PL104341B1 - METHOD OF MAKING POLYETER-ESTROAMIDE SUITABLE FOR THE ANTISTATIC AND ANTISTATIC FIBERS - Google Patents

Description

The invention relates to a manufacturing process of a copolyether esteramide suitable for the fiber on and on products with natural properties antistatic, such that no need for any additive causing reduction or removal electric charges generated during friction cia. y It is known that a number of ipo compounds their incorporation into polymers exhibits the ability giving them antistatic properties.

In particular, it is known that when to polyamide a copolyetheresteramide (e.g. from the description of Pa of French Tent No. 2 178 205) Polyurethane teroamide with a high content of ether groups (e.g. from French Patent No. 1 567 660) they give the product to be poured antistatic properties. However, this method of production removal of antistatic polyamides includes brave preparation of block copolymer by polyether-lyanide and then mixing it with fright with blown polyamide for a good result the chemical pornography of the materials obtained plastic.

The invention avoids these disadvantages by direct preparation of the poHieteroestro- midu "who by itself has the properties of an tistatic without having to add any a product giving it such properties.

The method according to the invention produces polyether esterimide with antistatic properties, suitable for fronts and fibers, general formula nym [—C / 0 / - ^ A— stands for an integer and A stands for one sequence polyamide types 6, 6-h 6, fr-40, 11 or 12 groups of groups seriousness —O— (B — O indicates an originating structure from p -dlyoxyalkylene glycol with a low liquid molecular particles obtained by dimerization them, trimerizations or oligomerizations of 1-4 diols carbon atoms. This method involves polycondene- the molten state of polyamide with particles terminated with carboxyl groups with 1 ^ -20% by weight of polyoxyethylene glycol oligomer, in the presence of 0.1-5% of tetraalkyl orthotitanate as well catalytic converter. ' The polyoxyalkylene glycol of low molecular weight (obtained by di- merizations, trimerizations, tetraimerizations or oli- gomerization of aliphatic didels of 1-4 atoms coal. An example of polyoxyalkylene glycols you can exchange the ethylene glycol, trioxyethylene glycol, tetroxypropylene glycol- flax, tetroxybutylene glycol or glycol polyoxyalkylene (C 1 -C 4) molecular weight Dimension 1-0O-500, preferably 200-350.

Copolyether ester amide sequences of structure An analogous period was prepared using the method described in French Patent No. 2 2713 G21 however, the products obtained were intended for mainly for the manufacture of cast products, sheet and foil extruded, as they did not have 104 3413 the strength required for the fibers and thread antistatic properties.

That the received fiber or yarn could not to be electrified by friction, at the same time not to obtain satisfactory properties, technically necessary - it is necessary that the plastic is it was generally manufactured on a polyamide basis and that polyLoxyalkylene sequences are included in a weight ratio of 1 to 20%, preferably between 3 and 15%.

Chain polyamide is used as the polyamide aliphatic of the polyamide type 0, 6-6, 6-, 10, 11 or 12 which contains cardoxy groups on the tap chain and which is produced by either polymerization of a lactam or amino acid in the present carry a small amount of an aliphatic chain an aromatic acid, a-dicarbo- xylowe, or in the inter-chain reaction and- sem a— a chain measure a— one whose task is to create a box at the ends of the chain by running drive at the same time as a chain length limiter.

Amount used a— it therefore depends on the desired length and average the molecular weight of the resulting system liamic. These systems may have particle mass a ratio of between 300 and 10,000, preferably around 2000. , Among the lactams that can be used important can be replaced, for example, butyrolaktaim, caprolactam, decanolactam, undecano-tactam and laurolactam.

Among the amino acids that can be a hundred can be replaced, for example, acid 6-a- minohexanoic acid, 10-4 iminodecanoic acid, acid 11-aminoundecanoic acid and 1B-aminododecanoic acid you.

From between chain, aliphatic <& - diamines -example ^ you can name six- tylenebiamdne, octomethylenedivuamine, luminous methylene double, tenth methylene double amkie, two-methylene diamine, sixteen- tylenediamine, 1,2-diaminoeicosan, 1,2 and 2-di- amiinodocosan.

Between chain and - lifatics can be mentioned in particular adipic acid, sebacic acid, azelaic acid, deca nodicarboxylic, uiidecane dicarboxylic, dodecane dicarboxylic acid.

[The reactions are carried out by heating the substrate to melt under significantly reduced pressure in the presence and presence of the catalyst which it is tetraalkyl orthothitandate of formula T1 / OR / 4 such as Tetraisdpropyil orthothitanate or x> rthotitanate tet-butyl.

The reactions are carried out at higher temperatures on the melting point of the ingredients used * and should be such that the reaction mass is maintained important, it was in a liquid state. The temperature was generally 100-6400 ° C, preferably -200-300 ° C. Time the duration of the reaction may be between 10 minutes with notes of a. 10 gCKizinami preferably amounts to 1-7 341 4 hours. The time depends on the desired viscosity capolyestroetheramide formed. The reactions started today under much reduced pressure, 0.5 to 5 mm mercury bar.

Using the weight ratio of polyoxyalkyl glycol flax such that the sequence of these bonds is involved The tine concentration was between 1 and 20%, preferably when between 3 and 15% of the total weight is lost formed sequential polycondensate, obtained a high-weight copolyetheresteramide is used particle size suitable for extruding fibers or yarns with spontaneous properties antistatic and for which no additional giving an antistatic compound usually necessary when extruding textile fibers onto based on polyamides.

Another advantage of the fibers and yarns made of copolyether amides obtained by the process of the invention of the bed is the preservation of its properties antistatic over time - while the wind is blowing domo, with antistatic properties due to admixtures they disappear slowly during the turn new pran. x Colpolyether esteramides obtained by the process of the debt of the invention will be on the device provided niajacym correct work with small amounts raw material, at the temperature of the heating part 265 ° C, the temperature of the filter Wb ° Ct winding speed 70 m, per minute.

JO The obtained fiber is a bundle of 23 fibers elementary not twisted. A cross-section of each the fiber is about 2µm to 24 microns.

, The produced fiber is then pulled out cold with a stretch ratio of 4y8, speed unwinding 35.4 per minute and winding speed 170 m per minute ^ Fibers made from raw materials obtained by the method according to the invention by they were cooked without greasing ^ while Rilsan, 4g of polyamide 11 is treated.

The electrical resistance was measured (Ohimowa) of such fibers with a length of 1 meter at a voltage of 400 volts at 20 ° C and at 65% relative humidity. Viscosity measurement 45 nano at 25X !, in metacresol with a 1 nu 0.5 g in 100 ml.

The invention is illustrated in the following examples clades. in Example I, For a 1 liter reactor 300 g of polyamide 11 dicarboxylate with an average molecular weight of 2090 exc formed by polycondensations of the acid 11-ami- noundecanoic acid in the presence of adipic acid.

Then 65 g of diethylene glycol was added it and 1 g of tetra-butyl orthotitanam. Mixture the reaction was heated under nitrogen until to reaching a temperature of 240 ° C, followed by reactions continued under reflux at the temperature of turn 250X1 for 4 hours with good behavior 60 mixing regime and under an inert gas atmosphere.

Then the temperature was raised to 2 and 60 ° C and the temperature was closed the pressure in the reactor was reduced so that excess Dioxyethylene glycol has been removed. Re¬ the actions were continued for 1 hour at a temperature 6S round 26 ° C and at a pressure of 0.1 mm mercury bar. 104 341 The product has shown the following properties: intrinsic viscosity 1.35 mp 173 ° C 0 glass transition temperature -16 ° C This product contained 5 wt% sequence of diethylene glycol based on weight complete. The product was divided after grinding under the conditions previously described. Received fiber with 23 monofilaments does not twist up to 4.0 denier and medium cross section a circle of 213.98 microns.

The product was subjected to dynamometric tests using the DYNSTRON dynaimeter, at a rate of change in tension of 20 cm to minute and pre-tension 0.5 centinewton. ABOUT- the following results were kept: elongation at break 17.9% rc * breaking resistance 525 g 29iJ spring module. g / denier titr 4i, 0 denier ohm resistance meter of fiber 7.14 X 10 The title of the comparison was made in the identity Under the experimental conditions of the study of of the liamide 111 subjected to the downstream treatment giving it a substance which gives it anti ¬ properties static.

The following results were obtained: fracture elongation 12:, 8 tear resistance 527 g tmodui with a resistivity of 48.2 g / denier titre 3.4 denier swelling resistance of a meter of fiber 4.46 X 10 Example II. Proceeding in a similar manner the procedure described in example 1 was carried out reactions of 209 g of polyamide 11 dicarboxylic acid (produced by polycondensations of the acid ami¬ no II-undecanoic acid in the presence of adipino- e) with a molecular weight of 2090 with 60 g of glycol of trioxyethylene in excess compared to polyamide and with 1 g of orthotitanium nu tetrabutyl.

The product obtained showed the following properties features: intrinsic viscosity melting temperature glass transition temperature 1.30 173 ° C -> 14 ° C and contained 7% by weight of the trioxy glycol sequence of ethylene based on total weight.

The product was subjected to three shades of gray.

The characteristics of the obtained fibers are included in array (1. 40 45 50 55 60 6 Table 1 Charge titr (in denier) % elongation at breaking up The load at the breaking (g) modulus of elasticity (g / denier) resistance in Oh¬ strokes per meter of thread on 1 3.49 17.6 440 14.1 ^ 00 X 00 " 2 3.22 _: 16.3 443 ' - , 7 October " 3 '. 3.98 164 432 171.2 7.00 X 1 " All products showed an¬ properties tistatic.

Example III. In a manner analogous to the description In example 1, the reactions were performed 209 g of polyamide 11 dicarboxylic acid, weight molecular weight 2090 with 412.5 g of polyoxyethylene glycol with an average molecular weight equal to nym 425 and with 1 g of cziterobutyi orthotytanate.

The reaction mixture was placed under an atmosphere of inert gas and heated until reaching a temperature of temperature 260 ° C. Then the reactor was lowered pressure, and the reaction was continued while energized stirring at 260 ° C for 4 hours, at a pressure of 0.1 mm mercury bar :. Out the product created showed the following properties good: 'intrinsic viscosity 11.40 Melting point 17-3 ° C vitrification temperature —G0K !. and contained 17% by weight of the glycol poflyo sequence xalkenyl based on total weight you. Two grays of product were stamped on the pillar.

The obtained fibers of both gray (23 fibers e- lementary not twisted) showed properties presented in table 2.

- Table 2 65 Charge titr {in denier) load at burst in (g) % elongation at growth breaking up modulus of elasticity (g / denier) resistance in ohims per meter of fiber 1 3.75 310 29.3 13.50 4.89 X * 2 3.12 308 18.0 15vl , 82X * 104 341 Antistatic properties. Comparing the results obtained in the first three examples, taken in table 3 it can be seen that the property you antistatic expressed in subway resistance the fibers in ohms are raised in proportion not to the weight share of pdliester-ether- in the produced copolyetroetercamide.

Conversely, the modulus of elasticity expressed as a game the stroke on the denier decreased as a function of growth weight fraction of pdliester ether sequences. 8 Antistatic properties of copolyesters containing 5-7% of polyester are equivalent to those exhibited by the polyacid mid 11 treated with an antistatic agent him. It is preferable not to enter more than 17% of the polyester ether sequences - and that for a reason large diminution of the modulus of elasticity, which is the greater the higher the share of the sequence polyester ether.

Table 3 % ^ share of the blows polyester relative to the towards the weight of the inch smack 0 polyamide LI with additional contribution factor 1 antistatic % 7% 7% 7% i 17% % wt you ^ iu) k'la- of iiamid- out 100% 95% 93% 93% 93 «/ r: 84% Fibers number fibers 23 23 23 '23 23v 23 23 average section in micro nach 21.17 23.98 21.07 21v36 21.92 \ 22, S6 19.80 Physical Characteristics number de- unequal 3.40 4.00 3.49 3.212 3.89 3.75 3.12 module speak os¬ those 4a, 2 ¦ - 29.1 * 14.1 . 17.2 13.5 , 1 properties antistatic expressed resistance ohm / m. 4.46 X 10 " 7.14 X 1012 .00 Xl014 , 71 X KO14 7.00 X 1014 4.89 X 1015 , 82, 1015 Example IV. In a reactor with a capacity of 6 liters 1 kg of stainless steel was placed 6'-dicarboxylic liamide of average weight / m 2000 produced by polyconidensation of capro of lactam in the presence of adipic acid. Added 170 g of dioxyethylene glycol and 3.5 g of or- tetra-butyl totitaniam.

The reaction mixture was heated under the atmosphere nitrogen to a temperature of 230 ° C at which the reaction con ¬ continued under cooling for an hour while maintaining vigorous stirring and in the atmosphere inert gas sphere. Then the vacuum is heated It is brought to 250 ° C and the overdimension of glycol is dfVuoxyethyl The flax mixture was distilled under a reduced pressure 0.1 mm of mercury column. In these shafts In some circumstances, the reactions were continued for another hour day. The product produced showed the following properties: intrinsic viscosity melting temperature 1.30 192 ° C This product contained 5% by weight of the glycine sequence of the dioxyethylene colon expressed as 45 50 95 Zar total. The product was crushed by freezing to give a powder with dimensions: worth between 80 and 200 microns. Resistance a meter of fiber in ohlms was equal to 6 ^ 1 X 109.

Example V. Proceeding in an identical manner ny with the described in example I carried out there is a reaction of 1 kg of polyamide 6 dicarboxylic acid with a molecular weight of 2000, with 200 g of glycol of trioxyethylene and 4 g of T, and (OBu) 4.

The product produced showed the following poured qualities: intrinsic viscosity melting temperature 1.35 192X! This product contained 7% by weight of the glycine sequence of the tri-oxyethylene column calculated as the heat Zar total. Its resistance in ohms per meter the fiber was equal to 3v5Xl0V Example VI. In a reactor with a capacity of 6 liters, 1 g po-9 reactions were carried out from stainless steel of the 6-dicarboxylic liamide with a molecular weight 2000 with 212 g of polyoxyethylene glycol o 425 i z, 3.5 g Til (OBu) 4. The above mixture the reaction was placed under an inert gas atmosphere and heated to 2 ° C. Next the pressure in the reactor was released and the reactions continued nounced with vigorous agitation for 4 hours at 260X! and with pressure! 0.1 mm slulpka mercury.

The product produced showed the following poured qualities: intrinsic viscosity 1.45 mp 192 ° C The above product contained 17% by weight of se of polyoxyethylene glycol based on not on the total weight. Resistance in ohms na meter of fiber was 7.5 X 108.

Example VII. f In a stainless steel reactor In a volume of 6 liters, reactions were carried out 1 class of 6 ^ -6 dibasic polyamide of weight molecular weight 2,000 produced by polyclon adipic acid hexomethylene airnide densations it in the presence of adipic acid. 170 g were added Dioxyethylene glycol and 3.5 g of Ti (QBu) 4. Have the reaction mixture was heated "under a nitrogen atmosphere." at 2WK2 for 4 hours under chilled backflow with glycol return and during mixing. The excess glycol was distilled off and the condensations were continued for an hour at reduced pressure 0.5 mm mercury column. (Off the product being developed showed the following properties you: intrinsic viscosity 1.25 mp 245 ° C This product contained 5% by weight of the glycine sequence a dimethylene wheel calculated on a weight basis total.

The resistance was 1.6 X 1010.

Example VIII. Following similar to v In Example 4, 1 kg of reactions were carried out 6-6 dicarboxylic liamide with a weight of 2000 tons 200 g of triothyethylene glycol and 4 g Ti (OBu) 4.

The product produced showed the following poured qualities: intrinsic viscosity 1.35 mp 245 ° C and contained 7% by weight of the glycol tri of xethylene based on the total weight you. The resistance in Ohms per meter of fiber is equal to was 4.4 X 109.

Example IX. In a stainless steel reactor In a volume of 6 liters, reactions were carried out 1341 1 kg of polyamide 6-6 dicarboxylic acid molecular weight 2000 with 212 g of polyoxyethylene glycol new with a mass of 425 and with 3.5 g of TiCOBu) * Mixture put the reaction under nitrogen and heat until reaching the temperature of 2703C. (React The operations were continued under reduced pressure 0.5 mm of mercury while vigorously stirring for one hour at 265 ° C and then not for an hour at 285X2.

The product produced showed the following properties features: 'intrinsic viscosity 1.40 mp 24 * 5 ° C - and contained 15% by weight of the polyoxy glycol sequence ethylene. Resistance in ohmaclh per meter of fiber • was 1.2 X 109. 28 and

Claims (8)

Patent claims 1. A method for producing a copolyether esteramide suitable for the front and antistatic fibers, characterized in that an aaitphatic chain polyiotosyaflkylene glycol being an oligomer of aliphatic diols with 1-4 carbon atoms and a molecular weight of 100M500 * is reacted not melted under high vacuum, at a temperature of 100-400 ° C with a chain aliphatic polyamide terminated with carboxyl groups, with a molecular weight of 300-10,000, in the presence of 0.1-5% tetrabutyl orthotitanate, or 35 tetraisopropyyl, with a polyoxyalkylene sequence content in the range of 1-20 wt%. 2. In accordance with claim A method according to claim 1, characterized in that the polyoxyethylene glycol has a molecular weight of 4A of 100-500, preferably 200-350. 3. The method according to p. The process as claimed in claim 1, characterized in that the polyoxyalkylene sequences are introduced in an amount of 1-20%, preferably 3-15%. 45 4. The method according to claim 1, characterized in that the polyoxyalkylene glycol is ethylene glycol. 50 5. The method according to p. A process according to claim 1, characterized in that the polyoxyalkylene glycol is trioxyethylene glycol. 6. A method according to claim 1, characterized in that polyamide 11 is derived as the polyamide sequence. 7. The method according to p. The process of claim 1, wherein polyamide 6 is introduced as the polyamide sequence. 8. The method according to p. The process of claim 1, wherein polyamide 6-6 is introduced as the polyamide sequence. \