JPS62129328A - Low coloring polyolefin composition - Google Patents

Abstract

PURPOSE:A composition, obtained by blending a polyolefin based polymer produced by using a catalyst containing a vanadium compound with phosphorus oxy acid and having very little coloring. CONSTITUTION:A composition obtained by blending (A) 100pts.wt. polyolefin based polymer prepared by using a coordination catalyst consisting essentially of a vanadium compound with (B) 0.001-10pts.wt. one or more selected from phosphorus oxy acids. Polyphosphoric acid, phorphorous acid, sodium dihydrogenphosphate . diammonium phosphate or sodium pyrophosphate .decahydrate is used as the component (B) and homogenized in the component (A) at 40-300 deg.C in an inert gas atmosphere.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a Zieg compound containing a vanadium compound as an essential component.
The present invention relates to a polyolefin composition with extremely little coloring, which is made by blending a specific coloring inhibitor into an olefin polymer or copolymer produced using a coordination catalyst such as a LER type.

Prior Art Zieg carried out with catalyst systems based on vanadium compounds
The olefin polymer produced by the ler type isocoordination anionic polymerization reaction has a vanadium content of 0.0% in the catalyst residue. l
ppm (by weight) or more, it takes on a shade of color that changes variously over time.

In particular, when the vanadium content exceeds 25 ppm, the commercial value of the polymer in terms of appearance is often significantly impaired by the coloring. This change in color and hue over time is caused by the vanadium compound in the coexistence of other substances such as the alkyl aluminum compound of the catalyst component, trace amounts of other elements, antioxidants, rust inhibitors, water, oxygen, etc. This is caused by a complex reaction in the polymer.

It is highly desirable from an economic and practical point of view to obtain near-colorless polymers that do not change color even during long storage and handling.

For example, to produce light-colored or white melt blends or vulcanizates, it is advantageous to start from polymers that are as colorless as possible.

On the other hand, in order to remove the defects that cause coloration, conventionally, a deashing treatment is used to remove catalyst residues in order to reduce the vanadium content of a single weight coalesce to at most 25 ppm or less, and in some cases to 1 ppm or less. He was giving a lot of help.

Such treatment complicates the manufacturing process and significantly reduces the price competitiveness of the product in terms of utility and the like.

Problems to be Solved by the Invention The present invention provides Zie41 containing a vanadium compound as an essential component.
The aim is to prevent coloring of olefin polymers produced using coordination catalysts such as er-type catalysts as much as possible.

Means for Solving the Problems The present invention aims to solve the above-mentioned drawbacks of the prior art, and as means thereof, provides the following composition.

That is, according to the present invention, one or more specific phosphorus oxyacids are combined into a compound of about 0.1 to 5 Qpp1 produced by a coordination anionic polymerization reaction such as Ziegler type.
By dispersing and homogenizing M in vanadium-containing olefinic polymers, polyolefin compositions which surprisingly remain colorless or only develop a very faint coloration during long working and storage times are obtained. can get things.

In addition, in applications that do not require much heat-resistant anti-aging performance, even olefin polymers or copolymers produced by coordination anionic polymerization reactions such as Ziegler type containing a large amount of vanadium of about 50 to 3 ooppm can be used. Similarly to the above, a polyolefin composition with good hue can be obtained.

action Each component of the present invention will be explained below.

The composition of the present invention is composed of an olefinic polymer and a phosphoric acid.

The olefin polymer constituting the composition is a general olefin polymer or copolymer produced by a catalyst containing the vanadium compound as an essential component, and two thereof.
It is a mixture of more than one species.

Common olefin polymers or copolymers include, for example, polyethylene, polypropylene, poly-1-olefins such as poly-1-butene, and i-ethylene, 1-olefin, cycloalkenes, bicycloalkenes, tricycloalkenes, etc. 2 such as alkenes, tetracycloalkenes, polyenes, etc.
Examples include copolymers made from more than one type of monomer.

Examples of the polyene include 5-ethylidene-2-fulbornene, 5-vinyl-2-norbornene, dicyclopentadiene, 1,4-hexadiene, and 1,5.9-cyclododecatriene.

The olefin polymer constituting the present composition can be produced by a known method.

The vanadium catalyst used in the production of the olefinic polymer is preferably a vanadium compound soluble in a hydrocarbon solvent, such as VCQ4. VOC
l2. VO(OR)Cij2. VO(OR)3,V
(acac) 3 , vanadium tri or tetrachloride, or tetrahydrofuran complex or ether complex of vanadyl trichloride, etc., and their 2
Mixtures of more than one species are preferably used.

Note that R represents a furkyl group, and aCaC represents acetylacetone.

The organometallic compound catalyst used together with the vanadium catalyst in the production of olefinic polymers is preferably a compound soluble in a hydrocarbon solvent, for example, a compound having the general formula RnMX3-n (0<n≦2, R=alkyl group). , an organic aluminum compound represented by
RnMgX2-n, RnZnX2-n (0<n≦2
, R=alkyl group, X: halogen group), and mixtures of two or more thereof are preferably used.

Further, in combination with the above catalyst, an activator selected from organic halogen compounds such as ethyl trichloroacetate, trichloroethane, benzyl chloride, and peroxides can also be used.

In the composition of the present invention, the following additives can be used alone or in combination of two or more as stabilizers for the olefin polymer.

# Heat stabilizers include phenol, phosphorus, amine, and sulfur stabilizers, such as 4-hydroxy-3,5-
Di-t-butyltoluene, vitamin E, styrenated cresol, inoctadecyl 3-(4'-hydroxy-3
', 5'-di-t-butylphenyl)propanoate,
Common compounds such as tris(nonylphenyl)phosphite, 4-benzoyloxy-2,2,6,6-titramethylbiperidine, bis(2-dodecoxylponylethyl)sulfide (also known as dilaurylthiodipropionate) can be suitably used.

Rust inhibitors include metal soaps, inorganic complex bases, epoxy compounds such as calcium laurate, zinc palmitate, magnesium stearate, synthetic hydrotalcite, calcium carbonate, cis-9, 10-epoxy stearate inoctyl. (also known as epoxidized isooctyl stearate), etc. can be used.

The phosphorous acid constituting the composition of the present invention is used as an additive for improving hue, and salts thereof may also be used.

Preferred additives are polyphosphoric acid, stoutous acid, sodium dihydrogen phosphate dihydrate, ammonium phosphate, sodium pyrophosphate decahydrate, or a mixture of two or more thereof.

Further, the blending amount of these is 0.001 to 10 parts by weight, preferably 0.001 to 10 parts by weight, based on 100 parts by weight of the olefin polymer.
If the vanadium content is as low as 0.1 to 59 ppm, 0.01 to 0.5 parts by weight, and if the vanadium content is 25 to 3 parts by weight.
When the amount is 0QpP@, the amount is 1 to 2 parts by weight.

The method for preparing the composition of the present invention includes adding the above-mentioned hue improving additive to a polymer having a vanadium content of 0.01 to 3000P.
pm, preferably 0.1 to 50 ppm, and in applications where heat aging resistance is not required, the olefinic polymer is dispersed and homogenized in the range of 50 to 300 PpH.

Homogenization is generally carried out at a temperature of 40 to 300 DEG C., preferably in an inert gas atmosphere such as nitrogen to eliminate the influence of oxygen.

In addition, if the olefin polymer is in a suspension or solution state in a solvent such as a hydrocarbon during the manufacturing process, the hue improving additive may be mixed as is and the solvent may be removed, or the olefin polymer may be further removed for 80 minutes after removal. Homogenization can also be carried out at temperatures of up to 300°C.

Examples 1 to 8 The composition was 85% by weight of ethylene, 4.7% by weight of 5-ethylidene-2-norbornene and 30.3% by weight of propylene by solution polymerization in hexane, deashed with caustic soda water, and Mooney Viscosity [ML1+4 (100℃)]
A bexane solution of 140 EPDM (this will be referred to as Polymer A) with a polymer concentration of 70 g/Q was obtained.

The catalyst residue in the above copolymer solution is a lubricant for EPDM.
/wppIl unit, ■=85, ALL=32
7, Gj = 503, Fe = 3.

5Q, in a separable flask, add 0.5 parts by weight of tris(nonylphenyl)phosphite (referred to as A-1) and calcium stearate (referred to as 8-2) to 100 parts by weight of the polymer. 0.5 parts by weight, tetrakis [3-(4'-hydroxy-3',5''-diL)
Add 0.5 parts by weight of -butylphenyl)propanoyloxymethylcomethane (referred to as A-3) and 0.5 parts by weight of an additive for hue improvement, and stir well at 60°C for 2 hours under a nitrogen atmosphere. I did.

Then, hexane was distilled off at a temperature of 120° C. in a vacuum dryer, and after cutting under a nitrogen atmosphere, Brabender Plasticoat'-PLV 15 was cut under a nitrogen seal.
1 (18,1+u+diameter, L/D=20) i, :te,
Cylinder Ct/Cylinder C2/Adapter die AD
= 150/210/250°C and pelletizing at 80 rpm to obtain about 300 g of pellets.

Next, at 250℃, 40Kg/cm2G c7)
Press sheet for ~6 minutes to form a sheet approximately 3II11 thick.

This sheet was subjected to a durability test for about one month under conditions of accelerated humidification at 70° C. to examine changes in color over time.

It has already been confirmed that one month under these promoting conditions corresponds to one to two years of actual color change.

The color change was described by selecting the closest color from the general color names defined in J (SZ-8102).

As a result, as shown in Table 1, the sheets of Examples 1 to 5 were transparent and only slightly colored, and had much better hues than Comparative Examples 1 to 6, which will be described later, and showed little change over time.

In addition, Examples 6 to 5 were carried out in exactly the same manner as in Examples 1 to 5, except that 0.3 parts by weight of styrenated cresol was added instead of A-1, A-2, and A-3 as a stabilizer. 8 sheets were obtained.

As a result, as shown in Table 1, Examples 6 to 8 were transparent and slightly colored, and had much better hues than Comparative Example 7, which will be described later, and showed little change over time.

As for the visual evaluation of coloring, ◯ means colorless, and the degree of coloring increases in the order of O1Δ and × (the same applies below).

Comparative Examples 1-7 No hue-improving additives were added (Comparative Example 1), or known hue-improving additives (Comparative Examples 2-4) or phosphoric acid-based analog compounds (Comparative Examples 5-6) Sheets of Comparative Examples 1 to 6 were obtained in exactly the same manner as in Examples 1 to 5, except that 0.5 parts by weight of .

Further, a sheet of Comparative Example 7 was obtained by performing the same operations as in Examples 6 to 8 except that no additive for improving hue was added. When the changes in these hues over time were examined in the same manner as in Examples 1 to 8, as shown in Table 1, the colors were deeply colored, opaque, and significantly changed over time.

Examples 9-11 Ethylene content 73% by weight and melt flow rate (2
After producing an ethylene/propylene copolymer (referred to as Polymer B) with a weight of 0.6 (30°C, 2180 g load), a hexane solution deashed with caustic soda water (polymer concentration 50 g/
Q,) was used.

The catalyst residue in the copolymer solution is w relative to the copolymer.
/ When the demineralization conditions are changed in two conditions expressed in wppm, V=50. A11=206, Cu=28
8, Fe=5 (poly-F-Bl), and V=10
．． M=20, CLl'=27, Fe=2 (polymer B2
).

Sheet molded products were obtained in exactly the same manner as in Examples 1 to 8, except that the amounts of various additives added were as shown in Table 2.

The change in color was measured using a Hunter Lab color difference meter by stacking two sheets and measuring the L value (whiteness), a value (red -> ← white <0> →
<+> green) and b value (blue <-> ← white 0> → <+> yellow).

As a result, as shown in Table 2, Examples 9 to 11 were transparent and slightly colored, and as far as the same polymers were compared, the hue was much better than Comparative Examples 8 to 9 described later, and the color change over time was much better. There were also few. Visual scores are relative scores between identical polymers.

Comparative Examples 8 to 9 The same operations as in Examples 9 to 11 were performed except that no additives for improving hue were added, and the changes in hue of the obtained sheets over time were observed as in Examples 9 to 1! When the same polymers were compared, as shown in Table 2, the polymers were deeply colored, opaque, and significantly changed in color over time.

(Hereinafter in the margins) As described in the detailed description of the invention, the composition of the present invention remains colorless or only develops a very pale color during long working and storage. Moreover, even if the olefin polymer is once colored, it will be decolorized if it is homogenized as described above and made into a composition.

Claims (1)

[Claims] 1. 0.001 to 10 parts by weight of one or more selected from phosphorus oxy acids is blended with 100 parts by weight of an olefin polymer produced using a coordination catalyst containing a vanadium compound as an essential component. A polyolefin composition with little coloration.