DE2335480C2 - Process for the preparation of water-soluble sulfonated polyesters - Google Patents

Description

The invention relates to processes for producing new water-soluble polyesters by sulfonation Unsaturated polyester are produced on the double bonds. It also relates to the application these products as water-soluble sizing agents for textile fibers

Sizing agents must be used because of it is impossible, the weakly twisted thread, the one insufficient resistance to scuffing for weaving has to weave These products must be removable with water before dyeing. It is common today to use thread that only have the twist imparted to the continuous thread by the spinning machine, i.e. 10 to 50 turns / m, to interweave the water-soluble products according to the Invention prove to be very advantageous in this case

From Japanese Patent 10 157/68 is a Process for the production of easily colorable polyester fibers by using minor sulfonation fibers sulphurous acid in a water-soluble ether than Known solvents

In DE-OS 1816163 are water-soluble Sizing agents based on polyester described which contain sulfonated aromatic radicals

From US-PS 20 28 091 esters are sulfonated Carboxylic acids known, which differ because of their surface-active Properties as emulsifiers and detergents are suitable

It is known to have a wide variety of unsaturated Polyester with a very wide range of applications by polycondensation of a polyol with a unsaturated dicarboxylic acid optionally in counter were to produce a saturated dicarboxylic acid resins obtained have a favorable combination of properties for numerous applications, however, they have the disadvantage that they are immersed in water are insoluble, which makes their application in fields where this property is considered absolutely necessary, is excluded

The invention addresses this disadvantage

ίο fix and make new polyester available for the most diverse applications are very advantageous The invention thus relates to three methods

for the production of new water-soluble sulfonated polyester, which is made from residues of aromatic dicarbon Acidic, sulfonated aliphatic dicarboxylic acids and saturated glycols are made up of these marked that either

A) 1 dimethyl terephthalate, dimethyl phthalate or isophthalic acid

2 dimethyl maleate, maleic anhydride or itaconic acid,

3 Di- and / or Tnathyleneglykol polycondensed and the product obtained with

/ 5 sodium bisulfite or sodium metabisulfite is sulfonated, the molar ratio being between 1 and 2 90 10 to 70 30, or that

B) 1 isophthalic acid

2 the sodium salt of dimethyl sulfosuccinate, 3 dietary glycol

be polycondensed, the molar ratio between 1 and 2 95 5 to 50 50, or that

C) 1 isophthalic acid

2 a solution which is obtained when 1 mol Bis (diethylene glycol) maleate in water with 04

Mol sodium metabisulfite is sulfonated and then diluted with water

3 dietary glycol

are polycondensed, with 736 g of a 50% or 117 g an 80% solution can be used

This sulfonation only occurs on the aliphati <hen double bonds in the case of the subsequent sulfonation (Embodiment A) of the condensation product could be detected analytically by infrared spectroscopy will

In the case of the present condensation of the various Reactants and subsequent sulfonation of the aliphatic double bonds formed Polyesters are due to the high viscosity of the polymer at the temperature of 100 ° C at which the Sulphonation is generally carried out more difficult but this difficulty can be overcome by appropriate technical methods By the previous sulfonation of the diester of the unsaturated aliphatic dicarboxylic acid and the Implementation of this sulfonated diester with the other two reactants with direct formation of the water-soluble sulfonated polyester are in The above-mentioned disadvantages of the high viscosity are simply eliminated. This method of operation it also enables it, precisely because of the lack of the problem of viscosity during sulfonation Obtain polyester with a high proportion of sulfonated groups

The direct sulfonation of the unsaturated aliphatic Dicarboxylic acid or its anhydrite

difficult and leads to unsatisfactory yields, so that it is technically necessary, the sulfonation alone on the diester of the unsaturated aliphatic carboxylic acid to undertake

Suitable aromatic dicarboxylic acid components are s isophthalic acid, dimethyl terephthalate, and dimethyl isophthalate

As an unsaturated aliphatic dicarboxylic acid compo Suitable components are dimethyl maleate and maleic anhydrite and ltaconic acid

Suitable glycols are diethyl glycol and / or Ethylene glycol

The condensation to produce these polyesters is carried out under the usual conditions, ie it is ^{heated for 2 to 5 h to a temperature gradually rising to 220 to 270 0} C and the reactants are used in stoichiometric amounts or one of the reactants is used in a slight excess

The sulfonation is then at an intermediate temperature between 20 and 100 ⁰ C for a Daue ^r of usually 3 to 6 hours in the presence of a small amount of water at atmospheric pressure or under pressure as a sulfonating agent, acting on the double bonds of aliphatic chains Natnumbisulfit is or Sodium metabisulphite used The sulphonating agent is used in the stoichiometric amount, based on the unsaturated dicarboxylic acid used

This sulfonation of the diesters of the unsaturated aliphatic dicarboxylic acids is carried out at an average temperature between 20 and 100 ^° C. for a period of usually 1 to 3 hours in the presence of water at normal pressure or elevated pressure. Sodium bisulfite or sodium metabisulfite is preferably used as the sulfonating agent

The condensation for the subsequent formation of the sulfonated polyester is carried out under the usual conditions, ie it is ^{heated for about 2 to 15 hours to a temperature gradually increasing to 180 to 250 0} C, and the reactants are used in stoichiometric amounts or one of the reactants is in slight excess used

The invention is illustrated by the following exemplary embodiments further explained

A) Previous condensation of the various
Components and subsequent sulfonation

Dimethyl phthalate
Dimethyl maleate
Diethyl Glycol
Tetraisopropyl ο titanate

174.6 g
14.4 g
111.0g
0.3 ml

The mixture is heated with stirring and under a gentle stream of nitrogen at normal pressure, the temperature being gradually increased from 20 to 220 ⁰ C over the course of two hours. During this time, 60 g of methanol are collected Temperature rise from 220 to 260 ⁰ C continued in 30 minutes This temperature and this pressure are maintained for 30 minutes This time is necessary to bring the condensation to completion and to remove the excess diethyl glycol. Before the vacuum is released, it is ^{cooled to 100 0} C, to avoid oxidation of the maleic acid double bonds

Sulfonation

The polyester obtained are added with stirring at 100 ⁰ C, 9.5 g of pulverulent Natnummetabisulfit and then 20 ml of distilled water, which is introduced in 30 minutes with a dropping funnel for 2 hours at reflux condenser (about 110 ⁰ C) is heated Here, an opaque , in the cold state a solid product is obtained which contains about 7% water. In hot water it spreads with stirring to form an opaque solution. The dry product has an intrinsic viscosity of 0.23 (the intrinsic viscosity is 0.25% and a temperature of 25 ° C in a solution consisting of 50 g of phenol and 40 g of tetrachloroethane)

Example 2

The experiment described in Example 1 (same condensation and sulfonation conditions) is using ethylene glycol in place of dietary glycol repeated the following reactants be used

example 1
condensation

In a 0.5 Litei reactor, the rr ^ is provided it stirrer and radiator, the following reactants are added

50

55

60

65 dimethyl phthalate
Dimethyl maleate
Ethylene glycol
Tetraisopropyl ο titanate

174.6 g
144g
1575g
0.3 ml

Sulfonation

The product obtained are based on the in Example 1 described way 9.5 g of sodium metabisulfi 'and 20 ml Water added. A dark-yellow product is obtained which softens even after drying and is sticky The limiting viscosity is 0.38 Das Product is soluble in hot water. The 20% The solution is white. After cooling, it turns into a gel above

Example 3

The experiment described in Example 1 is repeated using dimethyl terephthalate instead of repeatedly Dimethyhsophthalat The sulfonation is then carried out under a pressure of 2 bar at 130 ⁰ C, the following reactants are used

Dimethyl terephthalate
Dimethyl maleate
Diethylene glycol
Tetraisopropyl-o-titanate

174.6 g
14.4 g
159.0 g
0.3 ml

Sulfonation

9.5 g (0.05 mol) of sodium metabisulphite and 20 ml of water are added to the product obtained Reaction is carried out in a stainless steel reactor under a pressure of 2 bar at a temperature of 130 ° C for a period of 2 hours It becomes opaque, pretty hard, in hot Water-soluble yellow product obtained A 10% strength

Solution is white and viscous after cooling it goes in a gel over

Example 4

The condensation is under the conditions in Example 1 conditions described performed during the Sulphonation with a sodium bisulphite solution The following respondents are taken be used

Dimethyl isophthalate
Dimethyl maleate
Diethylene glycol
Tetraisopropyl-o-titanate

136.0 g 43.0 g 106.0 g 0.3 ml

Sulfonation

The polyester held at 100 ⁰ C with rapid stirring 400 ml of a solution of Natnumbisulfit of 36 ° Be and distilled water (Mengenver haltnis 1 1) within 1 hour was added, the temperature will be maintained with continued stirring 4 hours after cooling to 50 ⁰ C the two layers separated by centrifugation. The organic layer is the lower layer and consists of the sulfonated polyester, which contains about 30% water. The intrinsic viscosity is 0.23. The product is soluble in hot water and forms a slightly cloudy solution

Example 5

The experiment described in Example 1 is under slightly changed conditions carried out instead Dimethyl isophthalate uses isophthalic acid. A polymerization inhibitor is also added

condensation

In one with a stirrer and a cooler 2 1 reactor are given the following reactants

Isophthalic acid

Maleic anhydride

Diethylene glycol

2,5-di-tert-butylhydroquinone tetraisopropyl o-titanate

747 g

49 g

1060 g

Ig 1.5 ml condensation

In one with a stirrer and a cooler 0.5-1 reactor, the following reactants will participate mer given

The mixture is heated with stirring and under a weak nitrogen stiom at normal pressure, the temperature gradually increasing from 20 to 22 ° C. in 1.5 hours. The condensation is continued under a vacuum of 2 mm Hg, the temperature being in 1.5 Hours of 225 to 240 ⁰ C is increased. Then ^{allowed to cool to 140 0} C and the vacuum is removed

Sulfonation

The polyester obtained are (introduced in one hour) with stirring at 100 ° C 50 g Natnummetabisulfit and 100 ml of water was added, the temperature of 100 ⁰ C is 3 hours maintaining this case a soluble in hot water product is obtained, that a slightly cloudy solution forms The intrinsic viscosity of the dry product is 0.19

Example 6

Itaconic acid is used as an unsaturated dicarboxylic acid used

Isophthalic acid

Itaconic acid

Diethylene glycol

2.5 di-tert butyl hydroquinone

Tetraisopropyl orthotitanate

133 g

26 g
212g
0.5 g
0.3 ml

The mixture is heated with stirring and under a gentle stream of nitrogen, keeping the temperature in 1.5 hours increased from 20 to 220 ⁰ C. This holding 30 min at 220 ⁰ C, then under a vacuum of 2 mm Hg and then increased the temperature from 220 to 235 ° C. in one hour. 34 g of water and 100 g of diethyl glycol are collected here

Sulfonation

The polyester obtained in this manner are (introduced in one hour) with stirring at 100 ⁰ C 20 g Natnummetabisulfit and 20 ml of water were added with continued stirring, the temperature is maintained for 6 hours at 100 ⁰ C. The product is then 48 hours in warm oven at 105 ⁰ ° C. This gives a slightly colored product which dissolves well in water and forms an almost clear solution. The limiting viscosity of the dry product is 0.16

Example 7

The experiment described in Example 1 is repeatedly, but using a 1 1 Gemi cal of diethylene glycol and Tnathylenglykol

condensation

In one with a stirrer and a cooler The following reactants are used in the 2 liter reactor given

Dimethyl isophthalate 873 g

Dimethyl maleate 72 g

Diet glycol 265 g

Ethylene glycol 413 g
Tetraisopropyl orthotitanate 1.5 ml

The mixture is heated with stirring and under a gentle stream of nitrogen at normal pressure, the temperature gradually increasing from 20 to 225 ° C. in 1.5 hours ⁰ C increases Man let the temperature then at 120 ⁰ C sink and lifts the vacuum in this case, 280 g of methanol and 35 g Tnathylenglykol recovered

Sulfonation

The polyester obtained are (introduced in 1 hour) with stirring at 100 ° C 50 g Natnummetabisulfit and 100 g of water was added then the temperature is maintained for 5 hours at 100/105 ⁰ C. It is a yellow, opaque, slightly soluble in hot water product A 20% solution is viscous and opaque. The intrinsic viscosity of the dry product is 0.23

The water-soluble ones prepared according to the invention Sulphonated polyesters have advantageous properties in a wide variety of fields of application the textile sector promise them their special ones

Properties a very promising future, esp especially, as already mentioned, in the area of finishing

So far, the filament yarn has been given a strong twist of several hundred T / m, giving it sufficient resistance to scuffing for weaving However, the manufacturing cost to achieve this torsion is high Avoid twist by gradually replacing it with arbitration, the stronger the more the twist of the thread is decreased one is on this Way at the moment with a minimum rotation of 10 to 15 T / m reached, the thread exclusively in the Spinning machine is loaned Here, however, the usual sizing agents proved to be inadequate, the to give the thread coming out of the spinning machine an abrasion resistance that makes it possible to use it to weave under good conditions

Various products, ζ Β homopolymers of acrylic acid or methacrylic acid, are known for this Certain fibers such as viscose, cellulose acetate and nylon give good results received, but this is not the case with handelsubh Chen Terephthalic Acid Polyester Fibers It appears that in this case the affinity between the fiber and the sizing agent lacks sufficient adhesion between the individual fibers for weaving To achieve, polymers that form elastic films had to ζ B copolymers of ethyl acrylate and acrylic acid, but these films are kept at around 40 ° C by the action of heat slightly adhesive Their mechanical strength is low, so that a moderate abrasion resistance is the result Intense friction that the thread experiences during weaving, including in the weaver's comb, tear particles of the sizing agent and cause the formation of a powdery coating on the thread guides This coating quickly turns into a thick, Paste adhering to the metal around Meanwhile, polyester threads are woven on the premise that Regular cleaning of the reed, the reed hatch ken, leaf rod and the strands is made

It may be necessary in the case of dense Tissues this cleaning is done every 16 or 24 hours It is therefore known to these Disadvantage of the loom being soiled by the sizing agent deposits a glide wax on the thread in addition to the sizing agent to fix the frictional forces reduce and in this way partially to the tearing of the sizing agent from the thread avoid This path is also cut in practice

These wax products are in the case of fabrics of medium or low density are quite effective, but are not satisfactory for heavy tissues Furthermore, the waxes contained in this The most effective ways are, in general, products that are difficult to remove before staining because they have to be as hydrophobic as possible and only May be effective as a wetting agent and emulsifier to a minimum, in order to maintain their sliding and lubricating properties to preserve

Currently they are on the polyester filament Amounts of detergent used (calculated as dry matter) at least 3 to 4% by weight for one 300 turns / m thread This requires a Concentration of active material in the bath of about 6 to 8% by weight In the case of the thread with him This amount of sizing agent is insufficient in the rotation of 10 to 15 T / m imparted immediately during spinning It is necessary to increase the concentration of the bath of active material to 10% by weight in order to 5 Preserving weight% dry material on the chain This increase in the sizing agent concentration is reinforced even more the pollution of the parts of the loom This is one of the reasons for the low

ίο Extent of the use of torsion-free polyester thread as a chain

The use of the products according to the invention as a sizing agent allows eliminating the disadvantages described above can also these products, due to their better adhesive strength, in a smaller amount with increased protection can be used against abrasion

Tests were carried out with 40 threads / cm, 33-ply commercial polyester yarns of 65 denier were used. These warps were made into a aqueous solution immersed, which one with the according to Example 1 contained product obtained sizing agent, and then squeezed between 2 rollers and dried. Three sizing baths with concentrations of 3%, 4% and 6% by weight of active material were used for the experiments Chains sized in this way were then placed on the loom with a reduced weft density of 34 weft threads / cm woven in taffeta weave A flawless one Fabric without thread breakage was obtained. The more concentric, the better the protection of the thread the sizing bath was in the three traps had itself no sizing agent deposited on the Weber comb after about 50 m

In comparative tests with the same chains were carried out using today's commercially available Products based on acrylic acid copolymers dissolved in water-alcohol mixtures were, led to insufficient abrasion resistance, so that thread breaks during the Weaving occurred and a significant build-up of sizing agent on the weaver's comb after weaving a length of 50 m was available

By extraction with distilled water in a Soxhlet extraction apparatus in ammoniacal Medium and quantitative determination of the dry material in this washing water could be determined that the amount of dry sizing agent present on the thread is always half the concentration In other words, at a concentration of 3 % By weight of active material, the amount absorbed by the thread was 1.5% by weight those of the thread to be sized in the chain sizing machine The amount of diluted bath carried away was confirmed as it was found to be 1 kg of thread took about 500 g of the diluted bath with him

The new sizing agent based on the products according to the invention is very advantageous in weaving of polyester thread under productivity and quality conditions, which are comparable to those with Textile fibers like nylon and viscose that deal with Allow ease to settle, are achievable

With the sizing agent according to the invention when used on cellulose acetate and cellulose acetate thread also achieved good results in weaving. To date, these threads have not shown any Difficulty weaving when using

130 265/119

Vinyl polymers both from the standpoint of good cohesion of the monofilaments to one another and the complete absence of soiling of the loom, provided that these sheaves have a Had a twist of at least 80 Γ / m, for example τ for a 24-ply yarn of 110 decitex Aus The reason of the manufacturing price has been for some time intends to produce yarns with very little twist, e.g. 5 to 15 T / m, ζ B polyester yarns weaving For conventional products, the size bath must have a concentration of 6 or 7% by weight of active material in order to apply about 4 to 5% by weight of dry material to the fiber Amount is necessary for a no-mal protection of the yarn against abrasion. It should be noted that this applied amount corresponds to a minimum value without any significant margin of safety, since the Weaving is only possible under the essential condition that yarns with a particularly good textile Texture are used, i.e. yarns that do not contain any filaments on the package or Coils from which they are fed to the shear tree are broken

24 ply cellulose acetate yarn of 110 decitex and 10 T / n was achieved with a warp thread density of 40 / cm woven with 28 weft threads / cm. The size bath contained 4% by weight (dry material) of that according to Example 1 Manufactured Product This yarn was found to weave just as flawlessly as when using a sizing bath, that, just net as dry material, 6% by weight of one of the above-mentioned comparative products that were previously known as effective sizing agent for cellulose acetate yarns were known to weave the same warp with a size bath with a concentration of 4% by weight (calculated as Dry material) of a commercially available product based on a mixture of water and alcohol Acrylic acid polymer was sized It was extremely difficult to weave this yarn as it was stubborn was necessary filament of the yarn, which is under the influence of abrasion as a result of the friction of the Yarns among themselves and on the parts of the loom broke, tied or removed

It can thus be seen that the soluble polyester according to of the invention are also very effective with yarns based on cellulose esters. It can also other textile fibers, ζ B viscose fibers, acrylic fibers, polyamide fibers, glass fibers or fibers based on Polyvinyl chloride can also be successfully sized with the products according to the invention

B and C) Previous sulfonation of the diester

the unsaturated aliphatic

Dicarboxylic acids with subsequent condensation

of the various components

First is the production of a sulfonated one Described derivative based on dimethyl maleate, the dimethyl sulfosuccinate after sulfonation Sodium salt is obtained

In one with heater, stirrer, cooler and 20-1 flask fitted with a dropping funnel, 2.5 l (20 mol, 2883 g) of dimethyl maleate and 1440 g (80 moles) of water given The stirrer is switched on, a milky suspension is formed. In the dropping funnel placed on the flask, 10 Mol (1900 g) Natnummetabisulfit and 220 mol (3960 g) water. First, the temperature of the Flask brought to about 95 ° C, whereupon the insert in 300 to 500 ml aliquots are introduced in such a way that that the temperature remains between 93 and 98 ° C Introduction of the entire sodium metabisulphite solution (this takes about 50 minutes; the The temperature was kept at 100 ° C. for a further 1 hour The yield of the reaction is 98%. The mixture is left to crystallize overnight and filtered with a glass filter This produces a product in a yield of 51% obtained in a warming cabinet with air circulation tion is dried at 60 ° C

The following are exemplary embodiments of the inventor manure using the sodium salt of dimethyl sulfo prepared in the manner described above succinats described

Example 8

The following reaction parts are placed in a reactor »0 takers given

Isophthalic acid 3154g Dimethyl sulfosuccinate 24.8 g (Sodium salt) Dietary glycol 233.2 g Tetraisopropyl orthotitanate 06ml

Under flowing nitrogen, the temperature is first increased rapidly from 20 to 160 ⁰ C. This requires about 1 hour, then the temperature is raised slowly (in 3 hours from 160 to 200 ° C) The temperature of 200 ° C is continued for 2 hours maintaining While During this time, about 55 ml of a mixture of water and methanol are extracted. The excess diethyl glycol (about 20 ml) is then drawn off, still at 200 ° C. under a vacuum of 2 to 3 mm Hg. This takes 2 to 3 hours poured hot and extracted in the solid and anhydrous state

A 30% aqueous solution of the obtained Product looks milky At a concentration of 0.25% in a phenol tetrachlorathane mixture it has the solution has a viscosity limit of / 15dl g- 'you has the following further key figures

Acid number
Hydroxyl number
Number mean of the
Molecular weight
Sulfur content of
obtained polymer

I _A = 41.8 mgKOH / g IoH = 5.16 mgKOH / g

M _n = 2200

S = 0.83% (theoretical 0.67%)

Example 9

The following reactants are placed in a reactor given

Isophthalic acid

Dimethyl sulfosuccinate

(Sodium salt)

Dietary glycol

TetraisoDropyl orthotitanate

315.4 g 24.8 g

212.2 g 0.6 ml

The condensation is carried out under the conditions mentioned in Example 8. A 20% strength aqueous solution of the product obtained looks milky, but _{becomes clear after neutralization with NH 4} OH. The solution has the following characteristics

Pour viscosity
Acid number
OH number
Number mean of the
Molecular weight

Sulfur content

0.22 dl g " ¹ 34.3 mg KOH / g 0

3150

(compared to 2200 in example 1)

0.71% (theoretical 0.67%)

Example 10

The following reactants are placed in a reactor

10

15th

20th

The condensation is carried out under the above-mentioned in Example 8 conditions, however, the maximum temperature amounts to 190 ⁰ C. A 20% aqueous solution is opaque, but after neutralization (NH ₄ OH) transparent After a storage time of several days, the solution tends to form of an opaque gel The gel is reversible when it is ^{heated to 70 °} C. The product has the following key figures

Isophthalic acid 305.5 g Dimethyl sulfosuccinate 39.7 g (Sodium salt) Diethylene glycol 233.2 g Tetraisopropyl orthotitanate 0.6 ml

Limiting viscosity η

Acid number

OH number

M _n

Sulfur content

0.13dl g- ¹ 27.7 mg KOH / g 31.9 mg KOH / g 1750

1.02% (theoretical 1.06%)

30th

Example 11 In a reactor the following reactants are placed given

Isophthalic acid

Dimethyl sulfosuccinate

(Sodium salt)

Diethylene glycol

Tetraisopropyl orthotitanate

289.0 g 64.5 g

233.2 g 0.6 ml

40

45

The condensation is among those in Example 8 The conditions mentioned are carried out. The resin obtained is practically colorless and easily broken 30% aqueous solution is completely clear that so Product has the following metrics

Limiting viscosity η
Acid number
OH number

Sulfur content

0.16dl g- ¹ 15.8 mg KOH / g 20.8 mg KOH / g

2850

1.71%

(theoretical 1.71%)

Example 12

55

60

The same experiment as in Example 11 is carried out in Semi-industrial scale carried out without the use of excess glycol In a 40-1 glass reactor of the Pfaudler type, which has a column with receiver, a stirrer and a nitrogen inlet is provided, the following are agitated Starting products introduced in the order given

Diet glycol 10.610 kg

Tetraisopropyl orthotitanate 30 ml

Dimethyl sulfosuccinate (sodium salt) 3 224 kg
Isophthalic acid 14 442 kg

The mixture is heated with stirring (speed of Ruhrers 150UpM, nitrogen flow 90 l / hour), the temperature is in 8 hours from 20 to 200 ⁰ C increases this temperature for 2 hours is maintained, is applied followed by vacuum, the vacuum is gradually increased, in order to avoid that unreacted reactants are abruptly removed. The pressure is reduced from 760 to 15 mm Hg in 30 minutes and then maintained between 10 and 15 mm Hg for 5 to 6 hours with a weak stream of nitrogen (which is necessary for the stripping) The temperature is kept at 200 ^° C. After returning to normal pressure, the water of condensation (4.2 l) is first drawn off, whereupon the desired product is poured into plate molds lined with polytetrafluoroethylene films. The resin obtained is light yellow to yellow in color and the following metrics

Limiting viscosity η

Acid number

OH number

M _n

Sulfur content

0.17 dl g- '
28.0 mg KOH / g
10.7 mg KOH / g
2700
1.43%
(theoretical 1.71%)

A 20% aqueous solution looks and is milky stable over time

Example 13

The following reaction participants are placed in a reactor given

Isophthalic acid
Dimethv isulfosuccinate
(Sodium salt)
Diethylene glycol
Tetraisopropyl orthotitanate

232.4 g
1488g

233.2 g
Oo ml

The condensation is among those in Example 8 The product obtained has the following characteristics

Acid number
OH number
M _n
Sulfur content

Surface tension

21 4 mg KOH / g
9.7 mg KOH / g
3250

3.43%

(theoretically 3 8%)
55.5 dynes cm '

(in aqueous 1% solution at 20 ⁰ C)

A 30% aqueous solution of this product is perfectly clear It has a concentration of 0.25% in a mixture of phenol and tetrachloroathane a limiting viscosity of 0.9 dl g- '

Example 14

The following reactants are placed in a reactor given

Isophthalic acid 166 g Dimethyl sulfosuccinate 248 g (Sodium salt) Diethylene glycol 233.2 g Tetraisopropyl orthotitanate 0.6 ml

The condensation is among those in Example 8 conditions mentioned

The resin obtained is practically colorless and brittle It has good stability and the following metrics

Limiting viscosity η

Acid number

OH number

M _n

Sulfur content

Surface tension

0.095 dl g ι
34.8 mg KOH / g
22.8 mg KOH / g
1820

5.2%

(theoretically 6.1%)
53 dynes cm ¹

(in aqueous 1% solution at 20 ⁰ C)

The following example describes the preparation of a sulfonated derivative starting from ethylene glycol Colmaleate, which after sulfonation is the diethyl glycol sulfosuccinate results

Into a flask equipped with heater, screw stirrer and radiator flask is placed on the a Tropftnchter, 292 g (1 mole) of bis (Diathylenglykolmaleat) and 368 g of water are added The mixture is brought to 80 ⁰ C in the mounted on the piston Tropftnchter 76 g (0.4 mol) and 100 g of water Natnummetabisulfit the slurry thus formed is gradually added to the flask so that the temperature is maintained at 80 ⁰ C. the duration of the addition amounts to 25 minutes by addition of 268 g water a 50% Sulfosucci natlosung (Natnumsalz) formed at 2 hours is kept at 90 ⁰ C the solution prepared in this way is used for the production of a sulfonated polyester

Example 15

The following reactants are placed in a reactor given

Isophthalic acid

50% dietary glycol sulfo-

succinate solution

Diethylene glycol

Tetraisopropyl orthotitanate

166 g

736 g
21.2g
0.6 ml

The temperature is under a nitrogen stream quickly to 100 ⁰ C and then gradually increased to 170 ⁰ C. The mixture is then distilled and the temperature to 200 ⁰ C increases the condensation is now over the total duration of the condensation is 5 hours, the excess Diathylenglykol is within 3 5 Hours of distillation under a pressure of 20 mm Hg. The polyester is poured hot. The sulfonated product obtained in this way is orange-red, solid when cold and soluble in water

Example 16

The following reaction parts are placed in a reactor given taker

Isophthalic acid 166 g
80% concentric solution of

Diethylene glycol sulfosuccinate 117 g

Diet glycol 90 g

Tetraisopropyl orthotitanate 0.6 ml

The experiment is based on that described in Example 15 Carried out in a manner similar to this is obtained Product as in Example 15, but which is somewhat more hygroscopic

The manufactured in the manner described Polyesters were tested as sizing agents under the conditions described above. With three sizes rags, which were used for sizing commercial polyester warp thread, was after 50 m no deposit of the sizing agent was found on the weaver sheet. Cellulose acetate thread, which were sized with a sizing bath containing 4% by weight of that according to Example 11 produced product (calculated as dry matter), are perfectly woven

Except for textile applications, all of these water-soluble sulfonated polyesters can be used without consideration in the way of their production as dispersible in water, heat sensitive adhesives can be used This application is particularly beneficial with paper and plastic sheeting (cell glass, terephthalic acid, ethylene glycol, polyester, etc.) You can also use it as Packaging material in the form of water-soluble film containers that contain both solids and Can absorb liquids

Claims (3)

1
Claims 1 Process for the production of water-soluble sulfonated polyesters, which are made from residues of aromati see dicarboxylic acids, sulfonated aliphatic dicarboxylic acids and saturated glycols, characterized in that either A) 1 dimethyl terephthalate, dimethyl isophtha lat or isophthalic acid 2 dimethyl maleate, maleic anhydride or itaconic acid, 3 Di and / or Tnathyleneglykol polycondensed and the product obtained with Sodium bisulphite or sodium metabisulphite sulto is ned, the molar ratio between 1 and 2 90 10 to 70 30, or that B) 1 isophthalic acid 2 the sodium salt of dimethylsulfosucci nat, 3 dietary glycol be polycondensed, the molar ratio ms being between 1 and 2 95 5 to 50 50 or that C) 1 isophthalic acid 2 a solution obtained when 1 mole Bis (diethylene glycol) maleate in water with 0.4 mol of sodium metabisulfite sulfonated and is then diluted with water, 3 dietary glycol are polycondensed, with 736 g of a 50% or 117 g an 80% solution can be used 2 Use of the polyesters obtained according to claim 1 as sizing agents for textile fibers