DE1264068B - Process for the production of acrylonitrile polymers with improved colorability compared to basic dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN wt ^ PATENT OFFICE

EDITORIAL

Int. CL:

C08f

1

German class: 39 c -25/01

Number: 1264068

File number: M 57970IV d / 39 c

Filing date: August 26, 1963

Open date: March 21, 1968

Polymers with an acrylonitrile content of 80% or more are generally basic Dyes are not very absorbent, and so there were various agents have been used to increase their ability to absorb basic dyes. The dyeability of acrylonitrile polymers with basic dyes was made by incorporation improved by various compounds containing sulfonic acid or sulfonate groups. For example were sodium - ρ - methacrylamidobenzenesulfonate, vinylarylsulfonic acids and with an alkenyl radical substituted aromatic sulfonic acids or their salts copolymerized with acrylonitrile or with Polyacrylonitrile mixed to obtain dyeable masses for the production of fibers or threads.

It is also known that the dye affinity of acrylonitrile polymers towards basic dyes can be improved by copolymerizing acrylonitrile with vinyloxybenzenesulfonic acid. However, the vinyloxybenzenesulfonic acid used therein is obtained through a complicated manufacturing process over three stages, with isolation required after each stage, also maintains and tends to homopolymerization if a certain pH range is not maintained. Furthermore, the thus achievable improvement in the dye affinity of acrylonitrile polymers compared to basic ones Dyes not yet completely satisfactory.

A process has now been found for the production of acrylonitrile polymers with improved colorability to basic dyes by polymerizing a mixture of at least 80 percent by weight Acrylonitrile, 0 to 19.75 percent by weight of at least one other mischpolymerisiei ble monoolefinic Monomers and 0.25 to 10 percent by weight of an alkenyloxyarylsulfonic acid found, in which then, in a technically and economically advantageous manner, a superior increase in dye affinity is achieved when the alkenyloxyarylsulfonic acid is a compound of the general formula

SO ₃ Y

R '

'O-CH-C = CH ₂

Process for the production of
Acrylonitrile polymers with improved
Dyeability to basic dyes

Applicant:

Monsanto Company, St. Louis, Mo. (V. St. A.)

Representative:

Dr. E. Wiegand and Dipl.-Ing. W. Niemann,

Patent attorneys,

8000 Munich 15, Nussbaumstr. 10

Named as inventor:
James Carter Masson,
Chapel Hill, NC (V. St. A.)

Claimed priority:

V. St. v. America dated August 27, 1962 (219 761)

in which R and R 'represent a hydrogen atom or alkyl radicals with 1 to 3 carbon atoms and Y represent an alkali metal, is used.

Suitable compounds of the formula given are those in which the radicals R and R 'are a hydrogen atom, the methyl, ethyl or propyl ester and Y is an alkali metal, ζ. Β. Sodium, potassium, lithium, Cesium or rubidium. Examples are sodium allyloxybenzenesulfonate, potassium methallyloxybenzenesulfonate, Lithium allyloxybenzenesulfonate, sodium methallyloxybenzenesulfonate, sodium 2-ethylallyloxybenzenesulfonate, Sodium 2-propylally ioxybenzenesulfonate, Sodium 3-methylallyloxybenzenesulfonate, Potassium methallyloxybenzenesulfonate, potassium 2-ethylallyloxybenzenesulfonate, Sodium 3-ethylallyloxybenzenesulfonate, Sodium 3-propylallyloxybenzenesulfonate.

The superior properties of those according to the method of the invention with methallyloxy compounds Copolymers produced are based on the results of the examples described below and comparison tests clearly visible. These show that the mean improvement is expressed as a percentage Absorption of basic dye, each 1% of the added Acid monomers is greater than that of the comparative compounds examined.

The alkenyloxyarylsulfonic acids of the formula given come in an amount in the range of 0.25 to 10%) based on the total monomer weight, for use. The exact amount depends

809 519/661

3 4

of the intended absorption capacity of the mixture, for example from 80 to 97% acrylonitrile, 1 to

Polymer against basic dyes. 10% of a vinylpyridine or 1-vinylimidazole and

Less than 1%, for example 0.3 to 0.6%, has 1 to 18% of another substance, e.g. B. methacrylic

found to be entirely satisfactory, nitrile or vinyl chloride, in an appropriate amount

The sulfonic acid of the formula given must be 5 to allyloxybenzenesulfonate.

the acrylonitrile before the polymerisation due to The copolymers, produced after the Verder Water solubility of the sulfonate compounds in driving the invention shows an essential Vermonomerer Shape to be mixed. The mixed poly- improvement of the absorption capacity compared to basic ones merisat is no longer water-soluble. It can be any dyes. All kinds of basic or cationic ones Polymerization processes that have hitherto been seen in the io dyes are made satisfactory by them Technique is known to be used, e.g. B. absorbed. Relatively large improvements in the process of bulk polymerization, the solution or the absorption of basic dyes are used polymerization or method of polymerization in a smaller amount of acidic monomer aqueous Emulsion. However, the practical is enough.

Carrying out the suspension polymerization before 15 These polymers can be carried out by known

zugt, in which in a batch process customary methods, such as wet spinning and

the monomers, the aqueous medium, which the required dry spinning procedures, in filaments and fibers

Such a catalyst and the required dispersant are transferred.

contains lubricant, is added. Another invention is illustrated below with reference to FIG Working method forms the semi-continuous process, 20 examples explained in more detail, in which all parts in which the the aqueous medium containing and percentages are based on weight, Polymerization reactor continuously with the unless otherwise specified. The dye wanted Charged monomers and the polymer absorption towards basic dyes (BFA) of the is continuously withdrawn. Acrylonitrile polymers were made using a

The polymerization temperature is between 40 to 25 the method determines at which a basic 6O ⁰ C. Any suitable catalyst system may be used in dye (CI Basic Blue 22). In an amount between 0.1 to 3.0 percent by weight based on this procedure, a buffered solution will be used, e.g. B. water-soluble Peroxyverbindun- (pH 5.4) of the dye with the polymer in a gene, such as potassium, ammonium and other water-sealed tube at 100 ⁰ C for 2 hours, soluble salts of peroxy acids, sodium peroxide, 30 mixed. A ratio of liquid to hydrogen peroxide, sodium perborate and any polymer of 40: 1 was used. After filtration and other water-soluble compound which contains a per-wash, the filtrate was spectrophotometrically oxy-containing. analyzed to determine the amount of residual dye

The acrylonitrile polymers, which determine the practical, from this value the percentage

Carrying out the method according to the invention 35 dye uptake is determined. This is called the

basic dye uptake indicated by polymerization with allyloxybenzenesulfonates,
are produced are binary or ternary copolymers with a content of at least

80 percent by weight of acrylonitrile in the polymer molecule. example 1

For example, the polymer can consist of 80 to 98% 40

Acrylonitrile, 0.5 to 2% of an allyloxybenzenesulfonate. In this example, a semi-continuous

and up to 19.5% of another, the 5C = Ci- polymerisation process used, with the addition

Bond-containing and mixed poly-acrylonitrile with the monomer and initiator during a

merizable monomers are produced. Ger period of! Hours took place. The polymerisation

Suitable monoolefinic monomers are the acrylic * 45 tion vessel was kept at 50 ° C and filled with nitrogen

acid esters, e.g. B. methyl methacrylate, ethyl methacrylate flushed before and during the polymerization. In

lat butyl methacrylate, methoxymethyl methacrylate; the polymerization vessel were 5QO parts of water,

/ Ϊ-chloroethyl methacrylate and the corresponding esters 89 parts of acrylonitrile, 9 parts of vinyl acetate, 2 parts of allyl

of acrylic and α-chloroacrylic acid, vinyl chloride, oxybenzenesulfonate, 2 parts of potassium persulfate and 2 parts

Vinyl bromide, vinylidene chloride, 1-chloro-l-bromoethyr 50 sulfur dioxide (added as sodium bisulfite) einr

len, methacrylonitrile, acrylamide and methacrylamide, brought and mixed together. At the end of

"" Chloracrylamide or monoalkyl substitution pro polymerization reaction became a white polymer

products thereof, methyl vinyl ketone, vinyl carboxylic acid- in 86% yield with a normal specific

ester, e.g. B. vinyl acetate, vinyl chloroacetate, vinylpropio viscosity (rjsp), determined in a 0.1% solution

Nat and vinyl stearate, N-vinylimides, for example N-vinyl 55 obtained in dimethylformamide at 25 ⁰ C of 0.162,

phthalimide, and N-vinylsuccinimide, methylenemalon- This polymer gave a dye uptake of

acid esters, N-vinyl carbazole, vinyl furan, alkyl vinyl 20.7%.

ester, diethyl citraconate, diethyl mesaconate, dimethyl example 2
mesaconate, styrene, vinyl naphthalene, vinyl-substituted

tertiary heterocyclic amines, such as the vinyl pyridines 60 using a semi-continuous poly-

and alkyl substituted vinyl pyridines, e.g. B. 2-vinyl merization process, as in Example 1, were 500

pyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, parts of water, 90 parts of acrylonitrile, 9 parts of vinyl acetate,

1-vinylimidazole and alkyl-substituted 1-vinylimida- 1 part potassium p-methallyloxybenzenesulfonate, 1 part

zole, e.g. B. 2-, 4- or 5-methyl-l-vinylimidazo] and potassium persulfate and 1 part of sulfur dioxide in one

other polymerisation vessel containing rs C = C C bonds was introduced. A 90% discount

convertible monomers. booty of white polymer was obtained, its

Preferred ternary copolymers are made from rj _sv 0.33. This polymer had a recording

Acrylonitrile, methacrylonitrile and 2-vinylpyridine produce a basic dye of 15.5%.

Example 3

A continuous polymerization process was used in this example. The polymerization vessel was charged with 500 parts of water, 90.5 parts of acrylonitrile, 9 parts of vinyl acetate, 0.50 part of sodium p-methallyloxybenzenesulfonate, 1.2 parts of potassium persulfate and 2.4 parts of sulfur dioxide. The average residence time was 60 minutes, and the polymerization temperature was 4O ⁰ C. A yield of 63.3% ^of a white polymer having an _η ερ of 0.170 was obtained. The basic dye uptake of this polymer was 19.0%.

Example4

Using a semi-batch polymerization procedure, a polymer was prepared as indicated below. In a polymerization vessel were placed 500 parts of water, 80 parts of acrylonitrile, 19.5 parts of vinylidene chloride, 0.5 parts of sodium ao p-methallyloxybenzenesulfonate, 2 parts of potassium persulfate, 2 parts of sulfur dioxide and iron in an amount of 0.5 parts per million. After 3 hours at a polymerization temperature of 50 ⁰ C a white polymer in a yield of 74% as was with a viscosity _η βρ of 0.17 obtained. The basic dye uptake of this polymer was 16.1%, determined in the manner described above.

Example 5

In this example, all of the polymers listed in the table below were prepared in a continuous process in a polymerization reactor, a potassium persulfate to sulfur dioxide ratio of 1: 2, a residence time of 60 minutes and a polymerization temperature of 40 ° C. being used. The monomer composition consisted of 9% vinyl acetate, the sulfonic acid given in the table and the remainder to 100% of acrylonitrile. Basic dye uptake determinations were made using the standard test as described above. The basic dye (BFA) _{uptake values} for end groups alone were calculated with reference to the viscosity η ερ and the ratio of potassium persulfate to sulfur.

Investigations have shown that the BFA value of acrylonitrile-vinyl acetate copolymers is related to η _ίρ by the following equation:

+ 0.24

BFA = 2.48 + 0.714

Taking into account the viscosity r \ _{sp of} the polymer, it is therefore possible to determine the proportion of BFA on the basis of the amount of sulfonic acid.

Tabel

0.170 monomers
Sulfonic acid BFA des BFA the BFA monomers BFA pro
Weight percent Λ ft I f I J-ίΊ Il I ± X 1 * 1 ' 1 6.2 I. Weight
percent JrOIy-
merisats End groups Sulfonic acid polymerized
Sulfonic acid Average I 1 Λ Q Na-p-methallyloxy- 0.168 > 10.9 benzenesulfonate 0.5 19.0 10.8 8.2 16.4 L 1OO Na-p-methallyloxy- 0.151 j 12.9 benzenesulfonate 0.5 18.8 10.9 7.9 15.8 Na-p-methallyloxy- 0.192 • 14.4 benzenesulfonate 0.4 17.0 12.3 4.7 11.8 Na-p-methallyloxy- 0.144 10.16 benzenesulfonate 0.161 0.3 13.8 9.7 4.1 13.7 Comparative tests: 0.163 Na methallyl sulfonate 0.171 0.6 16.1 12.9 3.2 5.3 Na methallyl sulfonate 0.163 0.6 15.2 11.4 3.8 6.3 Na methallyl sulfonate 0.142 0.6 15.5 11.3 4.2 7.0 K-vinylbenzenesulfonate 0.166 0.4 15.9 10.8 5.1 12.8 K-vinylbenzenesulfonate 0.4 14.9 11.3 3.6 9.0 Na vinylbenzenesulfonate 0.174 0.4 19.3 13.1 6.2 15.5 Na vinylbenzenesulfonate 0.35 14.7 11.1 3.6 10.3 p-Na-sulfophenyl- 0.162 methacrylamide 0.6 16.0 10.6 5.4 9.0 p-Na-sulfophenyl- 0.162 methacrylamide 0.6 18.3 11.4 6.9 11.5 p-Na-sulfophenyl- 0.152 methacrylamide 0.170 0.6 17.4 11.4 6.0 10.0 Na vinyl oxybenzene sulfonate 0.5 11.5 11.7 0 0 1.0 11.9 10.5 1.4 1.4

An examination of the table above shows that sodium p-methallyloxybenzenesulfonate the previous is clearly superior to other sulfonate monomers in effectiveness in improving BFA.

Claims (2)

Patent claims: 1. Process for the production of acrylonitrile polymers with improved colorability compared to basic dyes by polymerizing a mixture of at least 80 percent by weight Acrylonitrile, 0 to 19.75 weight percent at least one other copolymerizable monoolefinic monomer and 0.25 to 10 percent by weight an alkenyloxyarylsulfonic acid, characterized in that the alkenyloxyarylsulfonic acid a compound of the general formula R ' 0-CH-C = CH. in which R and R 'represent a hydrogen atom or alkyl radicals having 1 to 3 carbon atoms and Y represents Represent alkali metal, is used. 2. The method according to claim 1, characterized in that that the monomers in the desired proportions to an aqueous medium at a Temperature of 40 to 6O ⁰ C in the presence of a water-soluble peroxy compound are added and polymerized. Considered publications:
French Patent No. 1,288,861. 809 519/661 3.68 © Bundesdruckerei Berlin