CS208717B2 - Method of making the alifatic linear copolyeteramides or copolyetheresteramides - Google Patents

Abstract

The fibres and filaments are based on a sequenced, linear aliphatic copoly(ether)esteramide. this is prepd. by reacting (1) a linear aliphatic polyamide sequence having a mol. wt. of 300-10,000 and terminal carboxylic functions, with (2) a linear aliphatic alpha, omega-diol or polyoxyalkylene glycol having hydroxylated chain ends, in the presence of tetra-alkyl orthotitanate catalyst. The polymer contains 1-20, esp. 3-15 wt.% poly(ether)ester sequences, and possesses sufficient inherent antistatic properties to prevent the development of an antistatic charge by rubbing. Good antistatic properties are obtd. without the need for incorporation of an antistatic agent. These properties are permanent, and unaffected by washing or dry cleaning. Good physical properties are also obtd.

Description

The invention relates to a process for the production of aliphatic linear copolyesteramides or copolyetheresteramides suitable for the production of antistatic fibers and staple fibers. These staple fibers based on the compounds of the present invention have natural antistatic properties without the need to add any additive to reduce or eliminate electrostatic charges due to friction.

It is known that some compounds are capable of conferring antistatic properties upon becoming part of polymers.

In particular, it is known that when copolyetheresteramide is mixed with polyamide (French Patent 2,178,205), the product produced from this mixture is obtained by compression or extrusion, which is characterized by the antistatic properties of the polyamide.

This process for the preparation of antistatic polyamides also includes the preparation of copolyetheresteramide, which is added to the polyamide whose properties are to be altered to achieve good thermal resistance of the plastic produced.

A disadvantage of these polymers with antistatic properties, obtained by mixing the base polymer with a compound having antistatic properties, is. That they gradually lose their antistatic properties both over time and through repeated washing.

The invention makes it possible to overcome the following drawbacks:

The invention therefore relates to a process for the production of aliphatic linear copolyesteramides or copolyetheresteramides in which the proportion by weight of polyester or polyether groups is between 1 and 20%, preferably between 3 and 15%, characterized in that at a pressure of 6,666 to 666,6 Pa at a temperature in the range 200 to 300 ° C, in the presence of tetrabutyl orthotitanate, reacts a linear polyamide having carboxyl end groups selected from the group consisting of polyamide 11, polyamide 6 and polyamide 6.6 having a molecular weight in the range 300 to 10,000, preferably about 2,000, with an aliphatic linear alpha, omega-diol having 1 to 6 carbon atoms, or a polyoxyalkylene glycol having a molecular weight in the range of 150 to 500 having 1 to 4 carbon atoms in the alkylene moiety, in a molecular ratio of alpha, omega a diol / dicarboxylic polyamide in the range of 1 to 10, preferably 2 to 4.

The aliphatic linear copolyesteramides or copolyetheresteramides produced have, in themselves, antistatic properties, without the need to add to them any additive capable of imparting such properties to the fibers or fibers thereof.

• ⁿ ATO and staple fibers are made of macromolecular materials based on polyamides containing polyether esters olyesterové or articles of formula

-C-A-C-O-B-O ° where n is an integer indicating the number of these repeating groups,

A is a polyamide cell of type 6, 6-6, 6-10, 11 or 12, and

O-B-O- means a moiety derived from an alpha-diol such as ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, oxyalkylene glycol or low molecular weight polyoxyalkylene glycol obtained by dimerization , trimerization or oligomerization of alpha, C 1 -C 4 omega-diols, such as trioxyethylene glycol, tetraoxypropylene glycol or low molecular weight polyoxyalkylene glycol.

When alpha, omega-diols are used which do not have an ether oxide group within the hydrocarbon chain, such as ethylene glycol or propylene glycol, a block copolyesteramide is obtained. When alpha, omega-diols containing ether-oxide groups in the chain, such as polyoxyethyl glycol, are used, a block copolyetheresteramide is obtained. Block copolyetheresteramides of similar structure are obtained as described in French patent application 74 8913; however, these products are primarily intended for the manufacture of molded articles or extruded films and films and do not have the properties necessary to obtain fibers and staple fibers with antistatic properties.

In order for the produced fiber or staple to resist electrification by friction while maintaining other technical properties, it is necessary that the plastic be made essentially based on polyamide and that the oxyalkylene or polyoxyalkylene chains are present in an amount of 1 to 20% by weight, preferably 3 up to 15 wt.

The polyamide used is a linear aliphatic polyamide of the polyamide type 6, 6-6, 6-10, 11, 12 having carboxyl groups at the chain end, which polyamide is obtained either by polymerization of lactam or an amino acid in the presence of a small amount of aromatic or aliphatic linear alpha, omega- of a dicarboxylic acid, or by reacting a linear aliphatic alpha, omega-diamine with a linear alpha, omega-dicarboxylic acid in the presence of an excess of a linear aliphatic alpha, omega-diacid, which reacts to form carboxyl termini of the chain and act as a chain restrictor.

Thus, the possibility of the linear alpha, omega-diacid employed depends on the length and average molecular weight of the polyamide block to be produced. The polyamide blocks have molecular tanoOots in the range of 300 to 10,000, preferably about 2,000.

Among the varnishes which may be used are, for example, butyrolactim, caprolactm, decanol nude Em, undlkanolactm or leurolact;

Among the amino amino acids which may be used are 6-aminocaproic acid, 10-aminocaproic acid, 11-aminoundecylic acid or 12-aminolyturtic acid.

The linear alpha-omega-diamine can be used, for example, hexane-ethylenediamine, octamethylenediamine, naphthalene, decanmeylenediamine, decanolmeylenediamine, hexanecalkylenediamine _with hexadecainediamine, hexadecylmethylenediamine, hexamethylenediamine, hexamethylenediamine, hexamethylenediamine, hexamethylenediamine, hexamethylenediamine, hexamethylenediamine , 2C-diteintliktsanz or 1,22-diminodocotane.

From pouužtelrých linear ALL ^ f ^ ch ^ eitibý -lfa omega-Remote Codes ^гs Protein may be mentioned in particular acid adipovouj pressure, tzeltintvtž, dekíaι0ikyltlinu, uodelkm0atk ^г Уtlinu or dodekaniikyseltož.

The reaction is carried out in a known manner by heating the raw materials until it is melted under reduced pressure in the presence of a catalyst of the formula TKC (R), for example tristotrophosphorothione, or ^ ^ г -Ь уууу. -о.

Неакбп! the temperature is higher than the melting point of the compounds used to be such that the reaction mixture is maintained in a liquid melt. This temperature is between 100 and 400 ° C, preferably between 200 and 300 ° C. The duration of the reaction may vary from 10 minutes to 10 hours, preferably from 1 to 7 hours. The duration of the reaction depends on the value of the desired viscosity of the polyester ester ether produced.

The reaction te is carried out under reduced pressure ranging from 6.75 to 675 Pa.

By using a pressurized hmoonoot-type of lfa, omega-ditl, or poly ₍ oxy-alkyl) or poly-oxyalkyl, the coating of the blocks of these compounds constitutes 1 to 20% by weight, preferably 3 to 15% by weight, of the total amount of polynitrated zinc block. The copolymers or copolymers of high molecular weight spheres suitable for spinning are obtained, wherein the fibers produced and the staple fibers themselves do not need to be added to them by the polystyrene compound which is usually necessary for spinning textile fibers.

A more common advantage of these fibers and of staple fibers from the polyether tether or polyester ether tertiary produced by the process of the present invention is that they permanently retain your character, while it is known that the alistatic properties obtained by adding the ingredients gradually time and washing.

The polyether or polyester amides obtained are also spun into a machine, allowing a small amount of material to be perfectly processed, with a melting chamber temperature of 265 ° C, a spinneret temperature of 255 ° C, a winding speed of 70 m / min. The obtained fibers coil 23 nonwoven fibers.

The circular cross-section of each fiber has a diameter of approximately 21 to 24 µm.

The produced fibers are then cold-drawn (degree of draw is 4.8) with a speed of 35.4 m / min and a speed of 170 m / min. Fibers made from the materials obtained according to the invention are spun without fiber, while the fiber R1'ls-n, which is made of polyamide 11, is subjected to such processing.

The ohmic resistance is measured for these fibers over a length of one mm tru at voltage

400 volts, 20 ° C and 65% relative humidity. Viscosity measurements are performed at 25 ° C in metacresol at a concentration of 0.5 g / 100 ml.

The following examples illustrate the invention in greater detail without limiting its scope.

A 1 liter reactor was charged with 300 g of a 2090 average molecular weight dicarboxylic polyamide 11 prepared by polycondensation of 11-aminoundecylic acid in the presence of adipic acid. Then 65 g of dioxyethylene glycol and 1 g of tetrabutyl orthotitanate are added. The reaction mixture was heated under nitrogen until the temperature reached 240 ° C. The reaction was allowed to proceed under reflux for 4 hours at 250 ° C, stirring vigorously under an inert atmosphere, then raising the temperature to 260 ° C and reducing the pressure in the reactor to strip off excess dioxyethylene glycol.

13.3 Pa - The product obtained was

Under these conditions, the reaction is allowed to proceed for 1 hour at 260 ° C under pressure and has the following characteristics:

limit temperature viscosity temperature Melting number of glass transition, 35 dl / g

173 ° C

5 ° C

This product contains weight.

% dioxyethylene glycol blocks based on total

After grinding, the product obtained is spun under the above conditions. The fibers obtained consisted of 23 nonwoven fibers of 4.0 denier; their circular cross-section has an average diameter of 23.96 ди.

With these fibers, tensile velocities are performed by dynamometer tests using a DYNSTRON dynamometer at 20 cm / min, and at a bias of 0.5 cent Newton.

The results measured in these tests are as follows:

ductility tensile strength modulus of elasticity titer ohmic resistance per 1 m (ohms / 1 m) fiber length

17.9%

525 g

25.98 g / dtex

3.65 dtex

7.14. I0 ¹²

For comparison, tests are carried out to determine the antistatic properties. The results are:

polyamide 11, these tests, processed by addition of additive k performed under the same conditions, are ductility tensile strength modulus of elasticity titer ohmic resistance per m

12.8%

52Ί g

43; 03 g / dtex

3,1 dtex

4.46. 10 ¹³ fiber length

206717

Example 2

In a similar manner to that of Example 1, 209 g of dicarboxylic polyamide 11 (obtained by polycondensation of 11-aminoundecylic acid in the presence of adipic acid) of molecular weight 2090 were reacted with 60 g of trioxyethylene glycol in excess of polyamide and 1 g of tetrabutyl orthotitanate.

The product obtained is characterized by the following parameters:

viscosity limit 1.30 dl / g melting point 173 ° C glass transition temperature -14 ° C

This product contains 7% by weight of trioxyethylene glycol groups based on the total weight. The product is spun in 3 lots. The fibers obtained from these 3 lots are characterized by the properties given in Table I.

Table I

Game 1 2 3 titre (dtex) 3.17 2.94 3.54 elongation,% 17.3 16.3 16.1 tensile strength, (G) 440 443 432 modulus of elasticity, (g / dtex) 16.7 - 19.1 ohmic resistance per (ohms / 1 m) 1 m fiber length 5.00. 10 ¹⁴ 5.71. 10 ¹⁴ 7.00. 10 ¹⁴

All these products are antistatic.

EXAMPLE 3 Following a procedure analogous to that of Example 1, 209 g of 2090 dicarboxylic polyamide 11 was reacted with 42.5 g of average molecular weight 425 and 1 g of tetrabutyl orthotitanate. The reaction mixture is heated under an inert atmosphere until the temperature reaches 260 ° C. Vacuum is then generated in the reactor and the reaction is then allowed to proceed with vigorous stirring for 4 hours at 260 ° C at 13.3 Pa.

The product obtained is characterized by the following parameters:

viscosity limit value 1.40 dl / g melting point 173 ° C glass transition temperature -60 ° C

The product obtained contains 17% by weight of polyoxyalkylene glycol groups, based on the total weight. This product is spun in two parts. Fibers from both lots (23 fibers not twisted) are characterized by the properties listed in Table II.

Table II

Lot titre (dtex) tensile strength (g) elongation% modulus of elasticity, (g / dtex) resistivity per 1 m fiber length (ohms / 1 m)

3.38 2.81 310 308 29.3 18.0 15.00 15.7 4.89. 10 ¹⁵ 5.82. 10 ¹⁵

Anti-static properties

By comparing the results obtained in the first three examples, which are summarized in Table III, it was found that the antistatic properties, expressed in ohmic resistance per m of fiber length, increased with increasing proportion of polyester ether groups in the copolyester etheramide produced. Conversely, the modulus of elasticity in g / denier decreases with increasing weight amounts of polyester ether groups. Antistatic properties are equivalent to those of polyamide 11 with the addition of an antistatic agent when the copolyester etheramide contains 5 to 7% by weight of polyester ether groups. It is advantageous to introduce at most 17% by weight of the polyester ether groups in view of the decrease in the modulus of elasticity, which is all the greater the higher the proportion of polyester ether groups.

Table III

Content of polyetherester groups (in.

in the chain, based on the total weight

Content of polyamide groups (in% by weight)

Fibers number mean diameter in / ж

Physical properties number modulus of elasticity (g / dtex) antistatic properties, expressed in ohmic resistance per 1 m of fiber length (Polyamide 11 with addition of antistatic

reagents) 100 ALIGN! 23 21.17 3.09. 53.4 4.46. ΊΟ ¹ - ' 5 95 23 23.98 3.65 32.0 7.14. Ю ¹² 7 93 23 21.67. 3.18 15.5 5.00. Ю ¹ . ⁴ 7 93 23 21.35 2.93 - . 5.71 ΙΟ ¹⁴ 7 93 23 21.92 3.54 18.9. . 7.00. . ΊΟ ¹⁴ 17 83 23 22.56 3.40 14.8 4,89 ·. 10 '^; 17 23 19.80 2.84 16.6 5.82 to ¹⁵ .

Example 4

In a similar manner to that of Example 1, 300 g of 2090 dicarboxylic polyamide 11 having a molecular weight of 2090 were reacted with 62 g of ethylene glycol in excess of the stoichiometric amount and 1 g of tetrabutyl orthotitanate. The reaction mixture was heated until the temperature reached 230 ° C, which temperature was then maintained for 4 hours under stirring in an inert atmosphere. After the excess glycol has been stripped off, the temperature is raised to 260 ° C, a vacuum is created in the reactor and the reaction is allowed to proceed for 1 hour at 260 ° C at a pressure of 13 to 3 Pa ·

The product obtained is characterized by the following parameters:

viscosity limit melting point glass transition temperature

1.40 dl / g

Mp 173 ° C -18 ° C

This product contains 3% by weight of ethylene glycol groups based on the total weight.

P г i. К 1 ad 5

Into a 6-liter stainless steel reactor was charged 1 kg of a 2000 molecular weight dicarboxylic polyamide 6 prepared by polycondensation of caprolactam in the presence of adipic acid. 170 g of dioxyethylene glycol and 3.5 g of tetramethyl orthotinate are added.

The reaction mixture was then heated under a nitrogen atmosphere until the temperature reached 230 ° C, where the reaction was allowed to proceed for 1 hour under reflux with vigorous stirring under an inert atmosphere. The temperature is then raised to 250 DEG C. and the excess dioxyethylene glycol is distilled off under reduced pressure of 13.3 Pa and the reaction is allowed to proceed under these conditions for an additional hour.

The product obtained is characterized by the following parameters:

viscosity limit melting point

1.30 dl / g

Mp 192 ° C

This product contains 5% by weight of dioxyethylene glycol groups based on the total weight

The product is then cryogenically pulverized to obtain a powdery mass with a particle size range of 80 to 200 x 10 ^-6 m.

The ohmic resistance per 1 m of fiber length is 6.1.10.

Example 6

In the same manner as in Example 1, 1 kg of a 2000 molecular weight dicarboxylic polyamide 6 is reacted with 200 g of trioxyethylene glycol and 4 g of tetrabutylthiotitanate

Ti (OBu) ₄

The product obtained is characterized by the following parameters:

viscosity limit melting point, 35 dl / g

Mp 192 ° C

This product contains 7% by weight of trioxyethylene glycol groups based on the total weight. Its ohmic resistance per 1 m of fiber length is 3.5 x 10.

Example 7

In a 6 liter stainless steel reactor, 1 kg of dicarboxylic acid is reacted. polyamide 6 having a molecular weight of 2,000 with 212 g of polyoxyethylene glycol having a molecular weight of 425 and 3.5 g of t-butyl orthotitanate Ti (OBu) ₄ ;

The reaction mixture was heated under an inert atmosphere until the temperature reached 260 ° C. Vacuum is then formed in the reactor and the reaction is allowed to proceed with vigorous stirring for 4 hours at 260 DEG C. under reduced pressure.

The product obtained is characterized by the following parameters:

viscosity number. melting point 1.45 dl / g Mp 192 ° C

This product contains .17 wt%, polyoxyethylene glycol groups, based on total hmotnost.'Ohmickýodpor 1 m distance, the fiber has a value of 7,5.10 ^eighth

Example.

1 kg of dicarboxylic polyamide 6-6 is reacted in a stainless steel reactor of 6 liters. of a mass of 2,000, prepared by polycondensation of hexamethylene adipamide in the presence of adipic acid. 170 g of dioxyethylene glycol and 3.5 g of Ti (QBu) tetrabutyl orthotitanate are added.

The reaction mixture was then stirred under heating at 270 ° C under nitrogen for 4 hours under reflux. Excess glycol is then distilled off and the polycondensation reaction is allowed to proceed for 1 hour under reduced pressure (67.5 Pa).

The product obtained is characterized by the following parameters:

viscosity limit _j melting point 1.25 dl / g 245 ° C

The product obtained contains 5% by weight, of dioxyethylene groups, based on the total weight.

nost. Its ohmic resistance per 1 m of fiber length is worth 1,6.10 ’.

Example 9

1 kg of a dicarboxylic polyamide 6-6 having a molecular weight of 2,000 8,200 g of trioxyethylene glycol and 4 g of Ti (0Bu) ₄ tetrabutyl orthotitanate was reacted as described in Example ₄ .

The product obtained is characterized by the following parameters;

viscosity limit melting point 1.35 dl / g 245 ° C

This product contains 7% by weight of trioxyethylene glycol groups based on the total weight. The ohmic resistance value is 4.4.10.

Example 10

In a 6-liter stainless steel reactor, 1 kg of 2000-molecular-weight dicarboxylic polyamide 6-6 is reacted with 212 g of polyoxyeeylene glycol of the moocular molarity of 425 and 3.5 g of non-butyl-ortho-titanate TiCO3.

The reaction mixture is gassed in an atmosphere until the temperature reaches ²⁷⁰ ° C. ^p and ^k , a vacuum of 67.5 Pa is created in the reactor and the reaction is allowed to proceed for 1 hour at 265 ° C with vigorous stirring, then for a further hour at 285 ° C.

The product obtained is characterized by the following parameters:

viscosity limit 1.40 dl / g melting point 245 ° C

This product contains 15% by weight, polyoxyethylene glycol groups, based on total moisture content.

Its OH ^ l.cký resistance per length of ¹ m has todnotu ¹ second ¹ 0 ^.

Claims (1)

SUBJECT OF THE INVENTION A process for the preparation of aliphatic linear polyester amides or copolyester esters of amides in which the proportion by weight of polyester or polyether groups is in the range of 1 to 20%, preferably in the range of 3 to 15%, is characterized by to 66 (6.6 Pa at 200-300 ° C) a linear polyamide having carboxyl end groups selected from the group consisting of polyamide 11, polyamide 6 and polyamide 6,6 having a molecular weight in the catalyst of reaction is reacted as catalyst. from 300 to 10,000, preferably about 2,000, with a large, linear, non-C1 to 6 carbon atom, or with a polyoxyalkylene glycol having a molecular weight of 150 to 500, having from 1 to 4 carbon atoms in the alkyl group The new part has a ratio in the range of from 1 to 10, preferably from 2 to 4, in an oocular ratio of from 1 to 10, mega-1 / dkVa, 2 to 4, and preferably from 2 to 4.