DE1494348A1 - Process for the treatment of polymeric substances - Google Patents

Description

EllBDle ··· HBVBM WALI. 411 · VBRNRTTV M 8 »28 AND ββ« 1β J.P. Stevens & Oo. In O. '*. 7th Hew York (USA) Process for the treatment of polymeric substances

The invention relates to chemical products including ohemisoh modified polymeric materials and methods of making the same.

In particular, the invention relates to new multi-functional compounds and new methods of reacting polymeric materials containing multiple free hydroxyl groups in a polymeric molecule with such Connections of several functions.

The polymeric reactants used in the invention have free hydroxyl groups and are not Cellulose regenerated to cellulose, partially esterified cellulose, polyvinyl alcohol, starch and the like limited- · The invention is also directed to the conversion of polymers with active hydrogens (other as the hydrogen contained in the hydroxyl groups) including polyamines, polyamides, keratins and the like without compounds of several functions. Since this one Compounds claimed with several functions are believed to be new, the invention relates to these compounds themselves and to the processes for their preparation 4.r..lb «.. 909112/1019

Sb will refer to various embodiments of the invention in conjunction with new methods for converting fiber-forming and non-fiber-forming polymeric substances described in each polymeric molecule containing multiple hydroxyl groups, with multiple functional sulfones to generate novel sulfonic ethers with valuable and extremely desirable properties, through which these fabrics are useful in the textile and other industries.

It is known that through the crosslinking of linear polymeric substances, such as cellulosic materials, fabrics so treated are given many desirable properties can. For example, the stability of the dimensions, the water resistance and the flexibility become considerable through cross-linking improved. In the case of textiles, in particular in the case of fabrics which are wholly or partly made of cellulose fibers in addition, the ability to remove wrinkles that have arisen and the resistance to wrinkling as a result of crosslinking treatments improved. The usability of these fabrics is also considerably increased by such a treatment «

For the treatment of cellulose and other related substances, many heating agents have been used for crosslinking, however, such treatments have shortcomings that limit their applicability

Such shortcomings include, for example, the need to perform the crosslinking implementation in the presence of highly acidic or acid generating catalysts at high temperature. This is necessary when thermosetting formaldehyde-containing Resins, polyacetals, polyepoxides and the like. Reactants

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be used for the crosslinking of the polymeric substances. Duron heating in the presence of acidic materials occurs in the generally a degradation of the polymeric substances. This degradation is reflected in the loss of strength, which increases with The accuracy of the reaction conditions increases

2. The development of objectionable odors in the treated Substances during storage or use. This occurs in particular in connection with formaldehyde which cures in the heat containing resins.

3. The slope of the nitrogen-containing, thermosetting Resins treated textiles, in the presence of bleaching solutions commonly used during washing a chlorine hold back. The retained chlorine is often converted into hydrochloric acid and causes considerable tissue degradation during subsequent operations such as the Plattens.

4. The sensitivity of the products formed with nitrogen-containing thermosetting resins to hydrolytic ones Attack leads to the dissolution of the chemical during the Wasohene Compounds formed during the crosslinking reactions and thus a loss of desirable properties, who originally owned the produce.

In the effort to overcome these shortcomings, networking too! procedures were used, which were carried out according to other principles. For example, cellulosic fabrics have been crosslinked in their swollen state in the presence of high concentrations of strongly alkaline substances with multi-functional reagents. These methods also have many disadvantages.

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For example, if the cellulose fibers are treated in a swollen state, then the elasticity becomes in dry Condition and ability of repairing gaps once accepted when dry improved little and in some cases even adversely affected. This disadvantage is characteristic in connection with the treatment of cellulosic materials, but especially for regenerated cellulose materials. Most procedures of this type that require treatment in strong alkali Requiring agents and in the presence of water also produce alkali damage. This makes such Process for the treatment of polymeric substances such as, for example regenerated cellulose that resides in aqueous alkali solutions are partially soluble, unsuitable.

According to the invention it has now been found that it is possible to use substituted and unsubstituted betaoxyethyl sulfones, such as

for example, polyhydroxyethyl or polyalkoxythyl sulfones with polymeric substances which contain free hydroxyl groups, under mild reaction conditions and practically in the absence of water. In the presence of weakly alkaline catalysts, short reaction times and moderate temperatures can be used. If strongly alkaline catalysts are used, the amount required is small, so that damage to the polymeric material is avoided even in the presence of strong alkalis. For example, concentrations of alkaline hydroxides in the range of about $ 0.5 to $ 5, based on the weight of the solution used, are effective. Since the reaction between the Betaoxyäthylsulfonen and the polymeric substance takes place when heated, after the water essentially from the

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Formation has been removed, the presence of a strong leads alkaline catalyst does not lead to dissolution or deterioration of the polymeric substance under these circumstances. It therefore becomes the need for the use of expensive toxic or other reactive agents to counteract from the economic point of view Objections to be raised are avoided in the crosslinking of polymeric substances, since the Betaoyxäthylsulfone and the alkaline catalysts are easy to handle with commercial systems without that special ventilation, corrosion-resistant or exceptional safety measures are required.

It is accordingly an object of the invention to provide new and useful ones chemical compounds, reaction products of such compounds with polymeric substances, and new, useful polymeric substances, by crosslinking polymeric substances that make a Heine freer Hydroxyl groups contained in a polymeric MolektUil, can be prepared with sulfonic compounds of several punctures, as well as the associated process to create.

The invention also seeks to provide new and useful ones polymeric substances that are produced by crosslinking polyamides, polyamines, keratins and similar substances with active hydrogen atoms and in particular those that have an active hydrogen atom linked to a nitrogen atom in a polymeric HoIemQ. included, formed with suIfon connections of several auctions.

be coded. The materials and the method of their preparation ο

<° are dealt with in a separate application. oo

^ The invention also seeks to create a new process for crosslinking polymeric substances with several free <° hydroxyl groups in a polymeric molecule # * l, the process essentially free of the known in connection with,

drive mentioned mangles and a method for networking of the polymeric substances mentioned, which do not require heating in the presence of an acidic catalyst or treatment in the presence requires high concentrations of strong aqueous alkalis, thereby avoiding decomposition of these materials.

In addition, it is the task of the invention to provide a new method to create crosslinking of the mentioned polymeric materials by using reactants that do not have strong smelling, eye-damaging heating materials or components that are corrosive to the skin or release them during the implementation and in which the resulting products do not tend to contain chlorine in the presence of bleach solutions used in washing operations hold back.

Another object of the invention is to create a new process for crosslinking the polymeric substances mentioned, wherein the resulting products are essentially stable to hydrolytic attack and thereby cross-linked Give products physical and chemophysical properties which are essentially permanent.

In addition, there is an object of the invention to provide a new method for crosslinking polymeric fiber-forming substances, which contain several free hydroxyl radicals in a polymeric Q molecule, with the resulting fibers

oo and the fabrics produced therefrom are characterized in that they have improved properties with regard to the resistance - ¹ to water, the stability of the dimensions, the elasticity, elimination of wrinkles in the wet and dry state and glass drying, as well a procedure for

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the manufacture of folded or shaped fabrics that suit them Maintain the once-given form during normal treatments and in use.

It is also an object of the invention to provide new methods of manufacture the twist in yarns that is retained during normal treatments or during use, as well as To create sulfone compounds together with processes for the production of the sulfone compounds mentioned.

Further features of the invention will become apparent from the description of various Examples.

The set forth and other features of the invention are achieved by crosslinking polymeric substances containing a number of free hydroxyl radicals contained in a polymer molecule, in the presence of alkaline substances under mild reaction conditions, for example with a poly-beta-hydroxylethyl or poly-beta-alkoxyethyl sulfone of the following formula »

(I) (ROOH ₂ CH ₂ SO ₂ ) n ^Q n

reached, where represents the number of unsaturated valencies and can assume a value of 2 to 4, Q is an organic radical, for example an aliphatic, aromatic or alkyl aromatic radical.

2For the determination of the invention, the polymeric substances

—Generally referred to as those who have a number of freer ^ ■ Hydroxyl radicals contained in a polymeric molecule, ale FoI-OH ^ and those polymeric substances in which some of the free

Hydroxyl groups, as indicated in the description, to

j have been set as pole.

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A particular example of a polymeric material containing free 'hydroxyl groups is cellulose, which as

Cell -OH
referred to as"

The sulfones contemplated according to the invention can be also by the following structural formula.

(II) ROCH ₂ CH ₂ SO ₂ M

wherein R is hydrogen or lower alkyl, M is selected from the group consisting of ROOH ₂ CH ₂ - and (ROCH ₂ CH ₂ SO ₂ ) _ß _ ^ _n , Q is an organic radical such as an aliphatic! aromatic or alkyl aromatic radical and η represents the number of unsaturated valencies and has a value from 1 to 3

A preferred group of the sulfones mentioned, which belong in the context of the formula II, are the bis-beta-hydroxyethyl and bisbeta-alkoxyethyl sulfones the formula

(III) ROCH ₂ CH ₂ (SO ₂ ) _a Q _a S0 ₂ ^GH 2 ^CH 2 ^OR

where R is hydrogen or a lower alkyl, ie CH- to C.Hq, a has a value of 0 or 1 and Q is an organic β radical such as EB an aliphatic, aromatic or alkyl aromatic

(o rest is.

oo While compounds that are within the scope of the formulas

Can be ^ (I), (II) and (III) are, for the method according to the OF INVENTION _o dung generally used, but the löallchen in water co compounds are particularly desirable as the use ▼ on solvents other than water in the economic Application of the process to polymeric substances costly or

Fährlioh and often both is · The Waseerlösliohkeit the duroh die given formulas represented compounds is to a large extent • a function of the structure of group Q, and it is established it has been found that the compounds of the following formula have excellent water solubility, which is accompanied by an exceptional Effectiveness in networking is linked.

(IV) ROOH ₂ CH ₂ (SO ₂ ) _b (0H ₂ 0H0) _m C _a H _2a S0 ₂ CH ₂ CH ₂ 0R "

wherein a has a value from 0 to 5, b has a value from J) to 1, m has a value from 0 to 5; however, if m has a value from 1 to 5, then a has a value of only 2-3 and b is 0 only when m and a are 0; R and R ¹¹ are hydrogen or lower alkyl, and R ¹ is selected from the group consisting of hydrogen and methyl

It also has a group of connections based on connections of the form »! IV related to polymeric crosslinking Substances proven to be effective} these correspond to the following formula:

(V) HIGH ₂ CH ₂ SO ₂ (CH ₂ CH ₂ O) _n CH ₂ CH ₂ SO ₂ CH ₂ CH ₂ OH

where η has a value from 2 to 12.

The SuIfons included in Formula 1 include auoh new sulfones, which are expressed by the following formula:

(VI) (ROCH ₂ CH ₂ SO ₂ ) _n Q _n

wherein R is hydrogen or a lower alkyl having 1 to 4 carbon atoms is, Q is an organic radical and η is the number of the unsaturated valencies and a value of 3

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to 4 has. - 10 -

Other novel sulfones contemplated by the invention have the formula

(VII) (R0CH ₂ CH ₂ S0 ₂ ) _n Q _n ,

where R is hydrogen or a lower alkyl having 1 to 4 carbon atoms, η is the number of unsaturated valencies and has a value from 2 to A and Q is an alkyl, an aromatic or alkyl aromatic radical having at least three carbon atoms. Additional sulfones contemplated by Formulas VI and VII include those expressed by the following formula

(VIII) ROCH-CH ₁ -SO ₀ (CH ₀ CHO) CH ₀ SO ₀ CH ₀ CH ₀ OR ¹¹ . 2 2 2 2AfJHa 2a 2 2 2

where R and R ^{M are} hydrogen or lower alkyl in which is an integer from 1 to 5 and m has a value from 0 to 5 j but if m has a value from 1 to 5 then a has a value of only 2 to 3 »and when m is 0 then a has a value of at least 3» half the -CL - can be branched or straight chain and R ¹ is selected from the group consisting of hydrogen and methyl. Other sulfones contemplated by Formulas VI and VIi are

IX (ROCH ₂ CH ₂ SO ₂ ) _b G _a H _{(2a + i)} _ _b S0 ₂ CH ₂ CH ₂ 0R% _o where R and R "have the same meaning as in the formula

oo (VIII), a has a value from 1 to 5 and b has a value from 1 to 3.

^ The new reaction products or crosslinked polymeric ethers are _ »By reacting polymeric substances that contain several free hydroxyl

radicals in a polymer molecule, namely contain PoI-OH, reached with the suIfons of the formulas (I) up to and including (IX),

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This conversion is illustrated in the form of an example by: 2PoI-OH ♦ HOOH ₂ Oh ₂ SO ₂ QSO ₂ CH ₂ CH ₂ OH

•> POI-OOH ₂ OH ₂ SO ₂ QSO ₂ CH ₂ CH ₂ O-PoI ♦ 2H ₃ O

where Q has the same meaning as in Formula 11

The crosslinking conversion of the hydroxylethyl sulfones and alkoxyethyl sulfones with cellulose (CeIl-OH) leads to the formation of cellulose ethers by implementation, each of which can be represented, for example, by the following equations:

2 cell-OH + HIGH ₂ Ch ₂ SO ₂ CH ₂ CH ₂ OH

I-> Cell-OOH ₂ CH ₂ SO ₂ CH ₂ CH ₂ O-Cell * 2H ₃ O

and
2-Cell-OH + ROCH ₂ CH ₂ So ₂ QSO ₂ CH ₂ CH ₂ OR

I-> OeII-OCH ₂ CH ₂ SO ₂ QSO ₂ CH ₂ CH ₂ O-CeIl + 2 ROH

The formation of the ethers by the reactions shown under mild temperature and catalysis conditions is completely unexpected and surprising, since the formation of the ethers normally requires the reaction of hydroxyl compounds with an alkalizing agent such as a halide, a sulfate, etc. However, the sulfones of the invention are not alkylating agents in the sense in which the term is used in the art. The compounds containing the groups ROOH ₂ CH ₂ SO ₂ thus have unexpected properties, which is believed to be important. ,

The reaction between the sulfones described and the polymer!

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Fabric can, for example, by touching the polymeric fabric be carried out with a solution containing the sulfone and ale catalyst an alkaline material such as an alkali salt a weak acid (for example sodium acetate, potassium bicarbonate, Alkali metal basketonate) or an alkaliBehes hydroxide contains in a low concentration or a non-volatile organic base, as well as by drying the polymer treated in this way Fabric and heating the treated product for a short time. Optionally, the polymeric fabric can be seen with an alkali Pretreated catalyst, then treated with the solution of the sulfone and then dried and heated.

On the other hand, the polymeric substance can be preheated with the sulfone solution and the catalyst will be used in a subsequent operation. The choice of procedure is partly dependent of the solubility properties of the particular as a crosslinking agent sulfones used · For textiles for which water-soluble sulfones are preferred and an application by means of aqueous solutions is desirable, the fabric can ί expediently with an aqueous solution that contains the sulfone and

contains a catalyst, impregnated and then simply dried and heated in a setting oven. The concentration of the hydroxyethyl and alkoxyethyl sulfones used is of the Equivalent weight of sulfones, of the amount of Ver-JfJ desired network and the range of properties that are

co acting material desired depending on. In cellulosic NJ textiles, such as cotton and rayon fabrics, - "* concentrations of the sulfone reactant between about 3 1 · ^ and 30 # of the weight of the solution give varying degrees of improvement in resolving faxes, with concentrations

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from about $ 5 to about $ 15 are preferred for cotton fabrics and concentrations of about $ 10 to $ 20 rayon fabrics impart excellent physical and chemophysical properties.

The catalysts which are effective for the process according to the invention are generally alkaline or potentially alkaline catalysts made from non-volatile organic bases, alkaline hydroxides and alkaline salts Acids exist. The acetates and bicarbonates have a ~ B alkaline Metals are preferred because they are economical and do not cause discoloration when the polymeric fabric is in their presence is heated. Alkaline metal carbonates, hydroxides, phosphates, silicates and borates are also effective. In general alkaline salts of acids, which have an ionizing

—4.

constants of less than about 10 can be used within a wide range of conversion, while alkaline hydroxides are only effective if the reaction conditions are carefully selected to minimize accompanying reactions. Non-volatile organic bases can also be used. Quaternary ammonium hydroxides are approximately the same as alkaline metal hydroxides in terms of their effectiveness. Non-volatile tertiary amines can also be used provided that the pH of their aqueous solutions is about 10 or higher, and also provided that their boiling point is high enough to prevent evaporation of the catalyst during drying. For example, 1,1,3,3-tetramethylguanidine (boiling point 159-160 ⁰ O) as a catalyst moderately effective. Primary and secondary amines are undesirable as catalysts because the hydrogen atoms attached to the amine groups interact with the beta-oxysulfones

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-H-

react and thus -the primary or secondary amine with the. ' polymeric substance because of the available sulfone reaction agent enters into competition.

The concentration of the catalyst required is a punctuation of the amount of crosslinking agent used, the particular catalyst chosen (equivalent weight alkali metal 'tat) and the heating time. Concentrations between about 5 µl and about 150 µl by weight of the crosslinking agent are effective. If the alkaline catalyst that is used is a strong base, as for example in the case of the alkali hydroxides and the quaternary ammonium hydroxides, then the amount used should preferably be between 5 and 50 fi of the weight of the crosslinking agent used, since larger amounts tend to to cause discoloration and disintegration of the polymeric material. When the alkaline catalyst is a weak base. for example an alkaline acetate or bicarbonate, then the amount lost can be varied within wide limits and amounts between about 20- $ and about 150 %, calculated on the basis of the crosslinking agent used, can be used with excellent results. Larger amounts of the catalyst generally tend to increase the rate of reaction. If a tertiary amine is used as a catalyst, then the amount required depends on its ionization constant (which is indicated by the pH of its aqueous solutions) and also on the amount retained in the polymeric material during drying and heating. - * th can be. This in turn depends on the vapor pressure of the ο

^ Armin connection and the applicable conditions of use addicted.

The time of heating required for the reaction to take place in the essential to bring it to completion is between about -15-

COPY

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10 seconds and more after removal of the water present and depends on the heating temperature and the other chosen conversion conditions. The preferred time range is between about 30 seconds and 5 minutes. The temperature at which the reaction takes place is between about 6O ⁰ C and 200 ⁰ O, with the preferred range is between about 100 ° and 180 ° 0th Heating at about 150 ° C. for about 30 seconds to about 5 minutes is very effective for cellulosic fabrics which have been impregnated with a solution containing the sulfone and the catalyst and then dried. After the reaction, it is desirable to wash the treated material and remove the remaining unreacted crosslinking agent and catalyst. When cotton fabrics or rayon fabrics are treated by the method according to the invention, they retain an attractive appearance and an excellent hand, and their ability to remove wrinkles in both wet and dry conditions is greatly improved. The acidic transformation becomes an inherent part of the cellulose molecule and is neither impaired nor removed during washing.

The sulfon compounds of the invention can, for example, by Implementation of a halide (X-Q-X) of several punctures with 2-mercapto-ethanol be prepared in the presence of an alkali hydroxide according to the following reaction:

2NaOH
XQX + 2 HIGH ₂ GH ₂ SH ^

and oxidation of the thiether formed as follows:

2O ₂
HIGH ₂ CH ₂ SQSCH ₂ Ch ₂ OH ^d ^ HIGH ₂ Ch ₂ SO ₂ QSO ₂ CH ₂ CH ₂ OH.

Alternatively, the compounds of the invention can be prepared by reacting a polymer cappan (HSQSH) with ethylene halohydrin (HOCHgCHgX)

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in the presence of alkali as follows:

2 NaOH

HSQSH + 2 HIGH ₂ CH ₂ X

and oxidation of the thioether are formed. They can also be formed by reacting the alkali salt of a sulfinic acid of several puncture ions (NaSO ₂ QSO ₂ Na) with ethylene halohydrian (XCH ₂ CH ₂ OH) as follows:

NaSO ₂ QSO ₂ Na ♦ 2 XCHgCHgOH ^

The ethers which contain the groups ROCH CH ₂ SO _2- can be prepared by various processes. It is known, for example, to prepare the sulfonic ethers from the corresponding sulfonic halide and alcohol in the presence of alkaline catalysts.

NaOH
XCH ₂ CH ₂ SO _2- + HOH ^ ROCH ₂ CH ₂ SO _2- + NaCl ^ H ₂ O.

Alternatively, they can be obtained by oxidation of the corresponding alkoxyethyl sulfides getting produced:

ROCH ₂ CH ₂ S- ° 2 ^ ROCH ₂ CH ₂ SO _2-

In some cases they can also be achieved by adding a vinyl sulfone compound to an alcohol. formed in the presence of an alkaline catalyst:

= CHSO _2- + ROH ν ROCH ₂ CH ₂ SO _2-

It was surprisingly found that the group containing ethers also from the corresponding hydroxyethyl sulfone compounds be prepared by direct reaction with an alcohol in the presence of an alkaline catalyst can:

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_ ₁₇ _

HIGH ₂ CH ₂ So _2- ♦ HOH ^ ROCH ₂ CH ₂ SO _2- +

This implementation involving the manufacture of ethers from two Hydroxyl components, even in the presence of a weak alkali, such as the alkali carbonates and bicarbonates, take place instead of. The function of the ether formation is similar to that of the crosslinking conversions on pages 9 and 10 have been described · The process of preparing the organic ethers that make up the group

HIGH ₂ CH ₂ SO _2-

included is new and is believed to be meaningful.

All these methods of manufacture that are necessary for beta-hydroxyethyl and beta-alkoxyethyl sulfones have been described excellent results of the desired compounds, and the choice of process may depend on availability and cost made dependent on the raw materials coming into minting.

In the case of the beta-alkoxyethyl sulfones, the new process is in which the products are obtained directly from the beta-hydroxyethyl sulfones omitting water or other beta-alkoxyethyl sulfones be prepared with omission of the volatile alcohol in the presence of an alkaline catalyst, extremely beneficial.

The invention can be further preferred by the following examples Embodiments will be explained, although it should be noted that these examples are given for illustration only and that it is not intended to limit the scope of the invention. 909812/1019

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"MM I Q Μ"

Manufacture of sulfones example 1

156 g (2 mol) of 2-mercaptolethanol are added with stirring to a solution of 80 g (2 mol) of sodium hydroxide in 80 g of water under a small stream of nitrogen. 143 g (1 mol) of 2.2 * dichloroethyl ether are then added dropwise at 20 ° to 30 ° C. with vigorous stirring. The reaction mixture is then refluxed with stirring for four hours or until titration for ionic chlorides indicates that the reaction is essentially complete. The mixture is then filtered to remove the sodium chloride and is concentrated under reduced pressure. The residue (HOCH ₂ OH ₂ SCH ₂ OH ₂ OCH ₂ CH ₂ SOH ₂ Ch ₂ OH) is a viscous syrupy material which crystallizes when left to stand and can be converted into the corresponding bis-sulfone by oxidation, for example with hydrogen peroxide, as follows:

3 g of phosphoric acid are added and, with stirring, 408 g a 33 # strength hydrogen peroxide was added dropwise, cooling at 30 to 40 ° 0 for the first half of the addition and then heating takes place at the reflux temperature. The resulting clear solution will last for about 15 hours

ο or exposed to a counterflow until a potassium;) odit-

™ sample for hydrogen peroxide is negative.

- »After the neutralization of the catalyst in the form of the phosphorus

- »acid, the mixture is subjected to vacuum distillation in order to

remove the water. What remains is a bright yellow viscous liquid, which by extraction of the solvent

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cleans and can then be crystallized. It has the structure HOGH ₂ OH ₂ SO ₂ CH ₂ CH ₂ OGH ₂ CH ₂ SO ₂ Ch ₂ GH ₂ OH.

example Z

156 g (2 mol) of 2-liercaptoethanol are added with cooling and stirring to a solution of 80 g (2 mol) of sodium hydroxide in 500 cm of ethanol. A gentle stream of nitrogen is constantly passed through the reaction mixture in order to oxidize the mercaptan. to avoid. Then 99 g (1 mol to 2 equivalents) of the ethylene dichloride are added with vigorous stirring and cooling. A precipitate of sodium chloride begins to form and the reaction mixture is stirred at 70 to 80 ° C (reflux) until an agentometric titration for ionic chloride indicates that the reaction is complete. This takes about 4 hours. The reaction mixture is filtered to remove the precipitated sodium chloride and concentrated under reduced pressure. The residue (HOCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ Oh) is then converted into the corresponding bis-sulfone by oxidation, for example with hydrogen peroxide, as follows.

3 g of phosphoric acid are added and 408 g of 33% hydrogen peroxide added dropwise with stirring and cooling at 70 to 80.degree. The resulting solution will last 15 hours reflux for a long time or until a sample with

J _{0 of} an aqueous potassium;) odide solution shows no release of iodine,

cd which indicates that the H ₂ 0 «has been completely used up.

^ The solution is neutralized with sodium hydroxide or another base up to Q to a pH value of 6.5 to 7 and concentrated in vacuo until the water has been completely removed (up to 10O ⁰ C at 20 mm) The remainder is a crystalline solid substance which, after Kekrystallisation, has a melting point of 114 to

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(O O CO OO

116 ° G. The product has the structure HOCH ₂ CH ₂ SO ₂ CH ₂ CH ₂ SO ₂ OH ₂ Ch ₂ OH. The percentage of sulfur is calculated to be 26.0, and found to be 25t95 5 ^ ·

Example 5

If 1,4 dichlorobutane with 2-mercaptoethanol by the in the Examples 1 and II described method is implemented, then the resulting bis-thioether has the structure

This can be oxidized to the corresponding bis-sulfone, which as a water soluble crystalline force component

ο
(Melting point 110 to 115 C) is reached after the water solution has been evaporated to dryness and the remainder has been washed with acetone. The calculated sulfur content is 23.4%, the found 24.0%.

Example 4

The reaction product of 2-mercaptoethanol with 3,3'-dichloroxylene HOCH ₂ CH ₂ SCH ₂ £ \\ CH ₂ SCH ₂ CH ₂ OH can be converted into the corresponding water-insoluble bis-sulfone (melting point 197-200 ° C.) according to Examples 1 and 2 are oxidized.

Example 5

Made from triethylene glycol dichloride

(ClCH ₂ CH ₂ (OCH ₂ OH ₂ ) ₂ C1 and 2-mercaptoethanol the following bis-thioether is achieved:

^ HIGH ₂ CH ₂ S (CH ₂ CH ₂ O) ₂ CH ₂ Ch ₂ S

- * the corresponding syrupy liquid bisco when oxidized

Sulfen gives what is soluble in flammable water,

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Example 6

From hexachlorobenzene, the method described in J. Org. Ohem · 2 ± _t 235

(1959) described a bis-thioether

SCH ₂ CH ₂ OH

Cl ^L '~' ~ " Cl

(Melting point 148 ° - 149 ° C) achieved. Oxidation with hydrogen superoxide. gives the corresponding bis-sulfone, which is a water-soluble white crystalline solid (Melting point 200 ° to 203 ° C).

Example 7

Bis / ^ - hydroxyethyl sulfide is converted, for example, by the process described in J. Org. Chem. 12, 1486, (1954) into the corresponding sulfon HOCH ₂ CH ₂ SO ₂ Ch ₂ CH ₂ OH. The product can be isolated in crystalline form (melting point 52 ° to 54 ° C) or the crude aqueous solution can be used without further purification.

Example 8

The bis-hydroxyethyl sulfone

HIGH ₀ CH ₀ SO ₀ CHCH ₀ SO ₀ CH ₀ Ch ₀ OH

> Cdi Λττ CCCC

is made by reacting one mole of propylene dichloride (dichloropropane

_o 1,2) with 2 mol of 2-meroaptoethanol and oxidizing the resulting

σο bis-Hydroxyäthylsulfids produced. The product is a * ■> water-soluble crystalline solid, melting point 125 ° bis ^ 128 ° C

Example 9

The trie-hydroxyethyl sulfone

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HIGH ₂ CH ₂ SO ₂ CH ₂ CHCH ₂ SO ₂ CH ₂ Ch ₂ OH

Γ ²

is obtained by reacting one mole of trichloropopane 1, 2, 3 with three moles of 2-mercaptolethanol and oxidizing the resulting tria-hydroxyethyl sulfide. The product is a water-soluble crystalline solid, melting point 147 ° to 158 ⁰ C.

Example 10

A mixture of 154 g (1 mol) of an anhydrous bis-beta-hydroxyethylsulfone (product of Example 7), 741 g (10 mol) of n-butanol, 200 g of xylene and 100 g of anhydrous potassium bicarbonate are refluxed with vigorous mechanical stirring, while the water formed in the reaction is removed by a Dean-Stark trap. The temperature of the reaction mixture "is at the start of reflux, about 112 ⁰ C and it rises in the course of the reaction slowly to about 118 ° to. The reflux is continued is completed until the liberation of water. This requires about 4 to 5 hours, and 33 g (1.8 moles) of water are recovered, the reaction mixture is cooled to room temperature and filtered to remove the potassium bicarbonate catalyst, which is recovered in quantity. The piltrate is then reduced under reduced pressure

oo stripped pressure, whereby it is heated to about 120 ° to 130 ° C at 25 mm NJ, to the xylene and unreacted butanol corresponds - ⁱ distant. When cooling, some crystalline material forms in the remainder. This is filtered off and has been found to be a P-0xathian-4-4-Dioxide. BATH ORIGINAL

OH ₂ CH ₂

OH ₂ GH ₂

(Melting powder 129 ° C), The amount of by-product is 34 g, corresponding to about 25 % of the bis-beta-hydroxyethyl sulfone used in the reaction.The piltrate obtained after the removal of the cyclic compound consists mainly of the desired product, namely the Dibutyl ether

This can be purified by vacuum distillation to a clear To give a colorless liquid that boils at 184 ° to 189 ° / 9mm.

Example 11

354 g of divinyl sulfone (3 mol) are added with stirring and cooling to a solution of 7.5 g of sodium methylate in 240 g (7.5 mol) of an anhydrous methanol. The reaction is warming and the temperature is controlled by regulating the additional speed and the use of an ice water bath. The addition of divinyl sulfones is carried out at 25 ° to 35 ⁰ C, and requires 3 hours. The Umsstzmischung is then heated to 60 ⁰ C and kept for about one hour at this temperature of 60 °. The sodium methate catalyst is then neutralized with 18 g of acetic acid, the mixture is filtered to remove salts and the filtrate is distilled under reduced pressure. The product CH-OGH ₂ UH ₂ SO ₂ Oh ₂ CH ₂ OOH- is a water-clear liquid that boils at a temperature of 138 to 140 ° C at 6 mm. The product is completely soluble in water and stable in aqueous solutions. The yield obtained in this way is 450 g or 83 f> des

theoretical value. 909812/1019 ^BAD OR / q ^ ²⁴ "

_ ₂₄ - U94348

Implementation of sulfones with polymeric substances

Example XlI

A simply woven cotton fabric commonly referred to as a printed cloth of 80 χ 80) is mixed with an aqueous solution containing 100 g of the cleaned product of Example VIl (bis- P -hydroxyethyl sulfone) and 110 g of a sodium bicarbonate per liter of water Three-roll impregnation device for laboratory use impregnated. The wet pick-up of the tissue is 85 ° and the amount of sulfone left on the tissue is thus 0 ^ 085 ρ per gram of the tissue. The treated fabric is dried, then, bring in an oven at 14-9 ° 0, heated for 2 minutes to provide the desired conversion. After washing to remove the impurities, the fabric was found to have a sulfur content of 1.496, indicating that the reaction between the sulfone and the cellulose had occurred in about 80% yield. If the ability to remove wrinkles in the so treated fabrics and those of the untreated fabrics by, for example, the in the book "Technical Manual of the Association of Textile Chemists and Ooloriats, Volume 35, Pages 171-173 (Tentative Test Method 67-1957" procedures described are determined, then the

determined the following values!
co

° Wrinkle Removal Example in Wrinkle Removal

*? 80 χ 80 when wet when dry

°° it prints cloth warp and weft warp and weft

At the start

At the start

after 5 washes

Untreated 14-9 150 146 139

Treated according to
the procedure

according to example 8 24-1 249 248 239

- 25 -

U943A8

These data show that the improvements are very large in resolving wrinkles remain in the washing and wet or are about gleioh even when dry.

Example XlIl

A viscous rayon fabric (plain woven Ohallis) is made by the method of Example XIl with a solution containing 150 g of the product according to Example VIl per liter and contains 150 g of potassium bicarbonate per liter, treated. The values obtained for the removal of wrinkles for this fabric and for untreated fabrics are shown in the form of a comparison:

Sample of a wrinkle removal in wrinkle removal in Rayon-Challis wet state dry state. Chain and weft chain and weft

untreated 164 210

according to the procedure according to

Example IX deals with 238,263

This treatment causes shrinkage of the fabric during washing completely excluded.

Example XIV

A plain woven cotton fabric is impregnated with a solution containing 170 g of the product of Example V per liter and 100 g of potassium bicarbonate. The fabric is dried, then heated in a Abbindeofen 30 seconds at a Teperatur of 16O ⁰ C and washed to remove the unreacted material and the catalyst. The values of the removal of wrinkles obtained for the treated fabric are as follows: Wrinkle removal in the dry state (warp and weft) 246 (untreated test piece: 143)

- 26 - 909812/1019

Gap removal in wet condition (warp and weft) 265, (unaffected tradea specimen * 168), whereby the treated tissue is partly made of a new cross-linked cellulose ether

Oil-OCH ₂ GH ₂ SO ₂ (CH ₂ CH ₂ O) ₂ GH ₂ CH ₂ SO ₂ CH ₂ CH ₂ O-Oil consists "

Example XV

The reaction of a water-insoluble polyhydroxylethyl sulfone with cellulose (for example the product of Example IV) can can be carried out as follows:

A cotton fabric sample (80 χ 80 printed cloth, bleached and desized) is impregnated on an impregnation machine for laboratory use with an aqueous solution containing 80 g of potassium bicarbonate per liter. The pressure on the press rollers is adjusted so that it gives a wet pick-up of about 90 ^. After drying, the fabric contains 0.072 grams of potassium bicarbonate per gram of the fabric. The dried fabric is then impregnated with a solution made from 100 g of the product of Example IV in 900 g of dimethylformamide. The wet pick-up of the organic solution is about 80 #. The fabric is again dried in order to remove the organic solvent, then set in an oven at 149 ^° C. for 10 minutes.

The treated fabric is rinsed in dimethylformamide to remove the unreacted sulfone, then in a cleaning solution washed. The weight of the treated fabric has increased significantly and the treated fabric contains sulfur, which proves that the implementation has taken place.

Example XVl

If a Wösoh ^o i? ^ ~ ^V ~> vur ~ ° ^ want with a solution that is 100 g

909Ö12 / 1019 BADOFMGfNAL ~ ²⁷ "

-27- 1A9A3A8

of the product lake of Example II per liter and contains 80 g of potassium bicarbonate per liter, treated, dried, ^{tied for two minutes at 149 0} C and washed, then some cellulose molecules are crosslinked in the tissue to form a cellulose ether with the formula

Oil OUH ₂ OH ₂ SO ₂ Oh ₂ CH ₂ SO ₂ GH ₂ CH ₂ O Cell

to build·

The treated fabric contains 0.97 # sulfur, and the sulfur content remains constant after several washes, proving that a chemical reaction has taken place. The implementation of networking has brought the laundry entering Portfall, and the fabric has adopted smooth-drying properties, which are far superior to those of the untreated sample tissue

Example IViI

A cotton twill fabric is treated with a solution containing 10 g of a nonionic polyethylene emulsion ⁺ , 150 g of the product of Example 1 per liter and 80 g of sodium bicarbonate. The fabric treated in this way is dried, tied off for one minute at 140.degree. C. and washed. With this treatment, a weight gain of $ 7.0 is achieved. The treated fabric and an untreated sample fabric were rated for "wash and wear properties" according to the method described in the American Association of Textile Chemists and Colorists' technical manual. Volume 35 (edition 1959) pages 154 - 156 described method evaluated. The following information was determined »*

Treated Untreated Example (sample cloth) XVIi

' ^{T and} washed, not dripping wet 4.5 1.5 Casohine washed, not dripping 4.8 1 | 5

909812/1019 BAD OR / ginal - 28 -

Treated Untreated (Example (Probetuoh) XVIl)

Masohine washed, drummed. 4.8 2.0 Idmachine washed, on the leash

separate 4.5 1.0

♦ Manufactured, for example, from the commercially available Product of the Semet Solvay Division of the Allied Chemical Corp., designated A C Polyethylene 629 - Reference: AM. Dyestuff Reporter 4J3, 46-29 (1959).

♦♦ Graduation from 1 (worst appearance) to 5 (best appearance).

Example XVlIl

A cotton fabric is treated with the product of Example 111, using an aqueous solution containing 100 g of bis-beta-hydroxyethyl sulfone per liter and 75 g of potassium bicarbonate (at 100 # wet absorption) per liter, after which this fabric is dried, Tied and washed at 177 ^{° C. for 30 seconds.} The weight gain is 6.3 or 74 1 ° of the calculated value for the reaction

2 Cell OH + (HIGH ₂ CH ₂ SO ₂ Ch ₂ CH ₂ ) ₂

Cell 0 CH ₂ CH ₂ SO ₂ (CH ₂ J ₄ SO ₂ CH ₂ CH ₂ O Cell

The treated fabric shows largely improved wrinkle removal properties in wet and dry condition.

Example XlX

A prepared, weighed sample of white cotton fabric

co is mixed with an aqueous solution containing 12 g of the product of the

to Example Xl and 7 g of anhydrous potassium bicarbonate per 100 g of the ~ * solution, impregnated. The impregnation is carried out in an impregnation machine for laboratory use and the pressure of the rollers is adjusted so that a wet pick-up of about $ 100 is achieved. (The tissue holds 1 g of the solution per g of the

- 29 -

Fabric back.) The tissue is then for two minutes, washed, conditioned at 9O ⁰ C baked at 150 ⁰ C (ligated) and under the same temperature and humidity conditions as used in the URR sprünglichen weight determination. The increase in weight of the fabric due to the treatment is 6.2 or 80 # i "of the calculated value for the reaction.

2Λ _Α ι τ ΛΧΤ j »flTX / ΛΛΙΧΤ fTT ΟΛ OTT OTT ΛΟΤΙ ^ / β ^ L ^ L yJSAi Tr ^ / XX · * V / ν XX .r» ν Jl .η κ? V / jl · ν Xa> t. ν π _ \ / \ / fl <· χ

Cell OCH ₂ CH ₂ SO ₂ CH ₂ CH ₂ O Cell ♦ 2 CH ₃ OH.

The fabric thus treated shows excellent resistance in terms of dimensions, wrinkle removal and ability to dry smoothly. The color, look and feel are unchanged.

Example XX

A plain weave white cotton fabric (commonly called 80 χ 80 printed cloth) is with an aqueous solution containing 100 g of the product of Example VI and 10 g of sodium hydroxide contains per liter of water in a three-roll impregnation machine impregnated for laboratory use. The wet pick-up of the fabric is 100 #. The treated fabric is in an oven Dried and heated for two minutes at 149 C, washed thoroughly and. dried. The weight gain as a result of the treatment is 4 #, indicating that a Yield of # 53 was achieved. The fabric is easily discolored but shows excellent. Wrinkle removal skills without that serious impairments in strength occur.

When using other polyhydroxyethyl or polyalkoxyethyl sulfones and other catalysts in the crosslinking treatment of fabrics made from cellulosic fibers will produce similar results as described in Examples XIl to XX achieved

909812/1019 -30-

- 30- H94348

f Example XXl

When repeating the procedure according to Example XX under Use of a higher concentration of NaOH (60 g per liter) there are comparable yields (52 ^) and wrinkle removal values achieved, but the fabric is severely discolored and the strength of the fabric is impaired. From these results of the experiments described in Examples XX and XXI it can be seen that strong concentrations of strong alkalis do not are advantageous and in fact the polymeric reaction product achieved in the reaction with the beta-oxyethylsulphone-ene are harmful.

Example XXIX

A cotton twill fabric is impregnated in an impregnation machine for laboratory use with a solution containing 30 g per liter of a polyvinyl alcohol resin (for example the product sold under the brand Gelvatol 1-90 by Shawingigan Resin Corporation), 30 g per liter of the product from Example VIl and contains 20 g per liter of potassium bicarbonate. The pressure of the impregnation rollers is adjusted so that the fabric retains a weight of solution equal to its weight (100 # wet pick-up). The thus treated fabric is dried at 93 ° 0, bonded for five minutes at 14-9 ⁰ C and washed to remove the soluble materials. In the course of this process, the polyvinyl alcohol resin has become insoluble and the finish left in the fabric is not removed by washing. If, for example, the stiffness of the treated fabric is measured by known methods and compared with the stiffness of untreated fabric and with a fabric that has only been treated with polyvinyl alcohol, then the following values are achieved: _ 31 _

_ 31 - H94348

Stiffness value * at the beginning after 5 washes

treated according to Example XXI

Tissue 20 35

Only fabric treated with polyvinyl alcohol 35 95

untreated fabric 125 130

♦ Expressed as the sum of the angles of curvature in the warp and weft direction on a Monsanto anti-wrinkle testing machine have been achieved; maximum stiffness * 0, lowest stiffness «180 °.

It can be seen that the rigidity of the only with polyvinyl alcohol treated tissue is lost in the course of the ash process and that the effect of the polyvinyl alcohol is retained during the washing processes when the resin finish according to e is made insoluble by the method of the invention.

Example XXlII

When following the procedure of Example XXIi using starch (for example, the product known as Kosol and manufactured by National Starch and Chemical Co.) in place of the

Polyvinylalkobj.8 is repeated, the following results are obtained. Stiffness value

as at the beginning after 5 washes

Fabric treated according to Example XXII 30 45 fabric treated with starch only 80 120 untreated fabric 125 130

Other finishing agents can be used with the curing agents as desired can be used according to the invention to achieve other special properties. It can, for example, upon request Plasticizers, bacteria-resistant agents, water-repellent agents, Stiffening agents and the like can be added to the treatment solutions without impairing the effectiveness of the process.

9 0 9 8 12/1019 - 32 -

The choice of "special finishing agents" is only due to their chemical properties Compatibility is limited in the system and it can be maintained Any mixture or combination of reactants may be used within this framework of chemical resistance.

The crosslinking treatments can also be applied to yarn, paper and others Substances that contain cellulose are used to make them insoluble in celluloses and their solvents To improve dimensional stability as well as their elasticity. They can also be used in the treatment of hydroxylated polymeric substances other than cellulose can be used. Finishing materials such as starch and polyvinyl alcohol hair can be put in place (on the paser, thread or fabric) insoluble and thus resistant to washing processes, as shown by Examples XXII and XXiII be made. The fibers made from polyvinyl alcohol can also be enhanced by crosslinking treatments by they are made resistant to water. Other applications of the new compounds and processes are possible

While the illustrative embodiments of the invention have been described in detail, there are many variations possible without deviating from the scope and concept of the invention

909812/1019

Claims (1)

■ AM B TT B Q ·· · mDU WAII 41 * · FJIRNHTTF M 89 SS TTNII M 41 16 8, <. 13151 JP Stevens & Co. Inc,
Hew York (USA) Claims 1. A method of treating a polymeric substance, thereby characterized in that the polymer containing a plurality of free hydroxyl groups in a polymeric molecule Substance containing multiple functions with the formula HOOH ₂ CH ₂ SO ₂ M
is treated, wherein M from the from HIGH ₂ CH ₂ - and existing group is selected and R is hydrogen or Alkyl, Q is an organic radical and η represents the number of unsaturated valencies and a value from 1-3, the process being carried out in the presence of an alkaline substance. 2. The method according to claim 1, characterized in that a polymeric, fiber-forming substance for the treatment is used. 909812/1019 iMte γι ι 3. The method according to claim 1, characterized in that for the treatment uses a fabric that is partially made of a polymeric material 4. A method for treating a polymeric substance thereby the indicates that / polymeric substance containing several free hydroxyl groups in a polymeric molecule is treated with a beta-oxyethylsulfone of the structure (HOCH ₂ CH ₂ SO ₂ J _n Q _n -, where R is hydrogen or an alkyl, Q is an organic radical, η represents the number of unsaturated valencies and has a value of 3 to 4, in the presence of an alkaline material to produce a polymeric substance with improved properties in terms of water resistance, solubility and swelling. 5β method according to claim 4, characterized in that for the Treatment a polymer? fiber-forming material is used 6 · The method according to claim 4, characterized in that for the treatment a fabric that is at least partially made of polymer Material is made, is used. 7 Process for the treatment of a polymeric substance, characterized in that that the polymeric substance having several free hydroxyl groups in a polymeric molecule with sulfone compounds <o fertilize the structure (ROCH ₉ CH ₀ SO ₉ ) n ^Q n '* · * "* ·« ^ ^rd »* ° * ei CD ccc ^ R is hydrogen or an alkyl, Q is a from dea / from aliphak> and alkylaromati look like radicals - * is the selected body that contains at least 3 carbon atoms, ο * "* η represents the number of unsaturated valencies and one Has a value of 2-4, the process taking place in the presence of an alkaline material to produce a polymer, U94348 the improved properties in terms of water resistance, of solubility and swelling. 8 · The method according to claim 7, characterized in that for the treatment uses a polymeric fiber-forming substance 9 · The method according to claim 71, characterized in that for the Treatment a fabric which is at least partially made of a polymeric material is used. 10. A method for treating a polymeric substance, characterized in that that the substance containing several free hydroxyl groups in a polymeric molecule, with substituted sulfone compounds of the following structure R0CH ₂ 0H ₂ S0 ₂ (CH ₂ CH0) _m 0 _a H _2a S0 ₂ CH ₂ GH ₂ 0R « ^H 1 is treated, wherein R and R "is hydrogen or an alkyl, a is an integer from 1-5, m has a value of 0-5, but if a value is equal to 1-5 a has a value of only 2-3 and wherein R _{1 is selected} from the group consisting of hydrogen and methyl and the process is carried out in the presence of an alkaline material to produce a polymer having improved water resistance, solubility and swelling properties. 11. The method according to claim 10, characterized in that a polymeric fiber-forming substance is used for the treatment will. 90981 2/1019 ~ ⁴ ~ H94348 j 12. The method according to claim 10, characterized in that a tissue for the treatment, which is at least partially made of one polymeric substance is used. 13. A method for treating a polymeric substance, characterized in that that for the treatment a polymeric fiber-forming substance with several free hydroxyl groups in one molecule selected and with a fJ-Oxyäthylsulfon of the following structure ROCH ₂ OH ₂ CSO ₂ ) _a Q _a S0 ₂ CH ₂ CH ₂ OR ", is treated, where R and R "are hydrogen or alkyls, a has a value of o-1 and Q is an organic radical, the process in the presence of an alkaline material is carried out to a fiber material with regard to the lent water resistance, resistance to dimensions, elasticity, solubility and swelling to produce improved properties. 14 Process for the treatment of a polymeric substance, characterized in that that for the treatment a polymeric, fiber-forming substance with a number of free hydroxyl groups in one polymeric molecule selected and with a sulfone, which is selected from the poly-Jl-Hydroxyäthylsulfon and poly / I-Alkoxyäthylsulfon existing group with the structure ® is selected, is treated, where R and R "are selected from the group consisting of • ^ hydrogen and an alkyl, ο a has a value of o-5, but with a value of m from 1-5 * ° a only has a value of 2-3, and where b is equal to zero only when a and m are equal to zero, R ^{1 is selected} from the group consisting of hydrogen and U9A348 Methyl, and wherein the process is carried out in the presence of an alkaline material is to produce a fiber material that with respect to the resistance to water, the resistance with respect to of dimensions, elasticity, solubility and swelling has improved properties « 15 · Process for the treatment of a polymeric substance, characterized in that that for the treatment a polymeric, fiber-forming substance with a number of free hydroxyl groups in one polymeric molecule selected and with a sulfone, which is selected from the poly-0-hydroxyethyl sulfone and poly-ji-alkoxyethyl sulfone existing group with the structure is selected, is treated, where β and R "are the same Have a meaning as in claim 14, b has a value of 1-3, a has a value of 1-5 and the process in the presence of a alkaline material is carried out to produce a fiber material, which in terms of resistance to Water, which improved dimensional stability, elasticity, solubility and swelling Has properties. 16 · The method according to claim 1, characterized in that as alkaline material an alkaline salt of a weak acid is used, which has an ionization constant of less than about 10 * -. 17. The method according to claim 16, characterized in that as Salt an alkali metal carbonate is used 909812/1019 " ⁶ " 18 · The method according to claim 16, characterized in that ale Salt an alkali metal bicarbonate is used 19. The method according to claim 16, characterized in that the reaction is carried out at a temperature of about 100 ° to 180 ⁰ C O · Method according to Claim 19, characterized in that the operation is carried out within about 30 seconds up to 5 minutes. 21. The method according to claim 16, characterized in that the Implementation is carried out essentially in the absence of water. Process according to Claim 1, characterized in that (HOCH ₂ CH ₂ SO ₂ ) ₂ G ₅ Hg is used as the sulfon. Process according to Claim 1, characterized in that HOCH ₂ CH ₂ SO ₂ CH ₂ CH ₂ OCH ₂ CH ₂ SO ₂ Ch ₂ CH ₂ OH is used as the sulfon. 24 · The method according to claim 1, characterized in that as SuIfon (HOOH ₂ OH ₂ SO ₂ > ₂ 0 ₊ H _{8 is} used Process according to Claim 1, characterized in that HOCH ₂ CH ₂ SO ₂ (CH ₂ CH ₂ O) ₂ CH ₂ CH ₂ SO ₂ CH ₂ Ch ₂ OH is used as the sulfon. 26. The method according to claim 1, characterized in that the sulfon used is HIGH CH ₂ SO ₂ CH ₂ CH ₂ OH. 27. The method according to claim 1, characterized in that the sulfon used is CH ₅ OCH ₂ CH ₂ SO ₂ CH ₂ Ch ₂ OCH, - 7 - 909812/1019 V- ³ » 28. Crosslinked polymers, characterized in that they are prepared according to claim 1, contain ether groups and the structure Pol-00H ₂ 0H ₂ S0 ₂ (QS0 ₂ ) _n (CH ₂ CH ₂ 0Pol) _m correspond, where Pol represents a residue of a polymeric molecule which has several hydroxyl groups, Q a represents organic radical, η has a value of 0-3 and m has a value of 1-3, where m is η, except when n = 0 is, in which case m takes the value 1. 29 · Cellulose ether, characterized by the structure CeII-OCH ₂ CH ₂ SO ₂ QSO ₂ CH ₂ GH ₂ O-CeIl in which Q is an organic radical and Cell represents the remainder that remains when the cellulose is designated as CeIl-OH will. 30. Cellulose ether characterized by the structure to where Cell- is a residue that remains when the σ ^ Cellulose is referred to as CeIl-OH, a an integer of J ^ 1-5, m has a value of 0-5, but a value of - »m is equal to 1-5 a only has a value of 2-3 and R ₁ from the out - * Hydrogen and methyl existing group is selected. 31. Cellulose ether, characterized by the formula CeIl-OCH ₀ CH ₀ SO ₀ C ₀ H-SO ₉ CH ₉ CH O-Cell ά ά cc 4 £ έ- where Gell- represents the remainder that remains when the cellulose is referred to as CeIl-OH. 32 · Cellulose ethers, characterized by the formula Oil-OCH ₂ GH ₂ SO ₂ CH ₂ CH ₂ OCH ₂ CH ₂ SO ₂ CH ₂ CH ₂ O-Cell where Cell- represents the remainder that remains when the cellulose is referred to as Cell-OH. 33 · Cellulose ether, characterized by the formula CeIl-OCH ₀ CH ₀ SO ₀ CH ^ SO ₀ CH ₀ CH ₀ O-CeIl dddjoddd in which Cell- represents a residue that remains when the cellulose is referred to as CeIl-OH. 34 · Cellulose ether characterized by the formula Cell-OCH ₂ CH ₂ SO ₂ (CH ₂ CH ₂ O) ₂ CH ₂ CH ₂ SO ₂ CH ₂ CH ₂ O-Cell in which Cell represents a residue that remains when the cellulose is called CeIl-OH 35 Cellulose ether characterized by the formula CeIl-OCH ₀ CH ₀ SO ₀ C ^ H ₀ SO ₀ CH ₀ CH ₀ O-CeIl ddd ^ -Oddd in which Cell- represents a residue that remains when the cellulose is referred to as CeIl-OH. 36 · Sulphone compounds characterized by the structure (HOCH ₂ CH ₂ SO ₂ ) n ^Q n in which R is a consisting of hydrogen and an alkyl Group is the selected substance, Q is an organic radical and η is the number of unsaturated valencies represents and has a value of 3 to 4. - 9 909812/1019 37. sulfone compound, characterized by the structure (R0CH ₂ CH ₂ S0 ₂ ) _n Q _n in which R is a consisting of hydrogen and an alkyl Group is selected substance, Q is one of the group consisting of aliphatic, aromatic and alkyl aromatic radicals existing group is selected substance which contains at least 3 carbon atoms, η is the number of unsaturated valencies represents and has a value of 2 to 4. 38 · Substituted sulfone compounds, characterized by the following structure ROGH ₂ CH ₂ SO ₂ (CH ₂ CHO) _m G _a H _2a S0 ₂ CH ₂ CH ₂ 0R in which R and R "are selected from the group consisting of hydrogen and an alkyl, a is an integer from 1-5, m has a value of 0-5, but assuming a value of 1-5 by ma Assumes a value of only 2-3, and with a value of m equal to 0 a value of a equal to at least 3 arises, where R ^{1 is} a body selected from the group consisting of hydrogen and methyl. 39. Sulphone compound, characterized by the structure HOCH ₂ CH ₂ SO ₂ (CH ₂ OH ₂ O) _n CH ₂ CH ₂ SO ₂ CH ₂ CH ₂ OH > in which η has a value of 2-12. \ \ 40.Sulfone compound, characterized by the structure: HIGH ₂ CH ₂ SO ₂ CH ₂ CH ₂ OCH ₂ Ch ₂ SO ₂ CH ₂ CH ₂ OH 9098 12/1019 - 10 - 41β sulfon compound, characterized by the structure: 42. Sulfone connection, characterized by the structure: HOCH ₂ CH ₂ SO ₂ (CH ₂ CH ₂ O) ₂ CH ₂ CH ₂ SO ₂ GH ₂ CH ₂ Oh 43 SuIfon connection, characterized by the structure: 44.Sulfon connection, characterized by the structure: (HOCH ₂ CH ₂ SO ₂ J ₂ C ₃ H ₆ 909812/1019