DE2309603A1 - AMINE SULPHONATES AS COLORS IN SUSPENSION POLYMERS - Google Patents

Description

Aminesulfonates as colored spots in suspension polymers

The invention relates to resins containing sulfo groups which are excellent Adoption for cationic dyes, as well as a new process for making the same.

So far there are various ethylenically unsaturated monomeric compositions copolymerized with simple sulfo-monomers to create polymers which are absorbent are for cationic dyes. However, it is difficult to carry out such copolymerizations in aqueous systems, such as emulsion or suspension systems, because of the solubility of the sulfonated monomers in the aqueous phase. Accordingly, such copolymerizations generally become more costly and more troublesome solvent-solution polymerization systems.

It is therefore an object of the invention to provide new copolymers with good To create acceptability for cationic dyes as well also to create copolymers in which sulfo-containing monomers are present. It also has the invention made the task of creating a process for the production of such a resin that can be used in aqueous systems, such as emulsion or suspension systems.

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Summary of the invention

The above and other objects are achieved in one according to the invention A process which comprises the free radical initiated copolymerization of a mixture in aqueous suspension, the mixture containing:

Table I. Parts by weight

(I) an ethylenically unsaturated monomer or mixture thereof Monomer

and

(II) an amine sulfonate salt of. 0.1-10.0 (II-a) a sulfo group-containing,

ethylenically unsaturated monomers
with

(II-b) a primary, secondary or tertiary containing higher alkyl groups Amino compound

A particularly preferred embodiment of the method of the invention involves the copolymerization of

Table II Parts by weight

(I) containing an ethylenically unsaturated monomer or mixture of monomers

(Ia) vinyl chloride 10-100 parts) (II-a) a third monomer or <. , . ~~

) all in all

Mixture of monomers,) copolymerizable with) Vinyl chloride 0-90 parts)

(II) an aminesulfonate salt as in

Table I 0.1-10.0

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The polymerization proceeds smoothly, effectively introducing the aminesulfonate salt II into the copolymer. The products show excellent Ability to accept cationic dyes and can-r can be molded into films, threads and molded parts.

Description of the preferred embodiments The sulfonic acid group-containing monomer (II-a)

The compound containing sulfonic acid groups, which is the anionic Creates novelty of the above salt (II) can be any compound of the formula

(II-a)

K at i oi

U-SO

₂
0

be in which

U is an ethylenically unsaturated group with one for copolymerization has adequate activity with the other monomers in the mixture, and

an hydrogen ion or suitable metallic ion
is. It can be seen that suitable compounds of this type are any
includes allyl or vinyl-containing alkyl or aryl sulfonic acid, for example styrene sulfonic acid, vinyl sulfonic acid, sulfoethyl methacrylate, 2-acrylamido-2-methylpropane sulfonic acid, methyl sulfonic acid,
^ -Iviethylstyrene sulfonic acid, Al IyI sulfonic acid, o-methylstyrene sulfonic acid, sulfoethyl acrylate, 2-acrylamido-2-methylbutane sulfonic acid, vinyl benzyl sulfonic acid. In general it exists
The criterion that the sulfo group-containing compound is suitable copolymerizable with typical commercial monomers is that it should be copolymerizable with vinyl chloride, since most monomers are in the same general reactivity range, as a rough rule, the criterion for the copolymerizability of the SuIfο connection with vinyl chloride (and expanding with most of the other monomers of Hanael) in that, on a mole basis, an initial charge of 90%

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Vinyl chloride, reads Comonomeres, is intended to give an initial copolymer which (a) contains at least 8üyo vinyl chloride and (b) not more than 99% vinyl chloride.

The amino compounds containing higher alkyl groups - (II-b)

The higher fatty amino compound, hereinafter referred to as (II-b), which provides the cationic half of the salt (II), can be any compound which has a primary, secondary or tertiary amine group and a higher alkyl group or groups which total 8 to Have 30 carbon atoms, contains, for example Üctyldecylamine, li-Goco - ^ - amino-butyric acid ("Coco" denotes the mixed ^ llryl groups with an average of about 12 carbon atoms, which are derived from coconut oil), n-Üctylamine, laurylamine, octadecylamine, hexadecylamine, iN-coco-.i-amino-propionic acid, di-2-ethylhexyl-amine, di-cyclo-hexylamine, n-laaryl-inr.'ristyl-ß-amino-propionic acid, dimethyl-octylamine, dimethyl-1-aurylamine, dimethyl- tetradecyl-amine, dimethyl-hexadecyl-amine, dimethyl-octadecyl-amine, dimethyl-behenyl-amine, tributylamine, triamylamine, methyl-methyl-octyl-aniine, dilaurylamine, behenylamine, diamylamine, ethyl-c7v ^r clohexyl-amine , long-chain ethanolamines and long-chain ethoxylated amines.

The ^ minsalz II

The amine sulfonate salt monomer (II) can be any salt, its isation of the sulfo compound (II-a) and the amino compound (II-b) is derived. if the monomeric compound is not available as such, it can easily be prepared by a sodium or other salt of sulfonic acid (II-a) with the amino compound is used in an acidified aqueous medium (II-b) implemented. The resulting monomeric salt compound is precipitated and can be obtained by filtration or decantation and then used in the polymerization reaction. Since aqueous media are included, the itionomer (H) optionally in situ in the aqueous medium in which the final Polymerization takes place, are produced. According to Another method is dacinin (II-b), sulfonic acid

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(II-a) and a small amount of water to the monomer or monomers, with which the salt (II) is to be copolymerized, added. The salt (II) is formed directly and quickly dissolves in the or the monomers, whichever is the case.

The Ethylenically Unsaturated Monomer (I)

As shown in the "Summary of the Invention" in Table II above, the preferred products are made from copolymers of the amine sulfonate salts II with vinyl chloride and mixtures of vinyl chloride with third monomers. As such a third monomer, acrylonitrile provides particularly excellent products when it is used in a weight ratio of 90-10 parts of acrylonitrile and 10-90 parts of vinyl chloride. However, other monomers can be used either in admixture with vinyl chloride and / or acrylonitrile or in the absence of these compounds. Examples of such other monomers include vinyl acetate, styrene, methacrylates such as diethyl methacrylate, di (2-ethylhexyl) methacrylate, acrylates such as ethyl acrylate, ethyl vinyl ether, methyl vinyl ketone, vinylidene chloride, vinylidene bromide, vinylidene fluorochloride and the like, unsaturated hydrocarbons such as ethylene, Propylene, isobutene and the like, allyl compounds such as allyl acetate, allyl chloride, allyl ethyl ether and the like, as well as conjugated and cross-conjugated compounds such as butadiene, isoprene, chloroprene, 2,3-dimethylbutadiene-1,3, piperylene, Divinyl ketone and the like ”As set forth above in the discussion of sulfo compound (II-a), the most useful monomer activities have activities in the same general range and are copolymerizable with vinyl chloride; thus it can be said that any monomer copolymerizable with vinyl chloride can be used in the invention with or without vinyl chloride. For a fairly complete list of substances known to copolymerize with vinyl chloride, see Krczil "Kurzes Handbuch der Polymerisierungstechnik-II, Mehrstof f-Polymerisierung", Edard Bros., Inc. 194-5 »pages 735-7 ^ 7 »under" Vinyl Chloride ". As a rough He; ~ el is the Lriterium for a practical application comonomer to Ve with vinyl chloride to produce copolymers WEL

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before 80% or more vinyl chloride contained in the fact that, on a mole% basis, an initial charge of 96% vinyl chloride, Re st comonomer to result in an initial copolymer containing (a) at least 90% of vinyl chloride and (b) does not contains more than 99% vinyl chloride.

The polymerization process

The polymerization process of the invention is carried out in suspension in an aqueous medium containing a <uspendiermittel from the colloidal type, and a free radical generating agent which is soluble in the monomer phase. The mass is agitated to keep the monomer in suspension as globules in the songium, and the product is recovered as granules which are physically separated from the aqueous medium as the polymerization proceeds. The aminesulfonate salt (II) can either have been prepared beforehand and added as such to the polymerization reaction mixture or it can be synthesized in situ in the polymerization mass by adding the constituents (the sulfonic acid II-a or a salt thereof and the ^ mino compound II-b ) introduced into the polymerization medium in stoichiometric proportions. Optionally, the amine (II-b), the sulfonic acid (II-a) and a small amount of water are added to the other monomers and thus agitated. The reaction starts practically instantaneously and quantitatively. Preferably, the medium should be acidified slightly, such as by adding acetic acid, to ensure reaction. In cases where the polymerization rates of the different monomers are not the same, it may be desirable to add the faster polymerizing monomers in portions during the polymerization in order to keep their effective concentration constant. For example, the effective concentration of vinyl chloride or other monomers which are volatile at the polymerization temperature can be kept constant by an isobaric reaction process, the vapor of the volatile monomer being continuously supplied at a constant pressure so that the pressure flows into the reactor as required by the ongoing polymerization.

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After the general discussion above, detailed information follows Explanation of the invention at ;;: · All parts and percentages are based on weight, unless otherwise stated.

.Example 1 Copolymers without a third monomer

water (deionized) 200 g

Vinyl chloride 100 g

LcLuroyl peroxide 1.5 g

ketnyicellulose (100 Gentipoise) 2.0 g

Ethylenically unsaturated sulfo compounds see Table III (see Table III)

Compounds containing higher alkyl groups, see Table III (see Table III

A number of experiments were carried out according to the above plan, where different ^ ulfonic acid ^ minoverbindungen in the individual experiments as listed in Table III. In each case, the sulfo compound and the amino compound were ": the selected T pen and quantities for the experiment with the asfer and methylcellulose in a polymerisation bottle filled. The .nasser was slightly acidified with acetic acid and the contents shaken. The reaction started practically immediately and the ouino salt of the oulfo compound separated turn out to be oily globules. There was then a slight excess filled in by vinyl chloride compared to the Kezept amount and on the amount of recipe allowed to evaporate (determined by empty weight and Carriage back), whereby the free space in the bottle was cleaned. The bottle was then fitted with a ron cap, which is a Jicatuns made of nitrile rubber and a perforation for the injection the action participant over, ate, closed. Then became the jjiiuroyl peroxide indexed and the bottle on a polymerization wheel placed, which immersed the bottle for 18 hours in a .i.-eat-.r bath of 50 ° 0 and circulated it, ^ at the end of this After a while, the unreacted monomers were drained into the bottle opened and the granular polymer filtered off and put on the filter washed with deionized water. Jas Polymers was then on

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a tray in an oven at 12O ⁰ C 24 hours dried.

Each resin was dissolved in cyclohexanone to form a 10% solution and cast as a film on a glass plate using a 10/1000 inch applicator stick. The film was dried on the plate in an oven at 130 ^° C. for 15 minutes and then stripped off. The IiIm was then tested for cationic dye acceptance by immersing it in a dye bath of the following composition for 15 minutes:

Water (with sodium acetate to pH 4.0 1000 ml

buffered)

Cationic dye 0.1 g

("Sevron Red GL", a product of EI duPont de Nemours & Co.)
cooked.
Excellent color shades were obtained in each case.

There will be the types and amounts of sulfo compounds and higher Alkyl-containing amino compounds that were used in the various experiments compiled.

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- 9 Table III

Ethylenically unsaturated

SuIfο connection

Amino compound

with higher alkyl group

VersJfc

Type

Sodium styrene

sulfonate

used Type g, used

N-coco-ß-amino-2.0 propionic acid 2.0

Sodium Methal1y1- 2.0 Octyl decyl 2.2 2 sulfonate amine Sodium vinyl 2.0 2.2 3 sulfonate 2.0 the same thing 2.2 4th SuIfäthylmethacrylat the same thing 2-acrylamido-2-methyl- 2.0 2.2 propanesulfonic acid the same thing

Example 2

Terpolymers with acrylonitrile varying amounts of amine sulfonate

V / ater (deionized) vinyl chloride
Acrylonitrile
Sodium styrene sulfonate

N-coco-fi-aminobutyric acid

Methyl cellulose (100 centipoise) azoisobutyronitrile

G G G

0.5 g (see Table IV)

0.5 S

(see Table IV) 2.0 g 1.5 g

None of the polymerization experiments were carried out according to the above schedule, using the sodium styrene sulfonate and the N-coco-ß-

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aminobutyric acid varied from one run to another as shown in Table IV below. In any case it followed the polymerization process and film coloring process of Example 1 with the difference that the polymerization at 60 ° C instead of 50 C. The dyeability of the film was subjectively rated on a 0-10 scale, with "0" meaning no dye uptake and "10" meaning the film is colored in a very deep shade. Details of the various attempts are given below.

Table IV

Attempt no.

Sodium styrene sulfonate 0.0 2.0 0.0 0.1 2.0 5.0 used, g

N-coco-β-aminobutyric acid, 0.0 0.0 2.0 0.1 2.0 5.0 used, g

Coloring rating 0.0 2 0 2 7

It can be seen that the sodium styrene sulfonate alone is essentially Proportions (Trial 2) gave only a modest improvement in dye uptake, but even if only very small proportions both styrene sulfonate and N-coco-ß-aminobutyric acid were used, an equal level of dye uptake was achieved (Run 4). <Venn more substantial proportions of these two Components were used, a very remarkable improvement was achieved (Trials 5 and 6).

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Example 3 Mixed monomers

Water (deionized) 200 g

monomeric composition 100 g

(see table V)

Methyl cellulose (100 gentipoise) 2.0 g

Lauroyl peroxide 1.5 g

Octyl-decyl-amine 0 or 2.0 g

(see Table V) 2- acrylamido-2-methyl-

propanesulfonic acid 0 or 2.0 g

("AiiPS" in Table V) (see Table V)

A series of polymerization runs were carried out using various monomer compositions as shown in Table V below is listed, performed, with some being the aminesulfonate salt contained and some did not. The procedure of Example 1 was followed, with the difference, of course, that the formation of the aminesulfonate salt has been omitted when its precursors (Octyl-decyl-amine and 2-acrylamido-2-methyl-propanesulfonic acid in Table V) have been omitted. The following are details of the various Try.

Tabel V 1 2 ? Gram in experiment no. 6th 7th 8th Monomer used 100 96 81 4th 5 0 0 0 0 0 15th 85 0 0 0 0 Vinyl chloride 0 0 0 15th 0 96 0 0 Vinyl acetate 0 0 0 0 100 0 100 96 otyrol 0 2 '2 0 0 2 0 2 Methyl methacrylate 0 2 2 0 0 2 0 2 "AMPS" 0 6th 7th 0 0 6th 0 8th Octyl-decyl-amine 1 0 Staining rating

It can be seen that a variety of monomers besides vinyl chloride (Vinyl acetate, styrene, methyl methacrylate, experiments 3 » G and 8) can be used in the invention with good results

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40 s S. 60 g e 2.0 G 2.0 S. 0.1 ε 1.0 G 0.2 200.0

can. You can also see that good dyeing ability with use of the aminesulfo salt (Runs 2, 3, 6 and 8) was obtained in contrast to the poor results in their absence (Trial 1, 4, 5 and 7).

Example 4

Vinyl chloride

Acrylonitrile

Vinyl sulfonic acid Dimethyl-hexadecyl-amine butyl mercaptan Azoisobutyronitrile partially hydrolyzed polyvinyl alcohol water

Temperature - 65 ° C

The vinyl sulfonic acid became the acrylonitrile in which it was did not come off, added. There were then 5 parts of water and all of the amine added and stirred. Upon gentle heating, the amine salt formed and uniformly dissolved in it Acrylonitrile.

The water, the polyvinyl alcohol, the azoisobutyronitrile, mercaptan, Vinyl chloride and 20 g of the acrylonitrile amine salt solution were placed in a 2 liter moving glass autoclave with was equipped with a heating and cooling jacket, filled.

The polymerization was initiated and maintained at 65 ° G. The remaining acrylonitrile-amine salt mixture was pumped into the reaction vessel in such a way that a constant pressure or isobaric Polymerization was maintained until it was completely consumed. The polymer was cooled, drained and placed in the ordinary v / ice isolated. The polymer was in 10 ^ -igem Dime thy1sulfoxyd dissolved and spun into fibers. The ability to dye was excellent.

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From the previous general description and the detailed Specific examples, it is seen that the invention enables the preparation of resins with excellent coloring properties from a great variety of monomeric substances in the enables highly economical aqueous polymerization systems. The key ingredient involved is the amine salt the unsaturated, sulfonic acid group-containing compound, which is used in smaller proportions and cheap and can be reliably obtained.

According to the invention, ethylenically unsaturated compounds and in particular vinyl chloride and mixtures which vinyl chloride and acrylonitrile, in aqueous suspension with salts of (a) sulfonic acids, which are polymerizable, ethylenic Containing groups, copolymerized with (b) amino compounds containing higher alkyl groups. The resulting copolymers have excellent ability to absorb cationic dyes and are useful in filaments, films and molded articles.

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Claims (1)

Claims \ y. A copolymerization process for the preparation of a dye-accepting polymeric product, characterized in that one Parts by weight (I) an ethylenically unsaturated monomer 100
or mixture of monomers (II) an amine sulfonate salt 0.1-10.0 of (II-a) one containing sulfo groups ethylenically unsaturated monomers
with (II-b) one containing higher alkyl groups
primary, secondary or tertiary
Amino compound in an aqueous suspension system in the presence of a free
Free radical initiator copolymerized. 2. The method according to claim 1, characterized in that the ethylenically unsaturated monomer is vinyl chloride. 3. The method according to claim 1, characterized in that the ethylenically unsaturated monomer mixture is a mixture of 95-5
Parts by weight of vinyl chloride and 5-95 parts by weight of acrylonitrile. 4. The method according to claim 1, characterized in that the amine is a primary amine. 5. Verfanren according to claim 1, characterized in that the amine is a secondary amine. 6. The method according to claim 1, characterized in that the amine is a tertiary amine. 309839/1094 7. The method according to claim 1, characterized in that the Unsaturated monomers containing sulfo groups, styrene sulfonic acid is. 8. The method according to claim 1, characterized in that the monomer containing sulfo groups is 2-acrylamido-2-methylpropanesulfonic acid is. 9. £ highly dye accepting copolymer Weight point (I) an ethylenically unsaturated monomer or mixture of monomers with (II) an aminesulfonate salt 0.1-10.0 from (II-a) a sulfo group containing, ethylenically unsaturated monomers with (II-b) a primary, secondary or tertiary containing higher alkyl groups Amino compound 10. Copolymer according to claim 9 »characterized in that the unsaturated monomer is vinyl chloride. 11. Copolymer according to claim 9 »characterized in that the mixture of monomers contains 95-5 parts of vinyl chloride and 5-95 parts of acrylonitrile. 12. Dine highly dye-accepting film made from the copolymer of claim 9 13 · -iiin highly dye-accepting thread from the copolymer of claim 9 309839/1094 14. A highly dye accepting film made from the copolymer of claim 9. 15 · The method according to claim 1 to 8, characterized in that that the monomers are fed by an isobaric feed process will. 309839/1094