DE1570968A1 - Synthetic linear polycarboxamides and processes for their preparation - Google Patents

Description

MTENTANWALTE 1 5 7 O S 6

DR. E. WIEGAND DIPL-ING, W. NIEMANN DR. M. KÖHLER DIPL-ING. C. GERNHARDT

MÖNCHEN HAMBURG

TELEPHONE: 55 54 7 <S 8000 MD N CH EN 15, - 0 · O6P.

TELEGRAMIC CARPATENT '. N USSBAUMSTRASSE 10

V. 12202/65 13 / de P 15 70 968.9

Monsanto Company
St. Louis »Missouri (7th St. A.)

Synthetic linear polycarboxamides and processes for their preparation

The invention relates to fiber-forming synthetic polymeric materials and to the molded articles made therefrom. In particular, the invention relates to a process for the production of novel, fiber-forming, synthetic, linear polycarboxamides and the products made from them, molded objects which are particularly resistant to acidic dyes.

Although those from fiber-forming polycarboxamides known to date produced textile fibers or threads are very valuable, they have disadvantageous or deficient Coloring properties in that they all have the same colorability by acidic dyes and each type only stains in a single shade. This is

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a particular and significant disadvantage because it makes the possibility to achieve other desired color effects _t wherein some of the fibers or filaments no dye, or absorb less dye is turned · There is therefore an interest in the production of PoIycnrbonsäureamiden acidic which such resistance characteristics against Have dyes that by combining such polycarboxamides with standard polycarboxamides in different? ^ tn quantities the production of polycarboxamide articles is made possible, which can be colored with different tints of the same color

The additives previously used for this purpose have not been found to be entirely satisfactory because they give the fibers or filaments only a limited degree of resistance to acidic dyes For example, in the German patent application C 22 554 IVb / 39 c fibers or threads with alkali dicarboxybenzene monosulfonates described. Although these additives serve to make the fibers receptive to basic dyes to make, they do not confer sufficient resistance to acidic dyes to the fibers or Technically suitable or acceptable for use with acidic dyes in the manufacture of fabrics or threads To make textiles with a wide range of graduated or deviating shades

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The purpose of the invention is to create novel and useful, fiber-forming, synthetic, linear polycarboxamides.

Another purpose of the invention is to provide shaped articles such as textile fibers or threads made from such polycarboxamides, these articles being superior in durability have properties against acidic dyes Another purpose of the invention is to provide a process for the preparation of polycarboxamides from which are the molded articles having superior resistance or resistance properties to acidic dyes can be produced «

These and other purposes are explained in more detail using the description below

The polycarboxamides according to the invention are at the production of shaped objects by injection molding or extrusion, compression molding or casting, for example of yarns, cloths or fabrics, foils or films, coatings (pellicles), bearings, decorations or ornaments or the like. useful. They are particularly useful in the manufacture of textile fibers or threads.

According to the invention there is a new polycarboxamide produced with repeating carboxamide bonds as an integral part of the polymer chain, as a

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mm i \. m.

Part of the polymer chain between about 0.1 and 2.0 Uol-? 0, and preferably between about 0.5 and 1.0 Mo 1-%, based on the weight of the polycarbonamide, in units of the following structural formula:

(a)

contains, in which η is a number from zero to 6 inclusive, Z is the radical -C- or - N -, X is hydrogen or a

Il I

lower alkyl radical and M is hydrogen, the ammonium radical or mean an alkali metal.

According to a particular embodiment of the process according to the invention, the polycarboxamide is carried out Copolymerization of a polycarboxamide mass (A) substantially equimolar proportions of at least one dibasic carboxylic acid of the general formula

HOOC - B-COOH (b)

in which E is a divalent hydrocarbon radical and at least one diamine of the formula below

XX
HNEHH (c)

in which X and E are as defined above, and (B) a monoaminomonocarboxylic acid of the following Formula ^

H-B-K-COOH

9 0 9 8 8 5/1 B 8 B

in which X and R have the meaning given above " and (c) a mixture of (A) and (B) in the presence of a monofunctional, disulfonated compound of below formula

(CH ₂ ) _n ZY

(β)

in which n, Z and M have the meanings given above

represents, and Y is hydrogen, -OH, -01 or OR '/ »where R · a represents a monovalent hydrocarbon radical of such a nature, that the compound R'-0H below the decomposition temperature of the polycarboxamide that is formed is volatile is made.

The nature of the radical R in the acid, diamine or Amino acid is not critical. Preferably R is a divalent one Hydrocarbon group having up to about 20 carbon atoms · Examples of those represented by the formula (b) Acids are oxalic acid, adipic acid, suberic acid, pimelic acid, azelaic acid, sebacic acid, brassylic acid, octadecanedioarboxylic acid, Undecanedicarboxylic acid, glutaric acid, tetradecanedicarboxylic acid, p-phenylenediacetic acid, isophthalic acid, Terephthalic acid, hexahydroterephthalic acid or the like., as well as mixtures thereof.

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Examples of suitable diamines of the class represented by the formula (c) are ethylenediamine, propylenediamine, Tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, p-xylylenediamine, p-phenylenediamine, hexahydro-p-phenylenediamine, aminocyclohexyl) methane, piperazine, dimethylpiperazine, Tetramethylpiperazine, the N ^ IT-dimethyl ,. the Ν, Ν'-diethyl and the KjN'-Diisopropyldei ^ ivate of the above compounds, or the like. as well as their mixtures.

Particularly suitable amino acids of the formula (d) class shown are 6-aminocaproic acid, 9-aminononanoic acid, 11-aminoundecanoic acid and "17-aminoheptadecanoic acid.

Instead of the dibasic carboxylic acids, diamino and amino acids mentioned above, their amide-forming Derivatives can be used to form the fiber-forming polymers. Amide-forming derivatives of dibasic carboxylic acids include the mono- and diesters, anhydrides, the mono- and diamides and the acid halides. Amide-forming derivatives of diamines include carbamates and the N-formylderitfata amide-forming Derivatives of the amino acids include the esters, anhydrides, amides, lactams, acid halides, N-formyl derivatives, Carbamates and, in the presence of water, the nitriles.

As indicated above, the compounds which are found to be useful in the practice of the invention are proven by two sulfonate groups and a carboxyI-

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group bound to the naphthalene ring and are given by the formula

shown in which n, Z, U and Y are those given above Have meaning · Examples of such compounds, in which 2 - - C-, are: Di- (calcium sulfonate) -na- » phthalene ^ -carboxylic acid, di- (aauaoniumsulfonat) -naphthalene-2-carboxylic acid, Di- (potassium sulfonate) naphthalene-1-carboxylic acid, Di- (sulphonic acid) -naphthalir> -2-carboxylic acid, di- (potassium sulfonate) -naphthalene-2-ethane iure, di (ammonium sulfonate) naphthalene -2-pentanoic acid and di- (sulfonic acid) -naphthalene-1-heptanecarboxylic acid j Examples of such compounds, in which Z »-N-, are: Di- (potassium sulfonate) -naphthalene-2-

methylamine, ^il i- (anuaoniumsulfonat) -naphthalin-2-methylanin, di- (sulfonic acid) -naphthalin-2-ethylamine, di- (potassium sulphonate) -naphthalin-1-ethylamine and di- (sodium sulfonate) -naphthalin-2-pentylamine .

The poly carboxylic acid amides are used according to the invention according to working methods known in the art, which are usually used in the production of simple polyamides arrive, manufactured. I.e. the respondents

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are heated at a temperature of 180 ° to 50O ⁰ C, and preferably from 200 ° to 295 ° C, until the product has a sufficiently high molecular weight to exhibit fiber-forming properties, which properties Bind achieved when the polyamide has an intrinsic viscosity of at least 0.4. The reaction can be carried out at super-atmospheric, atmospheric, or sub-atmospheric pressure. It is often desirable, particularly in the last stage of the reaction, to use conditions, for example reduced pressure, which aid in the removal of the reaction by-products. The reaction is preferably carried out in the absence of oxygen, for example in a nitrogen atmosphere.

The term "basic molar viscosity" used here is defined in the following way:

Lim.
? 0

where N is the relative viscosity of a dilute solution of the polymer in m-cresol in the same units the same temperature and C is the concentration in g of the polymer per 100 ml of solution.

The amount of additive that is ala part of the polymer chain of the polycarboxamides according to the invention may be present, depending on the type of

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desired polymer and the "particular shaped article, for which end use it is intended will vary. It was found to be necessary between about 0.1 and 2.0 Mo 1/3, based on the weight of the polycarboxamide., To use. A minimum amount of 0.1 mol% additive is required to achieve a significant level of resistance to obtain against acidic dyes * It has been found that optimal results are obtained when between see about 0.5 and 1.0 mole percent additive based on weight of the polycarboxamide, can be used. Amounts greater than 2.0 mol% have a disadvantageous influence on the viscosity of the polycarboxamide produced Invention used additives only one functional group, i.e. containing a carboxyl or an amino group, it can be seen that they are in the manner react to terminate or complete the polymer chain of the polycarboxamide. That kind of response is equivalent the heat, which takes place when additives are added, which are used in technology as chain terminators or Viscosity stabilizers are known. It is thus obvious that the greater the amount of the according to the invention The additive used, the shorter the polymer chain of the polycarboxamide and the lower the viscosity de3 are polycarboxamides. As stated above

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give, the use of additional amounts between about 0.5 and 1.0 Uol-% is preferred, since when using sclchar M

one

The polycarboxamide formed was found to be excellent Has resistance or resistance to acidic dyes and a viscosity in the range of fiber-forming properties.

The invention is illustrated below by way of examples η'her explained in which, unless otherwise stated is, the cited part »is based on weight.

example 1

This example illustrates the preparation of a common polycarboxamide, such as polyhexamethylene adipic acid amide. This polymer and the fibers or threads obtained therefrom are used as a comparison standard for the modified polycarboxamides according to the invention.

In a stainless steel evaporator, 8.47 moles Water with a content of 0.562 mol hexamethylenediammonium adipate salt, which dissolved therein, introduced. This unit was purged with nitrogen and then under a Pressured to about 0.91 atmospheres (13 psig). The saline solution was then heated to 137 ° C with continuous removal of Heated water vapor condensate. At that point, that became Salt concentrate transferred under pressure into a high pressure autoclave made of stainless steel, which was previously with

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Nitrogen was purged. In this equipped with a stirrer Realctor the pressure was increased immediately etwa17,6 atm (25O psig) and the temperature was raised to 220 ⁰ C. Steam was removed until the polymer melt ^{temperature of 243 °} C. was reached. At this point the reactor pressure was gradually lowered to atmospheric pressure over a period of 25 minutes and the polymer melt was allowed to equilibrate at 278 ° C. over 30 minutes.

The Endpolymericat thus prepared was schmelzgecponnen 28G at ⁰ C through a spinneret having holes t3 to obtain a white tlehrfadenGarn was obtained. The yarns thus obtained were over a hot pin (90 ⁰ C with a maximum S "creckausmaS or ratio of the 5 t 65 times the length ursrpünglichen stretched.

Staining of these yarns was carried out in that m _a n it in an acidic dye having a content of y / _o% based on the weight of the yarn, to Scarlet 4R.A Cone. CF (CI. Acid Hed 18) and 1.2 % formic acid ^ immersed. The weight ratio ν -η P är'bad to Paser was kept at 40: 1 and the dyeing was carried out for 2 hours at 100 ° C. and at a pH value of 3.1. These yarns absorbed 1.25% dyes ·· jff.

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Example 2

Di- (potassium sulfonate) -naphthalene-2-carboxylic acid was made by. Treatment of 100 g 2-naphthoic with 752 g of fuming sulfuric acid während3 hours "at 10O ⁰ C produced · The reaction product was then added to 1000 g of ice, followed by 250 g of potassium bicarbonate was added slowly · It formed" I precipitation, by adding was dissolved by 3 1 of water again and the resulting solution was then heated to 7O ⁰ C and treated with 2 g of activated carbon to the hot filtered solution was then 225 g of potassium chloride was added, followed by precipitation of the finely divided, white product, di- (. potassium sulfonate) -naphthalene-2-carboxylic acid, occurred. the product was filtered and purified by redissolution in 23C0 ml Sasser at 70 ⁰ C, followed by treatment with 1 g activated charcoal · After filtration in the hot state 100 g of potassium chloride were added and the product precipitated in the form of fine, white particles after cooling, which were separated off by filtration

The procedure of Example 1 was repeated except that the di- (potassium sulfo- nat) -naphthalene-2-carboxylic acid in a sufficient amount, a terminal polyhexamethylene adipic acid containing to give a 0.355 col-% addition, together with the courtship in The autoclave was introduced · This so produced

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modified rolyuniidpolymerisat was at 280 ⁰ C, a spinneret having 13 holes schiaelzgespcnnen to give a white üehriadengarn was obtained. These yarns were vcn over a hot pin (90 ⁰ C) with a maximum draw ratio StreckausmaS or your 4.60 times its original length, these yarns were stretched · an absorbance of 0.36 # Scarlet - 'RA + Cone. CF (CI. Acid Red 18), ie on an acidic dye, if the dyeing is carried out under the same conditions

Dyeing and using the same / bath composition as in

Example 1 described was carried out.

Example 3

The procedure of Example 2 was followed with the modification repeats that the addition used from Kaaiutfr-3,5-dicarboxybeDzenesulfonat existed, which is described in German patent application C 22 554-IVb / 39 c. This Yarn produced in this way showed on treatment un-

under the same conditions as described in Example 2, an absorption of 0.80% Scarlet ¹ '4-ΙϊΑ Cone. CF (CI. Acid Red 18). '·

Examples 4-6

The Arbßitsv.-cii; e the kit was repeated with the modification that other special additives were used in special amounts.

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In the following. Table are the results obtained compiled.

Tabel 0.139 0.71
0.21 • 34.0%
133.3% example Mol% to amount of
set in the dye -
Polymer absorbent
risat tion 0.139
0.780 0.98 Increase in color
fabric resistance
Example 4 example
P? EKeh 5 4 reefing 6 4 (a)
OO Di-Calcium ^ 0.139
sulfonate) -
naphthalene- 0.780
2-carboxylic acid 0.94
0.49 38.0%
147.9% 5 (a) Potassium-3,5-
dicarboxy 6 (a)
Cb) 3-sulfobene
zoic acid
monosodium
salt

These test results clearly show the marked superiority of the additives according to the invention over the bifunctional monosulfonate salt and the monofunctional Monosulfonate salt when used in appropriate amounts. Except for the increase or increase indicated in the table In the dye resistance, it should be noted that the additive used in Example 2 has an increase in resistance acid dyes of almost 122% compared to the in Example 3 used additive.

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Example 7

A resistance to acidic. Poly-r-caprolactam containing dyestuffs was prepared by introducing 100 g ζ, -caprolactam and 1.94 g di- (potassium sulfonate) -naphthalene-2-carboxylic acid into a high pressure stainless steel autoclave nitrogen, the autoclave was placed (250 psig) under a pressure of about 17 "6 atm and the temperature was raised to 250 ⁰ C while _{continuously%} water vapor was removed. At this time, the pressure was gradually lowered over a period of 25 minutes to atmospheric pressure and the temperature of the molten polymers reached 265 ⁰ C. Then, the vacuum level was applied to the above & oklaven by gradually reducing the pressure for a period of 30 minutes to a pressure of about 635 mm Hg (25 inches) was applied. Under these conditions, the polymer melt was allowed to equilibrate for 10 minutes before the autoclave was brought back to atmospheric pressure by allowing nitrogen to flow back into the system. The polymer was

immediately at 265 ⁰ C directly from the autoclave to a white
/ Monofilament yarn melt-spun from 13 threads.

The dyeing procedure given in Example 1 and the dyeing conditions used were repeated. It was found that this> arae 0.60% Scarlet Mr BA Cone. CF (CI. Acid Red 18) versus e ^ ner absorption of 1.08%,

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which in ordinary Po ^ £ ~ capr, ylamidgar © e8 with % tines content of 0.536

was observed under the same conditions

and have been dyed.

Example 8 Polyhexamethylene sebacamide, the geir.ä'ß der

was modified, was made "by a stainless steel evaporator with 0.393 moles of hexamethylenediammonium sebacate dissolved in 20.8 UoI of water, which? 0.968 g of di- (calcium sulfonate) -naphthalene-2-carboxylic acid contained "besehiekt" was. After purging with nitrogen, the unit of the evaporator was brought psig (13) under a pressure of about 0.91 atm, and heated to 137 ⁰ O with removal of water vapor "condensate. At this temperature, the concentrated salt is fed under pressure to a high pressure autoclave, which had been previously flushed with nitrogen, and the unit was atm under a pressure of about 17.6 brought (250 psig) and the! Temperature was continuous to about 23O ⁰ C under Removal of water vapor increased. At this temperature the pressure in the autoclave was gradually returned to -mosphärischen et pressure for a period of 25 minutes, with the Poljnerieatechmelze reached a temperature of 265 ⁰ G. Sit melt was then allowed to stand and cojuvenate into equilibrium for one of 30 minutes before directing at 265 ⁰ O

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from the autoclave through a spinneret with 13 holes, whereby a white multifilament yarn was obtained

The spun yarns were ο over a hot pen
(90 C) stretched at a maximum stretching amount "or ratio of 4.50 times their original length. JIe yarns were dyed according to the procedure described in Example 1 under the same conditions and an absorption of 0.39% was found Scarlet 4HA Cono.CF (CI Acid Red 18). yarns _t legendary prepared in the same way with the modification that potassium 3,5-dicarboxybenzenesulfonate was used as an additive, showed an absorption of 0.70% to the same dye It has been found that yarns containing the additive according to the present invention show an increase in resistance or resistance to acidic dyes x of 79-5%

hitherto the yarns which contain the known additives.

Example 9

Di- (sulfonic acid) -naphthalene-2-carboxylic acid was prepared by adding a dilute aqueous solution of di- (potassium sulfonate) -naphthalene-2-carboxylic acid with a cation exchange resin in an ion exchange resin in an ion exchange column treated wude. The treated solution then became Evaporated dry to give a white product, di- (sulfonic acid <-naphthalene-2-carboxylic acid) · The preparation

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of modified poly-hexamethyleneadipamide with a Content of 0.60 mol # of di (sulfonic acid) naphthalene-2-carboxylic acid was carried out according to the same procedure and under the same conditions as described in Example 1 » The addition was carried out in the polymer production in incorporated in the same way as described in Example 2

The polymer obtained was immediately at 280.degree

from the manufacturing autoclave to a w ^; A multi-filament yarn with 13 filaments of melt sponges, which has been stretched at a maximum stretching amount or ratio of 5-70 times the original length.

This yarn product reported an absorption of 0.73%

Cone.
Scarlet 4BA / CF (CI. Acid Eed 18), if staining was carried out according to the procedure given in Example 1 and under the same conditions. This dye absorption represents an improvement in dye resistance or resistance of almost 41.656 over the common polyhexamethylene adipamide which absorbs 1.25% of the same dye.

Example 10

The- (acuaoniunisulfonat) -naphthalen-2-carboxylic acid was by reacting 1 mole of di (sulfonic acid) naphth.alin-2-carboxylic acid with 2 moles of ammonium hydroxide in an aqueous solution Solution made; the diammonine salt product went into solution maintained. Modified poly-hexamethylene adipamide

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with a content of 0.60 K0I- / I of the diaamonium salt was According to the same procedure and under the same conditions as described in Example 1, the Addition was the polymer production in the same Weioo, as in example 2, incorporated

Sas polymer was melt-spun at 28Q ⁰ C to a white iiehrfadengarnprodukt with 12 threads, which could be cold drawn · This oarne showed an absorption on Scarlet 4HA C ο nc. CF (CI. Acid Bed 18) of 0.67 / j if the dyeing procedure and conditions given in Example 1 were used. which absorb 1.25% of the same dye.

From the results described above, it can be seen that the fibers or filaments made from the polycarboxamides according to the invention all have durability or have resistance to acidic dyes. This gives the manufacturer the option of using fibers dtr the same basic polycarboxamide molecular structure as with the usual polycarboxylic acid amides, but with different affinities for acidic dyes. This in turn enables e .a versatile dyeing for the Achieving color-on-white effects and various shading or tinting effects * on textile goods, which up to now have not been easily available ^ a. '

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Claims (7)

- 20 claims 1. fiber-forming synthetic linear polycarboxamides, characterized by repeating carbonamide bonds as an integral part of the polymer chain * and through the content as a component part of the polymer chain of about 0.1 and 2.0 mol #, based on the weight of the polymer chain of units of the structure below (CH ₂ ) Z - where η is a number from 0 to 6, Z is one of the radicals of -ΟΧ I. and -N-, X is hydrogen or a lower alkyl and M is hydrogen, Mean ammonium or an alkali metal. 2. Polycarboxamide according to claim 1, characterized in that the polycarboxamide consists of polyhexamethylene adipamide, poly £ - caproamide or polyhexamethylene sebacamide. ■ ■ * 3. Polycarboxamide according to claim 1 or 2, characterized in that M in the given formula represents potassium. 909885/1685 4. Polycarboxamide according to claim 1 or 2, characterized characterized in that it is in the form of textile fibers. 5 * adore to manufacture synthetic, linear Polycarboxamides according to one of Claims 1 to 3, characterized characterized in that a polycarboxamide-forming mass is made (A) Substantially equimolar proportions of a divalent Acid of the formula HOOC - R - COOH and a diamine of the formula H-N-R-Ιί, -Η or XX (B) a monoaminomonocarboxylic acid of the formula H-N-R-COOH where in the above formulas R is a divalent hydrocarbon radical and X represent hydrogen or a lower alkyl radical, in the presence of about 0.1 to 2.0 moles-56 based on the weight of the polycarbonamide, one monofunctional, (!! sulfonated compound of the general formula BAD ORaGiNAL 909885/1685 in which η is a number from zero to 6 inclusive, O Il Z is -C- or -N-, H is hydrogen, the ammonium radical or an alkali metal and 7 is hydrogen, -OH, -Cl or OR ¹ , where R * is a monovalent hydrocarbon radical such that the compound R'-OH is below the decomposition temperature of the polycarboxamide formed is volatile, polymerized. 6. The method according to claim 5, characterized in that as monofunctional, disulfonated Compound di (potassium sulfonate) naphthalene-2-carboxylic acid used. 7. The method according to claim 5 or 6, characterized in that the monofunctional, disulfonated compound in an amount of about 0.5 to 1.0 mol #, based based on the weight of the polycarboxamide. 909885/1685