DE1469465A1 - Sizing agent for synthetic fibers - Google Patents

Description

Blow-out materials for man-made fibers

It is known. Man-made fibers and mixed fibers containing them to size with the solution of carboxyl group-containing copolymers. Has been particularly beneficial the use of aqueous polymer solutions have been found, with good results being achieved if one initially uses one Mixture of a monomer, the homopolymer of which is insoluble in water, with an ethylene carboxylic acid by the emulsion polymerization process polymerized and the dispersion obtained by adding a base, preferably of Ammonia, converted into the sol state. Such sizing agents characterized by a high current viscosity however, have the disadvantage that the degree of softness of a resulting film surrounding the sized fibers depends to a large extent on the moisture content of the air. At a relative humidity of z. B. more than 75 # size films of the known type become sticky, making processing of the textile material difficult or even impossible is made. - Attempts to use sizing agents for man-made fibers based on copolymers containing carboxyl groups to produce the previously usual method, on the one hand one that adheres well to the fiber and on the other hand one After weaving, the result is a film that is easily washed out and that is soft and pliable at the same time, without being too high Humidity to become sticky have so far not led to satisfactory results, although a VjdL number of Monomer combinations has been tested.

It has now been found that a sizing agent for man-made fibers and mixed fibers containing them, which

8098 * 4/1711 .2-

ORJGlNAL INSPECTED

U69465

Cited requirements can be prepared by adding a monomer, the homopolymer of which is water-insoluble is, with a monobasic or polybasic carboxylic acid, optionally with further monomers, after the emulsion polymerisa tion process polymerized in the aqueous phase to obtain a dispersion and then by addition a base forms the corresponding polymer salt. According to the invention, a carboxylic acid content of 1-15 wt .- ^, based on the monomer mixture to be polymerized, and allows the polymerization to proceed in the presence of a Fe regulator.

The type and amount of the regulator to be used are selected so that an aqueous dispersion of the carboxyl-containing copolymer is obtained which, at a dry content of 10 % and when the copolymer is converted into an alkali or ammonium salt, experiences a viscosity increase that is not more than twenty times that Initial viscosity is. If a base is added to the dispersion of an identical, but without the use of a regulator, copolymer containing carboxyl groups, ie if the copolymer is converted into the corresponding salt, an increase in viscosity of at least a hundred or even thousands of times occurs .

Polymerization experts are familiar with the use of so-called regulators. He knows that growing one The polymer chain is terminated by certain compounds known as "regulators", d. H. the size of the MakromcLeküls can be adjusted in the desired sense within wide limits by using such controllers. the best known regulating substances are sulfur compounds, such as mercaptans, disulfides, z. B. diisopropylxanthogen disulfide or diphenyl disulfide, also thioethers or thio acids

909844/1711 bathroom omi _NAL

_ ₃ _ H69465

as well as the esters of these acids, e.g. B. Thioglycolic acid and its esters.

The polymer salts in question give slightly cloudy sizes which, however, dry up to give a clear film. If the given process specification is observed, copolymers are obtained which, when converted into the corresponding Alkali salt are generally just at the limit of water solubility. This behavior is natural depends on the qualitative and quantitative structure of the copolymers, whereby the carboxylic acid content in the case of copolymers, the monomers resulting from a hydrophobic homopolymer, such as. B. butyl methacrylate, oestehen, Within the specified quantity range of 1-15 wt .- ^ must be larger than when using a hydrophilic homopolymer resulting monomers, such as. B. methyl acrylate. In all cases, however, it is regulated Polymerization is an indispensable prerequisite for the formation of a dispersion, which is specified after the addition of alkali Meaning can be used as a sizing agent.

The main carboxylic acids are acrylic acid and methacrylic acid, furthermore, for example, itaconic acid, aconitic acid, maleic acid or dimeric or trimeric methacrylic acid can be used. - As comonomers, which can be used individually or in a mixture with one another, are, in turn preferred, the esters of acrylic and methacrylic acid, also called styrenes, vinyl ethers and esters. - In subordinate Quantities can be further, copolymerizing with the monomers mentioned, unsaturated compounds such as acrylonitrile, amides of unsaturated carboxylic acids and their derivatives are also used will.

It deserves to be emphasized that sizing agents of the type according to the invention are particularly advantageous

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H69465

Sizing of man-made fibers that show extremely low water absorption, such as threads made of polyesters, is suitable and polypropylene.

The characteristic of the new process, according to which the type and amount of the regulator to be used according to the invention is to be selected so that the aqueous dispersion obtained, at a dry content of 10 % , undergoes a viscosity increase marked with respect to its maximum value after setting a pH value of 9, initially appears to be problematic However, it is possible for the person skilled in the art in a simple manner and with the help of less orientational experiments to determine the degree of regulation required for each desired monomer combination. The examples given below give an indication of the composition of the new sizing agents. If other monomer combinations are chosen, simple experiments are all that is required to determine the amounts in which an intended regulator of the known type must be added to the polymerization batch in order to obtain a dispersion which exhibits the stated viscosity when a pH value of 9 is set . In this respect, the examples do not limit the scope of the property right sought.

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RÖHM & HAAS Annex to our submission of April 24, 1964 Shim.sche Ϊ · αβ * Λ i. S. R 36 98b IVd / 39 Q DARMSTADT - ~ T Pat. Dr.Be/Mur/6 1A69465 K " Examples; Production of the emulsion polymers

The copolymers listed in the table below were produced as follows:

In a 1 1 Witt ¹ see pot, which is provided with a blade stirrer, reflux cooler and thermometer, 450 g of deionized water containing 4.5 g of a sulfated emulsifier based on nonylphenol and 4 moles of ethylene oxide are heated to 80 °. After this temperature has been reached, 0.5 g of ammonium persulfate is added and 300 g of a monomer mixture are added dropwise over the course of one hour, it being possible for the monomer mixture to contain the regulator. When the monomer feed has ended, the temperature is held at 80 ° for a further half an hour and then cooled to room temperature. The dispersions obtained are free of coagulate, have a low viscosity and, after dilution to 10 % dry matter, show the viscosities listed in the table before or after the pH adjustment.

- 2 ORIGINAL INSPECTED

.5O

example

A = · »adapter
iSp «spindle

Composition of the monomer mixture in parts by weight

Acrylic acid ethyl ester / methacrylic acid »90/10

Acrylic acid ethers / methacrylic acid esters / methacrylic acid = 70/20/10

Acrylic acid methyl ester / acrylonitrile / methacrylic acid = 80/10/10

Acrylic acid ethers ter / methyl methacrylate / 2-methylene-5-methyl adipic acid «= 75/15/10

Regulator in % _t based on monomer

Prockengeialt the disp. Ln %

Current viscosity of the diluted disp., Measured in the Brookfleld viscometer type LVT

cP before pH adjustment (rpm)

2.5 thiogly- 39.8

colic acid-2-

ethylhexyl

ester

2.5 n-dodecyl-j 40.0 mercaptan

2.5 thioglycolic acid 2-ethylhexyl ester

j 2.5 thiogly-; 2-ethylhexyl colic acid ter

Isopropyl acrylate / / Ö

Acrylic acid = 92 / o. Mercaptan

2.5 n-dodecyl- 39.0

1.5 (60)

1.6 (6o) A

1.6 (60) A.

1.6 (60) A.

1.5 (60) A.

1.4 (60) 'A.

1.7 (60) A.

cP after pH adjustment with NaOH to 9 (rpm)

285OO (12) SpIV

8.0 (12) A.

3.8 (12) A "

4.1 (12) A.

14000 (1.5) SpII

16.0 (12) A.

20.5 (12) A.

U69A65 - \ -

Those mentioned in the table in Examples 2, 3, 4, 6 and 7 Mixed polymers in the form of their alkali salts are particularly good sizing agents for chemical threads. In all After weaving, the size is removed from the finished fabric with water or aqueous cleaning fluids easy to remove.

The sizing agent according to Example 2 is particularly suitable for sizing rayon of all degrees of fineness, the solutions having a dry matter content of 1.2 to 1.8 % and the sizing temperature being 60 to 70 °.

The product of Example J. is used with particular advantage as a sizing agent for acetate and triacetate. The concentration of the sizing baths, based on dry substance, is 3 % for acetate and 4 % for triacetate, and the sizing temperature is 60 to 70 °.

The copolymer recorded in Example 4 gives very good sizing effects on endless threads made of polyacrylonitrile. The dry matter content of the bottom baths used at 60 ° is 5 %.

The copolymer according to Example 6 is optimally used for sizing threads made of polyester. The size concentration, based on dry matter, is 5 to 6 % at a temperature of 60 to 70 °.

The emulsion polymer according to Example 7 shows particularly good effects when used for sizing threads made of polypropylene, the sizing temperature being 50 to 60 ° and the liquor concentration being 8 to 10 %, based on the dry substance.

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Claims (4)

Claims 1. Process for the preparation of a sizing agent for Man-made fibers and mixed fibers containing them by copolymerization of a monomer, its homopolymer is insoluble in water, with a monobasic or polybasic, unsaturated carboxylic acid, optionally with other monomers, by the emulsion polymerization process in the aqueous phase to obtain a dispersion and subsequent addition of a base, characterized, that the carboxylic acid content 1 - 15 wt .- ^, based on the Monomeregemlsch, makes up, the polymerization is carried out in the presence of a regulator and its amount is dimensioned so that a 10- ^ ige aqueous dispersion after the addition of a base until a pH value of 9 is set, an increase in viscosity is experienced that does not is more than twenty times the initial viscosity. 2. The method according to claim 1, characterized in that the structure of the copolymers acrylic acid in amounts of 4-8 wt. #, Based on the monomer mixture to be polymerized, involved 1st. 3. The method according to claim 1, characterized in that on the structure of the copolymers methacrylic acid in amounts of 6-12 wt .- ^, based on the to be polymerized Monomer mixture, is involved. 4. Process according to claims 1-3, characterized in that the lower esters of acrylic and / or methacrylic acid (C number in the alcohol radical 1-4) are used as the water-insoluble homopolymers resulting comonomers. 909844/171 1