New grafted polyester sulfones, their preparation process and their use for sizing yarns and textile fibres

RHONE-POULENC CHIMIE '' PROCESS FOR PREPARING NEW POLYESTERS

Grafted SULFONATES APPLICABLE TO COLLAR YARN AND TEXTILE FIBERS

The present invention relates to a process for the preparation of grafted sulfonated polyesters on the basis of vinyl monomer derivatives and the application of said polyesters in the bonding of yarns and textile fibers.

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The use in the textile industry of sizing products for improving the abrasion resistance of yarns and fibers is known in the textile industry, said sizing products being water-immersed after weaving.

For this purpose, aqueous dispersions or solutions of acrylic or more generally vinyl copolymers have been proposed; These products, in particular those based on vinyl acetate, have not been found to be suitable for bonding all textile yarns. for example, their adherence to polyester based yarns is insufficient.

Interesting products were obtained by copolymerizing (meth) acrylic esters and (meth) acrylic acid in the presence of a hydrodispersible sulfonated polyester (Japanese Patent Application Nos. 34153/1975 and 201079/1986). for example from 30 to 60% of a hydrodispersible sulfonated polyester 1 and from 70 to 40% of a (meth) acrylic esters / (meth) acrylic acid copolymer. These products, however, have the disadvantage that they are particularly expensive.

We have surprisingly found that an efficient sizing agent can be obtained by reducing the proportion of hydrodispersible sulfonated polyester on the one hand and replacing most (meth) acry esters on the other hand. It is generally appreciated by vinyl acetate, for example, which is sufficiently less expensive.

According to the invention, the novel sulfonated polyesters grafted for vinyl monomer motifs are characterized in that they contain:

3 to 30 parts by weight, preferably 3 to 15 and most particularly 5 to 8 parts by weight, of a stem polymer consisting of one or more_:hydrodispersible sulfonated polyester1

- and 100 parts by weight of grafts derived from a monomer composition comprising:

. 5 to 13 parts by weight, preferably 6 to 9 parts by weight, of at least one ethylenically unsaturated carboxylic acid;

-3. 12 to 25 parts by weight, preferably 17 to 22 parts by weight of butyl acrylate or 25 to 40 parts by weight, preferably 30 to 35 parts by weight of a mixture of different ethylenically unsaturated monomers ethylenically unsaturated carboxylic acids and monoethylenically unsaturated carboxylic acid esters, a mixture containing 60 to 70% by weight of butyl acrylate;

. and the complement to 100 parts by weight of at least. us a monoethylenically unsaturated ester of a carboxylic acid.

In a variant of the product object of the invention, up to about 10% by weight of butyl acrylate may be substituted by butyl methacrylate.

A preferred product according to the invention is a hydrodispersible sulfonated polyester stem having grafts derived from at least one ethylenically unsaturated butyl acrylate carboxylic acid (approximately 10% by weight of said acrylate may be substituted by butyl methacrylate) and at least one monoethylenically unsaturated ester of a carboxylic acid having a butyl acrylate / polyester weight ratio. water dispersible sulfonated ester of the order of 0.8 to 8.5 and preferably of the order of 2.5 to 4.

The base hydrodispersible sulfonated polyesters that make up the trunk are known products of the glue field

-4of textile yarn. They may be prepared by co-condensing an organic diacid (for example a saturated or saturated aliphatic diacid, an aromatic diacid, a multi-aromatic diacid, an arylaiiphatic diacid), one of its diesters or anhydride thereof and the like. of a sulfonated organic diacid or one of its diesters with a diol in the presence of a usual polyesterification catalyst such as tetraisopropion orthotitanate.

As starting monomers commonly used for the preparation of the hydrodispersible sulfonated polyester stem, they may be cited as:

- organic diacids: saturated or unsaturated aliphatic diacids, aromatic diacids, for example succinic, adipic, suberic, sebacic acids, maleic, fumaric, itaconic acids, orthophthalic, isophthalic, terephthalic acids, anhydrides of these acids and their diesters as methyl, ethyl, propyl, butyl diesters. Preferred compounds are adipic acid, orthophthalic, isophthalic, terephthalic acids;

- sulphonated organic diacids: sodium sulphonate diacids or their diesters such as diacylisophthalate and dialkylsulfonate such as sodium 5-dimethylisophtate sulfonate or sodium dimethylsulphosuccinate;

diols: aliphatic glycols such as ethylene glycol 1, diethylene glycol 1, dipropylene glycol and the higher homologues, 1,4-butanediol, 1,6-hexanedio 1, neopentylgene 1 and cyclic glycols such as lohexanedio 1, dicyclohexanediolpropane. Preferred diols chosen are ethylene 1 and diethylene.

Preferred hydrodispersible sulfonated polyesters for building the stem are those having a number average molecular weight of 10,000 to 35,000, an acid content of less than 5 mg KOH / g, a sulfur ratio of 0.8 to 2% by weight, preferably between 1.2 and 1.8%.

As monomers from which grafts are derived, they can be cited as:

- ethylenically unsaturated carboxylic acid: acrylic acid, methacrylic acid, etc.

- monoethylenically unsaturated carboxylic acid ester: vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, vinyl benzoate, etc.

copolymerizable comonomer (s) such as monoethylenically unsaturated carboxylic acids, monoethylenically unsaturated carboxylic acid esters and butyl acrylate: alkyl acrylates or methacrylates for example methyl, ethyl, propyl, heptadecanyl, etc .; acrylonitrile; acrylamide; styrene, etc.

The products which are the subject of the invention may be obtained by 100% by weight aqueous polymerization of a monomer composition comprising:

. by 5 to 13 parts by weight, preferably 6 to 9 parts by weight, of at least one ethylenically unsaturated carboxylic acid;

<img file="PT89975B_D0001.tif" />

. by 12 to 25 parts by weight, preferably 17 to 22 parts by weight of butyl acrylate or 25 to 40 parts by weight, preferably 30 to 35 parts by weight of a mixture of ethylenically saturated monomers other than carboxylic acids ethylenically unsaturated and monoethylenically unsaturated esters of carboxylic acids, which mixture contains 60 to 70% by weight of butyl acrylate;

. and the 100 parts by weight complement of at least one monoethylenically unsaturated ester of a carboxylic acid in the presence of 3 to 30 parts by weight, preferably 3 to 15 and most particularly 5 to 8 parts by weight of a hydrodispersible sulfonated polyester. .

In a variant of the process object of the invention, up to about 10% by weight of butyl acrylate may be substituted by methyl methacrylate.

A preferred embodiment is to use a mixture comprising at least one ethylenically unsaturated carboxylic acid butyl acrylate (up to about 10% by weight of said butyl acrylate) and at least one carboxylic acid ester, in the presence of shad, with a hydrodispersible weighted ratio in the order of being replaced by monoethylenically unsaturated methacrylate of a hydrodisperse sulfonated polyester. butyl acrylate / polyester sulfate 0.8 to 8.5 and preferably of the order

From 2.5 to 4.

The polymerization operation may be carried out in aqueous emulsion in a classical manner in the presence of a water soluble polymerization initiator, an emulsifier and optionally a chain limiting agent.

Examples of hydrodispersible sulfonated polyesters and monomers used are given above. The nature and quality of the ethylenically unsaturated monomer (s) optionally present alongside butyl acrylate can be readily determined by those skilled in the art depending on the conditions of future use of grafted polyester; in fact, these conditions of use determine the properties of said product, for example its glass transition temperature, its hardness, its hydrophilia, its mechanical properties such as elongation and breaking strength, etc .; It is known that the addition of styrene or methyl methacrylate, for example, gives rise to a harder polymer, whereas the addition of hexyl acrylate will have the opposite effect.

Water-soluble initiator may be represented more particularly by hydroperoxides such as hydrogen peroxide, cumene hydroperoxide, butylotrophydroperoxide, diisopropyl benzene hydroperoxide, and by persulphates such as sodium persulphate, potassium persulphate, persulphate Ammonium

Said initiator may be used in amounts of 0.05 to 2% by weight relative to the weight of the monomeric composition. These initiators are eventually associated with

<img file="PT89975B_D0002.tif" />

to a reductant, for example bisulfite or sodium dehydroxy formate, polyethylene amines, sugars: dextrose, sucrose, metal salts. waistband. The amounts of reducing agent used range from 0 to 3% by weight relative to the weight of the monomeric composition.

As an emulsifying agent, the classic anionic agents represented by salts of fatty acids, alkylsulfates, alkylsulfonates, alkylarylsulfonates, sulfosuccinates, alkali metal hydroxide phosphates, nonionic hydrogenated salts of salts, such as polyethoxy fatty acids, sulfated polyethoxy alkylphenols, polyethoxy fatty acids, etc.

Emulsifying agents are used at a rate of 0.01 to 5% by weight based on the weight of the monomeric composition.

chain limiting agent may optionally be applied in proportions of 0 to 3% by weight with respect to the monomeric composition. The agent is generally chosen from mercaptans such as N-dodecyl mercaptan, dodecyl ether mercaptan; cyclohexene; halogenated hydrocarbons such as chloroform, bromoform, carbon tetrachloride, carbon tetrabromide; the dimethyl-methyl dimers.

The polymerization operation may be carried out at a temperature of the order of 60 to 80 ° C, preferably of the order of 70 ° C.

This operation lasts 6 to 12 hours and is usually in the order of 10 hours.

If desired, the latex obtained, which generally contains

<img file="PT89975B_D0003.tif" />

About 10 to 60% by weight of grafted sulfonated polyester can be atomized for storage and delivery more easily.

Latex or dry product may be solubilized in water by means of an alkaline, preferably volatile substance (volatile amines, ammonia). The solution thus obtained generally contains 5 to 30% of its weight of grafted sulfonated polyester. Latex, or preferably its solution, is particularly suitable for bonding yarns or fibers, particularly in water jet looms or wet-dry looms.

The present invention also relates to a process of bonding textile yarns, which consists of applying the hydrodispersible grafted sulfonated polyesters described above in aqueous medium, according to a classical technique whose principle is to immerse the yarns in an aqueous bath containing contains the sizing product at the desired concentration and temperature, then rinsing said yarns by roll-through. dry the glued yarns on heating cylinders, if necessary by passing them in hot runners: the chain is now ready to be woven.

Classical bonding processes for continuous yarn (filament yarn or continuous filament yarn) include, for example, seam bonding (european system), conventional bonding (classic system or English system) and primary towel (single end sizing or Japan system). etc.

The sizing products according to the invention are of particular interest for finishing filament yarns sin-10-

<img file="PT89975B_D0004.tif" />

Ethylene polyethylene ethers are among the most difficult to bond yarns, but can also be used for ethylene glycol polyetherphthalate spun yarns (fibers) or for other yarns such as : synthetic yarns such as acrylics, polyimides, chlorofiber, polyethylene, polypropylene or artificial yarns such as acetates, triacetates, viscose, etc.

Moreover, these products make it possible to glue any kind of yarn, whether textured or not, twisted or not, and by any sizing technique, whether sectional, conventional, primary towel or other.

A very important advantage of these products is that they can withstand the performance restrictions of new looms. They allow for fast gluing and weaving. In addition, they are easily removable with water.

The following examples are given by way of illustration and cannot be construed as limiting the scope and spirit of the invention.

EXAMPLE 1

In a 6 liter reactor equipped with an anchor agitator enter:

<td colspan="5">2100 g of water</td>

<td> 9,4</td><td> 9</td><td>in</td><td>acetate</td><td>sodium</td>

<td> 9,4</td><td>g</td><td>in</td><td>nonylphenol</td><td>partially sulphated ethoxylate which</td>

-11 contains 25 ethylene oxide motifs.

- 502 g of GEROL PS 20 (sulfonated polyester marketed by RHONE-POULENC) in 26.1% aqueous solution (corresponding to 131 g of dry product).

The mixture is heated to 70 ° C under stirring at 150 r.

pm

9.4 g of ammonium persulate dissolved in 65 g of water are added. They are introduced continuously:

- on the one hand for -6 hours a mixture of:

- 1370 g of vinyl acetate (VA)

- 375 g of butyl acrylate (BuA)

- 131 g of acrylic acid (AA)

- 7.5 g of dodecyl tert-mercaptan

- on the other hand, for 8 hours, 7,5 g butiloterc hydroperoxide. dissolved in 46 g of water

- as well as for 8 hours

- 12.75_g of sodium formaldehyde sulfoxylate

- 4.7g of sodium hydrogen carbonate dissolved in 300g of water.

The three continuous introductions begin simultaneously.

At the end of the introductions, the medium is left at 70 ° C for 1 hour and then cooled.

A latex of 40.8% dry extract is obtained.

<img file="PT89975B_D0005.tif" />

EXAMPLE 2

The operation described in example 1 is repeated from the following product quantities:

- 2024 g of water

- 9.4 g of sodium acetate

--9,4 g partially sulfated ethoxylated nonylphenol -103 g GEROL PS 20, expressed as a dry product (392 g of 26,3% aqueous solution)

- 9,4 ammonium persulfate in 65 g of water

- 1294 g of vinyl acetate

- 169 g of acrylic acid

- 375 g of butyl acrylate

- 37.5 g of butyl methacrylate

- 0 g of deciItere.-mercaptan

- 7.5 g butiloterc hydroperoxide.

- 12.75 g of sodium formaldehyde sulphoxylate ~) diluted in

- 4.7 g of sodium hydrogen carbonate J 450g of water

A latex of 40% dry extract is obtained.

EXAMPLE 3

The operation described in example 1 is repeated from the following product quantities:

<img file="PT89975B_D0006.tif" />

- 1005 g of water

<td> - 7,5</td><td>g</td><td>of sodium acetate</td>

<td> - 7,5</td><td>g</td><td>of partially sulfated ethoxylated nonylphenol</td>

<td> - 450</td><td>g</td><td>of GEROL PS 20, expressed as dry product (1711</td>

26.3% aqueous solution)

- 7,5 g ammonium persulphate in 75 g water

- 1095 g of vinyl acetate

- 105 g of acrylic acid

- 300 g of butyl acrylate

- 0 g of dodeci Itere ·.-Mercaptan

- 8.57 g butiloterc hydroperoxide.

- 10,20 g of diluted sodium formaldehyde sulfoxylate Ί

- 3.75 g of sodium hydrogen carbonate J 450 g of in water

A latex of 40.5% dry extract is obtained.

EXAMPLE 4

The operation described in example 1 is repeated from the following product quantities:

- 909 g of water

- 6.25 g of sodium acetate

- 6.25 g of partially sulfated ethoxylated nonylphene 1

- 375 g of GEROL PS 20, expressed as dry product (1431 g of 26,2% aqueous solution)

- 6.25 g of ammonium persulphate in 30 g of water

- 1012.5 g of vinyl acetate

<img file="PT89975B_D0007.tif" />

- 87.5 g of acrylic acid

- 150 g of butyl acrylate

- 7.5 g of dodecyl tert-mercaptan

- 7.14 g butiloterc hydroperoxide.

- 8.5 g of sodium formaldehyde sulphoxylate

- 3,1 g of sodium bicarbonate

- 2,5 mercaptoethane1 diluted in

300 g of water

A latex of 40.5% dry extract is obtained.

EXAMPLE 5

The operation described in example 1 is repeated from the following product quantities:

<td>- 2084 g of</td><td>Water</td><td></td><td></td>

<td>- 9.36 g of</td><td>sodium acetate</td><td></td><td></td>

<td>- 9.37 g of</td><td>ethoxy nonylphenol</td><td>stop ia 1 mind</td><td>Suffected</td>

<td colspan="2">- 150 g of GEROL PS 20, expressed</td><td>in product</td><td>dry (569</td>

<td>of solution</td><td>26.4% aqueous)</td><td></td><td></td>

<td>- 9.37 g of</td><td>ammonium persulphate</td><td colspan="2">in 65 g of water</td>

<td>- 1406 g of</td><td>vinyl acetate</td><td></td><td></td>

<td>- 337.5 g of</td><td>butyl acrylate</td><td></td><td></td>

- 7.5 g of dodecyl tert.-mercaptan

- 131.2 g of acrylic acid

- 7.5 g butiloterc hydroperoxide.

- 12.75 g of sodium formaldehyde sulfoxylate diluted in

- 4.7 g of sodium hydrogen carbonate J 300 g of water

A latex of 41% dry extract is obtained.

<img file="PT89975B_D0008.tif" />

EXAMPLE 6 (comparative)

The operation described in example 1 is repeated from the following product quantities:

- 1385 g of water

- 7,5 g of sodium acetate

- 7,5 g of partially sulfated ethoxylated nonylphenol

- 180 g of GEROL PS 20, expressed as a dry product (679 g of 26,5% aqueous solution)

- 7,5 g of ammonium persulfate in 75 g of water

- 945 g of vinyl acetate

- 105 g of acrylic acid

- 450 g of butyl acrylate

- 0 g of dodeci Itere.-mercaptan

- 8.57 g butiloterc hydroperoxide.

- 102 g of sodium formaldehyde sulfoxylate^-} diluted in

3.75 g of sodium hydrogen carbonate 450 g of water A latex of 40.6% of dry extract is obtained.

EXAMPLE 7 (comparative)

The operation described in example 1 is repeated from the following product quantities:

- 1005 g of water

- 7,5 g of sodium acetate

- 7,5 g of partially sulfated ethoxylated nonylphenol

- 450 g of GEROL PS 20, expressed as a dry product (1711 g

-16i

<img file="PT89975B_D0009.tif" />

26.3% aqueous solution)

- 7,5 g ammonium persulphate in 75 g water

- 945 g of vinyl acetate

- 105 g of acrylic acid

- 450 g of butyl acrylate

- 0 g of dodeci Itere.-mercaptan

- 8.57 g butiloterc hydroperoxide.

- 10,20 g of sodium formaldehyde sulfoxylate3 diluted in

- 3.75 g of sodium hydrogen carbonate J 450g of water

A latex of 40.4% of dry extract is obtained.

EXAMPLE 8 (Comparative)

In a 6 liter reactor equipped with an anchor stirrer.

i introduce:

- 2156 g of water

- 1.5 g of NANZA SB 62 based on sodium dodecylbenzenesulfonate, available from ALBRIGHT &amp; WILSON

- 450 g of dry GEROL PS 20.

The mixture is heated to 80 ° C while stirring at 150 rpm. 1.875 g of ammonium persulfate dissolved in 20 g of water are added.

They are introduced continuously:

- on the one hand, for 8 hours, a mixture of:

<img file="PT89975B_D0010.tif" />

. 75 g of acrylic acid (AA). 75 g methacrylic acid (MAA)

<td> 300</td><td>g of</td><td>acrylate</td><td>ethyl</td><td>(AND THE)</td>

<td> 600</td><td>g of</td><td>acrylate</td><td>but i 1 o</td><td>(BuA)</td>

<td> 450</td><td>g of</td><td>metacri1 act</td><td colspan="2">methyl (MeMA)</td>

. 5.62 g of dodecyl tert.-mercaptan

- on the other hand, for 5 hours, a mixture of:

. 7.5 g of ammonium persulfate. 30 g of ethoxylated nonylphenol Ί dissolved in partially sulfated J^{420 9 water}

Both introductions begin simultaneously.

At the end of the introductions, leave the medium at room temperature.

80 ° C for 1 hour and cool.

A latex of 43% of dry extract is obtained.

EXAMPLE 9 (Comparative)

The operation described in example 8 is repeated using 150 g (instead of 450 g) of dry GEROL PS 20 and 1700 g (instead of 2156 g) of water.

Collage Test

Sizing tests were carried out by aqueous solutions of the products of Examples 1 to 9, which constitute the glue baths.

These solutions were prepared as follows: After dilution in demineralized water to a 20% dry extract, these products are heated to 60 ° C and then a 20% aqueous solution is added to them for half an hour. ammonia to a pH of 7.5.

The gluing operation is carried out with a SUCKER laboratory machine (marketed by SUCKER) adapted to work in a primary towel system, on a 100 decitex polyester chain, 88 fibers, untwisted, with a passage speed of 100 meters per minute. about the coladora; The settings are optimized to deposit 10% by weight of dry polymer on the yarn mass.

The principle of operation is as follows: the polyester chain is dipped in the glue bath, then dried by passing it in chambers heated to 145 ° C and then over heated cylinders at decreasing temperatures of 125 to 100 ° C; A lubricant (90 ° C molten wax) is applied to the yarn in a ratio of 0.3% to yarn mass at the outlet of the dryer rollers.

After cooling in a cooling chamber, the threads are wound over the primary loom rollers; They are then joined together to make a roll for the loom.

The effectiveness of the tested products is assessed prior to the assembly of the primary cylinders by means of the SHIRLEY FILAMENT COUNTER of Manchester SHIRLEY INSTITUT according to the method published at the 7th Mulhou Textile Collage Symposium-19-

<img file="PT89975B_D0011.tif" />

15, 16 and 17 October 1986.

This experiment consists of measuring the ability of a polymer to glue together the unitary yarns that form the yarn.

During the measurement, the device records and counts the vibrations emitted during the sectioning of the individual elements consisting of a single strand or several glued strands.

cohesion index C is expressed by the ratio

C = 100 (nx) / (n - 1) where £ represents the number of unit yarns constituting the yarn and _x represents the number of individualized elements counted.

With no glue, all single threads are independent; x is then equal to ane C = 0.

Cohesion is maximum when all unit wires are connected; x is then equal to 1 and C = 100.

Cohesion index is measured before and after work on a WEBTESTER usometer at the Reutligen Textile Institute (measured after 50, 150 and 300 cycles).

(This device simulates the work done by the yarn during the weaving operation).

A curve is then drawn which represents the loss of cohesion of the bonded wire as a function of the work suffered (abrasion).

<img file="PT89975B_D0012.tif" />

It is indicated after teeth to the tried products.

curves reference

Example Product

9

Reference

D

F

G

I

AND

J

H

K

Examples 1 to 5 are also compared:

- with a solution of GEROL AS 10 marketed by RHONE-POULENC (all acrylic butyl acrylate-based copolymer, ie not derived from monomers other than acrylic or methacrylic esters and without sulfonated polyester motifs),

- with a solution of GEROL VS 30 marketed by RHÔNE-POULENC (copolymer derived from vinyl acetate in large proportion, butyl acrylate and unsaturated carboxylic acid without sulfonated polyester motifs)

- and with a solution of GEROL PS 20 marketed by RHÔNE-POULENC (hydrodispersible sulfonated polyester1);

The reference of the curves corresponding to these products is as follows:

<img file="PT89975B_D0013.tif" />

<td colspan="3">Product</td><td>Reference</td>

<td>GEROL</td><td>AT</td><td> 10</td><td>Ç</td>

<td>GEROL</td><td>VS</td><td> 30</td><td>B</td>

<td>GEROL</td><td>PS</td><td> 20</td><td>THE</td>

set of curves corresponding to the products according to the invention or comparative products are the object of figures 1 and 2.

Analysis of these curves shows that:

- GEROL AS 10 (all-acrylic copolymer) gives significantly better results than GEROL VS 30 (vinyl acetate-based copolymer)

surprisingly, on the contrary, the product of Example 1 and Example 9, the compositions of which are respectively as follows:

<td></td><td></td><td>MAA</td><td> 5</td>

<td>AA</td><td> 77</td><td>AA</td><td> 5</td>

<td>GO</td><td> 73</td><td>AND THE</td><td> 20</td>

<td>BuA</td><td> 20</td><td>BuA</td><td> 40</td>

<td></td><td></td><td>MeMA</td><td>³⁰</td>

<td>PS</td><td> 20 7</td><td>PS 20</td><td> 7</td>

show similar results when they would be clearly superior to the product of example 9 acrylics are approximately 3 times higher than expected results the price of esters than that of

<img file="PT89975B_D0014.tif" />

vinyl, whereby the interest of the product of example 1 in comparison with that of example 9 is immediately understood.

It is true that the product of example 8 gives slightly better results than the product of example 1, but its proportion of butyl acrylate and GEROL PS 20 makes its price prohibitive for the corresponding results. In fact, the price of GEROL PS 20 is at least 10 times higher than that of vinyl acetate;

- in view of example 4, there is an interest in respecting a certain preferential relationship between the content of GEROL PS 20 and that of butyl acrylate.

The product of Example 7 gives good cohesive experiment results, but nevertheless cannot be used industrially because it gives rise to blocking on primary streams when assembling or unrolling the primary cylinders. the primary cylinder spool on the loom.

The process of example 6 could not be subjected to the cohesive experiment because many unitary breaks of the bonded wire due to blocking were observed during unwinding of the coils to perform the experiment.