafting polypropylene with polar monomers in U.S. Pat. A polyolefin comprising a combination of a small amount of a polymeric basic dye receptor, for example a copolymer of 3- (dimethylamino) propylmaleinimide-styrene (1: 1) and an ethylene-acrylic acid copolymer.

These drawbacks of the cohesion and dyeability of polypropylene are solved by the present invention, in which the dyeable polypropylene for the production of fibers, films and other products comprises the addition of a polymeric neat of the formula

CH ~ _CH2 ~ CH CH I | what what ⁰¹

CH-CH ₂ CH-CH

what what \ /

Where R ¹ is an aliphatic, linear C 12 -C 25 alkyl (which also serves as a compatibilizer and R ² is 4- (2,2,6,6-tetramethylpiperidyl), 1- (3-dimethylaminopropyl)), or 1- (3-morpholinpropyl), or mixtures thereof, wherein the ratio x: v is 1: 1 to 1: 4 and the sum of x-y corresponds to a molar mass of 1000 to 15 000. We have found that this polymeric imide prepared condensation of the alternating styrene-maleic anhydride copolymer with a mixture of a primary aliphatic amine and a suitable diamine, incorporated into polypropylene, yields a blend having high affinity for anionic dyes: thermally stable, white and thermoplastic imide having a melting point above 100 ° C, good Suitable diamines for its preparation are 3- (dimethylaminopropylpropylamine, 3- (4-morpholino) propylamine and 4-amino-2,2,6,6-tetramethylpiperidine and mixtures thereof.

Primary alkylamines are recommended with 12 to 25 carbon atoms such as dodecylamine, octadecylamine, pentacosylamine and technical mixtures thereof. The molar ratio of diamine to primary amine ranges from 1: 1 to 1: 4.

The imidation reaction is carried out in a suitable mutual solvent at a temperature greater than 125 ° C, similar to that described in U.S. Patent 3,645,903. The mixture is prepared by vortexing polypropylene with a mixed polymeric stabilizer and a dispersant. Polyolefinic stabilizers are antioxidants for example alkylphenol compounds, inhibitors of UV-degradation for example benzophenone derivatives and heat stabilizers for example thioether compounds of carboxylic acid esters.

Dispersants are added to achieve perfect uniformity of the dispersion. These are low molecular weight surfactants such as sodium stearate, calcium stearate, stearic acid, methylene bisstearamide, oxethylated lauryl alcohol, and mixtures thereof. The uniformity of the dispersion can be clearly detected by coloring the film or by microscopic evaluation of the cross-section of the fiber.

The mixture is good colorable even with a relatively low modifier addition of 5 to 8 wt. This eliminates the adverse effect on fiber roughness and brittleness, while at the same time minimizing the cost of modification.

The fibers produced according to the present invention can be washed and dyed by immersion in a 1-3% dye bath at pH 2.5-3.5. Typically, the mixture is colorable by acidic dyes.

Reactive dyes, such as C.I. Reactive Red 24, or acidic stain dyes, such as C.I. Mordant Blue 13, can also be used according to the invention.

The staining results are compared by visual evaluation, or by using optical methods, or by measuring the relative amount of dye fixed on the sample.

The addition was prepared by dissolving 101 g, t, in 200 ml of acerone with stirring. j. 0.5 mol of a styrene-maleic anhydride copolymer having a molecular weight of 3000, then a solution of 30 g, t. j. 0.1 mole of 90% octadecylamine in 200 ml xylene. After stirring for one hour, the temperature was raised and acetone was distilled off. 0.4 mol of 3-dimethylaminopropylamine in 200 ml of xylene is added. The mixture is refluxed while removing the water formed. Water separation takes about 6 hours, then the reaction mixture is cooled and the polymer is isolated by pouring it into 2.5 L of heptane. The white powder was washed well with heptane on the filter.

In a similar manner, other additive derivatives were prepared using dodecylamine or pentacosylamine instead of octadecylamine and the like was replaced by 3-dimethylaminopropylamine 4-amino (2,2,6,6-tetramethylpiperidine) or 1- (3-morpholinopropyl) aminoinone or a mixture thereof in equal amounts, if any, altered in relation to said x: y ratios, and hence in the altered molecular amounts.

Analysis of the products obtained revealed 3.5% basic nitrogen.

EXAMPLE

160 g, i.e. 8 wt. % of a mixed polymer imide wherein R ¹ is an aliphatic linear alkyl of 12 carbon atoms, R ² is 3-dimethylaminopropyl at a ratio of x: y of 1: 2 with a relative mol. weight 5 000, 20g, ie 1 percent wt. sodium stearate and 1,820 g, i.e. 91 wt. The stabilized polypropylene powder having a flow index of 25 g / 10 minutes is homogenized and granulated at 220 ^° C. The granulate is extruded at 200 ^° C and relies on a fiber with a 1: 3.0 ratio.

A sample of 10 g of fiber is dyed in a bath of the following composition:

500 ml of water

0,2 g Egacid red MOOL (C.I. Acid Red 73), ml formic acid,

0.5 g of carboxymethyl heptaglycollauryl ether as leveling agent.

The dyeing is started at 60 [deg.] C., which is raised to boiling for 15 minutes and then dyed for 45 minutes at this temperature. The material is rinsed with water and washed in a 2 g / l solution of sodium lauryl sulfate at 60 ^° C for 20 minutes.

The final content of the fixed dye is 95 percent by weight, the light fastness reaches grade 4.

The experiment was repeated with Egacid Blue B (C.I. Acid Blue 45). In this case, the final content of the fixed dye is 98% by weight, the light fastness reaches degree 5.

Example 2

Mixture 120 g, ie 6 wt. mixed polymer imide wherein R ¹ is an aliphatic linear alkyl of 18 carbon atoms, R ² is 4- (2,2,6,6-tetramethylpyperidyl) at a x: y ratio of 1: 3.5 with a relative molecular weight of 10,000, 20 g, ie 1 wt. sodium stearate and 1,860 g, i.e. 93 wt. The stabilized polypropylene powder having a flow index of 25 g / 10 minutes is well homogenized and granulated at 220 ^° C. The granulate is extruded at 260 ° C and relies on a fiber with a ratio of 1: 3.0.

A sample of 10 g of fiber is dyed as described in Example 1. The final content of the fixed dye using Egacid MOOL (C.I. Acid Red 73) is 89% by weight, stability to dye. the light reaches grade 4. The experiment is repeated with Egacid Blue B (C.I. Acid Blue 45j). In this case the final content of the fixed dye is 94% by weight, the light fastness reaches grade 5.

Example 3

Mixture of 100 g, i.e. 5 wt. mixed imide polymer where R ¹ is an aliphatic linear alkyl of 23 carbon atoms, R ² is 1- (3-morpholinopropyl j at a ratio of x: y of 1: 4.0 with a relative molecular weight of 13,000, 20 g, ie 1% weight of sodium stearate and 1,880 grams, i.e. 94 weight% of stabilized polypropylene powder with a flow index of 25 g / 10 minutes, are well homogenized and granulated at 220 DEG C. The granulate is extruded at 260 ^DEG C. and fed to a fiber with with a 1: 3.0 ratio.

A sample of 10 g of fiber is dyed as described in Example 1. The final content of the fixed dye using Egacid MOOL (CI Acid Red 73) is 87% by weight, the light fastness reaches grade 4. The experiment is repeated with Egacid Blue B (CI Acid) Blue 45). The final content of the fixed dye will be 92% by weight, the light fastness reaches grade 5.

Example 4

Mixture 120 g, ie 6 wt. mixed polymer imide wherein R ¹ is an aliphatic linear alkyl of 18 carbon atoms, R ² is a mixture of 4- (2,2,6,6-tetramethylpiperidyl) and 1- (3-morpholinopropyl) at a 1: 3.0 ratio x: y having a relative molecular weight of 9,000, 30 g, i.e. 1.5 wt.% sodium stearate, and 1,850 grams, i.e. 92.5 wt.% stabilized polypropylene powder with a flow index of 25 g / 10 min., is well homogenized and granulated at temperature. 220 ^C C. the granulate is extruded at a temperature of 260 C and ^Q Dizii the fiber drawing stage in a ratio of 1: 3.0.

A sample of 10 g of fiber is stained as described in Example 1. The final content of the fixed dye using Egacid MOOL (CI Acid Red 73) is 91 wt%, the light fastness reaches grade 4. The experiment is repeated with Egacid Blue B (CI Acid) Blue 45). In this case, the final content of the fixed dye is 96% by weight, the light fastness reaches degree 5.

Claims (1)

SUBJECT We claim: Dyestuffable polypropylene for the manufacture of fibers, films and other shaped articles, characterized in that it consists of 90 to 96% by weight of dye. % isotactic polypropylene and from 4.0 to 8.0 wt. a thermostable polymeric imide of the formula CH-CH _and -CH-CH CO CO Wherein R ¹ is linear aliphatic alkyl of 12 to 25 carbon atoms, R ² is 4- (2,2,6,6-tetramethylpiperidyl), 1- (3-dimethylaminopropyl) or 1- (3-morpholinopropyl) or a mixture thereof, wherein the ratio of x: y is 1: 1 to 1: 4 and the sum of x + y corresponds to a molecular weight of 1,000 to 15,000.