CA1117546A - Hydrolytically stable ortho-alkylated phenyl phosphonites and stabilized compositions - Google Patents

Abstract

Abstract of the Disclosure Hydrolytically stable ortho-alkylated phenyl phos-phonites of the formula

Description

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This invention reldtes to hindered ortho alkylated phenyl phosphonites whieh are effective in stabilizing or ganic materials particularly plastics, polymers and resins as vell as mineral and synthetic fluids and oils.

Organic polymeric.materials such as plastics and resins and lubricating and mineral oil are subject to thermal, oxidative and photodegradation. A great ~ariety o~ stabili-zers are known in the art for stabilizing various substrates.
Their effectiveness varies depending on the causes of degra-dation and the substrate stabilized. It is known that many stabilizers that are very effective long term antioxidants are relatively poor process stabilizers which require stabiliza-tion of the substrate, against thermal degradation for a short time, but at a relatively high temperature. Many stabi-lizers are relatively incompatible with the substrates which causes problems during the life of a product and les~ens the stabilizer's effectiveness. Some stabilizers are either too ~olatile or thermally or hydrolytically unstable to be practi-cal as commercial stabilizers.

In ~apanese 73J41,009 (CA, 81,121856g (1974)), a non-hindered phenylphosphonite and a non-hindered phenylthio-phosphonite are disclosed as heat stabilizers for ABS, PVC, polyolefins and other polymeric substances.

-2-7~

. Diphenylphosphonites, diphenylene bis-p~osphonites and terphenylene bis phosphonites are described in US 3,825,629 as stabilizers for organic materials. These compounds ~re structurally dif~erent from the instant compoun~s especially in ~reference to the diphenyl or terphenyl moiety directly attached -to the P atom in these molecules.

Thermostabilized linear polyesters coDtaining small amounts of diphenyl phenylphosphonite are claimed in US 3,609,118.
This patent contains a very broad generic reference to phenyl-phosphonites ~ith no subgeneric disclosures and with only diphenyl phenylphosphonite being exemplified.

US 3,809,676`and US 3,978,020 disclose generically some phosphonites of structures related to those of the in-stant invention, but do not exe~pllfy or specifically mention the specific genus of phosphonites of this invention. These references respectively pertain to thermally stable flame retardant polycarbonates containing a phosphonite or phosphi-nite in combination with a barium, calcium or cerium alkanoate or carbonate and to thermally stable polycarbonates containing a phosphonite and an epoxide compound.

The instant phosphonites are more effective as stabi-lizers than the closest prior art phosphonites. They also sur-prisingly exhibit far superior hydrolytic stability compared to many of the previously known phosphonites. This superior hydro-_ -3-lytic stability permits the lnstant phosphonites to be used in those~myriad of cases where water pickup is a disadvantage and presents practical end use problems in the produck composition being stabilized. One such example is in polyester fibers where the use of stabilizers ~hiCh hydrolyze and/or are hygroscopic cause undesired swelling of the fiber and ancillary deficiencies.

It was ~ound that the instant phosphonites presumedly because of their structural character overcome these deficiencies of the prior art phosphonites and thus combine excellent stabi-lizing efficacy with hydrolytic stability and the absence of secondary performance problems related to hydrolysis and/or the water pickup of the prior art phosphonite stabilizers. Indeed, the instant compounds possess a ccmbination of desired properties including outstanding stabilization efficiency especially at high temperatures, and not only do not detract ~rom light stabilization, but actually exhibit light stability properties, acceptable hydro-lytic stability and good color in stabili~ed compositions.

This invention pertains to hydrolytlcally stable ortho-alkylated phenyl phosphonites and to organic materials, both polymeric and non-polymerio, stabilized by said phospho~
nites.

~ . .

~7S~;

More particularly, the phosp~or.ites of this inven-tion are represented by the Formula I

R3 ~ O-P - R4 5I~
\ R5 . R~

wherein . .~
R1 is branched alkyl of 3 to 18 carbon atoms, benzyl, ~-methylbenzyl or ~,-dimethylbenzyl, . R2 is alkyl of 1 ~o 18 carbon atoms, benzyl, ~-methylbenzyl or ,3-dimethylbenzyl~

R3 is hydrogen, alkyl of 1 to 18 carbon atoms, carbo-O . alkoxy of 2 to 19 carbon atoms, canboalkoxyalkyl o~ 3 to 24 carbon atoms, carbophenoxy, carbophenoxyalkyl of 8 to 16 car-bon atoms; or carbophenoxy or carbophenoxyalkyl with the phe-noxy substituted with 1 to 3 alkyl groups with 1 to 8 carbon atoms in each alkyl group, R is alkyl o~ 1 to 18~carbon atoms, phenyl or phenyl substituted by 1 to 3 alkyl ~roups with 1 to 8 carbon atoms in each alkyl grGup, 1~7~i~6 R5 is halo~en, -XH or -XR6, X is O or S, R6 is phenyl, substituted by alkyl, having the formul2 . .
R7 ~
~ O ~ ~9 .' , ,>J . .
R

~here R is hydrogen,b~anched alkyl of 3 to 18 carbon atoms, benzyl, ~-methylbenzyl or ,a~dimethylbenzyl, -R8 is hydrogen, alkyl of 1 to 18 carbon atoms, benzyl,c-methylbenzyl or ~,-dimethylbenzyl, and R9 is hydrogen, alkyl. of 1 to 18 carbon atoms, carboalkoxy of 2 to 19 carbon atoms, carboalkoxyalkyl of 3 to 24 carbon atoms, carbophenoxy, carbophenoxyalkyl of 8 to 16 carbon atoms; or carbophenoxy or carbophenoxyalkyl with the phenoxy substituted with 1 to 3 alkyl groups with 1 to 8 car-bon atoms in each-alkyl group.

~7 ~

Rl is branched alkyl of 3 to 18 carbon atoms ~uch as isopropyl, tert-butyl, sec-butyl, isoamyl, tert-amyl, tert-octyl, tert-dodecyl or tert-octadecyl. Preferably R1 ls branched alkyl of 4 to 1Z carbon atoms such as tert-butyl, tert-amyl, tert-octyl or tert-dodecyl or is ~-methylbenzyl or ~,~-dimethylbenzyl. Most preferably R1 i5 tertiary alkyl of 4 to 8 carbon atoms such as tert-butyl or tert-octyl.

R2 is alkyl of 1 to 18 carbon ato~s such as methyl, i~opropyl, tert-butyl, n-octyl, tert-octyl, n-dodecyl or octa-decyl. Preferably R2 is alkyl of 3 to 12 carbon atoms, -~
methylbenzyl or t ~-dimethylbenzyl. Most preferably R2 is a branched alkyl of 4 to 8 carbon atoms such as tert-butyl, tert-amyl or tert-octyl.

R3 is alkyl of 1 to 18 carbon atoms such as methyl, butyl, hexyi, octyl, nonyl, dodecyl or octadecyl. R3 is also carboalkoxy of 2 to 19 carbon atoms such as carbomethoxy, carbo-ethoxy, carbooctoxy or carbooctadecyloxy. R3 can also be carbo-alkoxyalkyl of 3 to 24 carbon atoms such as carbomethoxymethyl, carbomethoxyethyl, carboethoxymethyl, carbobutoxybutyl, car-booctoxymethyl, carbododecyloxyethyl or carbooctadecyloxyhexyl.

7S~j R3 can also be carbophenoxy or carbophenoxyalkyl of 8 to 16 carbon atoms such as carbophenoxy~.ethyl, carbopheno~yethyl or carbophenoxynonyl. Iha phenoxy groups o~ carbophenoxy . or carbophenoxyalkyl can also be substituted with 1 to 3 al~yl groups with l to 8 carbon atoms in each alkyl ~roup. Such substituted phenoxy groups would include p-tolyloxy, p-tert-butylphenoxy, 2,4-di-tert-butylphenoxy, mesityloxy, 2,4,6-tri-tert-butylphenoxy or p-tert-octylpnenoxy.

Preferably R3 is hydrogen, alkyl of 1 to l8 carbcn O atoms, carboalkoxy of 2 to 19 carbon atoms, carboalkoxyalkyl of 3 to 21 carbon atoms or carbophenoxy with khe phenoxy sub-stituted with 1 to 3 alkyl groups witA 1 to 8 carbon atoms in each alkyl group.

Most preferab'y R3 is hydrogen, alkyl of 1 to 9 car-bon atoms, carboalkoxy of 2 to 9 carbon atoms, carboalkoxy-alkyl o~ 3 to 11 carbon atoms or carbophenoxy with the phenoxy substituted with 1 to 3 alkyl groups with l to 4 carbon atoms in each alkyl group.

R4 is alkyl of l to 18 carbon atoms such as methyl, O ethyl, butyl, octyl, dodecyl, hexa~ecyl or octadecyl. R4 can also be phenyl or phenyl substituted by 1 to 3 alkyl groups with 1 to 8 carbon sto~s in ~ach alkyl ~roup. Such substituted .

~ ~ 7 5~

phenyls would include o-tolyl, m-tolyl, p-tolyl, o-xylyl, m-xylyl, p-xylyl, mesityl, o-cumyl, p-tert-Sutylphenyl, 2,~,6-tri-tert-butylphenyl or 2,4,6-tri~tert octylphenyl.

Preferably R4 is alkyl of 1 to 18 carbon atoms, phenyl or phenyl substitued by l to 3 al~yl groups with l to 8 carbon atoms in each alkyl group.

Most preferably R4 is phenyl or phenyl substituted by 1 to 3 alkyl groups with 1 to 4 carbon atoms in each alkyl group.

R5 is halogen such as chlorine or bromine, prefer-ably chlorine, or -XH or -XR6.

Preferably RS ls chlorine or -XR6.

X is 0 or S, preferably 0.

R7 is hydrogen or is defined as is R1 above. Pref-erably R7 is hydrogen, branched al~kyl of 4 to 12 carbon atoms, ~-methylbenzyl or ~,~-dimethylbenzyl. Most preferably R7 is tertiary alkyl of 4 to 8 carbon atoms.

R8 is hydrogen or is defined as ls R2 above. Pref-erably R8 is hydrogen, alkyl of l to 12 carbon atoms, ~-methyl-_g_ benzyl or ~ di~ethylben~yl. Most pre~erably R8 is hJdrogen or alkyl of 1 to 8 carbon atoms.

R9 is hydrogen or is defined as R3 above. Preferably R9 is hydrogen, alkyl of l to 18 carbon atoms, carboalkoxy of 2 to 19 carbon atoms, carboalkoxyalkyl of 3 to 21 carbon atoms or carbophenoxy with the phenoxy substituted With 1 to 3 alkyl groups with 1 to 8 carbon atoms in each alkyl group.

. Most preferably R9 is hydrogen, alkyl Of 1 to 9 Car-bon atoms, carboalkoxy of 2 to 9 carbon atoms, carboalkoxyalkyl O Of 3 to 11 carbon atoms or carbophenoxy with the phenoxy substi-tuted with 1 to 3 alkyl groups With 1 to 4 carbon atomS ir. each alkyl group.

It iS understood ~hat preferably all Or R7, R8 an~ R9 cannot be hydrogen at the same time.

Particularly preferred embodiments of the instant phosphonites are those where Rl iS isopropyl or tert-butyl, R2 is alkyl of l to 4 carbon atoms, R3 is hydrogen, alkyl of t to 18 carbon atoms, -CH2CH2COOCH3, -COOCH3, -COOC18H37 or ~COO ~ t~C4H

t-C4H9 s~

R4 is alkyl of 1 to 18 carbon atoms or phenyl, R5 is chlorine, XH or XR~

X is 0, R6 is ~9 .' R7 is hydrogen, isopropyl or tert-butyl, R~ is hydrogen, or alkyl of 1 to 4 carbon~atoms, and R9 is alkyl o~ 1 to 4 carbon atoms, _COOCH3, -CH2CH2COOCH3 or -COO ~ tC~Hg with the ~ ~ t-C~Hg pro~iso that both of R7 and R8 cannot be hydrogen at the same time.

iO Synthesis of Compounds:

~ he compounds of this inYention are made by the fol-lowing procedure:

R3 ~ o ~ tcrtiatyR3 - C~ ~ O_p plJ
y Ofl-~ n E~C~.2 solve ~ <R2 ~'1 III IV Y

tertiary ~
2. V ~ HR5 amine ~ R3-~ O ~~~ o-P-R5 solv~ent' R2 \R4 YI

tertiarY ~ 11

3. V ~ H2X amine ~ R~- ~ O-P-R

~2 VII

.
The use of tertiary amines can be avo:ide~ by conver~-ing the phenols (or thiophenolsj Or formula III or VI to the phenolate (or thiophenolate) anion in ei.ther or both of the steps (1, 2) oi` the synthesis by reaction with stoichiometric amounts of alkali metal or alkali metal hydro~idQ and subse~

quently reacting the anion appropriately with IV or V.

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Aromatic hydrocar~ons such as benzene, toluene or xylene are useful as solYents for the syn~hesis, but are not essential.

The reaction steps can be convenienkly performed by using tertiary amines such as triethylamine, pyridine, N,N-dimethylaniline, but again their use is not essential.

Th~ use of excess tertiary amine over that required as a proton acceptor markedly increases the reaction rates in the synthe~ic steps. This is particularly important when III
and VI are highly hindered phenols.
.
Reaction temperatures may ~ary from below room kemp-erature to the reflux temperature of the solvent present.
~hen no solvent is used, temperatures up to about 200C are useful.

Although intermediate compound V may be isolated, it is possible to carry out the entire synthesis of I without the isolation of the intermediate product.

An alternative procedure to the synthesis o~ the instant compounds involves a reverse reaction sequence which prepares noYel intermediates IX of value as outlined below:
.
, . .
. . .

~ R7 1. ~0 \~- XH +R4PC12 inert atmosphere ~ R8 VI I I IY

R ~ ~
C ~ X-P-R4 ~J~
- R8 Cl IX

.

.
~, 2. IX + R3~ 0 ~ 0~3 ~
~.

Rl R3 ~)$---O- P - R4 ~R2 X

' R8 ~o ~/

X

, --1 4-- . .

s~

The meanin~sof R1, R2, R3, R4, h~7, R8 and R9 are as defined earlier. The inter~ediate IX differs from intermediate V in that in compound IX one of R7 and ~8 ma~ be hydrogen al~hough all of R7, R8 and R9 canno~ be hydrogen at the same time.

The Yarious starting materials, i.e., phenols, thio-phenols, chlorophosphines, are largely available as items of commeroe or can be easily prepared by ~nown methods.

The compounds of this invention are effective light stabilizers and/or antioxidants in a wide r~nge of organic O polymers. Polymers which can be stabilized include:

1. Polymers which are derived from mono- or diolefins e.g., polyethylene which can optionally be crosslinked, poly-propylene, polyisobutylene, polymethylbutene-l, polymethylpen-tene-t, polyisoprene, polybutadiene.

2. Mixtures o~ the homopolymers cited under 1), for example mixtures of polypropylene and polyethylene, polypropylene and polybutene-1, polypropylene and polyisobutylene.

3. Copolymers of the monomers based on the homopoly-mers cited under 1), ~or example ethylene/propylene copolymers, propylene/butene-1 copolymers, propylene/isobutylene copolymers, ~7~

ethylene/butene-1 copolymers as well as terpolymers of eth~lene and propylene with a diene, for example hexadiene, dicyclopenta-diene or ethylidene norbornene, and copolymers of ~-olefins, e.~., ethylene with acrylic or methacrylic acid.

4. Polystyrene.

5. Copolymers of styrene and of -methylstyrene, for example styrene/butadiene copolymers, styrene/acrylonitrile copolymers, styrene/acrylonitrile/methacrylate copolymers, styrene/acrylonitrile copolymers modified with acrylic ester polymers to provide impact strength as well as block copolymers, e.g., styrene/butadiene~styrene block copolymers.

6. Graft copolymers of styrene, for example the graft polymer of styrene to polybutadiene, the Braft polymer of sty-rene with acrylonitrile to polybutadiene as well as mixtures thereof with the copolymers cited under 5), commonly referred to as acrylonitrile/butadiene~styrene or ABS plastics~

7. Halogen-containing vinyl polymers, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene, chlorinated rubbers, vinyl chloride/vinylidene chloride copolymers, vinyl chloride/vinyl acetate copolymers, vinylidene chloride/vinyl acetate copolymers.

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8. Polymers which are derived ~rom ,~-unsaturated ~cids and derlvatives thereof, polyacrylates and polymethacry lates, polyacrylic amides and polyacryloni~rile.

9. Polymers which are derived from unsaturated alcohols and amines and from the acyl derivatives thereof or acetals~ for example polyvinyl alcohol, polyYinyl ~cetate, polyYinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine and copolymers thereof with other vinyl compounds, ~or example ethylene~vinyl acetate copolymers.

10. Homopolymers and copolymers which are derived from epoxides, for example polyethylene oxide or the poly-mers which are derived from bis-glycidyl ethers.

11. Polyacet21s, for example polyoxymethylene, as well as polyoxymethylenes which contain ethylene oxide as comonomer.

12. Polyalkylene oxides, for example polyoxyethylene, polypropylene oxide or polyisobutylene oxide.

13. Polyphenylene oxides.

~0 14. Polyurethanes and polyureas.

15. Polycarbonates.

16. Polysulfones.

17. Polyamides and copolyamides which are derived from diamines and dicarboxylic acids and/or from aminocarboxy-lic acids or the corresponding lactams, for example polyamide 6, polyamide 6/6, polyamide 6/lO, polyamide 11, polyamide 12, poly-m-phenylene-isophthalamide.

18. Polyesters which are derived from dicarboxylic acids and dialcohols and/or from hydroxycarboxylic acids or ~he corresponding lactones, ~or example polyethylene glycol terephthalate, poly~ 4-dimethylol-cyclohexane terephthalate.

19. Cross-linked polymers which are deriYed from aldehydes on the one hand and from phenols, ureas and melamine on the other~ for example phenol~formaldehyde, urea/formaldehyde and melamine/formaldehyde resins.

^ 20. Alkyd resins, for example glycerolJphthalic acid res~ns and mixtures thereof with melamine/formaldehyde resins~

21. Unsaturated polyester resins which are derived rrom copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols as well as from Yinyl compounds as cross-linking agents and also the halogen-containing, flame-resistant modifications thereof.

~7~6 22. Natural polymers, for example cellulose, rubber, as well as the chemically modified homologou~ derivatives khereo~, for exampie cellulose acetates, cellulose propionates and cellu-lose butyrates and the cellulose ethers, for sxample methyl cellulose.

Compounds o~ this invention are particularly effective in stabilizing organic materials such as plastics, polymers, resins in addition to mineral and synthetic fluids such as lubri-cating oils, circulating oils, etc.

The compounds of thiq invention are par~icularly use~ul as stabilizers, especially for the protection of polyole~ins, for instance, polyethylene, polypropylene, polyisobutylene, poly (butene-1), poly(pentene-1), poly(3-methylbutene-1), poly~4-methyl-pentene-1), various ethylene-propylene copolymers and the like.

Other substrates in which the compounds of this inven-tion are particularly useful are polystyrene, including impact polystyrene, ABS resin, SBR polyisoprene, as well as natur~l rubber, polyesters including polyethylene terephthalate and polybutylene ~O terephthlate, including copolymers. Also stabilized are poly-urethanes, polycarbonates, polyamides such as nylon 6, 6/6 and the like as well as copolyamides and polysulfones.

. -19-~1~7c~

The compounds of this invention may be used alone as the sole stabilizer performin~ either mainly an antioxidant func-ti~n or a light stabilizing function or the sta~ilizer may combine utility as an antioxidant and light stabilizer. The stabilizers may be used with phenolic antioxidants, lubricants such as cal-cium stearate, pigments, colorants or dyes, ~V absorbers, light stabilizers such as hindered amines, metal deactivators, talc and other fillers, etc.

In general, the stabilizers of this invention are employed from about 0.01 to about 5~ by weight of the stabilized composition, althou~h this will vary with the particular sub-strate and application. An advantageous range is from about Q.05 to about 2p, and especially 0.1 to about 1%.
.
Compounds of this invention stabilize polymers especially during high temperature processing with relatively little change in color, even though the polymer may undergo a number of extrusions. Among the polymers in which this property is especially apparent are polyprop~lene, polyethylene, styrenics such as ABS, polyethylene- and polybutylene-terephtha-lates, polycarbonates, natural rubber, synthetic rubber such as SBR. While many compounds which have been used as process stabilizers are only effective as process stabilizers for poly-ole~ins in the presence of phenolic antioxidants, etc., co~-pounds of this invention are effectlve in the absence of phenolic antioxidants.

75~

Many of the compounds of thls invention combine pro-cess stabilizirlg properties with the ability to confer light stdbility on the polymer. Thi~ i9 particularly important for polymer fibers where processing temperatures are among the highest and where skability to actinic light i~ a prime req~ire-ment. A particularly important property for stabilizers which are trivalent phosphorus esters is their non-hygroscopicity and resistance to hydrolysis ln the presence of moisture in the atmosphere during ambient storage. Hygroscopicity fre-quently results in difficulty in incorporating the process sta-bilizer uniformly into the polymer causing stickiness and blockage while hydroly~is of the phosphorus ester stabilizers during storage fre~uently results in compounds which are less effective. _-The stabilizers of Formula I may readily be incorpo-rated into the organic poly~ers by conventional techniques, at any convenient stage prior to the manufacture of shaped articles therefrom. For example, the stabilizer may be mixed with the polymer in dry powder form, or a 3uspension or emulsion of the ~0 stabilizer may be mixed with a solution, suspension, or emulsion of the polymer. The stabilized polymer compositions of the in-Yention may optionally also contain Yarious conYentional addi-tives, such as the following:
' ~

~21-7S~6i 1. Antioxidants _ 1.1 Simple 2,6-dialkylphenols, such as, for example, 2,6-di-tert.-butyl-4-~ethylphenol, 2-~ert.-butyl 4,6 dimethylphenol, 2,6-di-tert. butyl-4-methoxymethylphenol and 2,6-dioctadecyl-4-methylphenol.

1.2 DeriYatiYes of alkylated hydroauinones, such as for . .
example, 27 5-di-tert.-butyl-hydroquinone, 2,5-di-tert.-amyl-hydroquinone, 2,6-di-tert. butyl-hydroquinone, 2,5-di-tert.-butyl-4-hydroxy-anisole, 3,5-di-tert.-butyl-4-hydroxy-anisole, tris-(3,5-di-tert.-butyl-4-hydroxyphe-nyl) phosphite, 3,5-di-tert.-butyl-4-hydroxyphenyl stearate and bis-3,5-di-tert.-butyl 4-hydroxyphenylj adipate.

1.3 Hydroxylated thiodiphenyl ethers, such as, for example, 2,2'-thio~bis-(6-tert.-butyl-4-methylphenol), 2,2'-thio-bis-(4-octylphenol), 4,4'-thio-bis-(6-tert.-butyl-3~methylphenol), 4,4'-thio-bis-(3,6-di-sec.-amylphenol), 4,4'-thio-bis-(6-tert.-butyl-2-methylphenol) and 4,4'-bis-(2,6-dimethyl-4-hydroxy-phenyl) disulfide.

1.4 Alkylidene-bisphenols,such ast for example, 2,2'-methylene-bis-(6-tert.-butyl-4-methylphenol), 2,2'-methylene-bis-(6-tert.-butyl-4-ethylphenol~, 4,4'-methylene-bis-(6-tert.-butyl-2-methylphenol), 4,4'-methylene-bis-(2,6-di-tert.-butyl-phenoi), 2,6-di(3,-tert.-butyl-5-methyl-2-hydroxybenzyl)-7~i~6 .. . .
4-methylphenol, 2, 2' ~methylene bis-[4-methyl-6-(-methylcyclo-hexyl)-phenol], 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)-butane, 1,1-bis-(5-tert -butyl-4-hydroxy_2_methylphenyl)-butane, 2,2-.. .
bis-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propane, l,1,3-tris-t5-tert.-butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercapto-butane, 1,1,5,5-tetra-(5-tert.-butyl-4-hydroxy-2-methylph~nyl)-pentane and ethylene giycol bis-[3,3-bis-(3-tert.-bu~yl-4-hydroxyphenyl~-~utyrate~. -1~5 0-, N- and S-benzyl compounds, such as, ~or example, 3,5,3',5'-tetra-tert.-butyl-4,4'-dihydroxydibe-nzyl ether, octa-decyl 4-hydroxy-3,5-dimethylbenzyl-mercaptoacetate, tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)amine and bis-(4-tert.- L
butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate.

t.6 Hydroxybenzylated malonates, ~uch as for example, d~octa-decyl 2,2-bis-(3,5-di-tert.-butyl-2-hydroxybenzyl)-malonate, dioctadecyl 2-(3-tert.-butyl-4-hydroxy-5-methylbenzyl)-malonate?
di-dodecylmercapto-ethyl 2,2-bis-(3,5-di-tert.-butyl-4-bydroxybenzyl)-malonate and di-[4-(1,1,3,3-tetramethylbutyl)-phenyl] 2,2-bis-(3,5-di-tert.-butyl-4-hydroxybenzyl)~malonate.
. . .
, 1.7 Hydroxybenzyl-aromatic compounds, such as, f~r example, 1t3,5-tri-(3,5-di-tert.-~utyl-4-hy~roxybenzy1)-2,4,6-trime.thyl- ;
- benzene, 1,4-di-(3,5-di-tert-butyl-4-hydroxybenzyl~-2,3,5l6-tetramethylbenzene and 2,4,6-tri(3,5-di-tert.-butyl-4-hydrox~-benzyl~-phenol. -. . .
~. . ~

. -23-1.8 s-Triazine compounds, such as, for example, 2 t 4-bis-octylmercapto-6-(3,5--di-tert.~butyl-4-hydroxy-anilino)-s-tr.~azine, 2-octylmercapto,4,6-bis-(3,5-di-tert.-butyl-4-hydroxy anilino)-s-triazine, 2-octylmercapto-4,6-bis (3~5-di-tert.-butyl-4-hydroxyphenoxy)-s-triazine, 2,4,6-tris-(3,5-di-tert.-butyl-4-hydroxyphenoxy)-s-triazine, 2,4,6-tris-(3,5-di-tert butyl-4-hydroxyphenylethyl)-s-triaz~ne and 1,3,5-tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)isocyanurate.

1.9. Amides of g-(3,5-di-tert.-butyl-4-hydroxyphenyl?-propionic tO acid, such as, for example, 1,3,5-tris-(3,5-di-tert.-butyl-4-hydroxyphenyl-propionyl)-hexahydro-s triazin~ and N,~'-di ~3,5-di-tert.-butyl-4-hydroxyphenyl-propionyl)-hexamethylene-diamine. N,N'-bi~-g-(3,5-di-t-butyl-4-hydroxyphenyl)-propionyl-hydrazine. ~~

l.10 Esters of g-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic .. . . . _ . ~
acid with monohydric or polyhydric alcoholsl such as, for example, with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonane-diol, ethylene glycol, l,2-propanediol, diethylene glycol, thio-diethylene glycol, neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethylhexanediol, trimethylol-ethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-[2,2,2]octane.

1.11 Esters of B-( 5-tert.-butyl-4-hydrox~-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols, such as, for example, with methanol, ethanol, octadecanol, l,6-hexane ~4- -5~

diol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, di-ethylene glycol, thiodiethylene glycol, neopentylglycol, penta-erythritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethyl-hexanediol, trimethylolethane, trimethylolpropane, tris~
hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo~2,2,2]octane.

1.12 Esters of 3 5-di-tert.-butYl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, such as for example, with methanol, ethanol, octadecanol, 1,6-hexandiol, 1,9 nonanediol, ethylene glycol, 1,2-propenediol, diethylene glycol, thio-diethylene glycol, neopentylglycol, pentaerythritol, 3-thia-undecanol, 3~thia-pentadecanol, trimethylhexanediol, tri~
methylolethane, trimethylolpropane, tris-hydroxyethyl isocyanu-rate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclot2,2,2]-l~ octane, e~pecially ~he tetrakis ester of pentaerythritol.

1.13 Benzylphosphonates, such as, for examplet dimethyl 3,5-di-tert.-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert.-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert~-butyl-4-hydroxybenzylphosphonate and dioctadecyl 5-tert.-butyl-4-hydroxy-3-methylbenzylphosphonate.

The following may be mentioned as examples of further additives that can be used together with the stabi-lizer of this invention and the antioxidant:

5~6 1. Aminoaryl derivatives, e.g. phenyl-1-naphthylamine, phenyl 2-naphthylamine, N,N'-di-phenyl~p-phenylenediamine, N,N'-~di-2-naphthyl-p-phenylenediamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N~-di-sec.~butyl p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2 dihydroquinoline, 6-dodec-;1-2,2,4-trimethyl-1,2-dihydro~uinoline, mono- and dioctyliminodibenzyl, polymeri2ed 2,2,4-trimethyl-1,2-dihydroquinoline.

Octylated diphenylamine, nonylated diphenylamine, N-phenyl-tO h~-cyclohexyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N,N'-di-sec.octyl-p-phenylenediamine, N-phenyl-N'-sec.-octyl-p-phenylenediamine, N,N'-di~ 4-dimethylpentyl)-p-phenylenediamine, N,N'-dimethyl-N,N'-di-(sec.-octyl)-p-phenylenediamine, 2,6-dimethyl-4-methoxy-aniline, 4-ethoxy-N-sec.-butylaniline, diphenylamine-acetone condensation product, aldol-1-naphthyIamine and phenothiazine.

Discoloration effects have to be taken into account when using the above antioxidants.

2. UV-Absorbers and light-stabilizin~ a~ents 2.1 2-(2'-Hydroxyphenyl) benzotriazoles, e.s., the 5'-methyl-, 3',5'-di-tert.-butyl-, 5'-tert.-butyl-, 5'-(1,1,3,3-tetramethyl-butyl)-, 5-chloro-3',5'-di-tert.-butyl-, 5-chloro-3'-tert.-7S~ .

butyl-5'-methyl-, 3~-sec.-butyl-5'~tert.-butyl~, 3'-~-methyl-benzyl-5'-methyl, 3'~~-methylbenzyl-5'-methyl-5~chloro-, 41_ hydroxy-, 4~-methoxy-, 4~-oct,o%y-, 3',5'-di tert.-amyl-, 3'-methyl-5'-carbomethoxyethyl- and 5-chloro-3'~5'-di-tert.-amyl-derivative.

2.2 2,4-bis-(?'~Hydroxyphenyl)-6-alkyl-s-triazines, e.gO, the 6-ethyl-, 6-heptadecyl- or 6-undecyl-derivative.

2.3 2-Hydroxybenzophenones; e.g., the 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, ~,2',4'-trihydrGxy- or 2'-hydroxy-4,4'-dimethoxy-derivative.

O 2.4 1,3-bis-(2'-Hydroxybenzoyl)-ben~enes, e.g., 1,3-bis (2'-hydroxy-4'-hexyloxy-benzoyl)-benzene, 1,3-bis-(2'-hydroxy-4'-octyloxy-benzoyl)-benzene or 1,3-bis-(2'-hydroxy-4'-dodecyloxy-benzoyl)-benzene. ~~ I

2.5 Esters of optionally substituted benzoic acids, e.g., phenylsalicylate, octylphenylsalicylate, dibenzoylresorcin, bis-(4-tert.-butylbenzoyl)-resorcin, benzoylresorcin, 3,5-di-tert.-butyl-4-hydroxybenzoic acid-2,4-di-tert.-butylphenyl ester or -octadecyl ester or -2-methyl-4l6-di-tert.-butyl ester.

'O 2.6 Acrylates, e.g., -cyano-B,B-diphenylacrylic acid-ethyl ester or isooctyl ester7 1-carbomethoxy-cinnamic acid methyl S~b~

e~terJ 0,-cyano-~ methyl-p~methoxy-cinnamic acid methyl ester or -butyl ester or N-(g-carbomethoxyvinyl)-2-methyl-indoline.

2.7 Sterically hindered amines, e.g., 4-benzoyl-2,2,6,6-tetra-methylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis-(2,276,6-tetramethylpiperidyl)-sebacate or 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4,5]decane-2,4-dione.

2 8 Oxalic acid diamides, e.g., 4,4~-di-octyloxy-ox2nilide, 2,2'-di-octyloxy-5,5'-di-tert.-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert.-butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N,N'-bis-(3-dimethyl-aminopropyl)-oxalamide, 2-ethoxy-5-tert.-butyl-2'-ethyl-oxanilide and ~he mixture thereof with 2-ethoxy-2'-ethyl-5,4'-di-t~rt.-butyl-oxanilide, or mixtures of ortho- and para-methoxy- as ~ell as o~ o- and p-ethoxy-disubstituted o~anilides.

3. Metal deactivators, e.g., oxanilide, isophthalic acid di-. .
hydrazide, se~acic acid-bis-phenylhydrazide, bis-benzylidene-oxalic acid dihydrazide, N,N'-diacetal-adipic acid dihydrazide, N,N'-bis-salicyloyl-oxalic acid dihydrazide, N,N'-bis-salicyloyl-hydrazine, N,N'-bis-(3,5-di-tert.-butyl-4-hydroxyphenylpropionyl)~
hydrazine, N-salicyloyl-N'-salicylalhydrazine, 3-salicyloyl-amino-'O 1,2,4-triazole or N,N'-bis-salicyloyl-thiopropionic acid dihydra-zide.

~ 7S~i ., 4. ~ , e.g.1 alkali metal salts and alkaline-earth metal salts of higher fatty acids, for example Ca~stearate t Zn-stearate, Mg-behenate, Na-ricinoleate or K-palmitate.

5. Nucleation agents, e.g., 4-tert.-butylbenzoic acid, adipic acid or diphenylacetic acid.

6. Phosphites/ such 2S, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tri-~nonyl-` phenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, 3,9-isodecyloxy-2,4,8,10-tetraoxa-3,9-diphospha-[5,~]-undecane and tri-(4-hydroxy-3,5-di-tert.butylphenyl) phosphite.

Other additives that can be incorporated in the stabi-lized compositions are thiosynergists such as dilauryl thiodipro-prionate or distearyl thiodipropionate, lubricants s1~ch as stearyl alcohol, fillers, carbon black, asbestos, kaolin, talc, glass 1~ fibers, pigments, optical brighteners, flameproofing agents and antistatic agents.

The following examples are presented for the purpose of illustration only and are not to be construed to limit the nature or scope of the instant invention in any manner whatso-ever.

~; .

~7S~;

0-(2,6-Di-tert-butyl-4-methylphenyl) phenylphosDhonochloridite __ To a solution of 110 grams of 2,6-d~-tert-~utyl-p-cresol in 252 grams of triethylamine was added at 25-26C over a 15-minute period 89.5 grams of dichlorophenylphosphine. The reaction mixture was heated for 31 hours at 95-97C. The excess triethylamine solvent was then removed by distillation - under vacuum, the resulting residue was triturated with 200 ml 0 of dry benzene, and t~e white crystalline solid triethylamine hydrochloride was separated by filtration. The desired product named above was isolated from the filtrate by distillation Or the benzene under vacuum and crystallization of the residue . from acetonitrile. The product was obtained as white crystals melting at 103-106C.

7~i4~;

_ample 2 __ 0-(2,6-Di-tert-butyl-4-methylpherJyl)-0'-- (2,4-di-tert-butylphenyl) phenylphosphonite - 8.24 grams of 2,4-di-tert-butylphenol was dissolved in 250 ml o~ toluene. To this was added 4.85 grams of a 46.3%
aqueous solution of potassium hydroxide. The resulting disper-sion was heated at reflux for about 5.3 hours till 3.~5 grams of water was collected by azeotropic distillation, forming potssium 2,4-di-tert-butylphenolate as a white dispersion in 0 toluene~ ~

A solution of 14.48 grams of the product prepared in Example 1 in ~0 ml of toluene was added dropwise to the above dispersion at lO to 15C over a 10-minute period. The mix-ture was stirred overnight at room temperature.

The turbid mixture was then clarified by filtration and the ~iltrate concentrated under vacuum. The residue ob-tained was triturated with a mixture of acetonitrile and toluene to give the above named product as white crystals melt-~ng at 125-128C.

Examp_e 3 0-t224,6-Tri-tert-butylphen~l) phen~l~hosphonochloridite :
A dispersion of potassium 2,4,6-tri-tert-~utylpheno-late was prepared using the procedure o~ Example 2 starting from 21.6 grams of 2,4,6-tri-tert-butylphenol, 9.7 grams of a 46.3~ aqueous potassium hydroxide solution and 250 ml of toluene.

The above dispersion was cooled to 10C and 14.8 grams of dichlorophenylphosphine was added dropwise over a 7-minute period at 10 to 15C. The reaction mixture ~as stirred for 19 hours and the potassium chloride formed was separated by filtratian. The crude product wa~ isolated as a residue following removal of the toluene by distillation under acuum. The above named compound was isolated as white cry-- stals melting at 97;99C after trituration of the crude pro-tS duct with acetonitrile and then recrystallization.
.
Example 4 j 0-(2,4=Di-tert-but~lphenyl)-0'-(2,4,6-tri-tert-butylphenyl) phenylphosphonite The above named product was prepared by the general method of Example 2 when an equivalent amount of the product of Example 3 was substituted for the product of Example 1.
The desired produet was isolated as white crystals melting at 120-123C.

7~
Example 5 0-(2,6-Di-tert-butyl-4-methylp~,enyl)-0'-(2,6-di-tert-but~l~4-carbometh~:.yDhenyl) phenylphosphonite A ~olution of 21.7 grams of the compound of Example 1 in 50 ml of toluene was added at 20~25C over an 8-minute period to a solution of methyl 3,5-di-tert-butyl-4-hydroxy-benzoate in 60 ml of triethylamine. After heating at 80-85C
for 7 hours and refluxing for another 7 hours, 15 ml of N,N-dimethylformamide was added to accelerate the reaction. Heat-tO ing was continued for another 7 hours at 106-108C. The vola-tiles present were then removed by vacuum distillation and the residue formed was freed of triethylamine hydrochloride by add-.ing 100 ml of toluene followed by filtration. The filtrate ` ~as successively washed with water,.saturated aqueous sodium bicarbonate and water~ After drying over anhydrous sodium sulfate, the toluene was then removed and the isolated residue crystallized from a mixture of acetonitrile and isopropanol to give the above named product as white crystals melting at ` 138-141C.

Example 6 0-t2,6-Di-tert-butyl-4-(2-carbomethoxy-ethyl)phenyl] phenylphosphonochloridite When using the procedure of Example 1, an equivalent amount of methyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate was substituted for 2,6-di-tert-butyl-p-cresol, the above-named compound was obtained as white crystals melting at 86-88C, ~ 11759L~
Example 7 0-~2,6-Di-tert-butyl-4-(2-carbomethoxy-ethyl)phenyl]-0'-(4-tert-butylph~nyl) phenylphosphor1ite A soIution of 19.5 grams of the compound of Example 6 ln ~0 ml of dry ben~ene was added dropwise rapidly at 25-30C
to a solution of 6.75 grams of p-tert-butylphenol and 4.65 grams of triethylamine in 40 ml of benzene. The reaction mixture was heated at 65C for 3 hoursO The triethylamine hydrochloride formed was removed by filtration and the clear filtrate was con-centrated by vacuum distillation. The crude residue formed was dissolved in hexane and the solution was successiYely washed with 2N aqueous sodium hydroxide and water and finally dried over an-hydrous sodium sulfate. After filtration and remoYal of sol~ent in vacuo, the residue was recrystallized from isopropnaol as white crystals ~elting at 69-71C.

.

_ -34-~ 8 0-(2,6-Di-tert-butyl-4-methylphenyl)-01-(4-tert-butylphenyl) phenylphosphonite The above-named compound was made according to the procedure of Example 7, when an equivalent amount of the phenyl-phosphonochloridite o~ Example 1 was substituted for the phenyl-phosphonochloridite of Example 6, as white crystals melting at 101-103C.

Example 9 0-(4-tert-Butylphenyl)~0'-(2,4,6-tri-tert-butylphenyl) phenylphosphonite The above-named compound was prepared by the procedure Or Example 2 by substituting an equivalent amount of the compound of Example 3 for that Or ExampIe 1 and replacing 2,4-di-tert-butylphenol with an equiYalent amount o~ p-tert-butylphenol. The product was isolated as a viscous liqui~ boiling at 198C~0.0~ mm Hg.

Example 1 0 0~(2-tert-Butyl~4wme~hylphenyl)-O'-~2,6-di-tert-but~l-4-methylphenyl~ Dheny1phosphonite The above-named compound was prepared by the general procedure of Example 2 by substituting an equi;
Yalent amount of the 2-tert-butyl-p-cresol for 2,4-di-tert-butylphenol. The product was isolated as white crystals melting at 108-111C.

` Example 11 0-(2~6-Di-tert-butylphenyl) phenylphosphonochloridite .

This compound is made by the general procedure of Example 1 by replacing 2,6-di-tert-butyl-p-cresol with an equivalent amount Or 2,6-di-tert-butylphenol.

' ~ S~

Exam~le 12 .
0-(2,6-Di-tert-butylphenyl)-0'-(2,4-di-tert-butvlDhenyl) DhenYlDhoS~honite . ~

The above-named compound is made by the general method of Example 2 by replacing the cor~pound of Example 1 with an equivalent amount Or the phenylphosphonochloridite of . Example 11.

Ex_mple 13 , 0 0-(2-tert-Butyl-4,6-dimethylphenyl) pherylphosphonochloridite The above-named compound is made by the general pro-cedure of Example 1 by replacing 2,6-di-tert-butyl-p-cresol ~ith an equivalent amount of 2-tert-butyl-4,6-dimethylphenol.

5 . Example 14 ; . 0-(2-tert-Butyl-496-dimethylphenyl)-0'-(2,4-di-tert-butylphenyl) phenylphosphonite : The above-named compound is prepared by the general; procedure of Example 7 by replacing the phenylphosphonochlori-0 dite of Example 6 with an equivalent amount of the compound of ~xample 13 and p-tert-butylphenol by an equivalent amount of 2,4-di-tert-butylphenol.

s~

Example 15 Phenylphosphonous acid monoester of methyl _3,5-di-tert but~l~4-hydrohydrocinnamate To a solution of 40.9 gram~ of methyl 3,5~di-tert-butyl-4-hydroxyhydrocinnamate in 70.7 grams of triethylamine was added dropwise at 23 25C 12.5 grams of dichlorophenyl phosphine. The reaction mixture was heated for 12 hours at 75-80C and then poured onto chopped ice containing 60 grams of concentrated hydrochlorio acid. This mixture was stirred until all the ice had melted, and was then extracted with ben zene. The benzene phàse was washed with water and the repeat-edly with saturated sodium bicarbonate solution till the ben-zene showed no halogen to be present according to a Beilstein test. After removal of the benzene solvent from the dried benzene phase, the residue was topped at 125-152CJ0.20 mm ~g to remove unreacted methyl 3,5-di-tert-butyl-4-hydroxyhydro-cinnamate. The remaining residue was recrystallized from cyclohexane and hexane to give the above-named product as ~hite crystals melting at 87-91CC.

s~

~xample 16 0-(2,4,6-Tri-tert-butyl~henyl_ phenylphosphonite . 17.9 grams of dichlorophenylpho~phine was added dropwise at 10-15C over a 5-minute period to a solution of 26.2 grams of 2,4,6-tri-tert-butylphenol and 10.1 grams of triethylamine in lO0 ml of toluene. The reaction mixture was heated at 80-85C for 24 hours, cooled to room temperature - and freed of triethylamine hydrochloride ~y filtration. After washing with 6N hydrochloric acid and then water, the toluene !0 layer was concentrated under Yacuum. The residue formed was crystallized successively from acetonitrile and n-hexane to : give white crystals melting at 156-158C.

.

7S~

0,0'-Bi~(2,6-di~tert-butyl-4- -carbometho~ l) phen~ osphonite To a slurry of 26.4 grams of methyl 3,5-di-tert-butyl-4-hydroxybenzoate in 50.5 grams of triethylamine wa~ added drop-j wise at 25-30C 8.95 grams of dichlorophenylphosphine. The reaction mixture was then heated at 65 for 4 hours by which timè the mixture became very viscous. To aid stirring 90 ml of toluene was added and the reaction mixture-was heated at 65-70C
for 25 hours more. The reaction mixture was then poured into a rapidly stirred mixture of 300 grams of chopped ice and 50 grams of concentrated hydrochloric acid. After the ice had melted, the separated aqueous layer was extracted witn toluene. The combined toluene phases were successively washed with water, saturated sodium bicarbonate solution and water and then dried over an-hydrous sodium sulfate. After removal of the toluene in vacuo, the isolated residue was recrystallized from a solvent mixture of 250 ml of acetonitrile and 30 ml of benzene to yield white crystals melting at 168-171C.

Example 18 0,0'-Bls-[2,6-di-tert-butyl-4-(carbo-2,4-di-tert-butylphenoxy)phenyl] phenylphosphonite The above named compound was prepared by the general procedure of Example 17 by replacing methyl 3,5-di-tert-butyl-4-hydroxybenxoate with an equivalent amount of 2,4-di-kert-butylphenyl 2,6-di-tert-butyl-~-hydroxybenzoate. The product was obtained as white crystals melting at 229-231C.

Example 19 . 0,0'-Bls-(2-tert-butyl-4,6-- dimethyl~hen~l) phenylphos~onite The above-named compound was made by the general procedure of Example 17, by replacing methyl 3,5-di-tert-butyl-4-hydroxybenzoate by an equivalent amount of 2-tert-butyl-4,6-dimethylphenol, as a liquid boiling at 170~C/0~01 mm Hg.

Example 20 0,0'-Bis-~2-tert-bu~yl-11-(2-carbomethoxyethyl)-6-methylphenyl~ phen~lphosphonite The above-named product is made by the general ` 5 procedure of Example 17 by replacing methyl 3,5-di-tert-butyl-4-hydroxybenzoate by an equivalent amount of methyl 2-tert-butyl-4-hydroxy-6-methylhydrocinnamate.

. Example 21 O~O'-Bis-~2,4,6-triiso~ropylphenyl) phenylphosphonite The above-named compound was prepared following the general procedure of Example 17 by replacing methyl 3,5-di-tert-butyl-4-hydroxybenzoate by an equivalent amount of 2,4,6 tri-isopropylphenol. The product had a melting point of 75C.

Examp1es 2?-28 1~ Other compounds of Formula I may be prepared by the general procedure o~ Examples 2,5,7 or 17.

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Ex a~9 -0,0' Bis(2,6-di-tert-bufyl-4 ~ n _ 48.5 grams of 2,6-di-tert-butyl-4-methylphenol, 27.3 grams of 45.3~ aqueous potassium hydroxide and 300 ml of toluene were refluxed at 108-111C for about 5 hours while removing both bulk water and reaction water from the toluene~water azeo-trope. 17.9 grams of phenyldichlorophosphine was added to the cooled white slurry at 11C and the reaction mixture was stirred at room temperature for 2 hours. 3 ml of dry N,N-dimethylformamide was added and the mixture stirred overnight at room temperature and then at 50C for 3 hours. After add-ing 250 ml of water to the reaction mixture, the green color ~as discharged by the addition of 3 ml o~ acetic acid. The separated toluene phase was then washed with water and dried over sodium sulfate. The crude product, obtained by distilla-tion of the toluene, was triturated with isopropanol to give ~hite crystals which after recrystallization ~rom isopropanol melted at 181-183C.

Example 29(a) O,0~-Bis(2,4,6-tr.l-tert-b_tylphenyl~ phenylphosphonite The above named compound, which melted at 218-220C, was made by the general procedure of Example 2g by substituting 2,~l6-tri-tert-butylphenol for an equivalent amount of 2,6-di-tert-butyl-4-methylphenol.

0-(2,4-Di-tert-butylphenyl~ enylphosphonochloridite 16.5 grams of 2,4-di-tert-butylphenol and 14.8 grams of phenyldichlorophosphine were heated together in an atmos-phere o~ dry nitrogen at 80-goC over a period of 3 hours.
Volatiles were removed at -40-50C at 0.2 mm Hg and the pro-duct was distilled at 160-165~C/1-5 ~. The product crystal-lized to a white solid melting at 68-70C.

-4s-Example 31 0-(2,6 Di-tert-butyl-4-methylphenyl)-0'-(2,4-dl-tert-bu~ylpheny~ enylphosphonite 3-9 grams of 45.3~ aqueous potassium hydroxide and 7.0 grams of 2,6-di-tert-butyl-4-methylphenol was charged to 60 ml of toluene and heated at reflux with stir~ing till 2.7 ml o~ water was collected. 11.0 grams of the compound of Example 30 dissolved in 20 ml of toluene was added dropwise at -10C over a 10-minute period. The reaction mixture was stirred at -10C for 1 hour and allowed to warm to room temperature. 10 ml o~ dry dimethylformamide was added to the milky dispersion and the system was stirred o~ernight. The precipitated potassium chloride was removed by filtration, and all volatiles were removed by distillation. The dry residue was dissolved in 26 ml of isopropanol and isolated as - a white crystalline solid melting at 126-128C. Infrared spectroscopy and thin layer chromatography showed the mate-rial to be identical to that prepared in Example ~.

-~6-:

~ater Pickup at 80d ~elat~ve Huml~lty In order to measure the water pickup of the instant compounds,a 200 mg sample o~ a phg~phonite ~as weighed into a Pe~-ri dish of 5 cm diame~er an~ 1,5 cm wal~ height. The sample in the dish was then place~ in a glass chamber contain-~ng an aqueous solution Or 1~1,5 g~ams of ~mmonium chloride in 386.5 ml of water which pro~ ed an at~3sphere of 80p rela-tive humidity at room temperature.

The water pickup was determined ~y periodically weigh-ing the dish and sample. Any ch~nge in the physical state of the sample was also noted. Flnally the ch~ical products ~ormed are qualitatively determ~ned by runn~ng an infrared spectrum on a 1~ ~olution o~ the products in carbon tetra-chloride. The samples were ~lso analyzed ~y thin layer chroma-tography using glass plates coa~ed with si~Lca gel F-254 made commercially by E. Merck AG, Darmstadt, Ger~any. Results are gi~en on the following table:

5~6 Compound ,~ Gain Days at Or Example By Weight ~0~ RH Remarks 0.1 ll9 little or no hydrolysis 4 0.2 14 0.2 32 û.6 46 0.5 ~3 0. 5 62 little or no hydrolysis , 7 3. 3 21 almost completely hydrolyzed 8 1.8 18 some hydrolysis 17 0.5 20 0. 2 57 little or no hydrolysis .

~7~

.
Processing Stability of Polypropylene at 500F (?60C) ~he base formulation comprises 100 parts of unstabi-lized polypropylene (Profax 6801, Hercules) with 0.10 parts of calcium stearate. The test stabilizers were solYent blended into the polypropylene from solutiGns in methylene chloride.
After removal of the solvent by evaporation under reduced pressure, the stabilized resin formulation was extruded at 0 100 rpm from a 1 inch (2.54 cm) diameter extruder under the ~ollowing extruder condltions:

Temperature Extruder Location ~ , F C
. _ Cylinder ~1 450 232 Cylinder #2 475 246 Cylinder #3 500 260 Die ~1 500 260 Die ~2 500 260 During extrusion~ the internal extruder pressure was determined using a pressure transducer. A~ter each o~ the , .

-4~-fir~t, third and fifth extrusions, resin pellets were compres-sion molded into 125 mil (3.2 mm) thick plaques at 3~0F
~193C) and specimen yellowness index (YI) ~as determined according to ASTM D1925-63T. Low YI values indicate less yel-lowi ng .

The melt flow rate was determined by ASTM me~hod 1238 Condition L. The melt flow rate varies inversely as the trans-ducer pressure and both are relative measures of the molecular weight of the polypropylene. High melt flow rates indicate lower polymer molecular weights and indicate that polymer degra-dation may be occurring. Thus, if melt flow rate after the fifth extrusion shows minimum change from that after the first extrusion and i~ transducer pressure after the fi~th is nearly as high as after the first extrusion, the polypropylene is beirg well stabilized by the given stabilization formulation.

Results are seen in Tables I-II.

The instant compounds J particularly compounds of Examples 2, 4 and 7, not only stabilized polypropylene well against degradation as seen by transducer pressure measurements, but also against discoloration as well.

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~xample 34 Processing Stability of Pol~propylene at 550F (288C) U~ing the general procedure o~ Example 31, the pro-5cessing stability of polypropylenewas tested at 550F (305C) using a laboratory extruder operated at 110 rpm and with the extruder conditions below:

. , Temperature Extruder Location F C
_ Cylinder ~1 ~ 500 260 Cylinder ~2 525 274 Cylinder #3 550 2~8 Die ~1 550 288 Die ~2 550 288 Result~ are given in Table III.
.
The compounds of Example 2 exhibited excellent stabi-lization e~ficacy in this test.

7~
~ o CS ~ CO
~1 U~ o x U~ ~
: a~ ~ ~ ~ u-o ~ ~ r- t-,, ~
o _ ~ t_ ~ 0 O

~ a~o~ ~ o ~ aJ
t~ ~ ~ S:: . L

O O X O tr~ ~ C
~ ;
~ ~ ~a ~a ~ CO ~
C ~ 0 . ~ O O ~ -Hl ~ ~ c ~

O ~
a~ ~ 3 ~ ~ o o o _I
~ ~ ~ o~
v~ ~a ~ u~

~ 1 L ~1 ~ L
~ ~ 0 C) ~ ~ ,~
O C~ ' U ~ D
C~ ~
~ ~ o N ~ O O
~1 L X

~ E H
m H C_~ *

Example 35 Processing Stability of High Molecular ~ei~ht-High Density Polyethylene at 600F (316C) Using the general procedure of E~ample 33, the pro-cessing stability of high ~olecular weight-high density poly-ethylene (Union Carbide 10780-64A) having a nominal melt flow rate of 5.0 grams~10 minutes was measured.

Results are given on Table IV. - .

The compound of ~xample 2 exhibited excellent stabi-lization against discoloration for the polyethylene in this test.

~7~
: C ~ ~ . "~ CO
o : X .~ ~r~ ~ ~ a~
.~ ~ 3 ,_ ~ X
." O ~7 .: ~o ~ ~ ~ In ~I t--;~ . s:: ~) ~1 .~ ~n 3 ~d ,~
:`' C7 ~1 0 o ~1 t- ~J J o~
. ~ g . O .' ,,, O ~ a .` O ~ ¦o~ O L~ (U N o ., ~ ~ 0 3 ~a . .C ~; 3 3 ~ E3 t~l . ~ X~
,` O O ~ o~ ::s ~ S 3t~
., a. . ~ s ~3 ~ o - 3 ' ' ' O r-1 ~r s ~ ~ ~ s ~ D
~ b~ ~ O ~
~ :~: . IS~ ~ `~. ~ ~ ~ L 0 O LO O O O J~
E-l ''I ~ _ S
O ~ O ,_ I
~ 0 vl E U~
C... L 3 0 0 P~ L ~ t-- t-- t ~ ~ 0 :S ~ ~ l~ O O O ~ I .Y
~_1 3 ~ ~ O O ~ O O ~ ~.
o '~ T ~ ~

,_ ~ ~
u`~ O ~ eo ~ 0 O C: O ~' ~ O ~I ~
~ ~ 0 ~ o , o~ v tQ O ~
bl ~
0 ~ * * ~ ~ * c~ ~ o O N T~ ~1 0 0 ~ X X
P~ t'-l l~ ~ X ~ ~ ~; Z
5~ O O --~ ~ OO--` ~
Z Z; ~ 0 ~2; Z ~ O CC ~;
¢ ¢ ~ Ql ¢~: ~ Q. H H
cq ~ ~ . e U~ O Cl:; ~; O O C~: ~; O O *
~: H H ~--C~ H H ~--c~ *

-Example 36 Li~ht Stabilization of Polypropylene Using an FS/BL radlation unit cons~isting of 40 tubes o~ alternating fluorescent sunlamps and black lights ~20 of each); 5 mil (0.127 mm) films of polypropylene (Profax 6801~
Hercules) containing 0.3g by weight of the test stabilizer were mounted on 3" x 2~' (7.62 cm x 5. 08 cm), infrared card holders with 1" x l/47~ (2.54 cm x 0.635 cm) windows and placed on a rotating drum 2 inches ~5.08 cm) from-the tubes in the FS/BL
unit. The time in ho~rs required for de~elopment of 0.5 car-bonyl absorbance units in the test films as determined by in-frared spectroscopy was noted. The development of carbonyl groups in the polypropylene is proportional to the amount of degradation caused by the ultraviolet light exposure.

The test results are given on Table V.

The instant compounds, particularly the compound of Example 18, provided good stabilization against light degrada-tion of polypropylene in this test.

s~

Table V

Hours to Fa~lure Stabilizer (Development 0.5 carbonyl (0.3 ~ t) ab~orbance unit) None 200 Compound Ex 2 5g0 Compound Ex 4 770 Compound Ex 7 490 Compound Ex 8 520 Compound Ex 18 1010 -5~-~ S~
Ex2mple 37 .
Stabilizat~on_of Pol~hylene Terephthalate 1~ of the compound of ~xaMple 2 is added as a sta-bilizer ~o molten polyethylene terephthalate at 270C with , 5 stirring under a nitrogen atmosphere. The resulting formulated polymer is ground with solid carbon dioxide until the particle size is less than lO0 microns in diameter. The temperature at which the onset of oxidation takes place is then determined as rOllOws:

0 About 1 milligram of the polyester powder, as prepared above, is charged into the chamber of the Perkin-Elmer Differen-tial Scanning Calorimeter and heated under nitrogen till a ~emp-erature of 225C is reached. The nitrogen flow is stopped and oxygen is introduced at a ra~e of 15 ml per minute while heating at a rate of 1 degree per minute until the oxidation exotherm is recorded. The oxidation temperature Or the formulated powder is thus determined to be hi~her than that of the base polyester powder without the stabilizer. The hi~her oxidation temperature 0 provided by the stabilizer clearly shows the marked improvement in inhibition of oxidation of the pol~ester, The eolor of the ~tabilized polye~ter is also improved compared to that without the additive.

~ ~7 xample 38 Stabilization of Acrylonitrile -_ Butadiene - St~rene (ABS ~ _ ABS resin is prepared by heating at 80C for 7.5 hours the following ~ormulations:

Resin A: butadiene 10 parts acrylonitrile 24 styrene 65.8 2,2'-azobisisobutyronitrile 0.1 99~9 par~s Resin B: Thi~ resin i9 prepared in the same manner as Resin A
except that it contains additionally 0.25~ of the s~abilizer.

The oxidation temperature of each of the resins is determined by differential Scanning Calorimetry (DSC) employ-ing the following procedure:

10 mg is charged ~o the DSC pan and heated from ambient tempera-ture at a rate o~ 20C/minute in an oxygen stream ~lowing at the rate of 250 ml/minute. The temperature at which an exotherm i~ observed for each of the resi~s i~ recorded.

7~

Samples of ABS resins each made with 0.25~ of a stabilizer of Examples 1, 2, 4, 7, ~J 9 and 14 all exhibit an exotherm at a higher temperature than does the correspond-ing ABS resins containing no stabilizer indicating higher ther mal stability for the stabilized reslns.

Example 39 Stabilization of Polycarbonate Polycarbonate (Lexan, General Electric) is formulated by mixing the base resin in a Waring Blender with 1.0% the com-~0 pound of Example 129 the base resin also containing 0.1~ of octadecyl 3,S-di-t-butyl-4-hydroxyhydrocinnamate. The formu-lated resin is compression.molded, cut into chips and charged into a standard melt index apparatus. After maintaining at 350C for 30 minutes, a sample is removed, compressed into - plaques and examined for color. The sample containing both stabilizers is much lighter in color than that containing only octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate.

Claims (16)

WHAT IS CLAIMED IS:

1. A compound of the formula wherein R1 is branched alkyl of 3 to 18 carbon atoms, benzyl, .alpha.-methylbenzyl or .alpha.,.alpha.-dimethylbenzyl, R2 is alkyl of 1 to 18 carbon atoms, benzyl, .alpha.-methyl-benzyl or .alpha.,.alpha.-dimethylbenzyl, R3 is hydrogen, alkyl of 1 to 18 carbon atoms, carbo-alkoxy of 2 to 19 carbon atoms, carboalkoxyalkyl of 3 to 24 carbon atoms, carbophenoxy, carbophenoxyalkyl of 8 to 16 carbon atoms; or carbophenoxy or carbophenoxyalkyl with the phenoxy substituted with 1 to 3 alkyl groups with 1 to 8 carbon atoms in each alkyl group, R4 is alkyl of 1 to 18 carbon atoms, phenyl or phenyl substituted by 1 to 3 alkyl groups with 1 to 8 carbon atoms in each alkyl group, R5 is halogen, -XH or -XR6, X is O or S, R6 is phenyl, substituted by alkyl, having the formula R7 is hydrogen, branched alkyl of 3 to 18 carbon atoms, benzyl, .alpha.-methylbenzyl or .alpha.,.alpha.-dimethylbenzyl, R8 is hydrogen, alkyl of 1 to 18 carbon atoms, benzyl, .alpha.-methylbenzyl or .alpha.,.alpha.-dimethylbenzyl, and R9 is hydrogen, alkyl of 1 to 18 carbon atoms, carboalkoxy of 2 to 19 carbon atoms, carboalkoxyalkyl of 3 to 24 carbon atoms, carbophenoxy, carbophenoxyalkyl of 8 to 16 carbon atoms; or carbophenoxy or carbophenoxyalkyl with the phenoxy substituted with 1 to 3 alkyl groups with 1 to 8 carbon atoms in each alkyl group.

2. A compound according to Claim 1 wherein R1 is branched alkyl of 4 to 12 carbon atoms, .alpha.-methyl-benzyl or .alpha.,.alpha.-dimethylbenzyl, R2 is alkyl of 3 to 12 carbon atoms, .alpha.-methylbenzyl or .alpha.,.alpha.-dimethylbenzyl, R3 is hydrogen, alkyl of 1 to 18 carbon atoms, carboalkoxy of 2 to 19 carbon atoms, carboalkoxyalkyl of 3 to 21 carbon atoms or carbophenoxy with the phenoxy substituted with 1 to 3 alkyl groups with 1 to 8 carbon atoms in each alkyl group, R4 is alkyl of 1 to 18 carbon atoms, phenyl or phenyl substituted by 1 to 3 alkyl groups with 1 to 8 carbon atoms in each alkyl group, R5 is chlorine or -XR6, X is O, R7 is hydrogen, branched alkyl of 4 to 12 carbon atoms, .alpha.-methylbenzyl or .alpha.,.alpha.-dimethylbenzyl, R8 is hydrogen, alkyl of 1 to 12 carbon atoms, .alpha.-methylbenzyl or .alpha., .alpha.-dimethylbenzyl, and R9 is hydrogen, alkyl of 1 to 18 carbon atoms, carboalkoxy of 2 to 19 carbon atoms, carboalkoxyalkyl of 3 to 21 carbon atoms or carbophenoxy with the phenoxy substituted with 1 to 3 alkyl groups with 1 to 8 carbon atoms in each alkyl group, with the proviso that all of R7, R8 and R9 cannot be hydrogen at the same time.

3. A compound according to Claim 1 wherein R1 is tertiary alkyl of 4 to 8 carbon atoms, R2 is branched alkyl of 4 to 8 carbon atoms, R3 is hydrogen, alkyl of 1 to 9 carbon atoms, carbo-alkoxy of 2 to 9 carbon atoms, carboalkoxyalkyl of 3 to 11 carbon atoms or carbophenoxy with the phenoxy substituted with 1 to 3 alkyl groups with 1 to 4 carbon atoms in each alkyl group, R4 is phenyl or phenyl substituted by 1 to 3 alkyl groups with 1 to 4 carbon atoms in each alkyl group, R5 is chlorine or -XR6, X is O, R7 is tertiary alkyl of 4 to 8 carbon atoms.

R8 is hydrogen or alkyl of 1 to 8 carbon atoms, and R9 is hydrogen, alkyl of 1 to 9 carbon atoms, carbo-alkoxy of 2 to 9 carbon atoms, carboalkoxyalkyl of 3 to 11 carbon atoms or carbophenoxy with the phenoxy substituted with 1 to 3 alkyl groups with 1 to 4 carbon atoms in each alkyl group.

4. A compound according to Claim 1 wherein R1 is isopropyl or tert-butyl, R2 is alkyl of 1 to 4 carbon atoms, R3 is hydrogen, alkyl of 1 to 18 carbon atoms, -CH2CH2COOCH3, -COOCH3, -COOC18H37 or R4 is alkyl of 1 to 18 carbon atoms or phenyl, R5 is chlorine, -XH or XR6, X is O, R6 is R7 is hydrogen, isopropyl or tert-butyl, R8 is hydrogen or alkyl of 1 to 4 carbon atoms, and R9 is alkyl of 1 to 4 carbon atoms, -COOCH3, -CH2CH2COOCH3 or .

with the proviso that both R7 and R8 cannot be hydrogen at the same time.

5. The compound according to claim 1 which is O-(2,6-di-tert-butyl-4-methylphenyl)-O'-2,4-di-tert-butylphenyl) phenylphosphonite.

6. The compound according to Claim 1 which is O-(2,4-di-tert-butylphenyl)-O'-(2,4,6-tri-tert-butylphenyl) phenylphosphonite.

7. The compound according to Claim 1 which is O-[2,6-di-tert-butylphenyl-4-(2-carbomethoxyethyl)phenyl]-O'-(4-tert-butylphenyl) phenylphosphonite.

8. The compound according to Claim 1 which is 0-(2,6-di-tert.-butyl-4-methylphenyl)-0'-(4-tert.-butylphenyl) phenylphosphonite.

9. The compound according to Claim 1 which is 0,0'-bis(2,6-di-tert.-buty1-4-carbomethoxyphenyl) phenyl-phosphonite.

10. The compound according to Claim 1 which is 0,0'-bis-[2,6-di-tert.-butyl-4-(carbo-2,4-di-tert.-butyl-phenoxy)-phenyl] phenylphosphonite.

11. A composition of matter comprising an organic material selected from the group consisting of plastics,resins and lubricating and mineral oils subject to oxidative, thermal or actinic degradation, stabilized with from 0.01 to 5 % by weight of a compound according to Claim 1.

12. A composition according to Claim 11 wherein the organic material is a synthetic polymer.

13. A composition according to Claim 12 wherein the polymer is a polyolefin homopolymer or copolymer.

14. A composition according to Claim 13 stabilized with 0-(2,6-di-tert.-butyl-4-methylphenyl)-0'-(2,4-di-tert.-butylphenyl) phenylphosphonite, 0-(2,4-di-tert.-butylphenyl)-0'-(2,4,6-tri-tert.-butylphenyl) phenylphosphonite or 0,0'-bis [2,6-di-tert.-butyl-4-(carbo-2,4-di-tert.-butylphenoxy) phenyl] phenylphosphonite.

15. The compound according to Claim 1 which is 0,0'-bis(2,6-di-tert.-butyl-4-methylphenyl) phenylphosphonite.

16. The compound according to Claim 1 which is 0,0'-bis(2,4,6-tri-tert.-butylphenyl) phenylphosphonite.