JP2975371B2 - Ionomer polymer - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an ionomer polymer containing a fluorine compound, and more particularly, to a thermoplastic copolymer having improved physical properties and the like.

[Prior Art] Ionomers (polymers in which organic and inorganic components are bonded by covalent and ionic bonds) generally have a polar group in the molecular chain of a polyolefin, and a part of the intermolecular structure is formed by a metal ion or the like. Has a crosslinked structure.

By the way, an ionomer represented by Du Pont's trade name "Surlyn" is a polymer having some features not found in a conventional polyolefin-based polymer or the like, and is a material that has attracted attention in recent years. In other words, this "surlyn"
Is obtained by reacting a metal ion of sodium or zinc with an ethylene-methacrylic acid copolymer to perform ionic cross-linking.
It has moderate flexibility, heat resistance, abrasion resistance, heat sealability, adhesion to metals, melt strength, oil resistance, chemical resistance, and molding equivalent to ordinary polyolefin polymers. Since it can be processed, it is used for various applications such as packaging materials such as films and sheets, coating materials, molded articles such as golf balls and toys, and coating layers for laminates. However, ionomers such as this "Surlyn" are not necessarily said to have good water resistance, especially water resistance of adhesive strength, and the adhesive surface tends to peel when immersed in high humidity or water It has the defect of.

On the other hand, a block copolymer having a relatively high styrene content is a transparent impact-resistant resin, and such a resin is called "K Resin" (manufactured by Philips Petroleum),
Known as "Clearylene" (manufactured by Denki Kagaku Co., Ltd.) and the like, it is used in the field of packaging materials such as sheets, films, and hollow products. However, these resins have defects in water resistance, solvent resistance, heat resistance and the like.

〔Purpose〕

The present invention seeks to improve the water resistance, solvent resistance, and temperature resistance characteristics found in ionomers such as "Surlyn".

〔Constitution〕

In the ionomer polymer of the present invention, the polymer is composed of 20 to 90% by weight of an olefin monomer unit and one carboxyl group.
A copolymer comprising 5 to 50% by weight of an olefin monomer unit and 5 to 50% by weight of a fluoroalkyl acrylate or fluoroalkyl methacrylate monomer unit having at least one olefin monomer unit. It is characterized by being crosslinked.

Here, each monomer unit refers to a structural unit in which each of the above monomers is linearly bonded by olefinic addition polymerization.

Incidentally, the present inventors have confirmed that the above object can be achieved if the ionomer polymer is copolymerized using a fluorine-containing monomer as one of its monomer components. The present invention has been made based on this.

The ionomer polymer according to the present invention is at least a terpolymer.

The following are mentioned as each monomer component in these.

(1) Olefin monomers such as ethylene, propylene and butene; (2) Olefin monomers having at least one carboxyl group include α, β-unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, maleic acid and itaconic acid (3) Examples of the fluoroalkyl acrylate or fluoroalkyl methacrylate monomer include acids and unsaturated dicarboxylic acids, and the monomers shown in Table 1 below.

In addition to these, certain monomer components useful as ionomer polymers are described in JP-B-39-6810, and include olefin monomers disclosed therein, olefin monomers having at least one carboxyl group, and the like. Can also be used in the present invention.

In order to produce each of the copolymers in the present invention, for example, a copolymer of ethylene and acrylic acid may be monovalent, divalent, trivalent,
Any of the valent metal compounds may be reacted. In this case, these metal compounds neutralize 1 to 100 mol% of the carboxylic acid groups in the copolymer, and as a result, the ethylene-acrylic acid copolymer is obtained as ion-crosslinked.

Here, some specific examples of the copolymer in the present invention are as follows. The percentage in parentheses is% by weight, and the parenthesis at the end indicates a crosslinked metal or a crosslinked base.

No.1 Ethylene (30%)-propylene (30%)-methacrylic acid (15%)-heptafluorobutyl acrylate (25%) copolymer (Zn) No.2 Propylene (50%)-lauryl methacrylate (20% ) -Methacrylic acid (5%)-Heptadecafluorooctylethyl acrylate (25%) block copolymer (Mg) The metal ions used in the production of these ionomers are as described in the Periodic Tables I, II and III. , IV-A and VI
And monovalent ions such as Na ⁺ , Li ⁺ , K ⁺ , and Ag ⁺ , Ca ²⁺ , Mg ²⁺ , and the like.
^Examples include divalent ions such as Ba ²⁺ , Zn ²⁺ , Sr ²⁺ , and Hg ^2+, and trivalent ions such as Al ³⁺ and Fe ³⁺ . These are reacted with the copolymer as compounds such as hydroxides, alcoholates and lower carboxylic acid groups.

In addition, in the production of the ionomer, a base may be used as described above, and examples of the base include ammonia and amine, which may be reacted with the copolymer.

The ratio of each monomer component (composition ratio) of the polymer of the present invention is as follows: copolymer: olefin monomer / olefin monomer having at least one carboxyl group / olefin containing fluorine Monomer = 20 to 90/5 to 50/5 to 50 If the olefin monomer having one or more carboxyl groups is less than 5% by weight, ionic cross-linking does not easily occur, and if it is more than 50% by weight, the flexibility becomes poor. Ionic crosslinking is too strong to make processing difficult. Etc. may occur. Further, when the olefin monomer containing fluorine is 5
If it is less than 50% by weight, water resistance, heat resistance, oil resistance and the like are inferior.

In addition, the ionomer polymer of the present invention includes a reinforcing agent or a filler such as calcium carbonate, silica, carbon black, glass fiber, and clay, to the extent that its properties are not impaired, process oil, polyethylene glycol, and phthalic acid ester. It is also possible to add a plasticizer.
In addition, an antioxidant, an ultraviolet absorber, a coloring agent, a foaming agent, and the like can be added as additives.

Now, in this order, examples of the production of a copolymer of an olefin monomer and an olefin monomer having at least one carboxyl group are shown in the following (1) and (2).

(1) Preparation of chromium catalyst component A 5 to 10 mm diameter was placed in a 200 ml flask purged with argon.
Put 10 stainless steel balls and then chrome stearate
3.6 g (4 mmol) and 100 ml of toluene were added and ball-milled for 10 hours while stirring at room temperature. Next, toluene was added thereto to make the total amount 200 ml. As a result,
A black-purple gel-like chromium catalyst-containing component was obtained.

(2) Production of copolymer In a pressure-resistant glass container with an inner volume of 500 ml
300 ml of toluene, 3.4 ml of acrylic acid and 10 mmol of ethyl aluminum dichloride as a Lewis acid were added, and the mixture was stirred and reacted at 20 ° C. for 5 minutes. Next, 0.01 mmol of the chromium catalyst component prepared in the above (1) and 1 mmol of diethylaluminum monochloride were added thereto, ethylene was continuously introduced, and the internal pressure was maintained at ² kg / cm ² G at 20 ° C.
For 3 hours. After completion of the reaction, ethylene was depressurized and the product was poured into methanol to precipitate. The obtained solid was collected by filtration, deashed and washed with a mixed solution of hydrochloric acid and methanol to remove soluble components, and then subjected to acetone extraction for 5 hours to remove an amorphous polymer. Further, the extraction residue was dried under reduced pressure at 80 ° C. for 2 hours to obtain 6.6 g of a white copolymer. The catalytic activity (polymerization activity) is 12.7 kg / g
It was chrome.

Similarly, in order to produce a copolymer of a fluorine-containing olefin monomer and a polymerizable monomer having at least one carboxyl group, a fluorine-containing monomer is introduced instead of continuously introducing ethylene in the above-mentioned production example. I just need. In addition, in order to produce the random copolymer of the present invention, the fluorine-containing monomer may be continuously introduced together with the continuous introduction of ethylene in the above production example.

〔Example〕

Examples 1 and 2 The physical properties of the previously produced copolymer itself or the copolymer composition were measured. The results were as shown in Table-2.

[Effects] The ionomer polymer of the present invention has good adhesion to metals, paper, etc., and also has good water resistance, oil resistance and oil repellency.

Further, the ionomer polymer of the present invention can be molded by various conventional molding methods such as extrusion molding, injection molding, calendar molding, etc., and various molded products such as mechanical parts, automobile parts, electric parts, toys, and industrial products Parts, belts, hoses, footwear, medical supplies, anti-vibration rubber, daily necessities,
It is useful for various fields such as miscellaneous goods, building materials, sheets, films, hollow molded articles, solution type / hot melt type adhesives and pressure-sensitive adhesives.

Continuation of the front page (56) References JP-A-50-74700 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 210/00 C08F 8/42 C08F 220/22 C08F 297 / 06

Claims (1)

(57) [Claims] 1. An ionomer polymer in which a polymer component is ion-crosslinked by a metal ion or a base, wherein the polymer has an olefin monomer unit content of 20 to 90% by weight and an olefin monomer unit having at least one carboxyl group. An ionomer polymer, which is a copolymer comprising 50 to 50% by weight and 5 to 50% by weight of a fluoroalkyl acrylate or fluoroalkyl methacrylate monomer unit.