DE2031136A1 - Reactive acrylic polymers - contg 2(beta aminoethyl mercapto - sulphinyl or sulphonylethyl groups - Google Patents

Abstract

The polymers pref. having K value of 30-100, contain units:- where X is -S-, -SO- and/or -SO2-; R is H or methyl; R1 is H, methyl or phenyl; R2, R3 are H, alkyl, cycloalkyl, aralkyl and/or aryl and together can form part of a cycle. They are obtained by reaction of substituted ethyl acrylates and olefinically unsaturated monomers. Used as mouldings, coatings, adhesives or for paper and textile treatments, the polymers are easy to dye and are surface active and antistatic.

Description

2- [ß-Amino-ethyl-mercapto] -ethyl-, 2- [ß-Amino-ethyl-sulfinyl] -ethyl- or polymers bearing 2- [ß-amino-ethyl-sulfonyl] -ethyl groups. The invention relates to optionally substituted 2-Lß-aminoethyl-mercapto] -ethyl-, 2- [ß-amino-ethyl-sulfinyl] -ethyl- and / or 2- [ß-amino-ethyl-sulfonyl] -ethyl groups in the substituents Polymers and processes for the preparation of these polymers from appropriately substituted Methacrylic and / or acrylic acid ethyl esters.

Homo- and copolymers of acrylic or methacrylic esters with preferably 1 to 4 carbon atoms in the alcohol residue are known. The alcoholic leftovers can however, also contain heteroatoms such as N, P, O and / or halogen atoms or double bonds.

Such acrylic or methacrylic esters are for example in H. Rausch-Puntigam, T. Volker "Acrylic and methacrylic compounds Springer-Verlag, Berlin, Heidelberg, New York (1967) p. 336 ff.

described.

Despite the large number of known acrylate-containing polymers existed the task of developing cation-active, nitrogen- and sulfur-containing polymers, which are reactive due to the amino group or the mercapto, sulfinyl or sulfonyl radicals are.

The invention relates to polymerization products with X values of 30 to 100 which contain units of the formula I. in which X is an -S-, -SO- and / or -S02 bridge member, R is a hydrogen atom and / or a methyl group, R1 is a hydrogen atom, a methyl and / or phenyl group, R2 and R3 is a hydrogen atom, a methyl, Cycloalkyl, aralkyl and / or aryl groups or R2 and R3 together are components of a ring system.

Due to the optionally substituted amino group or the mercapto, These polymers are reactive and, if appropriate, sulfinyl and / or sulfonyl radicals accessible to further reactions.

The polymers according to the invention are obtained by homo- or copolymerization of a) acrylic esters of the formula II in which X, R9, R1, R2 and R3 have the meaning given above, and optionally b) one or more other olefinically unsaturated monomers in the presence of initiators which form free radicals.

As acrylates of the formula II, substituted ethyl esters are thus used Acrylic or methacrylic acid used The esters may contain, in addition to terminal ones N-mono or N9N-disubstituted amino groups as bridge members X divalent -S-, -SO- or -S02 residues.

Suitable acrylates or methacrylates containing mercapto groups are 2- [ß-amino-ethyl-mercapto] -1-methyl-ethyl acrylate or methacrylate, 2- [ß-amino-ethyl-mercapto-1-phenyl-ethyl acrylate or methacrylate and preferably 2-β-amino-ethyl-mercapto-ethyl acrylate or methacrylate as sulfinyl groups Acrylates or methacrylates are used: 2- [ß-Amino-ethy] @sulfinyl] -1-methyl-ethyl-acrylate or methacrylate, 2- [ß-amino-ethyl-sulfinyl] -1-phenyl-ethyl-acrylate or

methacrylate and preferably 2- [ß-amino-ethyl-sulfinyl] -ethyl acrylate or methacrylate.

The acrylates or methacrylate containing sulfonyl groups are 2- [ß-amino-ethyl-sulfonyl] -1-methyl-ethyl acrylate or methacrylate, 2- [ß-amino-ethyl-sulfonyl] -1-phenyl-ethyl-acrylate or

methacrylate and preferably 2-β-amino-ethyl-sulfonyl-ethyl acrylate or methacrylate into consideration.

The compounds mentioned can optionally be attached to the amino group with the radical R2 N-mono- or the radicals R2 and R3 N, N-disubstituted. The rest R2 and R3 can also jointly be components of a ring system.

In addition to hydrogen, the following may be mentioned as substituents R2 and R3: radicals with 6 to 12 carbon atoms of cycloaliphatics, such as cyclohexane, cyclooctane, of Aryl aliphatics, such as toluene or ethylbenzene, of aromatics, such as benzene, naphthalene or diphenyl. R2 and R3 preferably stand for aliphatic radicals with 1 to 10 Carbon atoms, such as propyl, isopropyl, n-butyl, tert-butyl, hexyl, 2-ethyl-hexyl, heptyl, octyl and preferably methyl and ethyl radicals.

Polymers with advantageous properties also produce such acrylates or methacrylates, in which the substituents R2 and R3 together with the nitrogen atom form a ring system. Ring systems such as piperidine, piperazine, N-methyl-piperazine or morpholine. Such monomers are therefore also preferred used.

Suitable substituted acrylic acid or methacrylic acid ethyl esters are for example: H 0112 = CH - CO - OCH2CH2 - S - CH2C 2 - CH3 OH 0112 = CH - CO - OCH2CH2 - SO - 0H20H2 - 2 5 \ 2H5 0112 = CH - CO - OCH2CH2 - S02 - CH2CH2 - 3H7 Acrylic or methacrylic acid esters of the formula II are produced, for example, by esterification of methacrylic acid or acrylic acid with optionally substituted 2- [ß-amino-ethyl-mercapto] -ethanols, 2- [ß-amino-ethyl-sulfinyl] -ethanols or 2- Amino-ethyl sulfonyl] -ethanols prepared by customary methods. The alcohols are obtained, for example, by adding ammonia or amines to optionally substituted 2-hydroxy-ethyl vinyl sulfides, 2-hydroxy-ethyl vinyl sulfoxides or 2-hydroxy-ethyl vinyl sulfones.

The monomers of the formula II mentioned can each be used on their own are polymerized. It is of course also possible to use mixtures of different to copolymerize these compounds. Besides, they are subject to copolymerization accessible with other olefinically unsaturated monomers.

Suitable olefinically unsaturated monomers, optionally with the ß-amino-ethyl-mercapto, ß-amino-ethyl-sulfinyl or ß-amino-ethyl-sulfonyl groups bearing ethyl (meth) acrylates of the formula Ii can be copolymerized, are for example olefins such as ethylene, butadiene, isoprene; Styrene and substituted Styrenes such as α-methylstyrene, p-chlorostyrene and p-methylstyrene; Acrylic esters and methacrylic esters, in particular those with 1 to 18, preferably 1 to 8 carbon atoms in the alcohol residue, belapiela way Acrylic or methacrylic esters of methanol, butanols, Ethylcyclohexanol or 2,3-dibromopropanol; Acrylic and methacrylic acid amide and substituted Amides, such as N-methylolacrylamide, or their ethers, such as N-methylolacrylamide butyl ether, N-methylol methacrylamide methyl ether; Acrylic and methacrylonitrile; Vinyl ester, like Vinyl acetate, vinyl propionate; Vinyl ethers, such as methyl, ethyl or alkyl vinyl ethers with alkyl radicals having 3 to 6 carbon atoms; also fumaric, maleic or itaconic acid, Esters of these acids with alcohols having 1 to 20 carbon atoms and maleic anhydride. Two or more of the abovementioned compounds can also be used at the same time with the mentioned acrylates or. Methacrylates of the formula II are copolymerized.

For the production of copolymers, the proportion of methacrylates or acrylates of the formula II in the monomer mixture vary within wide limits, for example between 1 and 99, in particular between 10 and 90, preferably between 20 and 65% by weight, based on the total weight of the monomers.

The usual free radicals are used to initiate the polymerization Initiators used. Suitable initiators are, for example, hydrogen peroxide, organic hydroperoxides and peroxides, such as caproyl peroxide, lauroyl peroxide, t-butyl perbenzoate, Dicumyl peroxide, p-menthane hydroperoxide, cumene hydroperoxide, succinic acid peroxide, also aliphatic azo compounds which decompose into radicals under polymerization conditions, such as 2,2'-azobis-2,4-dimethyl-valeronitrile, 2,2'-azo-bis-isobutyronitrile and the like Azonitriles, for example in J. Hine "Reactivity and Mechanism in Organic Chemie ", Verlag Georg Thieme, Stuttgart (1960), page 412, are listed, as well as Customary redox catalyst systems, such as the potassium or ammonium persulfate systems and ascorbic acid, sodium hydrosulfite or ferrous salts.

The chelates of known as radical formers are also suitable Transition metals, especially those in which the metal is in an unusual Valence is present, such as chelates of manganese (III), cobalt (III), copper (II) and cerium (IV). In general 1,3-dicarbonyl compounds are used as chelating agents used.

Examples are manganese (III) acetylacetonate and cobalt (III) acetoacetic ester.

The initiators are generally used in an amount from 0.05 to 5% by weight, preferably 0.1 to 1.0% by weight, based on the amount of monomers, is used. The optimal amount and the optimally effective initiator can be determined by experiments easy to determine.

The polymerization can be carried out in bulk. Advantageous however, one works in the presence of solvents or diluents. Suitable are for example alcohols such as methanol, ethanol, propanol, or isopropanol Butanol; Ketones such as methyl ethyl or methyl propyl ketone; Ethers, such as tetrahydrofuran or dioxane aliphatic, cycloaliphatic or aromatic hydrocarbons, such as heptane, hexane, cyclohexane or benzene. Pormamide and dimethylformamide are also very suitable.

Water is advantageously used as a diluting agent.

Those common for a variety of other monomers or mixtures of monomers Suspension, solution or emulsion polymerization processes are also for the new Procedure suitable. Also with regard to the aids that may be used, such as A distinction is made between buffer substances, dispersants, protective colloids and the like the new procedure is not familiar from it.

The polymerization can take place in a wide temperature range, for example between Oo and 15,000, preferably 500 to 12,000 with reaction times of 1 to 20 hours, preferably carried out for 2 to 8 hours. One generally works at Atmospheric pressure, but higher pressures, for example up to 3000 atü can be applied. In particular in the case of copolymerizations with low-boiling comonomers the use of higher pressures is indicated to ensure sufficient concentration to effect the comonomer in the reaction mixture.

Copolymerization of acrylates or methacrylates of the formula II with ethylene or butadiene is advantageously carried out in emulsion by using the monomers copolymerizable with one another into an aqueous, preferably emulsifier-containing Emulsion that one Initiator, a buffer system and optionally contains a protective colloid, introduces and at increased pressure, with ethylene as comonomers Approximately until 2000 atmospheric polymer dissipates.

The polymers according to the invention, the K values from 30 to 100, preferably from 40 to 80 are easy to color. For example, they will be used for the Manufacture of moldings, coatings or adhesives, also mixed with others Plastics, e.g. polyethylene, polypropylene or with copolymers made of vinyl acetate and ethylene are used. Because of their surface-active and antistatic properties the polymers are also suitable, among other things, for the finishing of paper and textiles. They can also be used to produce reactive paints.

The parts and percentages given in the examples relate to the weight.

The values were each 1% in dimethylformamide according to the specification determined by H. Fikentscher, Cellulosechemie 13, 58 (1932).

example 1 CH3 100 parts CH2 = CH - 000 - CH2CH2 - SO - CH2CH2N '3 CH3 and 0.1 part of azo-bis-isobutyronitrile are heated to 60 ° C. for 4 hours with stirring under a nitrogen atmosphere.

After precipitation with methanol, washing out with methanol and drying, 90.5 parts of a polymer with a K value of 62 are obtained, which has a glass transition temperature TG of -10 ° C and a refractive index @ 20 @@@ @ @@@ @@@ of 1.612 has. Example 2 H3 example 2 10 parts CH2 = C - 000 - CH2CH2 - S »- 0H20112 - are heated to 70 ° C. for 5 hours with 90 parts of ethyl acrylate and 0.5 part of azo-bisisobutyronitrile in 100 parts of isopropanol. A 50% strength polymer solution is obtained. The copolymer contains a content of polymerized 2- g -morpholino-ethyl-mercapto] -ethyl methacrylate of approx. 10% by weight, a K value of 76.5 and a glass transition temperature TG of -12 ° C. CH example 3 10 parts CH2 = b 000 - CH2CH2 - 5 - 01120112 29 are heated to 75 ° C for 6 hours with 90 parts of styrene and 0.3 part of azo-bis-isobutyronitrile. After precipitation with methanol, 98 parts of a copolymer with a K value of 64 and a glass transition temperature TG of 880 ° C. are obtained. The proportion of polymerized 2- [ß-morpholino-ethyl-mercapto] -ethyl methacrylate is approx. 12% by weight.

Examples 4 to 10 If the procedure is analogous to that of Example 1, but the reactants vary, the following polymers are obtained: hh IC) o r1 em Q % Pa h rl tr IO w is d. WH C! AMHH MP, H ax v tdJ O av @ I wH M aH ¢ sv M rl a) a h Eq 0 O O v H a H H H H O bD H O O H Ln ooo co ooo oooo rrr Ln cn o "cu cJ o \ Ln O Cc ul in o 5 CH2 = CH-COO-CH2CH2-5O2-CH2CH2-N (C2H5) 2 100 -. o 94 +8 \ 0 m $ O o Lf II + f 6 CH2 = CHCCOCH2CH2SCH2CH2N {M / H 10 CH2 = CH-COOC4H9 90 98 -48 72 9.5 OO ç CD OO «) OH3 7 CH2 = CHC00CH2CH2SCH2CH2N \ 10 styrene 90 85 +90 56 8 ç O th u-F9 I. C6H 90 8 CH2 = CH-COO-CH2CH2-5-CH2CH I 10 CH2 = CHC00CH2? HH2 100 +10 59 10 Br CM u W C6H5 oo uo u I. o X 9 CH2 =? C00CH2CH2S0CH2CH2i½ 100 hv I CH3 u W o CH2 =? CO0 100 oo 87 oo oorvoo OH3 vn V <) wl ¢ JQ) > J VaxV VuwV t mv N (M Cl VV N p: t VVVN m v vt wN mN mcq vv, cq vvv IN oo III oo NNNC \ JNNN mmmmwmm vvvvvv O OJ N CM CxJ N vm mv VW m tv wN mN VV OOOOO OOC) OOO ° VVVVVO ° vvvm Mv vv vOl-vo il 11 11 11 ll ll 11 V VN VVVVV +> CO OO Example 11 A. Preparation of 2-N, N-dimethylamino-ethyl-2-hydroxy-ethyl sulfoxide.

A solution of 250 parts of benzene and 12 parts of 2-hydroxy-ethyl vinyl sulfoxide and 4.5 parts of dimethylamine is added in the presence of 0.1 part of p-toluenesulfochloride Heated to 70 ° C for 3 hours. After distilling off the solvent and distillation of the crude product under reduced pressure, 15.3 parts (by weight) of 2N-CH2CH2-SO-CH2CH20H are obtained with a boiling point of 64 ° to 70 ° C 0.1 mm Hg. The elemental analysis gives the following Values: S found: 38.6% calc .: 38.8%; N found: 8.3% calc .: 8.5%.

B. Production of 2-N, N-diethylamino-ethyl-2-hydroxy-ethyl sulfone.

A solution of 250 parts of benzene and 13.6 parts of 2-hydroxy-ethylvinyl-sulfone and 5.8 parts of diethylamine is added in the presence of 0.1 part of p-toluenesulfonyl chloride Heated to 70 ° C for 3 hours. After distilling off the solvent and distillation of the crude product under reduced pressure, 16.5 parts (H502) 2N-CH2CX2-SO2-CH2CH20H are obtained with a boiling point of 780 to 83 C 0.1 mm Hg. The elemental analysis gives the following Values: S found: 34.4 calc .: 35.0; N found: 7.1% calc .: 7.2%.

C. Preparation of 2- [ß-N, N-dimethylamino-ethyl-sulfinyl] -ethyl acrylate.

Acrylic acid methyl ester and ß-N, N-dimethylamino-ethyl-2-hydroxyethyl sulfoxide are obtained in a molar ratio of 1: 1 in the presence of 0.1% aluminum isopropoxide reacted to the weight of the methyl acrylate by customary methods. That Acrylate, which is purified by distillation under reduced pressure, possesses @ a boiling point of 170 ° C / 2 mm Hg, a 20 refractive index ND of 1.5425 and a Sulfur content. of 14.3 ß calculates 14.6 46).

Claims (3)

Claims 1. Polymers bearing 2- [ß-amino-ethyl-mercapto] -ethyl, 2- [ß-amino-ethyl-sulfinyl] -ethyl and / or 2- [ß-amino-ethyl-sulfonyl] -ethyl groups with K values from 30 to 100, containing units of the formula I. in which X is a -S-, -SO- and / or -502 bridge member, R is a hydrogen atom and / or a methyl group, R1 is a hydrogen atom, a methyl and / or phenyl group, R2 and R3 are each a hydrogen atom, an alkyl group , Cycloalkyl, aralkyl and / or aryl groups or R2 and R3 together are components of a ring system. 2. Polymers according to claim 1 with K values from 30 to 100 consisting of units of the formulas Ia, Ib or Ic in which R, R1, R2 and R3 have the meaning given above. 3. Homopolymers or copolymers according to Claim 1 or 2 obtained by polymerizing a) substituted ethyl acrylates of the formula II in which X, R, R1, R2 and R3 have the abovementioned meaning, and optionally b) one or more other olefinically unsaturated monomers. Process for the preparation of optionally substituted 2- [ß-amino-ethyl-mercapto] -ethyl-, 2- [ß-amino-ethyl-sulfinyl] -ethyl- and / or 2- [ß-amino-ethyl-sulfonyl] - äthylgrup-bearing polymers, characterized in that acrylic esters of the formula II in which X, R, R19, R2 and R3 have the abovementioned meaning, polymerized alone or together with other olefinically unsaturated monomers in the presence of initiators which form free radicals.