JPS6312650A - Production of modified propylene based polymer - Google Patents

Abstract

PURPOSE:To obtain the titled polymer having improved coloration preventing property, moldability, etc., by blending a propylene based polymer containing a specific amount of vanadium with a polyol or a partial ester thereof with a fatty acid and subjecting the resultant blend to melt kneading treatment. CONSTITUTION:100pts.wt. propylene based polymer, e.g. propylene homopolymer, etc., containing >=0.5ppm vanadium which is a catalyst residue is blended with (A) 0.01-1pts.wt. polyol or a partial ester thereof with a fatty acid, e.g. trimethylolethane, etc., and (B) 0.01-1pts.wt. phenolic antioxidant, e.g. 2,6-di-tert- butyl-p-cresol, etc., and (C) 0.001-1pts.wt. radical generating agent, e.g. 2,5-di- methyl-2,5-di-)tert-butylperoxy)hexane, etc., and the resultant blend is then subjected to melt kneading treatment at 150-300 deg.C.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for producing a modified propylene polymer. More specifically, the vanadium content of the catalyst residue, H0,
A specific amount of 7 to a propylene polymer containing 5 ppm or more
An enol-based antioxidant, IJ, I--ol or a partial ester of the polyol and fatty acid (hereinafter referred to as compound A), and a radical generator are blended, and the temperature is 150°C.
The present invention relates to a method for producing a modified propylene polymer, which is characterized by carrying out a melt-kneading treatment at ~300°C. (Prior art) In general, propylene polymers are relatively inexpensive and have excellent mechanical properties, so they are used to manufacture various molded products such as injection molded products, blow molded products, films, sheets, and fibers. However, propylene-based polymers are molded at temperatures above the melting point of the propylene-based polymer, but are subject to oxidative deterioration due to the heat during melt-kneading, and the molecular chains of the propylene-based polymer are deteriorated. Problems arise due to a decrease in mechanical strength due to cutting, as well as coloration and odor due to oxidative deterioration.In particular, propylene-based polymers also have problems due to the presence of tertiary carbon in the polymer, which is easily susceptible to oxidation. For this reason, conventionally, low molecular weight phenolic antioxidants such as 2,6-di-t-butyl-p-cresol (BI(T)) have been used to prevent thermal oxidative deterioration during melt-kneading. High molecular weight 7-enol antioxidants are widely used to provide thermal stability in practical use.However, when a propylene polymer blended with the above-mentioned phenolic antioxidant is melt-kneaded The phenolic antioxidant is oxidized during melt-kneading by the vanadium complex compound that is the catalyst residue in the propylene polymer, producing a quinone compound, which causes problems such as coloring of the resulting propylene polymer. A propylene polymer composition (JP-A-58-213036) in which pentaerythritol or a polyol which is a reaction product of pentaerythritol and propylene oxide is blended with a polyol, a polyol, or a partial or complete mixture of a polyol and a fatty acid. Propylene-based polymer compositions containing one or more compounds of esters, heptosphites, or thiophosphites (Journal Op.
Applied Polymer Science, Volume 29, 4421
~4426 pages (1984) (Journal of
Applied Polymer 5science%V
o1.29, p. 4421-4426 (1984))
) has been proposed. In addition, in order to improve the moldability of propylene polymers, it is well known that propylene polymers are modified by melt-kneading them in the presence of a radical generator to reduce their molecular weight. It is being [Problems to be Solved by the Invention] In the process of researching the coloring properties of propylene-based polymers containing vanadium content as catalyst residues, the present inventors discovered that propylene-based polymers containing a large amount of vanadium content as catalyst residues Even if a polymer is blended with the above-mentioned phenolic antioxidant and subjected to melt-kneading treatment, no coloring occurs to the extent that it becomes a practical problem. It has been found that when the modified propylene polymer is modified by melt-kneading in the presence of an agent, the resulting modified propylene polymer is significantly colored. This phenomenon has been reported in the above-mentioned Japanese Patent Application Laid-Open No. 58-213036 and the journal
of Applied Polymer Science, Volume 29, 4
There is no description on pages 421-4426 (1984). The present inventors investigated the presence of a radical generator in order to improve the molding processability of a propylene polymer prepared by blending a phenolic antioxidant with a propylene polymer containing the vanadium component of the catalyst residue described above. We conducted intensive research on a method to obtain a modified propylene polymer that does not become discolored even when subjected to melt-kneading treatment. As a result, a specific amount of phenolic antioxidant, polyol or partial ester of polyol and fatty acid (hereinafter referred to as compound A) and radical generation were added to the propylene polymer containing 0.5 ppm or more of vanadium molecules r in the catalyst residue. It was discovered that a modified propylene polymer without coloring could be obtained by blending the additive with the compound and melt-kneading it, and based on this knowledge, the present invention was completed. As is clear from the above description, the purpose of the present invention is to blend a propylene polymer containing 0.5 ppm or more of vanadium in the catalyst residue with a compound A1 phenolic anti-oxidant and a radical generator, and melt it. The object of the present invention is to provide a method for producing a modified propylene polymer without coloring by kneading. (Means for Solving the Problems) The present invention has the following configuration. The vanadium content of the catalyst residue is 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 0.01 to 2000 are the vanadium content of the catalyst residue and the phenolic antioxidant, respectively. 1 part by weight, 0.001 to 0.5 parts of a radical generator, and heated to 150°C to 300°C.
A method for producing a modified propylene polymer, which comprises melt-kneading at ℃. The propylene polymer used in the production method of the present invention contains 0.5 ppm or more of vanadium in the catalyst residue, and can be used, for example, by solution polymerization using a saturated hydrocarbon solvent, bulk polymerization, or gas phase polymerization. It is a propylene polymer obtained by a polymerization method that is legal or a combination of a bulk polymerization method and a gas phase polymerization method. In the production method of the present invention, there is no problem in using a propylene polymer in which the vanadium content of the catalyst residue is less than 0, s ppm.
In this case, even if the above-mentioned compound A is not blended, the resulting modified propylene polymer will not be colored to the extent that it poses a practical problem. The propylene polymer used in the present invention is a propylene polymer containing 0.5 ppm or more of vanadium in the catalyst residue, such as propylene homopolymer, propylene and ethylene, butene-1, pentene-1, Crystalline random copolymer or crystalline block copolymer with one or more α-olefins such as 4-methyl-pentene-1, hexene-1, octene-1, propylene and vinyl acetate, acrylic acid Examples include copolymers with esters or saponified products of the copolymers, copolymers of propylene with unsaturated carboxylic acids or their anhydrides, and reaction products of the copolymers with metal ion compounds. These propylene polymers can of course be used alone, or two or more propylene polymers can be used in combination. In addition, the above-mentioned propylene polymer and various synthetic rubbers (e.g. ethylene-propylene copolymer rubber,
Ethylene-propylene-nonconjugated diene copolymer rubber, polybutadiene, polyisoprene, chlorinated polyethylene,
Chlorinated polypropylene, Styrene Jeep Tager/based 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 resins (e.g. polyethylene, polybutene, poly-4-methylpentene-1
Polyolefins other than propylene polymers such as polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyvinyl chloride, etc.) can also be used. . Propylene homopolymer, crystalline ethylene-propylene random copolymer, crystalline ethylene-propylene block copolymer, crystalline propylene-butene-
1 random copolymer, crystalline ethylene-propylene-butylene,/-13 element copolymer, crystalline propylene-hexene-butene-13 element copolymer containing vanadium content of catalyst residue of o, s ppm or more. Particularly preferred are propylene-based polymers. Compound A used in the present invention includes glycerin, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, cichentaerythritol,
Polyols such as tripentaerythritol, xylitol, nlupitol, mannitol, monoesters of glycerin and fatty acids, monoesters of diglycerin and fatty acids, monoesters of sorbitan and fatty acids, Schost and m
monoesters of fatty acids, monoesters of pentaerythritol and fatty acids, monoesters of trimethylolethane and fatty acids, monoesters of trimethylolpropane and fatty acids, monoesters of polyoxyethylene glycerin and fatty acids, monoesters of polyoxyethylene sorbitan and fatty acids Partial esters of polyols and fatty acids such as monoesters (fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, etc.) can be exemplified. Particularly preferred are trimethylolethane, monoesters of glycerin and fatty acids, and mono- or diesters of pentaerythritol and fatty acids. In addition, as a phenolic antioxidant, 2.6-di-
t-butyl-p-cresol, 2-t-butyl-4,6
-dimethylphenol, 2,6-di-t-butyl-4-
Ethylphenol, 2,6-di-t-butyl-4-n-
Butylphenol, 2,6-di-i-butyl-4-n-
Butylphenol, 2,6-di-cyclopentyl-4-
Methylphenol, 2-(α-methylcyclohexyl)
-4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-dolycyclohexylphenol, 2,6-di-t-butyl-4
-methoxymethylphenol, n-octadecyl-β-
(4'-hydroxy-3',5'-di-t-butylphenyl)propio*-), 2,6-diphenyl-4-octadecyloxyphenol, 2,4,6-)lis(3',
5'-di-t-butyl-4'-hydroxybenzylthio)-1,3゜5-triazine, 2,6-di-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone , 2.5-sheet t-7milhydroquinone, 2.2'-thio-bis-(6-butyl-4-methylphenol), 2.2'-thio-bis-(4-octylphenol), 2.゜2'-thio-bis-(6-t-
butyl-3-methylphenol), 4.4'-thio-bis-(6-t-butyl-2-methylphenol), 2.
2'-methylene-bis-(6-t-butyl-4-methylphenol), 2,2'-methylene-bis-(6-t-
butyl-4-ethylphenol), 2.2'-methylene-bis-C4-methyl-6-(α-methylcyclohexyl)-phenol], 2.2'-methylene-bis-(4
-methyl-6-cyclohexylphenol), 2.2'
-methylene-bis-(6-nonyl-4-methylphenol), 2.21-methylene-bis-(6-(α-methylbenzyl)-4-nonylphenol), 2.2'-methylene-bis-(5 -(a,a-dimethylbenzyl)-4
-/nylphenol], 2,2'-methylene-bis-(
4,6-di-monobutylphenol), 2,2'-ethyritene-bis(4,6-di-t-butylphenol)
, 2.2'-ethylidene-bis-(6-t-butyl-4
-1-butylphenol), 4,4'-methylethylbis-
(2,6-di-t-butylphenol), 4.41-methylene-bis-(6-t-butyl-2-methylphenol), 4.4'-butyrythene-bis-(6-t-butyl-2 -methylphenol), 4.4'-phthyritin-his-(6-t-butyl-3-methylphenol), 4.
4'-butylidene-bis-(2,6-di-t-butylphenol), 4,4'-butylidene-bis-(3,6-
di-t-butylphenol), 1,1-bis-(5-t
-butyl-4-hydroxy-2-methylphenyl)-butane, 2,6-di-(3-t-butyl-5-methyl-2
-hydroxybenzyl)-4-methylphenol, i,
i,a-tris-(5-t-butyl-4-hydroxy-
2-methylphenyl)-butane, bis[3,3-bis(
4'-Hydroxy-3'-butylphenyl)butyric acid] ethylene glycol ester, di(3
-t-butyl-4-hydroxy-5-methylphenyl)
-dicyclopentadiene, di(2-(3'-t-butyl-2'-hydroxy-51-methylbenzyl)-6-
t-Butyl-4-methylphenyl) terephthalate, 1
,3,5-trimethyl-2,4゜6-tris(3,5-
di-t-butyl-4-hydroxybenzyl)benzene,
1 3,5-)lis-(3,5-di-t-butyl-4-
hydroxybenzyl)incyanure), 1,3.5-
Tris-(4-t-butyl-3-hydroxy-2,6-
c) tilbenzyl) incyanurate, 1,3.5-)
Lis-((3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl)isocyanurate or tetrakis(methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl) ) Propionate comethane can be exemplified.The blending ratio of the compound A and the phenolic antioxidant is 0.01 to 1 part by weight, preferably 0.05 parts by weight, respectively, per 100 parts by weight of the propylene polymer. ~0.5 parts by weight.0.0
If the content is less than 1 part by weight, the effect of preventing coloring of the modified propylene polymer will not be sufficiently exhibited, and although it is possible to add 1 part by weight of all types, no further improvement in the coloring prevention effect can be expected. Not only is this impractical, but it is also uneconomical. In order to obtain a uniform composition, it is preferable that the decomposition temperature of the radical generator used in the present invention is not too low, and the temperature to obtain a half-life of 10 hours is 70°C or higher, preferably 100'C or higher. dibenzoyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl peroxyisopropyl carbonate, 2,5-di-methyl-2,5-di-(benzoyl peroxy) hexane, 2. 5-di-methyl-2,5-di-(benzoylperoxy)hexyne-3, t-butyl-Sieber adivate, t-butylperoxy-3,5
, 5-trimethylhexanoate, methyl 12thyl ketone peroxide, cyclohexanone ha+oxide,
Di-t-butyl peroxide, dicumyl peroxide, 2,5-di-methyl-2,5-di-(t-butylperoxy)hexane, 2,5-di-methyl-2,5-
Di-(t-7'thylperoxy)hexyne-3,1゜3
-bis-(t-butylperoxyisopropyl)benzene, t-butylcumyl peroxide, 1.1-bis-(t-butylperoxy)-3,3,5-)lyntylcyclohexane, 1°1 -bis-(t-butylperoxy)cyclohexane, 2,2-bis-(t-butylperoxy)butane, p-menthane hydroperoxide, c-isopropylbenzene hydroperoxide,
cumene hydroperoxide, t-butyl hydroperoxide, p-cymene hydroperoxide, 1,1.3,3-tetra-methylbutyl hydroperoxide or 2,5-di-methyl-2,5-di-
Examples include organic peroxides such as (hydroperoxy)hexane. In particular, 2,5-di-methyl-2,5-di-(
t-butylperoxy)hexane, 2,5-di-methyl-2,5-di-(t-butylperoxy)hexyne-3, and 1,3-his-(t-butylperoxyisopropyl)benzene. preferable. The ratio of the radical generator to 100 parts by weight of the propylene polymer is usually 0.
．． 001-0.5 parts by weight, preferably 0.01-0.2
Parts by weight. The melt-kneading process is carried out at a temperature of 15,000 to 300°C, preferably 180 to 270°C, using various melt-kneading apparatuses described below. If the melt-kneading temperature is less than 150°C, sufficient modification will not be carried out;
If the temperature exceeds 0°C, thermal oxidative deterioration of the propylene polymer will be accelerated and the propylene polymer will become noticeably colored, which is not preferable. In the production method of the present invention, various additives that are normally added to propylene polymers, such as thioether type, phosphorus type, etc. Antioxidants, light stabilizers, clarifying agents, nucleating agents, lubricants, antistatic agents, antifogging agents, anti-blocking agents, anti-drop agents, pigments, heavy metal deactivators (copper inhibitors), metal soaps dispersants or neutralizing agents, inorganic fillers (such as talc, mica, clay,
wollastonite, zeolite, asbestos, calcium carbonate, aluminum hydroxide, magnesium hydroxide, barium sulfate, calcium silicate, glass fiber, carbon fiber, etc.) or coupling agents (e.g. silane, titanate, boron, aluminate) For the purpose of the present invention, the above-mentioned inorganic fillers or organic fillers (for example, wood flour, pulp, waste paper, synthetic fibers, natural fibers, etc.) that have been surface-treated with a surface treatment agent such as They can be mixed and used within a range that does not impair the properties. In particular, when a phosphorus-based antioxidant is used in combination, a synergistic coloring prevention effect is exhibited, so it is preferable to use them together. Preferred phosphorus antioxidants include distearylpentaerythritol-diphosphite, tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene-di-7m), bisc2 .4-di-t--j tylphenyl)
- Pentaerythritol - Siphosphite, bis(2
, 6-di-t-butyl-4-methylphenyl)-pentaerythritol-siphosphite and tris(2,
An example is 4-di-t-butylphenyl) phosphite. The production method of the present invention is characterized in that the vanadium content of the catalyst residue is
The above-mentioned Compound A, phenolic antioxidant, radical generator, and the various additives mentioned above that are normally added to the propylene polymer are added to the propylene polymer containing 5 PPm or more in a predetermined amount, for example, in a conventional mixing device. Mixer mixer (product name) 1, using an X-bar mixer, ribbon blender, Pan Bali mixer, etc., at a temperature that does not decompose the blended radical generator, and then mix using an ordinary single-screw extruder or twin-screw extrusion ratio. Melt kneading temperature 150℃~300"C1 preferably 1
This is carried out by melt-kneading treatment at 80°C to 270°C.

[Effect]

In the present invention, the phenolic antioxidant is used as a radical chain inhibitor, and the radical generator generates radicals by melt kneading, that is, heating, and cuts the main chain of the propylene polymer. tt
- It is a well-known fact that this reduces the amount of carbon and improves moldability. In the production method of the present invention, when the above-mentioned compound A is melt-kneaded with a propylene polymer stabilized with a phenolic antioxidant in the presence of a radical generator, it is Although the mechanism of action itself is not clear, the effect of the present invention is not achieved when a complete ester of polyol and fatty acid is used. It is presumed that the chelate compound is active and stable. [Effect] The modified propylene polymer obtained by the production method of the present invention is produced by using a propylene polymer prepared by blending a conventionally known phosphorus antioxidant or polyol with a complete ester of fatty acid, and a radical generator. Compared to modified propylene polymers obtained through modification methods, there is no coloration;
Since the molding processability is improved, it can be suitably used for producing various desired molded products by various molding methods such as injection molding, extrusion molding, and blow molding. (Examples) Hereinafter, the present invention will be specifically explained using Examples, Comparative Examples, and Reference Examples, but the present invention is not limited thereto. The evaluation method was as follows: Colorability: YI (Yellowne
ssIndex) (JIS K 7103
), and the colorability was evaluated based on the magnitude of the YI value. The smaller this number is, the less coloring there is. Examples 1 to 16, Comparative Examples 1 to 3, Reference Examples 1 to 3 As a propylene polymer, MFR (load at 230°C
．． Discharge amount of molten resin for 10 minutes when adding 16 kg) 2.0 g/10 minutes of powdered propylene homopolymer (
Vanadium content: 0.6 ppm) To 100 parts by weight of Compound A, trimethylolethane, glycerin monostearate, pentaerythritol monostearate or pentaerythritol distearate, and 2,6-distearate as a phenolic antioxidant. -t-butyl-p
-cresol, tetrakis(methylene-3-(3',5
'-di-t-butyl-4'-hydroxyphenyl)propionate comethane, 1.3.5-trimethyl-2,4
,6-)Lis(3,5-di-t-butyl-4-hydroxybenzyl)benzene,1,3.5-)Lis-(3゜5
-di-t-butyl-4-hydroxybenzyl)isocyanurate or n-octadecyl-β-(4'-hydroxy-3', 5'-di-t-butylphenyl)propionate, 2.5- as a radical generator di-methyl-
2,5-di-(1-phthylbaroxy)hexane or 1,3-bis-(t-butylperoxyimprovil)benzene and other additives, respectively, at the specified t'r listed in Table 1 below. The mixture was put into a Hensel mixer (trade name) at the mixing ratio, stirred and mixed for 3 minutes, and then melt-kneaded at 200° C. in a single-screw extruder with a diameter of 40 flf for modification and pelletization. In addition, as Comparative Examples 1 to 3 and Reference Examples 1 to 3, 100 parts by weight of a powdered propylene homopolymer (vanadium content 0.6 ppm) with an MFR of 2.0/10 minutes was added to 100 parts by weight of Predetermined amounts of each of the additives were blended, and the mixture was stirred, mixed, and melt-kneaded in accordance with Examples 1 to 16 to obtain modified pellets. Using the obtained pellets, the colorability was evaluated according to the test method described above. The results are shown in Table 1. Examples 17 to 32, Comparative Examples 4 to 6, Reference Example 4 - As a propylene polymer, a powdery crystalline ethylene-propylene random copolymer with an MFR of 7.0 g/10 minutes and an ethylene content of 2.5 TL amount % , vanadium containing Ji0.6
ppm) to 100 parts by weight, trimethylolethane, glycerin monostearate, be/taerythritol monostearate or pentaerythritol distearate as compound A, and 2.6-di-t-butyl-p as a phenolic antioxidant. -cresol, tetrakis[methylene-3-(3',5'-di-t-7'thyl-4
'-Hydroxyphenyl)propionate comethane, 1
,3,5-trimethyl-2゜4.6-)lis(3,5-
di-t-butyl-4-hydroxybenzyl)benzene,
1,3,5-tris-(3,5-di-t-butyl-4-
hydroxybenzyl)in cyanurate or n-octadecyl-β-(4'-hydroxy-3'.5'-di-t-butylphenyl)propionate, 2,5-di-methyl-2°5-di −(
The predetermined amounts of t-butylperoxy)hexane or 1,3-bis-(t-butylperoxyisopropyl)benzene and other additives were mixed into a Hensel mixer (commercial product) at the mixing ratios listed in Table 2 below. After stirring and mixing for 3 minutes, use a single-screw extruder with a diameter of 40fl to
The mixture was melted and kneaded at C to be modified and pelletized. Moreover, as Comparative Examples 4 to 6 and Reference Examples 4 to 6, MFR was 7.
100 parts by weight of powdered crystalline ethylene-propylene random copolymer (ethylene content 2.51%, vanadium content 0-6 pPm) at 0g/10min.
Example 1
Modified pellets were obtained by stirring, mixing and melt-kneading in accordance with 7-32. Using the obtained pellets, colorability was evaluated according to the test method described above. The results are shown in Table 2. Examples 33 to 48, Comparative Examples 7 to 9, Reference Example 7 - As the propylene polymer, a powdery crystalline ethylene-propylene block copolymer with an MFR of 4.0 g/10 minutes (ethylene content 8.5% by weight) , vanadium content i0.6 ppm
) 100fi'a part contains trimethylolethane, glycerin monostearate, pentaerythritol monostearate or pentaerythritol distearate as compound A, and 2 as a phenolic antioxidant.
．． 6-di-t-butyl-p-cresol, tetrakis [
Methylene-3-(3',5'-di-monobutyl-4'-
Hydroxyphenyl)propionate comethane, 1,3
．． 5-trimethyl-2゜4.6-tris(3,5-di-
t-Butyl-4'-hydroxypenzyl)benzene, 1
, 3,5-tris-(3,5-di-t-butyl-4-hydroxybenzyl)incyanure)'! +'cldn
-octadecyl-β-(4'-hydroxy-3'.5'-di-t-butylphenyl) flobionate, 2,5-di-methyl-2°5-di-(
t-Butylperoxy)hexane is also used in the Hensel test using L<=1, 3-bis-(t-butylperoxyisopropyl)benzene, and other additives in the prescribed amounts in the proportions listed in Table 3 below. Add mixer (product name) K, stir and mix for 3 minutes, then heat to 200℃ using a single-screw extruder with diameter 4 Off.
The mixture was melt-kneaded, modified, and pelletized. Also,
MFR is 40g as Comparative Examples 7 to 9 and Reference Examples 7 to 9
100 parts by weight of a 710-minute powdered crystalline ethylsine-propylene block copolymer (ethylene content 8.5% by weight, vanadium content tO, 6pPm) was blended with a predetermined amount of each of the additives listed in Table 3 below. Example 33
Modified pellets were obtained by stirring, mixing and melt-kneading in accordance with 48. Using the obtained Beret) 1, the colorability was evaluated according to the test method described above. The results are shown in Table 3. Examples 49-64, Comparative Examples 10-12, Reference Examples 10-1
2 As the propylene polymer, a powdery crystalline ethylene-propylene-butene-13 copolymer with an MFR of 7.0 g/10 min (ethylene content 2.5% by weight, butene-1 content 4.5% by weight, Vanadium containing ftO,61)I)m
) 100N parts, trimethylolethane, glycerin monostearate, pentaerythritol monostearate or pentaerythritol distearate as a compound, and 2,6-di-t-butyl-p-cresol as a phenolic antioxidant. , tetrakis(methylene-3-(3',5'-di-t-phthyl-4'-hydroxyphenyl)propionate comethane, 1.3.5-trimethyl-2°4.6-)lis(3,5 -di-t-butyl-4-hydroxybenzyl)benzene, 1,3.5-
Tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate or tris-octadecyl-β
-(4'-hydroxy-3'.5'-di-t-butylphenyl) flobionate, 2,5-di-methyl-2°5-di-(
t-butylperoxy)hexa/or 1,3-bis-(t-butylperoxyisopropyl)benzene and other additives in a Hensel mixer ( (product name) and stirred and mixed for 3 minutes.
It was modified by melt-kneading at ℃ and pelletized. In addition, as Comparative Examples 10 to 12 and Reference Examples 10 to 12, MF
Powdered crystalline ethylene-propylene-butene-13 element copolymer with R of 7.0 g/10 min (ethylene content 2.5
% by weight, butene-1 content 4.51%, vanadium content 0.6 ppm) 100'lLi, and a predetermined Mk of each of the additives listed in Table 4 below was blended into a portion,
Modified pellets were obtained by stirring, mixing and melt-kneading according to Examples 49-64. Using the obtained pellets, colorability was evaluated according to the test method described above. The results are shown in Table 4. The various compounds and additives shown in Tables 1 to 4 are as follows. Compound A (1)
1); Glycerin monostearate compound A (1) i Pentaerythritol monostearate compound A (ff); Pentaerythritol distearate phenolic antioxidant (1) + 2.6-di-monobutyl-p-cresol phenol Antioxidant [■]; Tetrayasu [methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate comethane phenolic antioxidant (It[)] 1.3 .5-1rimether-2,4,6-)lis(3,5-di-t-butyl-4-hydroxybenzyl)benzenephenolic antioxidant (ff)+1.3.5-tris-(3, 5-di-t-butyl-4-hydroxybenzyl)in cyanurate phenolic antioxidant (V); n-octadecyl-β
-(4'-hydroxy-3', 5'-di-monobutylphenyl)propionate radical generator (1); 2,5-di-methyl-2゜5-
Di-(t-butylperoxy)hexane radical generator (1); 1,3-bis-(t-butylperoxyisopropyl)benzenephosphorus antioxidant l; Tetrakis (2)
,4-di-t-butylphenyl)-4,4'-biphenylene-diphos phosphorous phosphorous antioxidant 2; bis(2,4-di-t-butylphenyl)-pentaerythritol-cyphos Phytopolyol Compound (Complete Ester of Polyol and Fatty Acid) N Pentaerythritol Tetrastearate Ca -St Calcium Stearate The Examples and Comparative Examples listed in Table 1 are cases where a propylene homopolymer is used as the propylene polymer. It is. As can be seen from Table 1, in Examples 1 to 16, Compound A1 phenolic antioxidant and radical generator were blended with a propylene homopolymer containing 0.6 ppm of vanadium in the catalyst residue according to the present invention. , which has been modified by melt-kneading treatment. Comparing Examples 1 to 16 and Comparative Examples 1 to 2 fc<
It can be seen that Examples 1 to 16 have little coloring, and Comparative Examples 1 to 2, in which a phosphorous antioxidant was used instead of Compound A, have significant coloring. Comparing Comparative Example 3, in which a complete ester of polyol and fatty acid was used in place of Compound A, and Examples 1 to 16, Comparative Example 3 has improved colorability to some extent, but is still not fully satisfactory. Furthermore, Examples 9 to 10 were modified by melt-kneading the compound A1 according to the present invention, which was blended with a phenolic antioxidant, a radical generator, and a phosphorus-based fermentation inhibitor on each side, compared to Example 5. It can be seen that the excellent anti-coloring effect of Compound A is not inhibited, and a remarkable synergistic effect is observed when the phosphorus antioxidant is used in combination. In addition, in Reference Examples 1 to 3, which were melt-kneaded without using a radical generator, no significant coloring occurred as is clear when compared with Comparative Examples 1 to 2, and the aforementioned significant coloring was caused by the radical generator. This can be said to be a unique phenomenon that occurs when melt-kneading treatment is carried out in the presence of C. Tables 2 to 4 show crystalline ethylene-propylene random copolymer, crystalline ethylene-propylene block copolymer, and crystalline ethylene-propylene block copolymer as propylene polymers, respectively.
A propylene-butene-13-element copolymer was used, and the same effects as described above were confirmed for these as well. It can be seen that the modified propylene polymer obtained by the production method of the present invention is free from coloration and has improved moldability. Therefore, the modified propylene polymer obtained by the production method of the present invention is one obtained by blending a conventionally known compound with an anti-coloration effect and melt-kneading the mixture in the presence of a radical generator. It was found that the anti-coloring property was significantly superior compared to that of the conventional method, confirming the remarkable effect of the present invention. that's all

Claims (5)

[Claims] (1) To 100 parts by weight of a propylene polymer containing 0.5 ppm or more of vanadium in the catalyst residue, add 0% each of a polyol or a partial ester of the polyol and a fatty acid (hereinafter referred to as compound A) and a phenolic antioxidant. .01 to 1 part by weight, 0.001 part by weight of radical generator
A method for producing a modified propylene polymer, which comprises blending ~0.5 parts by weight and melt-kneading at 150°C to 300°C. (2) The method for producing a modified propylene polymer according to claim 1, wherein the compound A is trimethylolethane, a monoester of glycerin and a fatty acid, or a mono- or diester of pentaerythritol and a fatty acid. (3) 2,6-di-t- as a phenolic antioxidant
Butyl-p-cresol, tetrakis [methylene-3-
(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4
-hydroxybenzyl)benzene, 1,3,5-tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate or n-octadecyl-β-(4
The method for producing a modified propylene polymer according to claim 1, which comprises blending '-hydroxy-3',5'-di-t-butylphenyl) propionate. (4) 2,5-di-methyl-2, as a radical generator
5-di-(t-butylperoxy)hexane, 2,5-
The modification according to claim 1, which contains di-methyl-2,5-di-(t-butylperoxy)hexyne-3 or 1,3-bis-(t-butylperoxyisopropyl)benzene. A method for producing a high quality propylene polymer. (5) As a propylene polymer, propylene homopolymer, crystalline ethylene-propylene random copolymer, crystalline ethylene-propylene block copolymer, crystalline propylene-butene-1 random copolymer, crystalline ethylene-propylene The method for producing a modified propylene polymer according to claim 1, using a -butene-1 ternary copolymer or a crystalline propylene-hexene-butene-1 ternary copolymer.