JPS62129330A - Polyolefin composition for preventing coloring - Google Patents

Abstract

PURPOSE:A composition obtained by blending a polyolefin based polymer produced by using a catalyst containing a vanadium compound with a polyfunctional carboxylic acid or hydroxy carboxylic acid with very little coloring. CONSTITUTION:A composition obtained by blending (A) 100pts.wt. polyolefin based polymer produced by using a coordination catalyst consisting essentially of a vanadium compound with (B) 0.001-10pts.wt. one or more selected from the group consisting of polyfunctional carboxylic acids and hydroxy carboxylic acids. Succinic acid, malonic acid, maleic acid, diglycolic acid, o-phthalic acid, thiodipropionic acid, sodium citrate . dihydrate, etc., may be used as the component (B) and both components are homogenized at 40-300 deg.C in an inert gas atmosphere, e.g. nitrogen.

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.
It was produced using a coordination catalyst such as ler type. This invention relates to a polyolefin composition with very little bicoloration, which is obtained by blending a specific coloration inhibitor with an olefin polymer or copolymer.

Prior Art Zieg carried out with catalyst systems based on vanadium compounds
Olefin polymers produced by coordination anionic polymerization reactions such as ler type have vanadium content in the catalyst residue of 0.
lppm (weight basis) or more, the color takes on a shade of light and shade that changes 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 nearly 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 eliminate defects that cause coloration, conventional deashing treatment to remove catalyst residues has been carried out to reduce the vanadium content of the polymer to at most 25 ppm or less, and in some cases to 1 ppm or less. was doing. Such treatment steps complicate the manufacturing process and significantly reduce the price competitiveness of the product in terms of utility and the like.

Problems to be Solved by the Invention The present invention is directed to the production of Ziegl 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 types of certain polycarboxylic acids and their salts, oxycarboxylic acids and their salts, and about 0.1 to By dispersing and homogenizing in an olefin-based polymer containing 50 ppm vanadium, a polyolefin composition which surprisingly remains colorless or only develops a very light coloration during long working and storage periods. can get things.

In applications where heat-resistant anti-aging performance is not particularly required, olefin polymers or copolymers produced by coordinated anionic polymerization reactions such as Ziegler type containing a large amount of vanadium of about 50 to 300 ppm may also be used. , a polyolefin composition with good hue can be obtained in the same manner as above.

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

The composition of the present invention is composed of an olefin polymer and a polyhydric carboxylic acid and/or an oxycarboxylic 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 north of the species.

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

Examples of the polyene include 5-ethylidene-2-norbornene, 5-vinyl-2-fulbornene, dicyclopentadiene, 1,4-hexadiene, and 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 that is soluble in a hydrocarbon solvent. For example, VCL, VOCQ.
3. VD(OR')C(!2.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 an alkyl 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. Organoaluminum compounds represented by alkyl group, X = halogen group), RnMgX2-n, RnZnX2''
Organomagnesium compounds and organozinc compounds represented by 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.

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

Examples of heat-resistant stabilizers include phenol-based, phosphorus-based, amine-based, and sulfur-based stabilizers.1 For example, 4-hydroxy-3,5-
Di-t-butyltoluene, vitamin E, styrenated cresol, inoctadecyl 3-(4'-hydroxy-3
',5'-di-t-butylphenyl)propanoate,
Common drugs such as tris(nonylphenyl)phosphite, 4-benzoyloxy-2,2,6,6-titramethylpiperidine, bis(2-dodecoxycarponylethyl)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, and octyl cis-9,1o-epoxy stearate. (also known as epoxidized inoctyl stearate), etc. can be used.

The polyhydric carboxylic acids and oxycarboxylic acids constituting the composition of the present invention are used as additives for improving hue, and salts thereof may also be used.

Preferred additives are succinic acid, malonic acid, maleic acid,
diglycolic acid, 0-phthalic acid, thiodipropionic acid,
These include polyhydric carboxylic acids such as glycolic acid and malic acid, or oxycarboxylic acids 1, salts such as ammonium succinate, sodium L-glutamate, and sodium citrate dihydrate, or mixtures of two or more thereof.

The amount of these compounds is 0.001-10 parts by weight, preferably 0.001-10 parts by weight, based on 100 parts by weight of the olefin polymer.
If the vanadium content is as low as 0.1 to 50 ppm, 2 L*0.01 to 0.5 parts by weight, vanadium content 25
When the amount is as high as 300 ppm, the amount is 0.1 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 3000 p.
The purpose is to disperse and homogenize the olefinic polymer having a pI of 11, preferably 0.1 to 50 ppm, and in applications where heat aging resistance is not required, 50 to 300 ppffl.

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.

Further, when the olefin polymer is in a suspended state or a solution state in a solvent such as a hydrocarbon during the manufacturing process, the hue improving additive is mixed as is and the solvent is removed. Alternatively, it is also possible to homogenize at a temperature of 40 to 300"C after removal.

Examples 1 to 11 By solution polymerization in hexane, the composition was 65% by weight of ethylene, 4.7% by weight of 5-ethylidene-2-norbornene and 30.3% by weight of propylene, and the Mooney viscosity (M L i+4 (100 ℃）〕140 EPDM
(This is referred to as Polymer A) was obtained, and this was deashed with caustic soda water to obtain a hexane solution with a polymer concentration of 70 g/l.

If the catalyst remains in the copolymer solution, w against EPDM
/wppm, V=85. Ai=327
, C1=-503, Fe=3.

5Q, poly-F-
To the tooiffi part, 0.5 parts by weight of tris(nonylphenyl)phosphite (referred to as A-1), 0.5 parts by weight of calcium stearate (referred to as A-2), tetrakis[3-(4'- Hydroxy-3',5'-di-
0.5 parts by weight of t-butylphenyl)propanoyloxymethylcomethane (referred to as A-3) and 0.5 parts by weight of a hue improving additive were added, and the mixture was heated at 60°C for 2 hours under a nitrogen atmosphere. I stirred it.

The hexane was then distilled off at a temperature of 120° C. in a vacuum dryer, and after cutting under a nitrogen atmosphere, the Brabender Plasticorder PLV 151 was cut under a nitrogen blanket.
(19.1mm diameter, L/D=20) Nite, cylinder C+/cylinder 〇2/adapter die Ao=15
Pelletization was performed under the conditions of 0/210/250°C and 180 rpm to obtain about 300 g of pellets.

Next, under the conditions of 250'C140Kg/0m2G,
Form a 6-minute breath sheet into a sheet with a thickness of about 3 mm.

This sheet was kept under humidified fecal conditions at 70° C. for about one month 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 JIS Z-8102.

As a result, as shown in Table 1, the sheets of Examples 1 to 11 were transparent and only slightly colored, and had much better hues than Comparative Examples 1 to 6 described later, and showed little change over time.

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

Comparative Examples 1 to 6 No hue improving additive was added at all (Comparative Example 1), or 0.00% of a known hue improving additive (Comparative Examples 2 to 6) was added.
Sheets of Comparative Examples 1 to 6 were obtained by performing the same operations as in Examples 1 to 11 except that 5 parts by weight was added. Changes in these hues over time were investigated in the same manner as in Examples 1 to 11, and as shown in Table 1, they were either darkly colored or opaque, or significantly changed in color over time.

Examples 12-18 Ethylene content: jE73% by weight and melt flow rate)
(230°C 12180g load ff1) 0.6% ethylene/propylene copolymer (referred to as Polymer B)
After manufacturing, a hexane solution (polymer concentration 50 g/l) which was deashed with caustic soda water was used.

The catalyst residue in the copolymer solution is w/
Expressed in wppm, when two demineralization conditions are changed, V=50. M=208, CQ=288, Fe
=5 (poly?-81), and V=IO, Au=2
0, CQ=27, and Fe=2 (assumed to be poly-82).

Sheet molded products were obtained in exactly the same manner as in Examples 1 to 11, 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) and the a value (red<->←white<o>→
<+> green) and b value (blue <->←white <0>→<+> yellow).

As a result, as shown in Table 2, Examples 12 to 16 were transparent and slightly colored, and as far as comparing the same polymers used, the hues were much better than those of Comparative Examples 7 to 8 described later.
There was also little change over time. Visual scores are relative scores between identical polymers.

Comparative Examples 7-8 Examples 12-1 except that no additives for hue improvement were added.
The same procedure as in 8 was carried out, and the changes in color over time of the obtained sheets were examined in the same manner as in Examples 12 to 16. As far as the comparison between the same polymers used, as shown in Table 2, the sheets were deeply colored. It may be cloudy or opaque, or its color may change significantly 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% of one or more selected from the group consisting of polycarboxylic acids and oxycarboxylic acids to 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 coloring, characterized in that it contains parts by weight.