SE415840B - WATER-SOLUBLE SULPHONATED POLYESTER - Google Patents

Description

7309605-9 nowadays weave with a thread which has only the twist, which by means of the spinning chair is imparted to the continuous thread, i.e. 10-15 rpm. The water-soluble products according to the invention have proved to be of great interest in this context.

It is known that a very large number of unsaturated polyesters with a wide range of uses can be obtained by polycondensation of a polyol with an unsaturated carboxylic acid, possibly in the presence of a saturated dicarboxylic acid. Although the plastics obtained have many advantageous properties with respect to many areas of application, they have the disadvantage that they are insoluble in water, which limits their use to the areas where this property is to be regarded as fundamental. The object of the invention is to eliminate this disadvantage and to provide new polyesters which are important for different fields of application.

The invention thus relates to novel water-soluble sulfonated polyesters, which are prepared by polymerizing an aromatic diacid, its anhydride or its diester, of an unsaturated aliphatic diacid, its anhydride or diester of this acid, with a saturated glycol. It is characteristic of the polyester according to the invention that it is prepared by polycondensation: a) of an aromatic diacid, its anhydride or its diester, which acid or anhydride is selected from the group consisting of orthophthalic, isophthalic or terephthalic acid, a diacid with several benzene nuclei, an aromatic acid having aliphatic chains, in addition to which the diesters of these acids are the methyl, ethyl, propyl or butyl esters; b) of an aliphatic sulfonated diester, which is obtained by prior sulfonation with sodium bisulfite or sodium metabisulfite, an unsaturated aliphatic diester, e.g. methyl, ethyl, propyl, butyl diester, by means of ethylene glycol, propylene glycol, butylene glycol or diethylene glycol and 7309605-9 by maleic acid, fumaric acid or itaconic acid, the molar ratio of sulfonated aliphatic diester / aromatic diacid + sulfonated aliphatic diester ) of a saturated glycol selected from the group consisting of ethylene glycol, propylene glycols, butylene glycols, glycols with aromatic nuclei, polyethylene glycol, e.g. diethylene, triethylene, tetraethylene, pentaethylene glycols.

This sulfonation only at the level of these aliphatic unsaturations in the case of a later sulfonation of the condensation product has been analytically determined by infrared spectrophotometry.

The polyesters obtained by a previous condensation of various reactants, with subsequent sulfonation of the aliphatic double bonds, are more difficult to prepare due to the high viscosity of polymers at 10,000, at which temperature the sulfonation is usually carried out, but this difficulty can be overcome by suitable technical procedures.

In contrast, the foregoing sulfonation of the unsaturated aliphatic diacid diester and the reaction of this sulfonated diester with the other two reactants to directly give a water-soluble sulfonated polyester, easily and completely eliminate the above-explained viscosity disadvantages. This application also makes it possible to obtain polyesters with a very high content of sulfonated groups due to the absence of the viscosity problem during the sulfonation.

The direct sulfonation of the unsaturated aliphatic diacid or its anhydride is difficult to carry out, and under certain conditions the yield becomes unsatisfactory, which in practice has meant that the only diester of the unsaturated aliphatic diacid has to be sulfonated. 7309605-9 As aromatic diacids one can use such acids - or their anhydrides - as orthophthalic acid, isophthalic acid, terephthalic acid, which diacids represent several benzene nuclei, aromatic acids with aliphatic nucleus. Diesters of these acids can also be used, such as methyl, ethyl, propyl, butyl diesters, etc.

Maleic acid, fumaric acid, itaconic acid, etc. can be used as unsaturated aliphatic diacids or their anhydrides. and their diesters, e.g. methyl diester, ethyl diester, propyl diester, etc. As glycols one can use ethylene glycol, propylene glycols, butylene glycols, glycols with aromatic nuclei, polyethylene glycols, e.g. diethylene, triethylene, tatratylene, pentaethylene glycols, etc.

The condensation conditions for obtaining these products comprise the classical heating conditions of the order of 2-5 hours at a temperature which increases progressively from 220 to 27 ° C and the reactants are in stoichiometric proportions with or without a slight excess of one or the other.

The sulfonation is then carried out at an average temperature between 20 and 100 ° C for a time which is substantially between 5 and 6 hours in the presence of a small amount of water at atmospheric pressure or negative pressure.

Sodium bisulfite or sodium metabisulfite is suitably used as the sulfonating agent having an effect on the unsaturated bonds of the aliphatic chains. The amount of sulfonating agent is calculated stoichiometrically in relation to the unsaturated diacid used.

Examples of sulphonated aliphatic diesters which can be used in the preceding solfonation are those diesters obtained by sulphonating a diester of an unsaturated aliphatic diacid or its anhydride, e.g. the diesters of maleic, fumaric, itaconic acid. The methyl, ethyl, propyl, butyl diesters, ethylene glycol ether, propylene glycol, butylene glycol, etc. are suitably used. This sulfonation of the diesters of unsaturated aliphatic diacids is carried out at an average temperature between 20 and 100 ° C for a period of substantially between 1 and 5 hours in the presence of water at atmospheric pressure or negative pressure. Sodium disulfite or sodium metabisulfite is suitably used as the sulfonating agent.

The condensation conditions for a later obtaining of sulfonated polyesters are the known conditions with a heating for 2-15 hours to a temperature which increases progressively from 180 to 25000 and the reactants are present in stoichiometric proportions or with a slight excess of one or the other substance.

In the following, the invention will be explained with reference. to some embodiments, but the invention is of course not limited to these.

I) Previous condensation of various constituents with subsequent sulfonation Example 1 Condensation In a 0.5 L reaction vessel with a stirrer and a condenser were placed the following reactants: - dimethyl isophthalate 174.6 g - dimethyl maleate 14.4 "- diethylene glycol 111.0" - tetraisopromyl o-titanate 0.5 ml The mixture was heated with stirring in a gentle stream of nitrogen at atmospheric pressure with a progressive rise in temperature from 30 to 21006 for 2 hours, after which 60 g of methanol were collected.

The condensation continued at a negative pressure of 22 mm Hg with a rise in temperature from 220 to 260 ° C for 30 minutes. This temperature and this pressure were maintained for half an hour, which time was required to carry out the condensation and eliminate excess diethylene glycol.

It was cooled to 100 ° C before disengaging the negative pressure in order to eliminate oxidation of the double malein bonds. The resulting polyester was added with stirring and at 100 ° C with - 9.5 g of sodium metabisulfite in powder form and then - 20 ml of distilled water, which was added for 30 minutes with a bromine ampoule. Heated under reflux (about 110 ° C) for 2 hours.

An opaque yellow product was obtained, which was solid in the cold and contained about 7% water. The product was dispersed in hot water while stirring to give an opaque solution.

The intrinsic viscosity of the dry product was 0.23: (The intrinsic viscosity was determined at 25% and at 2500 in a solution consisting of 60 g of phenol + 40 g of tetrachloroethane.) Example 2 Under the same conditions as in Example 1 (the conditions for condensation and sulfonation were identical) diethylene glycol was replaced with triethylene glycol.

The following reactants were thus obtained: - dimethyl isophthalate 174.6-g - dimethyl maleate 14.4 "- triethylene glycol 7 157.5" - tetraisopropyl-o-titanate 0.3 ml Sulphonation The product obtained was added in the same manner as in Example 1 with: '- sodium metabisulfite 9.5 g - water 20 ml A dark yellow product was obtained, which was soft and adherent even after drying.

Intrinsic viscosity 0.58 The product was soluble in hot water.

The solution was at a concentration of 20% white. It was converted to a gel after cooling.

Exem e 3.

Under the same conditions as in Example 1, dimethyl isophthalate was replaced with dimethyl terephthalate, followed by sulfonation at a pressure of 2 bar and 15 ° C. The following reactants were thus obtained: - dimethyl terephthalate 174.6 g - dimethyl maleate 14.4 "- diethylene glycol 159.0" 4 tetraisopropyl-O-titanate 0.5 ml Sulfonation The product obtained was added with sodium metabisulfite 9.5 g ( 0.05 mol) - water 20 ml Work was carried out in a stainless steel reactor at a pressure of 2 bar and, a temperature of 13000 for 2 hours.

A yellow, opaque, rather hard product was obtained, which was soluble in hot water. A 10% solution was white and viscous. After cooling fl ß. it was converted into a gel.

Example 4 The condensation was carried out under the conditions described in Example 1, but the sulfonation was carried out by means of a solution of sodium bisulfite. The mixture used had the following composition: - dimethyl isophthalate 136.0'n - dimethyl maleate 43.0 "- diethylene glycol 106.0" - tetraisopropyl-O-titanate 0.5 ml Sulphonation The above polyester, which was kept at 10000, was added with fairly rapid stirring with 400 ml of a 50/50 solution of sodium bisulphite at 500 Éé and distilled water.

The temperature was maintained and stirring was continued for 4 hours.

After cooling to 5000, two layers were separated by centrifugation. The organic layer, which was at the bottom, consisted of sulfonated polyester with a content of about 50% water.

Intrinsic viscosity 0.25.

The product was soluble in hot water and gave a slightly cloudy solution. 7309605-9 'Example 5 The conditions of Example 1 were slightly modified. Dimethyl isophthalate was replaced with isophthalic acid and a polymerization inhibitor was added. Condensation In a 2 L reactor with a stirrer and a coolant were placed: - - Isophthalic acid - 747 g - Maleic anhydride 49 "- Diethylene glycol * 1060" - 2,5-Aiterticbutyl hyaroquinone - 1 "- Tetraisopropyl-o-titanate 1.5 ml Man heated with stirring and a weak stream of nitrogen at atmospheric pressure and progressively raised the temperature from 20 to 22,500 for 1.5 hours. Condensation was continued at a negative pressure of 2 mm Hg during the temperature rise at 1 hour and 50 minutes from 225 to 24000. It was cooled to 140 ° C and the negative pressure was disconnected.

Sulfonation The resulting polyester was added with stirring at 100 ° C with: - sodium metabisulfite 50 g - water 100 ml (added for 1 hour) the temperature was kept at 100 ° C for 3 hours.

A product was obtained which was soluble in hot water and which gave a slightly cloudy solution.

The intrinsic viscosity of the dry product was 0.19.

Example 6 The unsaturated diacid in this case was itaconic acid.

Condensation In a 0.5 l reactor equipped with a stirrer and coolant were introduced: - isophthalic acid 133 g - itaconic acid 26 "- diethylene glycol 212" - 2,5-ditertiobutyl-hydroquinone 0.5 "tetraisopropyl-o- titanate 0.3 ml 730960549 Man heated with stirring and at a slight stream of nitrogen and at a temperature increase from 20 to 21000 for one hour and 30 minutes and maintained the temperature at 21000 for half an hour and then raised at a negative pressure of 2 mm Hg the temperature further from 220 to 23,500 in 1 hour. The yield was 34 g of water and 100 g of diethylene glycol.

Sulfonation The polyester obtained according to the above was added with stirring and at 10,000 with: - sodium metabisulfite 20 g - water 20 ml (added for 1 hour). With continued stirring, the temperature was kept at 100 ° 0 for 6 hours.

The product is then az-dried for 48 hours in an oven at 105%.

A slightly colored product was obtained, which was readily soluble in water and gave an almost clear solution. The inherent viscosity of the dry product was 0.16.

Example 7 Under the conditions of Example 1, a 50/50 mixture of diethylene glycol and triethylene glycol was used.

Condensation In a 2 L reactor equipped with a stirrer and coolant were placed: - dimethyl isophthalate 873 g - dimethyl maleate 72 "- diethylene glycol 265" - triethylene glycol 415 "- tetraisopropyl-o-titanate '1.5 ml Man heated with stirring and weak nitrogen flow at atmospheric pressure and progressively raised the temperature from 20 to 22,500 for 1 hour and 30 minutes and then at a negative pressure of 2 mm Hg raised the temperature progressively to 250 ° C likewise for 1 hour and 30 minutes.The temperature was allowed to drop to 12000 and the negative pressure was released. In exchange, the following were obtained: - methanol 280 g - triethylene glycol 35 "7309605-9 Sulfonation The polyester obtained was added with stirring and at 100 ° C with: - sodium metabisulfite 50 g - water 100 g (added under 1 hour.) The temperature was maintained at 100/105 ° C for 5 hours.

A yellow, opaque product was obtained, which was readily soluble in hot water. A 20% solution was viscous and opaque.

The inherent viscosity of the dry product is 0.23.

The water-soluble sulfonated polyesters of the invention presented significant properties for many different types of applications.

In the field of textiles, the properties of the substances have made it probable that they will have a promising future, in particular for gluing in the manner already stated in the general part of this description.

In the practice applied hitherto, the twisting which has been imparted to threads and monofilaments has been considerable and of the order of several hundred revolutions per meter, and thus added to this thread a sufficient wear resistance in the weaving. However, the manufacturing costs of obtaining this twist were high. Attempts have therefore been made to eliminate the twisting by progressively replacing it with gluing or a sizing, which has been stronger the longer the twisting of the trees. Thus, a minimum twist of 10-15 turns has now been reached for the weaving threads alone. However, the conventional adhesives or sizing agents have proved insufficient to impart sufficient wear resistance to the wire coming from the spinning machine to enable weaving in good conditions. 7309605 -9 11 Various substances have been proposed, e.g. homopolymers of acrylic or methacrylic acids. Although good results have been achieved with certain fibers, e.g. viscose, cellulose acetate, nylo, this applies to fibers of terephthalic esters (ferylenáåj, Tergal). In this case, there seems to be a lack of affinity between the fiber and the sizing agent. In order to obtain an adhesion force of the fibers between them which is sufficient for the weaving, polymers have had to be used which, through soft films, e.g. copolymers of ethyl acrylate and acrylic acid. However, these films become somewhat heat-adhesive at about 4000 and their mechanical strength becomes weak and this results in a moderate wear resistance. The strong frictional stresses to which the thread is subjected during weaving, e.g. at the weave comb, tears off the sizing particles and causes a powdery deposit on the guide means for the thread, which deposit is rapidly converted into a sticky mass which adheres to the metal.

However, polyester trees can be woven provided that the ridges, stitches and separating rods of the webs are regularly cleaned.

This cleaning may be necessary to carry out as often nom var ïczn to Udßv hour, in the case of stretched fabric. In order to eliminate the disadvantages of the dirty soiling of the loom by sizing deposits, an application of a lubricating wax to the wire has been proposed and added as an additive to the adhesive, in order to reduce the frictional effects and thus partially eliminate the tearing of the adhesive on the thread.

'These wax products have an actual effectiveness in connection with a medium or weakly stretched fabric, but they do not give satisfactory results for heavy fabrics.

In addition, the waxes which show the best effect in this respect are products which are difficult to remove before dyeing, as they should be as hydrophobic as possible and have a minimal, surfactant emulsifier in order to maintain their lubricating properties.

In practice, the amounts of dry material of sizing agent commonly used on polyester monofilaments amount to at least 5-4% by weight for a wire at 300 rpm, necessitating a concentration of the active material bath of the order of 6-8% by weight. percent.

For a twisted wire, which comes directly from the spinning machine, this amount of adhesive is insufficient. It is necessary to increase the concentration in the bath of active material to 10% by weight in order to obtain 5% by weight of dry material on the warp.

This increase in charge increases to the same extent the soiling of the parts of the loom and this is one of the reasons for the low use of polyester filaments without twisting as a warp.

The use of the products according to the invention as sizing agents makes it possible to eliminate the disadvantages described above. Thanks to better adhesion, these products can be used in smaller quantities but still provide better protection against abrasion.

Experiments have thus been carried out with warp thread with 40 threads / cm of Terga and 65 denier, 55 fibers. These warp threads were immersed in an aqueous solution with an adhesive composition which had been prepared with the product of Example 1, and then they were squeezed between two cylinders and dried. Three glue baths were used in the experiments with concentrations of 3, 4 and 6% by weight of active material. The warp threads so glued were then woven in a loom with a reduction of the warp by 34 elements / if and .. ... .__ ... Jxua -... p -... mü- .... man »* Wšöêtlïs-s 13 taftbindning. Proper weaving without waste has been able to be obtained and the protection of the thread becomes stronger the more the glue bath is concentrated. In the three cases, no deposit of glue was obtained on the comb at a fabric length of 50 m.

Comparative experiments with weaving, which have been carried out with the same glued warp threads with common products on the market, e.g. Gerol ACR (Société Soprosoie) has shown that an insufficient wear resistance is obtained, which leads to a contamination during weaving and to a significant deposition of glue on the comb after weaving 50 m.

By extraction with de-distilled water in a Soxhlet flask in an ammoniacal environment and with the addition of dry material in the rinsing water, it has been possible to determine that the amount of dry glue on the wire regularly corresponds to half the concentration in the glue bath, ie. when the bath contained 5% by weight of active material, gave a coating of 1.5% by weight on the wire. This was confirmed by the amount of diluted spade which was carried by the wire to the gluing machine, since it was found that 1 kg of wire carried about 500 g of diluted bath.

The new composition of the adhesive based on the products according to the invention is of great importance for the weaving of polyester thread under the conditions of yield and amount comparable to those obtained with textile fibers, which present a gluing possibility similar to that of nylon and viscose.

The adhesive mixture according to the invention, which is applied to wire of cellulose acetate and the cellulose triacetate, has also given significant results in weaving. To date, these threads have not presented any difficulties in weaving when using vinyl polymers either in terms of the good cohesion of the fibers with each other or in the overall quality of the fibers. the absence of soiling of the loom, if only the twisting of these threads was at least 80 rpm, e.g. for a thread with 110 decitex, 24 fibers. Due to the acquisition costs, experiments with weaving with threads with low twist have been started for some time, e.g. 5-15 rpm such as with polyester. In the case of these conventional products, the adhesive bath should have a concentration of 6-7% by weight of active material for a deposit of about 4-5% by weight of dry material on the fiber, which dosage is necessary for a normal protection of the fiber against wear. It should be emphasized in particular that this coating appears to be a minimal value without a noticeable safety margin, since weaving is possible only on the absolute condition that a thread with particularly good textile properties is used, ie. it does not include elementally damaged fibers on the main body or bobbins that feed the cutting machine's cut.

It was woven with a thread of 110 decitex, 24 fibers, 10 twists of cellulose acetate with a warp of 40 fibers and a warp in the loom at 28 weights / cm of this warp. The gluing bath contained 4% by weight of dry material of the product obtained according to Example 1. A good possibility of weaving could be observed exactly corresponding to that obtained with a gluing in a bath with a content of 6% dry material of a reference product of the above specified kind, which has hitherto been regarded as a mixture with satisfactory adhesive capacity on a cellulose acetate wire. For comparison, an attempt was made to weave with an identical warp thread, which was glued in a glue bath with a concentration of 4% by weight of dry material of Gerol ACE (Société Soprosoie). The weaving was extremely difficult and required constant intervention for repair or elimination of elemental fibers from the thread, which was destroyed by the wear effect due to the friction of the threads among themselves and friction against parts of the loom. It is thus obvious that soluble polyesters Ä according to the invention show great efficiency against threads based on cellulose esters. Of course, the above examples of application should in no way be considered limiting and other textile fibers, e.g. viscose, acrylic fibers, polyamide fibers, glass fibers or fibers based on vinyl chloride can be successfully twisted using adhesives according to the invention.

II. Previous sulfonation of diester of unsaturated aliphatic diacid with subsequent condensation of the various constituents First, an example of the preparation of sulfonated derivatives starting from dimethyl maleate, which after sulfonation gives dimethylsulfosuccinate.

In a 20 L flask equipped with a heater, a propeller stirrer, cooling means and an ampoule of bromine were placed: - dimethyl maleate 20 moles (2883 g), i.e. 2.5 L - water 80 moles (1440 g) The stirrer was started and a milky suspension was obtained. In the bromine ampoule, which was placed on the flask, were placed: - sodium metabisulfite 10 moles (1900 g) - water 220 moles (3960 g) First the temperature of the flask was raised from room temperature to 95 ° C and then the charge was introduced in aliquot portions of 300 - 500 ml in such a way that the temperature itself was kept between 93 and 9800. When the whole solution of sodium metabisulfite had added (which took about 50 minutes), this temperature was still maintained at 10000 for 1 hour. The yield from reaction was 98%.

The product was allowed to stand and crystallize overnight and filtered on a glass frit. A product was obtained in a yield of 51%, which was dried in a ventilated oven at 60 ° C. In the following, some unrestricted examples of the practice of the invention using dimethyl sulfosuccinate, the preparation of which will be described in the following, are given below.

Example gel 8 In a reactor was placed the following mixture: - isophthalic acid 315.4 g - dimethylsulfosuccinate 24.8 g - diethylene glycol 235.2 g - tetraisoprypol-o-orthotitanate 0.6 ml In a stream of nitrogen, the temperature was first raised rapidly from 20 to 16000, which took about 1 hour and then it was raised more slowly (from 160 to 200 ° C in 3 hours). This temperature was maintained for an additional 2 hours at 200 ° C. g During this period, about 55 ml of a mixture of water and methanol was extracted. Thereafter, the excess diethylene glycol (ca. 20 ml) was still evaporated at 200 ° C and a negative pressure of 2-3 mm Hg, which required 2-3 hours. The polyester was then allowed to flow while still hot, and was collected in a solid and anhydrated state.

A 30% aqueous solution of the product obtained had a milky appearance. At a concentration of 0.25% in the mixture of phenol and acetylene tetrachloride, it had an intrinsic viscosity fl inh of 0.15 dl, g_1.

The other characteristics were as follows: 41.8 mg KOH / g acid index IA hydroxyl index IOH = 5.16 "2200 average molecular weight - A sulfur content of the obtained polymer S (%) = 0.83 (theoretical 0.67) Example 9 The reactor was charged with: - isophthalic acid 315.4 g - dimethylsynphosuccinate 24.8 g - diethylene glycol 212.2 g - tetraisopropyl-o-titanate 0.6 ml The condensation conditions were the same as in Example 8.

A 20% aqueous solution of the product obtained had a milky appearance but clarified after neutralization with NH 4 OH.

Its properties were as follows: IL inn = 0.22 al.g "1 IA = 54.3 mg Kon / g IoH = ° Mn = 5150 (1 instead of 2200 as in example 1) S (%) = 0.71 ( theoretical 0.67) Example 10 In a reactor were placed: - isolphthalic acid 305.5 g - dimethylsulfosuccinate 39.7 g - diethylene glycol 235.2 g - tetraisopropyl-o-titanate 0.6 ml The condensation conditions were the same as in example 8, but the maximum temperature was selected to 190 ° C.

A 20% aqueous solution was opaque and became transparent after neutralization (NH 4 OH). It tended to form an opaque gel after a few days of storage. The gel was reversible by heating to 70 ° C.

Its properties were as follows: 730960549 '18 v, - »-1 lnh = 0.15 a1.g' IA = 27.7 mg KOH / g IOH = 31.9 I" I / [n = 175Û's (%) = 1.02 (theoretical 1.06) Example gel 11 In a reactor were placed: - isophthalic acid 289.0 g - dimethylsulfosuccinate 64.5 "- diethylene glycol 235.2" - tetraisopropyl-o-titanate 0.6 ml The condensation conditions were the same as 1 Example 8. The plastic obtained was practically uncoloured and slightly brittle. A 50% aqueous solution was completely ready.

It had the following properties: 01 / inn = 0.16 d1.g'1 I 15.9 mg KOH / g Il Å: OH = 20.8 "Mn = 28§0 S (%) = 1.71 (theoretical 1 , 71) _ åwmilê This was the same structure as in Example 11, but the experiment was carried out on a semi-large industrial scale without excess glycol.

In a 40 l glass reactor of the Pfaudler type with a column, with a master, with a stirrer and with a nitrogen inlet, the basic products were placed under stirring in the following order: -_. ~ .4 ;. -_ .- .. u .. ~ n ...... .Aåum .amunnnnnnnnuuàgzn fl nk fl ø -, Au- fl ... V .. J'- 73ö9.6Û5-9 19 - diethylene glycol 10,610 g - tetraisopropylene-o- titanate 30 ml - dimethylsulfosuccinate 3,224 kg - isophthalic acid 14,442 kg Man heated with stirring (the speed being set at 150 rpm and the amount of nitrogen at 90 l / h).

The temperature was raised from 20 ° to 20 ° C in 8 hours. This temperature was maintained for 2 hours before the negative pressure was switched on.

The negative pressure should be switched on progressively to avoid a sudden entrainment of unreacted reactants. The pressure was reduced from 760 to 15 mm Hg in half an hour and kept between 10 and 15 mm for 5-6 hours with a weak supply of nitrogen (required for E "stripping").

The temperature was maintained at 200 ° C.

After restoring the atmospheric pressure, the condensation water (4.2 L) was first removed and then the desired product was allowed to flow down into trays, which were coated with Teflon foil.

The resulting plastic was light yellow - yellow in color.

It exhibited the following properties: "Linen = 0.17 arg * IA = 28.0 mg KOH / g IOH = 10.7" 'En = 2700 s (%) = 1.43 (tea ethic 1.71) A 20% aqueous solution had a milk-like appearance and was stable for a long time.

Example 13 A reactor was placed in: 7309605-9 Example 8. Properties: 1 Ion nu Mn sm Surface tension = 20 isophthalic acid 252.4 g dimethylsulfosuccinate (sodium salt) 148.8 "diethylene glycol 253.2" tetraisopropyl-o-titanate 0.6 The condensation conditions were the same as in The product obtained presented the following 21.4 mg KOH / g .___ 9.7 u = 325o = 3.43 (theoretical 3.8) 55.5 ayn-cm-1 (1% aqueous solution and 20% ° C) A 30% aqueous solution of this product was completely clear. At a concentration of 0.25% in the phenol / acetylene tetrachloride mixture, it had an intrinsic viscosity of 0.9 a1.g'1.

Example 14 in Example 8.

In a reactor were placed: - isophthalic acid 166 g - dimethylsulfosuccinate 248 g - diethylene glycol 233.2 g - tetraisopropyl-o-titanate 0.6 ml The condensation conditions were the same as The plastic obtained was practically colorless and brittle with good stability.

Its properties were as follows: 7369605-9 21 ïbinn = 0.095 dl.g_1 IA = 54.8 mg KOH / g IOH = 22.8 "n = 1820 s (%) = 5.2 (theoretical 6.1) Surface tension = 55 dyn.cm'1 (1% aqueous solution at 2000) The following is an example of the preparation of a sulfonated derivative starting from ethylene glycol maleate, which after sulfonation gives sulfosuccinate of diethylene glycol.

In a flask with a heating device and a propeller stirrer device and a cooling device and a mounted bromine ampoule were placed: - diethylene glycol maleate 1 mol ie. 292 g - water 368 g Man heated to 80 ° C.

In the bromine ampoule placed on the flask were placed: - sodium metabisulphite 0.4 mol ie. 76 g - water 100 g The resulting liquid was slowly introduced into the flask to maintain a temperature of 80 ° C. The addition took 25 minutes. 268 g of water were added to obtain a 50% sulfosuccinate solution and the temperature was maintained at 9000 for 2 hours.

The solution thus obtained was used for the preparation of a sulfonated polyester.

Example 15 A reactor was charged with: - isophthalic acid 166 g - 50% solution of ethylene glycol sulfosuccinate 736 g - diethylene glycol 21.2 g tetraisopropyl o-titanate 0.6 ml 7309605-9 The temperature was raised rapidly to 10,000 and nitrogen then progressively to 170 ° C. Thereafter, the temperature was raised to 200 ° C. The condensation was then terminated and the entire condensation lasted for five hours.

The excess diethylene glycol was then distilled under a negative pressure of 20 mm Hg for 3 hours and 30 minutes. The polyester was then allowed to flow on heat. The solar-obtained product thus obtained was orange-red, solid in the cold state and soluble in water.

Example 16 In a reactor were placed: - isophthalic acid 166 g - solution of diethylene glycol sulfo-117 g suocinate with a concentration of 80% - diethylene glycol 90 g - tetraisopropyl-o-titanate 0.6 ml Worked under the same conditions as in Example 15. obtained a product similar to the previous one but slightly more hygroscopic.

-These polyesters have also been tested as adhesives under the conditions already described above.

With the three glue baths used for gluing warp threads of Tergal, no deposition of glue on the weave comb could be observed during a weaving of 50 m. Even when gluing cellulose acetate wire with a glue bath containing 4% by weight dry material of the product according to Example 11, a completely satisfactory weavability could be found.

In addition to textile use, mention should be made of the use of all these water-soluble sulphonated polyesters - regardless of the manufacturing method - as thermosensitive binders, which are dispersible in water and in particular the suitability in the paper field or for plastic films (cellophane, mylar, etc.). It can also be used as packaging in the form of film containers, which are soluble in water and which can contain both a solid and a liquid.

Claims (5)

¿; 1309605-9 P e t e n t k r a v Water-soluble sulfonated polyester, characterized in that it is prepared by polycondensation: a) of an aromatic diacid, its anhydride or its diester, which acid or anhydride is selected from the group consisting of orthophthalate; , isophthalic or terephthalic acid, a diacid having several benzene nuclei, an aromatic acid with aliphatic chains, and the dietetics of these acids are the methyl, ethyl, propyl or butyl ethers; b) of an aliphatic sulfonated diester, obtained by the previous sulfon ring by means of sodium bisulfite or sodium metabisulfite, an unsaturated aliphatic diester, e.g. methyl, ethyl, propyl, butyl diester, by means of ethylene glycol, propylene glycol, butylene glycol or diethylene glycol and by maleic acid, Fumaric acid or itaconic acid, the molar ratio of sulphonated aliphatic diester / aromatic diacid + sulphonated aliphatic diester being 0.05, c) of a saturated glycol selected from the group consisting of ethylene glycol, propylene glycols, butylene glycols, aromatic nucleus glycols, polyethylene glycol, e.g. diethylene, triethylene, tetraethylene, pentaethylene glycols. Polyester according to claim 1, characterized in that the aromatic diacid consists of an isophthalic acid, terephthalic acid or their methyl, ethyl, propyl, butyl diesters. A polyester in that the sulphonated ring product of methyl, ethyl, propyl, butyl, according to claim 1, is a diester, of ethylene glycol, of diethylene glycol, of maleic or fumaric acid. Polyester according to claim 1, characterized in that the glycol consists of ethylene glycol, propylene glycol, butylene glycol, diethylene glycol or triethylene glycol. 1309605 - 9 ¶ 2; Polyester according to Claim 1, characterized in that the molar ratio of sulphonated aliphatic diester / / aromatic diacid + sulphonated aliphatic diester amounts to between 0.1 and Q5. PROMISED PUBLICATIONS: France 1,464,938 US 2,028,091 (260-106), 3,563,904 (252-152) Other publications: Derwent Japoneese Putents Report, 7 (1968): 17 (June 4) Jap- putent 10157/68.