JPH0781040B2 - Method for producing modified polyolefin - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a modified polyolefin. More specifically, a hindered amine-based compound (hereinafter referred to as compound A) that does not have a specific amount of phenolic hydroxyl group in polyolefin containing 5 ppm or more of titanium content of catalyst residue or 0.5 ppm or more of vanadium content, phosphorus-based antioxidant, radical generation Mixing agents and modifiers, temperature 150 ℃ ~ 300 ℃
The present invention relates to a method for producing a modified polyolefin, which comprises melt-kneading with.

[Conventional technology]

Generally, since polyolefin is relatively inexpensive and has excellent mechanical properties, it is used for producing various molded products such as injection molded products, hollow molded products, films, sheets and fibers. However, the polyolefin is molded and processed at a temperature higher than the melting point of the polyolefin, but is subjected to oxidative deterioration due to heat during melt kneading at that time, resulting in deterioration of processability and mechanical strength due to cleavage of the molecular chain of the polyolefin or cross-linking. Causes deterioration of processability and coloring and odor problems due to oxidative deterioration. In particular, a propylene-based polymer has a tertiary carbon that is easily oxidized in the polymer, and thus is easily subjected to thermal oxidative deterioration due to melt-kneading during molding and also has a thermal stability during practical use. Also has a problem. For this reason, conventionally, a low molecular weight phenolic antioxidant such as 2,6-di-t-butyl-p-cresol (BHT) has been used in practical use to prevent thermal oxidative deterioration during melt-kneading. High molecular weight phenolic antioxidants are widely used to impart the thermal stability of

However, when the polyolefin blended with the above-mentioned phenolic antioxidant is melt-kneaded, the phenolic antioxidant used is oxidized by the complex compound of titanium or vanadium, which is the catalyst residue in the polyolefin, at the time of melt-kneading to form a quinone compound. However, when the obtained polyolefin is colored, a problem occurs. In the process of studying the coloring property of a polyolefin containing a large amount of titanium or vanadium as a catalyst residue, the present inventors have found that the phenol-based antioxidants described above are added to the polyolefin containing a large amount of titanium or vanadium in the catalyst residue. Even if the agent is blended and melt-kneaded, coloring that does not pose a problem in practice does not occur, but the polyolefin blended with such a phenolic antioxidant is melt-blended in the presence of a radical generator using a modifier. It was found that the modified polyolefin obtained when treated and modified was markedly colored, and the polyol was first mixed with a polyol or a partial ester of a polyol and a fatty acid and a phenolic antioxidant, and the presence of a radical generator using the modifier. Method for producing modified polyolefin by melt-kneading underneath (Japanese Patent Application No. 61
No. 157316) was proposed.

Further, the polyolefin is a metal due to the non-polarity of the polyolefin, adhesion with a polar resin and printing, coating, hot stamping, because it is difficult to be plated, such introduction of a polar group to the polyolefin for the purpose of improving these defects,
In particular, a method of modifying a polyolefin by melt-kneading in the presence of a radical generator using a modifier composed of an unsaturated carboxylic acid or its derivative is well known.

[Problems to be solved by the invention]

The present inventors have not been satisfied with the method for producing a modified polyolefin previously proposed in Japanese Patent Application No. 61-157316,
A more intensive study was conducted on a method for obtaining a modified polyolefin containing no titanium or vanadium as a catalyst residue and having no coloring even when melt-kneaded with a modifier in the presence of a radical generator. As a result, a specific amount of hindered amine-based compound (hereinafter referred to as compound A) having no phenolic hydroxyl group in the polyolefin containing 5 ppm or more of titanium content or 0.5 ppm or more of vanadium content of the catalyst residue, phosphorus-based antioxidant, When a radical kneading agent and a modifier are mixed and melt-kneaded,
It was found that a modified polyolefin which is free from coloration and has a practically satisfactory thermal oxidative deterioration-preventing property during melt-kneading and thermal stability during practical use can be obtained, and the present invention was completed based on this finding.

As is clear from the above description, the object of the present invention is to obtain a catalyst residue having a titanium content of 5 ppm or more or a vanadium content of 0.5 ppm.
Compound A, a phosphorus-based antioxidant, a radical generator and a modifier are added to the above-mentioned polyolefin and the mixture is melt-kneaded to provide a method for producing a modified polyolefin without coloring.

[Means for solving problems]

 The present invention has the following configurations.

Titanium content of catalyst residue is 5 ppm or more or vanadium content is 0.
For 100 parts by weight of polyolefin containing 5 ppm or more,
0.05 to 5 parts by weight of a hindered amine compound having no phenolic hydroxyl group (hereinafter referred to as compound part A), 0.01 to 1 part by weight of a phosphorus antioxidant, and a radical generator
0.001 to 0.5 parts by weight, 0.01 to 5 parts by weight of a modifier consisting of an unsaturated carboxylic acid or its derivative, and blended at 150 to 300 ° C.
1. A method for producing a modified polyolefin, which comprises melt-kneading with.

The polyolefin used in the production method of the present invention contains titanium residue of the catalyst residue of 5 ppm or more or vanadium content of 0.5 ppm or more, for example, solution polymerization method using a saturated hydrocarbon solvent, bulk polymerization method, gas phase It is a polyolefin obtained by a polymerization method or a polymerization method combining a bulk polymerization method and a gas phase polymerization method. In the production method of the present invention, there is no problem even if a polyolefin having a titanium content of less than 5 ppm or a vanadium content of less than 0.5 ppm in the catalyst residue is used. The polyolefin used in the present invention is a polyolefin containing 5 ppm or more of titanium content or 0.5 ppm or more of vanadium content of the catalyst residue, and ethylene, propylene, butene-1, pentene-
Homopolymers of α-olefin such as 1,4-methyl-pentene-1, hexene-1, and octene-1, crystalline or amorphous random copolymers of these two or more α-olefins, or crystalline blocks Copolymer, amorphous ethylene-propylene-non-conjugated diene terpolymer, α
-Copolymers of olefin and vinyl acetate, acrylic acid ester or the like, or saponified products of the copolymers, copolymers of these α-olefins and unsaturated carboxylic acids or their anhydrides, the copolymers and metal ion compounds The reaction product with and the like can be exemplified, and not only these polyolefins can be used alone, but also two or more kinds of polyolefins can be mixed and used. Further, the above-mentioned polyolefin and various synthetic rubbers (for example, polybutadiene, polyisoprene, chlorinated polyethylene, chlorinated polypropylene, styrene-butadiene rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene). -Ethylene-Butylene-
Styrene block copolymer, styrene-propylene-butylene-styrene block copolymer, etc.) or thermoplastic synthetic resin (for example, polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, poly Butylene terephthalate, polyvinyl chloride, etc.) can also be used. Propylene homopolymer, crystalline or amorphous ethylene-propylene random copolymer, crystalline ethylene-propylene block copolymer, crystalline propylene-butene-1 random copolymer, crystalline ethylene-propylene-butene-1. Terpolymer, crystalline propylene-hexene-butene-1
A terpolymer and a mixture of two or more thereof, wherein the titanium content of the catalyst residue is 5 ppm or more or the vanadium content is 0.5 p
A propylene-based polymer containing pm or more is particularly preferably used.

The compound A used in the present invention includes 4-hydroxy-2,2,6,6-tetramethylpiperidine and 1-allyl-4.
-Hydroxy-2,2,6,6-tetramethylpiperidine, 1
-Benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1- (4-t-butyl-2-butenyl)-
4-hydroxy-2,2,6,6-tetramethylpiperidine,
4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine, 1-benzyl-2,2,6,6-tetramethyl -4-piperidyl maleate, bis (2,2,6,6
Tetramethyl-4-piperidyl) adipate, bis (2,
2,6,6-tetramethyl-4-piperidyl) sebacate,
Bis (2,2,6,6-tetramethyl-4-piperidyl) fumarate, bis (1,2,3,6-tetramethyl-2,6-diethyl-4-piperidyl) sebacate, bis (1-allyl- 2,
2,6,6-tetramethyl-4-piperidyl) phthalate,
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1-propargyl-4-β-cyanoethyloxy-2,2,6,6-tetramethylpiperidine, 1-acetyl-2,2 , 6,6-Tetramethyl-4-piperidyl-acetate, trimellitic acid-tri- (2,2,6,6-tetramethyl-4-piperidyl) ester, 1-acryloyl-4-
Benzyloxy-2,2,6,6-tetramethylpiperidine,
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) dibutylmalonate, bis (1,2,2,6,6-pentamethyl-
4-piperidyl) dibenzyl-malonate, bis (1,2,
3,6-Tetramethyl-2,6-diethyl-4-piperidyl)
Dibenzyl-malonate, hexane-1 ', 6'-bis-
4-carbamoyloxy-1-n-butyl-2,2,6,6-
Tetramethylpiperidine), toluene-2 ', 4'-bis- (4-carbamoyloxy-1-n-butyl-2,2,6,
6-tetramethylpiperidine), dimethyl-bis (2,2,
6,6-Tetramethylpiperidine-4-oxy) -silane, phenyl-tris- (2,2,6,6-tetramethylpiperidine-4-oxy) -silane, tris- (1-propyl-2,2,2 6,6-Tetramethyl-4-piperidyl) -phosphite, tris- (1-propyl-2,2,6,6-tetramethyl-4-piperidyl) -phosphate, phenyl- [bis- (1,2,2 , 6,6-Pentamethyl-4-piperidyl)]-phosphonate, tetrakis (2,2,6,6-
Tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate , Di (tridecyl) bis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, di (tridecyl) bis (1,2,2,6 ,
6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 2,2,4,4-tetramethyl-7-
Oxa-3,20-diazadisspiro [5,1,11,2] heneicosan-21-one, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl- 4-Piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,4,
8,10-Tetraoxaspiro [5,5] undecane, 3,9-bis [1,1-dimethyl-2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) butyl Carbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, dimethylsuccinate-2-
(4-Hydroxy-2,2,6,6-tetramethylpiperidyl) ethanol condensate, poly [hexamethylene [(2,2,
6,6-Tetramethyl-4-piperidyl) imino]], poly [ethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetra Methyl-4-piperidyl) imino]], poly [[6-
[(1,1,3,3-Tetramethylbutyl) amino] -1,3,5-
Triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,
6-Tetramethyl-4-piperidyl) imino]], poly [[6-morpholino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl ) Imino] hexamethylene [(2,2,6,6-tetramethyl-4
-Piperidyl) imino]], poly [[6-[(ethylacetyl) amino] -1,3,5-triazine-2,4-diyl]
[(2,2,6,6-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-
Piperidyl) imino]] and poly [[6-[(2,2,6,
6-Tetramethyl-4-piperidyl) butylamino]-
1,3,5-Triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexa-tylene [(2,2,6,6-tetramethyl-4-piperidyl ) Imino]]. Especially tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2- {tris (1, 2,2,6,6-Pentamethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,
4,8,10-Tetraoxaspiro [5,5] undecane, poly [[6-[(1,1,3,3-tetramethylbutyl) amino]
-1,3,5-Triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexathylene [(2,2,6,6-tetramethyl-4- Piperidyl) imino]], poly [[6-morpholino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [( 2,2,6,6-Tetramethyl-4-piperidyl) imino]] and mixtures of two or more thereof are preferred. Examples of phosphorus antioxidants include distearyl-pentaerythritol-diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,
4'-biphenylene-di-phosphononite, bis (2,4
-Di-t-butylphenyl) -pentaerythritol-
Diphosphite, bis (2,6-di-t-butyl-4-
Methylphenyl) -pentaerythritol-diphosphite, bis (2,6-di-t-butyl-4-n-octadecyloxycarbonylethyl-phenyl) -pentaerythritol-diphosphite, tris (2,4-di-
t-Butylphenyl) phosphite and these 2
The above mixture can be illustrated. The compounding ratio of the compound A is
The amount is 0.05 to 5 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of polyolefin. When the amount is less than 0.05 parts by weight, the thermal stability of the modified polyolefin is not sufficient for practical use, and it may be more than 5 parts by weight, but further improvement in thermal stability during practical use can be expected. Not only impractical but also uneconomical. The compounding ratio of the phosphorus-based antioxidant is 0.01 to 1 with respect to 100 parts by weight of polyolefin.
Parts by weight, preferably 0.05 to 0.5 parts by weight. If the amount is less than 0.01 parts by weight, the effect of preventing the thermal oxidative deterioration during melt-kneading of the modified polyolefin is not sufficiently exerted, and if it exceeds 1 part by weight, the effect of further preventing the thermal oxidative deterioration is improved. Not only is it unpredictable and impractical, it is also uneconomical.

As the radical generator used in the present invention, the decomposition temperature is preferably not too low to obtain a uniform composition, and the temperature for obtaining a half-life of 10 hours is 70 ° C or higher, preferably 100 ° C or higher. Benzoyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl peroxyisopropyl carbonate, 2,5-di-methyl-2,5-di- (benzoylperoxy) hexane, 2, 5-di-methyl-2,5-di- (benzoylperoxy) hexyne-3, t-butyl-di-peradipate, t-butylperoxy-3,5,5-trimethylhexanoate, methyl-ethyl Ketone peroxide, cyclohexanone peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,5-di-methyl-2,5-di- (t-butylperoxide) Xy) Hexane, 2,5-di-methyl-2,5-di- (t-butylperoxy) hexyne-3,1,3-bis- (t-butylperoxyisopropyl) benzene, t-butylquiumyl Peroxide, 1,1-bis- (t-butylperoxy) -3,
3,5-Trimethylcyclohexane, 1,1-bis- (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, p-menthane hydroperoxide, di-isopropylbenzene hydroperoxide , Quinene hydroperoxide, t-butyl hydroperoxide, p-cymene hydroperoxide, 1,1,3,3-tetra-methylbutyl hydroperoxide or 2,5-di-methyl-2,5-di Examples thereof include organic peroxides such as-(hydroperoxy) hexane. Particularly 2,5-di-methyl-2,5-di- (t-butylperoxy) hexane, 2,5-di-methyl-2,5-di-
(T-Butylperoxy) hexyne-3 or 1,3-bis (t-butylperoxyisopropyl) benzene are preferred. The mixing ratio of the radical generator is usually 0.001 to 0.5 part by weight, preferably 0.01 to 0.2 part by weight, based on 100 parts by weight of polyolefin. The melt-kneading treatment is carried out at a temperature of 150 ° C to 300 ° C, preferably 180 ° C to 270 ° C, using various melt-kneading devices described later. Melt kneading temperature
If the temperature is lower than 150 ° C, sufficient modification is not carried out, and if the temperature exceeds 300 ° C, deterioration of the polyolefin by thermooxidation is promoted and the coloring of the polyolefin becomes remarkable, which is not preferable.

Specific examples of the modifier (hereinafter, simply referred to as a modifier) composed of an unsaturated carboxylic acid or a derivative thereof used in the present invention are as follows. As the unsaturated carboxylic acid, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, nadic acid, (trade name; endocis-bicyclo [2,2,1] hept- 5-ene-2,3-dicarboxylic acid) methyl nadic acid (trade name; methyl-endocis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid), hymic acid, angelic acid, tetrahydro Examples thereof include phthalic acid, sorbic acid and mesaconic acid. Derivatives of unsaturated carboxylic acids include acid anhydrides, esters, amides, imides, acid halides, metal salts, and the like, and maleic anhydride, itaconic anhydride, citraconic anhydride, nadicuccinic anhydride, methylnadicuccinic anhydride, and hymic acid anhydride. , Methyl acrylate, methyl methacrylate, ethyl acrylate,
Ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, maleic acid monoethyl ester, maleic acid diethyl ester , Fumaric acid monomethyl ester, fumaric acid dimethyl ester, itaconic acid monomethyl ester, itaconic acid dimethyl ester, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N, N- Diethyl amide, maleic acid-N-monobutylamide, maleic acid-N, N-dibutylamide,
Fumaric acid monoamide, fumaric acid diamide, fumaric acid-N
-Monoethylamide, fumaric acid-N, N-diethylamide, fumaric acid-N-monobutylamide, fumaric acid-N, N
Examples thereof include dibutylamide, maleimide, N-butylmaleimide, N-phenylmaleimide, maleoyl chloride, sodium acrylate, sodium methacrylate, potassium acrylate and potassium methacrylate. Maleic anhydride is particularly preferable. The blending ratio of the modifier is
Usually, it is 0.01 to 5 parts by weight, preferably 0.05 to 2 parts by weight, based on 100 parts by weight of polyolefin. If the amount is less than 0.01 parts by weight, the effect of improving the adhesiveness of the modified polyolefin is not sufficiently exerted, and if it exceeds 5 parts by weight, the degree of improvement of the adhesiveness is small and the residual amount in the modified polyolefin does not remain. The amount of the modifier for the reaction increases, which causes the defects such as deterioration of the hue of the obtained molded product and generation of bubbles.

In the production method of the present invention, various additives such as thioether-based antioxidants and light stabilizers which are usually added to polyolefin in a polyolefin containing 5 ppm or more of titanium content or 0.5 ppm of vanadium content of the catalyst residue to be used. ,
Clarifying agents, nucleating agents, lubricants, antistatic agents, antifogging agents, antiblocking agents, non-dripping agents, pigments, heavy metal deactivators (copper damage inhibitors), dispersants such as metal soaps, or Neutralizer,
Inorganic fillers (eg talc, mica, clay, wollastonite, zeolite, asbestos, calcium carbonate,
Aluminum hydroxide, magnesium hydroxide, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide, zinc sulfide, barium sulfate, calcium silicate, glass fiber,
The inorganic filler surface-treated with a surface treatment agent such as carbon fiber, potassium titanate, metal fiber) or a coupling agent (eg, silane-based, titanate-based, boron-based, aluminate-based, zircoaluminate-based) or Organic fillers (for example, wood flour, pulp, waste paper, synthetic fibers, natural fibers, etc.) can be blended and used within a range that does not impair the object of the present invention.

In the production method of the present invention, the above compound A, a phosphorus-based antioxidant, a radical generator, is added to a polyolefin containing 5 ppm or more of titanium content or 0.5 ppm or more of vanadium content of a catalyst residue,
Using a conventional mixing device such as a Henschel mixer (trade name), a super mixer, a ribbon blender, or a Banbury mixer, a prescribed amount of the modifier and the above-mentioned various additives that are usually added to polyolefin are mixed with the radical generator. Mix at a temperature that does not decompose and use a normal single-screw extruder, twin-screw extruder, Brabender or roll,
It is carried out by melt-kneading at a melt-kneading temperature of 150 ° C to 300 ° C, preferably 180 ° C to 270 ° C.

[Work]

In the present invention, compound A is a plastic, 35, 11
No., pages 44 to 58 (1984 edition), it mainly acts as a radical scavenger and has thermal stability during use (heat resistance).
Contribute to the improvement of. Phosphorus-based antioxidants are peroxide decomposers to prevent thermal oxidative deterioration during melt-kneading, and radical generators generate radicals by melt-kneading treatment, that is, heating, to extract hydrogen atoms of polyolefin and to remove the polyolefin. It is well known that the modifier generates radicals and the modifier grafts onto the radicals of the polyolefin, that is, modifies the polyolefin and acts to improve adhesion and the like.

In the production method of the present invention, the reason why the compound A does not cause coloration is considered to be that the compound A does not form a generated atomic group such as a quinone compound as seen in the antioxidant process of the phenolic antioxidant.

[Effect] The modified polyolefin obtained by the production method of the present invention is further free from coloration as compared with the modified polyolefin related to the above-mentioned Japanese Patent Application No. 61-157316 filed by the present inventors, and the adhesiveness and the like are improved. Therefore, it can be suitably used for the production of a target molded article by various molding methods such as an injection molding method, an extrusion molding method (in particular, a laminated extrusion molding method), and a blow molding method.

〔Example〕

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

The evaluation methods used in Examples and Comparative Examples were as follows.

Colorability: VI (Vellowness lndex) of the obtained pellet
Was measured (in accordance with JIS K 7103), and the coloring property was evaluated from the magnitude of the value of this VI.

The smaller this value is, the less the coloring is.

Examples 1 to 16 and Comparative Examples 1 to 3 As polyolefins, MFR (load at 230 ° C. 2.16 kg
The amount of molten resin discharged for 10 minutes when added) was 2.0 g / 10 minutes, and 100 parts by weight of an unstabilized powdery propylene homopolymer (titanium content 30 ppm) was added to compound tetrakis (2,2 , 6,6-Tetramethyl-4-piperidyl) 1,2,
3,4-Butane tetracarboxylate, 3,9-bis [1,1
-Dimethyl-2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) butycarbonyloxy} ethyl] -2,4,8,10-tetraoxasulo [5,5]
Undecane, poly [[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl]
[(2,2,6,6-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-
Piperidyl) imino]] or poly [[6-morpholino-1,3,5-triazine-2,4-diyl] [(2,2,6,6
-Tetramethyl-4-piperidyl] imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], bis (2,4-di-t) as a phosphorus-based antioxidant
-Butylphenyl) -pentaerythritol-diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene-di-phosphonite or tris (2,4-di-t-butylphenyl) phosphite, radical generator As 2,5-di-methyl-2,5
-Di- (t-butylperoxy) hexane or 1,3
-Bis (t-butylperoxyisopropyl) benzene, maleic anhydride as a modifier, and a predetermined amount of each of the other additives were added to the Henschel mixer (trade name) at the compounding ratios shown in Table 1 below. After stirring and mixing for a minute, the mixture was melt-kneaded at 200 ° C. in a single-screw extruder with a diameter of 40 mm to modify and pelletize. Also, as Comparative Examples 1 to 3, MFR
Is 2.0 g / 10 min, and 100 parts by weight of unstabilized powdery propylene homopolymer (titanium content 30 ppm)
A predetermined amount of each of the additives shown in the table was blended, and Example 1 was added.
Melt-kneading treatment according to 16 to obtain modified pellets.

Using the pellets thus obtained, the coloring method was evaluated by the test method described above. The results are shown in Table 1.

Examples 17 to 32, Comparative Examples 4 to 6 As a polyolefin, MFR 7.0 g / 10 min unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight, titanium content 33 ppm). Ten
To 0 parts by weight, as compound A, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 3,9-bis [1,1-dimethyl- 2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,
4,8,10-Tetraoxaspiro [5,5] undecane, poly [[6-[(1,1,3,3-tetramethylbutyl) amino]
-1,3,5-Triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4 -Piperidyl) imino]] or poly [[6-morpholino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-
4-piperidyl) imino] hexamethylene [(2,2,6,6
-Tetramethyl-4-piperidyl) imino]], bis (2,4-di-t-butylphenyl) -pentaerythritol-diphosphite, tetrakis (2,4-di-t-butylphenyl) -4 as a phosphorus-based antioxidant , 4'-biphenylene-di-phosphononite or tris (2,4
-Di-t-butylphenyl) phosphite, 2,5-di-methyl-2,5-di- (t-butylperoxy) hexane or 1,3-bis- (t-butylperoxyisopropyl) as a radical generator Benzene, maleic anhydride as a modifier, and other additives were added in the Henschel mixer (trade name) in the prescribed proportions shown in Table 2 below, and the mixture was stirred and mixed for 3 minutes, then a uniaxial screw having a diameter of 40 mm The mixture was melted and kneaded at 200 ° C. in an extruder for modification and pelletized. Further, as Comparative Examples 4 to 6, powdery crystalline ethylene-propylene random copolymers having an MFR of 7.0 g / 10 min and not stabilized (ethylene content 2.5 wt%, titanium content 3
3 ppm) and 100 parts by weight of each of the additives shown in Table 2 below were blended and melt-kneaded in accordance with Examples 17 to 32 to obtain modified pellets.

Using the pellets thus obtained, the colorability was evaluated by the test method described above. The results are shown in Table 2.

Examples 33 to 48, Comparative Examples 7 to 9 As a polyolefin, MFR 4.0 g / 10 min unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight, titanium content 33 ppm). Ten
To 0 parts by weight, as compound A, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 3,9-bis [1,1-dimethyl- 2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,
4,8,10-Tetraoxaspiro [5,5] undecane, poly [[6-[(1,1,3,3-tetramethylbutyl) amino]
-1,3,5-Triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4 -Piperidyl) imino]] or poly [[6-morpholino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-
4-piperidyl) imino] hexamethylene [(2,2,6,6
-Tetramethyl-4-piperidyl) imino]], bis (2,4-di-t-butylphenyl) -pentaerythritol-diphosphite, tetrakis (2,4-di-t-butylphenyl) -4 as a phosphorus-based antioxidant -4'-
Biphenylene-di-phosphononite or tris (2,4-di-t-butylphenyl) phosphite, 2,5-di-methyl-2,5-di- (t- as a radical generator
Butyl peroxy) hexane or 1,3-bis- (t
-Butylperoxyisopropyl) benzene, maleic anhydride as a modifier, and other additives in the respective prescribed amounts in a Henschel mixer (trade name) at the blending ratios shown in Table 3 below, and the mixture was stirred and mixed for 3 minutes. The mixture was melt-kneaded at 200 ° C. in a single-screw extruder having a rear diameter of 40 mm to be modified and pelletized. Further, as Comparative Examples 7 to 9, 100 parts by weight of powdery crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight, titanium content 33 ppm) in which MFR is not stabilized at 4.0 g / 10 min will be described later. Predetermined pellets were obtained by blending predetermined amounts of the additives shown in Table 3 and melt-kneading in accordance with Examples 33 to 48.

Using the pellets thus obtained, the colorability was evaluated by the test method described above. The results are shown in Table 3.

Examples 49-64, Comparative Examples 10-12 As polyolefin, MFR 7.0 g / 10 min unstabilized powdery crystalline ethylene-propylene-butene-1.
Terpolymer (ethylene content 2.5% by weight, butene-1
4.5 wt%, titanium content 33ppm) 100 parts by weight,
Tetrakis (2,2,6,6-tetramethyl-
4-piperidyl) 1,2,3,4-butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2- {tris (1,2,
2,6,6-Pentamethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, poly [[6-
[(1,1,3,3-Tetramethylbutyl) amino] -1,3,5-
Triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,
6-Tetramethyl-4-piperidyl) imino]] or poly [[6-morpholino-1,3,5-triazine-2,4
-Diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], phosphorus-based antioxidant As bis (2,4-di-t-butylphenyl) -pentaerythritol-diphosphite, tetrakis (2,4-
Di-t-butylphenyl) -4,4'-biphenylene-di-phosphononite or tris (2,4-di-t-butylphenyl) phosphite as a radical generator
2,5-di-methyl-2,5-di- (t-butylperoxy)
Hexane or 1,3-bis- (t-butylperoxyisopropyl) benzene, maleic anhydride as a modifier, and other additives in the respective prescribed amounts at the blending ratios shown in Table 4 below are used in a Henschel mixer (commodity). Name)
After stirring and mixing for 3 minutes, the mixture was melt-kneaded at 200 ° C. in a single-screw extruder having a diameter of 40 mm to modify and pelletize. Further, as Comparative Examples 10 to 12, powdery crystalline ethylene-propylene-butene-1 terpolymer having an MFR of 7.0 g / 10 min and not stabilized (ethylene content 2.5% by weight, butene-1 content) 4.5 wt%, titanium content 33 ppm) 100 parts by weight of each of the predetermined amounts of the additives shown in Table 4 below, and melt kneading according to Examples 49 to 64 to obtain a modified pellet. It was

Using the pellets thus obtained, the colorability was evaluated by the test method described above. The results are shown in Table 4.

Examples 65 to 80, Comparative Examples 13 to 15 As polyolefins, MI (load at 190 ° C. 2.16 kg
The amount of molten resin discharged for 10 minutes when added) 15.0 g / 10 minutes of unstabilized powdered Ziegler-Natsuta high-density ethylene homopolymer (titanium content 8 ppm) to 100 parts by weight of compound A As tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2- {tris (1, 2,2,6,6-Pentamethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,4,8,
10-tetraoxaspiro [5,5] undecane, poly [[6-[(1,1,3,3-tetramethylbutyl) amino]
-1,3,5-Triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4 -Piperidyl) imino]] or poly [[6-morpholino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-
4-piperidyl) imino] hexamethylene [(2,2,6,6
-Tetramethyl-4-piperidyl) imino]], bis (2,4-di-t-butylphenyl) -pentaerythritol-diphosphite, tetrakis (2,4-di-t-butylphenyl) -4 as a phosphorus-based antioxidant , 4'-biphenylene-di-phosphononite or tris (2,4
-Di-t-butylphenyl) phosphite, 2,5-di-methyl-2,5-di- (t-butylperoxy) hexane or 1,3-bis- (t-butylperoxyisopropyl) as a radical generator A predetermined amount of benzene, maleic anhydride as a modifier and other additives were added to a Henschel mixer (trade name) at the compounding ratios shown in Table 5 below, and the mixture was stirred and mixed for 3 minutes, and then a uniaxial screw having a diameter of 40 mm was used. The mixture was melted and kneaded at 200 ° C. in an extruder for modification and pelletized. Further, as Comparative Examples 13 to 15, 100 parts by weight of unstabilized powdery Checla-Natsuta high-density ethylene homopolymer (titanium content 8 ppm) with MI of 15.0 g / 10 min is shown in Table 5 below. Each of the specified amount of each additive of
A modified pellet was obtained by melt-kneading in accordance with 65-80.

Using the pellets thus obtained, the colorability was evaluated by the test method described above. The results are shown in Table 5.

Examples 81-96, Comparative Examples 16-18 As polyolefins, MFR 4.0 g / 10 min unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 16.0 wt%, vanadium content 0.6 p
pm) 100 parts by weight, tetrakis (2,2,6,6) as compound A
-Tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2
-{Tris (1,2,6,6-pentatyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl]-
2,4,8,10-tetraoxaspiro [5,5] undecane, poly [[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2, 4-diyl] [(2,2,6,6
-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] or poly [[6-morpholino-1,3,5-
Triazine-2,4 diyl] [(2,2,6,6-tetramethyl-
4-piperidyl) imino] hexamethylene [(2,2,6,6
-Tetramethyl-4-piperidyl) imino]], and bis (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol-diphosphite as a phosphorus-based antioxidant, tetrakis (2,4-di-t- Butylphenyl)-
4,4'-Biphenylene-di-phosphonite or tris (2,4-di-t-butylphenyl) phosphite, 2,5-di-methyl-2,5-di-as a radical generator
(T-Butylperoxy) hexane or 1,3-bis- (t-butylperoxyisopropyl) benzene, maleic anhydride as a modifier, and other additives in prescribed amounts respectively shown in Table 6 below. Put in a Henschel mixer (trade name) at a ratio and stir and mix for 3 minutes, then caliber 40
mm uniaxial extruder at 200 ° C for melt-kneading to modify
Pelletized. In addition, MFR4.0g / 10 as Comparative Examples 16-18
Unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 16.0% by weight, vanadium content 0.6 ppm) in 100 parts by weight of each of the additives listed in Table 6 below. Was blended and melt-kneaded according to Examples 81 to 96 to obtain modified pellets.

Using the pellets thus obtained, the colorability was evaluated by the test method described above. The results are shown in Table 6.

Examples 97-112, Comparative Examples 19-21 As polyolefins, MI 6.0 g / 10 min unstabilized powdered Ziegler-Natsuta high-density ethylene-propylene copolymer (3.0 methyl branches / 1000 carbons, vanadium) Content 0.6 ppm) in 100 parts by weight of tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4 as compound A
-Butane tetracarboxylate, 3,9-bis [1,1-dimethyl-2- {tris (1,2,2,6,6-pentamethyl-4
-Piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5]
Undecane, poly [[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl]
[(2,2,6,6-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-
Piperidyl) imino]] or poly [[6-morpholino-1,3,5-triazine-2,4-diyl] [(2,2,6,6
-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], bis (2,6-di-t-) as a phosphorus-based antioxidant
-Butyl-4-methylphenyl) -pentaerythritol-diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene-di-phosphonite or tris (2,4-di-t-butylphenyl) phosphite 2,5-di-as a radical generator
Predetermined amounts of methyl-2,5-di- (t-butylperoxy) hexane or 1,3-bis- (t-butylperoxyisopropyl) benzene, maleic anhydride as a modifier and other additives will be described later. The mixture was put in a Henschel mixer (trade name) in the mixing ratio shown in Table 7 above, stirred and mixed for 3 minutes, and then melt-kneaded at 200 ° C. in a single screw extruder having a diameter of 40 mm to modify and pelletize. In addition, Comparative Example 19 ~
Unstabilized powdered Ziegler-Natsuta high-density ethylene-propylene copolymer with MI of 6.0 g / 10 min as 21 (methyl branch 3.0 / 1000 carbon, vanadium content 0.6 pp
m) 100 parts by weight of each of the additives shown in Table 7 described below were mixed in a predetermined amount, and melt-kneaded in accordance with Examples 97 to 112 to obtain modified pellets.

Using the pellets thus obtained, the colorability was evaluated by the test method described above. The results are shown in Table 7.

Examples 113 to 128, Comparative Examples 22 to 24 As a polyolefin, Mooney viscosity ML 1 + 4 (100
Tetrakis (2,2,6, ° C.) 25 as an unstabilized powdery amorphous ethylene-propylene random copolymer (propylene content 25%, vanadium content 0.6 ppm) in 100 parts by weight. 6-Tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2- {tris (1,2,2,6,6-pentamethyl -4-Piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, poly [[6-[(1,1,3,3-tetramethylbutyl ) Amino] -1,3,5-triazine-1,4-
Diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] or poly [[6-
Morphoorino-1,3,5-triazine-2,4-diyl]
[(2,2,6,6-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-
Piperidyl) imino]], bis (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol-diphosphite as a phosphorus-based antioxidant, and tetrakis (2,
4-di-t-butylphenyl) -4,4'-biphenylene-
Di-phosphononite or tris (2,4-di-t-
Butylphenyl) phosphite, 2,5-di-methyl-2,5-di- (t-butylperoxy) hexane or 1,3-bis- (t-butylperoxyisopropyl) benzene as a radical generator, and a modifier A predetermined amount of each of maleic anhydride and other additives was placed in a Henschel mixer (trade name) in a mixing ratio shown in Table 8 below, and the mixture was stirred and mixed for 3 minutes.
The mixture was melt-kneaded at ℃ to modify and pelletized. As Comparative Examples 22 to 24, Mooney viscosity ML 1 + 4 (100
Unstabilized powdery non-crystalline ethylene-
Propylene random copolymer (propylene content 25%,
Vanadium content 0.6 ppm) 100 parts by weight of each of the additives listed in Table 8 below were added in a predetermined amount, and each of Examples 113 to 1 was used.
Melt-kneading was performed in accordance with No. 28 to obtain a modified pellet.

Using the pellets thus obtained, the colorability was evaluated by the test method described above. The results are shown in Table 8.

Various compounds and additives shown in Tables 1 to 8 are as follows.

Compound A [I]; Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate Compound A [II]; 3,9-bis [1,1 -Dimethyl-2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,4,
8,10, -Tetraoxaspiro [5,5] undecane Compound A [III]; Poly [[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine- 2,4-Diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4
-Piperidyl) imino]] compound A [IV]; poly [[6-morpholino-1,3,5-
Triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,
6-Tetramethyl-4-piperidyl) imino]] Phosphorus antioxidant [I]; Bis (2,4-di-t-butylphenyl) -pentaerythritol-diphosphite phosphorus antioxidant [II]; Tetrakis (2 , 4-di-t-
(Butylphenyl) -4,4'-biphenylene-di-phosphonite Phosphorus antioxidant [III]; Tris (2,4-di-t-butylphenyl) phosphite phosphorus antioxidant [IV]; Bis (2,6- Di-t-butyl-4-methylphenyl) -pentaerythritol-diphosphite radical generator [I]; 2,5-di-methyl-2,5-di-
(T-Butylperoxy) hexane radical generator [II]; 13-bis- (t-butylperoxyisopropyl) benzene modifier; maleic anhydride phenolic antioxidant 1; 2,6-di-t-butyl -P-
Cresol phenolic antioxidant 2; tetrakis [methylene-3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane polyol compound (partial ester of polyol and fatty acid); pentaerythritol monostearate HALS (hindered amine compound having phenolic hydroxyl group) ); 1- [2- [3- (3,5-di-t-butyl-4
-Hydroxyphenyl) propionyloxy] ethyl]
-4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine Ca-St; calcium stearate The examples and comparative examples shown in Table 1 are the cases where a propylene homopolymer was used as the polyolefin. First
As can be seen from the table, in Examples 1 to 16, compound A, a phosphorus-based antioxidant, a radical generator and a modifier were blended with a propylene homopolymer containing 30 ppm of titanium in the catalyst residue according to the present invention and melted. It is a mixture that has been kneaded and modified. Examples 1 to 16 and Comparative Example 1 (Method for producing the modified polyolefin described in Japanese Patent Application No. 61-157316 previously proposed by the present inventors, that is, a partial ester of a polyol and a fatty acid, a phenolic antioxidant, and a radical are added to the polyolefin. (Modified by mixing with a generator and modifier, melt-kneaded)
Compared with Comparative Example 1, it can be seen that Examples 1 to 16 are less colored than Comparative Example 1 and have improved anti-coloring property. Comparing Comparative Example 2 and Examples 1 to 16 using a hindered amine-based compound having a phenolic hydroxyl group instead of the compound A, Comparative Example 2 is markedly colored, and this coloring is the phenolic hydroxyl group of the hindered amine-based compound. Is due to the formation of a quinone compound. Also, comparing Comparative Examples 3 and 1 to 16 in which the partial ester of the polyol and the fatty acid used in Comparative Example 1 is further added to Comparative Example 2, Comparative Example 3 is similar to Comparative Example 1 in that the coloring property is improved. It turns out that it is less than Examples 1-16.

Tables 2 to 8 show crystalline ethylene-propylene random copolymer, crystalline ethylene-propylene block copolymer, crystalline ethylene-propylene-butene-13 terpolymer, and Ziegler-Nutta ethylene alone as polyolefin. Polymers, crystalline ethylene-propylene block copolymers, Ziegler-Nutta ethylene-propylene copolymers, and amorphous ethylene-propylene random copolymers are used, and these have the same effects as described above. confirmed.

Therefore, it can be seen that the modified polyolefin obtained by the production method of the present invention has no coloring and its adhesiveness and the like are improved.

From this, the modified polyolefin obtained by the production method of the present invention is modified with a compound having a conventionally known anti-coloring effect and modified by melt-kneading in the presence of a radical generator using a modifier. It was found that the anti-coloring property was remarkably superior to that of the above, and the remarkable effect of the present invention was confirmed.

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Claims (5)

[Claims] 1. A hindered amine compound having no phenolic hydroxyl group (hereinafter referred to as compound A) is added in an amount of 0.05 to 5 with respect to 100 parts by weight of polyolefin containing 5 ppm or more of titanium content or 0.5 ppm or more of vanadium content of a catalyst residue. 15 parts by weight and 0.01 to 1 parts by weight of a phosphorus-based antioxidant, 0.001 to 0.5 parts by weight of a radical generator, and 0.01 to 5 parts by weight of a modifier composed of an unsaturated carboxylic acid or a derivative thereof, 15
A method for producing a modified polyolefin, which comprises melt-kneading at 0 ° C to 300 ° C. 2. A tetrakis (2,2,6,6-
Tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, 3,9-bis [1,1-dimethyl-2-
{Tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl]
-2,4,8,10-tetraoxaspiro [5,5] undecane,
Poly [[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [(2,2,6,6
-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [[6-morpholino-1,3,5-triazine-2, 4-diyl] [(2,2,6,6-tetramethyl-4-
Piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] or a mixture of two or more thereof modified polyolefin according to claim (1). Manufacturing method. 3. Bis (2,4-di-) as a phosphorus-based antioxidant
t-butylphenyl) -pentaerythritol-diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol-diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,
The method for producing a modified polyolefin according to claim 1, wherein 4'-biphenylene-di-phosphonite, tris (2,4-di-t-butylphenyl) phosphite, or a mixture of two or more thereof is blended. 4. A radical generator, 2,5-di-methyl-
2,5-di- (t-butylperoxy) hexane, 2,5-di-methyl-2,5-di- (t-butylperoxy) hexyne-3 or 1,3-bis- (t-butyl) Claim (1) in which peroxyisopropyl) benzene is blended.
A method for producing the modified polyolefin described in the above item. 5. Polyolefin as propylene homopolymer, crystalline or amorphous ethylene-propylene random copolymer, crystalline ethylene-propylene block copolymer, crystalline propylene-butene-1 random copolymer, crystal Ethylene-propylene-butene-1 terpolymer, crystalline propylene-hexene-butene-1 3
The method for producing a modified polyolefin according to claim 1, wherein the original copolymer or a mixture of two or more thereof is used.