DE2240534A1 - COLORABLE POLYOLEFINE-BASED PLASTICS - Google Patents

Description

" Colorable polyolefin-based plastics "

The invention relates to plastics on the basis of polyolefins, especially polypropylene, which can easily be dyed.

It is known that polyolefins such as crystalline polypropylene and polyethylene can be used to form fibers, films and other molded articles can be deformed with excellent physical and mechanical properties. These polyolefins alone however, they cannot be easily colored with the aid of the usual coloring processes and dyes. So one tries For many years, the affinity of polyolefins for dyes and a number of proposals in this direction have already been made.

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A widely used method to improve the dyeability is that one other in the polyolefin Polymers or copolymers incorporated that absorb the dye better. So was for a copolymer of ethylene and an aminoalkyl acrylate achieved considerable success in the Improvements in dyeability, particularly with acidic dyes, have been reported. By adding this copolymer it is true that the dyeability of the polyolefins can be improved without impairing their physical properties However, such an addition increases the production costs significantly, especially since the quantities are quite large (by about 10%) must be incorporated if you have a corresponding Wants to achieve dyeability. Another disadvantage of using polymers with better absorbency for the dyes, such as the above-mentioned copolymer of ethylene and aminoalkyl acrylate, consists in that, if you want to achieve sufficient exhaustion of the dye baths, strongly acidic (corrosive) dye baths (pH 2 or less) must use. In addition, the copolymer has only limited thermal stability, so that the spinning and extrusion temperatures must be kept precisely under control.

In contrast, a new class of additives has now been found that enable the coloring of polyolefin plastics and have various advantages over the known means for this purpose. Subject of Invention are dyeable plastic compositions based on polyolefin, characterized by a content of a polyamine adduct, the at least one hydrocarbon chain bonded to a nitrogen atom with at least 25, preferably at least

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has at least 50 carbon atoms, or with a content of a salt of such an adduct.

The term "hydrocarbon chain" "denotes one mono- or polyvalent hydrocarbon chain, the at least is essentially aliphatic, e.g., an alkyl, alkenyl, or alkylene chain, optionally aromatic or can have cycloaliphatic substituents, like the chains in polymers or copolymers of olefins. Depending on the type of manufacture, however, smaller Amounts of one or more elements other than carbon and hydrogen, e.g. chlorine, are present be.

The polyamine adduct can have one or more polyamine groups each of which contains two or more amino nitrogen atoms, at least one of the latter primary, secondary cr which is especially tertiary.

The polyamine groups come from aliphatic, cycloaliphatic, aromatic or heterocyclic diamines and higher amines - i.e. amines with two or more amino groups * -, which generally have a molecular weight of less than 300. Preferably is the polyamine group aliphatic. Examples of suitable diamines are ethylene-1,2-diamine, propylene-1,2-diamine, propylene-1,3-diamine, the butylenediamines, 1- (2-aminopropyl) piperazine and benzene-1,4-diamine, ■■ --e- A preferred diamine is N, N-dimethylpropylene-1,3-diamine. Examples of suitable higher amines are the polyalkylenepolyamines, such as the poly

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ethylene polyamines and the polypropylene polyamines. Specific Examples of the latter class are diethylenetriamine, triethylenetetramine and tetraethylenepentamine. The hydrocarbon chain of at least 25 carbon atoms sits on one nitrogen atom of the polyamine group.

Polyamine adducts with at least two polyamine groups are already available described in the patent literature. They can be produced by reacting a halogenated hydrocarbon, the at least two halogen atoms as substituents and a hydrocarbon chain of at least 25 carbon atoms with a polyamine. The halogen atom or atoms are replaced by polyamine groups, the relevant Hydrogen halide is formed.

Among the polyamine adducts, those are preferred which have only a single polyamine group in which at least one alkyl or Alkenyl group of at least 25, in particular at least 50 carbon atoms. Such polyamine adducts and their preparation are also described in the patent literature. In a particularly advantageous known manufacturing method one starts from an alkene polymer with a terminal double bond, such as polyisobutene. By chlorination in an inert Solvents with about the theoretical amount of chlorine (preferably an excess of 10 to 3%) are obtained a substituted allyl chloride with elimination of hydrogen chloride. Further chlorination gives chlorine substituents, which do not correspond to the allyl type. With the monochlorination product obtained in this way the polyamine is alkylated to a polyamine adduct, the one or several alkenyl substituents attached to nitrogen atoms

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has, the number of which depends on the molar ratio between the alkenyl chloride and the polyamine.

A preferred group of polyamine adducts are those represents "in which at least one monovalent hydrocarbon group with at least 50 carbon atoms and at least a monovalent hydrocarbon group with at most 10 C atoms are directly bound to nitrogen and in which the number of hydrogen atoms bound to nitrogen is smaller than the number of nitrogen atoms present in the polyamine adduct. Particularly useful adducts contain a tertiary nitrogen atom, such as the N-alkenyl-N, 'N'-dimethylpropylen-i, 3-diamine.

The average molecular weight of the polyamine adduct is generally at least 800 and can be up to 500,000 or be higher. A preferred molecular weight range is between 1,000 and 10,000, in particular between .1 500 and 5 000.

The polyamine adducts can also be used in the form of their salts e.g. in the form of your own British Patent Application No. 61769/70. The acids from which these salts are derived are organic or inorganic Acids such as phosphoric acid, sulfuric acid, p-toluenesulfonic acid and diethyl phosphate.

In order to be sufficiently dyeable, the plastic compositions according to the invention must be at least 0.01 % By weight amino nitrogen, with a preferred range for the nitrogen content at 0.05 Ms 0.5% by weight lies. To do this, the masses usually contain

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at least 3% by weight, preferably 5 to 15% by weight Polyamine adduct.

In addition to the polyamine adducts or their salts, the Plastic compounds according to the invention also have other additives, such as alkali salts of aralkanoic acids or hydrochloric acid contain or a copolymer of acrylonitrile, butadiene and styrene, a copolymer of ethylene and one Alkylaminoalkyl acrylate or heat and light stabilizers, Titanium dioxide and the like.

The plastic masses according to the invention can be produced ^ are made by mixing the polyolefin and the polyamine adduct or its salt in any way, e.g. by a mechanical mixing device, or by mixing the adduct in powder form or in solution with A polyolefin powder $ dry powder can optionally be granulated. The preparations obtained in this way can be used for the production of fibers, films, Textiles and other dyeable articles of daily use with the aid of known processes such as melt spinning, film fibrillation and injection deformation. After their production, foils and fibers are usually processed at a higher temperature, e.g. stretched at 373 ° K, the stretching ratio mostly is between 1: 2 and 1: 6. It can also be advantageous to use the object in question before it is colored to treat acidic agents in order to increase its ability to absorb the dye even further. Examples of such Agents are hydrochloric acid, phosphoric acid, sulfur dioxide, formic acid and sulfur monochloride.

The dyeing can be carried out in a known manner, wherein

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acidic dyes such as Trimacide Light 2 B, Anthraquinone Blue Sky, Palatine Qellow ELNA-CF, -Tectilon Red 5 B and Tectilon Blue E have proven to be the best. Among the others Suitable dyes are the pre-metallized and disperse dyes.

Emulsified or disperse carriers such as benzyl alcohol, cresotinic acid methyl ester, a mixture of phenol and trichlorophenol, glycerine esters of fatty acids, etc. can be used in the aqueous dyebath, and such carriers can be used in a proportion of 0.5 to 20 g / l of the dyebath will. The temperature of the dyebath is in general about 55O ⁰ C, for example at 573 ° K. Is a printing apparatus abil, so bath temperatures may be employed of from 570 to 4-20 ⁰ K. The pH of the bath is preferably between 2 and 6 and in particular between 5 and 5. The dyeing time varies between 5 minutes and 4 hours. A weight ratio between bath and material to be dyed of 10: 1 to 100: 1 is particularly suitable.

The dyeability can be compared visually based on the tones of the finished products, but can be more accurately compared with optical instruments or from the level of exhaustion in the bathroom. In the case of fibers in particular, it is common to to take bath exhaustion as a criterion.

example 1

Polypropylene powder with an intrinsic viscosity £ h 7 of

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2.5 dl / g (measured in decalin at 135 ^° C.) was mixed with 10% by weight of the following polyamine adducts:

(A) an adduct of polyisobutenyl chloride (molar weight 1250) and tetraethylene pentamine, converted in the molar ratio from 1.3 / 1; 0.26 wt% N in mass;

(B) As A, but converted in a molar ratio of 2.6: 1; 0.15 wt% F;

(C) As A, but converted in a molar ratio of 3 »6: 1; 0.105 wt% N;

(D) an adduct of polyisobutenyl chloride (molecular weight 1250) and N, N-dimethyl-1,3-propylenediamine, reacted in a molar ratio of 1.1: 1; 0.12% by weight of N in the Dimensions;

For comparison:

(E) a commercially available spinnable polypropylene with a ^ n_7 value of 2.5 and an ethylene / amino-alkyl acrylate content, which corresponds to 0.19 wt% amino nitrogen.

The plastic masses were dried overnight under vacuum at 70 ⁰ C, mixed and processed on a two roll mill at 180 C, after which they were spun at a spinneret temperature of 255-260 ⁰ C. The spinning speed was 3 »5» the take-up speed was 350 m / min. The spun fibers were tested for dyeability with Tectilon Eed 3 B and Tectilon Blue R at various

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Temperatures and different pH values of the acidic baths were investigated. The ratio of bath liquid to material to be dyed was 30: 1, the dye concentration was 4 % of the fiber weight and the dyeing time was one hour (after half an hour of heating).

The table shows the degree of exhaustion of the bath as a percentage: '

Polyamine adduct AB CDE

Tectilon Red 3 B: 4-5 70 60 100 100 125 ° O / pH 2 80 40 30th 80 100 100 ° C / pH 2 70 4-5 20th 100 30th 100 ° C / pH 3 25th 20th 90 10 100 ° C / pH 5

Tectilon blue R:

125 ° C / pH 2 2 95 85 35 100 100 100 ° C / pH 2 60 - 30th 100 100 100 ° C / pH 3 95 - 20th - 45 100 ° C / pH 5 70 100 20th B e i s ρ i e 1

A mixture of 30 g of polyethylene with an average molecular weight of 6,200 and an unsaturation of 0.16 meq / g

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and 20 ml of CCl ^ was refluxed, whereupon 10 mg of AIBN (α, α-azobusobutyronitrile) were added to it. 90 mmol of chlorine were passed through the mixture over a period of four hours. Every hour, ie three times, 10 mg of AIBN were added to it. After stripping off the CCl ^, 33 g of chlorinated product remained with a chlorine content of 9177% by weight. The product was mixed at 433 ⁰ K 91 mmol and 180 mmol Dimethylaininopropylamin Napco ^ and held for 5 hours at this temperature, whereupon it 125 mmol NaOH were added within a further hour. The resulting reaction mixture was diluted with n-heptane and extracted three times with water / methanol 90:10 at 363 ° K. After the organic layer had been removed from the solvent, it was dried in vacuo at 333 ° K overnight. Yield: 33 g of a light brown solid, insoluble in chlorinated and aromatic hydrocarbons; Chlorine content: 5.06% by weight, nitrogen content 0.72% by weight.

The product was pulverized and 10 g of it was mixed with 90 g of a polypropylene powder with a melt index of 5 »5 dg / min (at 503 ° K and a load of 2.16 kg). The mixture was kneaded and spun in a single-thread extruder, at a piston temperature of 523 ° K and a spinneret temperature of 533 ° K, a draw ratio of 100 and a nozzle opening diameter of 0.5 mm. The spun thread thus obtained was dyed with Tectilon Blue H and Tectilon Red 3 B; Ratio Bad to be dyed * 30: 1, pH = 3 j dye concentration = 4 wt .-% (based on the yarn), heating: within half an hour ▼ on 293 ⁰ K to 373 ° K, then for another hour at 373 ° K. With Tectilon Blue R the bath exhaustion was 80 % _t with Tectilon Bed 3 B 60 %. The thread was dyed in a deep tone in both cases. PATENT CLAIMS:

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Claims (10)

PATENT CLAIMS 1) Dyeable plastic compound based on polyolefin, gekennz ei cn net by a content of a polyamine adduct which has at least one nitrogen atom bonded hydrocarbon chain with at least 25 carbon atoms has, or on a salt of such an adduct. 2) plastic compound according to claim 1, characterized in that the polyamine adduct Hydrocarbon chain has at least 50 carbon atoms. 3) plastic compound according to claim 1 or 2, characterized in that the adduct or its Salt contains a polyamine group derived from a diamine or higher amine with a molecular weight of less than 300 is derived. 4) plastic compound according to claim 3 * characterized in that the polyamine group is aliphatic is. 5) plastic compound according to claim 1, characterized ge 1A-41 783 indicates that the polyamine group of Ν, Ν-Dimethylpropylen-1,3-diamine is derived. 6) Plastic compound according to one of the preceding claims, characterized in that the adduct has only a single polyamine group. 7) plastic compound according to one of the preceding claims, characterized in that the adduct has a molecular weight of 1,000 Ms 10,000, in particular of Has 1,500 to 5,000. 8) plastic compound according to any one of the preceding claims, characterized in that it is so much Adduct contains that their amino nitrogen content is 0.05 to 0.5% of their weight. 9) plastic compound according to one of the preceding claims, characterized in that it contains 5 to 15% of its weight in adduct. 10) plastic compound according to one of the preceding claims, characterized in that the polyolefin contained therein is polypropylene. 309808/1 257 3 Π ί) 8 DR / 1? ^c .