JPH0796587B2 - 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 phosphaite compound (hereinafter referred to as compound A), a thioether-based antioxidant, a radical generator and a silane compound, which are specific to polyolefin containing 5 ppm or more of titanium content or 0.5 ppm or more of vanadium content of a catalyst residue, are used. The present invention relates to a method for producing a silane-modified polyolefin, which comprises blending in a specific amount and melt-kneading 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. As a result, deterioration of processability and problems of coloring and odor caused by oxidative deterioration occur. 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. 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 the silane-modified polyolefin obtained by treatment and silane modification is markedly colored. First, a polyol or a partial ester of a polyol and a fatty acid and a phenolic antioxidant are blended with the polyolefin, and a silane compound is used as a radical generator. Silane-modified poly that is melt-kneaded in the presence of Proposed a method of manufacturing a Refuin (Japanese Patent Application No. Sho 61-149099
issue).

Further, by using a silane compound composed of an ethylenically unsaturated silane compound in the polyolefin, melt kneading treatment in the presence of a radical generator to silane-modify the polyolefin, the silane-modified polyolefin obtained is used for the following purposes. It is well known. 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]

The present inventors have not been satisfied with the method for producing a silane-modified polyolefin as previously proposed in Japanese Patent Application No. 61-149099, and have used a silane compound to produce a polyolefin containing a large amount of titanium or vanadium as a catalyst residue. Further studies were conducted on a method for obtaining a silane-modified polyolefin which is free from coloration even if it is melt-kneaded in the presence of a radical generator. As a result, a specific amount of a phosphite compound (hereinafter referred to as compound A), a thioether-based antioxidant, a radical generator and a silane compound is 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. When blended and melt-kneaded,
It was found that a silane-modified polyolefin can be obtained which is free from coloration and has a practically satisfactory thermal oxidative deterioration prevention property during melt-kneading and thermal stability during practical use, and based on this finding, the present invention was completed.

As is clear from the above description, the object of the present invention is to provide compound A, a thioether 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.
For 100 parts by weight of polyolefin containing 5 ppm or more,
A phosphite compound (hereinafter referred to as compound A) represented by the following general formula [I] and 0.01 to 1 part by weight of a thioether antioxidant, respectively, and a radical generator of 0.1 part by weight.
A method for producing a silane-modified polyolefin, which comprises blending 005 to 5 parts by weight and 0.1 to 10 parts by weight of a silane compound, and melt-kneading at 150 ° C to 300 ° C.

[Wherein, R ₁ is hydrogen, an alkyl group having 1 to 3 carbon atoms or —CH ₂ —CH (CH ₃ ) —R ₄ {R ₄ is —OP (OR ₅ ) ₂ (R
₅ represents an alkyl group having 8 to 18 carbon atoms)}. Also, R ₂
And R ₃ represent the same or different alkyl groups having 1 to 8 carbon atoms. ] 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 It is a polyolefin obtained by a phase 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 titanium content of the catalyst residue of 5 ppm or more or vanadium content of 0.5 ppm or more, and ethylene, propylene, butene-1, pentene-1,4-methyl-pentene-1, hexene. 1, homopolymers of α-olefins such as octene-1 and two or more α-olefins
A crystalline or amorphous random copolymer or a crystalline block copolymer of olefin, an amorphous ethylene-propylene-non-conjugated diene terpolymer, of these α-olefin and vinyl acetate, acrylic ester, etc. Examples thereof include a copolymer or a saponified product of the copolymer, a copolymer of these α-olefins and an unsaturated carboxylic acid or an anhydride thereof, and a reaction product of the copolymer and a metal ion compound. Of course, these polyolefins may be used alone or in combination of two or more kinds. 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,
It is also possible to use a mixture with polybutylene terephthalate, polyvinyl chloride, etc.). 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-13
The original copolymer and a mixture of two or more of these, in which 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.

Examples of the compound A used in the present invention include 1,1'-bis (4-di-nonylphosphite-3,5-di-t-butylphenyl) methane, 1,1'-bis (4-di-tridecylphene). Osphite-3,5-di-t-butylphenyl) methane, 1,1'-bis (4-di-stearylphosphite-3,5-di-t-butylphenyl) methane, 1,1'-bis (3 -Methyl-4-di-nonylphosphite-5-
t-butylphenyl) methane, 1,1'-bis (3-methyl-4-di-tridecylphosphite-5-t-butylphenyl) methane, 1,1'-bis (3-methyl-4-)
Di-stearyl phosphite-5-t-butylphenyl) methane, 4,4'-butylidene-bis (3-methyl-
6-t-butylphenyl) di-nonylphosphite,
4,4'-butylidene-bis (3-methyl-6-t-butylphenyl) di-tridecylphosphite, 4,4'-
Butylidene-bis (3-methyl-6-t-butylphenyl) di-stearyl phosphite, 1,1'-bis (2
-Di-nonylphosphite-3-t-butyl-5-methylphenyl) methane, 1,1'-bis (2-di-tridecylphosphite-3-t-butyl-5-methylphenyl) methane, 1,1 ′ -Bis (2-di-stearylphosphite-3-t-butyl-5-butylphenyl) methane, 1,1′-bis (2-di-nonylphosphite-
3-t-butyl-5-ethylphenyl) methane, 1,1 ′
-Bis (2-di-tridecylphosphite-3-t-
Butyl-5-ethylphenyl) methane, 1,1'-bis (2-di-stearylphosphite-3-t-butyl-5-ethylphenyl) methane, 1,1'-bis (2-di-nonylphosphite- 3,5-di-t-butylphenyl) methane, 1,1'-bis (2-di-tridecylphosphite-3,5-di-t-butylphenyl) methane, 1,
1'-bis (2-di-stearyl phosphite-3,5-
Di-t-butylphenyl) methane, 2,2'-bis (1-
Di-nonylphosphite-4,6-di-t-butylphenyl) ethane, 2,2'-bis (1-di-tridecylphosphite-4,6-di-t-butylphenyl) ethane,
2,2'-bis (1-di-stearyl phosphite-4,6
-Di-t-butylphenyl) ethane, 1,1'-bis (2
-Di-nonylphosphite-3-t-octyl-5-
Methylphenyl) methane, 1,1'-bis (2-di-tridecylphosphite-3-t-octyl-5-methylphenyl) methane, 1,1'-bis (2-di-stearylphosphite-3-t -Octyl-5-methylphenyl) methane, 1,1,3-tris (2-methyl-4-di-nonylphosphite-5-t-butylphenyl) butane, 1,1,3-tris (2-methyl-4) -Di-tridecyl phosphite-5-t-butylphenyl) butane, 1,
Examples thereof include 1,3-tris (2-methyl-4-di-stearylphosphaite-5-t-butylphenyl) butane and a mixture of two or more thereof. Especially 4,4'-
Butylidene-bis (3-methyl-6-t-butylphenyl) di-tridecylphosphite or 1,1,3-tris (2-methyl-4-di-tridecylphosphite-
5-t-Butylphenyl) butane and mixtures thereof are preferred. Examples of thioether antioxidants include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, dicetyl thiodipropionate, distearyl thiodipropionate, dilauryl thiodibutyrate, ditril Decylthiodibutyrate, dimyristylthiodibutyrate, dicetylthiodibutyrate, distearylthiodibutyrate, pentaerythritol-β-lauryl-thiodipropionate, laurylstearylthiodipropionate, pentaerythritol-tetrakis- (3- Lauryl thiopropionate), pentaerythritol-tetrakis- (3-myristyl thiopropionate), pentaerythritol-tetrakis- (3-stearyl thiopropionate), bis (4-t Amirufueniru) sulfides, distearyl Soo Ruff Id, thio ethylene glycol - bis - (beta-aminocrotonate) and poly ((1,4-bis (hydroxymethyl) cyclohexane - thio - dipropionate)) can be exemplified. Particularly dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol-tetrakis-
(3-lauryl thiopropionate and a mixture of two or more thereof are preferred. The compound A and the thioether-based antioxidant are mixed in proportions of 0.01 to 1 part by weight, preferably 0.05 part by weight, based on 100 parts by weight of polyolefin. ~
0.5 parts by weight. When the amount is less than 0.01 part by weight, the effect of preventing thermal oxidative deterioration during melt-kneading of silane-modified polyolefin and the thermal stability during practical use are insufficient, and the amount may exceed 1 part by weight. The effect of preventing thermal oxidative deterioration during melt-kneading and the improvement of thermal stability during practical use cannot be expected, which is impractical and 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-butyl peroxide) (Oxy) hexane, 2,5-di-methyl-2,5-di- (t-butylperoxy) hexane-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-
Butyl peroxy) butane, p-menthane hydroperoxide, di-isopropylbenzene hydroperoxide, quinene hydroperoxide, t-butyl hydroperoxide, p-cymen hydroperoxide, 1,1,3,3-tetra -Methylbutyl hydroperoxide or 2,5-di-methyl-2,5-di-
An organic peroxide such as (hydroperoxy) hexane can be exemplified. Especially 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. Melt kneading temperature is 15
If the temperature is lower than 0 ° C, sufficient silane modification is not performed, and if the temperature exceeds 300 ° C, deterioration of the polyolefin by thermal oxidation 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 represents vinyl, allyl, isopropenyl, butenyl, cyclohexenyl, cyclopentadienyl, cyclohexadienyl, γ-acryloyloxypropyl. , Γ
-Methacryloyloxypropyl, etc., R'is methyl, ethyl, propyl, decyl, tetradecyl, octadecyl, phenyl, benzine, etc., Y is methoxy, ethoxy, butoxy, formyloxy, acetoxy, propionyloxy, alkylamino, aryl Amino etc. can be mentioned. Particularly, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane or a mixture of two or more thereof is preferable. The compounding ratio of the silane compound is usually 0.1 to 10 parts by weight with respect to 100 parts by weight of polyolefin.
It is preferably 0.5 to 5 parts by weight. If the amount is less than 0.1 part by weight, the effect of improving the mechanical strength of the silane-modified polyolefin is not sufficiently exerted, and if the amount exceeds 10 parts by weight, the degree of improvement in the mechanical strength is small and the silane-modified polyolefin has However, the amount of unreacted silane compound remaining therein becomes large, and the resulting molded article has disadvantages such as deterioration in hue and generation of bubbles.

In the production method of the present invention, various additives such as a phosphorus-based antioxidant and a light stabilizer which are usually added to a polyolefin containing a titanium residue of a catalyst residue of 5 ppm or more or a vanadium content of 0.5 ppm or more. , Clearing agent,
Nucleating agents, lubricants, antistatic agents, anti-fog agents, anti-blocking agents, anti-drop agents, pigments, heavy metal deactivators (copper damage inhibitors), dispersants or neutralizers for metal soaps, etc. 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, carbon fiber, potassium titanate, metal fiber, etc. or coupling agent (for example, silane-based, titanate-based, boron-based,
For the purpose of the present invention, the inorganic filler or organic filler (for example, wood powder, bulb, waste paper, synthetic fiber, natural fiber, etc.) surface-treated with a surface treatment agent such as aluminate type, zircoaluminate type, etc. is used. It can be used by mixing within a range that does not impair it.

In the production method of the present invention, the compound A, the thioether-based antioxidant, the radical generator, the silane compound, and the polyolefin 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 usually added to the polyolefin. 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 compound A has the functions of both a phenol-based antioxidant and a phosphorus-based antioxidant, and acts as a radical scavenger and a peroxide decomposer to prevent thermal oxidative deterioration during melt kneading and to be used practically. It contributes to the improvement of thermal stability. Furthermore, the thioether antioxidant is used as a peroxide decomposer to improve the thermal stability during practical use, and the radical generator is a melt-kneading process, that is, it generates radicals by heating to abstract the hydrogen atoms of polyolefin. It is well known that a radical of polyolefin is generated and a silane compound grafts to the radical of polyolefin, that is, silane-modified the polyolefin, and acts to improve mechanical strength in the above-mentioned intended use.

In the production method of the present invention, the above-mentioned compound A does not cause coloration because the hydroxyl group of hindered phenol forms a phosphite unlike the usual phenol-based antioxidant of compound A. It is considered that this does not generate a chromophoric atomic group such as a quinone compound as seen in the antioxidant process.

〔effect〕

The silane-modified polyolefin obtained by the production method of the present invention is not further colored as compared with the silane-modified polyolefin according to the above-mentioned Japanese Patent Application No. 61-149099 filed by the inventors of the present invention, and the silane-modified polyolefin has the above-mentioned object. Since mechanical strength and the like are improved when it is used, it can be suitably used for producing a desired molded article by various molding methods such as an injection molding method, an 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; YI (Yellowness Index) of the obtained pellets was measured (in accordance with JIS K7103), and the colorability was evaluated from the magnitude of this YI value. The smaller this value is, the less the coloring is.

Examples 1-12, Comparative Examples 1-3 As polyolefin, MFR (load at 230 ° C 2.16 Kg
Amount of molten resin discharged for 10 minutes when added) 2.0 g / 10 minutes 100 parts by weight of unstabilized powdery propylene homopolymer (titanium content 30 ppm)
-Butylidene-bis (3-methyl-6-t-butylphenyl) di-tridecylphosphite or 1,1,3-
Tris (2-methyl-4-di-tridecylphosphite-5-t-butylphenyl) butane, dimyristyl thiodipropionate as a thioether antioxidant,
Distearyl thiodipropionate or pentaerythritol-tetrakis- (3-laurylthiopropionate), 2,5-di-methyl-2,5 as radical generator
-Di- (t-butylperoxy) hexane or 1,3
-Bis- (t-butylperoxyisopropyl) benzene, vinyltrimethoxysilane as a silane compound, and other additives were added to Henschel Mixer (trade name) in predetermined proportions shown in Table 1 below. 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. Also,
As Comparative Examples 1 to 3, MFR having an unstabilized powdery propylene homopolymer of 2.0 g / 10 min (titanium content 30 ppm) 1
A predetermined amount of each of the additives shown in Table 1 described below was mixed with 00 parts by weight, and melt-kneaded in accordance with Examples 1 to 12 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 13-24, Comparative Examples 4-6 As 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, 4,4'-butylidene-bis (3-methyl-6-t-butylphenyl) di-tridecylphosphite or 1,1,3-tris (2-methyl-4-di- Tridecyl phosphite-5-t-butylphenyl) butane, thioether antioxidant as dimyristyl thiodipropionate, distearyl thiodipropionate or pentaerythritol-tetrakis- (3-lauryl thiopropionate), radical generation 2,5-di-methyl-2,5-di- (t-butylperoxy) hexane or 1,3-bis- (t-butylperoxyisopropyl) benzene as an agent, vinyltrimethoxysilane as a silane compound, and others Add the specified amount of each of the additives to Henschel Mixer (trade name) in the blending ratios shown in Table 2 below. And melt kneaded with the silane-modified at 200 ° C. in a single-screw extruder having a diameter of 40mm was stirred and mixed for 3 minutes to Peretsuto of. In addition, as Comparative Examples 4 to 6
Unstabilized powder crystalline ethylene-propylene random copolymer with MFR 7.0g / 10min (ethylene content 2.5
% By weight, titanium content 33 ppm) and 100 parts by weight of each of the additives shown in Table 2 to be described below.
Melt-kneading was performed according to 24 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 2.

Examples 25-36, Comparative Examples 7-9 As polyolefins, MFR 4.0 g / 10 min unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 8.5 wt%, titanium content 33 ppm) Ten
To 0 parts by weight, as compound A, 4,4'-butylidene-bis (3-methyl-6-t-butylphenyl) di-tridecylphosphite or 1,1,3-tris (2-methyl-4-di- Tridecyl phosphite-5-t-butylphenyl) butane, thioether antioxidant as dimyristyl thiodipropionate, distearyl thiodipropionate or pentaerythritol-tetrakis- (3-lauryl thiopropionate), radical generation 2,5-di-methyl-2,5-di- (t-butylperoxy) hexane or 1,3-bis- (t-butylperoxyisopropyl) benzene as an agent, vinyltrimethoxysilane as a silane compound, and others Add the specified amount of each additive in the Henschel mixer (trade name) in the blending ratio shown in Table 3 below. And melt kneaded with the silane-modified at 200 ° C. in a single-screw extruder having a diameter of 40mm was stirred and mixed for 3 minutes to Peretsuto of. In addition, as Comparative Examples 7 to 9
Unstabilized powdery crystalline ethylene-propylene block copolymer with an MFR of 4.0 g / 10 min (ethylene content 8.
5 wt%, titanium content 33 ppm) 100 parts by weight of the third
Prescribed amounts of each of the additives listed in the table, Example 25
Melt-kneading treatment in accordance with .about.36 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 37-48, Comparative Examples 10-12 MFR 7.0 g / 10 min unstabilized powdery crystalline ethylene-propylene-butene-1 as polyolefin.
Terpolymer (ethylene content 2.5% by weight, butene-1
4.5 wt%, titanium content 33ppm) 100 parts by weight,
As compound A, 4,4'-butylidene-bis (3-methyl-6-t-butylphenyl) di-tridecylphosphite or 1,1,3-tris (2-methyl-4-di-tridecylphosphite- 5-t-butylphenyl) butane, dimyristyl thiodipropionate, distearyl thiodipropionate or pentaerythritol-tetrakis- (3- as a thioether antioxidant.
Lauryl thiopropionate), as a radical generator
2,5-di-methyl-2,5-di- (t-butylperoxy)
Hexane mixer with hexane or 1,3-bis- (t-butylperoxyisopropyl) benzene, vinyltrimethoxysilane as a silane modifier and predetermined amounts of other additives at the compounding ratios shown in Table 4 below. (Product name), stir and mix for 3 minutes, then melt knead at 200 ° C with a single screw extruder with a diameter of 40 mm to modify the silane,
Pelletized. Further, as Comparative Examples 10 to 12, the MFR is 7.0 g /
Unstabilized powdery crystalline ethylene-propylene-butene-1 terpolymer for 10 minutes (ethylene content 2.
5% by weight, butene-1 content 4.5% by weight, titanium content 33
(ppm) 100 parts by weight of each of the additives shown in Table 4 to be described later, and the mixture was melt-kneaded in accordance with Examples 37 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 4.

Examples 49 to 60, 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 4,4'-butylidene-bis (3-methyl-6-t-butylphenyl) di-tridecylphosphite or 1,1,3-tris (2-methyl-4-di-tridecylphosphite-5- t-butylphenyl) butane, dimyristyl thiodipropionate, distearyl thiodipropionate or pentaerythritol-tetrakis- as a thioether antioxidant
(3-laurylthiopropionate), 2,5-di-methyl-2,5-di- (t-butylperoxy) hexane or 1,3-bis- (t-butylperoxyisopropyl) as a radical generator ) Benzene, vinyltrimethoxysilane as a silane modifier, and other additives in the respective predetermined amounts in the blending ratios shown in Table 5 below are placed in a Henschel mixer (trade name), and the mixture is stirred and mixed for 3 minutes.
Was melt-kneaded at 200 ° C. with a single-screw extruder to modify the silane and pelletize. Also, as Comparative Examples 13 to 15, MI is 1
5.0g / 10min unstabilized powder Ziegura-Natsuta high density ethylene homopolymer (titanium content 8ppm) 10
A predetermined amount of each of the additives shown in Table 5 below was added to 0 part by weight, and melt-kneaded in accordance with Examples 49 to 60 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 5.

Examples 61-72, 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 of 4,4'-butylidene-as compound A
Bis (3-methyl-6-t-butylphenyl) di-tridecylphosphite or 1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-t-butylphenyl) butane, thioether type Dimyristyl thiodipropionate, distearyl thiodipropionate or pentaerythritol-tetrakis- (3-lauryl thiopropionate) as antioxidant, 2,5-di-methyl-2,5-di-diene as radical generator -(T-Butylperoxy) hexane or 1,3-bis- (t-
Butyl peroxyisopropyl) benzene, vinyltrimethoxysilane as a silane compound, and other additives in predetermined amounts in a Henschel mixer (trade name) at the blending ratios shown in Table 6 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 16 to 18, powdery crystalline ethylene-propylene block copolymer having an MFR of 4.0 g / 10 min (stabilized ethylene content)
16.0 wt%, vanadium content 0.6 ppm) 100 parts by weight of each of the additives listed in Table 6 below were added in a predetermined amount,
Melt-kneading was carried out according to Examples 61 to 72 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 73 to 84, Comparative Examples 19 to 21 As polyolefin, 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 4,4'-butylidene-bis (3-methyl-6-t-butylphenyl) di-tridecylphosphite or 1,1,3-tris (2-methyl) as compound A -4-di-tridecylphosphaite-5-t-butylphenyl) butane, thioether antioxidant as dimyristyl thiodipropionate, distearyl thiodipropionate or pentaerythritol-tetrakis- (3-lauryl thiopropio) ), As a radical generator, 2,5-di-methyl-2,5-
Di- (t-butylperoxy) hexane or 1,3-
A predetermined amount of bis- (t-butylperoxyisopropyl) benzene, vinyltrimethoxysilane as a silane compound, and other additives were placed in a Henschel mixer (trade name) at the compounding ratios shown in Table 7 below. 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. Also,
As Comparative Examples 19 to 21, powdered Ziegler-Natsuta high-density ethylene-propylene copolymer (MI: 6.0 g / 10 min, unstabilized) (methyl branch 3.0 / 1000 carbon, vanadium content 0.6 ppm) 100 weight Each part was blended with a predetermined amount of each of the additives described in Table 7 below, and melt-kneaded according to Examples 73 to 84 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 7.

Examples 85-96, Comparative Examples 22-24 Mooney viscosity ML1 + 4 (100 ° C.) as polyolefin
25 parts of non-stabilized powdery amorphous ethylene-propylene random copolymer (25% propylene content, 0.6 ppm vanadium content) in 100 parts by weight of 4,4 'as compound A
-Butylidene-bis (3-methyl-6-t-butylphenyl) di-tridecylphosphite or 1,1,3-
Tris (2-methyl-4-di-tridecylphosphite-5-t-butylphenyl) butane, dimyristyl thiodipropionate as a thioether antioxidant,
Distearyl thiodipropionate or pentaerythritol-tetrakis- (3-laurylthiopropionate), 2,5-di-methyl-2,5 as radical generator
-Di- (t-butylperoxy) hexane or 1,3
-Bis- (t-butylperoxyisopropyl) benzene, vinyltrimethoxysilane as a silane compound, and other additives were added in predetermined amounts in a Henschel mixer (trade name) at the compounding ratios shown in Table 8 below. 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. Also,
As Comparative Examples 22 to 24, the Mooney viscosity ML1 + 4 (100 ° C) is 25.
Unstabilized powdery amorphous ethylene-propylene random copolymer (propylene content 25%, vanadium content 0.6 ppm) is added to 100 parts by weight of each of predetermined amounts of the additives described in Table 8 below. The ingredients were blended and melt-kneaded according to Examples 85 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 8.

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

Compound A [I]; 4,4'-butylidene-bis (3-methyl-6-t-butylphenyl) di-tridecylphosphite Compound A [II]; 1,1,3-tris (2-methyl-4) -The-
Tridecyl phosphite-5-t-butylphenyl)
Butane thioether antioxidant [I]; dimyristyl thiodipropionate thioether antioxidant [II]; distearyl thiodipropionate thioether antioxidant [III]; pentaerythritol-tetrakis- (3-laurylthio Propionate) Radical generator [I]; 2,5-di-methyl-2,5-di-
(T-Butylperoxy) hexane radical generator [II]; 1,3-bis- (t-butylperoxyisopropylbenzene silane compound; vinyltrimethoxysilane 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 polyolate fatty acid); pentaerythritol monostearate phosphite compound (phenolic hydroxyl group remains Phosphite compounds); bis (p-octyl) phenyl-bis [2-t-butyl-5-methyl-4 [α-
(3-t-Butyl-6-methyl-4-hydroxyphenyl)] butylphenyl] -1,6-hexanediol-diphosphite 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 thioether-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. Examples 1 to 12 and Comparative Example 1 (Method for producing a silane-modified polyolefin described in Japanese Patent Application No. 61-149099 previously proposed by the present inventors, that is, a polyol ester and a partial ester of a fatty acid, a phenolic antioxidant, It is understood that Examples 1 to 12 are less colored than Comparative Example 1 and the anti-coloring property is improved by comparing the radical generator and the silane compound, which are melt-kneaded and silane-modified. Comparing Comparative Example 2 and Examples 1 to 12 using a phosphite-based compound in which a phenolic hydroxyl group remains instead of Compound A, Comparative Example 2 is markedly colored, and this coloring is the phenolic property of the phosphite-based compound. It can be seen that the hydroxyl group is caused by forming a quinone compound. Further, comparing Comparative Examples 3 and 1 to 12 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 1-12.

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. A polymer, a crystalline ethylene-propylene block copolymer, a Ziegler-Natta type ethylene-propylene polymer, and an amorphous ethylene-propylene random copolymer are used, and the same effects as those described above are confirmed. Was done.

Therefore, it can be seen that the silane-modified polyolefin modified polyolefin obtained by the production method of the present invention is not colored and its mechanical strength and the like are improved.

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 (7)

[Claims] 1. A phosphite compound (hereinafter referred to as compound A) represented by the following general formula [I] 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. And 0.01 to 1 part by weight of a thioether-based antioxidant, 0.005 to 5 parts by weight of a radical generator, and 0.1 to 10 parts by weight of a silane compound, and melt-kneading at 150 to 300 ° C. Method for producing silane-modified polyolefin. [Wherein, R ₁ is hydrogen, an alkyl group having 1 to 3 carbon atoms or —CH ₂ —CH (CH ₃ ) —R ₄ {R ₄ is —OP (OR ₅ ) ₂ (R
₅ represents an alkyl group having 8 to 18 carbon atoms)}. Also, R ₂
And R ₃ represent the same or different alkyl groups having 1 to 8 carbon atoms. ] 2. The method for producing a silane-modified polyolefin according to claim 1, wherein the alkyl group represented by R ₂ and R ₃ in the general formula [I] is a methyl group or a t-butyl group. . 3. As compound A, 4,4'-butylidene-bis (3-methyl-6-t-butylphenyl) di-tridecylphosphite, 1,1,3-tris (2-methyl-4)
A method for producing a silane-modified polyolefin according to claim (1), which comprises -di-tridecylphosphaite-5-t-butylphenyl) butane or a mixture of two or more thereof. 4. As a thioether antioxidant, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol-tetrakis- (3
-Lauryl thiopropionate) or a mixture of two or more thereof. A process for producing a silane-modified polyolefin according to claim (1). 5. As a radical generator, 2,5-di-methyl-2,5-di- (t-butylperoxy) hexane, 2,5-
The compound according to claim (1), which comprises di-methyl-2,5-di- (t-butylperoxy) hexyne-3 or 1,3-bis- (t-butylperoxyisopropyl) benzene. Method for producing silane-modified polyolefin. 6. The method for producing a silane-modified polyolefin according to claim 1, wherein an ethylenically unsaturated silane compound is blended as the silane compound. 7. 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 silane-modified polyolefin according to claim (1), which uses an original copolymer or two or more kinds thereof.