CA1340255C - Bis (tri-tertiary-alkylphenoxy) diphosphaspiroundecanes - Google Patents
Bis (tri-tertiary-alkylphenoxy) diphosphaspiroundecanesInfo
- Publication number
- CA1340255C CA1340255C CA 612324 CA612324A CA1340255C CA 1340255 C CA1340255 C CA 1340255C CA 612324 CA612324 CA 612324 CA 612324 A CA612324 A CA 612324A CA 1340255 C CA1340255 C CA 1340255C
- Authority
- CA
- Canada
- Prior art keywords
- bis
- tert
- composition
- butyl
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
Abstract
A composition is provided which comprises a 3,9-bis(2,4,6-tri-t-alkylphenoxy)-2,4,8,10-tetroxa-3,9-diphosphaspiro[5.5]undecane, and polymer compositions are provided which include a polymer and an effective amount of one or more 3,9-bis(2,4,6-tri-t-alkylphenoxy)-2,4,8,10-tetroxa-3,9-diphosphaspiro[5.5]
undecane.
undecane.
Description
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~
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] .
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 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
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 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
Claims (10)
1. A composition useful for improving the melt flow stability and/or the color stability of polymers comprising a diphosphaspiroundecane of the general formula wherein each of R1, R2, R3, R4, R5 and R6 is a tertiary- alkyl moiety.
2. The composition of claim 1 wherein R1, R2, R3, R4, R5 and R6 are independently selected from the group consisting of C4 to about C12 tertiary-alkyl moieties.
3. The composition of claim 2 wherein R1, R2, R3, R4, R5 and R6 are independently selected from the group consisting of t-butyl, t-pentyl, 1,1,4,4-tetramethyl butyl, t-dodecyl and 1-methylcyclohexyl moieties.
4. The composition of claim 3 wherein R1, R2, R3, R4, R5 and R6 are t-butyl moieties.
5. The composition of claim 1 wherein R1, R2, R3, R4, R5 and R6 are selected to be the same tertiary-alkyl moiety.
6. A polymer composition comprising a polymer and a sufficient amount of the diphosphaspiroundecane of claim 1 to improve the melt flow stability and/or the color stability of the polymer.
7. The composition of claim 6 wherein the polymer is selected from the group consisting of polyamide, polyolefin, polyester, polyphenylene ether, polycarbonate, polyvinylchlorides and styrenic resins, and mixtures thereof.
8. The composition of claim 7 wherein the polymer is selected from the group consisting of polyethylene, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12 and 4/6, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyphenylene ether, polystyrene, polyvinylchloride, impact polystyrene, and ABS-type graft copolymer resins, and mixtures thereof.
9. The composition of claim 6 wherein said diphosphaspiroundecane compound is present in an amount equal to about 0.01 to about 2 phr.
10. The composition of claim 6 wherein said diphosphaspiroundecane is present in an amount equal to about 0.01 to about 1 phr.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 612324 CA1340255C (en) | 1988-07-25 | 1989-09-21 | Bis (tri-tertiary-alkylphenoxy) diphosphaspiroundecanes |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US223,318 | 1981-01-08 | ||
| CA 612324 CA1340255C (en) | 1988-07-25 | 1989-09-21 | Bis (tri-tertiary-alkylphenoxy) diphosphaspiroundecanes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1340255C true CA1340255C (en) | 1998-12-15 |
Family
ID=4140643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 612324 Expired - Fee Related CA1340255C (en) | 1988-07-25 | 1989-09-21 | Bis (tri-tertiary-alkylphenoxy) diphosphaspiroundecanes |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1340255C (en) |
-
1989
- 1989-09-21 CA CA 612324 patent/CA1340255C/en not_active Expired - Fee Related
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1607400B1 (en) | Salts of dialkylphosphinic acids, process for their preparation and their use | |
| EP3505596B1 (en) | Halogen-free fixed flame retardant mixture and its use | |
| CA1340965C (en) | 3,9-disphosphaspiroundecanes and process for making 3,9-diphosphaspiroundecanes | |
| EP3321343B1 (en) | Flame protection agent compositions containing triazine intercalated metal phosphates | |
| EP1602685B1 (en) | Pressing granulated fire retardant composition | |
| AU623155B2 (en) | Bis (tri-tertiary - alkylphenoxy) diphosphaspiroundecanes | |
| EP1544206A1 (en) | Salts of dialkylphosphinic acids | |
| DE102015223432A1 (en) | Polymeric flame retardant mixtures | |
| EP2788286A1 (en) | Aluminium hydrogen phosphites, a process for preparing them and their use | |
| EP0576833B1 (en) | Process for preparing hydrolytically stable trivalent phosphorus compounds and their use as stabilisers for thermoplastic materials | |
| CA1340255C (en) | Bis (tri-tertiary-alkylphenoxy) diphosphaspiroundecanes | |
| US5308901A (en) | 3-9-diphosphaspiroundecane-stabilized polymer compositions | |
| JPH08120087A (en) | New poly(pentaerythrityl diphosphonate) and its use in self-extinguishing thermoplastic composition | |
| JP3004713B2 (en) | Novel aryl-phosphonite, process for its preparation and its use for stabilizing synthetic resins, especially polyolefin molding compounds | |
| CA2074614A1 (en) | Novel diarylphosphinous acid aryl esters, a process for their preparation and their use for stabilizing plastics, in particular polyolefin molding compositions | |
| JPH04235995A (en) | Phosphite stable against hydrolysis | |
| EP0026742B1 (en) | Diazaphospholanes and diazaphosphorinanes, their use as protecting agents against light and material stabilized therewith | |
| EP0635540A1 (en) | Phosphite blends | |
| JP2004018387A (en) | Method for producing pentaerythritol diphosphonate | |
| DE4240043A1 (en) | Improving the hydrolytic stability of phosphate stabilisers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |