IL25444A - Polymerisable carboxylic acid arylmethylamides,polymerisation products,and process for the manufacture of these compounds - Google Patents

Description

25444 3 New polymerisable carboxylic acid arylmethylaffiides, new polymerisation products, and process for the manufacture : of these compounds CI3A LIMITED C: 24238 The invention consists in new earboxylic acid arylmethylamides which may be optionally etherified and have the general formula . - Ar - D OH o wherein D is a grou -CH2-HH-C-R where R is an ethylenically unsaturated radical of 2 to 4 carbon atoms, is hydrogen or has the same meaning as D : and Ar is a benzene or naphthalene radical optionally further substituted with alkyl, alkoxy, halogen, trirfluoromotk- , alkyl-S^ carboxy¾A-e aeid, nitro or hydroxy groups.

The above earboxylic acid amides are compounds in which a residue of a monocarboxylic acid methylamide is bonded to a hydroxyaryl residue, or compounds in which two residues of a monocarboxylic acid methylamide are bonded to a hydroxyaryl residue represented, for example, by one of the following formulae HO —-Ar—R9Qr*—m—~Q——ii* II *· ft 0 in which R' denotes an ethylenically unsaturated residue having 2 to 3 carbon atoms and Ar denotes an aromatic residue bonded to the -CH„ group b a ring carbon atom; or in which R* and Ar have the same meaning as in formula II.

A specific example of the compound of formula II is the compound The new carboxylic acid amides of formula I above are produced by reacting a N-methylolamide o an ethylenically unsaturated polymerisable acid i an acid reaction medium with an optionally etherified hydroxyaryl compound.

Depending on the selection of the starting substances and the ratio of the molecular amounts of the reaction components, carboxylic acid amides of formulae II or III ma be obtained.

Thus for example compounds of formula II are obtained from B-methylolamides of unsaturated monocarboxylic acids and hydroxyaryl compounds having a single reactive position, such as 2-hydroxynaphthalene o l»h droxy 2,4^imethylbenzene. If monocarboxylic acid N-methylolamides are reacted with hydroxyaryl compounds having two reactive positions such as 1-hydroxy-2-chlorobenzene or 2,6-dihydroxynaphthalene, then depending en the ratio of the amounts of starting substances, compounds of formula II and/or compounds of formula III may be obtained.

As examples of K-methylolaraides which may be used in the production of the new carboxylic acid arylmethylamides there may be mentioned the K^-methylolamides of the following polymerlsable carboxylic acids, polymerisable acids to be understood as homopolymeris ble and/or copolymerisable acids: crotonic acid, a-chloracrylic acid, a-ethylacrylic acid, methacrylic acid and especially acrylic acid. fhe hydroxyaryl compounds which serve for the production of the carboxylic acid arylmethylamides are free of heteroeyclic l-hydroxy-2-methyl-4-sec . alkylbenzenes (obtainable by alkylation of l-hydroxy-2-¾ethylbenzene with a mixture of defines of composition CgH^g to ^4^28' n tne Presence °^ •perchloric acid), 3-hydroxy-p-cymene (thymol), l-hydroxy-2- methyl-5-isopropylbenzene (carvacrol)', l-hydroxy-2-methoxy- benzene , l-hydroxy- , 4- or -2 , 6-di-tertiary butyl benzene, ■l—fey^o -S—tf±f3rt-& o-a¾ h lbeng-&n» , l-hydroxy-2-methylmercapto- 4-methylbenzene .

As has already been mentioned, the new carboxylic acid aryl- Diethylamides are obtained by reaction of the carboxylic acid methylolamides with hydroxyaryl compounds in an acid medium. The acid reaction medium is appropriately obtained by adding a strong mineral acid such as hydrochloric acid, sulphuric acid, orthophosphoric acid or pyr.ophosphoric acid, or may also be obtained with acetic acid or phosphoric acid/boron fluoride complexes. It is generally advisable to work in an organic solvent, and a solvent which is easily soluble in water, or is soluble in water in all proportions, for example ethanol or glacial acetic acid, is advantageously used. The water content of the reaction mixture should be kept as low as possible.

However the addition of a small amount of water, as for example results if concentrated hydrochloric acid is used in order to achieve an acid medium, is generally of no disadvantage.

Warming the reaction mixture is generally unnecessary; it suffices to leave the mixture for a prolonged period, for example 20 to 100 hours, if possible with exclusion of air. The addition of an inhibitor, for example thiodiphenylamine ( thiophenazine ) is also advisable.

The new carboxylic acid arylmethylamides are valuable compounds of versatile applicability. Thus they may for example be used as antioxidants or bactericides. Above all, however, they are suited to the production of polymers, especially to copolymerisation with other ethylenically unsaturated compounds. The carboxylic acid arylmethylamides may be converted, in solution or in emulsion and in the presence of catalysts which release free radicals or which act ionically, by themselves or together with other polymerisable compounds, to give polymers which are generally straight chain. Depending, on the choice of starting substances one thereupon obtains linear polymer homologues, unipolymers or multipolymers .

Polymer homologues are obtained if a single carboxylic acid arylmethylamide is used. Unipolymers are obtained when two or more carboxylic acid arylme hylamides which differ from one another are used, and multipolymers are obtained when at least one carboxylic acid arylmethylamide and at least one other monomer are used. As examples of monomeric compounds which may be used for the production of multipolymers there may be mentioned: vinyl esters of organic acids, for example those of acetic acid, formic acid, butyric acid or benzoic acid, vinyl alkyl ketones such as vinyl methyl ketone, vinyl halides such as vinyl chloride, vinyl fluoride or vinylidene chloride, vinyl aryl compounds such as styrene and substituted styrenes, for example a-methylstyrene , other derivatives of polymerisable ethylenically unsaturated acids such as vinylpyrrolidone ,vinyl-carbazole, acrylonitrile , acrylamide, me hacrylamide , amides which are further substituted at the nitrogen atom by alkyl groups such as ethyl, methyl, tertiary butyl or hydroxyalkyl groups, for example the N-methyH.olamides and their ethers, basic amides such as methacrylic acid dimethylaminoethylamide or acrylic acid diethylaminopropylamide and their quaternisation products, but especially esters of polymerisable ethylenically unsaturated acids, for example of acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid, vinylsulphonic , allylsulphonic or styrene-sulphonic acids and mono-alcohols or di-alcohols having 1 to 18 carbon atoms or hydroxybenzenes, for example methyl meth-acrylate^ ethylacrylate , glycidyl aerylate, butyl acrylate, ydroxyethyl acrylate or the corresponding polyglycol esters, dodecyl acrylate, as well as free ethylenically unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, vinylsulphonic acid and allylsulphonic acid, vinylbenzenesulphonic acid, and polymerisable olefines such as isobutylene, butadiene, and 2-chlorobutadiene .

The polymers generally consist of 0.1 to 100 ^ of a carboxylic acid arylmethylamide or of several such amides, and 99.9 to 0 ia of at least one other polymerisable compound.

Depending on the choice of the polymerisation conditions the polymers are obtained in solution, as a gel, as an emulsion or as granules. The complete homopolymerisation or copolymerisation of the carboxylic acid arylmethylamides generally causes no difficulties and the usual methods may be employed. The homopolymers and copolymers form films which adhere well to substrates such as glass or metal so that they may successfully be used in lacquers. Copolymers with long chain alkyl acrylates such as octadecyl acrylate may easily be fused together with polyolefines , for example polyethylene, and are compatible therewith. The polymers^ may be cross-linked with bifunctional epoxides and then form insoluble films which The new carboxylic acid arylme hylamidea may be incorporated, for example by copolymerisation, into styrene and other plastics so as to act as phenolic stabilisers. This largely avoids blooming out, sweating out or crystallising out, which is normally a disadvantage of phenolic stabilisers. Good opportunities are also offered by the incorporation of copolymers of phenolic polymerisable antioxidants with such polymerisation constituents as assist good compatibility in the substrate (for example octadecyl methacrylate for the case of polyethylene). Carboxylic acid arylmethylamides based on . hydroxybenzenes which may be used as bactericides also show a . bactericidal effect if copolymerised with other monomers. By using suitable comonomers the polymers may be modified in such a way that they may be fixed' on to suitable substrates, for example they may be fixed on to fibrous materials such as cotton by means of the exhaustion method.

In the Examples which follow, the parts denote parts by weight and the percentages denote percentages by weight, unless otherwise stated.

Example 1 14.3 parts of 2-hydroxynaphthalene , 10.1 parts of acrylic acid methylolamide and 0.1 part thiodiphenylamine are dissolved in 60 parts by volume of absolute ethanol and 6 parts by volume of 37 i° hydrochloric acid is added thereto. The mixture is allowed to stand in a closed vessel for 30 hours. Thereafter, about 600 parts by volume of water are stirred in. A precipitate of about'19.6 parts (06 of theory) of the compound of. formula (6) (-0H is obtained. After recrystallisation from benzene, the melting point was 148°C Analysis: found: C 74.10, H 6.10, N 5.80 calculated: C 74.00, H 5.80, N 6.10 Example 2 91 parts of acrylic acid methylolamide , 73 parts of 1- hydroxy-2 , 4-dimethylbenzene and 0.1 part of thiodiphenylamine are dissolved in 500 parts by volume of absolute ethanol and 40 parts by volume of 37 "/<> hydrochloric acid are added thereto, with the mixture being cooled somewhat. The mixture is then allowed to stand in a closed vessel for 70 hours. The precipitate which has formed is filtered off.. J?urther product is obtained by concentrating the mother liquor. The combined products are washed with a little ethanol followed' by water, and are dried. About 72.5 parts (59 >) of the compound of formula -are obtained. After recrystallisation from an alcohol-water mixture (2 : 1) the melting point, was 155°C.

' Analysis: found: C 70.60, H 7.50, N 6.60; calculated: C 70.20,. H 7.40, N 6.80.

Example 3 24.4 parts of l-hydroxy-2 , 6-dime thylbenzene and 20.2 parts of acrylic acid methylolamide are dissolved in 110 parts by volume of absolute ethanol, with the addition of 0.1 part of thiodiphenylamine. 12 parts by volume of 37 S# hydrochloric acid are added and the mixture allowed to stand in a closed vessel are obtained. After recrystallisation from an alcohol-water mixture (1 : 3) the melting point was 142°C.

Analysis: found: C 70.30, H 7.30, N 6.80; calculated: C 70.20, H 7.40, N 6.80.

Example 4 32.8 parts of l-hydroxy-2-methyl-4-tert . butylb.enzene and 20.2 parts of acrylic acid methylolamide are dissolved in 110 parts by volume of absolute ethanol together with 0.1 part of thiodip enylamine . 12 parts by volume of 37 i* hydrochloric acid are added and the mixture allowed to stand in a closed vessel for 70 hours. The mixture is then poured at 0°C, with vigorous stirring, into a mixture of 500 parts of water and 300 parts by volume of petrol ether. About 9.5 parts (19 $> of theory) of the compound of formula -are obtained as a precipitate. After recrystallisation from toluene the melting pint was 160°C.

Analysis: found: C 73.00, H 8.40, N 5.90; calculated:. C 72,80, H 8.60, N 5.70.

Example 5 64.5 parts of l-hydroxy-4-chlorobenzene and 50.5 parts of acrylic acid methylolamide are, with the addition of 0.1 part parts by volume of glacial acetic acid which had been prepared at 15 to 20°C, and in each case the mixture is stirred until everything has dissolved. The mixture is allowed to stand for 70 hours in a closed vessel and is then stirred into 2500 parts of water. The smeary precipitate which forms is washed with water and after seeding is stirred with water at high speed, whereupon it completely crystallises. About 71.7 parts (68 o of' theory) of the compound of formula are obtained as a crude product. After three recrystallisations from xylene the melting point is 126°C. The product even then contains slight amounts of 2,6-bis-acrylamidomethyl-4-chloro- phenol which is difficult to remove by recrystallisation.

• Analysis: found: G 6.90, H 4.80, N 7.20; calculated: C 56.70, H 4,80, N 6.60.

Example 6 2 %_ > Using a charge containing l-hydroxy-z^-chlorobenzene in accordance with the data of Example 5, in 96 sulphuric acid as the solvent, the compound of formula is obtained. After recrystallisation from water the melting point is 158°C (crystals in the form of leaflets).

Analysis: found: C 57.10, H 4.90, N 9.50, CI 12.20; calculated: C 57.00, H 5.10, N 9.50, CI 12.00.

Example 7 benzene, following the method of Example 5, aft-ieea .? mixture is obtained. Fractional crystallisation thereof from benzene yields the substances of formulae of melting point 190°C, analysis: found: C 5.8.50, H 5.20, 9.00, CI 11.60; calculated: C 58.30, H 5.50, N 9.10, CI 11.50, of melting point 183°C, analysis: found: C 58..90, H 5.60, N 6.10, CI- 15.30; calculated: C 58.50, H 5.40, N 6.20, CI 15.70.

Example 8 28 parts of l-hydroxy-4— itrobenzene and 20.2 parts of acrylic acid methylolamide are successively dissolved, with cooling, in 80 parts by volume of concentrated sulphuric acid. The mixture is allowed to stand in a closed vessel for 60 hours, and then poured on to 500 parts of ice. The resulting precipitate is washed with water and recrystallised from 3000 parts of water. About 27 parts (61 ΰ/Ό of theory) of the compound of formula (14) —KH—OC—CH=CH2 Example 9 54 parts of the compound of formula (14) are dissolved in 400 parts by volume of acetone. 35 parts of finely powdered anhydrous potassium carbonate are added and 30.8 parts of dimethyl sulphate dissolved in 100 parts by volume of acetone, are added at boiling temperature. The mixture is then boiled for a further 4 hours under reflux. It is then filtered, the solvent removed in vacuo, and the residue stirred with 300 parts by volume of water, with the addition of 200 parts by volume of -caustic soda. The product is filtered off and washed until free of alkali. On drying, 47 parts (82 °β> of theory) of the compound of formula are obtained. After recrystallisation from ethanol or methanol the melting point is 183 to 184°C Analysis: found: C 56.20, H 5.20, N 11.80; calculated: C 55.90, H 5.10, N 11.80.

Examples 10 to 19 are summarised in Table I below. The compounds quoted are produced analogously to the compounds of the preceding Examples. b) These substances may be produced both using N-hydroxymethyl- methacrylamide or using N-methoxymethyl-methacrylamide .. The latter process gives better yields. c) The compounds of formulae (21) and (22) quoted in Example 15 are produced alongside one another in the same charge and are separated by fractional crystallisation from methanol.

Example 20 A solution of 5 parts of styrene and 5 parts of the compound of. formula (6) and 31 parts of 1 , 2-dichlorethane is heated to 70°G with stirring and with nitrogen being passed in, and is treated with a solution of 0.1 part of azodiisobutyronitrile in 2.5 parts of 1 , 2-dichlorethane . After 30 minutes a solution of 0.1 part of azodiisobutyronitrile in 2.5 parts of 1,2- dichlorethane is again added and the solution kept at 70°C for 17 hours. In order to test for complete polymerisation the polymer is precipitated from the cooled solution by means of petrol ether, filtered off, washed, dried and digested, in a finely powdered state, with 2 N caustic soda for 30 minutes.

The polymer is filtered off and the filtrate adjusted to pH 1.5 •by means of 2 N hydrochloric acid. No precipitate forms . The monomer of formula (6) which is easily soluble in 2 N caustic soda and which immediately precipitates on acidification, is ' quantitatively copolymerised.

Example 21 If 2' parts of the compound of formula (6) are polymerised in 8 parts of 1 , 2-dichlorethane by means of 0.02 parts of azodiisobutyronitrile, following the instructions of Example 20, then a film-forming homopolymer is again obtained, which is insoluble in 2 N caustic soda and contains no monomeric components.

Example 22 A copolymer in which no monomer of formula (6) could be detected y means of 2 N caustic soda is obtained fr-om 38 parts of 3 tyrene , 10 parts of butyl n-acrylate and 2 parts of the compound of formula (6) in 115 parts of benzene, using 1 part, of azoaiisobutyronitrile .

Example 23 If the reaction described in Example 22 is carried out with 39 parts of vinylidene chloride, 10 parts of n-butyl aer late and 1 part of the compound of formula (6), then a polymer is again obtained which contains no residual monomer of formula (6) Example 24 If 3 parts of the compound of formula (6) and 7 parts of stearyl methacrylate are polymerised in 11 parts of n-butyl alcohol by means of 0.2 parts of tert. butyl peroctoate' for 10 hours at 85°C, a copolymer is obtained which is compatible with polyethylene in amounts of up to 10 o , both in the melt and in films.

Example 25 If 15 parts of styrene, 7.5 parts of n-butyl acrylate and 2.5 parts of the compound of formula (6) are polymerised for 24 hours at 75°C in 25 parts of n-butyl alcohol by means of 0.6 parts of azodiisobutyronitrile , a polymer is obtained which forms very well adhering films on glass and metal.

Example 26 Polymerisation of 2.5 parts of the compound of formula (7) and 4.6 parts of stearyl methacrylate in 7.7 parts of benzene at 90°C over the course of 20 hours, using 0.14 parts of azo- diiso utyronitrile, yields a copolymer which is up to 10 ^ compatible with polyethylene both as a melt and as a film.

Example 27 Polymerisation of 1 part of the. compound of formula (7.) and 10 parts · of lauryl methacrylate in 8 parts of benzene by means of 0.5 parts of benzoyl peroxide over the course of 24 hours yields a copolymer which is up to 8 compatible with polyethylene both as, a melt and as a film.

Example 28 38 parts of styrene, 10 parts of ri-butyl acrylate and 2 parts of a compound of formula (7) in 115 parts of benzene in the course of 24 hours at 75°C by means of 1 part of azo-diisobutyronitrile yield a copolymer, treatment of which with 2 N caustic soda does not show any compound of formula (7) to be present .

Example 29 38 parts of styrene, 10 parts of n-butyl acrylate and 2 parts of the compound of formula (8) in 115 parts of benzene at 75°C over the course of 66 hours yield, with 1 part of azo-diisobutyronitrile , a copolymer which contains no monomer of formula (8).

Example '30 38 parts of styrene , 10 parts of n-butyl acrylate and 2 parts of the compound of formula (9) in 115 parts of benzene at 75°C over the course of 65 hours yield, by means of 1 part of azodiisobutyronitrile , a copolymer, treatment of which with 2 N caustic soda does not show any monomer of formula (9) to he present . - Example 31 benzene at 80°G over the course of 60 minutes yield, with 0.06 parts of azodiisobutyronitrile , a gel which is insoluble in all organic solvents.

Example 32 If a solution of 1.25 parts of . the compound of formula (14) and 3.75 parts of acrylamide in 23 parts of dime thylformamide is polymerised by means of 0.08 parts of a-jodiieobutyronitrile at 65°C over the course of 15 hours, a copolymer precipitates which is completely precipitated by means of ether ,. filtered off, washed with ether and dried. Yield, about 5 parts. The. monomer (14) cannot be detected in the polymer by fractional precipi tation f rom dime thylformamide by means of ether. The polymer forms a clear yellowish film from aqueous solution.

Example 55 37.5 parts of n-butyl acrylate, 5 parts of acrylonitrile , 2.5 parts of acrylic acid, 15 parts of methylene chloride and 5 parts of a compound of formula (7) are pre-emulsified in a solution of 2.5 parts of sodium laurylsulphonate in 70 parts of water, warmed to 65°C with stirring and with nitrogen being passed in, and treated with a solution of 0.2 part^ of potassium persulphate in 5 parts of water and a Solution of 0.05 parts of sodium matabisulphit e in 5 parts of water. 60 minutes later, a solution of 0.2 parts of potassium persulphate in 5 parts of water and a solution of 0.05 parts of sodium me tabisulphite in 5 parts of water are added', and the mixture allowed to post-polymerise for 4 hours-. After cooling to room temperature, the mixture is adjusted to a pH value of 7 by means of 10 o strength aqueous ammonia. It is then warmed to 70°C and the methylene chloride flushed out by means of nitrogen. On cooling and filtration, an emulsion having a resin content of about 34 °/o is obtained.

Example 34 Instead of the compound of formula (7), 5 parts of a compound of formula (16) are used in the process described in . Example 33, but with the difference that 85 parts of water are used to dissolve the sodium laurylsulphonate and hat an emulsion of about 32 , resin content is obtained.

The Table II which follows summarises Examples 35 to 62.

Notes on Table II; The polymers are precipitated from the solutions, and washed, by means of 1) petrol ether 2) ether ana 3) water. In the other Examples the polymers are obtained in a solid form by ■ distilling off the solvent in vacuo.

*) Polymerisable compound which absorbs ultra violet radiation, of formula B = benzene .

P = di ethylformamide BA = n-butyl alcohol ADBitf = azodiisobutyronitrile AHBP = tert. -butyl perester of 2-ethylhexanoic acid.

T A B L II .<;>;- Monomers Solvent Catalyst ample Wo. Parts Par s 45 Compound of formula (23) 10 n-butyl methacrylate 15 B 130 ADBN 46 Compound of formula (16) 5 Compound of formula *) 5 B 28 ADBN stearyi metliacrylate 10 47 Compound of formula (26) 10 methyl methacrylate 10 B 80 ADBN 48 Compound of formula (7) 10 B 120 ADBN 49 Compound of formula (17) 10 stearyi methacrylate 10 B 27 AHBP 50 Compound of formula (17) 10 methyl methacrylate 10 B 27 AHBP 51 Compound of formula (17) 10 styrene 10 B 27 AHBP 52 Compound of formula (18) 10 B 120 ADBN 53 Compound of formula (15) 10 n-butyl methacrylate 10 DMF 25 AHBP 54 Compound of formula -(7) 10 DMF 105 ADBN acrylamide 10 55 Compound of formula (7) 10 N-tert .-butyl acrylamide 10 DMF 105 ADBN 56 Compound of formula (23) 10 N-tert. -butyl acrylamide 10 DMF 100 ADBN ExMonomers Solvent Catalys ample No.

Parts Parts 57 Compound of formula (23) 10 DMF 100 ADM Acrylamide 10 58 Compound of formula (16) 10 DMP 100 ADBN Acrylamide 59 . Compound of formula (16) 10 DMP 100 ADEN N-tert .-butylacrylarnide 10 60 Compound of formula (6) 6 BA 22 ADBN stearyl me thacryla'te 14 61 Compound of formula (8) 6 BA 22 ADBN stearyl methacrylate 14 62 Compound of formula (23' 10 B 130 ADBN 1 part each of the polymers listed in Table III below are dissolved in 2 parts of benzene, treated with an epoxy-resin 'which contains 5.5 equivalents of epoxy-groups and with di-octadecyl dimethyl ammonium chloride as catalyst, and are cast into films. The films, which are dried at room temperature, are set for 10 minutes at 170°C.

Table' III jxample 64 Stabilisation of Natural Rubber against Heat Ageing Preparations of the follov/ing composition, in parts by weight, were shaped' into sheets of size 15 cm x 15 cm x 0.2 cm and given optimum vulcanisation at 141°C: Natural rubber (pale crepe) 100; zinc oxide 5; titanium dioxide 10; barium sulphate 75; stearic acid 1; N-cyclohexyl-2-benzthiazylsulphonamide 0.5; sulphur 2; antioxidant 1 (or 0, in one experiment) The samples were aged for 14 days at 70°C.

Polymeric antioxidant :according 35 37 38 39 to .example Duration of vulc nisation (minutes) 18 18 18 18 18 Tensile strengt (Z?) kg/cm2 238 228.5 228.5 204.5 196 Extension at break (ZD) in io 590 550 570 570 540 Reduction of Z? on ageing, in c/° 29 17 17. 5 19 x¾eduction of ZD i on ageing, in °/ 5 0 0 5 o - 1 Example 65 A mixture of 100 parts of unstabilised polypropylene and 0.5 parts of one of the compounds of Examples 10, 11, 39. 40, 49, 50, 51 and 62 is converted to a foil on a calender at 170°C.

This foil 'is subsequently pressed to a sheet 1 mm thick at 230 to 240oC and. a pressure of 40 kg//cm2. The sheet so obtained is then cut up into small pieces. 10 g thereof are brought into contact with pure oxygen (pressure 70 cm Hg) at exactly 160°C in a reaction flask equipped with an absolute monometer. The drop of oxygen pressure with time is then measured, the measurements always being carried out at constant volume.

Sigmoid-shaped curves of oxygen consumption are thus obtained.

The time up to the steep rise of the curves is described as the induction period.

The following results were obtained: Table IV polypropylene (Induction Period (hours ) without additives 0.5 + Compound according to Example (monomer 10 24.5 + Compound according to Example (monomer 11 39 + Compound according to Example (polymer) 39 7.2 + Compound"" acc ording to Example ( polymer) 0j 14.3 + Compound according to Example ( polymer) 49 6.9 + Compound acc ording to Example ( polymer) 50 24.5 + Compound according to Example ' polymer) 51 28 + Compound according to Example polymer) 62 25.5 Example 66 In order to test the stability and adhesion on dry cleaning (chlorinated hydrocarbons) as practised with polypropylene fibres, the following is carried but: the dry cleaning process is simulated by an extraction experiment in which the small pieces of polypropylene rjeferred to in Example 65 are treated for 30 minutes in a bath of trichlorethylene at 30°C. The pieces which have been thus treated are then again subjected to the oxygen uptake' test as described in Example 65. The permanence of the antioxidants in the substrate is deduced from the change in induction period before and after the extraction experiment. In this test, polymeric antioxidants appear to be of advantage 3$ may be seen from the following numerical examples: Table V Polypropylene Induction Period (hours) before treatment after, treatment without additive 0 .5 0.5 + polymeric compound 28 25 according to Example 51 + monomeric compound 39 18 according to Example 11

Claims (2)

1. 25444/2 WHAT WE CLAIM IS: 1. Carboxylic acid arylmethylamides, which may optionally be etherified, of the formula - Ar - D I OH 0 it wherein D is a group -CH^-NH-C-R where R is an ethylenically unsaturated radical of 2 to 4 carbon atoms, D is hydrogen or has the same meaning as ^ ; and Ar is a benzene or naphthalene radical optionally further substituted with alkyl, alkoxy, halogen, alkyl -S, carboxyi4-e—a-eid, nitro or hydroxy groups.
2. 2. Carboxylic acid arylmethylamides according to claim 1, of the formula 0 It H - Ar - CH - H - C - R1 II I 2 OH in which 1 denotes an ethylenically unsaturated residue having 2 to 3 carbon atoms and Ar has the meaning given in claim 1. J. Carboxylic acid arylmethylamides according to claim 1, of the formula C - NH - CH. Ar - CH. - NH - C R ,111 tt 2 t 2 It 0 OH 25444/3 4. , Carboxylic acid arylmeth lamiyides according to any one of claims 1 to 5, whose ethylenically unsaturated residues correspond to the formula H2C=CH-. 5. Process for the manufacture of carboxylic acid aryl-methylamides which may optionally be etherified,of the formula D, -Ar-D 1 I OH wherein Ar, D and have the meanings given in claim 1, characterised by reacting an N-methylolamide of the formula D-OH wherein D has the meaning given in claim 1 in an acid reaction medium with an optionally etherified hydroxy aryl compound of the formula H-Ar-H I OH wherein Ar has the meaning given in claim 1 and has two reactive positions. 6. Process for the manufacture of carboxylic acid aryl-methylamides which may optionally be etherified,of the formula HO-Ar-D wherein Ar and D have the meanings given in claim 1, characterised by reacting an N-methylolamide of the formula D-OH wherein D has the meaning given in claim 1 in an acid reaction medium with an optionally etherified hydroxy aryl compound of the formula HO-Ar-H wherein Ar has the meaning given in claim 1 and has one reactive position. 25444/3 - 30 - 7· New polymerisation products of (a) earboxylie acid arylreethylamides , which may optionally be etherified, of the formula I in Claim 1, (b) other copolyaierisable ethylenically unsaturated compounds* S. Polymerisation products according to Claim 7* consisting of (a) earboxylie acid arylmethylaraides of the composition stated and (b) styrene. 9» Polymerisation products according to Claim 7, consisting of (a) earboxylie acid arylraethyl mides of the composition stated and (b) an alkylester or an alkylamide of an ethylenically unsaturated polymorisable mono-carbexylie acid* 10· Polymerisation products according to Claim 7S consisting of (a) earboxylie acid arylmethylamides of the composition stated and (b) vinylideae chloride* 11· Polymerisation products according to Claim 7» consisting of (a) earboxylie acid arylsiethylasiides of the composition stated and (b) at least two compounds of the categories quoted under (b) in Claims 8 to 10· 25444/3 i . Process for the manufacture of new polymerisation products, characterized by polymerising (a) carboxylie acid arylmethylamides, vhich may optionally be etherifled, of the formula ∑ in Claim 1 together vith, if desired, (b) other copolymer!sab e ©thylenically unsaturated compounds* 13. Process according to Claim 12 characterised by using as the starting substances carboxylie acid arylmethyl-amides vhich as the aryl radical contain the radical of a phenolic stabiliser, 14« Process according to Ulaim 12 characterized by using as the starting substances carboxylie acid rylmethyl-amides vhich as the aryl radical contain the radical of a bactericidal hydroxy benzene* 15· Proeess for manufacturing coatings and covering layers on non-textile materials characterised by applying a polymerisation product according to any one of Claims 7 to 11* 16» Process for protecting organic isateriais from oxidation characterised by incorporating in thes a carboxylie aeid arylroethylaniid of any one of Claims 1 to 4· 17. Process for protecting organic materials from oxidation characterised by incorporating in them a polymerisation product of any on* of Claims 7 to 11* For the Applicants SR. ARTNERS