JPH0735423B2 - Method for producing silane-modified polyolefin - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a silane-modified polyolefin. More specifically, a specific amount of a phenolic antioxidant, a polyol or a partial ester of the polyol and a fatty acid (hereinafter, referred to as compound A) is added to a polyolefin having a titanium content of the catalyst residue of 5 ppm or more or a vanadium content of 0.5 ppm or more, The present invention relates to a method for producing a silane-modified polyolefin, which comprises blending a radical generator and a silane compound and melt-kneading the mixture at a temperature of 150 ° C to 300 ° C.

[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. Therefore, for the purpose of preventing thermal oxidative deterioration during melt-kneading, a low molecular weight phenolic antioxidant such as 2,6-di-t-butyl-p-cresol (BHT) has been conventionally used in practice. High molecular weight phenolic antioxidants are widely used to impart thermal stability.

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. For this reason, a polyolefin composition in which pentaerythritol or a polyol which is a reaction product of pentaerythritol and propylene oxide is blended with polyolefin (Japanese Patent Laid-open No. 58-213
No. 036), and a polypropylene composition containing one or more compounds of polyol, partial or complete ester of polyol and fatty acid, phosphite, or thiophosphite (Journal of Applied Polymer Science, 29, 4421). ~ 4426 (1984) [Journa
l of Applied Polymer Science, Vol.29, p.4421-4426
(1984)]) has been proposed.

Further, the polyolefin is silane-modified by melt-kneading the polyolefin in the presence of a radical generator using a silane modifier composed of an ethylenically unsaturated silane compound, and the resulting silane-modified polyolefin is used for the following purposes. It is well known to serve. Silane-modified polyolefin is water-crosslinked in the presence of a silanol condensation catalyst to improve the mechanical strength and heat resistance of polyolefin. The silane-modified polyolefin is used to improve the compatibility with the inorganic filler and improve the mechanical strength.

[Problems to be solved by the invention]

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 silane compound. It was found that upon treatment, the resulting silane-modified polyolefin was significantly colored. This phenomenon is described in JP-A-58-21303.
Nothing is described in Japanese Patent Publication No. 6 and Journal of Applied Polymer Science, 29, 4421-4426 (1984).

The inventors of the present invention have developed a polyolefin containing a large amount of titanium or vanadium contained in the above catalyst residue and a phenolic antioxidant in the polyolefin, for the purpose of improving its mechanical strength and the like, radical generation using a silane compound. The present inventors have earnestly studied a method for obtaining a silane-modified polyolefin which is not colored even if it is silane-modified by melt-kneading in the presence of an agent. As a result, a specific amount of a phenolic antioxidant, a polyol or a partial ester of the polyol and a fatty acid (hereinafter referred to as compound A), a radical 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. It was found that a silane-modified polyolefin without coloring can be obtained by blending a generator and a silane compound and subjecting to melt-kneading, and the present invention was completed based on this finding.

As is apparent from the above description, the object of the present invention is to provide compound A, a phenolic antioxidant, a radical generator and a silane compound to a polyolefin containing 5 ppm or more of titanium content or 0.5 ppm or more of vanadium content of a catalyst residue. It is intended to provide a method for producing a silane-modified polyolefin which is free from coloring by compounding and melt-kneading.

[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.
To 100 parts by weight of polyolefin containing 5 ppm or more, 0.01 to 1 part by weight of a polyol or a partial ester of the polyol and a fatty acid (hereinafter referred to as compound A) and a phenolic antioxidant, and 0.005 to 100 parts by weight of a radical generator.
5 parts by weight, 0.1 to 10 parts by weight of a silane compound are mixed, and the temperature is 150 ° C.
A method for producing a silane-modified polyolefin, which comprises performing a melt-kneading treatment at about 300 ° C.

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, it is possible to use a polyolefin having a titanium content of the catalyst residue of less than 5 ppm or a vanadium content of less than 0.5 ppm. Even if it is not blended, the resulting silane-modified polyolefin does not cause coloring to a degree that poses a practical problem. The polyolefin used in the present invention is a polyolefin containing titanium content of the catalyst residue of 5 ppm or more or vanadium content of 0.5 ppm or more, ethylene, propylene, butene-1, pentene-1,4-methyl-pentene-1, Homopolymers of α-olefins such as hexene-1, octene-1, crystalline or amorphous random copolymers or crystalline block copolymers of two or more types of α-olefins, amorphous ethylene-propylene A non-conjugated diene terpolymer, a copolymer of these α-olefins with vinyl acetate, an acrylic ester, or a saponified product of these copolymers, with these α-olefins and an unsaturated carboxylic acid or an anhydride thereof. And a reaction product of the metal ion compound with the copolymer, and the like. Of course, two or more kinds of polyolefins can be mixed and used alone. 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,
A mixture of styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, polybutylene 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. A terpolymer, a crystalline propylene-hexene-butene-1 terpolymer, and a propylene-based polymer containing 5 ppm or more of titanium content or 0.5 ppm or more of vanadium content of the catalyst residue are particularly preferable.

Examples of the compound A used in the present invention include glycerin, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol,
Polyols such as tripentaerythritol, xylitol, sorbitol and mannitol, monoesters of glycerin and fatty acids, monoesters of diglycerin and fatty acids, monoesters of sorbitan and fatty acids, monoesters of sucrose and fatty acids, monoesters of pentaerythritol and fatty acids or Partial esters of polyols and fatty acids such as diesters, trimethylolethane and fatty acid monoesters, trimethylolpropane and fatty acid monoesters, polyoxyethylene glycerin and fatty acid monoesters, polyoxyethylene sorbitan and fatty acid monoesters (as fatty acids Is lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, etc.)
Can be illustrated. Especially trimethylolethane,
Preference is given to monoesters of glycerin and fatty acids and mono- or diesters of pentaerythritol and fatty acids. Further, as the phenol-based 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-tri-cyclohexylphenol,
2,6-di-t-butyl-4-methoxymethylphenol, n-octadecyl-β- (4'-hydroxy-
3 ', 5'-di-t-butylphenyl) propionate,
2,6-diphenyl-4-octadecyloxyphenol,
2,4,6-Tris (3 ', 5'-di-t-butyl-4'-hydroxybenzylthio) -1,3,5-triazine, 2,6-di-t-butyl-4-methoxyphenol , 2,5-di-t
-Butyl hydroquinone, 2,5-di-t-amyl hydroquinone, 2,2'-thio-bis- (6-t-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-
[4-Methyl-6- (α-methylcyclohexyl) -phenol], 2,2'-methylene-bis- (4-methyl-
6-cyclohexylphenol), 2,2'-methylene-
Bis- (6-nonyl-4-methylphenol), 2,2 '
-Methylene-bis- [6- (α-methylbenzyl) -4
-Nonylphenol], 2,2'-methylene-bis- [6
-(Α, α-Dimethylbenzyl) -4-nonylphenol], 2,2′-methylene-bis- (4,6-di-t-butylphenol), 2,2′-ethylidene-bis- (4, 6-ge
t-butylphenol), 2,2'-ethylidene-bis-
(6-t-butyl-4-i-butylphenol), 4,
4'-methylene-bis- (2,6-di-t-butylphenol), 4,4'-methylene-bis- (6-t-butyl-2)
-Methylphenol), 4,4'-butylidene-bis-
(6-t-butyl-2-methylphenol), 4,4'-
Butylidene-bis- (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, 1,1,3
-Tris- (5-t-butyl-4-hydroxy-2-methylphenyl) -butane, bis [3,3-bis (4'-hydroxy-3'-t-butylphenyl) butyric acid] ethylene glycol ester, Di- (3-t-butyl-4-hydroxy-5-methylphenyl) -dicyclopentadiene, di- [2- (3'-t-butyl-2 '
-Hydroxy-5'-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-tris- (3,5
-Di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris- (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5- Tris-[(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate or tetrakis [methylene-3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane can be exemplified.
The compounding ratio of the compound A and the phenolic antioxidant is 0.01 to 100 parts by weight with respect to 100 parts by weight of polyolefin.
It is 1 part by weight, preferably 0.05 to 0.5 part by weight. If the amount is less than 0.01 parts by weight, the effect of preventing the obtained silane-modified polyolefin from being colored is not sufficiently exhibited, and if it exceeds 1 part by weight, no further improvement in the effect of preventing coloration can be expected. Not only is it irrelevant, but it is also uneconomical.

As the radical generator used in the present invention, it is desirable that the decomposition temperature is not too low in order 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-ethylketone peroxide, cyclohexanone peroxide, di-t-butylperoxide, diquimyl peroxide, 2,5-di-methyl-2, 5-di- (t-butylperoxy) hexane, 2,5-
Di-methyl-2,5-di- (t-butylperoxy) hexyne-3,1,3-bis- (t-butylperoxyisopropyl) benzene, t-butylquimyl 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 Examples of such organic peroxides include 5,5-di-methyl-2,5-di- (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 or 1,3
-Bis- (t-butylperoxyisopropyl) benzene is preferred. The mixing ratio of the radical generator is usually 0.005 to 5 parts by weight, preferably 0.01 to 1 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. When the melt-kneading temperature is lower than 150 ° C, sufficient silane modification is not carried out, and when it exceeds 300 ° C, the thermal oxidative deterioration of the polyolefin is promoted and the coloring of the polyolefin becomes remarkable, which is not preferable.

A preferable silane compound used in the present invention is an ethylenically unsaturated silane compound represented by the following general formula.

RSiR ' _n Y _3-n (wherein R is an ethylenically unsaturated hydrocarbon group or an ethylenically unsaturated hydrocarbon oxy group, R'is an aliphatic saturated hydrocarbon group or an aromatic hydrocarbon group, Y Represents a hydrolyzable organic group, and n represents an integer of 0 to 2.) For example, R in the general formula is vinyl, allyl, isopropenyl, butenyl, cyclohexenyl, cyclopentadienyl, cyclohexadienyl, γ. -Acryloyloxypropyl, γ-methacryloyloxypropyl and the like, R'is methyl, ethyl, propyl, decyl, tetradecyl, octadecyl, phenyl, benzyl and the like, and Y is methoxy, ethoxy, butoxy, formyloxy, acetoxy, propionyl. Examples thereof include oxy, alkylamino and arylamino. Particularly, vinyltrimethoxysilane, vinyltriethoxysilane or γ-methacryloxypropyltrimethoxysilane is preferable. The compounding ratio of the silane compound is usually 0.1 to 10 parts by weight, preferably 100 parts by weight of polyolefin, preferably
0.5 to 5 parts by weight. When the amount is less than 0.1 parts by weight, the improvement effect of the mechanical strength and the like of the obtained silane-modified polyolefin is not sufficiently exhibited, and even when it exceeds 10 parts by weight, the improvement effect of the mechanical strength and the like is small, and the silane The amount of the unreacted silane compound remaining in the modified polyolefin increases, which causes disadvantages such as deterioration in hue of the molded article and generation of bubbles, which is not preferable.

In the production method of the present invention, various additives such as thioether-based and phosphorus-based antioxidants that are usually added to polyolefin in the polyolefin containing 5 ppm or more of titanium content or 0.5 ppm of vanadium content of the catalyst residue used are antioxidants. Agents, light stabilizers, clarifying agents, nucleating agents, lubricants, antistatic agents,
Anti-fog agent, anti-blocking agent, non-dripping agent, pigment, heavy metal deactivator (copper damage inhibitor), dispersant or neutralizing agent for metal soaps, inorganic filler (eg talc, mica, clay) , Wollastonite, zeolite, asbestos, calcium carbonate, aluminum hydroxide, magnesium hydroxide, barium sulfate, calcium silicate, glass fiber, carbon fiber, etc. or coupling agent (for example, silane-based, titanate-based, boron-based, aluminate) The above-mentioned inorganic fillers or organic fillers (for example, wood flour, pulp, waste paper, synthetic fibers, natural fibers, etc.) surface-treated with a surface treating agent such as those of It can be used by blending it in a range that does not exist. In particular, when a phosphorus-based antioxidant is used in combination, a coloring preventing effect is synergistically exhibited. Preferred phosphorus-based antioxidants are distearyl-pentaerythritol-diphosphite and tetrakis (2,4-di-t-
Butylphenyl) -4,4'-biphenylene-di-phosphonite, bis (2,4-di-t-butylphenyl)-
Pentaerythritol-diphosphite, bis (2,6
Examples include -di-t-butyl-4-methylphenyl) -pentaerythritol-diphosphite and tris (2,4-di-t-butylphenyl) phosphite.

In the production method of the present invention, the compound A, the phenol-based antioxidant, the radical generator, the silane compound, and the polyolefin which are usually added to the polyolefin containing 5 ppm or more of titanium content or 0.5 ppm or more of vanadium content of the catalyst residue are used. Using a conventional mixer such as a Henschel mixer (trade name), a super mixer, a ribbon blender, or a Banbury mixer, a predetermined amount of each of the various additives is mixed at a temperature at which the combined radical generator does not decompose,
Using a conventional single-screw extruder, twin-screw extruder, Brabender or roll, the melt-kneading temperature is 150 ° C to 300 ° C, preferably 18
It is carried out by melt-kneading at 0 ° C to 270 ° C.

[Action]

In the present invention, the phenol-based antioxidant is a radical chain inhibitor, and the radical generator is a melt-kneading process, that is, a radical is generated by heating, a hydrogen atom of the polyolefin is abstracted to generate a radical of the polyolefin, and a silane compound is It is well known that the radicals of the polyolefin are grafted, that is, the polyolefin is silane-modified to improve the mechanical strength in the intended use.

In the production method of the present invention, the compound A is a polyolefin stabilized by a phenolic antioxidant,
When the silane compound is melt-kneaded in the presence of a radical generator using a silane compound to modify the silane, the action mechanism itself is not clear what action it has on the complex compound of titanium or vanadium. Since the effect of the present invention is not exhibited when a complete ester of fatty acid is used, it is presumed that the alcoholic hydroxyl group of Compound A acts on the complex compound of titanium or vanadium to form a stable chelate compound.

〔effect〕

The silane-modified polyolefin obtained by the production method of the present invention is a method of silane-modifying with a radical generator and a silane compound using a conventionally known phosphorus-based antioxidant or a polyolefin obtained by blending a polyol and a complete ester of a fatty acid. Compared to the silane-modified polyolefin obtained from the above, there is no coloration, and when the silane-modified polyolefin is used for the purposes described above, the mechanical strength is improved, so various molding methods such as injection molding, extrusion molding, blow molding, etc. According to the method, it can be suitably used for producing a desired molded article.

〔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: YI (Yellowness Index) of the obtained pellets was measured (in accordance with JIS K 7103), and the colorability was evaluated from the magnitude of this YI value.

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
Discharge of molten resin for 10 minutes when added) 2.0g / 10min powdery propylene homopolymer (titanium content 30ppm) 1
To 100 parts by weight, as compound A, trimethylolethane, glycerin monostearate, pentaerythritol monostearate or pentaerythritol distearate, 2,6-di-t-butyl-p-cresol, tetrakis as a phenolic antioxidant [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′-hydroxy-3 ′,
5'-di-t-butylphenyl) propionate, 2,5-di-methyl-2,5-di- (t-butylperoxy) hexane or 1,3-bis- (t- as a radical generator
Butyl peroxyisopropyl) benzene, vinyltrimethoxysilane as a silane compound, and other predetermined amounts of the other additives were placed in a Hensell mixer (trade name) at a blending ratio shown in Table 1 below, and mixed for 3 minutes with stirring. A single screw extruder having a rear diameter of 40 mm was melt-kneaded at 200 ° C. for silane modification and pelletization. Further, as Comparative Examples 1 to 3, 100 parts by weight of a powdery propylene homopolymer having a MFR of 2.0 g / 10 min (titanium content of 30 ppm) was mixed with respective predetermined amounts of the additives shown in Table 1 below. Melt-kneading was performed according to Examples 1 to 16 to obtain silane-modified pellets.

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

Examples 17-32, Comparative Examples 4-6 As polyolefin, powdery crystalline ethylene-propylene random copolymer (ethylene content of MFR 7.0 g / 10 min)
2.5 wt%, titanium content 33 ppm) 100 parts by weight, compound A as trimethylolethane, glycerin monostearate, pentaerythritol monostearate or pentaerythritol distearate, 2,6-di- as a phenol-based antioxidant t-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'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate, 2,5-as radical generator
Di-methyl-2,5-di- (t-butylperoxy) hexane or 1,3-bis- (t-butylperoxyisopropyl) benzene, vinyltrimethoxysilane as a silane compound, and other additives, respectively. A fixed amount was put in a Henschel mixer (trade name) at a blending ratio shown in Table 2 below, and the mixture was stirred and mixed for 3 minutes and then melt-kneaded at 200 ° C. in a single screw extruder with a diameter of 40 mm to modify the silane, Pelletized. Further, as Comparative Examples 4 to 6, powdery crystalline ethylene-propylene random copolymer having an MFR of 7.0 g / 10 min (ethylene content 2.5% by weight, titanium content 33 ppm) 100
Predetermined amounts of the additives shown in Table 2 below were mixed in parts by weight, and melt-kneaded in accordance with Examples 17 to 32 to obtain silane-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, powdery crystalline ethylene-propylene block copolymer having an MFR of 4.0 g / 10 min (ethylene content:
8.5 wt%, titanium content 33 ppm) 100 parts by weight, as compound A, trimethylolethane, glycerin monostearate, pentaerythritol monostearate or pentaerythritol distearate, 2,6-di- as a phenol antioxidant t-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'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate, 2,5-as radical generator
Di-methyl-2,5-di- (t-butylperoxy) hexane or 1,3-bis- (t-butylperoxyisopropyl) benzene, vinyltrimethoxysilane as a silane compound, and other additives, respectively. A fixed amount was put into a Henschel mixer (trade name) at a blending ratio shown in Table 3 below, and the mixture was stirred and mixed for 3 minutes, and then melt-kneaded at 200 ° C. in a single screw extruder with a diameter of 40 mm to modify the silane, Pelletized. Further, as Comparative Examples 7 to 9, powdery crystalline ethylene-propylene block copolymer having an MFR of 4.0 g / 10 min (ethylene content 8.5% by weight, titanium content 33 ppm) 100
Predetermined amounts of the additives shown in Table 3 below were mixed in parts by weight, and melt kneading was carried out according to Examples 33 to 48 to obtain silane-modified pellets.

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, powdery crystalline ethylene-propylene-butene-1 terpolymer (MFR 7.0 g / 10 min) (ethylene content 2.5% by weight, butene-1 content) 4.5 wt%, titanium content 33 ppm) 100 parts by weight, compound A as trimethylolethane, glycerin monostearate, pentaerythritol monostearate or pentaerythritol distearate, 2,6-di- as a phenol-based antioxidant t-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'-
Hydroxy-3 ′, 5′-di-t-butylphenyl) propionate, 2,5-di-methyl-as a radical generator
2,5-di- (t-butylperoxy) hexane or
1,3-Bis- (t-butylperoxyisopropyl) benzene, vinyltrimethoxysilane as a silane compound, and other additives were added in predetermined amounts at the blending ratios shown in Table 4 below. )put in,
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 be silane-modified and pelletized. Further, as Comparative Examples 10 to 12, powdery crystalline ethylene-propylene-butene-1 terpolymer having MFR of 7.0 g / 10 min (ethylene content 2.5 parts by weight, butene-1 content 4.5% by weight,
100 parts by weight of titanium content (33 ppm) was added with the respective predetermined amounts of the additives shown in Table 4 below, and melt-kneading was carried out in accordance with Examples 49 to 64 to obtain silane-modified pellets.

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
Discharge amount of molten resin for 10 minutes when added) 15.0 g / 10 min 100 parts by weight of powdered Ziegler-Natsuta ethylene homopolymer (titanium content 8 ppm), trimethylolethane as compound A, glycerin mono Stearate, pentaerythritol monostearate or pentaerythritol distearate, as a phenolic antioxidant
2,6-di-t-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'-
Hydroxy-3 ′, 5′-di-t-butylphenyl) propionate, 2,5-di-methyl-as a radical generator
2,5-di- (t-butylperoxy) hexane or
Predetermined amounts of 1,3- (t-butylperoxyisopropyl) benzene, vinyltrimethoxysilane as a silane compound, and other additives were added to a Henschel mixer (trade name) at the compounding ratios shown in Table 5 below. The mixture was put in, 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 be silane-modified and pelletized. Also,
As Comparative Examples 13 to 15, powdered Ziegura with MI of 15.0 g / 10 min.
Natsuta ethylene homopolymer (titanium content 8ppm) 100
Predetermined amounts of the additives shown in Table 5 below were mixed in parts by weight, and melt-kneaded in accordance with Examples 65 to 80 to obtain silane-modified pellets.

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 polyolefin, powdery crystalline ethylene-propylene block copolymer (ethylene content of MFR 4.0 g / 10 min)
16.0% by weight, vanadium content 0.6 ppm) 100 parts by weight,
Trimethylolethane, glycerin monostearate, pentaerythritol monostearate or pentaerythritol distearate as compound A, 2,6-di-t-butyl-p-cresol, tetrakis [methylene-3-methylene as a phenolic antioxidant (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-hydroxybenzine) isocyanurate or n-octadecyl-β- (4 '-Hydroxy-3', 5'-di-t-butylphenyl) propionate, as a radical generator
2,5-di-methyl-2,5-di- (t-butylperoxy)
Hexane mixer or 1,3-bis- (t-butylperoxyisopropyl) benzene, vinyltrimethoxysilane as a silane compound, and other additives were added in predetermined amounts at the blending ratios shown in Table 6 below. (Commercial name), stir and mix for 3 minutes, then melt knead at 200 ° C with a single-screw extruder with a diameter of 40 mm for silane modification,
Pelletized. Further, as Comparative Examples 16 to 18, MFR is 4.0 g /
10 minutes powdery crystalline ethylene-propylene block copolymer (ethylene content 16.0 wt%, vanadium content 0.
6 ppm) and 100 parts by weight of each of the additives shown in Table 6 described below were mixed in a predetermined amount and melt-kneaded according to Examples 81 to 96 to obtain silane-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 19-20 As polyolefins, powdery Ziegler-Natsuta high-density ethylene-propylene copolymer with MI 6.0 g / 10 min (3.0 methyl branches / 1000 carbon, vanadium content 0.6 ppm) 100
In parts by weight, as compound A, trimethylolethane, glycerin monostearate, pentaerythritol monostearate or pentaerythritol distearate, 2,6-di-t-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′-hydroxy-3 ′,
5'-di-t-butylphenyl) propionate, 2,5-di-methyl-2,5-di- (t-butylperoxy) hexane or 1,3-bis- (t- as a radical generator
Butylperoxyisopropyl) benzene, vinyltrimethoxysilane as a silane compound, and other additives in the respective predetermined amounts in a Henschel mixer (trade name) at the blending ratios shown in Table 7 below, and mixed with stirring for 3 minutes. A single screw extruder having a rear diameter of 40 mm was melt-kneaded at 200 ° C. for silane modification and pelletization. Further, as Comparative Examples 19 to 21, powdery Ziegler-Natsuta high-density ethylene-propylene copolymer having MI of 6.0 g / 10 min (methyl branch 3.0 / 1000
100 parts by weight of carbon and vanadium (0.6 ppm) were mixed with respective predetermined amounts of the additives shown in Table 7 below,
Melt-kneading treatment was performed according to 97 to 112 to obtain a silane-modified pellet.

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

Examples 113-128, Comparative Examples 22-24 Mooney viscosity ML1 + 4 (100 ° C.) as polyolefin
25 powdery amorphous ethylene-propylene random copolymers (propylene content 25%, vanadium content 0.6 ppm)
To 100 parts by weight, as compound A, trimethylolethane,
Glycerin monostearate, pentaerythritol monostearate or pentaerythritol distearate, 2,6-di-t-as phenol-based 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′-hydroxy-3 ′,
5'-di-t-butylphenyl) propionate, 2,5-di-methyl-2,5-di- (t-butylperoxy) hexane or 1,3-bis- (t- as a radical generator
Butyl peroxyisopropyl) benzene, vinyltrimethoxysilane as a silane compound, and other additives in predetermined amounts in a blending ratio shown in Table 8 below in a Henschel mixer (trade name) and mixed with stirring for 3 minutes. A single screw extruder having a rear diameter of 40 mm was melt-kneaded at 200 ° C. for silane modification and pelletization. In Comparative Examples 22 to 24, 100 parts by weight of a powdery amorphous ethylene-propylene random copolymer having a Mooney viscosity ML1 + 4 (100 ° C.) of 25 (propylene content 25%, vanadium content 0.6 ppm) was added to Predetermined amounts of the additives shown in Table 8 were mixed and melt-kneaded according to Examples 113 to 128 to obtain silane-modified pellets.

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]; trimethylolethane compound A [II]; glycerin monostearate compound A [III]; pentaerythritol monostearate compound A [IV]; pentaerythritol distearate phenolic antioxidant [I]; 2,6-di-t-butyl-
p-cresol phenolic antioxidant [II]; tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methanephenolic antioxidant [III]; 1,3,5-trimethyl-
2,4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene phenolic antioxidant [IV]; 1,3,5-tris- (3,5
-Di-t-butyl-4-hydroxybenzyl) isocyanurate phenolic antioxidant [V]; n-octadecyl-β-
(4'-Hydroxy-3 ', 5'-di-t-butylphenyl) propionate radical generator [I]; 2,5-di-methyl-2,5-di-
(T-Butylperoxy) hexane radical generator [II]; 1,3-bis- (t-butylperoxyisopropyl) benzene silane compound; vinyltrimethoxysilane phosphorous antioxidant 1; tetrakis (2,4- Di-t-butylphenyl) -4,4'-biphenylene-di-phosphonite Phosphorus antioxidant 2; Bis (2,4-di-t-butylphenyl) -pentaerythritol-diphosphite Polyol compound (complete of polyol and fatty acid Ester); pentaerythritol tetrastearate 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 phenol-based antioxidant, a radical generator and a silane compound were added to a propylene homopolymer containing 30 ppm of titanium in the catalyst residue according to the present invention and melted. It is kneaded and silane-modified. Comparing Examples 1 to 16 and Comparative Examples 1 and 2, Examples 1 to 16 showed less coloring, and Comparative Examples 1 and 2 in which a phosphorus-based antioxidant was used in place of the compound A showed remarkable coloring. I understand. Comparative Example 3 and Example 1 in which a complete ester of a polyol and a fatty acid was used instead of the compound A
When compared with -16, Comparative Example 3 is still not sufficiently satisfactory although the coloring property is improved to some extent. Further, in each Example, compound A according to the present invention, a phenol-based antioxidant, a radical generator, a silane compound and a phosphorus-based antioxidant were blended, melt-kneaded, and silane-modified. It can be seen that a remarkable synergistic effect by the combined use of the phosphorus-based antioxidant is recognized without inhibiting the excellent coloring preventing effect of the compound A as compared with the above.

Tables 2 to 8 show crystalline ethylene-propylene random copolymers, crystalline ethylene-propylene block copolymers, crystalline ethylene propylene-butene-13 terpolymers and Ziegler-Nutta ethylene homopolymers as polyolefins. Coalescence, crystalline ethylene-propylene block copolymer, Ziegler-Natsuta high-density ethylene-propylene copolymer, amorphous ethylene-propylene random copolymer is used, also for these, the same effect as described above. Was confirmed.

From this, the silane-modified polyolefin obtained by the production method of the present invention is silane-modified by melt-kneading in the presence of a radical generator using a silane compound by blending a compound having a conventionally known coloring preventing effect. 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.

Claims (6)

[Claims] 1. A polyol residue or a partial ester of said polyol and a fatty acid (hereinafter referred to as compound A) and a phenol-based antioxidant are added to 100 parts by weight of polyolefin containing a titanium content of the catalyst residue of 5 ppm or more or a vanadium content of 0.5 ppm or more. Preparation of silane-modified polyolefin, characterized in that 0.01 to 1 part by weight of each agent, 0.005 to 5 parts by weight of a radical generator, and 0.1 to 10 parts by weight of a silane compound are mixed and melt-kneaded at 150 to 300 ° C. Method. 2. The method for producing a silane-modified polyolefin according to claim 1, wherein trimethylolethane, glycerin and a fatty acid monoester or pentaerythritol and a fatty acid mono or diester are blended as the compound A. 3. As a phenol-based antioxidant, 2,6-di-
t-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'-hydroxy-
The method for producing a silane-modified polyolefin according to claim 1, wherein 3 ', 5'-di-t-butylphenyl) propionate is incorporated. 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) The method for producing a silane-modified polyolefin according to claim 1, wherein peroxyisopropyl) benzene is blended. 5. The method for producing a silane-modified polyolefin according to claim 1, wherein an ethylenically unsaturated silane compound is blended as the silane compound. 6. Polypropylene as propylene homopolymer, crystalline or amorphous ethylene-propylene random copolymer, crystalline ethylene-propylene block copolymer, crystalline propylene-butene-1 random copolymer, crystalline Ethylene-propylene-butene-13 terpolymer or crystalline propylene-hexene-butene-13
The method for producing a silane-modified polyolefin according to claim 1, wherein the original copolymer is used.