Thermally resistant polyolefin composition

Abstract: A thermally resistant polyolefin composition contains a phenolic compound of formula (I) wherein the R₁'s are selected from hydrogen and C₁-C₃ alkyl groups and phosphite compound in an amount of 0.1 to 15 times by weight based on the phenolic compound.

Description: The present invention relates to a polyolefin resin composition improved in stability to thermal processing. Polyolefin resins have excellent physical, chemical and electrical properties, and so are processed into molded products, pipes, sheets, films, fibers, etc. by various methods (such as blow molding, extrusion molding, injection molding, calendering, etc.) for use in many fields. It is well known that when polyolefin resins are used alone they deteriorate under the action of heat and oxygen on processing to show phenomena such as softening, embrittlement, discoloration, etc., so that their mechanical properties are too markedly lowered for practical use. For the purpose of solving this problem, it is well known to add various kinds of phenolic and phosphite etc. antioxidants during the processing of polyolefin resins. For example, methods are well known in which phenolic antioxidants such as 2,6-di-tert-butyl-4-methylphenol, 2,2'-methylenebis(4-methyl-6-tert-butyl-phenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, etc. are used alone or in combination with phosphite antioxidants such as tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)-phosphite, dipentaerythritol diphosphite, etc. These methods, however, are not yet quite satisfactory in terms of thermal and oxidation stability, thermal discoloration resistance, etc. and methods producing higher performance have been demanded. We have found that a polyolefin resin composition having high resistance to deterioration by the action of heat and oxygen during processing is obtained by blending polyolefin resins with phenolic compound of particular structure and phosphite or phosphonite compound in a particular proportion to the phenolic compound. The present invention provides polyolefin resin composition improved in stability to thermal processing containing phenolic compound of formula (I) wherein the R₁'s are selected from hydrogen and C₁-C₃ alkyl groups, and phosphite or phosphonite compound in an amount of 0.1 to 15 times by weight based on the phenolic compound. The phenolic compounds (I) used in the present invention can easily be produced by esterification of dihydric alcohols of formula (II) with propionic acid of formula (III); (wherein R₁ is as defined above) or acid halide, acid anhydride or lower alkyl ester thereof. In phenolic compound (I), the R₁'s are selected from hydrogen and methyl, ethyl, n-propyl and isopropyl groups, but a methyl group is preferred. Representative examples of the phosphorous compound used in the present invention include phosphites (IV-I) and (IV-2) : wherein R₂, R₃ and R₄ are selected independently from a hydrogen atom and C₁-C₉ alkyl groups, but R₃ and R₄ are not both branched alkyl groups: wherein the R₅'s are selected from C₈-C₁₈ alkyl and C₆-C₁₈ aryl groups ; the phosphonite compounds used are of formula (IV-3): wherein the R₆'s are selected from C₈-C₁₈ alkyl and C₆-C₁₈ aryl groups, and R₇ represents a C₆-C₁₈ alkylene or C₆-C₁₈ arylene group. Preferred phosphite compounds (IV-1) include tris(2,5-di-tert-butylphenyl)phosphite, tris(2-tert-butylphenyl)phosphite, tris[2,4-bis(1,1-dimethylpropyl)phenyl]phosphite and tris(2,4-di-tert-butylphenyl)phosphite. Preferred phosphite compounds (IV-2) include dilauryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis(2,5-di-tert-butylphenyl)pentaerythritol diphosphite and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite. Preferred phosphonite compounds (IV-3) include tetrastearyl-4,4'-biphenylene diphosphonite and tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite. The present invention involves a blend of polyolefin resin with the foregoing phenolic and phosphite or phosphonite compounds, and the ratio of the latter is 1 to 0.1-15 by weight, preferably 1 to 0.5-10 by weight, more preferably 1 to 1-5 by weight. The total amount of phenolic and phosphite or phosphonite compound used is usually not less than 0.01 wt.% based on the polyolefin resin, preferably 0.1 to 10 wt.%. Amounts exceeding 10 wt.% may be blended, but this is economically disadvantageous because correspondingly increased effects are not readily obtained. The polyolefin resin composition of the present invention may contain other additives such as ultraviolet absorbers, light stabilizers, antioxidants, metal deactivators, metal soaps, nucleating agents, lubricants, antistatic agents, flame retardants, pigments, fillers, etc. Polyolefin resins stabilized by the present invention include poly-α-olefins such as low-density polyethylene, medium- to high-density polyethylene, linear low-density polyethylene, polypropylene, polybutene-1, etc.,poly-α-olefin copolymers such as propylene/ethylene random or block copolymers, ethylene/butene-1 random copolymers, etc., copolymers of poly-α-olefin with vinyl monomer such as maleic anhydride-modified polypropylene, etc., and mixtures thereof. Further, there are given blends of the polyolefin resins with rubbers such as isoprene rubber (IR), butyl rubber (IIR), nitrile rubber (NBR), styrene/butadiene copolymeric rubber (SBR), ethylene/propylene rubber (EPM, EPDM), etc. Particularly, the present invention is effective to stabilize polypropylene. The present invention is illustrated in detail by the following Examples, but it is not limited to these Examples. Preparation Example 1 To a mixture of 30.2 g (0.121 mole) of methyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate and 15.3 g (0.0503 mole) of 3,9-bis (2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5 . 5]undecane was added 0.82 g (0.015 mole) of sodium methoxide. The mixture was heated and reacted at a temperature of 140°C for 3 hours and then at a temperature of from 140° to 160°C for 7 hours under a reduced pressure of 50 mmHg. After completion of the reaction, the reaction mass was dissolved in toluene and washed with aqueous dilute hydrochloric acid and then with water. Toluene was then removed under reduced pressure to obtain 42.9 g of a crude product of 77% in purity. This crude product was purified by column chromatography on silica gel to obtain 24 g of colorless and glassy 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[ 5 . 5]undecane having a purity of 99% (Compound I-1). m.p., 45-55°C. Preparation Example 2 A mixture of 33.6 g (0.121 mole) of methyl 3-(3-tert-butyl-4-hydroxy-5-isopropylphenyl)propionate, 15.3 g (0.0503 mole) of 3,9-bis (2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5 . 5]undecane and 0.82 g (0.015 mole) of sodium methoxide was reacted, after-treated and purified in the same manner as in Preparation Example 1, to obtain 29 g of colorless and glassy 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-isopropylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[ 5 . 5]undecane having a purity of 98% (compound I-2). m.p., 47-57°C. Preparation Example 3 A mixture of 35.3 g (0.121 mole) of methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 15.3 g (0. 0503 mole) of 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5 . 5]undecane and 0.82 g (0.015 mole) of sodium methoxide was reacted, after-treated and purified in the same manner as in Preparation Example 1, to obtain 21 g of white crystalline 3,9-bis{2-[3-(3,5-di-tertbutyl-4-hydroxyphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5 . 5]-undecane having a purity of 99% (compound AO-1). m.p., 98-100°C. Example 1 The blend described below was dry-blended and extruded five times running on a small extruder [screw diameter (D), 30 mm; L/D=22] under the following conditions. Pellets after 1st, 3rd and 5th extrusions were measured for melt index to evaluate processing stability. The results are shown in Table 1. Measurement conditions for melt index : According to JIS K 7210 Temperature 230°C Load 2,160 g Extrusion conditions: Rate of rotation 50 rpm Temperature C₁ C₂ D 190°C 220°C 210°C Compounding : Part by weight Unstabilized polypropylene resin 100 Calcium stearate 0.05 Test compound described in Table 1 In Tables 1 and 2, the test compound symbols other than those identified above represent compounds as follows : AO-2 : Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate] AO-3 : n-Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate AO-4 : Tris(2,4-di-tert-butylphenyl)phosphite AO-5 : Distearyl pentaerythritol diphosphite AO-6 : Bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite AO-7 : Tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene disphosphonite. Example 2 The procedure of Example 1 was repeated except that the extrusion conditions were changed as follows, to evaluate the processing stability. The results are shown in Table 2. Extrusion conditions: Rate of rotation 30 rpm Temperature C₁ C₂ D 220°C 250°C 240°C Example No. Phenolic compound Phosphorous compound Melt index after repetition of extrusion Kind Part by weight Kind Part by weight 1st 3rd 5th Present invention 1 I-1 0.025 AO-4 0.075 6.6 18.5 35.5 2 " " AO-5 " 6.7 19.6 37.3 3 " " AO-6 " 5.9 13.0 27.8 4 " " AO-7 " 6.5 18.3 35.4 5 I-2 " AO-4 " 6.9 18.9 35.8 6 " " AO-5 " 7.1 20.7 40.0 7 " " AO-6 " 6.1 13.3 28.0 8 " " AO-7 " 6.8 18.6 35.7 Comparative 9 AO-1 0.025 AO-4 0.075 9.6 29.2 55.6 10 " " AO-5 " 10.4 31.3 57.7 11 " " AO-6 " 9.3 28.2 51.0 12 " " AO-7 " 9.5 28.7 53.2 13 AO-2 " AO-4 " 9.3 28.2 51.3 14 " " AO-5 " 10.0 30.8 55.7 15 " " AO-6 " 8.9 27.3 49.3 16 " " AO-7 " 9.2 28.0 50.9 17 AO-3 " AO-4 " 9.8 31.0 59.1 18 " " AO-5 " 10.6 32.8 61.0 19 AO-3 " AO-6 " 9.5 30.1 54.2 20 " " AO-7 " 9.7 30.5 56.2 21 - - - - 23.1 75.2 -

Claims: A polyolefin resin composition containing phenolic compound of formula (I) wherein the R₁'s are selected from hydrogen and C₁-C₃ alkyl groups, and phosphite or phosphonite compound in an amount of 0.1 to 15 times by weight based on the phenolic compound, said phosphonite compound being of general formula (IV-3): wherein the R₆'s are selected from C₈-C₁₈ alkyl and C₆-C₁₈ aryl groups and R₇ represents a C₆-C₁₈ alkylene or C₆-C₁₈ arylene group. A composition according to clam 1 wherein R₁ is methyl. A composition according to claim 1 or 2 containing phosphite compound of formula (IV-1) : wherein R₂, R₃ and R₄ are selected independely from hydrogen atom and C₁-C₉ alkyl groups but R₃ and R₄ are not both branched alkyl groups. A composition according to claim 3 containing phosphite compound selected from tris(2,5-di-tert-butylphenyl)phosphite, tris(2-tert-butylphenyl)phosphite, tris[2,4-bis(1,1-dimethylpropyl)-phenyl]phosphite and tris(2,4-di-tert-butylphenyl)phosphite. A composition according to any preceding claim containing phosphite compound of formula (IV-2) : wherein the R₅'s are selected from C₈-C₁₈ alkyl and C₆-C₁₈ aryl groups. A composition according to claim 5 containing phosphite compound selected from dilauryl pentaearythritol diphosphite, distearyl pentaerythritol diphosphite, bis(2,5-di-tert-butylphenyl)pentaerythritol diphosphite and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite. A composition according to any preceding claim containing phosphonite compound selected from tetrastearyl-4,4'-biphenylene diphosphonite and tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite A composition according to any preceding claim wherein the total amount of phenolic and phosphite or phosphonite compound is at least 0.01% by weight based on the polyolefin resin.

Inventors: EBINA CHINEHITO, ISHII TAMAKI, OKITA TAISUKE, SASAKI MANJI, YACHIGO SHINICHI, EBINA, CHINEHITO, ISHII, TAMAKI, OKITA, TAISUKE, SASAKI, MANJI, YACHIGO, SHINICHI
Applicants: SUMITOMO CHEM IND, SUMITOMO CHEMICAL INDUSTRIES LTD.
Application year: 1986
Main classification: C08K5
IPC codes: C08K5, C08L23