JPS59215348A - Polymer composition - Google Patents

Abstract

PURPOSE:To provide a polymer compsn. having excellent adhesion to other materials such as metal and suitable for use in the production of electrodes for a solar battery, by blending a modified polyolefin with an acetylene high polymer in a specified weight ratio. CONSTITUTION:Acetylene, alone or a mixture thereof with its derivative such as ethynylbenzene or divinylbenzene is (co)polymerized in the presence of a Ziegler catalyst, etc. to prepare a powdered or lump acetylene high polymer. Separately, an alpha,beta-unsaturated carboxylic acid or its derivative (e.g. acrylic acid or maleic anhydride) is grafted onto a polyolefin such as polyethylene or polypropylene in the presence of a free radical-generating agent such as dicumyl peroxide to prepare a modified polyolefin. 0.1-200pts.wt. said modified polyolefin is blended with 100pts.wt. said acetylene high polymer to obtain the desired polymer compsn.

Description

[Detailed description of the invention] The present invention (d) relates to a polymer composition.

The acetylene polymer obtained by admixing an acetylene compound with gold using a so-called Ziegler-Natsuta catalyst consisting of a transition metal compound and an organometallic compound has an electrical conductivity of 10-10 by doping with a dopant.
~ ] -0'S/ Since it can be changed to sub-A, it is a conductive material with extremely high industrial utility value. However, even if an attempt is made to bond other substances, such as fIJ, to metals in order to take advantage of the electrical conductivity characteristic of acetylene-based polymers, it is difficult to easily peel and bond them. for example,
If an acetylene polymer is used as an electrode, it is possible to make a lightweight, compact, and inexpensive battery with high energy density, but since the bond between the current collector and the current collector is circular, it is not suitable for the purpose. High energy density has not yet been achieved.

The present inventors conducted various tests to improve the bonding properties between acetylene-based polymers and other substances.

It has been found that a polymer composition consisting of 0.1 to 200 parts by weight of an acetylenic high polymer and 0.1 to 200 parts by weight satisfies this object.

Do not use such polymer compositions with good bonding properties with metals for solar cells, rechargeable batteries, secondary batteries, or photoconductivity! It has a huge positive impact. For example, when used in a secondary battery, it adheres extremely well to a current collector, making it possible to fabricate a battery that is light and has a high energy density.

The acetylene-based high polymer in the present invention refers to an acetylene high polymer or a copolymer of acetylene and its derivative. Examples of acetylene derivatives include tehaethynylbenzene, divinylbenzene, phenylacetylene, methylacetylene, hexylacetylene, butylacetylene, naphthylacetylene, chloroacetylene, chloromethylacetylene, and the like.

It may also be a composite of an acetylene-based polymer and a conductive material such as carbon black, metal fiber, or metal powder.
(including short fibers smaller than 100 mm) or small lumps. Further, these acetylene-based polymers are produced using a Ziegler type catalyst, a Lunotinger catalyst, or a metasense catalyst.

The modified polyolefin in the present invention is obtained by grafting an α,β-unsaturated carboxylic acid or a derivative thereof to a polyolefin described below in the presence of a radical generator.

The polyolefins used in the modified polyolefin include low density, medium density and high density polyethylene, polypropylene, polybutene-1, polymethylpentene-1, ethylene and α-olefin copolymers, ethylene and vinyl monomer copolymers, and It is a mixture of these. Examples of ethylene and α-olefin copolymers include ethylene/propylene copolymers, ethylene/propylene/diene terpolymers, ethylene/butene-1 copolymers, and copolymers of ethylene and vinyl monomers. Copolymers include ethylene vinyl acetate copolymer, ethylene and acrylic acid or its ester copolymer, ethylene and methacrylic acid or its Nisdel copolymer, ethylene and acrylic acid or its ester and α-β-unsaturated ester. [1 Examples include terpolymer copolymers of carboxylic acids or derivatives thereof, ethylene and vinyl chloride copolymers, and the like.

Graft-modified α, β-unsaturated carboxylic acids or derivatives thereof (graft monomers) include acrylic acid,
Maleic acid, fumaric acid, itaconic acid, hemic acid or anhydrides thereof and their esters, alkylamino methacrylates such as 2-dimethylamine ethyl methacrylate-1, glycidyl methacrylate, etc.
Among these, acrylic acid, maleic acid, maleic anhydride, and iminocic anhydride are preferred. Of course, two or more of these may be used in combination.

Radical luminescent agents used for graft modification include dicumyl peroxide, benzoyl peroxide, di-t
-butyl peroxide, 2,5-dimethyl-2,5-
Di(1-butylperoxy)hexano, 2,5-dimethyl-2,5-di(1-butylperoxy)hexene-3
, lauroyl per-d-oxide, t-butyl peroxybenzoate and the like are preferably used,
A combination of two or more types may be used.

Graft modification methods include a method of adding a graft monomer and a radical generator to a polyolefin suspended or dissolved in an appropriate solvent and heating and stirring, or a method of mixing the polyolefin, a graft monomer, and a radical generator in advance and using an extruder. There are methods of melting and kneading using a Banbury mixer, a kneader, etc., but the latter method is generally preferred.

Note that the amounts of the radical generator and graft monomer used for graft modification are not particularly limited, but 1.00 parts by weight of polyolefin (000 parts by weight of the radical generator per C)
1 to 05 parts by weight is 0.1 to 10 parts by weight of the α,β-unsaturated carboxylic acid or derivative thereof.

The mixing ratio of the acetylenic high polymer and modified polyolefin in the present invention varies depending on the type of acetylenic high polymer and modified polyolefin, and the purpose of use of the polymer composition. parts by weight of the modified polyolefin, preferably 01 to 100 parts by weight. If the amount is less than 0.01 M parts, the effect referred to in the present invention is not observed, while if it is more than 200 M parts, no particular advantage is observed by increasing the amount.

Examples of methods for mixing an acetylene polymer and a modified polyolefin include (1) tri-blending the modified polyolefin with the acetylene polymer; (11) dissolving or slurrying the modified polyolefin in a suitable organic solvent; Or, after immersing the acetylene high polymer in a slurry, or applying or spraying this solution or slurry onto the acetylene high polymer,
Examples include a method of removing the solvent, and (iii) a method of polymerization and mixing in the presence of a modified polyolefin during polymerization.
It is not necessarily limited to these.

The adhesion between the polymer composition and other substances, especially metals, is carried out by heating or pressurizing, or by heating and pressurizing.

The effects of the present invention will be illustrated below with Examples and Comparative Examples. The adhesive strength of the polymer composition was tested using a cross-cut tape test. In other words, the composition is 17 vertically and horizontally 10 CT
n Pressure 30Kf/ct on 200μm thick aluminum foil
The adhesive composition was divided into 101 square segments measuring 1 m vertically and horizontally using a Carter knife. Next, an adhesive tape was attached to the top surface of the adhesive, and when it was removed by hand, the number of segments of the composition remaining on the adhesive was counted. The greater the number of segments, the greater the adhesive strength. The electrical conductivity of the shredded polymer composition was measured by a known method (four-probe method doped with concentrated sulfuric acid) on the adhesive with the aluminum foil. Examples of adhesive strength and electrical conductivity
1] l-glass crepe as a modified polyolefin with a density of 0.91 'j/art, MFIl, (,] I
SK 6760 method) 2. I YlI 0 minute maleic anhydride graph) Modified low density polyethylene 0.51i
', Toluev 500m1 s Tetrabutyl titanate 1
．． 29 (3.5 mmol), )! J Egil aluminum 1.2 S' (10.5 mmol) f:: was added thereto and acetylene gas was blown into the mixture while stirring at room temperature for 4 hours. After the polymerization is completed, the powder part is separated and treated with Citoluene 100 rn12 for 5 minutes.
Washed twice. The content of modified polyolefin in this acetylene high polymer composition was 5 wt%. This powder 12 was adhered to the aluminum foil (vertical, width 1.0 (li71 thickness 200 μm) at a temperature of 100° C. and a pressure of 30/c111 to obtain a sample for evaluation.

Example 2 Carbon black 12 and tetrabutyl titanate 1.2 were added to the maleic anhydride graft-modified low density polyethylene used in Example 1. f 0.6 fl(1,
Polymerization was carried out in the same manner as in Example 1, except that 0.69 (5.3 mmol>K) of triethylaluminum 1.2 S' (8 mmol), washed with toluene, and dried.

This powder contained 10% carbon black. This powder roy, 0.75' of the maleic anhydride graft-modified polyolefin used in Example 1, and 5 ml of toluene were thoroughly mixed in a glass pantry, and a planning sample was obtained in the same manner as in Example 1, followed by drying. did.

Example 3 An acetylene-based high polymer was obtained in exactly the same manner as in Example 1, except that phenylacetylene 'f:o, sy was used instead of the carbon blank in Example 2. According to the infrared spectrum, there is one phenylacetylene unit in this polymer.
I found out that it contains 0w1%. This acetylene-based high polymer powder 10! f' and the modified polyolefin 3f used in Example 1, tri-blended in f's house,
A polymer composition sample for evaluation was obtained in exactly the same manner as in Example 1.

Example 4 Ml”R (JIS K67
Method 58) The same procedure as in Example] was carried out except that 15.0 ft'/10 minutes of acrylic acid-modified polypropylene was used.

Comparative Example 1 Rig 1, in which no modified polyolefin was added in Example 1, was polymerized in exactly the same manner as in Example 1 to obtain an acetylene high polymer, and a polymer composition sample for planning was prepared in exactly the same manner as in Example 1. Obtained.

Table 1 shows that the adhesive strength was significantly improved without a significant decrease in electrical conductivity.

Patent applicant: Showa Denko Co., Ltd.

Claims (1)

[Claims] 100 parts by weight of acetylene-based high polymer and 0.1 to 20 parts by weight
0 parts by weight of a modified polyolefin.