CA1040212A - Hindered phenol pentaerythritol phosphonate - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Hindered phenol compounds are prepared having the formula:

Description

1(14~
The present invention relates to novel hindered phenolic hydroxyl group containing phosphonates.
The phosphonates of the present invention have the formula:
R OH R

L ~ ol o HO
(CH2)n P~ O CH ~C \ ~ P - (CH2)n ~

R' R' I

where n is an integer of 1 to 4, R is alkyl, hydrogen, cyclo-alkyl or aralkyl and R' is alkyl, cycloalkyl or aralkyl. Thus R and R' for example, can be alkyl of 1 to 20 or even 30 carbon atoms, e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec. butyl, t-butyl, t-amyl, amyl, hexyl, heptyl, octyl,

2-ethylhexyl, isooctyl, t-octyl, decyl, dodecyl, octadecyl, eicosanyl, tetracosyl or triacontyl, cycloalkyl of 5 to 12 carbon atoms or more, e.g. cyclopentyl cyclohexyl, methyl cyclohexyl, cyclooctyl, cyclodecyl or cyclododecyl, or aralkyl of 7 to 36 carbon atoms or more, e.g. benzyl, 4-methylbenzyl, phenethyl, 6-phenylhexyl, 12-phenyldodecyl, 12-alpha-naphthyl-dodecyl, 24-phenyltetracosyl, 30-phenyltriacontyl.
Preferably R and R' are both alkyl, more preferably at least one of R and R' is tertiary alkyl and most preferably both R and R' are tertiary alkyl.

~ .

1(~4(~i~1Z

Examples of compounds within the present invention are 3,9-di(3,5-di-t-butyl-4-hydroxybenzyl)-3,9-dioxo-2,4,8,10,

3,9-tetraoxadiphospha-spiro(5,5)hendecane; 3,9-di(2-(3,5-dimethyl-4-hydroxyphenyl)ethyl)-3,9-oxo-2,4,8,10,3,9-tetraoxa-diphospha-spiro(5,5)hendecane; 3,9-di(2-hydroxy-3-t-butyl-5-methylbenzyl)-3,9-dioxa-2,4,8,10,3,9-tetraoxadiphospha-spiro-(5,5)hendecane. Other examples of compounds within the present invention are set forth in Table 1 below. The compounds in Table 1 have the formula:
O O
R3 _ p~ ~C \ CH O ~ 4 .

Table 1 Compound R3 R4 1 3-t-butyl-4-hydroxybenzyl 4-hydroxybenzyl 2 3,5-di-t-octyl-4-hydroxy- 3,5-di-t-octyl-4-hydroxy-benzyl benzyl 3 3,5-di-n-octyl-4-hydroxy- 3,5-di-n-octyl-4-hydroxy-benzyl benzyl

4 3,5-di-t-butyl-4-hydroxy- 3,5-di-t-amyl-4-hydroxy-benzyl benzyl 3,5-di-dodecyl-4-hydroxy- 3,5-di-dodecyl-4-hydroxy-benzyl benzyl 6 3-eicosanyl-4-hydroxybenzyl 3-eicosanyl-4-hydroxybenzyl 7 3-triacontyl-4-hydroxy- 3-triacontyl-4-hydroxy-benzyl benzyl 8 3,5-dicyclohexyl-4-hydroxy- 3,5-dicyclohexyl-4-hydroxy-benzyl benzyl ` 9 3-cyclohexyl-5-ethyl-4- 3-cyclohexyl-5-ethyl-4-j hydroxybenzyl hydroxybenzyl 3,5-dicyclopentyl-4- 3,5-dicyclopentyl-4- -.~
hydroxybenzyl hydroxybenzyl 11 3-methylcyclohexyl-4- 3-methylcyclohexyl-4-i hydroxybenzyl hydroxybenzyl 12 3-cyclododecyl-4-hydroxy- 3-cyclododecyl-4-hydroxy-benzyl benzyl _ 3 _ - ~ - .

.
' ~', 13 3,5-dibenzyl- ~ ~ ~ ~ 3,5-dibenzyl-4-hydroxy-benzyl benzyl 14 3-benzyl-5-t-butyl-4- 3-benzyl-5-t-butyl-4-hydroxybenzyl hydroxybenzyl 15 3,5-di-t-butyl-2-hydroxy- 3,5-di-t-butyl-2-hydroxy-benzyl benzyl 16 3,5-dihexyl-2-hydroxybenzyl 3,5-dihexyl-2-hydroxybenzyl 17 3,5-dicyclohexyl-2-hydroxv- 3,5-dicyclohexyl-2-hydroxy-benzyl benzyl 18 4-(3-methyl-5-cyclohexyl-4- 4-(3-methyl-5-cyclohexyl-4-hydroxyphenyl)butyl hydroxyphenyl)butyl 19 4-(3,5-di-t-butyl-4- 4-(3,5-di-t-butyl-4-hydroxyphenyl)butyl hydroxyphenyl)butyl 20 3-(3,5-di-t-octyl-4- 3-(3,5-di-t-octyl-4-hydroxyphenyl)propyl hydroxyphenyl)propyl 21 2-(3,5-di-t-butyl-4- 2-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl hydroxyphenyl)ethyl 22 3,5-diethyl-4-hydroxybenzyl 3,5-diethyl-4-hydroxybenzyl 23 2-hydroxy-3-t-butyl-5-methylbenzyl The compounds of the present invention can be prepared by any of the following reactions:
O-CH ` ~ CH -O ~
(1) R40 - p\ 2~C ~ 2 ~ p - OR4 +

R OH

2 ~ (CH2)nX~~~ Formula I

R' ? where X is a halogen, preferably of atomic weight 35 to 80, i.e. chlorine, bromine or iodine.
~ O-CH ` ~ CH -O ~
(2) R50 - P~ 2,C ~ 2 ~ p - OR5 +

R OH

2 ~ (CH2)nOH + (alkaline catalyst) ~ Formula I

R' - , R OH

(3) Cl p~ -CH2`C / CH2- \ ~ Cl 2 ~ (CH2)nOH

+ 2 N-(C2H5)3 or other tertiary amine > Formula I

In formu1a (2) R5 can be aryl such as phenyl or cresyl or alkyl such as methyl, butyl, ethyl, isopropyl, hexyl or octyl, for example. Any conventional alkaline catalyst can be used, for example, sodium hydroxide, potassium hydroxide, sodium methylate, sodium phenolate, sodium hexylate, potassium methylate. -Typical examples of starting materials for reaction (2) are diphenyl pentaerythritol diphosphite, dimethyl penta-erythritol diphosphite, diethyl pentaerythritol diphosphite, dibutyl pentaerythritol diphosphite, diisooctyl pentaerythritol diphosphite.
~ In procedure (1) R4 can be any of the alkyl groups mentioned for R5. However, R4 cannot be an aryl group. Thus - in reaction (1) there can be used dimethyl pentaerythritol diphosphite,diethyl pentaerythritol diphosphite, dibutyl penta-erythritol diphosphite, dibutyl pentaerythritol diphosphite, .
diisopropyl pentaerythritol diphosphite, dioctyl pentaerythri-tol diphosphite.

-:

.. ~ . - ....... ~ . ................. - - .
.

~1~4~
In procedure (3) the tertiary amine can be tripropyl amine, tributyl amine, diethylmethyl amine, etc. In reaction 3 when n is 1, the phosphonate is the only product. In reaction 3 when n is 2, 3 or 4, any phosphite formed can be rearranged to the phosphonate by adding a small amount of sodium iodide or potassium iodide, e.g. 1 to 10 mol % of the dichloropentaeryth-ritol diphosphite.
As hindered phenols to be used as starting materials to make the final hindered phenol phosphonates there can be used, for example, 3,5-di-t-butyl-4-hydroxybenzyl chloride, 3,5-di-t-butyl-4-hydroxybenzyl alcohol, 3,5-di-t-butyl-4-hydroxybenzyl bromide, 3,5-di-t-butyl-4-hydroxybenzyl iodide, 3,5-dimethyl-4-hydroxybenzyl chloride, 3,5-dimethyl-4-hydroxy-benzyl alcohol, 4-(3-methyl-5-cyclohexyl-4-hydroxyphenyl)butyl chloride, 4-(3-methyl-5-cyclohexyl-4-hydroxyphenyl)butyl alcohol, 3-(2-hydroxy-4-t-butylphenyl)propyl chloride, 3-(2-hydroxy-4-t-butylphenyl)propyl alcohol, 3,5-di-t-octyl-4-hydroxybenzyl bromide, 3-t-butyl-4-hydroxybenzyl chloride, 3-t-butyl-4-hydroxybenzyl alcohol, 3,5-di-n-octyl-4-hydroxybenzyl chloride (and the corresponding alcohol), 3,5-di-t-amyl-4-hydroxybenzyl alcohol (and the corresponding chloride), 3,5-di-dodecyl-4-hydroxybenzyl chloride (and the corresponding alcohol), 3-eicosanyl-4-hydroxybenzyl alcohol (and the corre-sponding chloride), 3-triacontyl-4-hydroxybenzyl chloride (and the corresponding alcohol), 3,5-dicyclohexyl-4-hydroxybenzyl chloride (and the corresponding alcohol), 3-cyclohexyl-5-ethyl-4-hydroxybenzyl alcohol (and the corresponding chloride), 3,5-, - .
.. ' ~. ' ''' . ~
, .

1~)41~ZlZ
dicyclopentyl-4-hydroxybenzyl chloride (and the corresponding alcohol), 3-methylcyclohexyl-4-hydroxybenzyl alcohol, 3,5-dibenzyl-4-hydroxybenzyl chloride (and the corresponding alcohol), 3-benzyl-5-t-butyl-4-hydroxybenzyl alcohol (and the corresponding chloride), 2-hydroxy-3-t-butyl-5-methylbenzyl chloride (and the corresponding alcohol), 2-hydroxy-3,5-di-t-butyl-benzyl alcohol (and the corresponding chloride), 2-hydroxy-3,5-dihexylbenzyl chloride (and the corresponding alco-hol), 3,5-di-t-butyl-4-hydroxyphenyl-butyl alcohol (and the corresponding chloride), 2-(3,5-di-t-butyl-4-hydroxyphenyl)-ethyl alcohol (and the corresponding chloride).
If mixed products are desired such as that of compound 1 of Table 1, there can be used a mixture of starting ~-phenols.
The hindered phenol phosphonate compounds of the : present invention are useful as phenolic antioxidants. Thus they can be used to stabilize organic materials normally subject to oxidative deterioration.
The phenolic phosphonate antioxidant is used in an amount of 0.005 to 10 parts per 100 parts of the polymer or other material to be stabilized, preferably 0.1 to 5 parts per 100 parts of polymer. Thus they are useful with many different kinds of solid polymers. For example, they can be used with resins made from vinylidene compounds such as vinyl chloride, vinylidene chloride, vinyl chloroacetate, chlorostyrenes, vinyl bromide and chlorobutadienes.
Such vinylidene compounds may be polymerized alone or in admixture with each other or with vinylidene compounds free ., , ~ .
- .. . . .
- . .- - . . - .
- . , . ,~
,' 1~)4~212 from halogen. Among the halogen free materials which can be copolymerized with the halogen containing vinylidene compounds, e.g. vinyl chloride, are vinyl esters of carboxylic acids, e.g.
vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate, es~ers of unsaturated acids, e.g. alkyl and alkenyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and allyl acrylate as well as the corresponding methacrylates, e.g. methyl methacrylate and butyl methacrylate, vinyl aromatic compounds, e.g. styrene p-ethyl styrene, divinyl benzene, vinyl naphthalene, ~-methyl styrene, p-methyl styrene, dienes such as butadiene and isoprene, unsaturated amides such as acrylamide, methacrylamide and acrylanilide and the esters of ~ unsaturated carboxylic acids, e.g., the methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, allyl, methallyl and phenyl esters of maleic, crotonic, itaconic and fumaric acids and the like. Specific examples of such esters are diethyl maleate, dibutyl maleate and dibutyl fumarate.
The copolymers in which at least 50% of the copolymer is made from a halogen containing vinylidene compound such as vinyl chloride, are among the preferred materials treated according to the invention.
The antioxidants or stabilizers of the present invention are also effective when intimately mixed with halogen containing resins in which part or all of the halogen is intro-duced into a preformed resin, e.g. chlorinated polyvinyl acetate, chlorinated polystyrene, chlorinated polyethylene, 11~t4~ZlZ

chlorinated polyvinyl chloride, chlorinated natural and syn-thetic rubbers and rubber hydrochloride.
Typical examples of copolymers include vinyl chlo-ride-vinyl acetate (95:5 weight ratio), vinyl chloride-vinyl acetate (87:13 weight ratio), vinyl chloride-vinyl acetate-maleic anhydride (86:13:1 weight ratio), vinyl chloride-vinyl-idene chloride (95:5 weight ratio), vinyl chloride-diethyl fumarate (95:5 weight ratio), vinyl chloride-trichloroethylene (95:5 weight ratio).
The resin, e.g. polyvinyl chloride, can either be plasticized or unplasticized. As the plasticizer there can be employed conventional materials such as dioctyl phthalate, octyl decyl phthalate, tricresyl phosphate, 2-ethylhexyl - diphenyl phosphate, dodecyl dicresyl phosphate, tributyl acetyl citrate, dioctyl sebacate, dibutyl sebacate, etc. The plasti-cizer is used in conventional amount, e.g. 10 to 100 parts for each 100 parts of the vinyl chloride containing resin.
There can also be incorporated 0.1 to 10 parts per 100 parts of the halogen containing resin of a metal salt stabi-lizer. Thus, there can be used barium, strontium, calcium,cadmium, zinc, lead, tin, magnesium, cobalt, nickel, titanium and aluminium salts of phenols, aromatic carboxylic acids, fatty acids and epoxy fatty acids.
Examples of suitable salts include barium di(nonyl-phenolate), strontium di(nonylphenolate), strontium di(amyl-phenolate), barium di(octylphenolate), strontium di(octylpheno-late), barium di(nonyl-o-cresolate), lead di(octylphenolate), .

_ g _ 1(~4(~212 cadmium-2-ethylhexoate, cadmium laurate, cadmium stearate, zinc caprylate, cadmium caproate, barium stearate, barium-2-ethyl-hexoate, barium laurate, barium ricinoleate, lead stearate, aluminum stearate, magnesium stearate, calcium octoate, calcium stearate, cadmium naphthenate, cadmium benzoate, cadmium p-tert. butylbenzoate, barium octyl salicylate, cadmium epoxy stearate, strontium epoxy stearate, cadmium salt of epoxidized acids of soybean oil, and lead epoxy stearate.
In plastisol formulations there can also be included from 0.1 to 10 parts per 100 parts of resin of an epoxy vegeta-ble oil such as epoxidized soybean oil or epoxidized tall oil.
The antioxidants of the present invention are par-ticularly effective with solid unsaturated hydrocarbon polymers such as polyethylene, polypropylene, ethylene propylene co-polymers (e.g. 50:50, 80:20 and 20:80), ethylene-monoolefin copolymers wherein the monoolefin has 4-10 carbon atoms and is present in a minor amount, e.g. ethylene-butene-l copolymer (95:5) and ethylene-decene-l copolymer (90:10) polybutene.
Furthermore, they can be used to stabilize natural rubber, - 20 styrene-butadiene rubber (SBR rubber), e.g. (75% butadiene-25%
styrene), EPDM rubbers, ABS terpolymers (e.g. 20-30% acrylo-nitrile, 20-30% butadiene, 40-60% styrene), polyisoprene, poly-butadiene, styrene-acrylonitrile copolymers, butyl rubber, polyacrylonitrile and acrylonitrile copolymers (e.g. acrylo-nitrile-vinyl chloride 85:15), polystyrene, impact modified polystyrene, butadiene-acrylonitrile (e.g. 60:40)i polymerized acrylates and methacrylates, e.g. polymethyl acrylate poly-lU4~

methyl methacrylates and polybutyl acrylate, polyacetals, e.g.
polyoxymethylene polymers (e.g. Delrin and Celcon ), poly-carbonates (e.g. bisphenol A-carbonate polymer), polysulfones, polyphenylene oxides, phenoxy resins, epoxy resins, A-epichlor-hydrin, nylon, cellulose acetate, cellulose acetate-propionate, cellulose acetate-butyrate, cellulose nitrate, polyethylene oxide, ethyl cellulose linear polyesters, e.g. polyethylene terephthalate (Dacron~, Mylar~), unsaturated polyester, e.g.
vinyl compounds modified alkyds such as ethylene glycol phthalate-maleate modified with styrene or diallyl phthalate, oil modified alkyd resins, e.g. soybean oil-glyceryl phthalate resin, chlorosulfonated polyethylene, polyurethanes (e.g.
toluene diisocyanate reaction products with polypropylene glycol molecular weight 2025 or with glycerine-ethylene oxide adduct having a hydroxyl number of 56).
As the EPDM rubber there can be employed many of the - commercially available EPDM rubbers. The EPDM rubber normally - contains 30 to 70 molar percent (preferably 50 to 60 molar percent) of ethylene, 65 to 20 molar percent (preferably 35 to 20 45 molar percent) propylene and 1 to 15 molar percent (prefer-ably 3 to 5 molar percent) of the nonconjugated polyolefin.
Usually the polyolefin is not over 10 molar percent. The ethylene and propylene can each be 5 to 95 molar percent of the composition.
As used in the present specification and claims, the term nonconjugated polyolefin includes aliphatic nonconjugated polyene hydrocarbons and cycloaliphatic nonconjugated polyene ~ 04~iZlZ
hydrocarbons, e.g., endocyclic dienes. Specific examples of suitable nonconjugated polyolefins include pentadiene-1,4i hexadiene-1,4; dicyclopentadiene, methyl cyclopentadiene dimer, cyclododecatriene, cyclooctadiene-1,5; 5-methylene-2-nor-bornene.
Specific examples of suitable terpolymers are the Royalenes~ which contain 55 mole percent ethylene, 40 to 42 mole percent propylene and 3 to 5 mole percent dicyclopenta-diene, Enjay~ terpolymers, e.g. ERP-404 of Enjay~ and Enjay~
3509 which contains about 55 mole percent ethylene, 41 mole percent propylene and 4 mole percent 5-methylene-2-norbornene;
Nordel~, a terpolymer of 55 mole percent ethylene, 40 mole percent propylene and 5 mole percent hexadiene-1,4. Another suitable terpolymer is the one containing 50 mole percent ethylene, 47 mole percent propylene and 3 mole percent 1,5-cyclooctadiene (Dutrel ).
Examples of EPDM rubbers are given in United States Patents 2,933,480; 3,000,866; 3,063,973; 3,093,620; 3,093,621 and 3,136,739, in British Patent 880,904 and in Belgian Patent 623,698.
There can also be incorporated in the hydrocarbon polymers, e.g. polypropylene conventional additives such as phosphites in an amount of 0.1 to 10 parts per 100 parts of polymer. Typical of such phosphites are triphenyl phosphite, tris decyl phosphite, decyl diphenyl phosphite, di(p-t-butyl-phenyl)phenyl phosphite, di-phenyl-o-cresyl phosphite, trioctyl phosphite, tricresyl phosphite, tribenzyl phosphite, polymeric phosphites such as Westo~ 243-B (made in accordance with patent : .
.
- :
, . . .
- . . , ~, , ~ . : ~ ' :

1~)4(~1Z

3,341,629) and prepared from triphenyl phosphite and hydrogen-ated bisphenol and having a molecular weight of about 3000 and Weston 440 (a linear polymeric pentaerythritol hydrogenated bisphenol A phosphite made in accordance with patent 3,053,878, Weston WX 618-(distearyl pentaerythritol diphosphite), thio-phosphites such as trilauryl trithiophosphite and tristearyl trithiophosphite.
There can also be included thio compounds in an amount of 0.01 to 10%, usually 0.1 to 5% of the polymer. Thus, there can be used pentaerythritol tetra(mercaptoacetate), l,l,l-trimethylolethane tri(mercaptoacetate), l,l,l-trimethyl-- olpropane tri(mercaptoacetate), dioleyl thiodipropionate, di-lauryl thiodipropionate, other thio compounds include distearyl 3,3'-thiodipropionate, dicyclohexyl-3,3'-thiodipropionate, ~ dicetyl-3,3'-thiodipropionate, dioctyl-3,3'-thiodipropionate, - dibenzyl-3,3'-thiodipropionate, lauryl myristyl-3,3'-thiodi-propionate, diphenyl-3,3'-thiodipropionate, di-p-methoxyphenyl-3,3'-thiodipropionate, didecyl-3,3'-thiodipropionate, dibenzyl-3,3'-thiodipropionate, diethyl-3,3'-thiodipropionate, lauryl ester of 3-methyl-mercapto propionic acid, lauryl ester of 3-butyl-mercapto propionic acid, lauryl ester of 3-lauryl-mercapto propionic acid, phenyl ester of 3-octylmercapto propi-onic acid, lauryl ester of 3-phenylmercapto propionic acid, lauryl ester of 3-benzyl-mercapto propionic acid, lauryl ester ~ of 3-(p-methoxy)phenylmercapto propionic acid, lauryl ester of ; 3-cyclohexylmercapto propionic acid, lauryl ester of 3-hydroxy-methylmercapto propionic acid, myristyl ester of 3-hydroxy-ethylmercapto propionic acid, octyl ester of 3-methoxy-methyl-i(~4(~21Z
mercapto propionic acid, dilauryl ester of 3-carboxy-methyl-mercapto propionic acid, dilauryl ester of 3-carboxy-propyl-mercapto propionic acid, dilauryl-4,7-dithiasebacate, dilauryl-4,7,8,11-tetrathiotetradecandioate, dimyristyl-4,11-dithia-tetradecandioate, lauryl-3-benzothiazylmercaptopropionate.
Preferably the esterifying alcohol is an alkanol having 10 to 18 carbon atoms. Other esters of beta thiocarboxylic acids set forth in Gribbins Patent 2,519,744 can also be used.
Likewise, there can be included 0.01 - 10%, usually 0.1 - 5% of a metal salt stabilizer in the monoolefin polymer formulations. Examples of such salts are calcium stearate, calcium 2-ethylhexoate, calcium octoate, calcium oleate, calcium ricinoleate, calcium myristate, calcium palmitate, calcium laurate, barium laurate, barium stearate, magnesium stearate as well as zinc stearate, cadmium laurate, cadmium octoate, cadmium stearate and the other polyvalent metal salts of fatty acids set forth previously.
There can also be added conventional phenolic anti-oxidants in an amount of 0.01 - 10~, preferably 0.1 - 5%. Ex-amples of such phenols include 2,6-di-t-butyl-p-cresol (Ionol), butylated hydroxyanisole, propyl gallate, 4,4'-thiobis(6-t-butyl-m-cresol), 4,4'-cyclohexylidene diphenol, 2,5-di-t-amyl hydroquinone, 4,4'-butylidene bis(6-t-butyl-m-cresol), hydro-quinone monobenzyl ether, 2,2'-methylene-bis(4-methyl-6-t-butylphenol) (Catalin~ 14), 2,6-butyl-4-decyloxy-phenol, 2-t-butyl-4-dodecyloxyphenol, 2-t-butyl-4-octadecyloxyphenol, 4,4'-methylene-bis(2,6-di-t-butyl phenol), p-aminophenol, N-lauryl-oxy-p-aminophenol, 4,4'-thiobis(3-methyl-6-t-butylphenol), bis--(1,1,3,3-tetramethylbutyl)pheno ~sulfide, 4-acetyl-~-resor-1~4~i;212 cylic acid, A stage p-t-butylphenolformaldehyde resin, croton-aldehyde condensate of 3-methyl-6-t-butyl-phenol, 2,6-di-t-butyl p-cresol (Toponol~ CA), 2,2-methylene bis 4-ethyl-6-t-butylphenol (A0-425), 4-dodecyloxy-2-hydroxy-benzophenone, 3-hydroxy-4-(phenylcarbonyl)phenyl palmitate, n-dodecyl ester of 3-hydroxy-4-(phenylcarbonyl)phenoxy-acetic acid, t-butylphenol, octadecyl-13,5-di-t-butyl hydroxyphenyl)propionate (Irganox~' 1076).
Epoxy compounds in an amount of 0.01 - 5% in the 10 hydrocarbon polymer compositions can also be included. Ex-amples of such epoxy compounds include epoxidized soya bean oil, epoxidized lard oil, epoxidized olive oil, epoxidized linseed oil, epoxidized castor oil, epoxidized peanut oil, epoxidized corn oil, epoxidized tung oil, epoxidized cottonseed oil, epichlorhydrinbisphenol A resins (epichlorhydrin-diphenyl-olpropane resins), phenoxy-propylene oxide, butoxy propylene oxide, epoxidized neopentylene oleate, glycidyl epoxystearate, epoxidized a-olefins, epoxidized glycidyl soyate, dicyclopenta-diene dioxide, epoxidized butyl tallate, styrene oxide, di-20 pentene dioxide, glycidol, vinyl cyclohexene dioxide, glycidylether of resorcinol, glycidol ether of 1,5-dihydroxynaphthalene, epoxidized linseed oil fatty acids, allyl glycidyl ether, butyl glycidyl ether, cyclohexane oxide, 4-(2,3-epoxypropoxy)aceto-phenone, mesityl oxide epoxide, 2-ethyl-3-propyl glycidamide, glycidyl ethers of glycerine, pentaerythritol and sorbitol, and 3,4-epoxy-cyclohexane-1 ,l-dimethanol bis-9,10-epoxystearate.
The phenolic phosphonates of the invention can also ~` be used to stabilize lubricating oils, e.g. aliphatic esters such as di(2-ethylhexyl)azelate, pentaerythritol tetraceproate 104(~21Z
and the like; animal and vegetable derived oils, e.g., linseed oil, fat, tallow, lard, peanut oil, cod liver oil, castor oil, palm oil, corn oil, cotton seed oil and the like; hydrocarbon material such as gasoline, both natural and synthetic diesel oil, mineral oil, fuel oil, drying oil, cutting fluids, paraffin, waxes, resins and the like, fatty acids such as soaps and the like. The stabilizer in such cases can also be used in an amount of 0.005 to 10% of the material to be stabilized.
Unless otherwi~e indicated all parts and percentages are by weight.
Example l 3,9-Di(3,5-di-t-butyl-4-hydroxybenzyl)-3,9-dioxo-2, 4,8,10,3,9-tetraoxadiphospha-spiro(5,5)hendecane.
One mol(256 g.) of 3,9-dimethoxy-2,4-8-10-tetraoxa_ 3,9-diphospha-spiro(5,5)hendecane was dissolved in 1 liter of - toluene and 2 mols (509 g.) of 3,5-di-t-butyl-4_hydroxybenzyl chloride in 500 ml heptane were added. The mixture was heated 810wly to 100-110C. and methyl chloride was allowed to distill off. After 3 hours at 100C. methyl chloride evolution had ceased and a heavy precipitate had separated. The mixture was cooled and flltered. The filter cake was washed with toluene d to give 600 g. (90%) of the title compounds as a colorless, j crystalline, hlgh-melting solid.
- Examole 2 One mol (166 g.) of 2(3,5-dimethyl-4-hydroxyph~nyl) ethyl alcohol was mixed with 128 g. (0.5 mol) of 3,9-dimethoxy-2,4~8,10,3,9-tetraoxadiphospha-spiro(5,5) hendecane. Five grams - , . , ' ... ~ :
.

' ' '' 1~)4(3~1Z

of sodium methylate was added and the mixture was heated sl~wly to 150~C. Methanol started to distill off at 100C. and in 2 hours 0.95 mol of methanol was recovered. Five grams of sodium iodide was then added and the mixture was heated for 10 hours at 150C. At the end of this period a test with iodine showed the absence of trivalent phosphorus. The product was a colorless solid which was recrystallized ~rom toluene. Infrared spectrum and phosphorus analysis were in agreement with the compound: 3,9-di-2(3,5-dimethyl-4-hydroxyphenyl)ethyl-3,9-oxo-.
2,4,8,10,3,9-tetraoxadiphospha-spiro(5,5) hendecane.
- Example 3 3,9-Di(2-hydroxy-3-t-butyl-5-methylbenzyl)-3,9-dioxo-2,4,8,10,3,9-tetraoxadiphospha-spiro(5,5)hendecane.
; ~ One mol (256 g.) of 3,9-dichloro-2,4,8~10,3,9-tetraoxa-diphospha-spiro(5,5)hendecane dissolved in 1 liter of toluene was added to 384 g.t2 mols) of 2-hydroxy-3-t-butyl-5-methyl-benzyl alcohol dissol~ed in 500 ml of toluene. Two hundred grams (2.05 mols) of triethylamine were added to the benzyl alcohol solution. The chloride solution was added to the amine-alcohol solution with cooling. When the additLon was complete, the mixture was heated to 80C. and filtered hot ro~ the amlne hydrochloride. Upon cooling, 520 g. (92~) of a colorless. crvstalline solid was recovered. A phosph~r~
analysis and infrared spectrum confirmed the compound to be consistent with the title compound.

. ~

~. .
.: ,..,.- - . .
.

Example 4 Unstabilized polypropylene powder (Hercules Profax~
6501) was thoroughly blended with 0.5~ of the compound of Example 1 to produce a stabilized polypropylene. Blending can be accomplished in any suitable manner, e.g. in a Banbury mixer.
Stability can be tested in any conventional manner, e.g. using the oven aging test and the Fadeometer test described in Spivack patent 3,714,300, col. 5, lines 23-48.
Example 5 100 parts of unstabilized polypropylene powder (Hercules Powder 6501) were thoroughly blended with 0.2 parts of the compound prepared in Example 2 and 0.5 part of dilauryl-thiodipropionate to obtain a stabilized polypropylene.
The phenolic phosphonate compounds of the present invention also act as flame and fire retardants for solid hydrocarbon polymers such as polyethylene, polypropylene, poly-isoprene, butadiene-styrene copolymer, EPDM polymers, ethylene-propylene copolymer, etc.

Claims (12)

The embodiments of the invention in which an exclu-sive property or privilege is claimed are defined as follows:

1. A compound having the formula:

where R is hydrogen, alkyl of 1 to 30 carbon atoms, cycloalkyl of 5 to 12 carbon atoms or aralkyl of 7 to 36 carbon atoms, R' is alkyl of 1 to 30 carbon atoms, cycloalkyl of 5 to 12 carbon atoms or aralkyl of 7 to 36 carbon atoms and n is an integer of 1 to 4.

2. A compound according to Claim 1, wherein the OH
groups are in the 2 or 4 position and in the 2' or 4' position.

3. A compound according to Claim 1, wherein R is other than hydrogen.

4. A compound according to Claim 3, wherein R and R' are both alkyl of 1 to 20 carbon atoms.

5. A compound according to Claim 4, wherein the OH
groups are in the 2 and 2' positions.

6. A compound according to Claim 4, wherein the OH

groups are in the 4 and 4' positions.

7. A compound according to Claim 4, wherein R is t-butyl.

8. A compound according to Claim 7, wherein R' is t-butyl.

9. A compound according to Claim 7, wherein R' is alkyl of 1 to 20 carbon atoms.

10. A compound according to Claim 9, wherein n is 1.

11. A compound according to Claim 4, wherein n is 1.

12. A compound according to Claim 2, wherein n is 1.