# Patent

## Title
High solids solvent-based polyester coating composition

## Abstract

Bis(2,6-di tert butyl-4-branched propyl or butyl phenyl)-pentaerythritol spiro phosphites are provided having the formula: ##STR1## wherein R is a branched propyl or butyl group, such as isopropyl, iso-butyl, or sec-butyl, as well as synthetic resin compositions having enhanced resistance to deterioration upon exposure to the heat and light comprising such as bis(2,6-di-t-butyl-4-branched propyl or butyl phenyl)pentaerythritol spiro phosphites.

## Background
Synthetic resins such as polyethylene, polypropylene, polystyrene and polyvinyl chloride are subject to degradation upon exposure to heat and light, with resulting discoloration and deterioration of mechanical strength. Therefore, various stabilizers have been added to inhibit the deterioration of polymers, among them, phosphite compounds, which are important and effective stabilizers.

As a result of long extended research and development many special phosphites have been provided having improved stabilizing effectiveness and compatibility and ease of compounding with the resin and with other stabilizers.

L. Friedman, U.S. Pat. No. 3,047,608, patented July 31, 1962, discloses a class of spiro-bisphosphites having the formula: ##STR2## in which R.sub.1 and R.sub.2 are alkyl or aryl.

Hechenbleikner, U.S. Pat. No. 4,290,976, patented Sept. 22, 1981, states that dialkyl pentaerythritol diphosphites having the structural formula ##STR3## where R.sub.1 and R.sub.2 are alkyl groups, have been known for some time as effective stabilizers for vinyl polymers. They have been used primarily to stabilize vinyl chloride polymers and polyolefins, but have found use also in the stabilization of styrene polymers such as ABS.

U.S. Pat. No. 4,086,304, patented Apr. 25, 1978, to Hutton et al, provides organic triphosphites having improved hydrolytic stability and a process for stabilizing organic triphosphites.

The hydrolytically stable composition contains as its essential components at least about 85% by weight of an organic triphosphite and from about 0.1% to 5% by weight of a salt of a metal from Group I or Group II of the Periodic System and an organic acid having at least 8 carbon atoms.

Among the triphosphites disclosed are those having the formula: ##STR4## where n=0 or an integer from 1 to 8, and wherein the R's are the same or different and R is an aryl, alkyl, cycloalkyl, aralkyl or alkaryl group.

Typical examples of such phosphites include bis(nonylphenyl) pentaerythrityl diphosphite, di-n-dodecyl pentaerythrityl diphosphite, and di-isodecyl pentaerythrityl diphosphite.

U.S. Pat. No. 4,180,498, patented Dec. 25, 1979, to Spivack provides compounds of the formula ##STR5## wherein: R.sub.1 and R.sub.2 are independently lower alkyl or hydrogen, provided that only one of R.sub.1 and R.sub.2 is hydrogen; phenyl, and thermal, oxidative and ultraviolet light degradation.

U.S. Pat. No. 4,371,647, patented Feb. 1, 1983, to Minagawa et al, provides 2,6-di-tertiary butyl phenyl pentaerythritol spiro bisphosphites having the structure: ##STR6## wherein: R is alkyl having from one to six carbon atoms; to about eighteen carbon atoms;

cycloalkyl having from three up to about twelve carbon atoms; and alkaryl and aryl having from six to about thirty carbon atoms; such groups substituted with from one to about four oxy ether --O-- and/or carboxylic ester --COO-- groups; the residue of a polyhydric alcohol having from two to about eighteen carbon atoms, and from two to about ten hydroxyl groups; and the residue of a polyphenol having from six to about eighteen carbon atoms and from two to about ten phenolic hydroxyl groups.

U.S. Pat. No. 4,385,145, patented May 24, 1983, to Horn, Jr., provides poly(alkylene terephthalate) compositions containing a stabilizing proportion of a pentaerythritol diphosphite ester.

The pentaerythritol diphosphite ester preferably is a bis-(alkylphenyl) or dialkyl pentaerythritol diphosphite. The alkylphenyl groups may include monoalkylphenyl, dialkylphenyl and trialkylphenyl groups although dialkylphenyl groups are preferred. Especially preferred are 2,4-dialkylphenyl groups. The alkyl groups should have 3-6 carbon atoms and tertiarybutyl groups are found most often because of their effect on solubility.

U.S. Pat. No. 4,496,677, patented Jan. 29, 1985, to Briggs, Jr. et al, provides a melt processable fluoropolymer composition stabilized against thermal degradation by incorporating therein a stabilizing system comprising Table.

The hindered phenol pentaerythritol diphosphite has the general formula: ##STR7## wherein the R substituents, which may be the same or different, are independently selected from the group consisting of hydrogen and alkyl, straight or branched chain, having from 1 to about 18 carbon atoms; and wherein m and n are integers from 0 to 2, and o and p are integers from 1 to 5, with the proviso that the sums of m+o, and n+p may not exceed 5. A preferred hindered phenol pentaerythritol is bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite.

However, the bis spiro pentaerythritol diphosphites have not in general been characterized by good hydrolytic stability. In a moist environment they tend to undergo hydrolytic decomposition, with a corresponding loss of polymer-stabilizing effectiveness. Attempts to solve this problem of hydrolysis have utilized additives and these have been somewhat successful, but the problem remains, according to Hechenbleikner

Hodan and Schall, U.S. Pat. No. 3,553,298, patented Jan. 5, 1971 suggested that the hydrolytic stability of phosphite esters of a wide class could be improved by combination therewith of an additive that is nitrogen-containing and selected from the group consisting of heterocyclic alkyl, nitrogen compounds, aromatic heterocyclic nitrogen compounds, dialkanolamines, trialkanolamines, ammonia and alkyl amines.

York, U.S. Pat. No. 4,116,926, patented Sept. 26, 1978 found triisopropanolamine to be a particularly effective stabilizer for dialkylpentaerythritol diphosphites and polyalkyl bisphenol-A polyphosphites.

The dialkylpentaerythritol diphosphites have the structural formula: ##STR8## where R and R' are alkyl groups.

EPO Pat. No. 143,464, published June 5, 1985, to Argus Chemical Corporation, notes that most alkyl and alkylaryl pentaerythritol-spiro-bis phosphites having fourteen or more carbon atoms in the alkyl or alkylaryl groups, and indeed even pentaerythritol-spiro-bis phosphite itself, are solid materials. When their melting point is above 40.degree. C., they are readily reduced to particulate form, and therefore are easily blended with other solid stabilizers for combination with synthetic resin. When however triisopropanolamine is used to improve hydrolytic stability, the desirable qualities of these pentaerythritol-spiro-bis-phosphites as an easily-handled particulate solid material are lost, and the material is converted into a sticky solid that is rather difficult to work with. It is not readily reduced to particulate form, and when in particulate form tends to agglomerate with itself and with other materials that are sought to be blended therewith, in formulating multicomponent stabilizer systems.

Argus accordingly employs long-chain aliphatic amines to improve the hydrolytic stability of pentaerythritol-spiro-bis-phosphites, and to form nonsticky solid compositions that are readily reduced to particulate form, and can easily be blended with other stabilizers and with synthetic resins, thus overcoming the stickiness problem inherent in the use of triisopropanolamine.

The pentaerythritol-spiro-bis-phosphite of these compositions have the formula: ##STR9## wherein: R.sub.1 and R.sub.2 are selected from the group consisting of alkyl and alkylaryl groups having at least fourteen carbon atoms up to about thirty-six carbon atoms.

R.sub.1 and R.sub.2 alkaryl groups in the phosphite include octylphenyl, 2,6-di-t-butyl-4-methylphenyl, 2,6-di-t-butyl-4-methoxycarbonyl, ethylphenyl, isooctylphenyl, t-octylphenyl, nonylphenyl, 2,4-di-t-butylphenyl, benzylphenyl and phenethylphenyl.

Exemplary pentaerythritol spiro-bis-phosphites include dimyristyl pentaerythritol diphosphite, dihexadecyl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite, di-(2,6-di-t-butylphenyl) pentaerythritol diphosphite, di-(2-t-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,4-di-t-butyl-6-methylphenyl octylphenyl pentaerythritol diphosphite, 2,4-di-t-butyl-6-methylphenyl nonylphenyl pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2,6-di-t-butylphenyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2,4-di-t-butylphenyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2,4-di-t-octylphenyl pentaerythritol diphosphite, 2,6-di-t-amyl-4-methylphenyl phenyl pentaerythritol diphosphite, bis(2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,6-di-t-octyl-4-methylphenyl) pentaerythritol diphosphite.

However, the melting point of the alkylaryl phosphites, such as bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite and bis(2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, are above 235.degree. C., and the compatibility thereof with many synthetic resins is not satisfactory. These problems are avoided, in the bis 2,6-di tert butyl phenyl pentaerythritol spiro phosphites by substituting a branched propyl or butyl group in the 40position of the phenyl group. These new pentaerythritol spiro bis phosphites have the formula: ##STR10## wherein R is isopropyl or iso or secondary butyl.

These pentaerythritol spiro bis phosphites have good hydrolytic stability. However, an aliphatic or cycloaliphatic or heterocyclic amine, as disclosed in Hodan et al, No. 3,553,298, York No. 4,116,926 or Argus EPO No. 143,464, the disclosures of which are hereby incorporated by reference, can be added to the spiro bisphosphite to improve the hydrolytic stability.

Exemplary amines include, for example, trialkanolamines such as triethanolamine, triisopropanolamine and tri-n-propanolamine; dialkanolamines such as diethanol dodecylamine, diethanol octadecylamine, diethanol oleylamine, diethanol octylamine, diethanol hexadecylamine, diisopropanol dodecylamine, diisopropanol octadecylamine and di-n-propanol octadecylamine; dialkanolamines such as diisopropanolamine and diethanolamine; alkanebis(dialkanolamines) such as ethylenebis(diethanolamine) and ethylenebis (diisopropanolamine); heterocyclic amines such as hexamethylenetetramine, piperidine, pyrrolidine, N-methyl piperidine, N-methylpyrrolidine, oxazolidine and isooxazolidine; and amine oxides such as lauryldimethyloxide and stearyldimethylamineoxide.

The preferred amount of the amine is from 0.01 to 5 parts by weight, preferably from 0.1 to 2 parts by weight, per 100 parts by weight of the spiro-bis phosphite.

Synthetic resins which can have their resistance to deterioration when exposed to heat and light enhanced by the spiro bisphosphites of this invention include .alpha.-olefin polymers and copolymers such as polyethylene, polypropylene, polybutene, poly-3-methylpentene, ethylene/vinylacetate copolymer and ethylene/propylene copolymer; halogen-containing resins such as polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, vinyl chloride/vinylacetate copolymer, vinyl chloride/ethylene copolymer, vinyl chloride/propylene copolymer, vinyl chloride/styrene copolymer, vinyl chloride/styrene/maleic anhydride terpolymer, vinyl chloride/butadiene copolymer, vinyl chloride/acrylic acid ester copolymer, vinyl chloride/methacrylic acid copolymer, vinyl chloride/acrylonitrile copolymer; polyvinyl acetate; polyacrylic acid and polyacrylic acid esters; polystyrene, copolymers of styrene with other copolymerizable monomers such as maleic anhydride, butadiene and acrylonitrile; acrylonitrile/butadiene/styrene terpolymer; acrylic acid ester/butadiene/styrene terpolymer; methacrylic acid ester/butadiene/styrene terpolymer; polymethyl methacrylate; polyvinyl alcohol; polyvinyl butyral; linear polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyphenylene oxide; polyamide; polycarbonate; polyacetal; polyurethane; and epoxy resin.

The preferred amount of the spiro bisphosphite is within the range from about 0.01 to about 10 parts by weight per 100 parts by weight of the synthetic resin.

The spiro bisphosphites of this invention can be used together with other conventional heat and light stabilizers, such as, for example, phenolic antioxidants, thioether antioxidants, and ultraviolet light stabilizers.

Exemplary phenolic antioxidants which can be employed with the spiro bisphosphites include 2,6-di-t-butyl-p-cresol, 2,6-di-phenyl-4-octadecyloxyphenol, stearyl(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, distearyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, thiodiethylenebis(3,5-di-t-butyl-4-hydroxyphenylpropionate, hexamethylenebis(3,5-di-t-butyl-4hydroxyphenylpropionate, 4,4'-thiobis(6-t-butyl-m-cresol), 2-octylthio-4,6-bis(3,5-di-t-butyl-4-hydroxyphenoxy)-s-triazine, 2,2'-methylenebis(4-methyl-5-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), bis(3,3-bis (4-hydroxy-3-t-butylphenyl)butylic acid) glycol ester, 4,4'-butylidenebis(6-t-butyl-m-cresol), 2,2'-ethylidenebis(4,6-di-t-butylphenol), 2,2'-ethylidenebis(4-sec-butyl-6-t-butylphenol), 3,6-dioxaoctylenebis(3-methyl-5-t-butyl-4-hydroxyphenylpropionate), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl) butane, bis(2-t-butyl-4-methyl-6-(2-hydroxy-3-t-butyl-5methyl benzyl)phenyl) terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris((3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl) isocyanurate, tetrakis (methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate) methane.

The thioether antioxidants which can be employed with the spiro bisphosphites of the invention include dialkylthiodipropionates such as dilauryl-, dimyristyl- and di-stearylthiodipropionate; and esters of .beta.-alkylthiopropionic acid with polyhydric alcohols such as pentaerythritol tetrakis (.beta.-dodecylthiopropionate).

The ultraviolet light stabilizers which can be employed with the spiro bisphosphites include hydroxybenzophenones such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzephenone, 2,2'-dihydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone; benzotriazoles such as 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methylphenyl) benzotriazole and 2-(2'-hydroxy-3',5'-di-t-amylphenyl) benzotriazole; benzoates such as phenyl salicylate, p-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3, 5-di-t-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate; Ni compounds such as 2, 2'-thiobis(4-t-octylphenol) Ni salt, (2,2'-thio bis(4-t-octylphenolate))-n-butylamine Ni and (3,5-di-t-butyl-4-hydroxybenzyl) phosphonic acid monoethyl ester Ni salt; substituted acrylonitriles such as .alpha.-cyano-.beta.-methyl-.beta.-(p-methoxyphenyl)acrylic) acid methyl ester; oxanilides such as N-2-ethylphenyl-N'-2-ethoxy-5-t-butylphenyloxanilide and N-2-ethylphenyl-N'-2-ethoxyphenyloxanilide; and piperidine compounds such as bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-n-butyl-3,5-di-t-butyl-4-hydroxyben zylmalonate, bis(1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl)bis(3,5 -di-t-butyl-4-hydroxybenzyl) malonate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-butane, 1,2,3,4-tetracarboxylate, condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol with diethylsuccinate and condensate of 2-t-octylamino-4,6-dichlorotriazine with 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino) hexane.

In addition, other conventional additives for synthetic resins, such as heavy metal deactivators, nucleating agents, metal soaps, plasticizers, flame retardants, lubricants, processing aids, blowing agents, pigments, fillers and antistatic agents can be employed.

The synthetic resins stabilized with the stabilizer of the invention can be in any physical form, including powders, filaments, yarns, films, sheets, molded articles, latex, foams and coatings.

The spiro bisphosphites can be readily prepared by reacting 2,6-di-t-butyl-4-R-phenol with pentaerythritol and phosphorous trichloride, in the presence of an acid acceptor. The following is an Example. diphosphite

2,6-Di-t-butyl-4-sec-butyl-phenol 57.8 g (0.220 mole), pentaerythritol 15.0 g (0.110 mole) and triethylamine 0.7 g were dissolved in 70 g of toluene. Phosphorous trichloride 31.5 g (0.229 mole) was added dropwise at room temperature over one hour under a stream of nitrogen.

The reaction mixture was stirred for 2 hours at 65.degree. C., and then excess phosphorous trichloride was removed under vacuum. Triethylamine 24.4 g and tetraethyl ammonium bromide 0.7 g was added, and the reaction mixture was stirred for 5 hours at 80.degree. C.

A white precipitate was produced by adding methanol to the solution. The white precipitate were filtered and recrystallized from n-hexane. The product, bis(2,6-di-t-butyl-4-sec-butyl-phenyl) spiro pentaerythritol diphosphite melted at 204.5.degree..about.205.5.degree. C.

IR analysis: 1020 cm.sup.-1 and 110 cm.sup.-1 based on P--O--CH.sub.2, 855 cm.sup.-1 based on P--O--C (aromatic) and 1600 cm.sup.-1 based on benzene ring.

The following Examples represent preferred embodiments of synthetic resin compositions of the invention.

Polypropylene compositions were prepared using spiro bisphophites of the invention and of the prior art, and having the following formulation: Ingredient             Parts by Weight ______________________________________ Polypropylene          100 Calcium stearate       0.1 Stearyl-(3,5-di-t-butyl-4- 0.1 hydroxyphenyl)propionate Spiro bisphosphite as shown in Table I 0.1 ______________________________________

The compositions were thoroughly blended in a mixer for 5 minutes, and then extruded to prepare pellets. (Cylinder temperature: 230.degree. C. and 240.degree. C., head die temperature: 250.degree. C., velocity: 20 rpm). Test pieces were then molded by injection-molding at 250.degree. C.

The test pieces were heated at 150.degree. C. in a Geer oven, and the hours to failure were noted. The yellowness index of the pieces before and after exposure to fluorescent light for 72 hours was also noted.

the results are shown in Table I. ______________________________________ Yellowness Index Hours         After Example                  to      Or-   72 No.    Spiro bisphosphite Failure iginal hours ______________________________________ Control Bis(2,6-di-t-butyl-4- 240     9.2   13.1 1      methyl-phenyl) pentaery- thritol diphosphite Control Bis(2,6-di-t-butyl-4- 230     9.4   13.4 2      ethyl-phenyl) pentaery- thritol diphosphite Example Bis(2,6-di-t-butyl-4-sec- 280     8.7   11.1 1      butyl-phenyl) pentaerythri- tol diphosphite Example Bis(2,6-di-t-butyl-4- 270     8.9   11.3 2      isopropyl-phenyl) pentaery- thritol-diphosphite Example Bis(2,6-di-t-butyl-4- 270     9.0   11.3 3      isobutyl-phenyl) pentaery- thritol-diphosphite ______________________________________

It is apparent from the data that the spiro bisphosphites of the invention are superior to the prior art homologues of the controls.

Polypropylene compositions were prepared using spiro bisphosphites of the invention and of the prior art, and having the following formulation: Ingredient           Parts by Weight ______________________________________ Polypropylene        100 Calcium stearate     0.2 Pentaerythritol tetrakis((3,5-di-t- 0.2 butyl-4-hydroxyphenyl) propionate) Dilaurylthiodipropionate 0.1 Phosphite as shown in Table II 0.1 ______________________________________

The compositions were thoroughly blended in a mixer, and then extruded at 300.degree. C. to prepare pellets. The extrusion was repeated for 5 times, to examine processing stability at high processing temperature. The melt index (MI:g/10 min) after the first and fifty extrusions was noted. The yellowness index of the pieces after immersion in NO.sub.x gas for 72 hours also was noted.

The results are shown in Table II. ______________________________________ Yel- low-  MI after extrusion for Example                ness    1    5    MI-5/ No.    Spiro bisphosphite Index   time times MI-1 ______________________________________ Control Bis(2,6-di-t-butyl-4- 12.8    2.8  6.5  2.32 methyl-phenyl) pent- aerythritol diphosphite Example Bis(2,6-di-t-butyl-4- 11.0    2.5  4.7  1.88 4      sec-butyl-phenyl) pentaerythritol diphosphite Example Bis(2,6-di-t-butyl-4- 11.8    2.5  4.9  1.96 5      isopropyl-phenyl) pentaerythritol diphosphite Example Bis(2,6-di-t-butyl-4- 11.9    2.6  5.0  1.92 6      isobutyl-phenyl) pentaerythritol diphosphite ______________________________________

It is apparent from the data that the spiro bisphosphites of the invention are superior to the prior art homologue of the control.

Test pieces were prepared as in Example 1, and immersed in hot water at 70.degree. C. for 12 days. The yellowness index of the pieces before and after immersion was noted. The results are shown in Table III. ______________________________________ Yellowness Index Not Example                   immersed Immersed No.     Spiro bisphosphite parts    parts ______________________________________ Control 1 Bis(2,6-di-t-butyl-4-methyl- 7.8      8.5 phenyl) pentaerythritol diphosphite Control 2 Bis(2,6-di-t-butyl-4-ethyl- 8.0      8.7 phenyl) pentaerythritol diphosphite Example 7 Bis(2,6-di-t-butyl-4-sec- 7.3      7.8 butyl-phenyl) pentaerythritol diphosphite Example 8 Bis(2,6-di-t-butyl-4-isopropyl- 7.5      8.1 phenyl) pentaerythritol diphosphite Example 9 Bis(2,6-di-t-butyl-4-isobutyl- 7.6      8.1 phenyl) pentaerythritol diphosphite ______________________________________

It is apparent from the data that the spiro bisphosphites of the invention are superior to the prior art homologues of the controls.

High density polyethylene compositions were prepared using spiro bisphosphites of the invention and of the prior art, and having the following formulation. Ingredient          Parts by Weight ______________________________________ High density polyethylene 100 3,9-Bis(1,1-dimethyl-2-(.beta.-(3-t- 0.05 butyl-4-hydroxy-5-methylphenyl) propionyloxy)ethyl)-2,4,8,10- tetraoxaspiro(5.5) undecane Phosphite shown in Table IV 0.15 ______________________________________

The stabilizers were blended with the polymer on a two-roll mill at 150.degree. C. for 5 minutes, and sheets 1 mm thick were prepared by compression-molding of the blend at 150.degree. C. and 180 kg/cm.sup.2.

Test pieces 10.times.20 mm were cut off from the sheets, and heated in a Geer oven at 150.degree. C. The hours to failure were noted, and the results are shown in Table IV. ______________________________________ Hours to Example No. Spiro bisphosphite  Failure ______________________________________ Control   Bis(2,6-di-t-butyl-4- 480 methylphenyl) pentaerythritol diphosphite Example 10 Bis(2,6-di-t-butyl-4-sec- 520 butylphenyl) pentaerythritol diphosphite Example 11 Bis(2,6-di-t-butyl-4- 505 isopropylphenyl) pentaerythritol diphosphite Example 12 Bis(2,6-di-t-butyl-4-isobutyl- 500 phenyl) pentaerythritol diphosphite ______________________________________

It is apparent from the data that the spiro bisphosphites of the invention are superior to the prior art homologue of the control.

Ethylene-vinyl acetate copolymer compositions were prepared using spiro bis phosphites of the invention and of the prior art, and having the following formulation: Ingredient             Parts by Weight ______________________________________ Ethylene-vinyl acetate copolymer 100 Montan wax lubricant   0.2 Triethylene glycol bis(.beta.-(3-t-butyl- 0.05 4-hydroxy-5-methylphenyl) propionate) Phosphite shown in Table V 0.1 ______________________________________

The stabilizers were blended with the polymer on a two-roll mill, and sheets 1 mm thick were prepared. Test pieces 2.5 cm square were cut off from the sheets, and heated in a Geer oven at 180.degree. C.

The time when degradation set in and the initial color (Yellowness Index) of the sheets measured by a Hunter color differential meter were noted, and the results are shown in Table V. ______________________________________ Onset of Heat Example                   Degrada- Yellowness No.    Spiro bisphosphite tion     Index ______________________________________ Control Bis(2,6-di-t-butyl-4- 95       19 methylphenyl) pentaerythritol diphosphite Example Bis(2,6-di-t-butyl-4-sec- 110      16 13     butylphenyl) pentaerythritol diphosphite Example Bis(2,6-di-t-butyl-4- 105      17 14     isopropylphenyl) pentaerythritol diphosphite Example Bis(2,6-di-t-butyl-4-isobutyl- 105      17 15     phenyl) pentaerythritol diphosphite ______________________________________

It is apparent from the data that the spiro bisphosphites of the invention are superior to the prior art homologue of the control.

Polybutylene terephthalate compositions were prepared using spiro bisphosphites of the invention and of the prior art, and having the following formulation. Ingredient           Parts by Weight ______________________________________ Polybutylene terephthalate 100 Pentaerythritol tetrakis(.beta.-(3,5-di-t- 0.2 butyl-4-hydroxyphenyl) propionate Phosphite shown in Table VI 0.2 ______________________________________

The ingredients of the compositions were thoroughly blended in a mixer, and then injection-molded to prepare test specimens.

The specimens were heated at 150.degree. C. for 300 hours, and tensile strength before and after heating was noted. The % tensile strength retained is shown in Table VI. ______________________________________ Example                     % Tensile Strength No.     Spiro bisphosphite  Retained ______________________________________ Control 1 None                65 Control 2 Bis(2,6-di-t-butyl-4- 71 methylphenyl) pentaerythritol diphosphite Example 16 Bis(2,6-di-t-butyl-4-sec- 78 butylphenyl) pentaerythritol diphosphite Example 17 Bis(2,6-di-t-butyl-4- 75 isopropylphenyl) pentaerythritol diphosphite Example 18 Bis(2,6-di-t-butyl-4- 76 isobutylphenyl) pentaerythritol diphosphite ______________________________________

It is apparent from the data that the spiro bisphosphites of the invention are superior to the prior art homologues of the controls.

Polyphenylene oxide resin compositions were prepared using spiro bisphosphites of the invention and of the prior art, and having the following formulation: Ingredient           Parts by Weight ______________________________________ Poly(2,6-dimethyl-1,4-phenyleneoxide 50 Polystyrene          47.5 Polycarbonate        2.5 TiO.sub.2            3.0 1,1,3-Tris(2-methyl-4-hydroxy-5-t- 0.1 butylphenyl) butane Phosphite shown in Table VII 0.1 ______________________________________

The ingredients of the compositions were mixed and then extruded, followed by injection-molding to prepare test pieces. The heat stability was evaluated by heating the test pieces in a Geer oven at 125.degree. C. for 100 hours. Elongation and Izod impact strength were measured before and after the heating, and the percent elongation and percent Izod impact strength retained were calculated.

The results are shown in Table VII. ______________________________________ %         % Impact Elongation Strength Example No. Spiro bisphosphite Retained  Retained ______________________________________ Control 1 Bis(2,6-di-t-butyl-4- 65        74 methylphenyl) pentaerythritol diphosphite Control 2 Bis(2,6-di-t-butyl-4- 63        71 ethylphenyl) pentaerythritol diphosphite Example 19 Bis(2,6-di-t-butyl-4-sec- 67        79 butylphenyl) pentaerythritol diphosphite Example 20 Bis(2,6-di-t-butyl-4- 66        76 isopropylphenyl) pentaerythritol diphosphite Example 21 Bis(2,6-di-t-butyl-4- 66        76 isobutylphenyl) pentaerythritol diphosphite ______________________________________

It is apparent from the data that the spiro bisphosphites of the invention are superior to the prior art homologues of the controls.

Cis-1,4-isoprene polymer (M.W. 680,000) 100 g and 0.5 g of the spiro bisphosphite shown in Table VIII were dissolved in 250 ml of isooctane, and then the isooctane was evaporated.

The polyisoprene compositions were heated in a Geer oven at 100.degree. C. for 4 hours, and the color of the compositions was observed. The inherent viscosity (in toluene) was measured before and after heating.

The results are shown in Table VIII. ______________________________________ Inherent Viscosity (.eta.) Example              Color after      After No.     Spiro bisphosphite Heating   Original Heating ______________________________________ Control Bis(2,6-di-t-butyl-4- Yellow    4.2    3.6 methylphenyl) pentaerythritol diphosphite Example 22 Bis(2,6-di-t-butyl-4- Pale      4.5    4.0 sec-butylphenyl) Yellow pentaerythritol diphoshite Example 23 Bis(2,6-di-t-butyl-4- Pale      4.4    3.9 isopropylphenyl) Yellow pentaerythritol diphosphite Example 24 Bis(2,,6-di-t-butyl-4- Pale      4.4    3.9 isobutylphenyl) Yellow pentaerythritol diphosphite ______________________________________

It is apparent from the data that the spiro bisphosphites of the invention are superior to the prior art homologue of the control.

Polycarbonate resin compositions were prepared having the following formulation: Ingredient            Parts by Weight ______________________________________ Polycarbonate         100 Spiro bisphosphite shown in Table IX 0.15 ______________________________________

the ingredients were mixed and compression-molded at 260.degree. C. to prepare sheets 1 mm thick. Heat stability was evaluated by heating the sheets in a Geer oven at 230.degree. C. for 45 minutes, and then observing the color of sheets.

The results are shown in Table IX. ______________________________________ Example No. Spiro bisphosphite Color of Sheets ______________________________________ Control 1 None              Yellowish Brown Control 2 Bis(2,6-di-t-butyl-4- Yellow methylphenyl) pentaerythritol diphosphite Example 25 Bis(2,6-di-t-butyl-4- Pale Yellow sec-butylphenyl) pentaerythritol diphosphite Example 26 Bis(2,6-di-t-butyl-4- Pale Yellow isopropylphenyl) pentaerythritol diphosphite Example 27 Bis(2,6-di-t-butyl-4- Pale Yellow isobutylphenyl) pentaerythritol diphosphite ______________________________________

It is apparent from the data that the spiro bisphosphites of the invention are superior to the prior art homologues of the controls.

Acrylonitrile-butadiene-styrene terpolymer resin compositions were prepared using spiro bisphosphites of the invention and of the prior art, and having the following formulation: Ingredient           Parts by Weight ______________________________________ Acrylonitrile-butadiene-styrene 100 terpolymer Calcium stearate     1.0 Tris(3,5-di-t-butyl-4-hydroxybenzyl) 0.2 isocyanurate Phosphite shown in Table X 0.1 ______________________________________

The ingredients were thoroughly mixed and the compositions then extruded at 200.degree. C. to prepare pellets. Test pieces were then molded by injection molding at 230.degree. C.

The test pieces were heated at 135.degree. C. in a Geer oven for 30 hours. The whiteness index of the pieces after heating was determined by a Hunter color difference meter. The Izod impact strength (kg.cm/cm) before and after heating was also measured.

The results are shown in Table X Izod White- impact strength Example                 ness    Origin- After No.    Spiro bisphosphite Index   al    Heating ______________________________________ Control Bis(2,6-di-t-butyl-4- 36.2    18.1  16.5 1      methylphenyl) pentaerythritol diphosphite Control Bis(2,6-di-t-butyl-4- 34.8    17.8  15.9 2      ethylphenyl) pentaerythritol diphosphite Example Bis(2,6-di-t-butyl-4- 38.7    18.7  17.5 28     sec-butylphenyl) pentaerythritol diphosphite Example Bis(2,6-di-t-butyl-4- 37.5    18.5  17.2 29     isopropylphenyl) pentaerythritol diphosphite Example Bis(2,6-di-t-butyl-4- 37.4    18.5  17.2 30     isobutylphenyl) pentaerythritol diphosphite ______________________________________

It is apparent from the data that the spiro bisphosphites of the invention are superior to the prior art homologues of the controls.

## Claims

inventive and patentable embodiments thereof:

1. Bis(2,6-di-tert-butyl-4-branched propyl or butyl phenyl)-pentaerythritol spiro phosphites having the formula: ##STR11## wherein both R's are selected from the group consisting of isopropyl, iso-butyl, and sec-butyl.

2. Bis(2,6-di-tert-butyl-4-branched propyl or butyl phenyl)-pentaerythritol spiro phosphites according to claim 1 wherein R is isopropyl.

3. Bis(2,6-di-tert-butyl-4-branched propyl or butyl phenyl)-pentaerythritol spiro phosphites according to claim 1 where R is isobutyl.

4. Bis(2,6-di-tert-butyl-4-branched propyl or butyl phenyl)-pentaerythritol spiro phosphites according to claim 1 wherein R is sec-butyl.

5. A polyvinyl chloride resin composition having improved resistance to deterioration upon exposure to heat and light comprising a polyvinyl chloride resin formed at least in part of the recurring group: ##STR12## and having a chlorine content in excess of 40%, where X is either hydrogen or chlorine; and a phosphite in accordance with claim 1.

6. A polyvinyl chloride resin composition in accordance with claim 5 in which the polyvinyl chloride resin is polyvinyl chloride homopolymer.

7. A polyvinyl chloride resin composition in accordance with claim 5 in which the polyvinyl chloride resin is a copolymer of vinyl chloride and vinyl acetate.

8. An olefin polymer composition having improved resistance to deterioration upon exposure to heat and light comprising an olefin polymer selected from the group consisting of polymers of alpha-olefins having from two to six carbon atoms and polystyrene, and a phosphite in accordance with claim 1.

9. An olefin polymer composition in accordance with claim 8 wherein the polyolefin is polypropylene.

10. An olefin polymer composition in accordance with claim 8 wherein the polyolefin is polyethylene.

11. An olefin polymer composition in accordance with claim 8 wherein the polyolefin is ethylene-propylene copolymer.

12. An olefin polymer composition in accordance with claim 8 wherein the polyolefin is cis-1,4-isoprene polymer.

13. An ethylene-vinyl acetate copolymer composition having improved resistance to deterioration upon exposure to heat and light comprising an ethylene-vinyl acetate copolymer and phosphite in accordance with claim 1.

14. An acrylonitrile-butadiene-styrene copolymer composition having improved resistance to deterioration upon exposure to heat and light comprising an acrylonitrile-butadiene-styrene copolymer and a phosphite in accordance with claim 1.

15. A polyester resin composition having improved resistance to deterioration upon exposure to heat and light comprising a polyester and a phosphite in accordance with claim 1.

16. A polyester resin composition according to claim 15 in which the polyester is polybutylene terephthalate.

17. A polycarbonate resin composition having improved resistance to deterioration upon exposure to heat and light comprising a poly carbonate and a phosphite in accordance with claim 1.