1~2~
BI8(TRI ~h~ lARY-ALRYLPHENOXY)DIPHO8PHA8PIROUNDECANE8
B~ckground of the Invention
The present invention relates to bis(tri-tert-alkyl-
phenoxy)diphosphaspiroundecanes, and to bis(2,4,6-tri-t-
alkylphenoxy)diphosphaspiroundecanes in particular, as
well as to polymer compositions while include tri-t-
alkylphenoxy diphosphaspiroundecanes in stabilizing
amounts.
A variety of alkylphenoxy diphosphaspiroundecanes are
known in the art. Japanese Early Disclosure 1986-225,191
of October 9, 1986 by Tajima et al. discloses a number of
bis(alkylphenoxy)diphosphaspiroundecanes, such as bis(2-
tert-butyl-4,6- dimethylphenoxy) diphosphaspiroundecane
and bis(2,4-di-t-octylphenoxy) diphosphaspiroundecane.
Bis(alkylphenoxy)diphosphaspiroundecanes are also
disclosed by Japanese Patent 49-128044; U.S. Patent No.
4,066,611 to Axelrod; U.S. Patent Nos. 4,094,855 and
4,207,229 to Spivack; U.S. Patent No. 4,305,866 to York
et al; U.S. Patent No. 4,520,149 to Golder; U.S. Patent
No. 4,585,818 to Jung et al and published U.K. Patent
Application GE 2 156 358. Other diphosphaspiroundecane
compounds known in the art include bis(2,6-di-t-butyl-4-
methylphenoxy) diphosphaspiroundecane and bis(2,6-di-t-
butyl-4-ethylphenoxy) diphosphaspiroundecane.
13~255
Virtuaily all collllller~ ;dl poiymers contain one or rnore stabiiking compounds to protect the
polymer against deyldddlion of polymer p-upe-lias by chain scission or u~ des;-~d cn )- . ;ng during
prucess;.,g and product use. This deylddation is particulariy prc~'e lldliwl with lhe"~,oplaslic
poiymers, which typically are subjecteci to extreme process;.,g te",pe-dllJres. Not only does such
deg- dddtion effect the physical p~pe- lies of the co, ~ Ipoaition but may also cause the polymer to
become d;sc ~ 'c ~d thereby making the polymer aeall-etically unappealing and causing the product to
be rejecteci.
I Ic/:_-cr polymer stabilkers may be ~ i to various ad~;erse conditions during the course
of their production shipment storage and use. One such condition which may adversely affect
stabilizers is excessive exposure to moisture either in the form of humidity or wetness. Although
many stabilkers are used in the form of powders or granules abso"~lion of moisture may cause a
stabilker to ciump or ~blocK thereby making the ~ Pr difficult to handle during feeding and
mking ope,dlions. A consequence of such moisture exposure may be hydrolysis which frequently
reduces stabilking prope,lies and leaves the resin vulnerable to dey,dddlion.
Many phosph ~e s~ inciuding some of the above-. "e, nioned d;, I~osph- sr ~ oundecanes may provide
: 'ent stabilkation when properiy stored either neat or after being compounded into the
polymer. A few phosph-t 3 ~, such as tris(2~4-di~ butylphenol)phoa~uhite (TBPP) may exhibit good
storage stability in humid env;.u---"enta, but do not provide the stabilking efficacy of many
",e"-be-~ of the d;,.hosph~ ùul~iecdne ciass of stabilker.
Although many of the above diphosph~s~- oundecanes are capable of acting as polymer
s'~ ers an improvement in the overall balance of properties would be realked if moisture
,~a;~tance could be improved while maintaining c 'le n stabilking prupe,lies. Indeed a st~ ~er
which imparts good physical and color stability to a polymer while exhibiting improved resistance to
moisture and hydrolysis offers significant ,GIdCtioai advantages over many stabilkers known in the
art.
13~25~
Summarv of the Invention
The present invention is a co,-lV,o~itioll which c~J~Ilv~ es a diphosph~v o(,lldecal-e of the
general formula:
R2 ~--CH2 /CH2--~\ R4
R~ O--P C P--o~R5
R3 ~--CH2 CH2--0 R6
whereineachofR1,R2,R3,R4,R5andR6isatertiaryalkyimoiety. Intheelllixi llelllwhichis
pref~l.ed R1, R2, R3, R4, R5 and R6 are seiected from the group cons;~ti"g of C4 to about C12
tertiary alkyl " . ~- ~ 9 Tertiary-butyi is the moiety which is most prefe, led.The present invention also is directed to a stabilized pdymer colllposition which co",plises a
poiymer and an effective amount of the diphospha:.pirou, ~iecaue of the invention. Then, loplaslic
poiymers are pretelled~ with pdyethyiene, poiypropyiene, polyethyiene telephthaldle, polyphenyiene
ether, polystyrene, impact polystyrene and ABS-type graft copdymers being most plefelled.
Detaileai Deseli~tion of the Invention
The present invention cGIIlprises a 3,9-bis(2,4,6-tri~ rip'lel)G~y)-2,4,8,10-tetroxa-3,9-
diphosph~l~, o[5.51ulldeeane. These compounds, also known as bis (2,4,6-tri-t-alkylphenyi)
pentaerythritol ~i~ hosphi~e 9, may be l~plesellted by the generai formula:
R2 / ~--CH2 / CH2--~ R4
R1~0--P ~C R--O~RS
R3 ~--CH2 CH2--~ R6
1~2.~
wherein each of R1, R2, R3, R4, R5 anci R6 are tertiary (or ~tert~ or ~t~) ali<y ",~
Exal", 'es of such ~ t'es inciudet-buty, t-penty, 1,1,4,4-te- Irdl I~ell,~r butyi, t-octy, 1-
methyi cyciohexyi, t~iodecyi and 2-phenyi-2-propyi. l lo~ or, C4 to about C12 "~ 'ie s such as t-
butyi, t-pentyi, t octy anci t-dodecyi are prefe..~ci. i'~~a~vcly smaller groups, such as t-buty, t-
pentyi, 1-methyicyciohexyi anci 1,1,4,4-t~ -.,ell,yi butyi are more pl~fel-td. Tertiary buty moieties
are most ptefer,~i. Aithough any or all of R1, R2, R3, R4, R5 and R6 may be selected to be
different, such as in 2,4-di- -butyi-4- pentyi, it is pref.~ c that R1, R2, R3, R4, R5 and R6 be
the same.
The ii~hospi- 1e i-- oundecanes of the present invention may be rnade by means known in the
art, such as by the reaction of a tri-t-alkyiphend with 3,9-dichloro-2,4,8, 1 o-tetroxa-3.9-
di~.hosph~ s~' o[5.5]ulldecdne (which may be formed by the reaction of pentaerythritoi with
phosphorous l-icl,'cride by means known in the art). For eAa..-, 'e, 3,9-bis(2,4,6-tri-I-buty1phenoAy)-
2,4,8,1 0-tetroxa-3,9-diphos~h- lp. o~5.5]1J"decane may b~e forrned by the reaction of 2,4,6-tri- -
butylphend with 3,9-dichloro-2,4,8,10-tetroxa-3,9-diphospl,~s~' o[5.5]undecane (dichlorope"lile).
Similariy, 3,9-bis(2,4,6-tri-I-penty phenoxy)-2,4,8,10-tetroxa-3,9-d4)1)osph7 r u l5.5l undecane may
be formed by the reaction of 2,4,6-tri-I-penty phend with dic~ r~pe. ~ e. Other bis(tri-I-
alky4,henùAy)-tetroxa~ cispi 1e, ul.- .decanes may be forrned by reacting the tri-I-alkyiphenol
co--esponding to the desired tri-t-alky~.her.oAy group with dicl '~upenlile.
The diphosph - r - ou~ ,deceanes of the present invention may also be made by reacting a phenol
co- ~espork~i;. ,9 to the desired tri-t-alkyl~JhenoAy group with phospl-orous l,i~;i ,'~ride to form a tri-t-
alkyl~,henùAy iJhosphor~ 'Icr,!c ~ "e followed by reactlon of the phospho.. ' ' 'arid ~ with
pentaerythritd to form a bis (tri-t-alky4,1,enûAy)-tetroAa-diphosp~ 1S, ~ oulldecane. For example
2,4,6-tri-t-butyiphenol may be reacted with phosphorous l.i~;l ,'oride and then with pentaerythritol to
form bis(2,4,6-tri-t-butyl-phenoAy)-tetroxa-diphosph~.~~ ou- decane. Similarly, 2,4,6-tri-t-
dodecylphenol might be reacted with phosphorous Irl~h' ~ ide and then with pentaerythritol to form
' 13~2~
bis(2,4,6-tri-t do~yl~hP~nYy) -tetraxa-~i nhn.~rh~ ~r i n~ ~ - ~Pr ~ r ~ .
E~xrYhlres for forming ~i~~.n~~A.Acpir~u~e~u~s by the ~i~hl~ro--
pentite and the phn~rhnro~i~hnridite routes are known in the art.
u~l~vcr, whereas the prior art may show the ~i~lh~~A~riroundecane
being formed in cnll~in~ in the ~J~ ~f an amine, such as
triethuylamine, which serves as an acid a~t~L~ by forming an
insoluble hydrochloride C~lt~ it is preferred that the ~ipn~ph-
aspirx~u~e xule be formed in a tri-n-aLkylamine, such as tri-n-
butylamine, wherein each n-alkyl group is a C3 or larger n-aLkyl
moiety, wherein the hydrochloride salt remains in solution and the
~i~A~ h~pir~ e product is suLaL~.Lially i~coll~hle.
Preferred ~~ are ~Yp~ ed further in Canadian Patent
Prrli~Ation Serial No. 612,323 filed September 21, 1989, entitled
"3,9-Di~J.n~L~A~riro~u~lF~ and PLU~SS for M~king
3~g-ni~lh~ A~in~u~xu~all~ by S.J. Hobbs, K.J. .~ ~ and W.P.
Enlaw. Examples of both prior art and ~,Le~eLLe~ ~Lo~Cc~e~ for
making ~iLJ-n~J~A~piro~u~eLcu ~ of the invention are shawn belaw in
the section entitled ll.SPPC;f;C F~Q~iments".
The ~JLea~l~ invention also is a R~Ahili~P~ polymer camposition
which incl~ an effective amount of one or more of the
bis(tri-t-aLkylphenoxy)-tetroxa-~i~J~n~.A~~;r~u~e xu~S described
abave. An amcunt of the ~i~J~n~ ~.iro~u~e~xu ~ of the invention is
considered to be an '~rre~ive amcunt", when the polymer oomposition
containing the ~i~~na~ A~~iro~u~e~xule of the invention shaws
improved stability in any of its physical or color p~u~Lies in
comparison to an an~lo~ polymer composition which does not
include a ~i~J-o~J~ARriro~u~e xu e of the invention. In most polymer
oompositions, h~h~evcr, it will be ~L~fe~ed that the ~i~~n~~l~A-
spircau~e~cule of the invention be ~~Les~.L in an amaunt equal to
about .01 to abaut 2 parts by wriqht per 100 parts by w~iqh~ resin
(phr). Amaunts of abaut .01 to abaut 1 ihr are mare ~LereLL~,
althau~h most oompcsitions will oQntain abaut 0.025 phr or more.
The polymer may be a~y of the polymers known in the art, such as
polyesters, polyurethanes, polyaLkylene ter~~~ tes, poly-
sulfones, polyimides, poly~phenylene ethers, styrenic polymers, poly
A
:134025~
cs, I,or~as, acrylic polymers, polyamides, poly~ce~ls halide containing polymers and polyolefin
hG,.,opolymers and copolymers. Mixtures of different polymers, such as polyphenylene ether/styrenic
resin blends, polyvin~ch' - ride/ABS or other impact rnodified polymers, such as methacrylonitrile
containing ABS, and polyester/ABS or polyester plus some other impact modifier may also be used.
Such polymers are available cG"""e-c~lly or may be rnade by means well known in the art.
I lorr~;cr the di~.hosph~ l uundecanes of the invention are particularly useful in II ,e" "oplaslic
polymers, such as polyolefins, poly-;a- bor~les, polyesters, polyphenylene ethers and styrenic
polymers, due to the extreme temperatures at which II,e.",oplaalic polymers are often processed
and/or used.
Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybutene-
1, polymethylpentene-1, poly;sop.t:ne or polybutadiene, as well as polymers of cycloolefins, for
ina~nce of cyclopentene or no.bo."ene, polyethylene (which optionally can be crosslinked), for
exa",, 'E high density polyethylene (HDPE), low density polyethylene (LDPE) and linear low density
polyethylene (LLDPE) may be used. Mixtures of these polymers, for example mixtures of
poiypropylene with (PP) polyisobut~lene, polypropylene with poiyethyiene (for example PP/HDPE,
PP/LDPE) and mixtures of different types of polyethylene (for e~",, '8 LDPE/HDPE), may also be
used. Also useful are copolymers of monoolefins and d':'~qnes with each other or with other vinyl
" ,ono",e,a, such as, for example, ethylene/propyiene, I I npE and its mixtures with LDPE,
propylene/butene-1, ethylene/hexene. ethylene/ethylpe,ltane, ethylene/heptene. ethylene/octene.
propylene/isobutylene, ethylene/butane-1, propylene/butadiene, isobutylene/isoprene, ethylene/alkyl
acrylates, ethylene/alkyi methacryiates, ethylene/vinyi acetate (EVA) or ethyiene/acrylic acid
copolymers (EAA) and their saits (iono"~era) and terpolymers of ethylene with propylene and a
diene, such as hex~diGne, dicyclope,ltadiene or ethylWene-no,L~,.,ene, as well as mixtures of such
copolymers and their mixtures with polymers r"en~ioned above, for example polypropylene/ethylene-
propylene-copolymers, LDPE/EVA, LDPE/EAA, I I nPE/EVA and I I nPE/EAA.
The""oplas~ic polymers may also include styrenic polymers, such as polystyrene, poly-(p-
13~0~55
methylstyrene), poly-(alpha-methyistyrene), copolymers of styrene or alpha-methyistyrene with
dienes or acrylic derivatives, such as, for exampie, styrene/butadiene. styrene/acryonitrile,
styrene/alkyl ",e~l~c,ylate, styrene/maleic anhydride, styrene/butadiene/ethyl acryiate/
styrene/acrylonitrile/methyiacrylate; mixtures of high impact strength from styrene copoiymers and
another polymer, such as, for e-.d" ")le, from a poiyacryiate, a diene poiymer or an
ethylene/propylene/diene terpoiymer; and biock copoiymers of styrene, such as, for exd""~le,
styrene/butadiene/styrene, styrene/isop,ene/styrene, styrene/ethyiene/butyiene/styrene or
styrene/ethylene/propylene/styrene. Styrenic poiymers may additionally or dltéll~li~/ely include
graft copolymers of styrene or alpha-methyistyrene such as, for exampie, styrene on polybl ~ad ~ne,
styrene on poiybl ~ ne-styrene or polybutadiene-acryionitrile; styrene and acryionitrile (or
l"ell~cl~10nitrile) on poiybutadiene; styrene and maleic anhydride or maleimide on polybutadiene;
styrene, acrylonitrile and maleic anhydride or maleimide on poiybutadiene; styrene, acrylonitrile and
methyl ",etl,aclylate on polybutadiene, styrene and alkyi acryiates or ",etl~clyiates on
polybutadiene, styrene and acryionitrile on ethyiene/propyiene/diene terpoiymers, styrene and
acrylonitrile on polyacrylates or pol~" ,ell ,acr~1ates, styrene and acryionitrile on acryiate/butadiene
copolymers, as well as mixtures of with the styrenic copolymers il~i;ctted above.
Nitrile polymers are also useful in the polymer colllpoaition of the invention. These include
ho",opolymers and copolymers of acrylonitrile and its analogs such as ,.,etl~cryionitrile, such as
polyacrylonitrile, acryionitrile/butadiene polymers, acryionitrile/alky acryiate poiymers,
acrylonitrile/alkyi ",~I,acrylate/but2 ~' ne polymers, ABS, and ABS which indudes ."~tl,acrylonitrile.
Polymers based on acrylic acids, such as acryiic acid""~l~clyiic acid, methyi methacrylic
acid and ethacrylic acid and esters thereof may also be used. Such polymers inciude
polymethyl" ,e~l ,acryiate, and ABS-type graft copoiymers wherein ail or part of the acrylonitrile-type
" ,ono" ,er has been, ~placed by an acryiic acid ester or an acryiic acid amide. Poiymers including
other acrylic-type monoll,t:,a, such as acrolein, ."~ c~de- " acryiamide and m~ cryiamide may
also be used.
i340255
Halogen-containing pdymers may also be useful. These include resins such as polych!cropr~ne
lch!crohydrin homo-and copolymers polyvinyl chloride polyvinyl bro~ Q, polyvinyl fluoride
pdyvinylidene chloride cl,'c i-,dted pdyethylene c:l-'c i-,dtad polypropylene flori- ated
pdyvinylidene brominated pdyethylene ch'ari"dtad nubber vinyl chloride-vinylacetate copolymer
vinyl chloride-ethylene copdymer vinyl chloride-propylene copolymer. vinyl chloride-styrene
copolymer vinyl chloride-isobutylene copolymer vinyl chloride-vinylidene chloride copolymer vinyl
chloride-styrene-maleic anhydride tercopolymer vinyl chloride-styrene-acrylonitrile copolymer vinyl
chloride-b~ ~e copolymer vinyl chloride-isop-t:ne copolymer. vinyl chloride-chlorinated propylene
copolymer vinyl chloride-vinylidene chloride-vinyl acetate tercopolymer vinyl chloride-acrylic acid
ester copolymers vinyl chloride-maleic acid ester copolymers vinyl chloride-methacrylic acid ester
copolymers vinyl chloride-acrylonitrile copolymer and internally p'~tic;~d polyvinyl chloride.
Other useful the...,opla~lic polymers include ho",opol~/mers and copolymers of cyclic ethers
such as polyalkylene glycols polyethylene oxide polypropylene oxide or copolymers thereof with
bis~lycidyl ethers; polyace~ such as polyoxymethylene and those polyoxymethylene which contain
ethylene oxide as a co-"ono",er polyacetals ",odified with ll,e---,oplaslic polyu,~ll,anes acrylates or
n.e~l,acrylonitrile containing ABS; polyphenylene oxides and sulfides and mixtures of polyphenylene
oxides with polystyrene or polyamides; pOIyC,dl Londles and polyester-carbonates; polysulfones
polyethersulfones and polyetl~er~etones and polyesters which are derived from dicarboxylic acids
and diols and/or from hydroxycarboxylic acids or the co--as~r ,9 laetones such as polyethylene
tel~Allldldle polybutylene te,t:~htl,ald~e poly-1 4-dimethylol-cy~ loht:~dne ten:~,hll,aldle poly-[2 2 -
4(4-hydroxyphenyl)-propane] te,~ph~l,dldta and polyhydroxyberuoates as well as block-copolyether-
esters derived from polyethers having hydroxyl end groups.
Polyamides and copolyamides which are derived from diamines and dicarboxylic acids and/or
from dl I ' ~oca- L~xylic acids or the co, .~:")or ~9 Iactams such as polyamide 4 polyamide 6
polyamide 6/6, 6/10, 6/9, 6/12 and 4/6, polyamide 1 1, polyamide 12, aro" ,dlic polyamides obtdi"ed by
condensdlion of m-xylene diamine and adipic acid; polyamides prepa,ed from h~xd",~l,y1ene diamine
~ 3~02~
and isophthalic or/and tél e~hll ~ - acid and optionally an ela:.lo- ~ ~er as modifer, for eAal "~ ~e poly-
2,4,4-trimethylhe~d-~lel1l)~1ene te-e~Jhtlldld-.l ~ or poly-m-phe-.~lene isophtlldld.-l '~ may be useful.
Further copdymers of the a~o, e" ,e, ltioned pdyamides with polyolefins, olefin copolymers, iono" lel s
or chel" ~-lly bonded or grafted eld~tt,"le-~, or with polyethers, such as for i":,ldnce, with
polyethylene glycd, pdypropylene glycd or pdytet~d---etl,~lenel glycds, and polyamides or
copolyamides ~ qe d with EPDM or ABS may be used.
Pdyolefin, polyalkylene terephthdldle, polyphenylene ether and styrenic resins, and mixtures
thereof are more pl~fe. ~ed, with polyethylene, polypropylene, pdyethylene tereplltl aldte,
polyphenylene ether ho,l.opolymers and copolymers, polystyrene, high impact polystyrene,
pdycdrLondtes and ABS-type graft copolymers and mixtures thereof being particularly preft:rl~d.
The resulting stabilized polymer co-,-~,ositions of the invention may optionally also contain
various conve, Itiondl additives, such as the fd lu .~i .9.
1. A. Itiuxida, It~
1;1 Alkylated ...onophenols, for exdlllr~e 2,6-di-ten-butyl4-methylphenol, 2-tert-butyl4,6-
dimethylphenol, 2,6-di-tert-butyl4-ethylphenol, 2,6-dl-tert-butyl4-n-butylphenol, 2,6-di-tert-butyl4-
i-butylphenol, 2,6-dl-cyelop6ntyl4-methylphenol, 2-(alpha-methylcydohexyl)4,6-dimethylphenol, 2,6-
di-octadecyl4-meth~ henol, 2,4,6-tri~yclohexylphenol, 2,6-di-tert-butyi4-methoxymethylphenol.
1.2 Alkylated hydroquinones for example, 2,6~di-tert-butyl4-methoxyphenol, 2,5-di-tert-butyl-
hydroqu ~one, 2,5-di-tert-amyl-hydroquinone, 2,6-diphenyl4-octadecyloxyphenol.
1.3 Hydroxylated thiodiphenyl ethers, for example, 2,2'-thio-bis-(6-ten-butyl4-methylphenol),
2,2'-thio-bis-(4 octylphenol), 4,4'-thio-bis-(6-tert-butyl~-methylphenol), 4,4'-thio-bis-(6-tert-butyl-2-
methyl"henol).
1.4 Alkyliden-bisphenols, for exd-,-,~'e 2,2'-methylene-bis-(6-tert-butyl4-methylphenol), 2,2'-
methylene-bis-(6-tert-butyl4-ethylphenol), 2,2'-methylene-bis-[4-methyl~(alpha-
methylcyclohexyl)phenoll, 2,2'-methylene-bis-(4-methyl~cyclohexylphenol), 2,2'-methylene-bis-(6-
nonyl4-methy1"henol), 2,2'-methylene-bis-[6-(alpha-methylbenzyl)4-non~ henoll, 2,2'-methylene-bis-
~025~
[6-(alpha,alpha-dimethylbenzyl)4-nonyl,uhenol], 2,2'-methylene-bis-(4,6-di-tert-butylphenol), 2,2'-
ethylidene-bis-(4,6-di-tert-but~1phend), 2,2'-ethylidene~;a (6 tert-butyl4-isobutyl~,henol), 4,4~
methylene-bis-(2,6-di-tert-butyl~l-enol), 4,4'-methylenebis-(6-tert-but~1-2-methyl,uhenol), 1,1-bis-(5-
tert-but~1-4-hydroxy-2-rnethylphenyl)butane, 2,6-di-(3-tert-but~l-5-methyl-2-hydroxybenzyl)4-
methylphend, 1,1,3-tris-(5-tert-butyl4-hydroxy-2-methylphenyl)butane, 1,1-bis-(5-tert-butyl4-
hydroxy-2-methylphenyl)-3-dodecy~"er~-~plobut~rle, ethylenglycol-bis-13,3-bis-(3'-tert-butyl4'-
hydroxy-phenyl)-butyratel, di-(3-tert-buty14-hydroxy-5-methylphenyl)-dicyclopentadiene, di-[2-(3'-
tert-butyl-2'-hydroxy-5'-methyl-benzyl)-6-tert-butyl~methylphenyll-te.t:ph~l ~late.
1.5 Benzyl compounds,fore~", 'e 1,3,5-tris-(3,5-di-tert-butyl4-hydroxybenzyl)-2,4,6-
trimeth~1berkal-e, bis-(3,5-di-tert-butyl4-hydroxybenzyl)sulfde, isooctyl 3,5-di-tert-butyl4-
hydroxybenzyl-" ,er~apto-acetate, bis-(4-tert-but~/1-3-hydroxy-2,6-dimethylbenzyl)dill . 'te, ~pl ,ll ,alate,
1,3,5-tris-(3,5-di-tert-butyl4-hydroxybenzyl)isocyanurate, 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-
dimethylbenzyl)isocyanurate, dioct~dec~1 3,5-di-tert-butyl4-hydroxybenzyl-phosphonate, calcium salt
of ,.,ono~th~1 3,5-di-tert-butyl4-hydroxybenzylphosphor~dle, 1,3,5-tris(3,5-dicyclohexyl4-
hydroxybenzyl)isocyanurate.
1.6 Acylam ,ophenols, for example, 4-hydroxy~auric acid anilide, 4-hydroxy-stearic acid
anilide, 2,4-bis octyl",a,capto~(3,5-tert-butyl4-hydrox-yanilino)-s-triazine, octyl-N-(3,5-di-tert-
butyl4-hydroxyphenyl)~, l~" ~te.
1.7 Esters of beta-(3,5-di-tert-butyl4-hydroxyphenyl)-p,.p, l ~ acid with monohydric or
pdyhydric ~ hds, for example" "~tl ,and, diethyleneglycol, o~lec~nd, triethyleneglycol, 1,6-
hexaneJid, pentaerythritd, neopent~1glycod, tris-hydroxyethyl isocyanurate, Ih r ~i~ lyleneglycol, di-
hydroxyethyl oxalic acid diamide.
1.8 Esters of beta-(5-ten-butyl4-hydroxy-3-methylphenyl)-p,-p ~ r. acid with monohydric or
polyhydric alcohols, for exampe",l~tl-and, diethylen~lycd, o~n~decAnd~ triethyleneglycol, 1,6-
h,a~n-~ 1 c l, pentaerythritol, neopentylglycol, tris-hydroxyethyl isocyanurate, ll, ~ ,yleneglycol, di-
hydroxyethyl oxalic acid d;a",'~
13~02~
1.9 Esters of beta-(5-tert-butyl4-hydroxy-3-methylphenyl)prcp ~n c acid with mono-or
pdyhydric alcohols, e.g. with .~thdlwi, diethylene glycol, oc'YIec~l oi. triethylene glycol, 1,6-
ht xdh~ '- 1, pentaerythritd, neo~ntyi glycd, tris(hy~i~oA~yethyl) Isocyanurate, ltl;c ~ ,ylene glycol,
N,N'-bis(hydroxyethyl)oxalic acid diamide.
1.10 Amides of beta-(3,5 di-tert-butyl~hydroxyphenyl)-p,.plc Y c acid for eAd"")le, N,N'-di-
(3,5-di-tert-butyl~hydroxyphenyl~rc F bn~l)-h~d",~tl,~iend a"line, N,N'-di-(3,5-di-tert-butyl~
hydroxyphenylpr~FIc~i)-trimethyiendidriline~ N,N'-di-(3,5-di-tert-butyl~hydroxyphenylp,c~ ~ny1)-
hydra_ine.
2. UV absc,.be,:, and light ,~ ~ !';7Prs.
2.1 2-(2'-Hydroxyphenyl)-be,~cl-ia~oles, for ~Xd"" 'e. the 5'methyl-, 3',5'~i-tert-butyl-, s'-
tert-butyl-, 5'-(1,1,3,3-te~r~,."~th~1butyi)-, 5-chloro-3',5'-di-tert-butyi-, 5-chloro-3'-tert-butyl-5'-
methyl-, 3'-sec-butyl-5'-tert-butyi-. 4'-octoxy, 3',5'-di-tert-amyl-, 3',5'-bis-(alpha,alpha-
dimethylbenzyl)-derivatives.
2.2 2-Hydroxy-beh~ophenones, for example, the 4-hydroxy-, 4-methoxy-, 4-octoxy, 4-
decyloxy-, 4-dodecyloxy-. 4-benzyloxy, 4,2',4'-trihydroxy- and 2'-hydroxy4,4'-dimethoxy derivative
2.3 Ester of substh~ dsd and unsubstd~ d~d benzoic acWs for aAd" " ' e phenyi salicylate, 4-
tert-butyi-phenyl~3' c;~t~ octylphenyl salicyiate, dibenzoyi,eso~;.,~, bis (~i tert-butyibenzoyl)-
I esGrc;"~i, benzoyi, esoi c;. ,oi, 2,4-di-tert-butyi-phenyi-3,5-di-tert-butyi-4-hydroxybenzoate and
hexadecyi-3,5-di-tert-butyl-4-hydroxyLe~odt~ .
2.4 Acryiates, for example, alpha-cyano-be'~ bet~-diphenylacrylic acid ethyl ester or isooctyl
ester, alpha4arbo,"~tll~,Ay~;.lndl" c acid methyl ester, alpha-cyano-beta-methyl-p-methoxy~;. Inall~ c
acid methyi ester or butyl ester, alpha~dlbolll~ttl-~Ay-p-methoxy~;.ll all ~~ acid methyi ester, N-
(beta~-i, ~" ,t~tt ,oA~y-beta-cyano-vinyl)-2 -methyt-indoiine.
2.5 Nicket compounds, for exd" "~ 'e. nickei complexes of 2,2'-thio-bis-[4-(1, 1,3,3-
t~trarl~etllyibutyi)-phenoil~ such as the 1:1 or 1:2 complex, optionallywith r~d ~n;ll ligands such as
n-butyiamine, l.i~tt,dnola"line or N-cyclohexyi-dt~tt,anola"line, nickei dibutyldithiocarbamate, nickel
. ,
1~2~i~
salts of 4-hydroxy~,5-di-tert-butyibenzyiphosphor'~ acid n,onoaikyi esters, such as of the methyl,
ethyi or butyl ester, nickei compiexes of k~t(Jxi.lles such as of 2-hydroxy-4-methyi-penyi undecyl
ketoxime, nickei compiexes of 1-phenyi4~auroyl-5-hydroxy-pyrazoi, optionally with additional
ligands.
2.6 Sterically hindered amines, for ~all r ~e bis-(2,2,6,6-telralll~thyipiperidyi)-seh~r~te~ bis-
(1,2,2,6,6-pt nta."~l-yipiperidyl)-sP~ e n-butyi-3,5-di-tert-butyi4-hydroxybenzyi malonic acid bis-
(1,2,2,6,6-p~ al"~ll~yipiperidyl)ester, conciensdtion product of 1-hydroxyethyi-2.2,6,6-te~ra-1~ 4-
hydroxy-piperidine and succinic acid, condensalion product of N,N'-(2,2,6,6-tellall-elhyipiperidyi)-
h~Aa. . .~l .yendiamine and 4-tert octyiamino-2,6-dichioro-1 ,3,5-s-triazine, tris-(2,2,6,6-
tetra...t1~hylpiperidyi)-nitri!~l iac~t~e, tetrakis-(2,2,6,6-t~-a---~U.yi4-piperWyl)-1 ,2,3,4-butane-tetra-
carbonic acid, 1,1'(1,2-e~l,anecii~1)-bis-(3,3,5,5-tet-a---eU.yipipe.a~i--one). Such amines include
hydroxyiamines derived from hindered amines, such as di(1-hydroxy-2,2,6,6-tetramethyipiperidin4-
yi)seba~1~. 1-hydroxy-2~2~6~6-t~lalll~lllyi4-benzoxypiperidine; 1-hydroxy-2,2,6,6-t~l.a."e~yl-4-(3,5-
di-tert-butyi4-hydroxy hydrùu;~ .nai . .uyloxy) -piperidine; and N-(1 -hydroxy-2,2,6,6-te~-al . ~ell ~yi-
piperWin4-yl)-epsilon cap~lacta- - -.
2.7 Oxalic acW diamWes, for t:xalll, ~e, 4,4'-di-octyloxy-oxan "~o, 2,2'-di~ctyloxy-5,5'-di-tert-
butyi~.<ar,' ~n, 2,2'-di-dodecyioxy-5,5'-di-tert-butyi-oxa"' ~e, 2-ethoxy-2'-ethyi-oxar,'idQ, N,N'-
bis(3-dimethyiaminopropyi)~lan W?. 2-ethoxy-5-tert-butyi-2'-ethyioAvanilide and its mixture with 2-
ethoxy-2'-ethyi-5,4'-di-tert-buty10Aa" "'e and mixtures of ortho- and para-methoxy- as well as of
o-and p-ethoxy-disub~it~ed uAail '~--
3. Metai deactivators, for example, N,N'-diphenyioxaiic acW diamide, N-salicyial-N'-
salicyioyihydrazine, N,N'-bis-salicyioylhydrazine, N,N'-bis-(3,5-di-tert-butyl4-
hydroxyphenylpr~ F' :ny)-hydrazine, saiicyioyiamino-1 ,2,4-triazoie, bis-benzyiiden-oxalic acid
dihydrazWe.
4. Pl ~Gsph~ s and phospl ~or t ~ s, for eAa~ ~r ~e triphenyi phosp~'~e . diphenyialkyl phosph t s,
phenyidialkyl phosphites, tris(nonyi-phenyi) phosph'~ ~ trilauryi pho~hi~e l-i~~ ~yi phosph te
1~025~
distearyi pentaerythritd diphosph-~e. tris(2,4-di-tert-butylphenyl)phospi i~e ~d' ~-de~,y pentaerythritol
diphosph- ., bis(2,4-di-tert-butyphenyi) pentaerythritd ~ osphit~ tristearyisorbitd ~ )GSPI '~ .
and tetrakis (2,4-di-tert-butypheny) 4,4'biphenyiene dipl ~sph~ni~
5. Per~xicie scavengers, for exampie esters of beta-thiodipr p'~n-c acici, for exampie the
lauryi stearyi, myristyi or tridecyi esters, ~ I ~e~ ~plobe~ idazde or the zinc salt of 2-
",e-~l~loben~;.,. '-~-'e, zinc-dibuty~ nate, .' -~tadecyidisuifide, pentaerythritol-tetrakis-
(beta-dodecyi" ,e. ~ptù)-p- ~ ndte.
6. Poiyamide stabilkers, for exampie copper salts in comblnation with iodides and/or
phosphorus compounds and salts of divalent ~.,anganese.
7. Basic co-stabilkers, for ~:~d...,c'e melamine, pdyvinyipy--~'id~ae, dicyandiamide, triallyi
cyanurate, urea derivatives, hydrazine derivatives, amines, poiyamWes, polyu-~lhanes, alkali metal
salts and alkaline earth metai salts of higher fatty acids for exd.. ~, '~ Ca stearate, Zn stearate, Mg
stearate, Na ricinoleate and K palmitate, alltilllully pyrùc-dt~hoidte or zinc p~ruc~tecl~old~e.
8. N~ e<~li-,9 agents, for e,<alll,~ 'e. 4-tert-buty-benzoic acid, adipic acid, diphenyiacetic acid.
9. Fillers and .~ fur~,;. ,g agents, for ~Ad", 'e. calcium c~,.L~rdte, . 'k ~e s glass fibres,
~sbe~os talc, kaoiin, mica, barium sulfate, metai oxides and hy~in,xicies, carbon black, s,aph'~e
10. The present invention may also be used in conjunction with aminoxy propdnodle
derivatives such as methyi~-[N,N-dibenzyiaminoxyj,oropanodte, ethyl-3-[N,N-
dibenzyla.., ,uxylp.opdnodta; 1,6-h~a---ell-yiene-bis[3-(N,N-dibenzyiaminoxy)propdnc,d~al; methyl-[2-
(methyl)-3(N,N-dibenzyiaminoxy)pn~pdn~àlel; o~;tade~ i-3-[N,N-dibenzyi-aminoxy]plo;-~an ~'c acid;
tetrakis[(N,N-dibenzyaminoxy)ethyl carbonyi oxymethyi]...~tl,ane, o.,tdde.;~l-3-[N,N-diethyi
aminoxy]p.upanoata, 3-[N,N-dibenzyiaminoxy]p.u~,~an~'~ acici p~t~s;~l-n sait; and 1,6-h~ a--,~ll-yiene
bis[3-(N-allyl-N~odecyl aminoxy) p- upanodte] .
11. Other additives, for ~.-.,:'e ~ ., lui-,t~dl~t~, emulsiflers, pigments, optical
brighteners, flame-prooflng agents, anti-static agents, biowing agents anci thiosynergists such as
dilaurylthiodip~.p~c dta ordistealyithiodip-o~~ ,dla.
13~255
Hindered phen ~ ;c a ntiùxiJal It~ may also be present in the pdymer composition. Use of
dil,hosph~ ;r ! uu- ,decdnes of the present invention may result in ~ Ihdnced polymer protection by
reducing the to- " lalion of color resulting from the prese~e of the phenols. Such pher.
antiuAiddl t:j indude n-octadecyl 3,5-di-tert-butyl4-hydroxyhy Jroc;nna",dte, neope,na"et~,dyl
t~tlah (3,5-di-tert-butyl4-hydroxyl-hyd,~c;"na."dle), di-n~adecyl 3,5-di-tert-butyl4-
hydroxybenzyi-phosphorate, 1,3,5-tris(3,5-di-tert-butyl~hydroxybenZyl-)isocyanurate, thiodiethylene
bis(3,5-di-tert-butyl4-hydroxyhy.J, ùci. Indl, ~le). 1 ,3,5-trimethyt-2,4,6-tris(3,5-di-tert-butyl4-
hydroxybenzyl)be,~ene, 3,6-dl~Y~ "etl,)r1ene bis(3-methyl-5-tert-butyl4-hydroxyhy Irùcinnamate),
2,6-di-tert-butyl-p-cresol, 2,2 -ethylidene-bis(4,6-di-ten-butt, I~Jheru~l), 1 ,3,5-tris-(2,6-di-methyi4-tert-
butyl-3-hydroxybenzyi)isocyanurate. 1,1 ,3-tris-(2-methyi4-hydro,y-5-ten-butylphenyl)butane, 1,3,5-
tris-[2-(3,5-di-ten-butyl4-hydroxyhyd, ul,;. ")a" ,o~oxy)-ethyl]-isocyanurate, 3,5-di-(3,5-di-ten-butyl-
4-hydroxybenzyl)-mesitol, hexa-methylene bis(3,5-di-ten-but~14-hydroxyh~-~rù-,;. Inal "a~e), 1 -(3,5-di-
tert-butyl4-hydroxyanilino)-3,5-di(octyllhio)-s-triazine, N,N -he, a.,.~tl,~lene-bis(3,5-di-ten-butyl4-
hydroxyhydro~;."~a"~"lide), calcium bis(ethyi-3,5-di-ten-but~yl4-hydroxybenzylphosphondle),
ethyiene bis[3,3-di(3-ten-butyl4-hydroxyphenyl)butyrate], octyl 3,5-di-ten-butyl4-
hydroxybenzy1",e,~ ~o~ e bis(3,5-di-ten-butyi4-hydroxyhyl,oc;.,nd,,,uOhydrazide,andN,N-
bis-[2-(3,5-ten-butyl4-hydroxyhyJr.,xoc;.,nd",ù~loxy)-ethyil~xa",~eandpreferably
neope,Itdl,etet,a~ tetrakis(3,5-di-ten-butyi4-hydroxyh~ u-,;. u aindte), n-octadecyl 3,5-di-ten-butyl-
4-hydroxyhyd, u ,i~ ,nd" ,dle, 1 ,3,5-trimethyl-2,4,6-tris(3,5-di-ten-but~14-hydroxy-benzyl)be, ~ene, 1 ,3,5-
tris-(3,5-di-ten-butyl4-hydroxybenzyl)isocyanurate, 2,6-di-ten-buty~-p-cresoi or 2,2 -ethylidene-
bis(4,6-di-ten-butylphenol).
Other additives, such as oxazdphospholirli"es, may additionally or alternatively be present.
- .~;se, the instant compounds prevent cdor fo",~lion when hindered amine light stabilkers
are present, such hindered amines induding bis(1,2,2,6,6-perlta,..~ ,1 4 piperidyi)-2-n-butyl-2-(3,5-
di-ten-butyl4-hydroxy-benzyl)malonate; bis(2 ~.6,6-te:tlalll~tllyl4-piperidyi) se~-~te:
dimethyisuccinate polymerwith 4-hydroxy-2,2,6,6-t~t~a",~tl,~1-1-piperi li"etl~nol, and polymer of 2,4-
~3~25~
dichloro-6-octylamino-s~riazine with N'-(2,2,6,6-tel lld~ ll ,yl4-piperidyl)h~Ad- ~ 1ene diamine.
Consi~e-l~ with the invention, the diphosph-, ' olJ-,decdnes of the invention may be added to
the polymer at any time prior to or during tabricdli~n into anicles, and may be co-"b; ,ed with the
polymer by any of a variety of means known in the an, such as by ,G..t'ending or by being fed
directly into fabricdtion equipment.
The present invention may funher be u, ~ ood by ~ _fe~ ~nce to the Specific C, ~ ~bodi, . ~ents
outlined below, which are provided herein to illustrate various aspects of the invention, either by
de...on:.l.dli..g an aspect of the invention, such as poly..-er stabilkation or hydrolysis ~e~ ldnce, or
providing a basis for co-"pd-ison.
SDecific EIllL,c ' "e,lt~
Acid number, when measured, was determined by one of the f~'low;.lg ~--ell-ods. The Sodium
B u~Yide Method was used to determine acid number for all eAd--, '~s unless i-ldiodted otherwise.
Potassium Hvdroxide Method
Bromo thymoi (0.1% in 1-butanol) i.Klicdlor soiution is added (4-6 drops) to 100 ml of 1-
butanol in a 250 ml Erier" "eyer flask. The butand Is neutralked to a biu~green endpc It of pH7
with 0.02N ",etl,anolic KOH (1.32 gm KOH (ACS, 85%) in anhydrous reagent grade l"etl,anol and
diluted to 1 liter and s~ndarJked against s~andd-J 0.1 N Ha). The sampie to be tested is v ~i~l ,ed
to the nearest 0.1 gm and added to the flask. When the sample is a soiid the cord~rlt~ of the flask
are warmed slightly to 176~F (80~C) before addition of the sample. The approp-idle sample weight
to be used is determined from the f~'le ~:;ng table:
Weight to
be used E~li",ated Acid Number
20 gm less than 0.1
5 gm 0.1 - 2.0
1 gm greater than 2.0
After addition of the sample the flask is swiried to dissdve the sample, and the co, lle. d:i of
the flask are then i-.,.,.edidtely titrated with 0.02N KOH (deso-iiJed above) to a blue-green ens', ~ Il.
Sodium Butoxide Method 1~140 2 ~ ~
Bromothymd blue i-, 'ic~or (0.1%) is p-~par~d as desc-il ed above. A 2 gm sample of the
material to be tested is ~ _kJI -ed out in a 250 ml ~rler....~yer flask to the nearest .01 gm.
Methylene chloride (75 ml) is added to another Erlenr ~eyer flask, f .\~d by 4-6 drops of the
bro.---~ll,ymd i" ~~-or solution, and the resulting sdution is neutralked with 0.02N sodium butoxide
(0.46 gm sodium metal dissolved in anhydrous butand, diluted to 1 liter and ~landa,di~ed against
0.01 N HCI) to a blue-green en~ua lt of pH-7. The neutralked methylene chloride solution is then
added to the flask containing the sample and swirled to dissdve the sample. The resulting solution
is i~- ~- ~ ,edid~ely titrated with 0.02N sodium butoY~e (p,~pared as i" -~Sed above) to a blue-green
en~, o IL
The acid number for either method is obtained from the f DW;. 19 equation:
Acid Number
(mg. reagent/gm sample) = (M) (N) (56.1)
where:
M = ml. titrating reagent consumed in the titration
N = normality of the titrating reagent
S = weight (gms) of sample
Example 1 illustrates the prep~,a~ion of a d4 hosphaspirol, decane of the present invention,
3,9-bis(2,4,6-tri- -butyl~Jhenoxy)-2,4,8,10-tetroxa-3,9-diphos~l r O[5.5] undecane.
Examcle 1
A suspension of 210.1 gms (800 mmols) of 2,4,6-tri-t-bu~ her,~1, 105.9 gms (400 mmols) of
3,9-dichloro-2,4,8,10-tetroxa~,9-diphosph-, ~ o[5.5~ ecal-e and 118 mL (847 mmols) of trieth~-
amine was ~lissolved in 200 mL of ch'orobe~ene and refluxed and ~--echa~ lly stirred under a
13~2~$
nitrogen dl,- osphe-~: for 46 hrs. The resulting dark brown suspsusion was diluted with 500 mL of
ch'c ~obe- ,~ene and filtered to remove triethylamine hyui~ ide formed during the reaction. On
coding the filtrate, 214 gms of wet crystals were obtalned. The crystals were recrystallked from
toluene containing a small amount (iess than 5 vdume %) of triethylamine. The product was
isolated by filtration to afford 76.2 9 (26% yield) of bls(2,4,~tri-tbutyl,uheh.,~y)-tetroxa-
di~uhGaphl~ r uundecdne as crystals, with mp 253.5-256~C and acid number 3.0 (KOH-Ill~ll,anol
method, des-;-il,ed above). Funher recrystallkation from toluene containing a small amount of
triethylamine afforded 48.8 9 (17% yield) of the desired product as a white crystalline solid, mp
250-255~C, acid number 0.99. Infrared, nmr, and mass spect~usc~u~ fi.-.-ed the stnucture of the
product.
Example 2 de",onsl-dles p,epa,dtion of bis(2,4,6-tri- -butyl~henoxy)-tetroxa-
di,,hosph~, uu, ~ecane by a method preferred over the method of Cxa. . -,~
Exd.nLI~ 2
To a stirred solution of 120.3 9 (458 mmol) of 2,4,6,-tri- -butyl~henoi in 382 mL of tri-n-
butylamine under argon was added 60.7 9 (229 mmol) of 3,9-dichloro-2,4,8,10-tetroxa-3,9-
d;~Jhosph~ ~F U[5.5]UI ~ecane. The suspension was then heated and stirred under argon at an
internal te",perdlLIre of 110~C for 8 hrs. The resulting suaper,:,;on was ailowed to cod to room
te" "~erdlure and 400 mL of isopropyl alcohd added. Soiids were isdated by vacuum filtration and
washed on the funnel with an additional 1 L of isopropyl alcohd and then 1 L of n-heptane to afford
145.4 9 (89% of ll,eor~tiodl yield) of the desired ~ hGsph , uu,,decane as a white powder, with mp
253-254~C and acid number 0.92. This product was cGnfi-,-,ed by :.tandarJ Ill~tlloJ5.
Exampie 3 de-,-ohal-dles p-epa-a~ion of bis(2,4,6-tri~ -butylphen~, (y)-tetroxa-
diphosph ~ ~, ' ùu- ,decane by another method p-_fe. Ied over the method of Example 1.
1 3 ~
i~dlllU ~ 3
To 73.0 9 (530 mmd) of phosphG"~s ll i~;l ,'c ~ icie at app, u.~ ~tsly 0~C was siowiy added 16.9 9
(170 mmd) of triethyiamine. The mixture was stirred for ten minutes anci then 35.0 9 (130 mmol)
of 2,4,~tri- -butyl,uhend was added in 7.0 9 portions over a period of 20 minutes with continued
cooiing. After addition of 2,4,6-tri- -butylphend was CG-- ~, 'e '.~ the reaction mixture was heated at
reflux for 3.5 hrs. and then allowed to cod to room te..,perdlure. The reaction mixture was diluted
with 200 mL of heptane and cooied and filtered. The filter cake was washeci twice with 80 mL (2
x 80) of heptane. Co- - ,t ' ,ed organic filtrates were conce- lt-dlad under vacuum to afford 48.2 9 (99%
of II-e~lical yieid) of the phospholodicl~'a . ' te as a sdid prociuct, with mp 81 86~C. Similar
resuits were obtained when this reaction was carried out in tduene sdvent.
In the next step, a mixture of 47.0 9 (130 mmol) of 2,4,~tri-t butylphenylphospholû
-" :h!e iJ ~e and 80 mL of toiuene was added to 48.8 9 (260 mmd) of pentaerythrhol. An ex~)tl.e-",
to 55~C was ac~o- - ,uan e ~ by the f~- " dlion of a whhe predphate. ARer stirring for one hour the
reaction mixture, which had returned to room te""~e,dlure, was filtered under vacuum and the filter
cake washed four times whh 50 mL (4 x 50) of isopropyl alcohd. The resulting filter cake was
dried to afford 33.2 g (71 % of theoretical yield) of the desirecl d;~.hosp~ o~ndecane as a whhe
sdid, mp 253-257~C, acid number 0.31. This product was confi- ",ed by standard methods.
i~d" ,.~les 4 - 8
Other an ~ 'c 3e - l~ spirocyclic compounds were syntl ,esi~ed by s' ~hSth~dirlg other phenols for
2,4,6-tri-t-but51,ul.el)d in ~dlll, ~e 1. These phenols were:
C~d",_'e Phend
4 2,6-Dt--butylphenod
2,6-Di--butyl4-methyl~Jhenol
6 2,6-Di- -butyl 4 cthy!~,henol
7 2,6-Di--butyl-4-_-butylphend
8 2,4-Di-t-butylphenol
Synthesis of the an ' ag ~us d;"hosph~s~ ~ uu, ~ecanes was co. ~i, ---ed by one or more slandar.~
method, such as meiting point, infrared spec~ruscG~ (IR), nucleamlldyll~tic ~sonance spe~t,oscopy
18
3 ~340255
(NMR) and mass s~,osco~,)/. The compounds thus prepdr~ci were useci in the testing disc~ ~ssed in
the fl 'Ic v:. ~g examp-ies.
i~alll 'es 9 - 20
3 9-Bls(2.4-di-t-butvl ~ alkvi~Jher~,xv)-2.4.8-10-tetroxa-
3.9~:~ .)hosl~hP s ù~5.51 Ltl ,decanes as Stabilizers for I L npE
The stabilization effectiveness of variously s~ ~hs~i~u~ed 3 9-bis(2 ~di-t-butyl-4-alkyiphehuAy)-
2 4 8 10-tetroxa-3,9-dlphosph~ ,l)i.o[5.5]L",decdnes during process;"g of Unear Low Density
Polyethyiene (i I nPE) was evaluated by i"co- i~,dtion of the spirodiphûsph ~e s into Unipol process
resin GR-7042 availabie from the Union Carbide Co"~o, alion. Every test co" ~ ûa;tion also included
5ûO ppm of calcium stearate as an acid neutralizer.
P.,.~!t ~d caicium stearate and d;~hospi-,- ~ uul~ecane~ or any other phosph 'e which was
present were i"co~i~olaled into the GR-7042 powder by dry L~'en ,9 for 45 minutes in a Turbula
blender. The dry biended resin mixture was extruded at a stock te" ,perdllJre of 525~C through a
one-inch single screw extruder equipped with a 2-stage screw ftted with a Maddox mker. The
extrudate was ps'l~'i7ed and reextruded for a total of seven extrusions. Material was saved from
the first third ffflh and seventh extrusions. The melt flow of these samples was measured using
ASTM test method D-12~8 Condition E.
The meit flow of I I nPE generally dec,t ases with each extnusion as the poiymem."de,goes
deyldddlion by an overall crossiinking reaction, thereby decrea~;.,g melt flow. The ~ i. .enu~ of a
stabilizer may ther~ ~ bel evaluated by measuring its melt flow over su~cess~e extrusions and
determining how ciose the melt flow of successlve extrusions are to the melt flow of the initial
extrusion.
The color of the retalneci Sdlll 'e s was measured using a Hunter s ~ 'c r",eter and ~anddl i
13402~
techn ~ 'es pr~:su.iilJed for use with that equipment, and cG---~ri--g the yello.~-ess index (Yl) change
betweEn the first and seventh s~ e9 of each extn~sion. The coior measu~n~d~ts were made on
onc ei~Jh~l- inch by one and one half inch d~-.-~t~r discs that were co---ufession moided at 330OF
from the retained sampie peilets. Higher values indicate more color d~clop-- .~nt.
For convenience. the diphospl ~ ' ou. ,decane products of Exampies 1, 4-8 were denoted as
d below in Table 1. (All are 3,9-bis(di or tri-alkyi\JhenuAy)-2,4,8,10-tetroxa-3,9-
il~Jhosph 9, u[5.5llJ-- iecanes. I l~ cr, all nu.~~bet-i- ~g except that of the alkyi s~ ~bs~ituerlts on the
phenoxy moiety have been deleted beiow as a matter of convenience.)
Resuits of meit flow and color testing of I I nPE co- Itdi~ ~ ,g these compounds are i-, 'ic~
below in Table ll.l ~ding levels of the diphosph-, ' olJ"decanes in the I I nPE are i,ld;~leci in parts
per hundred parts resin. The h e - ' ~y~ ~first, third, fifth, seventh- indicate the number of
extrusions the CGI "~,osition had u, de~ryone when the sample was taken. ~TBPP- denotes tris(2,4~i-
-butyl phenyi) phosphP~ a noncyclic phospl~ ~e stabilizer known in the an
Cx~ ules 21 - 27
3.9-Bis(2.6-di-t-but~14~1kvluhen~,Av~ -2.4.8.10-tetroxa-3.9-
hosDhe s~' ol5.51undecanes as Stabilizers for PP
The 3,9-bis(2,6-di- -butyl~alkyl\,her,uAy)-2,4,8,10-tetroAa-3,9~-:"hospl,~s.~ ul5.51undecanes of
Table I and of the present invention were evaluated in poiy(propyiene) as process s -' "~rs by
co",pa,i-,g their pet,flJ",~nce in an unstabilked Ziegler-Natta process resin, Profax 6501from
Hercules. The resin powder was v~i~l ~ed tog~tl ~er with 250 ppm of pentae~ythritoi tetrakis [3-(3,5-
di- -butyi~hydroxyphenyi)~-op;cndte], 500 ppm of calcium stearate, and 500 ppm of the phospi-.ite
The resulting dry blend was mixed in a Turbula biender for 45 minutes. The dry blend was then
extruded at a stock tet."pet.dture of 525~F to fomm polymer pellets. The pellets were reextruded
under the same corKiilions for a total of fve extrusions. Peilet sampies saved from the first, third
and frfth extnusions were measured for melt flow r~tention using ASTM D-1238, Condition L Color
134~55
measu.e---6nt-~ were made on onc ei~htl, inch cdor discs c~-,u~essi~n moided from pellets retained
from the first and f~th extrusions. Coior measu,~:...ent~ were done on a Hunter Coiormeter. The
y~'h .~.-ess index (Yi) of the sampies was used to COIllpal'b the reiative cdor of the spec;..,ens. The
results of the testing appear in Table lll.
CAvd~ es28-34
Moisture Sensitivitv of Subs~it~ed 3.~Bis(2.6-di-t-butvi-
4-alk~uhehuAv)-2.4.8. 1 0-tetroxa-3.~diDl1os~h ~ s _ o~5.51 u- ~decanes
The moisture sensitivity of the spirocyciic diphOauhPI s of Table I anci of TBPP were ~Ad--, ~ed
by piacing the compounds into an dt---ospheric cha---l~r reg~ ~ at about 80% relative humidity.
The Sdll ., 'e s were maintained In the cl ~-- ~i er and ~, ~on~ored for weight gain and in~, ~ase in acid
value(AV)withrespecttotime. (Weightgainisani-- '1c~bnofthehyg..sccF c natureofthe
compound and may reflect sample hydroiysis, while an i--c-~ase in acid value is indicative of some
hydroiysis occuring in the sample.) The time required for the compounds to gain 1% weight during
molsture exposure was ass;y- ~ed as the failure point. The results are i, 'k --~d below in Table IV.
Acid value WdS measured by the Na-butoxide/methyiene chloride method both before the sample was
piaced in the dl...ospl1eric cl~---ber (denoted ~Initial AV~) and after the sample had attained a 1%
weight gain (denoted ~i-inal AV~).
Cxdl ",~.~s 35 - 41
Testing of Compound A, cons;;,l~-d with one e"-i A ~ ..e ,n of the invention, and TBPP and
Compound E, not embodying the Invention, were tested in GR7042 1 I nPE containing 300 ppm of
octadecyl 3,5-dl-t-butyi4-hydroxyhy l~oc;..i~i.~te, and 500 ppm of calcium stearate. Results of this
testing are in ' ~ed below in Tabie V.
~. 3 ~
~a~ e s 42 - 48
Additional testing was pe,fo---,ed using Profax 6501 poly (propylene) resin. The c~."~Gaitions
tested included 0.025 phr of pentaerythritd tetrakis [3-(3 5-di-t-butyl 4 hydroxy phenyl)pr~ - nalel
and 0.05 phr. Ca Stearate. The amount of additive compound present and the results are i" ~ed
below in Table Vl.
Data in Table V above indicate that 3,9-bis(2,4 ~tri~-buty1,uhenoxy)-2 4 8 10-tetroxa-3 g-
di~,hosph OL~I ,decane (Compound A) may exhibit greatly improved moisture ,~si:i~nce as measured
byweightgain,incG""~a(isontoothersimilar,an ~c3;:sorhomolcgousdil.hosphas~,,io~",decanes,
while data in Tables ll Ill V and Vl indicate that good polymer melt flow and color s ~~ tion
p.upe.lies may be maintained.
The above ~)~d~l, '~ S are presented to illustrate various aspects of the invention. The
invention is defined only by the f ~ i. ,g claims and is not limited in scope to the particular
emb~ "~lt~ or pdldlllt~tt~ desc;libed as ll,od~':c~;ol~s of these teachings will be apparent to those
skilled in the art in view of the present disc~osu~e.
13~0255
Table I
Comoound Examole Name
A 1 bis(2,4,6-tri-t-butylphenoxy)-tetroxa-di~ oa~,aayiroundecane6 4 bis(2,6-di-t-butylphenoxy)-tetroxa-di~lua~ha~iroundecane
C 5 bis(2,6-di-t-butyl 4 U~flphenoxy)-tetroxa-di~lua~h~a~iroundecane
D 6 bis(2,6-di-t-butyl-4-ethylphenoxy)-tetroxa-di~loa~ ~ ~decaneE 7 bis(2,6-di-t-butyl-4-s-butylphenoxy)-t~hu~_ dipl,ua~l~apiroundecane
F 8 bis(2,4-di-t-butylphenoxy)-tetroxa-di~lua~haa~iroundecane
Table II
Amount Melt Flow, 9/10 min Color, YI
Example Compound Phr first third fifth seventh first seventh
9 - -~ 1.63 1.02 0.78 0.62 11.24 18.84
A 0.04 2.11 1.73 1.23 0.98 9.87 15.07
11 A 0.07 2.18 2.12 1.90 1.40 10.40 14.58
12 8 0.04 2.10 1.60 1.13 0.91 9.78 14.69
13 8 0.07 2.16 2.07 1.78 1.47 15.25 13.90
14 C 0.04 2.13 1.88 1.32 0.98 10.35 13.70
C 0.07 2.20 2.10 2.08 1.65 10.05 14.05
16 D 0.04 2.08 1.61 1.07 0.86 9.72 15.69
17 D 0.07 2.15 2.09 1.62 1.20 9.85 15.35
18 F 0.04 2.13 1.89 1.47 1.21 10.10 14.47
19 F 0.07 2.20 2.16 2.01 1.67 9.39 12.73
T8PP0.04 1.86 1.30 1.00 0.85 9.70 14.33
Table III
Amount Melt Flo~, 9/10 min Color, YI
Examole Compound phr first third fifth first fifth
21 -- - 7.614.019.0 7.05 9.71
22 A 0.05 4.5 4.8 5.3 9.41 9.89
23 8 O.OS 4.9 6.1 6.9 9.72 9.79
24 C 0.05 4.8 5.3 7.2 8.54 9.48
D O.OS 3.7 4.6 5.4 9.43 9.74
26 F 0.05 3.7 4.2 4.4 9.71 10.29
27 T8PP 0.05 S.0 6.7 9.9 10.15 10.42
~ 34~2~5
Table IV
Time to 1%
ExampleCompound Weiqht Gain Initial AvFinal AV
28 A 1674 0.23 4.70
29 8 96 0.54 3.32
C 66 0.26 21.60
31 D 72 2.55 9.5
32 E 216 0.13 7
33 F 66 1.06 14.2
34 TBPP >1200 0.21 0.96
Table V
Amount ~elt Flow, 9/10 min Color, YI
ExampleCompound Dhr first third fifth first fifth
_ -- 1.59O.9B 0-75 15-1319-55
36 A 0.04 2.041.27 0.93 12.6314.90
37 A 0.07 1.981.87 1.62 11.9013.39
38 E 0.04 1.981.53 0.93 12.5915.63
39 E 0.07 1.941.88 1.71 11.2812.66
TBPP 0.04 1.641.19 0.86 13.4418.57
41 TBPP 0.07 1.621.12 0.86 12.9317.96
Table VI
Amount ~elt Flow, 9/10 min Color, YI
ExampleCompound phr first third fifthfirst fifth
42 -- -- 5.712.4 19.4 8.99.78
43* A 0.05 2.12.6 3.2 9.399.56
44* A 0.0375 2.4 2.7 3.4 9.75 9.63
E 0.05 2.62.8 2.9 8.989.26
46 E 0.0375 2.0 3.0 4.2 8.04 9.47
47 T8PP 0.05 3.35.2 8.3 9.089.24
48 TBPP 0.0375 2.9 4.8 7.3 9.56 9.57
* R~ ts sverage of values for examole in Table VII.
Table VII
Amount ~elt Flo~, 9/10 min Color, YI
ExampleCompound phr first third fifthfirst fifth
43 A 0.05 2.02.7 3.4 9.069.16
2.62.8 3.4 9.379-50
2.12.6 3.2 9.399.56
2.12.3 2.7 9.259.56
44 A .0375 2.1 2.4 3.4 9.78 10.38
2.42.7 3.4 9.759.63
2.62.8 3.0 9.949.58
2.82.9 3.2 9.379.83
24
