GB1580914A

GB1580914A - Hindered phosphite esters

Info

Publication number: GB1580914A
Application number: GB3172577A
Authority: GB
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1976-07-30
Filing date: 1977-07-28
Publication date: 1980-12-10
Also published as: DE2733796A1; JPS5318544A; NL7708452A; FR2359845A1; FR2359845B1

Description

(54) NEW HINDERED PHOSPHITE ESTERS (71) We, CIBA-GEIGY AG, a Swiss Body Corporate of Basle, Switzerland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to new hindered phosphites, the preparation thereof, their use as antioxidants and light stabilizers for stabilizing organic materials and the organic compositions stabilized therewith.

It is e.g. known from the US patent No. 3,419,024 to use hindered phosphites as antioxidants in polyolefines. It is also known to combine phosphites with light stabilizers, such as benzophenones or benztriazoles to achieve improved stabilization of polypropylene on out door exposure to sun light. However, a phosphite is generally not used as the sole light stabilizer in organic materials, because of its limited effectiveness. Unexpectedly, it has been found that the phosphites of this invention can be used effectively in polymers, as the sole light stabilizer. Furthermore the phosphites of this invention act as antioxidants for polymers, both when used alone and in combination with thiosynergists.

The hindered phenyl phosphites of this invention have the formula

wherein Rl and R2 are independently C-Cl2 alkyl, C5-C8 cycloalkyl, C7-C9 aralkyl or hydrogen, provided that only one of R1 and R2 can be hydrogen.

R3 is- (CtH2t)-COOR4 (11) -(CtH2t)-COOM1:q (III) or-CN, wherein (CtH2t)COOMIkI (III) or -CN, t denotes 0 to 6, and R4 is C1-C24 alkyl, phenyl or alkyl substituted phenyl with 1 to 18 carbon atoms in the alkyl moieties, and M is a metallic cation with the valency 1, 2 or 3 and 9 is 1, 2 or 3, n* is 0 or 1, and m and n are each 1 or 2, the values of m, n and n* being such that the trivalent state of P is satisfied, and R* is -XH, wherein X is -O- or -S- and R denotes halogen, -XH or -XR5, wherein X is -S- or -0- and R5 denotes C1-C24 alkyl, phenyl or alkyl substituted phenyl with 1-18 carbon atoms in the alkyl moieties or R5 is, when n* is 1, also M'iiq, wherein M and q are as defined above, or R5 is, when X is -O-,C1-C30 alkanoyl, benzoyl or alkyl substituted benzovl with 1 to 18 carbon atoms in the alkvl moieties, or n* is 0 and two R groups taken together are a group of the formula

wherein R6 is phenylene, alkyl substituted phenylene with 1-18 carbon atoms in the alkyl moieties or C2-C24 alkylene and X is as defined above, and m and n are each 1 and 2 respectively and R is furthermore a group of the formula

wherein R7 is a group

wherein Rl l denotes alkylene of 1 to 34 carbon atoms, C6-Cl() arylene or the direct bond, and R1, R2 and R3 are as defined above, and m is 2 and n is 1, or furthermore n* is 0 and two R groups taken together denote a group of the formula

wherein Rl, R2 and R3 are as defined above, and m and n are each 1 and 2 respectively.

R1 and R2 are independently as C1-C12 alkyl e.g. methyl, ethyl, propyl, t-butyl, hexyl, t-octyl, a-methylhexyl, t-octyl or t-dodecyl. Preferred are alkyl groups having 1 to 8, and especially 4 to 8 carbon atoms. Most preferably, both R1 and R2 are tertiary alkyl of 4 to 8 carbon atoms, as e.g. t-butyl.

R, and R2 are as C5-C8 cycloalkyl e.g. cyclopentyl, cyclohexyl or cyclooctyl.

R1 and R2 are as C-C9 aralkyl e.g. benzyl, a-phenylethyl or a,a-dimethylbenzyl.

R3 is preferably a group of the formula II or III, most preferably of the formula II t is 0 to 6, preferably 0 to 2 most preferably 0.

Substituent R4 is alkyl of 1 to 24 preferably 1-18 carbon atoms, phenyl or phenyl substituted by 1 to 3 alkyl groups of the formula

in which R8, R9 and R,(, independently of one another are alkyl with 1 to 18 preferably 1 to 12, most preferably 1 to 8 carbon atoms or hydrogen. Examples of R4 are methyl, ethyl, n-propyl, isopropyl, n-butyl, n-octyl, n-octadecyl, n-docosyl, and n-tetracosyl. Examples of R8, R9 and R1( are methyl, ethyl, iso-propyl, sec-butyl, tert-butyl, sec-amyl, tert-amyl, tert-hexyl, iso-octyl, tert-octyl, sec-nonyl, tert-nonyl, sec-dodecyl, tert-dodecyl, sec .tetradecyl, sec-hexadecyl, and octadecyl.

M is a metallic cation with the valency 1, 2 or 3 and may, be selected from alkali-, alkaline earth- and transition metals, such as Na+, K+, Mg +, Ca-+, Cr3+, Co2+, Ni2+ Zn2+, Al3+ and Sn2+. Preferred metals are Ca2+, Co2+, Ni2+ and Zn2+, and especially Co+ and Ni2+.

in preferred compounds of the invention having the substitutent -XR5, R5 is alkyl of l to 18 carbon atoms, phenyl, benzoyl, phenyl or benzoyl substituted by 1 or 2 alkyl groups of 1 to 18, preferably 1 to 12 carbon atoms each, and alkanoyl having 1 to 30, more preferably 1 to 22 carbon atoms.

Examples of Rg as C1-C24 alkyl are methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, dodecyl, octadecyl, and tetracosyl. Examples of R5 as alkyl substituted phenyl are methylphenyl, ethylphenyl, butylphenyl, octylphenyl, octadecylphenyl, dimethyiphenyl, dibutylphenyl, dioctadecylphenyl. Examples of alkyl substituted benzoyl are 4-tertoctyl- benzoyl, 4-tert-butyl-benzoyl, and 3,4-dimethylbenzoyl. Examples of R5 as C,-C" alkanoyl are acetyl, propionyl, butyroyl, pelargonyl, stearoyl, caproyl, capryloyl, 2-ethylhexanoyl, lauroyl, valeroyl, palmitoyl, tridecanoyl and octanoyl. * Preferred compounds are furthermore such, wherein n* is 1. R* is -XH and R5 denotes Mik1. in these compounds the preferred meaning of X is -O-. M and q are as defined above. In preferred compounds ot the formula

the cyclic structure

is a 5 or 6 membered ring where R" is alkylene of 2 to 24, preferably 2 to lX, carbon atoms. Examples of R6 are ethylene, trimethylene, 2.2- dimethyltrimethylene, hexadecylethylene, 1,2-phenylene and alkyl substituted 1,2- phenylene where the alkyl group has l to 18 carbon atoms.

Other preferred compounds are those of the formula

R11 is alkylene of 1 to 34 carbon atoms, C6-C,(, arylene or the direct bond.

Examples of R1 as alkylene are methylene, ethylene, propylene, trimethylene, tetramethylene, hexamethylene, octamethylene, decamethylene and octadecamethylene.

Examples of R7 as arylene are 0-, m- or p-phenylene, and 2,3-naphthylene.

Preferred are compounds of the fonnula I, wherein Rl and R2 are independently C-C.

alkyl or hydrogen. provided that only one of R1 and R2 is hydrogen.

R3 is -(C1H21)-COOR4 or -CN, where t is 0 to 6 and R4 is C1-C24 alkyl, phenyl or alkyl substituted phenyl with 1 to 18 carbon atoms in the alkyl moieties, and n* is 0 and R is halogen or when m is 2 and n is 1, hydroxyl, or R denotes -XRs wherein X is -O- or -S- and Rs is C1-C24 alkyl, phenyl or alkyl substituted phenyl with I to 18 carbon atoms in the alkyl moieties, and when X is -O-, denotes additionally C,-C(, alkanoyl, benzoyl, or alkyl substituted benzoyl with 1 to 18 carbon atoms in the alkyl moieties or when n* is 0 two R's together denote a group of the formula wherein R6 is phenylene, alkyl substituted phenylene with 1 to 18 carbon atoms in the alkyl moieties or C2-C24 alkylene, X is as defined above, and m and n are each 1 and Z respectively or R is furthermore a group of the formula

wherein R7 is a group

wherein R11 denotes alkylene with 1 to 34 carbon atoms, C6 to C10 arylene or the direct bond, R1, R2 and R3 are as defined above, and mis 2 and n is 1, or n* is 0 and two R groups together denote a group of the formula

wherein, R2 and R3 are as defined above, and m and n are each 1 and 2 respectively.

Preferred are also compounds of the formula I wherein R1 and R2 are independently C1-C8 alkyl, C5-C5 cycloalkyl or C7-Cg aralkyl and R3 denotes -(CtH2t)-CO OR4 (11) or -(CtH2t)-COOM,,q (III) or-CN, wherein M is a metallic cation with the valency 1, 2 or 3 and q is 1, 2 or 3 and t denotes 0 to 6, and R4 isC,-C24 alkyl, phenyl or alkyl substituted phenyl with 1-18 carbon atoms in the alkyl moieties, and n* island R* is -XH wherein Xis -O- or -S- and m and n are 1, and R is -XR5, wherein X is -O- or -S- and R5 denotes Ml/q wherein M and q are as defined above.

Most preferred are compounds of the formula I wherein R1 and R2 are t-alkyl groups having 4 to 8 carbon atoms, R3 is a group -(CtH2t)-COOR4 or -CN, wherein t is 0 to 2 and R4 denotes C1-C24 alkyl, phenyl or phenyl substituted by 1 to 3 alkyl groups with 1 to 12 carbon atoms in the alkyl moieties, and n* is 0, with R, m and n being as defined above.

Most preferred are also compounds of the formula I, wherein R1 and R2 are t-alkyl groups having 4 to 8 carbon atoms and R3 denotes a group of the formula II or III wherein t is 0 and R4 is C1-C18 alkyl, phenyl or alkyl substituted phenyl with 1 to 8 carbon atoms in the alkyl moieties and m, n and n* are each 1, R* is hydroxyl and R is -XR5 wherein R5 denotes Mi/q where X is -0- and M is Co2+ or Ni2+ and q is 2.

Very interesting are compounds of the formula I wherein R1 and R2 are t-butyl, n* isO, n is 1 and m is 2 and R denotes -OH whereas R is as defined above.

Examples of compounds of the formula l are: bis-[2.6-di-t.-butyl-4-(n octadecyloxvcarbonyl-ethyl)-phenyl]-phosphorochloridite .

O-acetyl-bis[2 . -butyl-4-( n-octadecyloxycarbonylethyl)-phenyl]-phosphite.

bis- 26-di-t.-butyl-4-(n-octadexyloxvcarbonylethyl)-phenyl-]phosphorous acid diester.

bis- 2,6-di-t.-butyl-4-(2,4-di-tbutyl phenoxycarbonyl)-phenyl]-phosphorochloridite.

bis-2 2.6-di-t.-butyl-4-(methoxy-carbonylethyl)-phenyl]-phosphorochloridite.

cyclic 2.2 dimethylene trimethylene phosphite of 2.4-di-ten-butylphenyl 3.5-di-tert-butyl-4 hydroxybenzoate.

cyclic ethylene phosphite of 2 .4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

cyclic ethylene phosphite of n-octyl-3 .5-di-tert-butyl-4-hydroxybenzoate.

O-acetyl-bis(2.6-di-tert-butyl-p-methoxphenyl)phosphitejiester.

bis(2.6-di-tert-butyl-p-methoxvclrbonvl-phenyl)phosphorous acid diester.

O-acetyl-bis]2,6-di-tert-butyl-4-(2' 4w-di-telt-butyl phenoxycarbonyl)-phenyl]phosphite.

bis[2, 6-di-tert-butyl-4-(2' ,4 -di-tert-butylphenoxycarbonyl)-phenylj phosphorous acid diester.

c)-acetyl-(2,6-di-tert-butyl-4-methoxycarbonylethylphenyl)-phosphite.

bis(2,6-di-tert-butyl-4-methoxycarbonylethyl-phenyl)phosphorous acid diester.

bis(2,6-di-tert-butyl-4.n-octadecyloxycarbonyl-phenyl)phosphorochloridite.

O-acetyl-bis(2,6-di-tert-butyl-4-n-octadecyloxyCarbonylphenyl)phosphite .

bis(2,6-di-tert-butyl-4-n-octadecyloxycarbonyl-phenyl)phosphorous acid diester.

The following exampes are to illustrate not only the phosphorous acid ester-derivatives, but also the preferred salts thereof with M4+, wherein M and q are as defined above.

2,6-di-t.-butyl-4-(2,4-di-t.-butyl-phenyloxyzarbonyl)phenyl]-phosphorous acid monoester.

2,6-di-t. -butyl-4- n-octadecyloxy-carbonyl)-phenyl]-phosphorous acid monoester.

2,6-di-t.-butyl-4- dodecyloxy-carbonyl)-phenyl]-phosphorous acid monoester.

2;6-di-t.-butyl-4-(6-octyloxy-carbonyl)-phenyl -phosphorous acid monoester.

2,6-di-t.-butyl-4- methyloxy-carbonyl)-phenyl -phosphorous acid monoester.

2,6-di-t.-butyl-4-(2,4-dimethylphenyloxy-carbonyl)-phenyl]-phosphorous acid monoester.

2,6-di-t.-butyl-4-(phenyloxy-carbonylethyl)-phenylj-phosphorous acid monoester.

The compounds of this invention may be prepared by a number of methods, which are known per se. Compounds of the formula I, wherein n* is 0 can be prepared e.g. by reacting about m moles of a compound of the formula

with about one mole of a compound of the formula (R)nP(Y)m (V) where M* is an alkali metal preferably sodium or potassium; or hydrogen and Y is halogen, preferably bromine or chlorine, more preferably chlorine, and the other symbols are as previously defined, optionally in an inert solvent. The reaction temperature is not critical and can vary from 0 C to refluxing temperature, e.g. about 1300C. The preferred temperature range is between 0 and 25"C. The compounds of the formula I wherein n* is 1 are prepared in the same way, by using compounds of the formula V, wherein R is halogen, and by treating the intermediate obtained with a compound H2X in a known hydrolysis reaction. If desired the hydrolyzed compounds may be reacted with an alkali metal hydroxide and the alkali salt thus obtained may be converted into the analogous alkaline earth metal salt or transistion metal salt by reacting it with an inorganic salt of the formula M(Y)q, such as e.g. COCK, or NiC12.2HIO, to get compounds of the formula I wherein R5 denotes M1/,. Nevertheless it is in some cases also possible to combine the last two steps, and to hydrolyse the halogeno-intermediate directly with a suitable metalhydroxide M(OH) If in tEe above described reaction a solvent is used, this may be an inert solvent, such as ether, benzene, toluene. chloroform or tetrachloromethane. It is also possible to work without solvent.

If in the formula IV M denotes hydrogen it is advantageous to perform the reaction in the presence of a base; which acts as HCl-acceptor. Preferred bases are organic nitrogen-containing bases. such as triethylamine, tributylamine, N,N-diethylaniline, pyridine or chinoline.

Compounds of the formula I, wherein R4 denotes Miki can be easily obtained by neutralizing the corresponding compound with R4 being hydrogen with a metal salt, e.g.

M(Y)q.

A method. illustrated below, has been found particularly advantageous in producing compounds of this invention where m=2, n=1 and R=OH, by selective hydrolysis of compounds of this invention where m=2, n=1, and -XR5 is alkanoyloxy, e.g., acetoxy, as shown in the following equation:

wherein R19 is hydrogen or alkyl of 1 to 17 carbon atoms and the other symbols are as previously defined. This novel method makes possible the synthesis of stabilizers not directly accessible from the phosphorochloridite VIII.

Compound VI above can be made as follows:

where the symbols are as previously defined.

Some of the compounds of this invention, tautomers VII and Villa shown above, can also be made by hydrolysis or alcoholysis of the phosphorochloridite as shown in the method below:

wherein R" is alkyl, preferably of 1 to 8 carbon atoms, and the other symbols are as defined above.

The compounds of this invention with n* being 0 of the formula

where X is O or S and Rs is alkyl, phenyl, or alkyl substituted phenyl and'the' other symbols are as previously defined, can be made in known manner by reaction of a compound of the formula

and the desired hydroxy or thiol compound, or the alkoxide or aroxide or the thiolate.

The compounds of this invention of the formula

can be made in known manner by reaction of a compound of the formula

and a compound of the formula IV where the symbols are as previously defined. Where M is hydrogen, a proton acceptor. preferably a tertiary amine, such as triethylamine, is used to neutralize the acid HY which is produced as a by-product.

The starting materials for making the compounds of the present invention are available commercially and/or may readily be prepared by those skilled in the art from the teachings of the prior art.

It has to be noted that e.g. the Ni2+ and Co2+ salts of compounds of the formula I, wherein R5 denotes My,., show good dye site properties in polyolefins, especially in polypropylene. Such salts are stable against heat and do not effect discoloration. even when used in combination with sulphur-containing compounds.

As previously stated, the compounds of the present invention are useful as antioxidant and as light stabilizers. Preferred compounds, showing good light stabilization effectiveness are compounds of the formula I, wherein t is 0.

The compounds of the formula I are useful as stabilizers in polymeric organic materials.

Examples of organic polymers which may be stabilized against deterioration caused by oxygen, heat and light are given in the DT-OS 2,456,864, pp 12-14.

They include, for example, the following industrially important categories: polymers which are derived from singly or doubly unsaturated hydrocarbons; halogen-containing vinyl polymers such as polyvinyl chloride; polymers which are derived from a,- unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitrile; polymers which are derived from unsaturated alcohols or their acyl derivatives or acetals; homo- and copolymers which are derived from epoxides such as polyethylene oxide: polyacetals, polyphenylene oxides, polyurethanes and polyureas, polycarbonates, polysulphones; polyamines and copolyamides which are derived from diamines and dicarboxylic acids and/or from aminocarbxylic acids or the corresponding lactams; polyesters which are derived from dicarboxylic acids and dialcohols and/or from hydroxy-carboxylic acids or the corresponding lactones; cross-linked polymers which are derived from aldehydes on the one hand and from phenols, ureas and melamines on the other hand; alkyd resins; unsaturated polyester resins which are derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols, as well as vinyl compounds as cross-linking agents, and also the halogen-containing, difficultly combustible modifications thereof; natural polymers such as cellulose, rubber, as well as their polymerhomologously chemically modified derivatives, such as cellulose acetates, cellulose propionates and cellulose butyrates and the cellulose ethers, such as methylcellulose.

Of importance is the stabilization of polyolefines, polystyrenes and polyurethanes.

Examples are polystyrene, acrylonitrile-butadiene-styrene-copolymers, mixtures of polyolefines, styrenes or polyurethanes on the bases of polyether or polyester in varnishes, elastomers and foams of particular interest are: 1. polymers that are derived from singly unsaturated hydrocarbons, such as polyolefins, e.g. polyethylene of low and high density, which can optionally be cross-linked, polypropylene, polyisobutylene, polymethylbutene-1 and polymethylphentene-1; 2. mixtures of the homopolymers mentioned under 1., such as mixtures of polypropylene and polyethylene, polypropylene and polybutene-1, polypropylene and polyisobuty lene; 3. copolymers of the monomers on which the homopolymers mentioned under 1. are based, such as ethylene/propylene copolymers, propylene/butene-1 copolymers, propylene/isobutylene copolymers, ethylene/butene-1 copolymers, as well as terpolym ers of ethylene and propylene with a diene, such as hexadiene, di-cyclopentadiene or ethylidenenorbornene.

The new compounds are normally added to the substrates at a concentration of 0.005 to 5 per cent by weight, calculated on the material to be stabilized. There is incorporated into the material to be stabilized preferably 0.01 to 1.0 per cent by weight, particularly 0.05 to 0.5 per cent by weight, of the compounds, relative to the said material.

Incorporation can be effected after polymerisation, for example by mixing the compounds and, if required, further additives into the melt by the methods customary in the art, before or during moulding; or by application of the dissolved or dispersed compounds to the polymers, optionaly with subsequent removal of the solvent by evaporation.

The new compounds can be added, to the polymers to be stabilized, also in the form of a master batch containing these compounds at a concentration of, for example, 2.5 to 25 per cent by weight.

In the case of cross-linked polyethylene, the compounds are added before cross-linking.

The compounds of the invention may also be used with other additives, whereby synergistic mixtures can be formed.

..The following may be mentioned as examples of further additives together with which the stabilizers usable according to the invention may be employed: antioxidants such as simple 2,6-dialkylphenols, derivatives of alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylidene-bisphenols, 0-, N- and S-benzyl compounds, hydroxybenzylated malonic esters, hydroxybenzylaromatics, s-triazine compounds, amides of -(3,5-di-tert.-butyl-4- hydroxyphenyl)-propionic acid. esters of t3-(3 ,5-di-tert . -butyl-4-hydroxyphenyl)-propionic acid, esters of (3-(5-tert.-butyl-4-hydroxy-3-methylphenyl)-propionic acid, esters of 3,5-di tert . -butyl-4-hydroxyphenylacetic acid, acylaminophenols, benzylphosphonates, aminoaryl derivatives, UV absorbers and light stabilizers, such as 2-(2 -hydroxyphenyl)-benztriazoles, 2,4-bis-(2'-hydroxyphenyl)-6-alkyl-s-triazines, 2-hydroxybenzophenones, 1,3-bis-(2'hydroxybenzoyl)-benzoles, esters of optionally substituted benzoic acids, acrylates and also nickel compounds, sterically hindered amines, oxalic acid diamides, metal deactivators, phosphites, compounds decomposing peroxide, polyamide stabilizers, basic Co-stabilizers, PVC-stabilizers, nucleating agents or other additives such as plasticisers, lubricants, emulsifiers, fillers, carbon black, asbestos, kaolin, talcum, glass fibres, pigments, optical brighteners, flameproofing agents and antistatic agents.

Examples of further additives together with which the stabilizers usable according to the invention can be employed are to be found in DT-OS 2,427,853 on pages 18-24.

The invention is further illustrated by the following Examples.

Except where otherwise stated. amounts in the Examples are given as per cent by weight and as parts by weight.

EXAMPLE 1 Bis- (2, 6-di-tert-bttyI-4-nzellox5carbotyIq,ii eiyI) qJi osphorochiondite 27.48 grams of phosphorous trichloride was added dropwise at 24 to 30"C over a period of 15 minutes to a solution of 105.6 grams of methyl 3,5-di-tert-butyl-4- hydroxybenzoate and 40.4 grams of triethylamine in 375 ml. of dry toluene. The turbid light-brown reaction mixture was stirred at 75 to 80"C for three hours. The precipitated triethylamine hydrochloride was filtered and the clear filtrate concentrated to dryness at reduced pressure, the isolated residue being crystallized from toluene yielding the desired product as colorless crystals melting at 174-176"C.

Analysis: % C % H % Cl Calculated for C32H46ClQ6P, 64.78 7.82 5.98 M.W. - 593.13 Found 64.68 7.53 5.58 EXAMPLE 2 Bis- (2, 6-d i-tert-butyl-4-2 '4'-d i-tert-butylphenoxycarbonyl-phenyl) phosphorochloridite The compound of this example was made by a similar procedure as the analogous methyl ester (Example 1) by substituting 2',4'-di-tert-butylphenyl 3,5-di-tert-butyl-4hydroxybenzoate for methyl 3,5-di-tert-butyl-4-hydroxybenzoate. The desired compound is isolated as white crystals melting at 212-2150C.

Analysis: % C % H No Cl Calc. for C58H82Cl06P 73.97 8.77 3.76 M.W. - 941.67 Found 74.17 8.49 4.13 EXAMPLE 3 Bis- (2, 6-d i-tert-butyl-4-methoxycarbonylethyl-phenyl) -phosphorochlorid ite 20.5 grams of phosphorous trichloride was added dropwise at 30 to 380C over a period of 20 minutes to a solution of 87.6 grams of methyl 3-(3,5-di-tert-butyl-4hydroxyphenyl)propionate in 117 grams of triethylamine. The reaction mixture was then heated at reflux with stirring under nitrogen for 3-1/2 hours. 100 ml of benzene was added and heating at reflux continued for an additional 4 hours. The reaction mixture was diluted with about 300 ml of ether, washed twice with 300 ml portions of 3N HC1 and then washed thoroughly with water and finally dried over anhydrous sodium sulfate. After removal of drying agent by filtration and solvent by distillation at reduced pressures, the isolated residue was crystallized successively from n-heptane and acetonitrile yielding the desired product as white crystals melting at 93-95"C.

Analysis: % C % H % Cl Calc. for CA6H54C106P 66.61 8.39 5.46 M.W. - 649.23 Found 66.37 8.40 5.77 EXAMPLE 4 Cyclic 2,2 Dimethy/-trimethvlenephosphite of 2,4-di-tert-butyl-phenyl 3,5-di-tert-butyl-4hydroxybenzoate 10.1 grams of triethylamine was added dropwise to a solution of 16.7 grams of 4,4-dimethyl-2,6-dioxa-1-chloro-phosphorinane and 43.8 grams of 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate dissolved in 200 ml methylene chloride at room temperature. The reaction mixture was then heated at reflux for 1 hour, cooled to room temperature, freed of precipitated triethylamine hydrochloride by filtration and finally concentrated to dryness by distillation of the solvent at reduced pressure. The residual solid was then crystallized from a solvent mixture of hexane and toluene, yielding the desired product in the form of colorless crystals melting at 196-197"C.

EXAMPLE 5 Cyclic ethylene phosphite of 2, 4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate 10.12 grams of triethylamine was added dropwise at about 25 to 400C to a solution of 12.6 grams of cyclic ethylene phosphorochloridite and 43.8 grams of 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate in 200 ml of methylene chloride. The reaction mixture was then heated at reflux for two hours, the precipitated triethylamine hydrochloride removed by filtration and the crude product isolated as a solid after removal of the solvent by distillation at reduced pressure. The crude was crystallized twice from toluene yielding the desired product as colorless crystals melting at 155-156"C.

Analysis: %C %H %P Calculated for C31H4705P 70.40 8.58 5.86 M.W. - 530.67 Found 70.66 8.89 5.69 70.40 8.82 EXAMPLE 6 Cyclic ethylene phosphite of n-octyl-3,5-di-tert-butyl-4-hydroxybenzoate 18.1 grams of n-octyl 3,5-di-tert-butyl-4-hydroxybenzoate and 6.3 grams of cyclic ethylene phosphorochloridite and 5.0 grams of triethylamine are allowed to react together in 200 ml of methylene chloride while being heated at reflux for 12 hours. After cooling the reaction mixture

Analysis: %C %H %P Calc. for C34H490SP 66.21 8.00 5.02 M.W. - 616.7 Found 66.04 7.80 4.95 5.00 EXAMPLE 8 Bis(2,6-di-tert-hutyl-4-methoxyearbonyl-phenyl)phosphorous acid diester A solution of 10.5 grams of O-acetyl-(2,6-di-tert-butyl-p-methoxycarbonyl-phenyl ester)phosphite (Example 7) was dissolved in 100 ml of dioxane containing 9.0 grams of water and 1.0 gram of acetic acid and the materials heated together at reflux for 8 hours.

After removal of the solvent at reduced pressures, the residue was crystallized successively from acetonitrile and ethyl acetate yielding the desired product as white crystals melting at about 211-213 C.

Analysis: % C % H Calc. for C,j2H4v07P 66.81 8.26 M.W. - 574.7 Found 66.43 7.72 EXAMPLE 8A Bis (2,6-di-tert-butethoxycarbonyl-4-methoxycarbonyl-phenyl)phosphorous acid diester 6.0 grams of triethylamine dissolved in 100 ml of toluene are added dropwise at 5 C to 2.7 grams of phosphorous trichloride and 15.9 grams of methyl-3,5-di-tertiary-butyl-4hydroxybenzoate dissolved in 50 ml of toluene and heated at reflux overnight. After cooling to room temperature and removing the triethylamine hydrochloride by filtration, the organic phase is washed three times with water, the separated organic solution is dried over sodium sulfate. After removal of the organic solvent by distillation at reduced pressure; the isolated residue is crystallized from a hexane-toluene mixture yielding the desired compound as white crystals M.P. 200-201 C contaminated by by-products.

EXAMPLE 9 O-acetvl- (2, 6-d i-tert-butyl-4-2 ', -4'-di-tert-butylphenoxycarbonyl-phenyl)phosphite The compound of this example (M.P. 174-177 C) is prepared by an analogous method as that shown in Example 7 by substituting bis-(2,6-di-tert-butyl-4-2',4'-di-tert-butyl- phenoxycarbonyl-phenyl)phosphorochloridite (Example 2) for bis-(2,6-di-tert-butyl-4- methoxycarbonyl-phenyl )phosphorochloridite.

EXAMPLE 10 Bis(2, 6-di-tert-butyl-4-2',4' -di-tert-butylphenoxycarbonyl-phenyl) phosphorous acid diester The compound of this example is prepared by an analogous method as that disclosed in Example 8 by hydrolyzing the title compound of Example 9 except that p-toluenesulfonic acid is used as catalyst. The compound of this example has a melting point of 234-237 C.

EXAMPLE 11 O-A cetyl-bis (2,6-di-tert-butyl-4 m tert- (2 ethorycarbollylethyl-phenyl) phosphite The compound of this example (M.P. 123-125 C) is prepared by an analogous method to that shown in Example 7 by substituting bis(2.6-di-tert-butyl-4 methoxycarbonylethylphenyl)phosphorochloridite (Example 3) for bis(2,6-di-tert-butyl-4methoxycarbonyl-phenyl)phosphorochloridite .

EXAMPLE 12 Bis(2,6-di-tert-bzityl-4-metho oxycorbon.',l-edylph et'yl)phosphoroiis acid diester The compound of this example is prepared by an analogous method to that disclosed in Example 8 by hydrolyzing the title compound of Example 11. The melting range observed is 105-113"C on crystallization from m-heptane.

EXAMPLE 13 By essentially following the procedure of Example 1 and substituting the following esters for methyl 3,5-di-tert-butyl-4-hydroxybenzoate: (a) n-octadecyl 3-tert-butyl-4-hydroxy-benzoate -'(b) n-dodecyl 3-methyl-5-tert-butyl-4-hydroxy-benzoate (c) n-hexyl 3,5-di-isopropyl-4-hydroxybenzoate there are respectively obtained: (a) bis-(2-tert-butyl-4-n-octadecyloxy-carbonylphenyl)phosphornchlondite.

(b) bis-(2-methyl-6-tert-butyl-4-n-dodecyloxycarbonylphenyl)phosphorochloridite.

(c) bis-(2,6-di-isopropyl-4-n-hexoxy-carbonylphenyl)phosphorochloridite.

EXAMPLE 14 By essentially following the procedure of Example 2 and substituting the following esters for 2' ,4'-di-tert-'butylphenyl 3 3,5-di-tert-butyl-4-hydroxybenzoate: (a) 2'-methyl-4',6'-di-tert-butylphenyl 3 ,5-di-tert-butyl-4-hydroxybenzoate (b)- 2',6'-di-sec.-butyl-4'-methylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate (c) 2' ,4' ,6'-tri-isopropylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate (d) 2',4' ,6'-tri-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate (e) 4'-n-dodecyl-2',6'-dimethylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate there are respectively obtained: (a) bis-(2,6-di-tert-butyl-2'-methyl-4',6'-di-tert-butylphenoxycarbonylphenyl)- phosphorochloridite.

(b1 bis-(2,6-di tert-butyl-4-2',6'-di-sec.-butyl-4'-methylphenoxyCarbonylphenyl)- phosphorochloridite.

(c) bis-(2 butyl-4-2',4',6'-triisopropylphenoxycarbonylphenyl)phosphoro- chloridite.

(d) bis-(2,6-di-tert-4-2 ' .6'-tri-tert-butylphenoxycarbonylphenyl)phosphorochloridite.

(e) bis-(2,6-di-tert-butyl-4-2',6'-di-methyl-4'-n-dodecylphenoxyCarbonylphenyl)- phosphorochloridite.

EXAMPLE 15 By essentially following the procedure of Example 3 and substituting the following esters for methyl-3-(3 ,5-di-tert-biityl-4-hydroxyphenyl)propionate: (a) n-6ctadecyl 6-(3,5-di-tert-butyl-4-hydroxyphenyl)hexanoate.

(b) n-tetracosyl 3-(3 ,5-di-tert-butyl-4-hydroxyphenyl)propionate (c) n-octyl 3,5-di-tert-butyl-4-hydroxyphenylacetate there are respectively obtained: (a) bis-(2,6-di-tert-butyl-4 n-octadecyloxycarbonyl-n-pentylphenyl)phosphorochloridite.

(b) bis-(2,6-di-tert-butyl-4-n-tetracosyloxycarbonyl-ethylphenyl)phosphorochloridite.

(c) bis-(2.6-di-tert-butyl-4-n-octyloxycarbonylmethylphenyl)phosphorochlondite.

EXAMPLE 16 By essentially following the procedure of Example 5 and substituting the following phosphorochloridites for cyclic ethylene phosphorochloridite (a) 2-Chloro-1.3.2-benzodithiaphosphole (b) 2-Chloro-l .3.2-benzodioxaphosphole (c) ethylene phosphorochlorodithioate there are obtained the corresponding cyclic phosphites of 2,4-di-tert-butyl 3,5-di-tert-butyl4-hydroxybenzoate.

EXAMPLE 16A In a similar manner to Example 16 there are obtained the corresponding cyclic phosphites by reaction of each of (a) cyclic ethylene ester of phosphorochloridous acid and (b) cyclic 2.2-dimethyltrimethyle,ne ester of phosphorochloridous acid with each of the following: (c) methyl 3.5-di-tert-butyl-4-hydroxybenzoate (d) octadecyl 3.5-di-tert-butyl-4-hydroxybenzoate (e) methyl 3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate (f) n-octyl (3 .5-di-tert-butyl-4-hydroxyphenyl)acetate (g) n-octadecyl 3-(3.5-di-tert-butyl-4-hydroxypheny{)propionate EXAMPLE 17 By essentially following the procedure of Example 7 and substituting the following salts for sodium acetate: (á) sodium benzoate (b) sodium propionate (c) sodium stearate there are respectively obtained: (a) O-benzoyl-bis(2,6-di-tert-butyl-p-methoxycarbonyl-phenyl)phosphite (b) O-propionyl-bis(2.6-di-tert-butyl-p-methoxycarbonyl-phenyl)phosphite (c) O-stearyl-bis(2,6-di-tert-butyl-p-methoxycarbonyl-phenyl)phosphite EXAMPLE 18 Bis- (2, utyl-4-n 6-di-tert-butyl-4-n-octadecyloxy-carbonylphetiyl)phosphorochloridite The compound of this example was made in a similar manner to that of Example 1 by reacting phosphorous trichloride with n-octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate employing triethylamine as acid acceptor. The product was isolated as a waxy white solid.

Analysis: % Cl Calc. 3.31 Found 2.82 EXAMPLE 19 O-A cetyl-bis (2, 6-di-tert-butyl-4-n -octad eevloxyearbonyl-phenyl) phosphite The compound of this example was made in a similar manner to that of Example 7 by reacting the compound of Example 18 with sodium acetate dissolved in a solvent mixture of methanol and benzene. The compound of this example melts at 70-75"C after successive crystallization from ethyl acetate and isopropanol.

EXAMPLE 20 Bis(2, 6-di-tert-butyl-4-tz-octydecyloxy-ca'.bonylphenyl)phospliorous acid diester The compound of this example was made in a similar manner to that of Example 8 by hydrolyzing the compound of Example 19 in a water-dioxane medium at reflux (95-96"C) in the presence of a catalytic amount of p-toluenesulfonic acid. The compound of this example is isolated as white crystals melting at 114-116 after crystallization from methyl ethyl ketone.

Analysis: % C % H Calc. 75.38 11.02 Found 75.17 11.14 EXAMPLE 21 Bis- 0 7, (2. 6-di-tert-butyl-4-n-octadecyloxy-carbonylethyl)phosphorochloridite The compound of this example was made in a similar manner to that of Example 3 by reacting n-octadecyl 3-(3.5-di-tert-butvl-4-hydroxyphenyl)-propionate with phosphorus trichloride in triethylamine. The product was isolated as a white waxv solid. Infrared absorption spectrum conformed to the structure of this product.

EXAMPLE 22 O-Acetyl-lvis(2.6-cli-telt-blgtvl-st-etllvlcclrbo-n-octclctec\loXvcalrbonvl-ethv/-phenyl)phosphite A. The compound of this example (M.P. 44-47 ) was prepared by an analogous method to that disclosed in Example 7 by reacting the compound of Example 21 with sodium acetate dissolved in methanol.

B. By following the above procedure (A) and employing the appropriate phosphorochloridite starting compounds the following compounds are prepared: (a) 0-acetyl-bis (2-tert-btityl-4-n-octadecyloxycarbonyl-phenyl)phosphite (b) O-acetVl-bis(7.6-di-isopropvl-4-ll-hexoxvcarbonyl-phenyl)phosphite (c) Q-acetyl-bis(2.6-di-tert-butyl-4-2' .4' .6'-tri-isopropylphenoxycarbonyl- phenyl)phosphite (d) O-acetyl-bis(2,6-di-tert-butyl-4-2',4',6'-tri-tert-butylphenoxycarbonyl- phenyl)phosphite (e) O-acetyl-bis(2,6-di-tert-butyl-4-n-octadecyloxycarbonyl-n-pentyl-phenyl)phosphite (f) 0-acetyl-bis(2,6-di-tert-butyl-4-n-octyloxycarbonyl-methyl-phenyl)phosphite EXAMPLE 23 Bis (2, i-tert-butyl-4-ethylcarbo-n-octydecyloxy-carbonyl-ethyl-phenyl)phosphorous acid diester A. The compound of this example was prepared by an analogous method to that disclosed in Example 8 by hydrolyzing the compound of Example 22 in aqueous dioxane at reflux (Ca. 96 ) using p-toluene sulfonic acid as catalyst. The compound melts at 72-750C after being purified by dry-column chromotography using silica-gel.

Analysis: % C % H Calc. 75.90 11.19 Found 75.87 10.88 B. By following the above procedure (A) and employing the appropriate O-acetyl bis-phosphite starting compounds listed in Example 22(b) the following compounds are prepared: (a) bis(2-tert-butyl-4-n-octadecyloxy-carbonylphenyl)phosphorous acid diester (b) bis(2 ,6-di-isopropyl-4-n-hexoxy-carbonylphenyl)phosphorous acid diester (c) bis(2,6-di-tert-butyl-4-2'4',6'-tri-isopropylphenoxycarbonyl-phenyl)phosphorous acid diester (d) bis(2,6-di-tert-butyl-4-2',4'.6'-tri-tert-butylphenoxyCarbonyl-phenyl)phosphorous acid diester (e) bis(2,6-di-tert-butyl-4-n-pentyl-n-octadecyloxycarbonyl-phenyl)phosphorous acid diester (f) bis(2,6-di-tert-butyl-4-methyl-n-octyloxycarbonyl-phenyl)phosphorous acid diester.

EXAMPLE 24 [2, 4-Di-t. -butyl-4- (2,4-di-t. -butyl-phenoxv-carbonyl) -phenylJ-phosphorous acid monoester A solution of 4.3 g phosphorous trichloride in 50 ml toluene was added dropwise to a solution of 13.2 g 2',4'-di-t.-butylphenyl-3,5-di-t.butyl-4-hydroxy-benzoate and 3.2 g of triethvlamine in 100 ml toluene. The reaction mixture was stirred at room temperature during 12 h. The precipitate consisting of triethyl-hydrochloride was filtered off and filtrate washed twice with 250 ml of H20 and afterwards dried over sodum sulfate (sicc.). The toluene was vacuum-evaporated and the residue was recrystallized from, toluene/ligroine.

The title compound had a melting point of 182-83 C.

Analysis: C2()H4,PO5 (502.63) Calc. 69.29% C.8.62% H,6,16% P Found 69,32 8.66 6,23 EXAMPLE 25 Ni2 -salt of J2, 4-Di-t. -b't5,l-4- (2. 4-di-t. -bzitylphenoxycarbo'zyl) -phetiyll-ph osphoroits acid monoester To a suspension of 50.2 g (O. I mole) of the title compound of Example 24 in 80() ml water was added 10 ml of a l()-N sodiumhvdroxide solution. 12.5 g (0.0525 mole) of NiCl2.6H20 in 50 ml water were added dropwise to the clear solution. The precipitating product was washed and dried at 6()0C/l 1 mm Hg. The title compound decomposes at 220 C.

Analysis C58H86P201(1Ni (1061.9) Calc. 5,5% Ni, 5,8% P Found 5,4 5,6 EXAMPLE 26 1,000 parts of polypropylene powder (Moplen Fiber Grade - Moplen is a Trade Mark) powder melt index 20 (230"C, 2,160 g)] are mixed in a Brabender kneader at 200"C with 2 parts of (3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid octadecyl ester and 2.5 parts of the light stabilizer of the invention.

The mixture homogenised in this way is withdrawn from the kneader and is pre-pressed, by means of a toggle press, into sheets 2-3 mm thick which are then converted at 260"C in a heated platen press by means of suitable matrices, first into films 0.3 mm thick and, in a further process step, into films 0.1 mm thick.

The films thus produced are heat-treated for 1 hour at 1500C, while avoiding cooling below 1500C, and directly afterwards, are chilled in water at 15"C. The films produced in this way have a homogeneous structure of fine spherulites. Test pieces punched from them have an elongation of approx. 800%.

The films without light stabilizer which were used as a comparison are produced in the same manner.

The polypropylene films are mounted on sample carriers and exposed in a Xeno-150 testing apparatus. After varying periods of time, pieces of film are withdrawn, 5 test pieces are punched from each in the form of tensile test bars and the residual elongation of the latter is determined. The time of exposure, after which the elongation at break of the films has declined to 50% of its value before exposure, is taken as a measure of the protective action of the light stabilizer. The value obtained are listed in the tables which follow.

TABLE A Light srabilization data in polypropylet,ie Hours of exposure in the Xeno apparatus when the elongation at break has declined to 50% of the Stabilizer initial value cyclic ethylene phosphite of 2,4-di-tert-butylphenyl 3.5 di-tert-butyl-4-hydroxybenzoate 4310 cyclic 2.2-dimethyl-trimethylene- phosphite of 2.4-di-tert-butylphenyl- 3.5-di-tert-butyl-4-hydroxybenzoate 2560 None 800 TABLE Ib Hours of exposure in the Xeno apparatus when the elongation at break has declined to 50% of the Stabilizer* initial value cyclic ethylene phosphite of n-octyl 3,5-di-tert-butyl-4 hydroxybenzoate 4340 bis(2,6-di-tert-butyl-p carbomethoxy phenyl) phosphorous acid diester 5193 None 1040 *0.25% of the indicated stabilizer is present in the above formulations. Each formulation and the blank also contain 0.2% octadecyl 3-(3',5'-di-t-butyl-4'-hydroxyphenol)propionate.

Comparatively good stabilization is obtained when the concentration of hindered phosphite varies from 0.05% to 1%.

Other hindered phenolic antioxidants may be used in place of octadecyl 3-(3',5'-di-tbutyl-4'-hydroxyphenyl)propionate in the above mentioned compositions with the hindered phosphites as. for example, di-n-octadecyl a-(3-t-butyl-4-hydroxy-4methylbenzyl)malonate, 2,4-bis(n-octylthio)-6-(3 ,4-di-t-butyl-4-hydroxyaniline)-1 ,3 5- triazine, tetrakis-[methylene-3-(3'.5 '-di-tert-butyl-4 ' -hydroxyphenyl)propionatejmethane, di-octadecyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate, tris-(3,5-di-t-butyl-4hydroxybenzyl)isocyanurate. 26,-di-tert-butyl-4-methylphenol, N,N,N-tris-(3,5-di-tertbutyl-4-hydroxybenzyl)isocyanurate. and 2,4,6-tris(3,5-di-tert-butyl-4-hydroxylbenzyl)- 1,3 ,5-trimethylbenzene.

The hindered phosphite compositions of the above tables are also stabilized when the following UV absorbers are added to the compositions: (a) 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate (b) 2-hydroxy-4-n-octoxybenzophenone (c) 2,2' -thiobis(4-t-octylphenolate)-1-n-butylamine nickel II (d) p-octylphenyl salicylate (e) 2,2' -dihydroxy-4,4'-dimethoxybenzophenone (f) 2(2 '-hydroxy-5 '-methylphenyl)-benzotriazole (g) 2(2' -hydroxy-3'.5 '-di-t-butylphenyl)-5-chlorobenzotriazole.

The compositions of the above tables are also stabilized when the indicated phosphites are replaced with the following stabilizers: (a) O-acetyl-bis-(2,6-tert-butyl-4-carbomethoxyphenyl ester)phosphite (b) bis(2,6-di-tert-butyl-4-carbomethoxy-phenyl)phosphorous acid diester (c) bis(2 .6-di-tert-butyl-4-carbo-2'.4' .di-tert-butylphenoxyphenyl)phosphorous acid diester (d) O-acetyl-(2.6-di-tert-butyl-4-carbo-2',4'-di-tert-butylphenoxyphenyl)phosphite (e) bis(2,6-di-tert-butyl-4-carbomethoxy-ethyl-phenyl)phosphorous acid diester (f) bis-(2.6-di-tert-butyl-4-carbomethoxyphenyl)phosphorochloridite (g) O-acetyl-(2.6-di-tert-butvl-4-carbomethoxyethylphenyl)phosphite (h) bis-(2.6-di-tert-butyl-4-carbo-n-octadecyloxyphenyl) phosphorous acid diester (i) bis-(2,6-di-tert-butyl-4-carbo-n-octadecyloxyethylphenyl)phosphorous acid diester.

EXAMPLE 27 High impact polystyrene resin containing elastomer (i.e.. butadiene-styrene) is stabilized against loss of elongation properties due to exposure to ultraviolet light by incorporation of 0.7cue by weight of cyclic 2.2-dimethyltrimethylene phosphite of 2.4-di-tert-butylphenyl 3.5-di-tert-butyl-4-hydroxybenzoate.

The unstabilized resin is dissolved in chloroform and the stabilizer then added. after which the mixture is cast on a glass plate and the solvent evaporated to yield a uniform film which, upon drying. is removed and cut up. and then pressed for 7 minutes at a temperature of 163"C and a pressure of 140.6 kg/cm2 into sheet of uniform thickness of 0.635 mm. The sheets are then cut into strips approximately 10.2 x 1.3 cm. A portion of these strips is then measured for percent of elongation in the Instron Tensile Testing Apparatus (Instron Engineering Corporation. Quincv. Massachusetts - Instron is a Trade Mark). The remaining portions of the strips are placed in an FS/BL chamber where the samples are mounted on white cardboard stock and the time to 50% reduction in elongation is measured. The stabilized polystyrene resin retains its elongation property longer than the unstabilized resin.

EXAMPLE 28 Unstabilized linear polyethylene is solvent blended in methylene chloride with 0.5% by weight of the substrate of O-acetyl-bis(2,6-di-tert-butyl-p-carbomethoxyphenyl ester)phosphite and then vacuum dried. The resin is then extrusion compounded on a 1 inch 24/1=L/D extruder, melt temperature 450"F (232"C) and pressed for 7 minutes at a temperature of 163"C and a pressure of 140.6 kg/cm2 into a sheet of uniform thickness of 2.54 mm. The sheets are then cut into plaques of 5.1 x 5.1 cm. The plaques are then exposed in an FS/BL exposure device and color measurements made periodically using a Hunter Color Difference Meter Model D25. Polyethylene stabilized with the above compound is found to be much more stable then the unstabilized polyethylene or the polyethylene stabilized only with an antioxidant.

EXAMPLE 29 A quantity of SBR emulsion containing 100 g of rubber (500 ml of 20% SBR obtained from Texas U,.S., Synpol 1500) previously stored under nitrogen, is placed in a beaker and stirred vigorausly. The pH of the emulsion is adjusted to 10.5 with a 0.5N NaOH solution.

To the emulsion is added 50 ml of 25% NaCI solution. A 6% NaCI solution adjusted with hydrochloric acid to a pH 1.5 is added in a thin stream with vigorous stirring. When pH 6.5 is reached, the rubber begins to coagulate and the addition is slowed down in order to maintain uniform agitation. The addition of the acidic 6% NaCI solution is terminated when a pH 3.5 is reached. The coagulated crumb-rubber slurry at pH 3.5 is stirred for 1/2 hour.

The coagulated rubber is isolated by filtration through cheese cloth, and rinsed with distilled water After three subsequent washings with fresh distilled water, the coagulated rubber is dried. first at 25 mm Hg and finally to constant weight under high vacuum ( > 1 mm) at 40-45"C.

The dried rubber (25 g) is heated under nitrogen at 1250C in a Brabender mixer and to this is added with mixing 0.25 g (0.5%) of the cyclic ethylene phosphite of 2,4-di-tertbutylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate. The composition is mixed for 5 minutes after which it is cooled and compression molded at 125"C into 5" x 0.025" plaques.

The plaques are exposed to an Xenon Arc weather-ometer (Xenon is a Trade Mark) and the color measurement (L-b) is made after 45, 125 and 290 hours. The samples stabilized with the above compound are found to be much more light stable than the unstabilized samples.

EXAMPLE 30 Unstabilized thoroughly dried polyethylene terphthalate chips are dry blended with 1.0% of bis(2,6-di-tert-butyl-p-carbomethoxyphenyl)phosphorous acid diester 60/10 denier multifilament is melt spun at a melt temperature of 290"C. The oriented fiber is wound on white cards and exposed in an Xenon Arc Fadeometer. Color measurements are made periodically with a Hunter Color Difference Meter Model D25. The stabilized samples are found to be much more light stable then the unstabilized samples.

EXAMPLE 31 a) A composition comprising acrylonitrilebutadiene-styrene terpolymer and 1% by weight of bis(2,6-di-tert-butyl-4-carbo-2' 4' -di-tert-butylphenoxyphenyl)phosphorous acid diester resists embrittlement due to exposure to ultraviolet light longer than one which does not contain the stabilizer.

b) A composition comprising polyurethane prepared from toluene diisocyanate and alkylene polyols and 1.0% by weight of O-acetyl-(2,6-di-tert-butyl-4-carbo-2',4'-di-tert- butylphenoxyphenyl)phosphite is more stable to sunlight. fluorescent sunlamps, black lights and fluorescent lights than the unformulated polyurethane.

c) A composition comprising a polycarbonate prepared from bisphenol-A and phosgene and 1% by weight of bis(2.6-di-tert-butyl-4-carbo-2'.4'-di-tert- butylphenoxyphenyl)phosphorous acid diester resists discoloration due to exposure to ultraviolet light longer than one which does not contain the stabilizer.

d) A composition comprising polymethylmethacrylate and 0.25% by weight of bis(2.6-di-tert-butyl-4-carbo-2' ,4'-di-tert-butylphenoxyphenyl)phosphorous acid diester resists discoloration due to exposure to ultraviolet light longer than one which does not contain the stabilizer.

EXAMPLE 32 a) A stabilized polyamide (nylon 6,6) is prepared by incorporating therein 0.1% of bis(2,6-di-te, t-butyl-p-carbomethoxyphenyl)phosphorous acid diester. The light stability of the stabilized composition is superior to that of an unstabilized polyamide.

b) A stabilized polyphenylene oxide polymer (prepared by polymerizing 2,6dimethylphenol is prepared by incorporating therein 0.5% by weight of the cyclic ethylene phosphite of n-octyl-3,5-di-tert-butyl-4-hydroxybenzoate. The stabilized compositions resist embrittlement due to exposure to ultraviolet light longer than one which does not contain the stabilizer.

c) A stabilized crystalline polystyrene is prepared by incorporating therein 0.1% weight of the cyclic ethylene phosphite of 3,5-di-tert-butyl-4-hydroxybenzonitrile. The stabilized composition resists embrittlement due to exposure to ultraviolet light longer than one which does not contain the stabilizer.

Antioxidants may also be incorporated into each of the above mentioned compositions, for example, di-n-octadecyl-a,a'-bis(3-t-butyl-4-hydroxy-5-methylbenzyl) malonate, 2,4 bis(4-hydroxy-3 5-di-t-butylphenoxy)-6-(n-octylthioethylthio)-1 ,3 ,5-triazine, 2 ,4-bis(3 ,5-di- t-butyl-hydroxyphenoxy)-6-(n-octylthio-1 ,3 5-triazine, di-n-octadecyl 3(3' ,5'-di-t-butyl-4- hydroxyphenyl)propionate, respectively.

EXAMPLE 33 Method of testing antioxidants in polypropylene Unstabilized polypropylene powder (Hercules Profax 6501 - Profax is a Trade Mark) was thoroughly blended with the indicated amounts of additives. The blended materials were then milled on a two-roll mill at 182"C for 5 minutes, after which time the stabilized polypropylene was sheeted from the mill and allowed to cool.

The milled polypropylene sheets were then cut into pieces and compression molded on a hydraulic press at 220"C, 12.3 kg/cm2 into 0.635 mm thick plaques.

Testing method: Rotary oven-aging test The resulting plaques of 0.635 mm thickness were tested for resistance to accelerated aging in a rotary oven at 1500C. When the plaques showed the first signs of decomposition (e.g., cracking or brown edges) they were considered to have failed. The results are shown below in the table. The amounts of the additives are expressed in weight percent based on the weight of the polymer.

TABLE 2 Stabilzing effectiveness of bis-(2,6-di-tert-butyl-4-ethvlcarbo-n-octadecyloxyphenyl ester) - phosphonic acid (Ex. 23) in polypropylene 6501 Time to Failure Formulations Hrs.

Blank 3 0.3% Bis-(2,6-di-tert-butyl-4 carbo-n-octadecyloxyethylphenyl) phosphorous acid diester 250 0.3cue DSTDP 100 O.1C/e (Bis-(2 .6-di-tert-butyl-4- carbo-n-octadecyloxyethylphenyl t 0.3cue DSTDP phosphorous acid diester 400 The results of Table 2 show that the compound is an effective antioxidant for polypropylene alone and with distearylthiodipropionate (DSTDP).

EXAMPLE 34 100 parts of polypropylene powder (Moplen. fibre grade. Montedison - Moplen and Montedison are Trade Marks) are homogenised with 0.2 part of P-(3,5-di-tert. -butyl-4- hydroxyphenyl)propionic acid-octadecvl ester and 0.25 part of the stabilizer of Example 24 at 200"C in a Brabender plastograph for l() minutes. The mixture thus obtained is removed as quickly as possible from the kneading machine. and is then pressed out in a toggle press subsequently pressed between two highly polished hard-aluminium sheets in a handhydraulic laboratory press for 6 minutes at 260"C under a pressure of 12 tons to form a-sheet having a thickness of 0.5 mm; the sheet is quenched immediately in cold water. From this 0.5 mm thick sheet there are prepared under exactly identical conditions the 0.1 mm thick test sheet. Test specimens each 60 x 44 mm in size are then stamped out from this sheet, and are irradiated in a Xenotest 150. At regular intervals of time, these specimens are removed from the irradiation apparatus and tested in an IR-spectrophotometer for their carbonyl content. The increase of the carbonyl extinction at 5.85 Z on irradiation is a measure for the photooxidative degradation of the polymer (see L. Balaban et al., J. Polymer Sci. Part C, 22, 1059-1071 (1969); J.F. Heacock, J. Polymer Sci. Part A-1, 22, 2921-34 (1969); D.J.

Carlsson and DM. Wiles, Macromolecules 2, 587-606 (1969)), and is from experience associated with a decrease of the mechanical properties of the polymer. Thus, for example, the sheet is completely brittle with the attainment of a carbonyl extinction of about 0.3.

The protective action of the stabilizers of the invention can be clearly seen from the following Table 3: TABLE 3 Stabilizer Irradiation time in hours Example No. until CO-extinction = 0.3 comparison 1040 stabilizer of Example 24 4800 EXAMPLE 35 1000 parts of polypropylene powder [melt index 1,5 g / 10 minutes (230"C, 2160 g) were mixed in a drum mixer with 1 part of tetrakis-ss-(3,5-di-t.-butyl-4-hydroxyphenyl)- pentaerithritpropionate, 3 parts of dilaurylthiodipropionate (DLTDP) and 5 parts of the compound of Example 25. The sample was homogenized in a Brabender-plastograph for 10 minutes at 200"C. The stabilized polymer was pressed in a platen press at 300"C for 6 minutes to give 1 mm thick sheets. The test specimen does not shown any discoloration.

EXAMPLE 36 1000 parts of polypropylene powder (melt index 1.5 g / 10 minutes at 230"C, 2160 g) are mixed in a drum mixer with 1 part of pentaerythritol-tetrakis-[3-(3',5',-di-tert.-butyl-4- hydroxy-phenyl)propionate] and 1.5 parts of a mixture of stabiliser as in Table 4 and subsequently granulated in an extruder at a temperature of 200"-220"C. The resultant granules are processed to a sheet in the conventional manner using an extruder with slot die. This sheet is cut into ribbons which are then stretched to 6 times their length at elevated temperature. The titre of the ribbons is 700-900 den., and their ultimate tensile strength is 5.5-6.5 g/den.

These polypropylene ribbons are applied without tension to test carriers and exposed in a Xenotest apparatus 1200. Five test specimens are taken after different times and their ultimate tensile strength determined. Criterion for the protective action of the individual nickel compounds is the 'protectiye factor", which is defined as follows: exposure time of the light stabilized sample up to "protective factor" = 50% loss of ultimate tensile strength exposure time of the unstabilized sample up to 50% loss of ultimate tensile strength The values obtained are listed in the following Table 4 TABLE 4 Stabilizer exposure time (h) protective factor none 337 1.0 Compound of Example 25 5550 4.6 EXAMPLE 37 Stabilization of polypropylene against degradation during processing 0.1 part of the stabilizer of Example 25 is homogeneously mixed with 100 parts of polypropylene powder ("Propathene HF 20" of Messrs. ICI - Propathene is a Trade Mark) and the mixture is re-granulated 5 times successively in a single screw extruder at a maximum temperature of 260 C and 100 r.p.m. The melt index (MI) of the material is measured after the 1st, 3rd and 5th extrusion respectively (see Table 5) (2,160 g load at 230 C; figures in grams per 10 minutes). Degradation of the polymer manifests itself by a rapid increase of the melt index. An experiment was carried out in the same way in parallel, no stabilizer being added.

TABLE 5 Melt index Stabilizer 1st 3rd 5th extrusion extrusion extrusion none 9.6 32.4 66.2 Stabilizer of Example 25 6.8 13.6 21.6 Stabilizer of Example 25 t 0.1% Ca-stearate 5.7 13.3 19.0 WHAT WE CLAIM IS: 1. Compounds of the formula

wherein Rl and R2 are independently C1-C12 alkyl. C5-C5 cycloalkyl, C7-C. aralkyl or hydrogen. provided that only one of R, and R2 can be hydrogen, R 3 is -(CtH2t)-COOR4 (II) -(CtH2t)-COOM1/q (III) or-CN, wherein t denotes 0 to 6. and R4 is C1-C24 alkyl. phenyl or alkyl substituted phenyl with 1 to 18 carbon atoms in the alkyl moieties. and M is a metallic cation with the valency 1, 2 or 3 and q is 1. 2 or 3.

is is 0 or 1, and m and n are each 1 or 2. the values of m, n and n; being such that the trivalent state of P is satisfied.

and is is -XH. wherein X is -O- or -S-. and R denotes halogen. -XH or -XR5. wherein X is -S- or -0- and R5 denotes C-C.4 alkyl. phenyl or alkyl substituted phenyl with 1-18 carbon atoms in the alkyl moieties or R, is, when n is 1, also Mli,l, wherein M and q are as defined above. or R5 is, when X is -O. C-C, alkanoyl. benzoyl or alkyl substituted benzoyl with 1 to 18 carbon atoms in the alkyl moieties. n;' is 0 and two R groups taken together are a group of the formula

wherein R(, is phenylene. alkyl substituted phenylene with 1-18 carbon atoms in the alkyl

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. EXAMPLE 37 Stabilization of polypropylene against degradation during processing 0.1 part of the stabilizer of Example 25 is homogeneously mixed with 100 parts of polypropylene powder ("Propathene HF 20" of Messrs. ICI - Propathene is a Trade Mark) and the mixture is re-granulated 5 times successively in a single screw extruder at a maximum temperature of 260 C and 100 r.p.m. The melt index (MI) of the material is measured after the 1st, 3rd and 5th extrusion respectively (see Table 5) (2,160 g load at 230 C; figures in grams per 10 minutes). Degradation of the polymer manifests itself by a rapid increase of the melt index. An experiment was carried out in the same way in parallel, no stabilizer being added. TABLE 5 Melt index Stabilizer 1st 3rd 5th extrusion extrusion extrusion none 9.6 32.4 66.2 Stabilizer of Example 25 6.8 13.6 21.6 Stabilizer of Example 25 t 0.1% Ca-stearate 5.7 13.3 19.0 WHAT WE CLAIM IS:

1. Compounds of the formula

moieties or C2-C24 alkylene and X is as defined above, and m and n are each 1 and 2 respectively, and R is furthermore a group of the formula

wherein R7 is a group

wherein Rl1 denotes alkylene of 1 to 34 carbon atoms, C6-Cio arylene or the direct bond, and R1, R2 and R3 are as defined above, and m is 2 and n is 1, or furthermore nazis 0 and two R groups taken together denotes a group of the formula

wherein R,, R2 and R3 are as defined above, and m and n are each 1 and 2 respectively.

2. Compounds according to claim 1 of the formula

wherein the cyclic structure

is a 5 or 6 membered ring where R6 is alkylene of 2 to 24 carbon atoms. and R,, R2, R3 and X are as defined in claim 1.

3. Compounds according to claim 1 of the formula

wherein R11 is alkylene of 1 to 34 carbon atoms, arylene or the direct bond and R1, R2 and R3 are as defined in claim 1.

4. Compounds of the formula I. wherein Rl and R2 are independently C-Cl2 alkyl or hydrogen, provided that only one of R1 and R2 can be hydrogen.

R3 is -(C,H2,)-COOR4 or -CN, where t is 0 to 6 and R4 is C-C24 alkyl. phenyl or alkyl substituted phenyl with 1 to 18 carbon atoms in the alkyl moieties, and n is 0 R is halogen or when m is 2 and n is 1, hydroxyl, or R denotes -XR5 wherein X is -O- or -S- and R5 is C1-C24 alkyl, phenyl or alkyl substituted phenyl with 1 to 18 carbon atoms in the alkyl moieties, and when X is -O-, R5 denotes additionally C1-C30 alkanoyl, benzoyl, or alkyl substituted benzoyl with 1 to 18 carbon atoms in the alkyl moieties or n* is 0 and two R groups taken together are a group of the formula

wherein R6 is phenylene, alkyl substituted phenylene with 1 to 18 carbon atoms in the alkyl moieties or C2-C24 alkylene, X is as defined above, and m and n are each 1 and 2 respectively, or R is furthermore a group of the formula

wherein R7 is a group

wherein R11 denotes alkylene with 1 to 34 carbon atoms, C6 to C10 arylene or the direct bond, R1, R2 and R3 are as defined above, and m is 2 and n is 1, or n* is 0 and two R groups together a group of the formula

wherein R1, R2 and R3 are as defined above, and m and n are each 1 and 2 respectively.

5. Compounds of the formula I, wherein R1 and R2 are independently C-C8 alkyl, C5-Cx cycloalkyl or C7-C9 aralkyl and R3 denotes -(C,H2t)-COOR4 (Il) or -(CtH2t)-COOM1/9 (III) or-CN, wherein M is a metallic cation with the valency 1, 2 or 3 and q is 1, 2 or 3 and t denotes 0 to 6, and R4 is C,-C24 alkyl, phenyl or alkyl substituted phenyl with 1-18 carbon atoms in the alkyl moieties, and is is 1, and RR is -XH, wherein X is -O- or -S-, and m and n are 1, and R is -XRS, wherein X is -O- or -S- and R5 denotes M1/4 wherein M and q are as defined above.

6. Compounds according to claim 4 of the formula I wherein R1 and R, are t-alkyl groups having 4 to 8 carbon atoms, R3 is a group -(CtH2t)-COOR4 or -CN, wherein t is 0 to 2 and R4 denotes C1-C24 alkyl. phenyl or phenyl substituted by 1 to 3 alkyl groups with 1 to 12 carbon atoms in the alkyl moieties, and n S is 0, with R, m and n being as defined in claim 4.

7. Compounds according to claim 5 of the formula I, wherein R1 and R2 are t-alkyl groups having 4 to 8 carbon atoms and R3 denotes a group of the formula II or III wherein t is 0 and R4 is C,-C,8 alkyl, phenyl or alkyl substituted phenyl with 1 to 8 carbon atoms in the alkyl moieties and m, n and n:b are each 1, RF is hydroxyl and R is -XRS wherein X is -O- and M is Co2+ or Ni2 and q is 2.

8. Compounds according to claim 1 of the formula I, wherein R1 and R2 are t-butyl. n is 0, n is 1 and m is 2 and R denotes -OH, whereas R3 is as defined in claim 1.

9. Compounds according to claim 1 of the formula I, wherein R3 is a group of the formula II and R1, R2, R4, R R*, n, n* and m are as defined in claim 1.

1.fi. Compounds according to claim 1 of the formula I, wherein n* is 1, R* is -OH and R5 denotes My/4, where M and q are as defined in claim 1.

11. Compounds according to claim 10, wherein M is Ni2+ or Co2+.

12. A composition comprising a polymeric organic material and a compound of the formula I, as defined in any one of claims 1 to 11.

13. A composition according to claim 12, in which the organic material is a polyolefine or polystyrene.

14. A composition according to claim 13, in which the polyolefine is polypropylene.

15. Process for the preparation of compounds of the formula I, according to claim 1, which comprises reacting about m moles of a compound of the formula

with about one mole of a compound of the formula (R)nP(Y)m (V) where M* is an alkali metal or hydrogen and Y denotes halogen, and R, RI, R2, R3, n and m are as defined in claim 1, and if desired hydrolyzing remaining halogen atoms or forming salts from halogen atoms, or from free hydroxyls resulting from hydrolysis.

16. A compound of the formula I, defined in claim 1, substantially as hereinbefore described with reference to any one of the foregoing Examples 1 to 25.

17. A composition as claimed in claim 12, substantially as hereinbefore described.

18. A composition as claimed in Claim 12, substantially as hereinbefore described with reference to any one of Examples 26 to 37.

19. A process for preparing a compound of formula I, as claimed in claim 15, substantially as hereinbefore described with reference to any one of Examples 1 to 25.