RU2068903C1 - Composition for modified polyamide synthesis - Google Patents

Abstract

FIELD: chemical technology. SUBSTANCE: composition has polyamide and compound involving from 1 to 3 groups of the formula:

or

, or

, or

where R - hydrogen or methyl bound directly or through -O-, -NH-, -NHCO-, -CONH-, NHalkNH- with benzene nucleus that can contain COCl-group, or with reactive with regard to hydroxy- or amino-groups heterocyclic nucleus, or with group of the formula: -COCH= CH₂, or -CO--CH₂-CH₂SO₂C₆H₅, or -SO₂CH=CH₂, or with residue of reactive dye, or with polyamide residue at amount 1-5% of polyamide mass. Composition is prepared by mixing above mentioned compound with melted polyamide, for example, in extruder before spinning or in the process of polycondensation. EFFECT: enhanced effectiveness of composition, improved method of synthesis. 2 cl, 3 tbl

Description

 The invention relates to dyeing and finishing production, in particular to a composition for producing a modified polyamide.

 A known composition containing polyamide, a colorless organic compound containing a chlorotriazine moiety, and an acid dye (1).

 The introduction of a colorless compound into polyamide is carried out by the method of depletion of the bath, which provides a surface effect on the substrate and insufficient resistance of the color to wet treatments.

 A number of patents describe methods for producing a colored polyamide by surface dyeing of a polyamide in a solution of a reactive dye (2) or in a solution of a reactive colorless compound containing acid groups and a reactive dye (3). Colored polyamides have similar disadvantages due to the surface effect of the dye and excipients on the substrate.

It was found that the tintability of synthetic polyamides can be improved by using one or more of the following compounds for staining them in bulk:
a) a compound having at least one sterically blocked amino group / hereinafter referred to as compound (a) /; or
b) trimesic acid trialkylamide, at least one alkyl group of which is substituted by at least one free amino and / or alkylamino group, hereinafter referred to as compound (b) /; or
c) a trialkylamino-substituted triazine, at least one alkyl group of which is substituted with a free amino and / or alkylamino group, hereinafter referred to as compound (c) /; or
d) a dye (preferably an azo, anthraquinone or perinone series) that does not have free sulfonic acid groups and contains at least one group that is reactive with a hydroxy and / or amino group (hereinafter referred to as compound (d) /; or
e) a synthetic polyamide (preferably a polymeric or oligomeric isophthalic acid amide or terephthalic acid amide) containing at least one group that is chemically active with a hydroxy and / or amino group (hereinafter referred to as compound (e) /.

Compounds containing a sterically blocked amino group are preferably compounds containing a group of the formula
C (C _1-4 alkyl) ₂ —NR-C (C _1-4 alkyl) ₂
in which R is hydrogen, C _1-8 alkyl, C _1-8 alkoxy, or —COR ₅ ,
where R ₅ is hydrogen, C _1-6 alkyl, phenyl, COO (C _1-4 alkyl) or NR ₁₅ R ₁₆ ;
where R ₁₅ is hydrogen, C _1-12 alkyl, C _5-6 cycloalkyl, phenyl or (C _1-12 alkyl) phenyl; and R ₁₆ is C _1-12 alkyl or hydrogen; or R ₁₅ and R _16, together with the N atom to which they are attached, form a five to seven membered ring, which may contain an additional nitrogen or oxygen atom (preferably forming a piperidine or morpholine ring).

или

,
где СО образует часть циклической структуры;
каждый R₆ независимо является выбранным из водорода, С_1-2 алкил или фенила, при условии что только одна группа R₆ может быть фенилом, или обе группы R₆ образуют группу (СН₂)₁₁-, -(CH₂)_n-, -C(CH₃)₂-, -C(CH₃) -CH₂CH₂-, или -C(CH₃)₂ CH₂CH₂CH(CH₃)-, и n есть 1 или 2.Preferred groups containing sterically blocked amines are groups of formulas I to VI at the end of the description
where R is hydrogen, C _1-8 alkyl, C _1-8 alkoxy, or —COR ₅ ;
where R ₅ is hydrogen, C _1-6 alkyl, phenyl, -COO (C _1-4 alkyl) or NR ₁₅ R ₁₆ ;
where R ₁₅ is hydrogen, C _1-12 alkyl, C _5-6 cycloalkyl, phenyl, or (C _1-12 alkyl) phenyl; and R ₁₆ is C _1-12 alkyl or hydrogen, or R ₁₅ and R ₁₆ together with the N atom to which they are attached form from five to seven membered rings, which may contain an additional nitrogen or oxygen atom (preferably forming a piperidine or morpholine ring) ; and
Y is a group

or

,
where CO forms part of a cyclic structure;
each R _{6 is} independently selected from hydrogen, C _1-2 alkyl or phenyl, provided that only one R ₆ group can be phenyl, or both R ₆ groups form a group (CH ₂ ) ₁₁ -, - (CH ₂ ) _n - , -C (CH ₃ ) ₂ -, -C (CH ₃ ) -CH ₂ CH ₂ -, or -C (CH ₃ ) ₂ CH ₂ CH ₂ CH (CH ₃ ) -, and n is 1 or 2.

 Compounds containing groups of formulas III, IV and V are known, for example, from US Pat. US 4292240 and Japanen Kokai 62-190786, the contents of which are incorporated herein by reference.

 More preferred compounds a) to c) are compounds of formulas 1 to 38 (see formulas 1 to 38 at the end of the description).

,

где R' есть водород, С_1-6 алкил, С_1-4 алкокси или -СО-С_1-4 - алкил;
A есть С_2-3 алкилен;
R₄' есть формула α′ или α″

,

R₂ есть С_1-3 алкил.where each R ₃ independently is hydrogen or C _1-12 alkyl;
R ₄ is a group of formula α

,

where R 'is hydrogen, C _1-6 alkyl, C _1-4 alkoxy or —CO — C _1-4 alkyl;
A is C _2-3 alkylene;
R ₄ 'is the formula α ′ or α ″

,

R ₂ is C _1-3 alkyl.

D₂ D₇ есть группы, приведенные в конце описания.D ₁ is a group

D ₂ D ₇ are the groups listed at the end of the description.

Preferred groups that are reactive with —OH or —NH ₂ (compounds d) and / or e) are, for example, groups known as reactive groups in the chemistry of active dyes. More preferred groups are cyclic groups having at least two nitrogen atoms (preferably separated by one or two carbon atoms), for example triazinyl, pyrimidyl, quinoxalyl, quinazolyl groups of phthalazinyl, benzoxazolyl and benzothiazolyl groups having from 1 to 3 chlorine atoms on carbon atoms adjacent to nitrogen atoms.

в которых Z есть галоид (предпочтительно хлор) или группу формулы

где есть анион.More preferably, such groups have the formula I) to XI)

in which Z is a halogen (preferably chlorine) or a group of the formula

where is the anion.

Preferred alkyl is C _1-4 alkyl.

Such groups are described in Chemistry of Synthetic Dyes, Volume VI, Chapter I - E. Siegel (ed. K. Venrataraman) Academic Press (1972);
Chimica, Supplement Maiz 1968, Farban Syneposium Interlaken p. 102 et seq. E. Siegel Chemie der Raactiv farbstoff and Andew, Chem. 76, (1964), N 10 R. 423 et seq. KG Kleb "Ueber new Reactiv farbstoff".

Preferred compounds a) to c) for dyeing synthetic polyamides are compounds having one or two sterically blocked amino groups and one or two groups reactive with —OH and / or —NH ₂ .

Such compounds having one or two sterically blocked amino groups and one or two groups reactive with OH and / or —NH ₂ have the formulas 39 to 46 at the end of the description.

 The compounds of formulas 39 to 45 can usually be obtained, for example, by condensation of the corresponding acid chloride or acid chloride of cyanuric acid with a free amino or imino group of a sterically blocked amine-containing compound in appropriate quantities.

 Preferred azo, anthroquinone or perinone dyes of compounds o) having groups that are chemically active to hydroxy and / or amino groups are the compounds described in Examples 50 to 69 inclusive, described later.

Preferred compounds of polymeric amides of isophthalic or terephthalic acid e) are compounds of formulas VII and VIII
Pa (R ₁₁ ) _m VII
Pa (CO R ₁₂ ) _n VIII
in which Ra is a nitrogen-containing radical of a synthetic polyamide;
R ₁₁ is a group attached to the nitrogen atom of a polyamide molecule containing one or more hydroxy and / or amino reactive groups;
R ₁₂ is a group containing a sterically blocked amino group;
m is 1 or 2.

 The compounds of formulas VII and VIII can be added to the synthetic polyamide during its synthesis by polycondensation or added to the molten mass.

 The compounds of formula VIII can be obtained by known methods.

Compounds of formula VIII can be prepared when a synthetic polyamide having a terminal carboxyl group or a functional derivative thereof (e.g., an acid chloride or an ester) is reacted during the polycondensation process with compounds containing one or more amino groups or one or more sterically blocked amino groups, preferably aromatic nature. Reactive groups are preferably the groups described above as groups of formula A ^⊖ .

Compounds of formula R ₁₂ H that are used to prepare compounds of formula VIII have a reactive nitrogen atom, which is either an amino group or part of a cyclic group, for example a piperazine group,
These compounds may also contain one or two sterically blocked nitrogen atoms in a cyclic structure, for example, NC _1-4 alkyl or N-acyl substituted 2,2,6,6-tetraalkylpiperidyl-4-groups.

 Obtaining such modified synthetic polyamides having reactive groups and amino groups, well known to qualified specialists in this field of technology.

 The synthetic polyamides according to the invention can be colored in bulk with any dye, provided that it is stable at high temperatures (melt). Preferred dye groups are monoazo-metal complexes, in particular chromium complexes, which are sufficiently stable at high temperatures to be usable. Preferred chemically active dyes that can be used are metallized azo dampers containing a halogen, triazinyl or vinyl group (i.e., dyes metallized with chromium, nickel or copper). Such reactive dyes have been commercially available for a number of years.

 The preparation of the modified synthetic polyamides according to the invention can be carried out in the usual way, preferably by mixing the reactive compounds with the molten synthetic polyamide, for example, in an extruder before spinning or before or during the polycondensation of the synthetic amide itself.

 Usually use from 0.5 to 5 wt. compounds a) to e) based on the weight of the synthetic polyamide. More preferably, 1 to 2 wt. compounds a) to e).

 The synthetic polyamides according to the invention (for example containing a compound from a) to e) are outstanding in many respects compared to a synthetic polyamide that does not contain a compound from a) to e), hereinafter referred to as "untreated polyamide". When an untreated polyamide and a polyamide according to the invention are stained with an acid dye (using the same amount of dye per substrate), a significantly deeper and brighter color is obtained for synthetic polyamides c) according to the invention than an untreated polyamide. The depletion of the bath is noticeably better and the stability, especially the resistance to wet processing, is improved.

 If you use reactive dyes for coloring synthetic polyamides according to the invention, then generally use reactive dyes in an amount between 0.05 and 5 wt. calculated on the weight of the synthetic polyamide. A more preferred amount of reactive dye used is between 1 and 3 wt. The stains thus obtained are deeper than the staining intensity of the untreated synthetic polyamide with the same amount of dye.

-капролактама в гранулированной форме смешивают в барабанном смесителе с 2 частями соединения формулы Ia
ε
где R₄' есть 2,2,6,6-тетраметилпиперидинил 4, (полученного конденсацией 2 молей 2,2,6,6-тетраметил-4-аминопиперидина с 1 молем 2,4,6-трихлортриазина в 5 молях толуола, после которой раствор кипятят с обратным холодильником в течение 10 ч, остаток отфильтровывают, промывают ацетоном, затем нагревают с водным NaOH при рН 12, отфильтpовывают, промывают и сушат) в порошкообразной форме. Порошок смешивают в барабанном смесителе и диспергиpуют очень быстро и очень равномерно и сцепляют с гранулами. После приблизительно 10 мин смесь сушат в течение 8 ч при 120^oC, вводят в машину для прядения из расплава и после выдерживания в течение 8 мин при 275 - 280^oC в атмосфере азота, прядут в волокна.Example 1. 98 parts poly-

-caprolactam in granular form is mixed in a drum mixer with 2 parts of a compound of formula Ia
ε
where R ₄ 'is 2,2,6,6-tetramethylpiperidinyl 4, (obtained by condensation of 2 moles of 2,2,6,6-tetramethyl-4-aminopiperidine with 1 mole of 2,4,6-trichlorotriazine in 5 moles of toluene, after wherein the solution is refluxed for 10 hours, the residue is filtered off, washed with acetone, then heated with aqueous NaOH at pH 12, filtered off, washed and dried) in powder form. The powder is mixed in a drum mixer and dispersed very quickly and very evenly and adhered to the granules. After about 10 minutes, the mixture was dried for 8 hours at 120 ^° C, introduced into the melt spinning machine, and after standing for 8 minutes at 275-280 ^° C under nitrogen, spun into fibers.

 The fibers thus obtained can be dyed or stuffed with fabric by known methods or after processing into yarn, or fabric or knitted materials, as is usual for polyamide fiber material, using appropriate acidic dyes, for example, dyes C. I. Acid Red 216, C. I. Acid Purple 66, C. I. Acid Yellow, 155, C. I. Acid Blue 230, C. I. Acid Red 129, C. I. Acid Yellow 184, C. I. Acid Red 119 or C I. Acid Blue 80.

-капролактаме), придает хорошую яркость и свойство хорошей устойчивости (красителя) к мокрой обработке.Dyeing performed in this way increases the color depth (compared to the same dyeing performed on untreated poly-

-caprolactam), gives good brightness and the property of good resistance (dye) to wet processing.

 An appropriate amount of the following compounds may be included in the synthetic polyamide material as described in Example 1 instead of the compound of formula Ia.

 Example 2

R ' ₄ -NH-CO-CH = CH ₂
Example 3

R ' ₄ -NH-CO-CH ₂ CH ₂ SO ₂ C ₆ H ₅
Example 4

R ' ₄ -NH-SO ₂ -CH = CH ₂
Example 5

ε
Example 6

В примерах с 1 до 6, R'₄ есть 2,2,6,6-тетраметилпиперидинил-4.

In examples 1 to 6, R ' ₄ is 2,2,6,6-tetramethylpiperidinyl-4.

 Examples 7-11. The following compounds can be obtained by a method similar to the method in example 1 from the corresponding reagents (examples 7-11 are given at the end of the description).

 The products of examples 7 to 11 can be washed in polyamide, which can be used for spinning.

 Example 12. a) Obtaining an amide of 1,3,5-tri- (2 ', 2', 6 ', 6'-tetramethylpiperidyl-4') -trimesinic acid.

42.0 g of trimesic acid is heated for 5 hours at 80 ^{° C.} with 144.0 ml of thionyl chloride in the presence of catalytic amounts (3 ml) of dimethylformamide and then the excess thionyl chloride is distilled off. The resulting trimesic acid trichloride thus dissolved in 500 ml of dioxane, then a total of 187.2 g of 2,2,6,6-tetramethyl-4-aminopyridine is added dropwise with stirring, with dioxane being constantly added (2000 ml total). so that the reaction mixture, the temperature of which should not exceed 30 ^o C, remained capable of stirring. Then the reaction mixture is refluxed for 48 hours, the residue is filtered off, washed with acetone, dissolved in approximately 1000 ml of water, precipitated again with soda solution (at pH 10 to 11), filtered off, the residue is washed with water and dried in vacuum (yield 89, 2 g of 72% white powder having a melting point> 320 ^o C).

-капролактама в порошковой форме смешивают с 1,0 частью соединения, полученного по вышеупомянутому 12 а) в барабанном смесителе. После короткого времени порошок диспергируют очень равномерно. После приблизительно 10 мин смесь сушат в течение 16 ч при 120^oC, вводят в машину для прядения в расплаве и после выдерживания в течение 8 мин при 275 280^oC в атмосфере азота прядут в волокна.b) Obtaining a modified synthetic polyamide 100 parts poly-

β-caprolactam in powder form is mixed with 1.0 part of the compound obtained according to the above 12 a) in a drum mixer. After a short time, the powder is dispersed very evenly. After about 10 minutes, the mixture was dried for 16 hours at 120 ^° C., introduced into the melt spinning machine and, after standing for 8 minutes at 275,280 ^° C. under nitrogen, was spun into fibers.

 Fibers are usually dyed by absorbing 0.5% of dye C. I. Acid Red 216.

 A very uniformly red-dyed fiber is obtained having excellent brightness, with very good washing, gloss and abrasion resistance. Poly-ε - caprolactam fibers, unmodified according to the invention, but dyed in the same way, have a significantly lower color depth and poorer brightness and markedly reduced stability.

Instead of C. I. Acid Red 216, an appropriate amount of one of the following dyes can be used C. I. Acid Blue 80
CI Acid Yellow 155
CI Acid Purple 66
CI Acid Blue 230
CI Acid Red 151
CI Acid Blue 260
C. I. Acid Orange 169
CI Acid Green 28 and
CI Acid Red 119
By a method similar to that of Example 12, an appropriate amount of any one of the compounds 1 to 21 as defined above can be added to the polyamide in bulk, which is then spun into fibers and dyed with one of the acid dyes described above.

Example 13.872 parts of N-methylpyrrolidone are charged into a 1.5 liter reaction vessel. 28.35 parts (0.2625 mol) of 1.4 diaminobenzene are added at 20 ^{° C.} (± 2 ^{° C.} ) to this reaction vessel. The mixture was then cooled to 0 ^{° C.} and 50.75 parts (0.25 mol) of terephthalic acid dichloride were added portion by portion, mixing well, and the mixture was kept at a constant temperature. After the addition is complete, the mixture is heated for 4 hours from 20-80 ^o With stepwise. 5.3 Parts (0.0125 mol) of 1-chloro-3,5-bis (2 ′, 2 ′, 6 ′, 6′-tetramethylpiperidinyl-4-amino) triazine are added and the mixture is stirred at 100 ^{° C.} for 4 hours

The resulting solid was then filtered off, washed with water and separated from the filtrate. Then it is dried in vacuum at 100 ^o C at 20 mm Hg (Hg). 66.0 Parts of the polyamide are obtained in the form of a light beige powder, which has good staining properties.

Examples 14-32. Example 13 can be repeated by condensation of 0.2625 moles of diamine of column 1, with 0.25 moles of dicarboxylic acid dichloride column 2 and 0.0125 moles of chlorine compound column 3 (see table 1). R ₄ 'in the following tables is always the group 2,2,6,6-tetramethylpiperidyl-4 and R ₅ is a group 1, 2,2,6,6-pentamethylpiperidyl-4.

 Example 33. Example 13 is repeated using 27.0 parts (0.25 mol) of 1,4-diaminobenzene (instead of 28, 35 parts in example 13); 51 parts (0.25125 mol) of terephthalic acid dichloride (instead of 50.75 parts in example 13) and 0.3 parts (0.00125 mol) of 1-amino-4 (2 ', 2', 6 ', 6'- tetramethylpiperidinyl-4-amino) benzene (instead of 53 parts of 1-chloro-3,5-bis (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4-amino) triazine.

 61.3 Parts of the modified polyamide are prepared with good properties.

Examples 34 48. Example 33 is repeated by condensing 0.25 mol of the amine column 1, 0.25125 mol of the dichloride column 2, and 0.00125 mol of the amino compound column 3 (see Table 2). R ₄ 'is 2,2,6,6-tetramethylpiperidinyl-4.

 Example 49. 908 parts of granular Nylon 6 are stirred for 1 h with 2% 2-chloro-4,6-bis- (2 ', 2', 6'6'-tetramethylpiperidyl-4'-amino) triazine in a powder mixer (Rhoenrad), then it is processed in a laboratory extruder (MAPIS TM 33 U / 32 D) and then spun into fibers under the following conditions.

Screw speed 321
40% dosing rate
Extrusion Speed 23 kg / h
Pressure 2 bar
Temperature in zones, ^o C
1,168
2-6 300
7 259
8 256
9,263
The resulting fibers can be used on their own or can be used in the form of yarn or non-woven material or products, such as polyamide fibrous material. The fibers can be dyed with suitable acid dyes, for example,
CI Acid Red 216,
CI Acid Purple 66,
CI Acid Yellow 155,
CI Acid Blue 230,
CI Acid Red 129,
CI Acid Yellow 184,
C. I. Acid Red 119 or
CI Acid Blue.

 Depletion dyeing can be carried out by known methods. Fabrics can also be cushioned. The resulting coloration shows excellent color depth (compared to the same colorant with unmodified poly-ε-caprolactam). They have good brightness and the property of good resistance to wet processing.

Example 50. Example 1 is repeated, but instead of 2 parts of a compound of formula Ia, 1.5 parts of 1: 2 chromium complex dye of formula 50a is used
e
The resulting dyeing results in very full of bright and quickly dyed red fibers.

Аналогично этому получают глубоко, ярко и очень быстро окрашенные волокна.Example 51. Example 50 is repeated using an equivalent amount of a 1: 2 chromium complex dye of formula 51a

Similarly, deeply, brightly and very quickly dyed fibers are obtained.

 Examples 52 69. In a manner analogous to the method of example 50, using a molar equivalent amount of one of the following compounds of table. 3, instead of the component of formula 50a, a rapidly and brightly colored fibrous material can be obtained. The colors of the resulting stains are also given in table. 3.

(2,2,5,5-тетраметил-3-карбокси-пирролидин, описанный в Japanen Kokai 60-190786) подвергают взаимодействию с 1 молем тионилхлорида с образованием хлорангидрида. Его растворяют в диоксане и конденсируют с 1 молем 1,4-диаминобензолом. Продукт реакции отфильтровывают, обрабатывают водной щелочью, снова фильтруют, промывают и сушат под вакуумом. Образующийся продукт обрабатывают согласно способу образца 12b и получают модифицированные волокна поли-

-капролактама, которые могут быть окрашены красителями, описанными в примере 12b. Крашения, которые получают, являются яркими по цвету и имеют хорошую стойкость.Example 70. By a method similar to that of example 12a, 2 moles of the compounds of formula 70a

(2,2,5,5-tetramethyl-3-carboxy-pyrrolidine described in Japanen Kokai 60-190786) is reacted with 1 mole of thionyl chloride to form an acid chloride. It is dissolved in dioxane and condensed with 1 mole of 1,4-diaminobenzene. The reaction product is filtered off, treated with aqueous alkali, filtered again, washed and dried under vacuum. The resulting product is treated according to the method of sample 12b and receive modified poly-

-caprolactam, which can be stained with the dyes described in example 12b. The dyes that receive are bright in color and have good durability.

Пример 73. 1,2,2,5,5-пентаметил-3-карбокси-пирролин

Примеры 74-77. Пример 70 повторяют, используя молярные эквиваленты соединений, указанных в примерах 74 77.Examples 71-73. Example 70 is repeated using molar equivalents of one of the following
Example 71. 1,2,2,5,5-pentamethyl-3-carboxy-pyrrolidine
ε
Example 72. 2,2,5,5-tetramethyl-3-carboxy-pyrroline

Example 73. 1,2,2,5,5-pentamethyl-3-carboxy-pyrroline

Examples 74-77. Example 70 is repeated using molar equivalents of the compounds described in examples 74 to 77.

 Example 74. 2,2,5,5-tetramethyl-3-carboxy-pyrrolidine.

 Example 75. 1,2,2,5,5-pentamethyl-3-carboxy-pyrrolidine.

 Example 76. 2,2,5,5-tetramethyl-3-carboxy-pyrroline.

 Example 77. 1,2,2,5,5-pentamethyl-3-carboxy-pyrroline.

 These compounds are reacted with 1,6-hexamethyleneamine to give modified polyamide fibers having properties for good dyeing.

-капролактам (Найлон 6), который можно прясть в волокна. Получают волокнистый материал с очень хорошей способностью к окрашиванию и результирующее окрашивание имеет очень высокое качество.Examples 78 and 79. Example 12 is repeated using 2 moles of 2,2,6,6-tetramethylpiperazin-3-one with 1 mole of terephthalic acid dichloride. Get poly

-caprolactam (Nylon 6), which can be spun into fibers. A fibrous material with a very good dyeing ability is obtained, and the resulting dyeing is of very high quality.

 Example 12 can also be repeated using a condensation product obtained from 2 moles of 1,2,2,6,6-pentamethylpiperazin-3-one with 1 mole of isophthalic acid dichloride.

Examples 80 and 81. The product of the addition of 2 moles of the compounds of formula 80a
ε
and 1 mole of bis- (4-isocyanatphenylene) methane (from Example 2 of US Pat. No. 4,816,585) can be included in Nylon 6 according to the method of Example 12b to produce a polyamide of similar quality to the polyamide of Example 12b.

 A similar effect can be obtained by using the addition product of 1 mole of 1,6-diisocyanatehexamethylene and 2 moles of the aforementioned product of formula 80 described above.

 Examples 82 and 83. 1 mol of 2,4,6-trichlorotriazine can be condensed with 1 mol of 2,2,6,6-tetramethylene-4-aminopiperidine and 1 mol of 2,2,6,6-tetramethylpiperazin-3-one according to the method of example 1.

 1 mole of 2,4,6-trichlorotriazine can be condensed with 1 mole of 3,3,5,5,7-pentamethyl-1,4-diazepin-2-one (described in US Pat. No. 4,292,240) and 1 mole 2, 2,6,6-tetramethyl-4-aminopiperidine.

-капролактам и полученные полиамидные волокна имеют свойства хорошей окрашиваемости.Both reaction products can be included in poly-

-caprolactam and the resulting polyamide fibers have good dyeability.

D₂ есть

D₃ есть

D₄ есть

D₅ есть

D₆ есть

D₇ есть

Пример 50.Preferred groups containing sterically blocked amines are groups of formulas I to VI
ε

D ₂ is

D ₃ is

D ₄ is

D ₅ is

D ₆ is

D ₇ is

Example 50

Пример 51.

Example 51

Пример 52.

Example 52

Пример 53.

Example 53

Пример 54.

Example 54

Пример 55.

Example 55

Пример 56.

Example 56

Пример 57.

Example 57

Пример 58.

Example 58

Пример 59.

Example 59

Пример 60.

Example 60

Пример 61.

Example 61

Пример 62.

Example 62

Пример 63.

Example 63

Пример 64.

Example 64

Пример 65.

Example 65

Пример 66.

Example 66

Пример 67.

Example 67

Пример 68.

Example 68

Пример 69.

Example 69

Пример 7.

Example 7

Пример 8.

Example 8

Пример 9.

Example 9

Пример 10.

Example 10

Пример 11.

Example 11

ТТТ1 ТТТ2 ТТТ3 ТТТ4 ТТТ5 ТТТ6 ТТТ7

TTT1 TTT2 TTT3 TTT4 TTT5 TTT6 TTT7

Claims (2)

1. A composition for producing a modified polyamide containing polyamide and an auxiliary additive, characterized in that as an auxiliary additive it contains a compound comprising 1 to 3 groups of general formulas a), or b), or c), or d)

or

where R is hydrogen or methyl, directly or via a bridging group —O—, —NH—, —NHCO—, —CONH—, N alkalNH— with a benzene core, which may contain a COCl group, or reactive with hydroxy or amino groups the heterocyclic core of a series of mono- or dichlorotriazine, pyrimidine or dichloroquinoxaline, or with a group of the formula —CO — CH═CH ₂ , or —CO — CH ₂ —CH ₂ SO ₂ —C ₆ H ₅ , or SO ₂ —CH = CH ₂ , or with a dye residue containing the same reactive groups, or with a polyamide residue,
in the amount of 1 to 5% by weight of polyamide.  2. The composition according to claim 1, characterized in that, as an auxiliary additive, it contains a compound comprising 2 3 groups of the formula a), or b), or c), or d), where R has the indicated meaning, connected directly or via a bridging group —O—, —NH—, —NHCO—, —CONH— with 1,3- or 1,4-, or 1,3,4-, or 1,3,5-positions of the benzene core, or with 2,4- or 2,4,6-positions of the triazine nucleus.

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