JPH0681797B2 - Olefin polymer composition - Google Patents

Description

Detailed Description of the Invention

The present invention relates to an olefin polymer composition having improved stability and heat resistance when heated by melting.

[0002] Olefin polymers are heated to a high temperature and held in a molten state during molding such as extrusion molding, injection molding and blow molding, so that oxidative deterioration is accelerated. From this point, various antioxidant stabilizer formulations have been proposed in order to prevent deterioration during melting and heating, that is, formulations containing sulfur compounds, organic phosphorus compounds, metal soaps, and nitrogen compounds in combination with phenolic antioxidants as the main component. Has been done. For example, phenol-based antioxidants include 2,6-di-t-butyl-p-cresol and n-octadecyl-β- (4'-
Hydroxy-3 ', 5'-di-t-butylphenyl) propionate, 4,4'-butylidene bis (3-methyl-6-t-butylphenol), 1,1,3-tris (2
-Methyl-5-t-butyl-4-hydroxyphenyl)
Butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Benzene, tetra [methylene-3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate] methane, etc., and these phenol-based antioxidants include sulfur compounds such as dilaurylthiodipropionate and distearylthiodipropionate, metallic soaps such as calcium stearate, and distearyl. Pentaerythritol diphosphite, tributyl phosphite, tri-p
-Organophosphorus compounds such as cresol phosphite are used in combination. However, these known stabilizer formulations do not sufficiently improve the thermal stability of the olefin polymer during melt heating. Therefore, in recent years, a stabilizer formulation mainly containing tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylenediphosphonite has been proposed as an alternative to these known stabilizer formulations. For example, 1,3,5-tris (4-t- as disclosed in JP-A-57-3842)
Butyl-3-hydroxy-2,6-dimethylbenzyl)
Combination system with isocyanurate, JP-A-57-57736
Combination system with 4,4'-thiobis (6-t-butyl-m-cresol) as disclosed in JP-A-57-21439, 2,2'methylenebis (4-methyl-6-t-butylphenol) as disclosed in JP-A-57-21439. ) And tetra [methylene-3- (3,5-
A combination system with di-t-butyl-4-hydroxyphenyl) propionate] methane has been proposed. However, the stabilizer formulations proposed by these proposals cannot show sufficient thermal stability in the melting heating temperature range exceeding 260 ° C., and the resin deteriorates due to oxidative deterioration, resulting in deterioration of product quality.
That is, as shown in Comparative Examples below, the molecular weight may be reduced and may be colored or may have a odor of decomposition.

The present inventors have found that the temperature is 260 ° C. or higher, especially 280 °
Maintains stability and heat resistance in high temperature range above ℃ 4-
With the aim of providing a homopolymer of methyl-1-pentene, 3-methyl-1-pentene or a homopolymer of 3-methyl-1-butene or a copolymer thereof, as a result of intensive studies, the present invention was completed. It arrived.

That is, the present invention is based on 100 parts by weight of the olefin polymer which is the homopolymer or copolymer.
(A) Tetrakis (2,4-di-t-butylphenyl)
0.01 to 1.0 parts by weight of 4,4'-biphenylene diphosphonite and (B) 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl)
-S-triazine-2,4,6- (1H, 3H, 5H) -trione 0.01 to 1.0 parts by weight of the olefin polymer composition.

In the present invention, (A) tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylenediphosphonite and (B) 1,3,5-tris (3,5-) Di-t-butyl-4-hydroxybenzyl)
The combined use of -s-triazine-2,4,6- (1H, 3H, 5H) -trione is essential. Even if the compound similar to (B) is used in combination with (A), the stability and heat resistance in the high temperature region such as 280 ° C. brought about by the constitution of the present invention cannot be obtained. That is, the molecular weight is reduced, and in some cases, it may be colored and odorous. (A) and (B)
The same applies when each is used alone. Further, in these cases, a large amount is required to obtain the same effect, which may cause adverse effects such as coloring the product. In the case of the above combined use, coloring does not occur even if a relatively large amount is blended.

The blending amount of (A) and (B) in the present invention is 0.01 to 1.0 part by weight of (A), particularly preferably 0.03 to 0, based on 100 parts by weight of the olefin polymer. .25 parts by weight of (B) 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H)
0.01 to 1.0 part by weight of trione, particularly preferably 0.03 to 0.25 part by weight. A compounding amount less than the above range does not show sufficient stability and heat resistance, and an amount exceeding the above range is not only economically disadvantageous, but also may impair the performance of the resin itself.

Olefin polymers are 3-methyl-1-butene, 3-methyl-1-pentene or 4-methyl-1.
Homopolymers or copolymers of pentene, as well as other copolymerizable monomers such as styrene, acrylonitrile, vinyl chloride, vinyl acetate, acrylates,
Examples thereof include copolymers with methacrylic acid esters and the like, and blends with the above-mentioned compounds or other thermoplastic resins or synthetic rubbers, block copolymers, graft copolymers and the like. Among these, 4-methyl-1-pentene polymer, 3-methyl-1-pentene polymer and 3-methyl-1-butene polymer are particularly preferable because the effects of the present invention are remarkably exhibited.

In order to obtain the composition of the present invention, various known methods, for example, a method of mixing with a ribbon blender, a Henschel mixer, etc., followed by melt mixing with an extruder, Banbury mixer, two rolls, etc. can be exemplified.

In the composition of the present invention, of course, other known resin additives, namely, lubricants, slip agents, anti-blocking agents, antistatic agents, antifogging agents, weather resistance stabilizers, heat resistance stabilizers, pigments, Dyes, inorganic fillers, flame retardants, etc. can be used in combination.
Among them, the heat resistance stabilizer is tetrakis [methylene-
3 (3,5-di-t-butyl-4- (hydroxyphenyl) propionate] methane and 1,3,5-trimethyl-
It is preferable to use 2,4,6-tris (3,5-di-t-butyl-4-hydroxyphenyl) benzylbenzene or the like.

According to the present invention, the stability and heat resistance of the olefin polymer at the time of melting and heating at a high temperature are remarkably improved. It should be noted that the composition of the present invention naturally has a higher heat resistance effect than the composition using the conventional stabilizer even at a lower temperature.

The present invention will be described below with reference to examples.

[0012]

EXAMPLES Example 1 and Comparative Examples 1-8 MFR 7.0 g / 10 min (ASTM D 1238,
260 ℃, 5kg), density 0.835g / cm ³ (AST
M D 1505) of poly-4-methyl-1-pentene (TPX ^R MX-002; manufactured by Mitsui Petrochemical Industries) in 100 parts by weight blended with compounds shown in Table 1, were mixed in a Henschel mixer, an extruder Granulated at 340 ° C. Table 1 shows the MFR, intrinsic viscosity, decomposed gas, coloring and presence of odor of the produced pellets. Incidentally, poly-4-methyl-1-pentene was simultaneously mixed with zinc stearate or calcium stearate as a halogen promoter.

Measurement method MFR; ASTM D 1238 (260 ° C., 5 kg) Intrinsic viscosity [η]; 135 ° C., decalin decomposition gas; The gas (C _{1 to} C ₁₃ ) discharged into the head space was measured by the gas chromatography method. The unit is (vol / vo at 100 ℃
l) ppm.

[0014]

[Table 1]

A tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylenediphosphonite B ₁ 4-hydroxymethyl-2,6-di-t-butylphenol B ₂ 1,3, 5-tris (3,5-di-t-butyl-4-
Hydroxybenzyl) -s-triazine-2,4,6-
(1H, 3H, 5H) -Trione C tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane D 1,3,5-trimethyl-2,4,6- Tris (3.5
-Di-t-butyl-4-hydroxyphenyl) benzylbenzene E 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate F calcium stearate G zinc stearate

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C08K 5: 5393)

Claims (1)

[Claims] 1. To 100 parts by weight of a homopolymer of 4-methyl-1-pentene, 3-methyl-1-pentene or 3-methyl-1-butene or a copolymer thereof,
(A) Tetrakis (2,4-di-t-butylphenyl)
0.01 to 1.0 parts by weight of 4,4'-biphenylene diphosphonite and (B) 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl)
-Os-triazine-2,4,6- (1H, 3H, 5H) -trione in an amount of 0.01 to 1.0 parts by weight.