DE2335480A1 - WATER-SOLUBLE SULFONIZED POLYESTER - Google Patents

Description

PATENT ADVOCATE DR. KAxNiS-GUNTHER EGGERT, DIPLOMA CHEMIXER

5 COLOGNE 51, OBERLÄNDER UFER 90 2 -3 3 t) H ö U

Cologne, July 11, 1973 Eg / Ax / pz / lol

SA Rhone-Progil, 6, rue Piccini _f 75ol6 Paris (France)

Water soluble sulfonated polyesters

The invention relates to new water-soluble polyesters, which are produced by sulfonating unsaturated polyesters at the double bonds. It also concerns the applications of these products, especially in the textile industry as water-soluble chain lubricants for weaving.

Sizing agents must be used because it is impossible is to weave the weakly twisted thread, which has insufficient abrasion resistance for the V /. These Products must be removable with water before dyeing. It is customary today to use threads that are only those of the endless thread the twist imparted by the spinning machine, i.e. having 10 to 15 twists / meter. the water-soluble products according to the invention proved to be very advantageous in this case.

It is known to use a wide variety of unsaturated polyesters with a very wide range of applications Polycondensation of a polyol with an unsaturated dicarboxylic acid, optionally in the presence of a saturated one To produce dicarboxylic acid. The resins obtained have a combination that is favorable for numerous applications of properties, however, they have the disadvantage that they are insoluble in water, which makes them useful on areas-: where this property as absolute

309886 / 13TT

is necessary, is excluded. The invention sets itself the task of eliminating this disadvantage and makes new ones Polyesters available which are very beneficial for a wide variety of applications.

The invention thus relates to new water-soluble sulfonated ones Polyesters obtained by polycondensation of an aromatic dicarboxylic acid, its anhydride or its diester, an unsaturated aliphatic dicarboxylic acid, its anhydride or a diester of this acid with a saturated one Glycol, the result of which is the sulfonation made on the unsaturated aliphatic chains a subsequent sulphonation of the product of the polycondensation of the various constituents or a previous one Sulphonation of the diester of the unsaturated aliphatic dicarboxylic acid is and the saturated sulphonated one formed in the process Diester then reacted with the other two reactants and thereby directly into the water-soluble sulfonated polyester has been converted.

only
This sulfonation / on the aliphatic double bonds in the case of the subsequent sulfonation of the condensation product could be detected analytically by infrared spectrophotometry.

The polyesters formed during the previous condensation of the various reactants and subsequent sulfonation of the aliphatic double bonds are due to their high viscosity:. ^ ..- oiy / uerisats at the temperature of -'0 ⁰ C, eel ^ - r aie Su _; \ ~ _erung irr, general carried out .- ■ £, seoi-ii · ":, ■ -" - ". ε ".-.-...--;. * on, but this difficulty

'j .c.- .:'. «-. Ι- .. -. . cna procedure overv / ur.cen '.'erder ..

I '- - .;. Y' Ieι diesters of ur.g --- ■ -'ät-

308885/131 1
BAÖ ORIGINAL

take with direct formation of the water-soluble sulfonated Polyesters, the above-mentioned disadvantages of high viscosity are eliminated in a simple manner. Liese It also works because of the lack of the problem of viscosity during sulfonation Polyester with a high proportion of sulfonated groups obtained su.

The direct sulfonation of the unsaturated aliphatic dicarboxylic acid or their anhydride runs difficult and leads to unsatisfactory yields, so that it is practically necessary is to carry out the sulfonation aliein on the diester of the unsaturated aliphatic carboxylic acid,

Suitable aromatic dicarboxylic acids are, for example, o-phthalic acid, isophthalic acid, terephthalic acid and dicarboxylic acids with multiple benzene rings and aromatic acids with aliphatic Chain and the anhydrides of these acids. The diesters of these acids, e.g. the methyl, Ethlyl, propyl and butyl diesters.

Examples of suitable unsaturated aliphatic dicarboxylic acids are Maleic acid, fumaric acid and itaconic acid and their anhydrides and diesters, ζ.3. the methyl, ethyl, propyi and Butyl diester.

Suitable glycols are, for example, ethylene glycol, propylene glycol, Butylene glycol, glycols with aromatic hangings, polyethylene glycol, e.g. diethylene glycol, triethylene glycol, Tetraethylene glycol and pentethylene glycol.

The condensation z \; _- production of this polyester is under jicr. i '.' olic ^ er Bc-din, - ,,. ^ r. carried out, i.e. 2 to 5 scu ;; aer. on an a. .... 1..1Li.:. at 220 to 270 ⁰ C rising Te--

.: - '': ■.:. * ■■ -:: .x. :.:. ? '". ^ :; Ions participants will be in szzz: * Lz-: λ ..CV-- · :: ·' ■ .Γ. /.:..:. £! '· One of the E

£ 08886/1311 BATH,

mer is used in a slight excess.

The sulfonation is then carried out at an average temperature between 20 and 100 ^° C. for a period of usually 3 to 6 hours in the presence of a small amount of water at normal pressure or under pressure. Sodium bisulfite or sodium metabisulfite is preferably used as the sulfonating agent which acts on the double bonds of the aliphatic chains. The sulfonating agent is used in the stoichiometric amount, based on the unsaturated dicarboxylic acid used.

Suitable sulfonated aliphatic diesters in the case of the previous sulfonation are, for example, the diesters which by sulfonation of diesters of unsaturated aliphatic dicarboxylic acids or their anhydrides, e.g., diesters from maleic acid, fumaric acid and itaconic acid. The methyl diesters, ethyl diesters, prop7ldiester, Butyl diester, the ethylene glycol diester, the propylene glycol diester, the butylene glycol diester, etc. are 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 ex post formation of the sulfonated polyester is durengefUhrt under the usual conditions, that is, about 2 to 15 hours, heated to a gradually increased to l80 to 250 ⁰ C rising temperature, and "the Reaktic-isteil.ielirr.ei '· v / he der. ver. in stoichiometric intervals.

";: -" aw: ier 2 ";. £: - .-. Sr respondent will be in the easy

-. v ^ iAU 'C * ..-.

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BAD ORIG (NAL

The invention is further illustrated by the following exemplary embodiments.

I) Prior condensation of the various components and subsequent sulfonation

example 1 condensation

In a 0.5 liter reactor equipped with a stirrer and condenser the following respondents are given:

Dimethyl isophthalate 17.6 g

Dimethyl maleate 14.4 g

Diethylene glycol 111.0 g

Tetraisopropyl-o-titanate 0.3 ml

The mixture is heated with stirring and under a gentle stream of nitrogen at normal pressure, the temperature gradually increasing from 20 to 220 ^° C. over the course of two hours. During this time, 60 g of methanol are collected. The condensation is continued under a vacuum of 2 mmHg with a temperature rise from 220 to 260 ° C in 30 minutes. This temperature and pressure are maintained for 30 minutes. This time is necessary to bring the condensation to completion and to remove the excess diethylene glycol. Before the release of vacuum is cooled to 10O ⁰ C in order to avoid oxidation of the Kalein acid double bonds.

Sulfonation

Derr. obtained, polyester v / earth with stirring, at ICO ⁰ C 9.5 ζ powdery Xav-r ^ ummfet ^ bisulfite and then 20 ml of distilled water; . "· I. \ ^: .- s ^ zzt _t ^f - ~ i- ~ 30 min. With a;. Return flow>: cooler 'et-

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BATH ORIGINAL

wa HO ⁰ C) heated. This gives an opaque product that is solid when cold and contains about 7 / ^ water. In hot water it spreads while stirring to form an opaque solution. The dry product has an intrinsic viscosity of 0.23. (The intrinsic viscosity is determined at a concentration of 0.25 % and a temperature of 25 ° C in a solution consisting of 6ö g phenol and 40 g tetrachloroethane.)

Example 2

The experiment described in Example 1 (same condensation and Sulfonation conditions) is made using triethylene glycol repeated instead of diethylene glycol. The following respondents are used:

Dimethyl isophthalate 17 * 1.6 g

Dimethyl maleate 14.4 g

Triethylene glycol 157.5 g

Tetraisopropyl-o-titanate 0.5

Sulfonation

9.5 g of sodium metabisulphite and 20 ml of water are added to the product obtained in the manner described in Example 1. This gives a dark yellow product which is soft and sticky even after drying. The intrinsic viscosity is 0.38. The product is soluble in hot water. The 20 pound solution is white. After cooling, it turns into a gel.

Example 3

The experiment described in Example 1 is repeated using dimethyl terephthalate instead of dimethyl isophthalate. The sulfonation is then carried out under a pressure of 2 bar at 130 G ^0. The following respondents are used:

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mVülnO GAB

Dimethyl terephthalate 17 ^, 6 g

Dimethyl maleate 14.4 g

Diethylene glycol 159.0 g

Tetraisopropyl-o-titanate 0.5 ml

Sulfonation

9.5 g (0.05 mol) of sodium metabisulphite and 20 ml of water are added to the product obtained. The reaction is carried out in a stainless steel reactor under a pressure of 2 bar at a temperature of 150 ^° C. for a period of hours. An opaque, fairly hard, hot water soluble yellow product is obtained. A 10 # solution is white and viscous. After cooling, it turns into a gel.

Example 4

The condensation is among those described in Example 1 Conditions carried out while the sulfonation is carried out with a sodium bisulfite solution. The following participants be used:

Dimethyl isophthalate 156.0 g

Dimethyl maleate 45.0 g

Diethylene glycol 106.0 g

Tetraisopropyl-o-titanate "0.5 ml

Sulfonation

The polyester held at 100 ⁰ C with rapid stirring 400 ml of a solution of sodium bisulfite distilled of 56 ° Be and; water (quantity ratio 1: 1) within 1 hour zu.ieso ^ zt. Zl ^ temperature is under further F.üh- ? A. ~ Ν S'cuaänen s; .fr --- c /.* ce; .vs.lten. After cooling down. to 50 ⁰ C .ο.de-- eic "joilc-. ..... .. -" λ U ^ rch centrifugation separated.

. _ö rr ^ a ^ -ii . S ~ c . c :: * - ". v. annoying shift and" oes ^ eht off

- i O · «*. wv 4 ¹ ^ ν - O ν --- -.

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Water soluble and forms a slightly cloudy solution.

Example 5

The experiment described in Example 1 is slightly modified Conditions carried out. Instead of dimethyl isophthalate isophthalic acid is used. A polymerization inhibitor is also added.

condensation

In a 2-liter reactor equipped with a stirrer and condenser given the following respondents:

Isophthalic acid JkJ g

Maleic anhydride 49 g

Diethylene glycol 1060 g

2,5-di-tert-butylhydroquinone 1 g

Tetraisopropyl-o-titanate 1.5 ml

The mixture is heated with stirring and under a gentle stream of nitrogen at normal pressure, the temperature is gradually increased from 20 to 225 ° C in 1.5 hours. The condensation continues under a vacuum of 2 mmHg, the temperature increased from 225 to 240 ° C. in 1.5 hours

will. The mixture is then allowed to cool to 140 ° C. and the vacuum is lifted on.

Sulfonation

59 g of sodium metabisulphite and 100 ml of water (introduced in one hour) are added to the polyester obtained with stirring at 100.degree. The temperature of 100 ^° C. is maintained for 3 hours. This gives a product which is soluble in hot water and which forms a slightly cloudy solution. The intrinsic viscosity of the dry product is 0.19.

Example 6
Itaconic acid is used as the unsaturated dicarboxylic acid.

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BATH ORIGINAL

condensation

In a 0.5 l reactor equipped with a stirrer and condenser given by the following respondents:

Isophthalic acid 135 S

Itaconic acid 26 g

Diethylene glycol 212 g

2,5-di-tert-butylhydroquinone 0.5 g

Tetraisopropyl orthotitanate 0.3 ml

The mixture is heated with stirring and under a gentle stream of nitrogen, the temperature being increased from 20 to 220 ^° C. in 1.5 hours. It is held at 220 ^° C. for 30 minutes,

then under a vacuum of 2 mmHg and then increases the temperature from 220 to 235 ° C in one hour. This collects 34 g of water and 100 g of diethylene glycol.

Sulfonation

The polyester obtained in this manner \ be (introduced in one hour) with stirring at 100 ⁰ C, 20 g of sodium metabisulfite and 20 ml of water. ^{The temperature is kept at 100 °} C. for β hours with further stirring. The product is then dried in a heating cabinet at 105 ° C. for 48 hours. This gives a slightly colored product which dissolves well in water and forms an almost clear solution. The intrinsic viscosity of the dry product is 0.16.

Example 7

The experiment described in Example 1 is repeated, but using a 1: 1 mixture of diethylene glycol and triethylene glycol.

-ation

I ;: oi.ienr.it EC ^ r ν λ ... cooler-equipped 2 1 reactor .1: folder.-isr *. ■ .3ak "ci - nG ': i'i: .r.enmer given

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^{BATH 1} ORlGiNAU:

- ίο -

Dimethyl isophthalate 875 g

Dimethyl maleate 72 g

Diethylene glycol 265 g

Triethylene glycol 4l3 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. The temperature is then gradually increased to 250 ° C. in 1.5 hours under a vacuum of 2 mmHg. The temperature is then allowed to drop to 120 ° C. and the vacuum is released. Here, 2So g of methanoi and _x 35 g of triethylene glycol are recovered. .

Sulfonation

The polyester obtained are stirred at 100 ° C. 53 ° C. Sodium metabisulphite and 100 g of water (introduced in 1 hour) are added. The temperature is then increased for 5 hours at 100/105 ° C held. Ss becomes a yellow, opaque, ir. Easily soluble product obtained in hot water. A 20 ^ - ige solution is viscous and opaque. The intrinsic viscosity of the dry product is 0.25.

The v / water-soluble sulfonated polyesters according to the invention have advantageous properties in a wide variety of fields of application. Theirs promise them in the textile sector special properties a very promising future, especially, as already mentioned, in the field of Arbitration.

So far the, l · ¹ !! ^ ;;. ent yarn a strong twist of several hundred 7 / .r: ^; ß 3eben and thereby given him a firmness // or ί · .ν ο which is sufficient ^{for äas V. :.} Die Herste Hur. "- cost to achieve '., Η .; olener torsion are however' high.

309885/1311

is replaced by an arbitration, which is all the more is stronger, the more the twist of the thread is reduced. In this way, one is at a minimum at the moment Rotation of 10 to 15 T / m reached, the thread exclusively is awarded in the spinning machine. Here, however, the usual sizing agents proved to be inadequate, to give the thread coming out of the spinning machine an abrasion resistance that enables it to weave in good conditions.

Various products such _o 3. homopolymers of acrylic or methacrylic acid have been proposed. Although good results are obtained with certain fibers made from, for example, viscose, cellulose acetate and nylon, this is not the case with fibers made from terephthalic acid polyester (terylene and tergal) sizing agent is absent. in order to achieve sufficient for weaving adhesion between the Einzeifasern each other, had to polymers that form elastomeric films such as copolymers of ethyl acrylate and acrylic acid are used. These films are, however, readily at about 40 ⁰ C by the action of heat Their mechanical strength is low, so that a similar abrasion resistance is the result. The intense friction that the thread experiences during weaving, among other things in the weaver's chamber, tears out particles of the sizing agent and causes the formation of a powdery coating on the thread guides * This coating quickly turns into a thick paste that adheres to metal. Inzwise hen polyesxerfäaen are woven under the "prerequisite, QaS regular cleaning of the webbTatts, the leaf gaps, leaf sticks and strands is carried out (r.ettoyage du psigne, des mal lies et des baguettes d.6 separately st Ion aas nappes).

309885/1311 BATH

It may be necessary that in the case of dense beings this cleaning is done every 16 or 24 hours. It has been suggested to address this disadvantage of pollution of the loom through the deposits of the sizing agent © - * · by applying a glide wax to the thread to fix the sizing agent in order to reduce the frictional forces and in this way partially the tearing out of the Avoid sizing agent from the thread. This path is also followed in practice.

These wax products are medium in the case of fabrics or low density quite effective, but are not a satisfactory solution for heavy fabrics The waxes that are most effective in this regard are generally products that just stand before staining difficult to remove because they have to be as hydrophobic as possible and only to a minimal extent as a wetting agent and emulsifier may be effective in order to preserve their sliding and lubricating properties.

Currently, those used on the polyester filament are Sizing agent quantities (calculated as dry matter) at least 3 to 4 wt .- ^ for a thread with 300 turns / m. This requires a concentration of active material in the bath of about 6 to 8 wt .- #. In the case of the thread With the twist of 10 to 15 T / m given to it directly during spinning, this amount of sizing agent is insufficient, It is necessary to increase the concentration of the bath of active material to 10% by weight to 5% by weight of dry material to get on the chain. This increase in the sizing agent concentration increases the pollution even more of the parts of the loom. This is one of the reasons for the low level of use of torsion-free Po Iy es te. "" Iac er. as a chain.

Zie Verv.Vi. '.:. ,.: ^ .. ^ uktc according to the invention as ichlichtiiiv: ^ - "- ;: -.?Λ cie elimination of the understanding

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because of their "better adhesive strength in a lower. Amount "can be used with increased protection against abrasion

Experiments were carried out with 40 threads / cm, with 33 threads Polyester seeds ("Tergal") of 65 denier were used. These chains were immersed in an aqueous solution which obtained a product prepared according to Example 1 Containing sizing agent, and then squeezed between 2 rollers and dried. Three Schlichtmitteibäer egg ":

Concentrations of 5%, 4% and 6% by weight of active material were used for the experiments. The one in this
Wise sized chains were then placed on the loom
with a reduced weft density of 34 faeces / cs
woven in taffeta binding. A flawless fabric without cracking was obtained. The protection of the thread was so

the more concentrated the sizing bath was, the better. In
In the three cases, no sizing agent had settled on the Weber comb after about 50 m.

In comparative tests using the same chains: - that were carried out with today's commercially available products such as "Gerol ACR" (manufacturer Societe Sc ^ rosoie / smoothed resulted in insufficient abrasion resistance, so that thread breakage occurred during weaving and there is a significant deposit of sizing agent on the weaver's comb after weaving a length of 50 a was.

By extraction with distilled water in a 3oxhie ~ extraction apparatus in ammoniacal medium and quantitative determination of the dry material in these v.asci: water it was possible to establish that the on the thread
The amount of dry sizing agent present is always greater
Half of the concentration of the S _c hlichtmittelbaäes corresponded. In other words, "at a concentration of the 3aäes ve π 3 wt .-> o of active material, the thread & \ xfge-

I-tenre 1,3 f.ν '■ /.-> ">. lies was given by the. from äe ~ to

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Λα

arbitrating thread taken along in the chain arbitration machine The amount of the diluted bath was confirmed, as it was found that 1 kg of thread contained about 500 g of the diluted bath.

The new sizing agent based on the paintings Invention is very advantageous in weaving polyester threads under productivity and quality conditions that comparable to those made with textile fibers such as nylon and viscose, which can be sized with ease, can be obtained.

With the sizing agent according to the invention, when applied to cellulose acetate and cellulose triacetate fibers, also achieved good results in weaving. To date, these threads have not shown any difficulty in weaving when using vinyl polymers both from the standpoint of good cohesion of the individual filaments with one another as also the complete absence of soiling of the 7'-chair, provided that these yarns have a twist of had at least 80 T / m, for example with a 24-ply yarn of 110 decitex. For reasons of the manufacturing price it has been intended for some time to produce yarns with a very low twist of, for example, 5 to 15 T / n, e.g. polyester yarns to weave. For conventional products, the size bath must have a concentration of 6 or 7% by weight of active material to about 4 to Apply 5 wt .- ^ dry material to the fiber. These Amount is necessary for normal protection of the yarn against abrasion. Ea should be noted that this angry Quantity corresponds to a minimum value with no significant margin of safety, since the weaving is only below the indispensable prerequisite is possible that Yarns cit particularly good textile properties are used, i.e. yarns that do not contain any element threads that are exposed to the bobbins or bobbins from which they are sent to the Scherbaua are fed, are broken.

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BATH ORIGINAL

24-thread cellulose acetate yarn of 110 decitex and 10 x / z was woven with a warp thread density of 40 / cm with 28 Scbu3 threads / cm. The Scblichtebad contained 4 wt -. $> (Dry matter) of the product prepared according to Example 1. It was found that this yarn could be woven just as properly as in "using a sizing bath which, calculated as dry material, 6 percent -. Contained $> of the above comparative products that were previously known to be effective sizing agents for Celluloseacetatgarne to. As a comparison, an attempt was made to weave an identical warp which was sized with a size _{bath with a concentration of 4 & ew e} - $> (calculated as dry material) of the product of the trade name "Gerol ACR" (manufacturer Societe Soprosoie). It was extremely difficult to To weave these yarns, since it was always necessary to tie or remove filaments of the yarn which broke under the influence of abrasion as a result of the friction of the yarns among themselves and on the parts of the loom.

Ss thus evident that the _r-soluble polyesters of the invention are very effective also in accordance with yarns based on Celluloseestern. Of course, it is not intended to be limited to the above embodiments; rather, other textile fibers, for example viscose fibers, acrylic fibers, polyamide fibers, glass fibers or fibers based on polyvinyl chloride, can likewise be successfully sized with the products according to the invention.

II) Previous sulfonation of the diester of the unsaturated aliphatic dicarboxylic acids with subsequent condensation of the various components

First of all, let us consider the production of a sulfonated one as an example Described derivative ausjehenc of dirnethyl maleate, whereby obtained after the sulfonation, the dimethyl sulfosuccinate Vfira.

3 0 9 8 8 5 / Ί 3 1

2.5 l (20 mol, 2883 g) of diethyl maleate and 1440 g (80 col) of water are placed in a 20 l flask equipped with a heating device, stirrer, condenser and attached dropping funnel. The stirrer is switched on, forming a milky suspension. In the dropping funnel placed on the flask, 10 moles (1900 g) of sodium tetabisulfite and 220 moles (3960 g) of v / water are added. First of all, the temperature of the flask is raised to approx. 95 is brought C, followed by the use in aliquots T _e ilen of 300 to 500 el introduced so that the temperature of 93-98 ⁰ O remains ο After the introduction of the entire Natriumaetabisulfitlösung (this, about 50 minutes is required) is n the temperature ~ ? h 1 hour gebalten at 100 ⁰ C. The yield of the reaction is $ 98. A laugh is allowed to crystallize and filtered with a glass frit. This gives a product in a yield of $ 51 which is dried at 60 ^° C. in a heating cabinet with air circulation.

Embodiments of the invention using the dimethyl sulfosuccinate prepared in the manner described above are described below.

Example 8

The following reactants are placed in a reactor given:

Isophthalic acid 315.4 g

Dimethyl sulfosuccinate 24.8 g

Diethylene glycol 233.2 g

Tetraisopropyl orthotitanate 0.6 al

Under flowing nitrogen, the temperature is first increased rapidly from 20 to 16O ⁰ G. This requires etv / a 1 hour ο Subsequently, the temperature slowly ER- r.'is.x (ir, 3 ^ stuen on VCN 160 to 200 ⁰ C). The temperature ve π 2CO ⁰ C is noc /. 2 Keep sending. V. 'Earn these: Z: ~~ will .. · ,: 35 ;;.! . ^ s air Geaiscb.es of V'asser unc ίο '' He..-lcr :. . .% ^! c-; l:; ' 3nc becomes err ^ er r. .cn at 2CC "

4 <λ ti V

309885/1311

the excess diethylene glycol (about 20 ml) is drawn off under a vacuum of 2 to 3 mm Hg. This requires 2 to 3 hours. The polyester is then cast in the hot state and obtained in a solid and anhydrous state.

See a 30 $ aqueous solution of the product obtained milky carrion. At a concentration of 0.255 »in one The solution has a phenol-acetylenetetrachloride mixture

-1
Intrinsic viscosity of 0.15 dl "g. It has the following further key figures:

Acid number I _A = 41.8 mg KCH / g

Hydroxyl number I _QH = 5.16 "

Number average molecular weight M _n = 2200

Sulfur content of the obtained
Polymer "S = 0.8356

(theoretically 0.67 #)

Example 9

The following reactants are placed in a reactor;

Isophthalic acid 515.4 g

Dimethyl sulfosuccinate 24.8 g

Diethylene glycol 212.2 g

Tetraisopropyl orthotitanate 0.6 ml

The condensation is among those mentioned in Example 8 Conditions carried out. A 20 $ aqueous solution of the ' The product obtained looks milky, but becomes clear after neutralization with NH.OH. The solution has the following Key figures:

Intrinsic viscosity 1 £ 0.22 dl.g

Acid number 34.3 ag ZCH / -

OH number 0

Number average molecular weight 3150 (versus

2200 in 5eisp, 1)

Sulfur content Ο, 7ΐ5ί

(theoretical · 0.67, ';)

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Example 10

In a reactor, the following R _e are aktionsteilnehn; he added:

Isophthalic acid 305.5 g

Dimethyl sulfosuccinate 39.7 g

Diethylene glycol 233.2 g

Tetraisopropyl orthotitanate 0.6 ml

The condensation is carried out under the above conditions in Example 8, but the maximum temperature is 19O ⁰ C. A 20 $ aqueous solution is opaque, but transparent after neutralization (ΐϊΗ, ΟΗ). After a storage time of a few days , the solution tends to form an opaque gel. The gel is reversible when it is heated to 70 ^{° C.} The product has the following key figures:

Intrinsic viscosity η 0.13 dl.g " ¹

Acid number 27.7 mg KOH / g OH number 31.9 mg KOH / g

M _n 1750

Sulfur content 1.02 # (theoretical

1.06 i »)

Example 11

The following reactants are placed in a reactor:

Isophthalic acid 289.0 g

Dimethyl sulfosuccinate 64.5 g

Diethylene glycol 233.2 g

Tetraisopropyl orthotitanate 0.6 ml

The condensation is carried out under the conditions mentioned in Example 8. The resin obtained is practical colorless and slightly brittle. A 30% aqueous solution is full .tänai. clear. The product has the following characteristics

Al

': ■ - .-. .-vis' .3: ^ u V /. C, 16 dl.g "'

S. '. Avzzsh'. 15.8 ng ZC-Jz

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BATH

OH number 20.8 mg KOH / g

M 2850

Sulfur content 1.71 # (-theoretically 1,

Example 12

The same experiment as in Example 11 is carried out in the field of technology Scale without using excess glycol carried out »In a 40 l glass reactor of the Pfaudler type, the one with a column with receiver, a stirrer and a = Nitrogen inlet is provided, while stirring the The following starting products were introduced in the order given:

Diethylene glycol 10.610 kg

! Eetraisopropyl orthotitanate 30 ml

Dimethyl sulfosuccinate. 3.224 kg

Isophthalic acid 14.442 kg

The mixture is heated with stirring (stirrer speed 150 rpm, nitrogen supply ^{90 l / hour). The temperature is increased from 20 to 200 ° C. in 8 hours.} This temperature is maintained for a further 2 hours, after which a vacuum is applied. The vacuum is gradually increased in order to avoid that unreacted reactants are suddenly removed. The pressure is lowered to 30 Kinuten of 760 to 15 mm Hg and then, kept 5 to 6 hours between 10 and 15 mm Hg with a gentle stream of nitrogen "(which is necessary for the stripping). The temperature is maintained at 200 ⁰ G. After returning to normal pressure, the water of condensation (£, 2 l) is first drawn off, whereupon the desired product is poured into sheets which are lined with polycetrafluoroethylene films

5C will. The resin obtained has a light yellow his gelee zarce and äi = fclAc -nding key figures:

■ -: rer.z7_SAO £ i "äx 'n 0.17 ül.g

-., r; 2 ^ * "" "" ■ "26, C ag ZGE / g

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BAD QfSRSiM 0

Sulfur content 1.43 ^ (theoretically 1

A 20 $ aqueous solution looks milky and is with stable over time.

Example 13

The following reactants are placed in a reactor:
Isophthalic acid 232 # 4 g

Dimethyl sulfosuccinate

(Sodium salt) 148.8 g

Diet ethylene glycol 233.2 g

Tetraisopropyl orthotitanate 0.6 ml

The condensation is carried out under the conditions mentioned in Example 8. The product obtained has the the following key figures:

Acid number 21.4 mg KOH / g

OH number 9.7 "

Tl _n ' 3250

Sulfur content $ 3.43 (theoretical

Surface tension 55.5 Dyn. Cm ~ (in aqueous 1 $ solution at 20 ⁰ C)

A 30 $ aqueous solution of this product is perfectly clear. At a concentration of 0.25? S in a mixture of phenol and acetylene tetrachloride, it has an intrinsic viscosity of 0.9 dl.g "* ¹ .

Example 14

The following reactants are placed in a reactor

given:

Isophthalic acid 166 g

Dimethyl sulfosuccinate 248 g

Diethylene glycol 233.2 g

Tetraisopropylcrthotitanate 0.6 ml

The condensation is carried out under the conditions mentioned in Example 8.

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The resin obtained is practically colorless and "brittle. Ss has good stability and the following parameters: intrinsic viscosity ^ 0.095 dl.g" ¹

Acid number 34.8 mg KOH / g

OH number - 22.8 "

M 1820

Sulfur content $ 5.2 (theoretically 6, \ <f)

Surface tension 53 Dyn.cm

(in aqueous 1 $ solution at 20 ⁰ C)

The following example describes the preparation of a sulfonated derivative, starting from ethylene glycol maleate, after sulfonation the diethylene glycol sulfosuccinate results.

292 g (1 mol) of diethylene glycol maleate and 368 g of water are placed in a flask equipped with a heating device, screw stirrer and condenser, on which a dropping funnel is attached. The mixture is brought to -80.degree. In the fitted on the piston dropping funnel 76 g (0.4 mol) sodium metabisulfite and 100 g of water are added · 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 is 25 minutes. 50 $ sodium sulfosuccinate solution is formed by adding 268 g of water, which is maintained for 2 hours at 90 ⁰ C. The solution produced in this way is used to produce a sulfonated polyester.

Example 15

The following reactants are placed in a reactor given:

Isophthalic acid 166 g 50% diethyls. Glycol sulfosuccinate solution 736 g

- diethylene glycol. 21.2 g

Tetraisoproptier- ^ iotitanat 0.6 ml

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The temperature is increased rapidly to 100 ^° C. and then gradually to 170 ^° C. under a stream of nitrogen. Anscbliessend is distilled and the temperature was raised to 200 ⁰ C. The condensation has now ended. The total duration of the condensation "is 5 hours. The excess dietbylene glycol is distilled off within 3.5 hours under a pressure of 20 mm Hg. The polyester is poured hot. The sulfonated product obtained is orange-red, solid when cold and in Water soluble.

Example 16

The following reactants are placed in a reactor given:

Isophthalic acid 166 g

80% concentrated solution of
Diethylene glycol sulfosuccinate 117 g

Diethylene glycol 90 g

Tetraisopropyl orthotitanate 0.6 ml

The experiment is carried out in the manner described in Example 15. A product similar to that in Example 15, which is, however, a little more hygroscopic.

The polyesters produced in the manner described were tested as sizing agents under the conditions described above. Three sizing baths, which were used for sizing "Terg" al "-Kettfäden was 50 meters no deposition of the sizing agent on dea Weber Journal noted. It was also possible cellulose acetate threads that have been sized with a size bath containing 4 wt. -I» the product produced according to Example 11 (calculated as dry matter) «, can be interwoven completely flawlessly.

Except for textile applications, all of these water-soluble sulfonated polyesters can be used regardless of the Way of their preparation as dispersible in water, värcieecpfindlieho Glue can be used. This application is ~

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particularly advantageous for paper and plastic films (cellulose glass, terephthalic acid-ethylene glycol-polyester, etc.). They can also be used as packaging material in the form of water-soluble film containers that can hold both solids and liquids .

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Claims (8)

Pat e η tan claims e 1) Water-soluble sulfonated polyesters made by polycondensation an aromatic dicarboxylic acid, its anhydride or its diester, a ^ -üngesättiitecaliphatic Dicarboxylic acid, its anhydride or one Diester of this acid with a saturated glycol nacc a process produced "with either the sulfonation of the unsaturated aliphatic. Jletten by a sulfonation treatment of the product of the polycondensation of the various constituents or by a previous sulfonation of the diester of the unsaturated aliphatic dicarboxylic acid with B ^ lcung a saturated sulfonated diester takes place, which is then with the other two components of the Polycondensation reaction is implemented with direct formation of the water-soluble sulfonated polyester. 2) Water-soluble sulfonated polyester according to claim 1, characterized in that they are "using" o-phthalic acid, isophthalic acid, terephthalic acid, dicarboxylic acids with several benzene rings or the anhydrides of these acids as aromatic dicarboxylic acids or their Anhydride and using the methyl, ethyl, propyl or butyl diesters of these acids have been. 3) Water-soluble sulfonated polyester according to claim 1 and 2, characterized in that as unsaturated '' aliphatic dicarboxylic acids or their anhydrides maleic acid, Fumaric acid, itaconic acid or their anhydrides and as diesters of these acids, the methyl, ethyl, propyl or butyl diesters of these acids for their preparation have been used " 4) Water-soluble sulfonated polyester according to claim 1 to 3, characterized in that the sulfonated aliphatic diesters by prior sulfonation of a 309885/1311 Diester of an unsaturated aliphatic 2icarbcn-. acid, e.g. the diester of maleic acid, fumaric acid or itaconic acid, with a sulfonating agent, e.g. 3. Sodium bisulfite and sodium metabisulfite has been" 5) Water-soluble sulfonated polyester according to claim 1 to 4, characterized in that as saturated Glycol ethylene glycol, a propylene glycol, sutylene glycol, a glycol with an aromatic ring or a polyethylene glycol has been used. 6) Water-soluble sulfonated polyester according to claim 1 to 5, characterized in that the polycondensation by Z- to 15-hour heating to a ^{temperature gradually increasing from 180 to 27O 0} C and the sulfonation at a temperature of 20 to 10O ⁰ C for a Has been carried out for 1 to 6 hours in the presence of a small amount of water at normal pressure or overpressure. 7) Water-soluble sulfonated polyester according to claim 1 to 6, characterized in that the sulfonation 3-agent Sodium bisulfite or sodium metabisulfite is used has been, 8) Use of the water-soluble sulfonated polyesters according to claims 1 to 7 as heat-sensitive, water-dispersible adhesives and as packaging in Jors of water-soluble Jolien containers. 9} Use of the water-soluble sulfonated polyester . <.: h claims 1 to 7 as sizing agents for textile-use. Thread anc yarns one for the Verwec-ni • -er_ c. . ^ cL:. ^^ .._ αΩ ^ cr / ugende abrasion resistance ^ 309885/1311
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