CA1340965C - 3,9-disphosphaspiroundecanes and process for making 3,9-diphosphaspiroundecanes - Google Patents

Abstract

The present invention provides an improved process for making diphosphaspiroundecanes and product-by-process, wherein the process comprises reacting a hydroxyl-substituted organic compound, phosphorous trichloride and pentaerythritol to form an organic-substituted diphosphaspiroundecane such that formation of said organic-substituted diphosphaspiroundecane takes place in the presence of a tri-n-alkylamine having n-alkyl moieties such that each n-alkyl moiety has at least three carbon atoms. The present invention is also directed to bis-3,9-(2,6-di-t -alkyl-4-alkylphenoxy)-2,4,8,10-tetroxa-3,9-diphosphas-prio[5.5]undecanes and polymer composition containing an effective amount of same.

Description

~ 340 96 .~
3.9-D~~haspiroundecanes And Process 1.
For Making 3.9-Diohosohasoiroundecanes The present invention relates to organic-substituted 3.9~iphosphaspiroundecanes and an improved process whereby organic-substituted 3,9~liphosphaspiroundecanes may be made.
A variety of processes for making organic-substituted 3,9-dlphosphaspiroundecanes are known in the art. For example, Japanese PateW Early Disclosure No. 1986-225,191 of October 9, 1986 discloses a process for synthesizing hindered diary) diphosphaspiroundecanes by reacting phosphorus trichloride, pentaerythritd and an ortho-alkyl phend in the presence of an amine catalyst such as propyi-,n-butyl, t-butyl, methyl or tributyiamine. This catalyst is present in about 0.005-10 wt.96 with respect to pentaerythritd. This process is performed in an inert solvent such as xylene.
U.S. 4,094,855 and 4,20'7,229 to Spivack disclose the synthesis of organic-substituted diphosphaspiroundecanes by reacting ~,9-dichloro-2,4,8,10-tetroxa~.9-diphosphaspiroundecane (dichioropentite) with a phenol in the presence of a proton acceptor such as a tertiary amine such as triethylamine-U.S. 3,271,481 to Kujawa et al. disdoses the formation of primary aryl phosphates in tertiary amine such as triethylamine or tributylamine.

U.S. Patent 4,305,86E~ to York et al. discloses the preparation of substituted di~o~phaspixnundecanes by reacting an alkylphenol with a diphenoxy or lowew dialkoxy diphosphaspiroundecane and removing the phenol or alkanol formed by distillation.
U.S. Patent 4,371,647 to Minagawa et al. discloses the preparation of substituted di~hospba..~iecanes by the reaction of a phenol with phosphorus trichloride in chloroform in the presence of triethylamine, followed by reaction with pentaerythritol in the presence of more triethylamine.
A variety of alkylphe~noxy di~phaspiroundecane ccm~ounds are known in the art. Japanese Early Disclosure 1986-225,191 of October 9, 1986 by Tajima et al. mentioned above, discloses a rnunber of bis(alkylphenoxy)diaspiiro~decanes, such as bis(2-tent-butyl-4,6-dimethylprier~oxy) diphosphaspirourrlecane acrd bis (2, 4-di-t-octyl~) diphosphaspirourxiecane. Bis (alkyl~er~y) diptwsphaspiroundecanes are also disclosed by 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 alt U.S. Patent No. 4,520,149 to Golden; and U.S. Patent No.
4,585,818 to Jung. Other diphosphaspiroundecane c~ounds known in the art include bis(2,6-di-t-butyl-4- methylphenoxy) diphosphaspiro~undecane and bis(2,6-di-t- :butyl-4-ethylp~henoxy) diphosphaspiroundecane.
Virtually all ocial polymers contain ors or more stabilizing ccanpo~u~ds to protect the ;polymer against degradation of polymer properties by chain scission or undesired cx~sslinking during processing and product use. This degradation is particularly problematical with thermoplastic polymers, which typically are subjected to extreme processing t.~eratures. Not only does such degradation effect the physical properties of the oc~g~osition, but may also cause the polymer to bec~ne discolored, thereby making the polymer aesthetically unapgpealing the cause the product to be rejected.
However, polymer stabilizers may be exposed to various adverse con-ditions during the course of their production, shipmelzt storage arxi use.
One such condition which may adversely affect stabilizers is excessive e~~posure to moisture either in the form of humidity or wetness. Although 1340965 ' many stabilizers are used in the form of powders or granules, absorption of moisture may cause a stab~izer to dump or'Wod~' thereby making the stabilizer diffia~tt to handle during feeding and mixing operations. A consequ~ance of such moisture exposure may be hydrdysis, which frequently reduces stabilizing properties and leaves the resin vulnerable to degradation.
Many phosphates, including some of the above-mentioned diphosphaspiroundecanes, may provide excellent stab~ization when properly stored, either neat a after being compounded into the pdymer. A few phosphates, such as tris~2,4-di-I-butylphend)phosphite (TBPP), may exhibit good storage stability in humid environments, but do not provide the stabilizing efficacy of many members of the diphosphaspiroundecane Bass of stab0izer.
Although many of the at~we diphosphaspiroundecanes are capable of acting as polymer stabilizers, an improvement in the overall balance of properties would be realized if moisture resistance could be improved vvhile maintaining excellent stabilizing properties. Indeed, a stabilizer which imparts good physical and cdor stability to a pdymer whHe exhibiting improved resistance to moisture and hydrolysis offers sign~cant practical advantages over many stabilizers known in the art.
Known processes for making diphosphaspiroundecanes also suffer from several disadvantages.
Many, such as that of Japanese Early Patent Disclosure No. 1986-225.191 and 4,207,229 and 4,094,855 to Spivack, are performed in a reaction medium such that the product is produced as a solution. Product Isolation wfth such a process requires initial removal of amine-hydrochloride by filtration and subsequent removal of solvent via a distillation process. The product is then purified by crystallisation from a second solvent. From a practical standpoint the process is both cumbersome and energy intensive in comparison to a process wherein the product crystallizes directly from the reaction media in which the art~inne-hydrochlorkie remains soluble. This would also offer a practical advaraage in dhat the amine could be regenerated without isdation of the hydrochloride salt by simply washing with aqueous base.
It is also preferred that the yield of the desired product be as dose as possible to 100% of the theoretical yield since higher yields generally result in more effective use of raw materials and decrease the amount of by-pnoduds from which the desired product must be separated and which are available for undesinad side-reactions. A process for making diphosphaspiroundecanes which results in high yields of the de:qired diphosphaspiroundecane product and wherein the desired product is produced as a sdbl therefore would offer signif'~M practical advantages over many pnxesses known in the art.
Summary of the Invention The presets invention is .a compos'ttion which comprises a diphosphaspiroundecane of the general formula:
R2 .O- CH' ,.CH2 0\ R4 Rt ~-p_ /C~ /p-O ~ R5 O- CIH2 CH~-O/ Rs wherein each of R2, R3, R4, and Rs is a tertiary alkyl moiety and each of Rt and R5 is a secondary alkyl moiety. In the embodiment which is preferred R~, R3, R4, and R6 are selected from the group consisting of C,s to about C~ 2 tertiary alkyl moieties with tertiary-butyl being the moiety which is most preferred. It is also preferred that R~ and R5 be secondary-butyl moieties.
The present invention indludes a stabilized polymer composition which comprises a polymer and an effective amount of the diphosphaspiroundecane of the invention.
Thermoplastic polymers are preferred, with polyethylene, polypropylene, polyethylene terephthalate, polyphenylene ether, pdystyrene, impact polystyrene and ABS-type graft copolymers being most preferred.
The presets invention further comprises a process for making an organic-subsYrtuted diphosphaspiroundecane comprising reacting a hydroxyl-substituted organic compound, phosphorous trichloride and pentaerythritol to form said organic-substituted diphosphaspiroundecane such that 134pg6~ , fom~ation of said organic-substituted diphosphaspin~undecane takes piece in the presence of a tri-n-alkylamine having n-alkyl moieties such that each n-alkyl moiety has at least thn3e carbon atoms.
It fs preferred that the tri-~-alkyiamine be present in an amount which is at least the molar equivalent of the acid produced by this reaction.
The present invention is ~~Iso directed to the product of the embodiment of the process of the irnention which employs dichloropentfte, and to pdymer compositkx~s which indude this product.
Detailed Description of the Invention The present irnention comprises a 3,9-bis(2,6~ii-alkyl-4-~-alkyl phenoxy)-2,4,8,10-tetroxa-3,9-diphosphaspiro[5.5]undecane. These compounds, also known as bis(2,6~i-t-alkyl-4-~-alkylphenyl) pentaerythr'ttol diphosphites, may be represented by the general formula:
RZ O- C;H2 , CH2-O R4 R O-p/ ~C~ ~p_ O ~ R5 R3 O - C;H2 CH2-O R6 wherein each of R2, R3, R4, arxi R6 are tertiary (or 'tent' or'~ alkyl moieties and wherein each of R1 and R5 are secondary (or'sec' or'~~ alkyl moieties.
Examples of tertiary moieties indude t-butyl, t-pentyl, 1,1,4,4-tertramethyl butyl, t-octyl, 1-methyl cydohexyl, t~odecyi, .and 2-phenyl-2-propyl. However, C4 to about C12 moieties, such as t-butyl, t-pentyl, t-octyl and t-dodecyl are preferred. Relatively smaller groups, such as t-butyl, t-pentyl, 1-methylcydohexyl arwd 1,1,4,4-tetramethyl but~A are more preferred.
Tertiary butyl moieties are most preferred. Although any or ail of R2, R3, R4 and R6 may be selected to be different, such as in 2-t-butyl-~-butyl-ir~-t-pentylphenoxy, it is preferred that R2, R3, R4 and Rs be the same.

134~O~s5 Examples d secondary ,alkyl moieties include s-butyl, s-pentyl, iso-propyl, s-hexyl, s~iecyl, cydopentyl, cylohexyl and cydooctyl. However, C~ to about Cg moieties, such as s-butyl, s-pentyl, iso-propyl and cydohexyl are preferred. Relatively smaller groups, such as s-butyl and s-pentyl are more preferred, with s-butyl being particularly preferred. Although R1 and R5 may be selected to be different, such as when R1 Is s-butyl and R5 is s-pentyl, it Is preferred that R1 and R5 be selected to be the same.
The diphOSphaspifoundE~canes of the present Invention may be made by means known in the art, such as by the reaction of a di-t-alkyl-~-alkylphend with 3,9-dk;hloro-2,4,8,10-tetroxa~,9-diphosphaspiro[5.5]undecane (which may be formed by the reaction of pentaerythr'ttd with phosphorous trichloride by msrans knov~m in the art). For example, 3,9-bis(2,6~Ji-t-butyl-4-~ butylphenoxy)-2,4,8,10-tetroxa-3,9~iiphosphaspiro[5.5]undecane may be formed by the reaction of 2,6~ii-t-butyl-4-~-butylphend with 3,9~ichloro-2,4,8,10-tetroxa-3,9~diphosphaspiro[5.5]undecane (dichloropentite). Similarly, 3,Si-bis(2,6~c1i-~-pentyl-4-~-butylphenoxy)-2,4,8,10-tetroxa-3,9-diphosphaspiro [5.5] undecan~a may be formed by the reaction of 2,6~ii-t-pentyl~-~-butylphend with dichloropentite. Other 3,9-bis(tri-t-alkyiphenoxy)-2,4,8,10-tetroxa~,9-diphosphaspiroundecanes may be formed by reacting the di-t~alkyl-~-aikylphend corresponding to the desired di-t-alkyl-~-alkylphenoxy group with dichloropentite.
The diphosphaspiroundecanes of the present invention may also be made by reacting a phend corresponding to the d~ssired di-t-alkyl-~-alkylphenoxy group w'tth phosphorus trichloride to form a di-,alkyl-~-alkylphenoxy phosphorodichioridite, fdlowed by reaction of the phosphorodichloridite with pentaerythritd to form a 3,9-bis(di-~-alkyl-~-alkylphenoxy)-2,4,8,10-tetroxa-3,9~liphosphaspiroundecane. For example 2,6~1i-~-butyl-4-~-butylphend may be reacted with phosphorus trichloride and then with perttaerythritd to form 3,9-bis(2,6-di-~-butyl-~-butylphenoxy)-2,4,8,10-tetroxa~3,9~iphosphaspiroundecane. Similarly, 2,6~fi-~-dodecyl-4-~-pentylphend might be reacted with phosphorus trichloride and then with pentaerythritd to form 3,9-bis(2,6~di->i-dodecyh4-~-pentylphenoxy)-2,4,8,10-tetroxa-3,9~iphosphaspiroundecane.

~34pgfi5 Procedures for forming ~iiphosphaspiroundecanes by the dichloropentite and the phosphorodichoridite routes acre known in the art. However, whereas the prior art may show the diphosphaspiroundecane being formed in solution in the presence of an amine, such as triethylamine, which serves as an acid acceErtor by forming an insduble hydrochloride salt, It is preferred that the diphosphaspiroundecane be formed according to the process d the invention, described below.
The present invention irn~udes an improved process fa making organic-substituted diphosphaspiroundecanes including the bis(2,6-di-~,aikyl-4-~.~alkylphenoxyj diphosphaspiroundecanes discussed above. This process involves reacting a hydroxyl-substituted organic compound, phosphorus trichloride and pentaerythritd to fomn an organic-substituted diphosphaspiroundecane, wherein the improvement comprises the fom~ation of the organic-substituted diphosphaspiroundecane r' taking place in the presence of a tri-n_-alkylamine.
It is cr'ttical to the invention that the tri-n_-alkylamine be one wherein each n-alkyl moiety has at least three carbon atoms, such as n-propyl, n-butyl, n-pentyl and n-hexyl, and preferably less than 10 carbon atoms. N-butyl and n-pentyl moieties are preferred, such as in tri-n-butyl amine, tri-n_-pentyl amine and di-n-butyl-_n-pentylamine. Tri-_n-butylamine is particularly preferred.
The reaction usually will be pertormed using one of two sequences. In one sequence ('dichloropentite route') phosphorus trichloride is reacted with perttaerythritd to form 3,9~ichloro-2,4,8,10-tetroxa~,9-diphospha~spiroundecane (also known as'd~hloropentite' or'dichloro-pentaerythritd diphosphite'j, followed by reaction of the dichioropentlte with the hydroxyl-substituted organic compound in the presence of the tri-n_-alkylamine to form the organic substituted diphosphaspiroundecane. I~n the other sequence ('dichioridite route') phosphorus trichloride and the hydroxyl-substituted organic compound are reacted to form a phosphorodichioridite, followed by reaction of the phosphorod~hloridite with perttaerythr'ttol in the presence of the tri-n_-alkylamirne to form an organic- substituted diphosphaspiroundecane.
The tri-n_,alkylamine usually will be present in an amount which is at least sufficient to substantially neutralize the acid formed during the formation of the diphosphaspiroundecane. For example, if the diphosphaspiroundecane is fom~ed by reaction of a hydroxyl-substituted organic compound with did~loropeMitEi, wherein two miles of hydrogen chloride are liberated, the tri-r~-alkylamine should be presets ad least in an amount equal to about two miles of tri-n_~alkylamine per mile of dichloropeMite. Similarly, ff the diphosphaspiroundecane is formed by reaction of peMaerythritd with an organic phosphorodichioridite, the tri-~-alkylamine will be present in an amount at least approximately squad to two miles of tri-r~-alkylamine to one mile of phosphorodid~loridite. However, it is preferred that a molar excess of tri-n_-alkylamine be used.
According to the process: of the irnreMion, fom~ation of the diphosphaspiroundecane takes place in a readJon medium which includes the tri-nalkylamine. The reaction medium may also include sdvents such as xylene, chlorobenzene, tduene, ethylbenzene and the like. The relative proportions of co-solvent to tri-n-alkylamine is limited only by the requirement that the amine be present to the mdar extent required to neutralize the theoretical quantity of liberated hydrogen chloride and by sdubility considerations. Minor amounts of other chemicals, such as catalysts, may also be included. According to the invention, the reaction medium is selected so that the reaction medium is one in which the desired diphosphaspiroundecane product is substantially insoluble, thereby facilitating product separation. It is also preferred that the tri-n_aikylamine and the reaction medium be selected so that the tri-n-alkylamine is one having a hydrogen chloride salt which is substantially sduble in the reaction medium so that significant amounts of the chloride salt do not precipitate under the conditions of the reaction and product separation.
Consistent with the invention, the hydroxyl-substituted organic compound may be any of a variety of hydroxyl-substituted' organic compounds, including adkands, phends, and hydroxyl-substituted cydoalkanes, and hydroxyl-substituted aralkyls, such as octadecand, alkylated phenols, cydohexand and phenylethand. However, phends are preferred, such as 2,4,6-tri-methylphenol, 2,6~i1-~-butyiphend, 2,4,&iri-~~~butylphend, 2,4,di-t-peMylphend, and 2,4~i-~-butyl-methylphenol.
When the dichloropeMite route is used, the phend preferably is selected from the group consisting of 2.4,6-tri-alkyl phends and 2~,4~cli-alkyl phends, such as 2,4,&tri-t- butyl phend, 2,4~i-t-butyl phend, 2,4,6-tri-t-pentylphend, 2,6~ii-~-butyl-sec-butylphend, 2,4-di-~-butylphend, and 2-t-butyi-4-methylphend. However, 2,4~di3,alkyl phenols such as 2,4~i-~-butylphend and 2,6-di-~,alkyi-4-alkyl phends, such as 2,4,6-tri-~-butylphend, 2,611-~-butylyl phenol, 2,6~ii~-butyl-ethyl phend, 2,4-di-t-butylphend, arid 2,6~i-~-butyl~t-~-butyl phenol are preferred.
The 2,4,6-tri-t-alkyl phends, 2.6-di-1i-alkyl-n_-alkyl phends, 2.6-di-i~aikyl~-~-alkyl phenols and 2.4-di-i~alkyl phenols are most preferred.
If the phosphorodid~loridlite route is fdlowed, the hydroxyl-substituted organic compound also preferably is a phend, with 2,4,6-trialkyl phends, as described above, being preferred. However, unlike in the process using the dichloropentite route, dt-alkyl phends other than those containing 2,6~ialkyl substitution are not preferred due to the fact that their generally greater reactivity may lead to complications during plhosphoro~iichloridite preparation. Phends selected from the group consisting of 2,4,6-tri-t-alkyl phends, 2,6~1i-~-alkyls-methyl phends, 2,6-di-t,alkyl-4-ethyl phenols and 2,6~i-~-alkyl-4-~-alkyl phends, as described above, are more preferred.
2,4,6-tri-~-butyl phend, 2,6~fi-t-butyl-4-methyl phend, 2,.6-di-~-butyl-4-ethyl phend and 2,6~ii-t-4-~-butyl phenol are particularly preferred.
In the process of the invention employing the dichloropentite route it is preferred that the mdar ratio of the hydroxyl-substituted organic compound to the dichloropentite (3,9~ichloro-2,4,8,10-tetroxa~,9~iphosphaspiroundecane) be about 2a to about 3:1. in the process using the phosphorodichloridite route it is preferred that the mdar ratio of the phosphorodichloridite to pentaerythritd be about 2:1, unless digameric products are desired.
The present invention also includes improvement in the preparation of phosphoro~iichlorid'rtes, such as those useful in the phc~sphoro-dichioridite route described above.
Whereas previous preparations of this compound) may require purification via distillation of the desired product, the present invention provides product withaut the energy intensive distillation step. This improved process for making phosphorc~ichloridites comprises contacting a hydroxyl-substituted organic compound w'tth phosphorus triichloride in a reaction medium which includes triethylamine.

~340~6'' Triethyiamine should be present in an amount at least sufficient to substantially neutralize the liberated hydrogen chloride. although phosphorus trichloride serves as the reaction sdvent, the readlon medium may optionally include co-solvents such as tduene or other hydrocarbons.
The improved process fcx making phosphoro~dichloridftes also requires that the mdar ratio of phosphorus trichloride to hydroxyl-substituted organic compound be greater than 3a, w'tth mdar ratios of about 3.5:1 or more ~;eing preferred. Molar ratios of about 4.5:1 or less are even further preferred.
The improved process provides a simplified isolation and purification sequence. The product is isdated from the reaction medium by first removing amine hydrochloride by filtration, followed by concentration of the filtrate to yield relatively pure phosphoro~ichlorid'tte.
Although a variety of hydroxyl-substituted organic compbunds may be used in this improved process for making phosphorWichloridites, such as aliphatic alcohds and phends, this process is particularly useful for hydroxyl'-substituted organic compounds such as alkylated phends.
The present invention ai;so is directed to the product of the dichlorop~ent'rte route, one of the preferred embodiments of the process of the invention. The preferred product of the process of the invention is that produced by the preferred embodiments of the process of the invention, as described above. In its most preferred embodiment, the product ~ the invention is that product produced fdlowing the dichlorop~entite route wherein the tri-n-alkylamine is tri-n-butyl amine and is present in an amount sufficient to neutralize substantially ail of the hydrochloride produced in the reaction of the dichloropentite with the hydroxyl-substituted organic compound. The preferred product is that produced using a phenol, and more preferably 2,4,6-tri-alkyl and 2,4~ii-alkyl phenols as the hydroxyl-substituted organic compound. Especially preferred are 2,4-di-t-alkyl phends, such as 2,4<ii-~-butyl phend, and 2,6~i->:,alkyl-4-alkyl phends, such as 2,4,6-tri-~-butyl phend, 2,6~i->:-butyl-methyl phend, 2,6-di-~-butyl-4-ethyl phend, and 2,6~di-~-butyl-4-~-butyl phend.
The present invention also is direc.~ted to stabilized pdymer compositions which include at least one of the diphosphaspiroundecane composition of the invention and/or the diphosphaspiroundecane product of the process of the inversion, as described above.
An amount of the diphoshhaspiroundecane composition of the Invention or the product by process of the invention is considered to be an'effedlve amount', when the pdymer composition containing the composition or Ixodud of the invention shows improved stability in any of its physical or cda properties In «mpariscx~ to an analogous pdymer composition which does not indude a composition a product of the Invention. In most pdymer compositions, however, it will be preferred that the composition or product of the invention be present in an amount equal to about .Ot to about 2 parts by weight per 100 parts by weight resin (plu).
Amounts of about .O1 to about 1 phr are more preferred, although most compositions will contain about 0.025 phr or more.
The polymer may be any of the polymers known in the art, such as polyesters, polyurethanes, pdyaikylene terephthatates, pc~ysulfones, pdyimides, polyphenylene ethers, styrenic pdymers, poly carbonates, acrylic polymers, polyamides, polyacetals, halide containing polymers and polyolefin homopolymers and copdymers. Mixtures of different pdyment, such as polyphenylene ether/styrenic resin blends, polyvinyichloride,~ABS or other impact mod~ed polymers, such as methacrylon'ttrile containing ABS, and polyester,/ABS or polyester plus some other impact modifier may also be used.
Such polymers are available commercially or may be made by means well known in the art.
However the diphosphaspiroundecanes of the invention are particularly useful in thermoplastic polymers, such as polyolefins, pdycarbonates, pdyesters, pdyphenylene ethers and styrenic polymers, due to the extreme temperatures at which thermoplastic polymers are often processed and/or used.
Polymers of monoolefins and diolefins, for example pdypropylene, polyisobutylene, polybutene-1, polymethylpentene-t, pdyisoprene or' pdybutadiene, as well as polymers of cydoolefins, for instance of cydopentene or norbomene, pdyethylene (which optionally can be crosslinked), for example high density polyethyllene (HDPE), low density polyethylene (LDP and linear low density polyethylene (ILDPE) may be used. Mixtures of these polymers, for example mixtures of polypropylene with (PP) polyisobutylene, polypropylene with pdyethylene (for example PP/HDPE, PP/LDPE) and mixtures of drffierent types of pdyethyiene (for example LDPE/HDPE), may also be used. Also useful are copdyrr~ers of monoolefins and diolefrnes with each other or with other vinyl monomers, such as, for examF~e, ethylene/propylene. LLDPE and its moctures with LDPE.
propylene/butene-1, ethylene/hexene, ethylene/ethylpe~ene, ethylene/heptene, ethylene/octene, propylene/isobutylene, ethyler~e/butane~-1, propylene/butadiene, Isobut~Aene/isoprene, ethylene/alkyl acrylates, ethyiene/alkyl methacrylates, ethylene/vinyl acetate (E1IA) or ethylene/acryiic acid copolymers (EAA) and their sallts (ionom~ers) and terpdymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene-norbomene; as well as mbctures of such copolymers and their matures with pdyrners mentioned above, for example pdypropyiene/ethylene-propylene-copdymers, tDPE/EVA, LDPE/EAA, L1DPE/EVA and llDPE/EAA.
Thermoplastic pdymers may also include styrenic pdymers, such as pdystyrene, poly-(p-methylstyrene), poly-(alpha-mEathylstyrene), copdymers of styrene or alpha-methylstyrene with dienes or acrylic derivatives, such as, for example, styrene/butadiene, styrene/acrylon'ttrile, styrene/alkyl methacrylate, styrene/maleic anhydride, styrene/butadiene/ethyl acrytate/
styrene/acrylonitrile/methylacrylate; matures of high impact strength from styrene copolymers and another polymer, such as, for caxample, from a pdyacryiate, a diene polymer or an ethylene/propylene/dfene terFiolymer; and block copdymers of styrene, such as, for example, styrene/butadiene/styrene, st)~rene/isoprene/styrene, styrene/ethylene/bucylene/styrene or styrene/ethylene/propylene/styrene. Styrenic pdymers may additionally or altemativeiy include graft copdymers of styrene or alpha-methylstyrene such as, for example, styrene on polybutadiene, styrene on polybutadiene-styrene or pdybutadiene-acrylonitrile; styrene and acrylon'rtrile (or methacrylonitrife) on pdybutadiene; styrene and malefic anhydride or maleimide on pdybutadiene;
styrene, acrylonitrile and malefic anhydride or maleimide on pdybutadiene;
styrene, acrylonitrile and methyl methacrylate on pdybutadiene, styrene and alkyl acrylates or methacrylates on pdybutadiene, styrene and acrylonitrHe on ethylene/propylene/diene terpdymers, styrene and acrylonitrile on polyacrylates o~r pdymethacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers. as well as mtxtures of with the styrenic copolymers indicated above.
Nitre pdymers are also useful in the pdymer composition of the invention.
These include homopdymers and copdyme~rs of acrylonitre and fls analogs such as methacryloniire, such as pdyacrylonitre, acrylonitre/butadiene pdymers, acrylonitre/ailcyl acxylate pdymers, acrylonitre/alkyl methacxylate/butadiene pdymers, ABS, and ABS which includes methacrylonitrile.
Pdymers based on acrylic acids, such as acrylic acid, methacrylic acid, methyl methacryiic acid and ethacrylic add and e:~ters thereof may also be used. Such pdymers include pdymethylmethacrylate, and IBS-type graft copdymers wherein all or part of the acrylonitrile-type monomer has been replaced by an acrylic acid ester or an acrylic acid amide.
Polymers including other acrylic-type monomers, such as acrdein, methacrdein, acrylamide and methacrylamide may r' alSO be USed.
Halogen-containing pdymers may also be useful. These include resins such as polychloroprene, epichlorohydrin homo-and copolymers, pdyvinyl chloride, pdyvinyl bromide, pdyvinyl fluoride.
polyvinyiidene chloride, chlorbnated polyethylene, chlorinated polypropylene, florinated pdyvinylidene, brominated pc~yethylene, chlorinated rubber, vinyl chloride-vinylacetate copolymer, vinyl chloride-ethylene copdymer, vinyl chloride-propylene copdymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copdymer, vinyl chloride-vinyiidene chloride copdymer, vinyl chloride-styrene-malefic anhyclride tercapolymer, vinyl d~loride-styrene-acrylonitrile copdymer, vinyl chloride-butadiene copdymer, vinyl chloride-isoprene copdymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinyiidene chloride-vinyl acetate teroopdymer, vinyl chloride-acrylic acid ester copolymers, vinyl chloride-malefic acid ester copdymers, vinyl chloride-methacrylic acid ester copolymers, vinyl chloride-aciylonitrile copdymer and internally plasticized polyvinyl chloride.
Other useful thermoplastic pdymers include homopdymers and copdymers of cyclic ethers, such as polyalkylene glycds, pdyethylene oxide, pdypropylene oxide a copdymers thereof w'tth bis-glycidyl ethers; pdyacetals, such as pdyoxymethylene and those pdyoxymethylene which contain ethylene oxide as a comonomer; pdyacetals modified wfth thermoplastic pdyurethanes, acrylates or methacr~Aonitr~le contatnfng ABS; polyphenylene oxides and su~ides, and moctures of polyphenylene oxides with pdystyrene or poilyamides; pdycarbonates and pdyester-carbonates;
pdysulfones, pdyethersuifones and pdyetinerketones; and pdyesters which are derived from dicarboxylic acids and dills and/or from hydro~:ycarboxylic acids or the corresponding lactones, such as pdyethyiene terephthalate, pdybutylene tE:repMhalate, pdy-1,4-dimethyld-cydohexane terephthalate, pdy-[2,2.-4(4-hydroxyphenyi)-propane] terephthalate and pdyhydroxybenzoates as well as block-copdyether-esters derived from pdyethers having hydroxyl end groups.
Pdyamides and copdyamides which are derived from dfamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as pdyamide. 4, polyamide 6, pdyamide 6/6, 6/10, 6/9, 6/12 and 4/6, pdyamide 11, polyamide 12, aromatic pdyamides obtained by condensation of m-xytene, deamine anti adipic acid; pdyamides prepared from hexamethylene diamine and isopMhalic or/and terepi>thalic acid and optionally an elastomer as modifer, for example pdy-2,4,4-trimethylhexamethylene~ terephthalamide or pdy-m-phenyiene isophthalamide may be useful.
Further copdymers of the aforementioned pdyamides with pdydefins, defin copdymers, ionomers or chemically bonded or grafted elastomers; or w'tth pdyethers, such as for instance, with pdyethylene gtycd, pdypropylene glycd or polytetramethylene glycds, and pdyamides or copdyamides modified with i=PDM or ABS may be used.
Pdydefin, pdyalkylene~ terephthalate, pdyphenylene ether and styrenic resins, and mixtures thereof are more preferred, with pdyethylene, pdypropylene, pdyethylene terephthalate, pdyphenylene ether homopdymers arx! copolymers, pdystyrene, high impact pdystyrene, polycarbonates and ABS-type graft copdymers and mixtures thereof being particularly preferred.
The resulting stabilized pdymer compositions of the invention may optionally also contain various conventional additives, such as the fdlow~ing.
1. Antioxidants 1.1 Alkylated monophends, for example: 2,6~ii-tert-butyl-4-methylphend, 2-tert-butyl-4,6-dimethylphend, 2,6-di-tert-btrtyl-4-ethylphend, 2,6~Ji-tert-butyl-4-n-butylphend, 2,6-di-tert-butyl-4-1~4~9fi5 i-butytphend, 2,6~i-cydopentyl~-methylphend, 2-(alpha-me~thylcydohexyl)~.6~imethylphenol, 2,6-di-octadecyl~-methylphend, a,4,6-tri-cydohexylphend, 2,6-di-tart-butyl-4-methoxymethylphenol.
1.2 Alkylated hydroquinones for example, 2,6-di-tart-butyl-4-methoxyphend, 2,5~ii-tert-butyl-hydroquinone, 2,5~i-tert~,amyl-hydroquinone, 2,6-diphenyl~-octadecyloxyphend.
1.3 Hydroxytated thiocliphenyl ethers, for example, 2,2'-thio-bis-(6-tart-butyl~-methylphend), 2,2'~hio-bis-(4~octylphenol). 4,4'-thin-bis-(6-tart-butyl-methylphenol), 4,4'-thio-bis-(6-tart-but)A-2-methylphend).
1.4 Alkyliden-bisphenc~is, for example, 2,2'-methylene-bis-(6-tart-butyl-methylphend), 2,2'-methylene-bis-(6-tart-butyl~thylphenal), 2,2'-methylene-bis-[4-methyl~6-(aipha-methylcydohexyl)phenol], 2,2'-methylene-bis-(4-methyl-cydohexylphend), 2,2'-methylene-bis-(6-nonyl-4-methylphenol), 2,2'-m~ethylene-bis-[6-(alpha-methylbenzyl)-4-nonylphenoi], 2,2'-methylene-bis-[6-(alpha,alpha~Jimethylbenz)~).4-nonylphend], 2,2'-methylene-bis-(4,6-di-tart-butylphenol), 2,2'-ethylidene-bis-(4,6~ii-tart-butylphend), 2,2'-ethylidene-bis-(6-tart-butyl-isobutylphenol), 4,4'-methylene-bis-(2,6~ii-tart-butyiphenol), 4,4'-methylene-bis-(6-tart-butyl-2-methylphenol), 1,1-bis-(5-tart-butyl-hydroxy-2-methylphenyl)butane, 2,6-di-(3-tart-butyl-5-methyl-2-hydroxybenzyl)~-methylphenol, 1,1,3-tris-(5-tart-butyl-4-hydroxy-2-methylphenyl)butane, i,t-bis-(5-tart-butyl-4-hydroxy-2-methylphenyl)-3~lc~decylmercaptobutane, ethylenglycd-bis-[3,3-bis-(3'-tart-butyl~'-hydroxy-phenyl)-butyrate], dl-(3-tart-butyl-4-hydroxy-5-methylphenyl)~tiicydopentadiene, di-[2-(3'-tart-butyl-2'-hydroxy-5'-methyl-benzyi)~i-tart-butyl-methylphenyl]-terephthalate.
1.5 Benzyi compounds, for example, 1,3.5-tris-(3,5-di-tart-butyl-4-hydroxybenzyl)-2,4,6-trimethylbeniene, bis(3,5~iI-tsrrt-butyl-hydroxybenzyl)sulfide, isooctyl 3,5~i-tart-butyl-4-hydroxybenzyl-mercapto-acetate, bis-(4-tart-butyl-hydroxy-2,6-dimethylbenryl)dithidterephthalate, 1,3,5-tris-(3,5~i-tart-butyl-4-h)rdroxybenzyl)isocyanurate, 1,3,5-tris(4-tart-butyl-3-hydroxy-2,6-dimethylbenzyi)isocyanurate, dioctadecyl 3,5~i-tart-butyl-4-hydroxybenzyl-phosphonate, calcium salt of monoethyl 3,5~i-tart-butyl-4-hydroxybenzylphosphonate. 1,3.5-tris-1,3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

1.6 Acylaminophends, for example, 4fiydroxyaauric acid anilide, 4-hydroxy-stearic acid anilide, 2,4-bis-oc~ylmercapto-n(3,5-tert-butyl~4-hydrox-yanilino)-s-triazine, octyl-N-(3,5-di-tert-but~A~-hydroxyphenyi)~arbannate.
1.7 Esters of beta-(3,5-di-tert-bulyi~4-hydroxyphenyi)-propionic acid w'tth monohydric or pdyhydric alcohols, for exam~~e, methand, diethyleneglycd, odadecand, triethyleneglycd, 1,6-hexanedid, perrtaerythritd, ne~opentylglycol, tris-hydroxyethyl isocyanurate, thfodiethyleneglycol, di-hydroxyethyl oxalic acid diamide.
1.8 Esters of beta-(5-te~rt-butyl-hydroxyl-methylphenyl)-propfonic acid with monohydric or pdyhydric alcohds, for exam~~le, methand, diethyleneglycd, octadecand, triethylenegiycol, 1,6-hexanedid, pentaerythritd, neopentylglycd, tris-hydroxyethyl isocyanurate, thiodiethylenegtycol, di-hydroxyethyl oxalic acid diamide.
1.9 Esters of beta-(5-tert:-butyl-4-h~ydroxy-3-methylphenyl)propionic acid with mono-or pdyhydric alcohds, e.g. with methand, diethylene glycd, octadecand, triethylene glycd, 1,6-hexanedid, pentaerythritd, neopentyl glycol, tris(hydroxyethyl) isocyanurate, thiodiethylene glycol, N,N'-bis(hydroxyethyl)oxalic acid diamide.
1.10 Amides of beta-(3"iii-tart-butyl-hydroxyphenyl)-propionic acid for example, N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropianyl)-hexamethylendiamine, N,N'~Ji-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylendiamine, N,N'~i-(3,5~ii-tart-butyl-4-hydroxyphenylpropionyl)-hydrazine.
2. UV absorbers and light stabilizers.
2.1 2-(2'-Hydroxyphenyl)-benzotriazdes, for example, the 5'methyl-, 3',5'-di-tert-butyl-, 5'-tent-butyl-, 5'-(1,1,3.3-tetramethylbutyl)-, 5-chioro~',5'~,ii-tent-butyl-, 5-chloro~'-tent-butyl-5'-methyl-, 3'-sec-butyl-5'-tert-butyl-, 4'-octoxy, 3',5'~di-tert-amyl-, 3',5'-bis-(alpha,alpha-dimethylbenzyl)-derivatives.
2.2 2-Hydroxy-benzophenones, for example, the 4-hydroxy-, 4-methoxy-, 4-octoxy, 4-decyioxy-, 4~odecyloxy-, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'~imethoxy derivative.

134b ~6 2.3 Ester of substituted and unsubstftuted benzoic adds for example, phenyl salicylate, 4-tart-butyl-phenylsaiicilate, odyfphenyl salicylate. dibenzoylresordnd, bis-(4-tart-but~Abenzoyl)-resorcind, benzoyiresorcinol, 2,4~ii-tart-butyl-phenyi~,5~i1-tart-butyl-4-hydroxybenzoate and hexadecyl~,5~i-tart-butyl-~-h~ydroxybenzoate .
2.4 Acxylates, fa example, alpha-cyano-beta,beta-diphenyiacrylic acid ethyl ester or isooctyl ester, alpha-carbomethoxy-ciru~amic acid methyl ester, alpha-cyano-beta-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester, alpha~arbomethoxy-p-mathoxy-ciru~amic acid methyl ester, N-(beta~arbomethoxy-beta~yano-vinyl)-2 -methyl-inddine.
2.5 Nickel compounds, for example, nickel complexes of 2,2'-thin-bis-[4-(1,1,3,3-tetramethyibutyl)-phend), suclh as the 1:1 or 1:2 complex, optionally with addftionai ligands such as n-burylamine, triethandamine or N-cydohexyl~ii-ethandamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxyl,5-di-tart-butylbenzylphosphonic acid monoalkyl esters, such as of the methyl, ethyl or butyl ester, nickel complexes of ketoximes such as of 2-hydroxy-4-methyl-penyl undecyl ketoxime, nickel complexes of 1-phenyl~~aauroyl-5-hydroxy-pyrazd, optionally with additional ligands.
2.6 Stericaily hindered amines, for example bis-(2,2,6,6-tetramethylpiperidyl)-sebacate, bis-(1,2,2,6.6-pentamethylpiperidyl)-sebacate, n-butyl-3,5~di-tart-butyl-4-hydroxybenzyl malonic acid bis-(1,2,2,6.6-pentamethylpiperidy~l)ester, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidine and succiniic acid, condensation product of N,N'-(2,2,6,6-tetramethylpiperidyl)-hexamethylendiamine and 4-tart-octylamino-2,6-dich~oro-1,3,5-s-triazine, tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriac;etate, tetrakis-(2,2,6.6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetra-carbonic acid, 1,1'(1,2-ethanecliyl)-bis-(3.3.5,5-tetramethylpiperazinone).
Such amines indude hydroxylamines derived from hindered amines, such as di(1 fiydroxy-2,2,6,6-tetramethylpiperidin~-yl)sebacate; 1-hydroxy-2,2,6,&~tetramett~yi-4-benzoxypiperidine; 1-hydroxy-2,2,6,6-tetramethyl-4-(3,5-di-tart-butyl-4-hydroxy hydrocinnamoyloxy)-piperidine; and N-(1-hydroxy-2,2,6,6-tetramethyl-piperidin-4-yl)-epsilon-caprdactam.

13409fi5 2.T Oxalic add diamides, fa example, 4,4'-di~ctyloxy~xanfiide, 2,2'-di-octyloxy-5,5'~.li-tert-butyl-oxanUide, 2.2'~ii~dodecyloxy-5,5'~ii-tart-butyi~xanflide, 2~thoxy-2'-ethyhxanilide. N,N'-bas(3-dimethylaminopropyl)~xalamide, 2-ethoxy-5-tart-butyl-2'-ethyloxanilide and its mbcture with 2-ethoxy-2'-ethyl-5,4'~li-tart-but)Aoxanilide and mbdures of ortho- and pare-methoxy- as well as of o-and p-ethoxy~isubstituted cucanilides., 3. Metal deactavators, for example, N,N'~liphenyloxalic acid diamide, N-salicylal-N'-salicyloylhydrazane, N,N'-bas-s~alicyloylhydrazine, N,N'-bas-(3,5i1i-tart-butyl~-hydroxyphenylpropionya)-hydrazine, salicyloylamino-1,2,4-triazde, bas-benzyiiden-oxalic acid dihydrazide.
4. Phosphates and phosphonites, for example triphenyl phosph'tte, diphenylalkyl phosph'ttes, phenyldaalkyl phosphates, tris(nonyl-phenyl) phosphate, trilauryl phosphate, trioctadecyl phosphate, distearyl pentaerythritd diphosphite, tris(2,4~Ji-tart-butylphenyl)phosphite, diisodecyl pentaerythr'rtol diphosphite, bis(2,4~di-tart-butylphenyl) pentaerythritd diphosphite, tristearya sorb'ttd triphosphite, and tetrakis (2,4-di-tart-butylphenyl) 4,4'-biphenylene diphosphonite.

5. Peroxide scavengerrs, for example esters of beta-thiodipropionic acid, for example the lauryl stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc~~ibutyl~iithiocaramate, dioctadecyldisutfide, pentaerythritol-tetrakis-(beta~odecylmercapto)-propi~~nate.

6. Polyamide stabilizers, for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.

7. f3asic co-stabilizers, for example, melamine, pdyvinylpyrrdidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, pdyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate and K palmatate, antimony pyrocatecholate or zinc pyrocatecholate.

8. Nudeating agents, for example, 4-tart-butyl-benzoic acid, adipic acid, diphenyiacetic acid.

9. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibres, asbestos, talc, kadin, mica, barium sulfate, metal oxides and hydro~ddes, carbon black, graphite.

10. The present invention may also be used in conjuration with aminoxy propanoate derivatives such as methyl-[N,N~ibenzylaminoxy]propanoate; ethyh3-[N,N-dibenzylaminoxyjpropanoate; 1,6-hexamethylene-bis[3-(N,N~Iibenzylaminoxy)pn~panoate]; methyl-[2-(methyl)~3(N,N~libenzylamirxury)propanoate]; octadecyl~-[N,N-dibenzyl-aminoxyjpropanoic acid;
teirakis[(N,N~iibenzylaminoxy)ethyl carbonyl oxymethyljmethane; odadecyl~-[N,N~Jiethyl aminoxyjpropanoate; 3-[N,N-dlbenzylamlnoxyjproparaic acid potassium salt; and 1,6-hexamethylene bis[3-(N,ailyl-N~lodecyl amint~cy)propanoate].

11. Other additives, four example, plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame-proofing agents, anti-static agents, blowing agents and thiosynergists such as r dilaurylthiodipropionate or distearylthiodipropionate.
Hindered phendic antioxidants may also be present in the pdymer composition.
Use of diphosphaspiroundecanes of the present Invention may result in enhanced pdymer protection by reducing the formation of color resulting from the presence of the phends.
Such phendic antioxidants include n-octade~cyl 3,5~i=tart-butyl-4-hydroxyhydrocinnamate, neopentanetetrayl tetrakis-(3,5-di-tart-butyl-4-hytlroxyi-hydrocinnamate), di-n-octadecyi 3,5~ii-tart-butyl-4-hydroxybenzyl-phosphonate. 1,3,5-tris(3,5~i-tart-butyl~t-hydroxybenzyi-)isocyanurate, thiodiethylene bis(3,5-di-tart-butyl-4-hydroxylhydrocinnamate). 1,3,5-trimethyl-2,4,6-tris(3,5-di-tart-butyl-4-hydroxybenzyl)benzene, 3,6-cli-oxaoctamethylene bis(3-methyl-5-tart-butyl-4-hydroxyhydrocinnamate), 2,6~i-tart-butyl-p-cresd, 2,2'-~sthylidene-bis(4,6~i-tart-butylphend), 1,3,5-Iris-(2,6-di-methyl-4-tert-butyl-3-hydroxybenzyl)isocyanurate. 1,1,3-tris-(2-methyl-hydroxy-5-tart-butyiphenyl)butane, 1,3,5-tris-[2-(3,5-di-tart-butyl-4-hydn~xyhydrocinnamdoxy)-ethyl]-Isocyanurate, 3,5-di-(3,5-di-tart-butyl-4-hydroxybenryl)-mesitd, hexa-methylene bis(3,5~1i-tart-butyl-hydroxyhydrocinnamate), 1-(3,5~Ji-tart-butyl-4-hydroxyanilino)-3"i~di(octyithio)-s-triazine. N,N'-hexamethylene-bis(3,5~i-tart-butyl-4-hydroxyhydro-cinnamamide), calcium bis(ethyl,5~di-tart-butyl-4-hydroxybenzylphosphonate), ethylene bis[3,3-di(3-tart-butyl-4-hydroxyphenyl)butyrate], octyl 3,5-di-tart-butyl~-hydroxybenzyimercaptoacetade, bis(3,5-di-tart-butyl-4-hydroxyhydrocinnamoyl)hydrazide, and N,N'-bis-[2-(3,5-tart-butyl-4-hydroxyhydroxocinnamoyloxy)-ethyl]-oxamide, and preferably neopentanetetrayi tetrakis(3,5~~di-tart-butyl-4-hydroxyhydnxinnamate), n-octadecyi 3,5~i-tart-butyl-4-hydroxyhydrocinnamate, 1,3,5-trimethyl-2,4,6-tris(3,5~di-tart-butyl-hydroxy-benryl)benzene, 1,3,5-tris-(3,5~ii-tart-butyl-hydroxybenzyi)i,~ocyanurate, 2,6-di-tart-butyl-p-creed or 2,2'-ethylidene-bts(4,6-di-tart-butylphend).
Other additives, such a;: oxazaphosphdidines, may additionally or alternatively be present.
Ukewise, the instant compounds prevent color formation when hindered amine light stabilizers are present, such hindered arnines including bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-n-butyl-2-(3,5-di-tart-butyl-4-hydroxy-benzyli)malonate; bis(2,2,6,6-tertramehtyl-~4-piperidyl) sebacate;
dimethylsuccinate polymer with 4fiydroxy-2,2,6,6-tertramehtyi-t-piperidinethanoi; and pdymer of 2,4~Jichloro~-octylamino-s-triazine w'tth N'-(2,2,6,6-tertramethyl-~-piperidyl)hexamethylene diamine.
Consistent with the inverntion, the diphosphaspiroundecanes of the invention or the product of the process of the invention rnay be added to the polymer at any time prior to or during fabrication into articles, and rnay be combined w'tth the polymer by any of a variety of means known in the art, such as by preblending or by being fed directly into fabrication equipment.
The present invention may further be understood by reference to the Specific Embodiments outlined below, which are provided herein to illustrate various aspects of the invention, either by demonstrating an aspect of tihe invention, such as polymer stabilization or hydrolysis resistance, or providing a basis for compariison.
Soecrfic Embodiments Acid number, when measured, was determined by one of the following methods.
The Sodium Butoxide Method was used to determine acid number for all examples unless indicated otherwise.

1 3 40 9fi 5 Potassium Hyrdroxide Method Bromothymd (0.1% in 1-butanol) indicator sdution is added (4~ drops) to 100 MI
of 1-bucand in a 250 MI Erlenmeyer flask. The butand is neutralized to a blue-green endpoint of pH7 with 0.02N methandic KOH (1.32 gm KOH (ACS, 85%) in anhydrous reagent grade methand and d~uted to 1 liter and standaniized against standard 0.1 N HCI). The sample to be tested is weighed to the nearest 0.1 gm and added to the flask. When the sample Is a sdid the contents of the flask are warmed slightly to 176°F (t30oC) before addition of the sample. The appropriate sample weight to be used is determined from the fdiowing table:
Weight to be used Estimated Acid Number 20 gm less than 0.1 gm 0.1 - 2.0 1 gm greater than 2.0 After addition of the sample the flask is swirled to dissolve the sample, and the contents of the flask are then immediately t:ftrated with 0.02N KOH (described above) to a blue-green endpoint.
,odium Butoxide Method Bromothymd blue indicator (0.1 %) is prepared as described above. A 2 gm sample of the material to be tested is weighed out in a 250 ml Erlenmeyer flask to the nearest .01 gm.
Methylene chloride (75 ml) is added to another Erlenmeyer flask, fdlowed by 4~
drops of the bromothymd indicator sdution, and the resulting sdution is neutralized with 0.02N sodium butoxide (0.46 gm sodium metal dissdv~ad in anhydrous butand, dAuted to 1 liter and standardized against 0.01 N HCI) to a blue-green endpoint of pH-7. The neutralized methylene chloride sdution is then added to the flask containing the sample and swirled to dissolve the sample.
The resulting sdution is immediately titrated with 0.02N sodium butoxide (prepared as indicated above) to a blue-green endpoint.

The acid number for efth~er method is obtained from the fdlowing equation:
Acid Number' (mg. reagent/gm sample) _ (M) lN) (56.11 S
where:
M = ml. tiirating reagent consumed in the titration N = normality of the titrating reagent S = weight (gins) of sample Example 1 illustrates the preparation, by a process known in the art, of 3,9-bis(2,4,6-tri-t-butylphenoxy)-2,4,8,10-tetroxa~3,9-diphosphaspiro[5.5]undecane.
Examgle 1 A suspension of 210.1 gins (800 minds) of 2,4,6-tri-~-butylphend, 105.9 gins (400 mmols) of 3,9~lichforo-2,4,8,10-tetroxa-3,9-diphosphaspiro[5.5]undecane and 118 mL (847 mmols) of triethyl-amine was dissdved in 200 mIL of chlorobenzene and refluxed and mechanically stirred under a nitrogen atmosphere for 46 hrs. The resulting dark brown suspension was diluted with 500 mL of chlorobenzene and filtered to remove triethylamine hydrochloride formed during the reaction. On coding the filtrate, 214 gins of wet crystals were obtained. The crystals were recrystallized from tduene containing a small amount (less than 5 vdume %) of triethylamine. The product was isdated by filtration to afford T6.2 g (26% yield) of bis(2,4,6-trf-t-butylphenoxy)-tetroxa-diphosphaspiroundecane as crystals, with mp 253.5-256oC and acid number 3.0 (KOH-methand method, described above). Further recrystallization from tduene containing a small amount of triethylamine afforded 48.8 g (1796 yield) of the desired product as a white crystalline slid, mp 250-255oC, acid number 0.99. Infrared,. nmr, and mass spectroscopy cor~frmed the structure of the product.

~ 344 96 5 Example 2 demonstrate;: preparation of bis(2,4,6-tri-t-butylphenoxy)-tetroxa-diphosphaspiroundecane by am embodiment of the dichloropentfte route of the process of the invention.
To a stirred sdution of 120.3 g (45.8 mmd) of 2,4,6,-trl-~-butylphend in 382 mL of tri-n-butylamine under argon was added 60.7 g (229 mmd) of 3,9~dichloro-2,4,8,10-tetroxa-3,9-diphosphaspiro[5.5]undecane~. The suspension was then heated and stirred under argon at an internal temperature of 1 t OoC for 8 hrs. The resulting suspension was allowed to cod to room temperature and 400 mL of isopropyl adcohd added. Sdids were isdated by vacuum filtration and washed on the funnel with an additional 1 L of isopropyl aJcohd and then t L
of n-heptane to afford 145.4 g (8996 of theoretical yield) of the desired diphosphaspiroundecane as a white powder, w'tth mp 253-254oC and acid number Oi.92. This product was confirmed by standard methods. Thus 'rt appears that the above proce:~s consistent with that of the present invention gives improved product yield in comparison to the prior' art process of Example 1.
Example 3 demonstrate.; preparation of bis(2,4,6-tri t-butylphenoxy)-tetroxa-diphosphaspiroundecane by am embodiment of the dichloridite route, another embodiment of the process of the invention.
~xamde 3 To 73.0 g (530 mmd) of phosphorus trichloride in an ice water bash was slowly added 16.9 g (170 mmd) of triethylamine. 1'he mixture was stirred for ten minutes and then 35.0 g (130 mmol) of 2,4,6-tri-~-butylphend was added in T.0 g portions over a period of 20 minutes with continued coding. After addition ~ 2,4,Ei-tri-t-butylphend was complete the reaction mature was heated at reflux for 3.5 hrs. and then alicwed to cod to room temperature. The reaction mixture was diluted with 200 mL of hept:ane and cooled and filtered. The filter cake was washed twice with ~~0 mL (~! x 80) of heptane. Ccanbined organic filtrates were concentrated Lu~der vacu~n to afford 48.2 g (99% of theoretical yield) of the dichloriditE: as a :solid product, with mp 81-86°C. Similar results were obtained when this rEaction was carried out in toluene solvent.
In the next stE:p, a miLxture of 47.0 g (130 mmol) of 2,4,6-tri-t-butylphenylphosphoz:~odi.chloridite and 80 mL of toluene was added to 48.8 g (260 mmol) of tribntylamir~ and 8.8 g (65 mmol) of pentaerythritol. An exotherm to 55°C was aece~~anied by the formation of a white precipitate.
After stirring for one ho~ir the reaction mixture, which had returned to room temperature, was fili:ered under vas and the filter cake washed four times with 50 mL (4 x 50) of isopropyl alcohol. The resulting filter cake was dried to afford 33.2 g (71% of theoretical yield) of the desired diphosphapirour~das a white solid, mp 253-257°C, acid number 0.31. This produci~ was confirmed by standard methods. Thus it appears that the process of Example 3, consistent with the process of the present invention, gives :it~raved product yield in o~parison to the prior art process of Exang?le 1.
ales 4 - 13 Other spirocyc:Lic earnpaunds (Examples 4 - 8) were synthesized by substituting the s~~me molar proportion of other phenols for 2,4,6-tri-t-butylphenol in ~~le 1. Other spirocyclic eaca~unds (ales 9 - 12) were also synthesi;aed by substituting the same molar proportion of other phenols for 2,4,6=tri-t ~utylphenol in Example 2. These phenols were:
ale phenol 4 2,6-Di-t butylphenol 5,9 2,6-Di-t-butyl-4 methylphenol 6,10 2,6-Di-t butyl-4-ethylphenol 7,11 2,6-Di-t-butyl-4-s-butylphenol 8,12 2,4-Di-t butylphenol Synthesis of the analogous diphosphaspiroundecanes, shown in Table I, was confirmed by one or more standard method, such as melting point, infrared spectroscopy (IR.), nuclear magnetic resonance spectroscopy (1~) and mass spectroscopy. The oampo~u~ds thus prepared waere used in the testing discussed in the follcxaing exa~les.

For convenience, the diphosphaspiroundecane products of Examples 1, 4 - ,12 were denoted as indicated below. (All are 3,9-bis(di a tri-alkylphenoxy)-2,4,8,103etroxs~3,9-diphosphaspiro[5.5]undecanErs. However, all numbering except that of the alkyl substituents on the phenoxy moiety have been deleted belc~nr as a matter of convenience.) Moisture Sensitivity of Substituted 3.9-Bi~.6-di-t-buM
4-aikvohenoy,r)-2 4.8.'10-tetroxa~.9-diohosnhwasoiro(5.51undecanes The moisture sensitivity of the spirocydk; diphosphites of Table I and of TBPP
(tris(2,4,-di-t-butylphenyl) phosphate, a noncydic phasphite stabilizer known in the art) were examined by placing the compounds into an atmospheric chamber regulated at about 80% relative humidity at ambient r' laboratory temperature (about 70oF). The samples were maintained in the chamber and monitored for weight gain and increase in acid value (A~ with respect to time. (Weight gain is an indication of the hygroscopic nature of the compaund and may reflect sample hydrdysis, while an increase in acid value is indicative of some hydrdysis occuring in the sample.) The time required for the compounds to gain 1 % weighrt during moisture exposure was assigned as the failure point. The results are indicated below in Table II. .Acid value was measured by the Na-butoxide/methylene chloride method both before the sample was placed in the atmospheric chamber (denoted 'Initial AV') and after the sample hall attained a 1 % weight gain (denoted 'Final AV'). Data in Table il indicate that diphosphaspiroundecane compositions prepan3d by a process consistent with the process of the present invention may exhibit Improved moisture properties in,comparison to compositions prepared by a process known in the ant.
Examde 14 The procedure of Example 2 was repeated eleven times using slight variations in the relative amount of 2,4,6-tri-t-butylphe~nd (2.0 to 2.2 relative to chloropentite on a mdar basis) and/or tri-1 340 9s 5 _n-butylamine present, (3.0 to ti.0 relative to chloropentite on a molar basis). The products of these reactions were then aged In a humid environment under the conditkms described above for 2000 hours to demonstrate the consistency of the process with respect to product moisture sens'rtiv'tty.
For the eleven samples tested, the average initial AV was 1.6 (high 5.08, low 0.37). These samples gained an average of 0.796 in weight (low 0.2%, high 1.13%).during the aging period. The average Final AV for these samples was 5 (low 1.6, high 12.4). An additional preparation of Compound E, made from 2,6~i-~-butyl-sec.-butylphend, was also aged in this study. The sample had an Initial AV of 0.34, had gained 1.7% weight during the 2000 hours and had attained a Final AV of 18.3.
Examples 15 - 21 Compound A and Compound E were prepared according to the procedure of Examples 1 and 7, respectively. Testing of Compound E, consistent with one embodiment of the diphosphaspiroundecane of the invention, and TBPP and Compound A, not embodying the invention, were tested in an 11DPE conti~ining 300 ppm of octadecyl 3,5~ii-t-butyl-4-hydroxyhydrocinnamate, and 500 ppm of calcium steanite. Results of this testing are indicated below in Table III.
In these and subsequent examples, powdered calcium stearate and diphosphaspiroundecane (and other additives which were present) were incorporated into the resin by dry blending for 45 minutes in a Turbula blender. The dry blended resin mbcture was extruded at a stock temperature of 525oC through a one-inch single screw extruder equipped with a 2-stage screw fitted w'tth a Maddox mover. The extrudate~ was palletized and reextnxied for a total of seven extrusions.
Material was saved from the first, third, fifth and seventh extrusions. The melt flow of these samples was measured using ~ASTM test method D-1238, Condition E.
The melt flow of 11DPE generally decreases with each extrusion as the pdymer undergoes degradation by an overall crosslinking reaction, thereby decreasing melt flow.
The efficiency of a stabilizer may therefore be evaluated by measuring its melt flow over successive extrusions and 134~965 determining how dose the melt flow of successive extrusions are to the melt flow of the initial extrusion.
The cda of the retained samples 'was measured using a Hunter colormeter and standard techniques prescribed for use with that equipment, and comparing the yellowness index (YI) change between the first and seventh samples c~ each extrusion. The odor measurements were made on one-eighth inch by one and onefialf inch diameter discs that were compression molded at 330oF
from the retained sample pellets. Higher values indicate mae odor development.
Results of melt flow and cdor testing of resin containing these compounds are indicated below in Table III. loading levels of the diphosphaspiroundecanes in the resin are indicated in parts per hundred parts resin. The headings 'first, third, fifth, seventh' Indicate the number of extrusions the composition had undergone when the sample was taken.
Exam~ies 22 - 28 Additional testing of TBF'P and Compound A and Compound E, prepared according to Examples 1 and 7, was performed using Profax 6501 pdy (propylene) resin from Hercules.
The compositions tested included 0.025 phr of pentaerythritd tetrakis [3-(3,5-di-~-butyl-4-hydroxy phenyl)propionate]
and 0.05 phr. Ca Stearate. The amount of additive compound present and the results are indicated below in Table IV.
The above examples are presented to illustrate various aspects of the irnention. The invention is defined only by the fdlowing claims, and is not limited in scope to the particular embodiments or parameters described as modifications of these teachings will be apparent to those skilled in the art in view of the present disclosure.

13409fi5 Table I
CompoundExample Name A 1,2 bis(2,4,6-tri-t-butylphenoxy)-tetroxa-diphosphaspiroundecane 8 4 bis(f,6-di-t-butylphenoxy)-tetroxa-diphosphaspiroundecane C 5,9 bis(f,6-di-t-butyl-4-methylphenoxy)-tetroxa-diphosphaspiroundecane D 6,10 bis(f.,6-di-t-butyl-4-ethylphenoxy)-tetroxa-diphosphaspiroundecane E 7,11 bis(f,6-di-t-butyl-4-s-butylphenoxy)-tetroxa-diphosphaspiroundecane F 8,12 bis(f,4-di-t-butylphenoxy)-tetroxa-diphosphaspiroundecane Table II
Time to 1~
Exa Compound Weioht GainInitial Final le Av AU

1 A 1674 0.23 4.70 2 A >2200 1 --4 B 96 0.54 3.32 C 66 0.26 21.60 9 C 1500 1.25 16 6 D ?2 2.55 9.5 D 40? 0.22 8.5 7 E 216 0.13 ?

11 E 947 0.85 14.2 8 F 66 1.06 14.2 12 F 336 0.53 4.3 13 TBPP >1200 0.21 0.96 Table III
Amount Melt Color,YI
Flout, g/10 min Exa Compound - phr firstthirdfifthfirst fifth le - -- 1.59 0.98 0.75 15.13 19.55 16 A 0.04 2.04 1.27 0.93 12.63 14.90 1? A 0.0? 1.98 1.8? 1.62 11.90 13.39 18 E 0.04 1.98 1.53 0.93 12.59 15.63 19 E 0.0? 1.94 1.88 1.?1 11.28 12.68 TBPP 0.04 1.64 1.19 0.86 13.44 18.5?

21 TBPP 0.0? 1.62 1.12 0.86 12.93 1?.96 1 340 9fi 5 Table iv Amount Irlelt Color, Flak YI
g/10 min ExampleCam ound~p~hr firstthirdfifth first fifth -- - 5.? 12.4 19.4 8.9 9.78 23* A 0.05 2.1 2.6 3.2 9.39 9.56 24* A 0.03?5 2.4 2.? 3.4 9.?5 9.63 25 E 0.05 2.6 2.8 2.9 8.98 9.26 26 E 0.03?5 2.0 3.0 4.2 8.04 9.4?

2? TBPP 0.05 3.3 5.2 8.3 9.08 9.24 28 TBPP 0.0375 2.9 4.8 ?.3 9.56 9.5?

*represents an average of t;he follauing values obtained from four different runs:
Table U
Amount Irlelt Color, Flout, YI
g/10 min Example Corm aymd her firstthirdfifth first fifth 23 A 0.05 2.0 2.? 3.4 9.06 9.16 2.6 2.8 3.4 9.3? 9.50 2.1 2.6 3.2 9.39 9.56 2.1 2.3 2.? 9.25 9.56 24 A 0.03?5 2.1 2.4 3.4 9.?8 10.38 2.4 2.? 3.4 9.75 9.63 2.6 2.8 3.0 9.94 9.58 2.8 2.9 3.2 9.3? 9.83

Claims (43)

1. A process for making an organic-substituted diphosphaspiroundecane comprising first reacting phosphorus trichloride with one of (a) pentaerythritol and (b) a second hydroxy-substituted organic compound selected from the group consisting of alkanols, phenols, hydroxyl-substituted cycloalkanes and hydroxyl-substituted aralkyls, and second reacting the resulting reaction product with the other of (a) and (b), said second reaction being conducted in the presence of a tri-n-alkyl-amine in which each n-alkyl moiety has three or more carbon atoms, wherein said tri-n-alkylamine is present in a molar amount which is equal to or greater than the molar amount of hydrogen chloride produced by said second reaction, and wherein said organic-substituted diphosphaspiroundecane is a solid product and substantially insoluble in the medium of the second reaction.

2. The process of claim 1 wherein said tri-n-alkyl-amine is one having a hydrochloride salt which is substantially soluble in said reaction medium.

3. The process of claim 2 wherein said phosphorous trichloride and said pentaerythritol are reacted to form 3,9-dichloro-2,4,8,10-tetroxa-3,9-diphosphaspiroundecane before reaction with said hydroxyl-substituted organic compound to foam said organic-substituted diphosphaspiroundecane.

4. The process of claim 2 wherein said phosphorous trichloride anc3 said hydroxyl-substituted organic compound are reacted to form a phosphorodichloridite before reaction with pentaerythritol to form said organic-substituted diphosphaspiroundecane.

5. The process of claim 2 wherein the n-alkyl moieties of said tri-n-alkylamine have about 3 to about 10 carbon atoms.

6. The process of claim 5 wherein said amine is selected from the group consisting of tri-n-propylamine, tri-n-butylamine and tri-n-pentylamine.

7. The process of claim 6 wherein said tri-n-alkylamine is tri-n-butylamine.

8. The process of claim 1 wherein said reaction medium consists essentially of said tri-n-alkylamine.

9. The process of claim 3 wherein said organic compound is an aliphatic alcohol.

10. The process of claim 3 wherein said organic compound is a phenol.

11. The process of claim 3 wherein said phenol is selected from the group consisting of 2,4,6-tri-alkyl and 2,4-di-alkyl substituted phenols.

12. The process of claim 11 wherein said phenol is selected from the group consisting of 2,4-di-t-alkyl phenols and 2,6-di-t-alkyl-4-alkyl phenols.

13. The process of claim 12 wherein said phenol is selected from the group consisting of 2,4,6-tri-t-alkyl phenols, 2,6-di-t-alkyl-4-n-alkyl phenols, 2,6-di-t-alkyl-4-s-alkyl phenols, and 2,4-di-t-alkyl phenols.

14. The process of claim 13 wherein said phenol is selected from the group consisting of 2,4,6-tri-t-butyl phenol, 2,6-di-t-butyl-4-methyl phenol, 2,6-di-t-butyl-4-ethyl phenol, 2,6-di-t-butyl-4-s-butyl phenol, and 2,4,6-di-t-butyl phenol.

15. The process of claim 13 wherein said phenol is a 2,6-di-t-alkyl-4-s-alkyl phenol.

16. The process of claim 13 wherein said phenol is a 2,4,6-tri-t-alkyl phenol .

17. The process of claim 3 wherein the molar ratio of said organic compound to said 3,9-dichloro-2,4,8,10-tetroxa-3, 9-diphosphaspiroundecane is about 2:1 to about 3:1.

18. The process of claim 4 wherein said organic compound is a phenol.

19. The process of claim 18 wherein said phenol is selected from the group consisting of 2,4,6-tri-alkyl substituted phenols.

20. The process of claim 19 wherein said phenol is selected from the group consisting of 2,4,6-tri-t-alkyl phenols, 2,6-di-t-alkyl-4-methyl phenols, 2,6-di-t-alkyl-4-ethyl phenols, and 2,6-di-t-alkyl-4-s-alkyl phenols.

21. The process of claim 20 wherein said phenol is selected from the group consisting of 2,4,6-tri-t-butyl phenol, 2,6-di-t-butyl-4-methyl phenol, 2,6-di-t-butyl-4-ethyl phenol, and 2,6-di-t-butyl-4-s-butyl phenol.

22. The process of claim 4 wherein the improvement further comprises the ratio of mole equivalents of phosphorus trichloride to said hydroxyl-substituted organic compound being greater than 3:1.

23. The process of claim 22 wherein the ratio of mole equivalents of phosphorus trichloride to mole equivalents of said organic compound is about 3.5:1 to about 4.5:1.

24. The process of claim 4 wherein said tri-n-alkylamine is present in an amount greater than the stoichiometric amount required to neutralize hydrogen chloride liberated during reaction of said phosphorodichloridite with pentaerythritol.

25. The product of the process of claim 3.

26. The product of claim 25 wherein the n-alkyl moieties of said tri-n-alkylamine have about 3 to about 10 carbon atoms.

27. The product of claim 26 wherein said n-alkyl moieties are n-butyl moieties.

28. The product of claim 24 wherein said reaction medium consists essentially of tri-n-alkylamine.

29. The product of claim 25 wherein said organic compound is an aliphatic alcohol.

30. The product of claim 25 wherein said organic compound is a phenol.

31. The product of claim 25 wherein said phenol is selected from the group consisting of 2,4,6-tri-alkyl and 2,4-di-alkyl substituted phenols.

32. The product of claim 31 wherein said phenol is selected from the group consisting of 2,4-di-t-alkyl phenols and 2,6-di-t-alkyl-4-alkyl phenols.

33. The product of claim 32 wherein said phenol is selected from the group consisting of 2,4,6-tri-t-alkyl phenols, 2,6-di-t-alkyl-4-methyl phenols, 2,6-di-t-alkyl-4-ethyl phenols, 2,6-di-t-alkyl-4-s-alkyl phenols, and 2,4-di-t-alkyl phenols.

34. The product of claim 33 wherein said phenol is selected from the group consisting of 2,4,6-tri-t-butyl phenol, 2,6-di-t-butyl-4-methyl phenol, 2,6-di-t-butyl-4-ethyl phenol, 2,6-di-t-butyl-4-s-butyl phenol, and 2,4-di-t-butyl phenol.

35. The product of claim 34 wherein said phenol is selected from the group consisting of 2,6-di-t-butyl-4-s-butyl phenol, 2,6-di-t-butyl-4-methylphenol and 2,4-di-t-butylphenol.

36. A composition for improving the melt flow stability and/or the color stability of polymers comprising a diphosphaspiroundecane of the general formula:
wherein each of R2, R3,R4, and R6 is a tertiary alkyl moiety; and each of R1 and R5 is a secondary alkyl moiety.

37. The composition of claim 36 wherein each R2, R3, R4, and R6 is a t-butyl moiety, and each of R1 and R5 is a sec-butyl moiety.

38. A polymer composition comprising a polymer and a sufficient amount of the product of claim 25 to improve the melt flow stability and/or the color stability of the polymer.

39. The polymer composition of claim 38 wherein the polymer is selected from the group consisting of polyolefin, polyester, polycarbonate, polyphenylene ether, and styrenic resins, and mixtures thereof.

40. The composition of claim 39 wherein the polymer is selected from the group consisting of polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12 and 4/6, polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyphenylene ether, polycarbonate, polystyrene, impact polystyrene and ABS-type graft copolymer resins, and mixtures thereof.

41. The polymer composition of claim 38 wherein the product of claim 25 is present in a.n amount equal to about 0.01 to about 2 phr.

42. The polymer composition of claim 41 wherein the product of claim 25 is present in an amount equal to about 0.01 to about 1 phr.

43. A stabilized polymer composition comprising a polymer and an effective amount of a bis-3,9-(2,6-di-t-alkyl-4-s-alkylphenoxy)-2,4,8,10-tetroxa-3,9-diphosph-aspiro[5.5]undecane.