Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
  • C08K5/5333—Esters of phosphonic acids

Definitions

• the product exhibits improved receptivity for acid dyes with a minimum reduction of its solution viscosity.
• This invention relates to a process for improving the dye receptivity of polylactams for acid dyes, and more particularly, the invention is directed to a process of incorporating a combination of certain organic phosphorous compounds and amines into a fiber-forming polylactam, especially polycaprolactam, so as to obtain a product which is easily spun into textile fibers and which can be dyed in an improved manner with acid dyes.
• the dye receptivity of fiber-forming polyamides for acid dyes can be improved if the polyamide is initially treated so as to contain an increased number of amino end groups.
• One method of achieving this result has been to add free amines to the polyamide-forming initial materials prior to polycondensation. Suitable amines which have been suggested for this purpose include aliphatic monoamines or diamines and heterocyclic amines. Where the polyamide is obtained by polycondensation of dicarboxylic acids and diamines, e.g., in the preparation of polyhexamethylene adipamide, only a small excess of the above-noted free amines is necessary.
• this defect in the polyamide caused by the addition of the amine is supposed to be avoided by adding phosphorous compounds to the polyamide prior to spinning.
• Suitable phosphorous compounds suggested for this purpose are hypophosphites of alkali and alkaline earth metals as well as those of zinc, cadmium, manganese, aluminum and tin, and also salts of phosphinic acid.
• the dye receptivity of polyamides is supposed to be improved by the addition of alkylor aryl-phosphinic acids or their amine salts.
• One object of the present invention is to provide a process whereby a substantially improved acid dye receptivity can be imparted to a fiber-forming polylactam without impairing the subsequent spinning of the polymer into filaments.
• Another object of the invention is to provide a process for improving the receptivity of a fiber-forming polylactam for acid dyes by using a novel combination of additives which can be easily incorporated into the polylactam either before or during polycondensation of the lactam monomer or subsequently to the polylactam before it is spun into textile fibers.
• polylactams which are improved by the proc ess of this invention are well known fiber-forming polymers containing recurring NHCO groups connected by an alkylene group in the polymer chain.
• Polycaprolactam sometimes referred to as nylon 6, is most often used for commercial textiles, and the production of the polyamide fromthe monomeric lactam, such as epsiloncaprolactam is quite well known and requires no further explanation.
• the two essential additives of the invention i.e., the organic phosphorous compound and the polyamine can be introduced and incorporated into the polycaprolactam at any point prior to spinning filaments or fibers therefrom, under conditions which ensure an homogeneous mixture of the polymer and the additives, e.g., by thorough mixing during polycondensation or by kneading and homogenizing the additives with the molten polymer in an extruder or similar mixing device.
• the additives may be introduced before the polycondensation of the lactam monomer or at any suitable time during the polycondensation reaction.
• the two essential components of the invention with the polylactam product, which is in the form of cuttings, granules or small pellets at a point prior to spinning, e.g., by panniering the cuttings or otherwise surface coating the polymer particles.
• the organic phosphorous compound and the polyamine are homogeneously mixed with the polylactam by any conventional method, e.g., by reextruding the treated material in a screw extruder or even in a mixing section just preceding the melt spinning operation.
• organic phosphorous compound employed as component (a) in the process of the invention it is particularly desirable to employ those compounds of the formula in which X stands for aryl or alkyl, preferably phenyl and lower alkyl such as methyl, ethyl, propyl or butyl, X stands for aryl such as phenyl, aralkyl such as benzyl or lower alkyl, i.e., alkyl of 1 to 4 carbon atoms, and Y stands for hydrogen, aryl such as phenyl, or lower alkyl of 1 to 4 carbon atoms.
• Specific organic phosphorous compounds suitable for the purposes of the invention can be listed as follows:
• the acid dye receptivity cannot be further increased simply by the addition of larger amounts of this component because the viscosity of the polylactam is then simultaneously reduced.
• the acid dye receptivity of the polylactam increases quite sharply in a very surprising manner.
• the amines just as the organic phosphorous compounds cause a lowering of the viscosity, it has been found that a definite synergistic effect takes place with the dye receptivity increasing much more rapidly than any accompanying decrease in viscosity.
• the suitable selection of the phosphorous compounds and amines as well as by choosing appropriate amounts of these compounds within the prescribed limits of the invention.
• the preferred polyethylene polyamines as noted above offer the greatest advantage because they yield a very substantial increase in dye absorption even when using quite small amounts, and these small amounts of the polyamine have only a slight influence on the viscosity.
• the invention is further illustrated by without being limited to the following examples.
• the percentages of the phosphorous and amine compounds are by weight with reference to the particular lactam or polylactam which is being treated.
• the solution viscosity is measured in each instance by measuring the flew rate of a 1% solution of the polylactam in formic acid. Extinction values are obtained by conventional measurement of the dye solutions.
• Ethanephosphonic diethyl ester 1.0 2 05 1 3 8O "i g g h i 3 anep osp euro 2101 re y " ⁇ Diethylene triamine 0.4 i 1 3 ⁇ Ethanephosphonic acid diethyl es 0.1 2 14 1 2 34 gtefiametlhylefie diamigeafilnfuy 0.3
• EXAMPLE II Dried polycaprolactam cuttings ready for spinning with a solution viscosity of 2.55 are mixed in a tumbler drier successively with 0.3% by weight of hexamethylene diamine and 1% by weight of tributyl phosphate. Thereafter, these cuttings are regranulated in an extruder. After the regranulation, the modified polycaprolactam exhibits a solution viscosity of 2.53. The cuttings are then spun and the resulting filaments dyed as described in EX- ample I. By measuring the extinction proportion of the dyestuff extracted from each of the filament samples, the dyeing improvement of the modified polyamide by comparison with the unmodified polyamide is ascertained. The extinction proportion in this case amounts to 1:2.63 (polyamide without additive:polyamide-i-phosphorous compound-i-amine) As described in Example II above, further tests are carried out with changes in the compounds or additive amounts as summarized in the following table:
• a further advantage of the process according to the invention is to be seen in the fact that during the spinning of 'the polyamide the added phosphorous compounds cause a considerable after-condensation, so that even if in Example I.
• a process for improving the receptivity of a fiberforming polycaprolactam for acid dyes which comprises: homogeneously incorporating into said polycaprolactam:
• component (a) is a phosphoric acid ester of the formula X0 OX wherein X represents a substituent selected from the group consisting of lower alkyl and phenyl.
• component (a) is a compound of the formula YO OY wherein X' represents a substituent selected from the 8 group consisting of lower alkyl, phenyl and benzyl and Y represents a suhstituent selected from the group consisting of hydrogen, lower alkyl and phenyl.
• component (b) is a compound of the formula wherein p represents an integer of 2 to 4.
• component (b) is hexamethylene diamine.
• component (a) is ethanephosphonic acid diethyl ester.
• component (a) is methanephosphonic acid dimethyl ester.
• component (a) is tributyl phosphate.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyamides (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=7583786

Family Applications (1)

Country Status (9)

Cited By (8)

Citations (6)

Family Cites Families (1)

• 1965
  • 1965-03-03 DE DEV27948A patent/DE1232735B/de active Pending
• 1966
  • 1966-02-19 ES ES0323294A patent/ES323294A1/es not_active Expired
  • 1966-02-22 CH CH255766A patent/CH466563A/de unknown
  • 1966-02-28 BE BE677106D patent/BE677106A/xx unknown
  • 1966-02-28 FR FR51380A patent/FR1470218A/fr not_active Expired
  • 1966-02-28 US US530374A patent/US3437641A/en not_active Expired - Lifetime
  • 1966-03-01 NL NL6602666A patent/NL6602666A/xx unknown
  • 1966-03-03 GB GB9403/66A patent/GB1125633A/en not_active Expired
  • 1966-03-03 AT AT201766A patent/AT262223B/de active

Patent Citations (7)

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