COMBINATION OF PHENOLIC OXAMIDE AND PHOSPHITE STABILIZERS FOR ORGANIC MATERIALS

Abstract: A stabilizing composition for organic materials (e.g., polypropylene resin) comprising a mixture of a phenolic oxamide of the formula with tris (2,4-di-t-butylphenyl)phosphite, distearyl pen­ taerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl)-4,4′-­ biphenylene diphosphonite, tris(nonylphenyl) phosphite, bis(2,4-di-t-butyl)pentaerythritol diphosphite, or triphenyl phosphite.

Description: COMBINATION OF PHENOLIC OXAMIDE AND PHOSPHlTE STABILIZERS FOR ORGANIC MATERIALS This application is a continuation-in-part of copending application Serial No. 188,190 filed Sept. 18, 1980. This invention relates to a combination of stabilizers for organic materials. More particularly the invention relates to a stabilizing composition comprising (A) a phenolic oxamide compound having the structural formula EMI1.1 wherein R1 is alkyl (linear or branched, primary, secondary or tertiary) having 1 to 8 carbon atoms, R2 is hydrogen or alkyl having 1 to 8 carbon atoms, and X is alkylene having 1 to 12 carbon atoms, and (B) a phosphite compound selected from the group consisting of tris (2, 4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetrakis (2, 4-di -t-butylphenyl) -4 ,41-biphenylene diphosphonite, tris (nonylphenyl) phosphite, bis(2,4-di-t-butyl) pentaerythritol diphosphite and triphenyl phosphite. The stabilization of organic materials, especially polymers, normally subiect to deterioration over a period of time by exposure to such adverse influences as air and elevated temperature, by the addition of various stabilizers such as certain phenolic oxamides or phosphites has previously been known, but it has been desired to provide more satisfactory protection in an economical and convenient manner. Typical prior stabilization practices are il]ustrated in such U.S. patents as 4,145,556, Hirsch et al, Mar. 20, 1979; 4,154,723, Hirsch et al, May 15, 1979; and 4,187,212, Zinka et al, Feb. 5, 1980. The present invention is based on the surprising discovery that a remarkably high level of protection is achieved by employing a combination of the above-defined phenolic oxamide compound (A) and phosphite compound (B) as the stabilizer system. The phenolic oxamide compounds (A) employed in the combination ol the invention are described in detail in U. S. patent 4,145,556, the disclosure of which is hereby incorporated herein by reference, particularly the working examples therein which illustrate a varies'; of phenolic oxamides which may be used in the present invention. The ratio of phenolic oxamide compound (A) to phosphite compound (B) employed in the mixed stabilizer composition of the inver.uull may vary widely, for example from 1:9 to 9:1, preferably from. 2:8 to 8:2, and more preferably from 4:6 to 6:4, by weight. To stabilize an organic material in accordance with the invention the material'is mixed, by any suitable cbnventional means, with at least one of the phenolic oxamide compounds (A) and at least one of the described phosphite compounds (B), separately or together, in a stabilizingly effective amount. Remarkably small quantities of the mixed stabilizer composition of the invention are effective, e.g., from 0.(':S% or less to 5% or more, preferably from 0.05 to 1%, more preferably from 0.1 to 0.5%, based on the weight of the material to be stabilized. The optimum amount in any given case will depend on surb variables as the degree of stabilization desired, the particular material being stabilized, etc., and is readily determinable with the aid of standard tests for evaluating stabilizers in various materials. If desired, the stabilizer composition of the invention can be employed in combination with other stabilizers, e.g. dilau'ryl or distearyl beta-thiodipropionate, antiozonants, thermal stabilizers, ultraviolet light absorbers and/or with coloring materials, dyes, pigments, metal chelating agents, etc. The organic materials which can be stabilized in accordance with this invention by admixing with phenclic oxamide (A) and phosphite (B), include polyolefins which can be homopolyrners of unsubstituted olefinic hydrocarbons such as, e.g. ethylne, propylene, 1-butylene, 1,3-butadjene and styrene, hornopo])rmers of sub stituted olefinic hydrocarbons such as, e.g. vinyl halides such as vinyl chloride and esters such as acetate, vinyl alcohols, acrylonitrile and methacrylonitrile, or copolymers of two or more of such substituted and/or unsubstituted olefinic hydrocarbons. Also included are condensation polymers such as, e.g. polyalkylene oxides, polyurethanes, polycarbonates, polyesters such as polyethylene terephthalates and polyamides such as polyhexamethylene adipamide and polycaprolactam. Other organic materials which can be stabilized by this invention include lubricating oils, e.g. of the aliphatic ester type such as di(2-ethylhexyl)azelate and pentaerythritol tetracaprolate, animal and vegetable derived oils such as linsef µ oil, fat, tallow, lard, peanut oil, cod liver oil, castor oil, palm , corn oil and cottonseed oil, fatty acids such as soaps, and other hydrocarbon materials such as gasoline, mineral oil, fuel oil, drying oil, cutting fluids and waxes. It is possible with the stabilizer mixture according to the invention to stabilize, for example, the following polyolefins: 1. polymers that are derived from singly unsaturated hydrocarbons, such as polyolefins, e.g. polyethylene of low dild high density, which can optionally be crosslinked, poly pylene, polyisobutylene, polymethylbutene-1 and poly mthylpentene-1; 2. mixtures of the homopolymers mentioned under 1, such as mixtures of polypropylene and polyethylene, polypro pylene and po]ybutene-1, polypropylene and polyisobutylene; ; 3. copolymers of the monomers on which the homopoly mers mentioned under 1 are based, such as ethylene/propylene copolymers, propylene/butene-1 copolymers, propylene/ iso butylene copolymers, ethylene/butene-1 copolymers, as well as terpolymers of ethylene and propylene with a diene, such as hexadiene, di-cyclopentadiene or ethylidenenorbornene. The following examples, in which all quantities are expressed by weight unless otherwise indicated, will serve to illustrate the practice of the invention in more detail. Example 1 This example illustrate the stabilization of polypropylene resin with combinations of (A) a phenolic oxamide, N,N'-bis!2-(3-!3.5-di- t-butyl-4-hydroxyphenyl ) propionyloxy)ethyl ] oxamide, identified as "BPEO" in Table I, and (B) the following phosphites (identified in Table I by the letters indicated): tris (2 , 4-di-t-butylphenyl)phosphite "TBPP" d istearylpenta erythritol diphosphite "DSPD " tetrakis(2, 4-di-t-butylphenyl)-4 ,4'-biphenylene diphos phonite "TPBD" The effectiveness of the stabilizer combinations is evaluated by observing changes in the melt flow index of the polypropylene after multiple extrusions. Control stocks containing no stabilizer (Run 1 in Table 1), or the stabilizing components individually (Runs 2, 3, 4 and 5 in Table I), are included for comparison with stocks of the invention containing both the phenolic oxamide (A) and a phosphite (B) (Runs 6, 7 and 8 in Table I). The stocks represented in Table I are prepared by dry mixing in a Hobart (trademark) mixer 100 parts of powdered unstabilized polypropylene (average molecular weight about 72,000; "Profax 6501" Itrademark) with 0.1 part of the stabilizers shown. The mixtures are extruded on a 11 < " Davis Standard (trademark) extruder equipped with three screens (60/80/100 mesh) and a 3/4" bar die (length to diameter ratio 30:1), using a single stage screw. The extrusion is conducted with the following temperature profile: feed 188 ; transition 1900, 1930; metering 1960 199 , and die 2050C, at 20 RPM. Forty gram samples are taken and re-chopped in a Wiley (trademark) size 0 mill and the melt flow index is measured according to ASTM D 1238-70, condition L, and recorded as the initial melt flow index. The remaining chopped resin after the initial pass is re-extruded 5 times at a temperature of 260"C throughout the extruder (a condition designed to bring about thermal degradation of the polypropylene, i.e., a chain scission with consequent decrease in molecular weight and increased tendency to flow), at 20 RPM. The final extrudate is chopped, 40 gram samples taken and re-chopped on a Wiley mill. The melt flow index is measured as before and recorded as the final melt flow index. The effectiveness of the stabilizers is reflected in the melt flow index; the lower melt flow index values indicate higher viscosities, i.e., less chain scission is taking place. Tab]e I shows the initial values of the melt flow index1 and the values after 5 posses through the extruder at 260do. It is manifest from the data in Table I that the stocks containing the stabilizer combinations of the invention (Runs 6, 7 and 8) are remarkably resistant to degradation. This is particularly unexpected in view of the antagoism sometimes observed between phosphites and other stabilizers. Table I Melt Flow Index of Stabilized Polypropylene Run No.: 1 2 3 4 5 6 7 8 Composition (parts) Polyprone 100 100 100 100 100 100 100 100 BPEO - .1 - - - .1 .1 .1 TBPP - - .1 - - .1 - DSPD - - - .1 - - .1 TPBD - - - - .1 - - .1 Melt Flow Index Initial 5.7 3.9 3.5 4.1 3.2 2.8 3.6 3.1 After 5 passes at 2600C 24.2 9.6 12.1 20.6 7.8 8.2 8.8 7.1 Change 18.5 5.7 8.6 16.5 4.6 5.4 5.2 4.0 Example 2 Polypropylene/antioxidant mixtures were essentially prepared according to the procedure of Example 1. The polypropylene also contained about 0.1 pph calcium stearate, and the initial melt flow '-"cx (MFI) was determined to be about 4. This example illustrates the stabilization of the polypropylene resin with combinations of phenolic oxamide, viz., N,N'-bis[2-(3-[3,5-di-t-butyl-4hydroxyphenyl] propionyloxy)ethyl]oxamide, identified as "BPEO" in Table II, and the following phosphites (identified in Table II by the letters indicated): tris(2,4-di-t-butylphenyl)phosphite "TBPP" distearylpentacrythritol diphosphite "DSPD" tetrakis(2,4-di-t-butylphenyl)-4,4'biphenylene diphosphonite "'rPBD" The effectiveness of the stabilizer combinations is evaluated by observing changes in the melt flow index of the polypropylene after multiple extrusions. Control stocks containing no stabilizer (Run 9 in Table II), or the stabilizing components individually (Runs 10, 11, 12 and 13 in Table II), are included for comparison with stocks of the invention containing both the phenolic oxamide and a phosphite (Runs 14, 15 and 16 in Table II). The various resin/antioxidant mixtures were kneaded for 30 minutes at 4000F (2040C) in a Brabender Plastograph (Trademark) at 25 RPM. Subsequently, these samples were chopped according to Example 1, and their MFI's were measured. Table II Run No.: 9 10 11 12 13 14 15 16 Composition (parts) Polypropylene 100 100 100 100 100 100 100 100 BPEO - 0.1 - - - 0.05 0.05 0.05 TBPP - - 0.1 - - 0.05 - DSPD - - - 0.1 - - 0.05 TPBD - - - - 0.1 - - 0.05 NFI (After Kneading) 20.8 8.0 9.2 8.9 5.9 5.5 4.6 5.1 The above results clearly indicate that in every instance the polypropylene containing the antioxidative mixtures exhibits considerably enhanced stability (i.e., lower MFI) over the polypropylene protected by the single antioxidants, at the same total concentration. Examnle 3 Example 2 is separated using the same phenolic oxamide (BPEO) as previously, but substituting the following phosphites: TNPP tris(nonylphenyl) phosphite (70% on silica, 30%); BBPD bis (2,4-di-t-butyl) pentaerythritol diphosphite; TPP triphenyl phosphite. The results are as shown in Table III, wherein Runs 22, 23 and 24 (containing both the oxamide and the phosphite) repre sent the invention. Runs 17-21 are for comparison only. Table III Run No.: 17 18 19 20 21 22 23 24 Composition (parts) Polypropylene 100 100 100 100 100 100 700 100 BPR0 - 0.1 - - - 0.05 0.05 0.05 TNPP(1) - - 0.1 - - 0.05 - BBPD(2) - - - 0.1 - - 0.05 BBPD(3) - - - - 0.1 - - 0.05 MFI (After Kneading) 20.8 8.0 10.9 5.0 16.2 7.2 4.2 4.8 Remarks: 1. Tris(nonylphenyl) phosphite (70% on silica, 30%). 2. Bis(2 , 4-di-t-butyl )pentaerythritol diphosphite. 3. Triphenyl phosphite. Experiments of Table III were carried out simultaneously with those of Table II; Runs 9 and 17 are one and the same experi ment, also 10 and 18. In all instances (Runs 22-23) synergistic behavior of the mixtures is clearly demonstrated over the respective antioxidants alone (Runs 18-21).

Claims: CLAIMS: 1. A stabilizing composition characterised in that it comprises (A) a phenolic oxamide compound having the structural formula EMI8.1 wherein R1 is alkyl having 1 to 8 carbon atoms, R2 is hydrogen or alkyl having 1 to 8 carbon atoms and X is alkylene having 1 to 12 carbon atoms, in admixture with (B) a phosphite compound selected from tris(2,4-di-t-butylphenyl)phosphite distearyl pentaerythritol diphosphite, tetrakis(2,4-di-t-butylphenyl)-4-4'-biphenylenedi phosphonite, tris (nonylphenyl) phosphite, bis (2, 4-di-t-butyl) pentaerythritoldiphosphite, and tri-phenyl phosphite. 2. A composition according to claim 1 characterised in that the said phenolic oxamide (A) is N,N'-bisC2-(3-E3, 5-di-t-butyl-4-hydroxyphenylj propionyloxy) -ethyl oxamide. 3. A stabilized composition characterised in that it comprises an organic material normally subject to deterioration upon aging, in admixture with a stabilizingly effective amount of a stabilizer composition as clairned in claim 1 or claim 2. 4. A composition according to claim 3 characterised in that the said organic material is polypropylene resin. 5. A method of stabilizing an organic material normally subject to deterioration upon aging characterised in that the methdd comprises mixing said material with a stabilizingly effective amount of a stabilizer composition as claimed in claim 1 or claim 2. 6. A method according to claim 5 characterized in that the said organic material is polypropylene resin.

Inventors: PAOLINO, PAULA ANN
Applicants: UNIROYAL, INC.
Application year: 1981
Main classification: C08K5
IPC codes: C09K15, C08L101, C08L23, C08K5