JPS619403A - Coordinated ionic ethylene copolymer - Google Patents

Abstract

PURPOSE:The titled copolymer excellent in mechanical properties, flow and heat stability, prepared by coordinating a specific bivalent cation-affording metal compound and a specified diamine compound with an ethylene/unsaturated carboxylic acid copolymer. CONSTITUTION:The titled copolymer is prepared by melt-kneading an ethylene/ unsaturated carboxylic acid copolymer [e.g., ethylene/(meth)acrylic acid copolymer] with a metal compound capable of affording bivalent cations such as Zn<2+>, CO<2+>, Ni<2+>, Cu<2+>, Pb<2+> or Mg<2+> (e.g., acetates, nitrates, oxides or like compounds of said metals) and an aromatic or resinous compound containing a bisaminoalkyl group (e.g., 1,3-bisaminomethylcyclohexane or m-xylylenediamine). This copolymer is excellent in mechanical properties (especially, rigidity), flow and heat stability. It can be suitably used in producing moldings such as films or sheets by extrusion, injection molding or a light process.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to coordination ionic ethylene copolymers.

More specifically, the present invention relates to a coordination ionic ethylene copolymer having excellent mechanical properties and thermal stability.

[Conventional technology]

A coordination ionic ethylene copolymer can be obtained by melt-kneading an ethylene-unsaturated carboxylic acid copolymer with a metal compound capable of supplying a specific divalent cation and piperazine; Ionic copolymers are said to exhibit improved properties in terms of physical properties, optical transparency, climate resistance (stability against ultraviolet light, heat, or water vapor), and additive retention (Tokuko Showa). 46-2
5624).

[Problem that the invention seeks to solve]

However, when using the above-mentioned piperazine, although it is said that the thermal stability is good, it is not sufficient, and as with many other amine compounds, the commonly used molding Under processing conditions, smoke and odor may be observed, and the molded product may also be noticeably discolored. Furthermore, existing cavities where the amine compound bleeds out can be seen on the surface of the molded product after molding. For these reasons, the coordination ionic copolymer of ethylene-unsaturated carboxylic acid copolymer has not been used industrially as a molding material. It has now been discovered that a coordination ionic ethylene copolymer which does not exhibit the above-mentioned drawbacks can be obtained by coordinating the copolymers.

[Means for solving the problem] and [Operation] Therefore, the present invention relates to a coordination ionic ethylene co-assembly,
This coordinating ionic ethylene-based copolymer can supply (1) an ethylene-unsaturated carboxylic acid-based copolymer, and (2) divalent cations of lead, cobalt, nickel, copper, and lead-based magnesium. It is obtained from a metal compound and (3) an aromatic or alicyclic compound having a bisaminoalkyl group, preferably a copolymer obtained by melt-kneading them.

The ethylene-unsaturated carboxylic acid copolymer of component (1) above includes ethylene and an unsaturated carboxylic acid having 3 to 6 carbon atoms, such as acrylic acid, methacrylic acid, maleic acid, 7
A copolymer with malic acid or vinyl benzoate is used, and this copolymer further contains an unsaturated carboxylic acid ester, vinyl ester, α-olefin, etc. For example, in the case of an unsaturated carboxylic acid ester, It may be copolymerized in a proportion of about 10 mol % or less, preferably about 6 mol % or less. The proportion of unsaturated carboxylic acid in the copolymer is generally about 0.5 to 15 mol%, preferably about 1 to 8 mol%. If the copolymerization ratio of unsaturated carboxylic acid is less than this, the binding concentration of coordination ions will be low when modified, and the improvement effect will not be seen much compared to the copolymer that is the base polymer. Formability will be impaired.

Further, the melt index of the copolymer as the base polymer is preferably within the range of 0.1 to 10009/10 minutes; if it is less than this, the flowability of the resulting coordination ionic copolymer will be poor; Processability will be impaired, and on the other hand, if it exceeds this value, the strength of the coordinated ionic co-claw union will decrease.

(2) Examples of the metal compound 7 that can supply divalent cations of the component include zinc, cobalt, nickel, steel weight, or magnesium that can coordinate with the amine compound, such as formate, acetate, 6j
It is used in the form of borates, carbonates, hydrogencarbonates, oxides, hydroxides, and alkoxides.

In general, sodium salts and potassium salts, which are used as ionomer resins along with zinc salts, do not have the property of coordinating with amine compounds, so they can form coordination ion 11 co-coalescence. For example, when m-xylylene diamine is added to sodium eye A polymer made of ethylene-methacrylic acid co-combined material, the rigidity and other properties decrease, and the sintered polymer itself has no amine retention ability. , resulting in a bleed-out phenomenon of m-xylylenediamine.

These divalent metal compounds are contained in an amount of 5 to 45 mol% based on the amount of carboxylic acid in the ethylene-unsaturated carboxylic acid copolymer.
It is used in the reduction of If less than this amount is used, the binding concentration of the coordination ion will be low when modified, and the improvement effect will not be seen much compared to the base polymer base copolymer. The flowability of the merging becomes poor and the workability 2 is impaired.

As the aromatic or alicyclic compound having a bisaminoalkyl group as the component (3) as a coordination compound, for example, m
-xylylenediamine, 0-xylylenediamine, p-
1, 3 which is xylylene diamine or a hydrogenated product thereof
-bisaminomethylcyclohexane, 1,2-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, etc. are used. Only these specific diamine compounds provide the desired coordination ionic copolymer with excellent moldability, and other amine compounds cannot be employed for the reasons described below.

Monoamine compounds such as n-hexylamine adversely reduce the mechanical properties of coordination ionic copolymers due to their plasticizing effect. Aliphatic diamines such as ethylenediamine have the property of forming chelate compounds with transition metals, but when they are added to ionomer resins of this metal, chelation takes priority rather than crosslinking or coordination. Therefore, the results are insufficient for improving the gutter mechanical properties of the ionomer IMJ resin. However, with highly sterically hindered tertiary amines such as hexamethylenetetramine and aromatic diamines with low basicity such as p-phenylenediamine, the coordination bond between the amine compound and the metal ion is insufficient. Even when such an amine compound is blended into an ionomer resin, no particular improvement in mechanical properties is observed.

Furthermore, piperazine, aminoethylpiperazine, 1.14
- Other amine compounds such as diaminobenzene glycol cause smoke, odor, etc. during the coloring process.
The disadvantage is that the molded product is noticeably discolored.

On the other hand, an aromatic spanning alicyclic compound having a bisaminoalkyl group has ionic crosslinking between polymer chains and coordination bonds due to the presence of a diamino group. These crosslinks significantly improve the mechanical properties and thermal stability of the coordination ionic copolymer. In order to achieve these educational purposes, the bisaminoalkyl compound is generally used in an amount of 8 to 100 mol% based on the amount of carboxylic acid in the ethylenically unsaturated carboxylic acid copolymer.
used in amounts of If the amount used is less than this, the desired improvement effect cannot be obtained, while if it is used in an amount greater than this, the amine compound will exhibit a bleed-out phenomenon.

The coordination ionic copolymer according to the present invention includes the above (1) to (
It is obtained by preferably uniformly melting and kneading each component of 3). There are no particular limitations on the melt-kneading method, but
For example, after forming an ionomer resin by reacting the copolymer (1) with the metal compound (2), the ionomer resin is formed with the amine compound (3).
) and a method of melt-kneading the copolymer (1) with a metal compound (
This can be carried out by any method such as adding an amine complex salt of 2) and amine compound (3) and melt-kneading, or melt-kneading these three components at the same time. Melt mixing is carried out using an extruder, rolls, etc. at a temperature above the melting point of the ionomer resin to be formed, generally from about 100 to 350°C, preferably from about 150 to 250°C.

Here, when examining the structure of the obtained coordination ionic copolymer, Japanese Patent Publication No. 39-22588 states:
When an amine is added to an unionized ethylene-unsaturated carboxylic acid co-claw polymer, an ionization reaction (neutralization reaction) occurs between the carboxylic acid group in the copolymer and the amine, forming a complex between the carboxylic acid ion and ammonium ion. Although it is described that a (salt) is formed, the coordination ionic copolymer according to the present invention can also be analyzed by analyzing its infrared absorption spectrum, particularly by measuring the absorption peaks of -000H and -000-. From this, it is analyzed that, in addition to the ammonium ion/carboxylic acid ion complex structure described above, the amine forms a structure in which the amine is coordinately bonded to the metal ion.

For example, in the zn++ ionomer of ethylene-methacrylic acid copolymer, the absorption peak at -000H (17
00cm-') and Zn++ ionization group (-000-
An absorption peak (1580 cm-') of
Compared to the ionomer, the absorption peak of -floOH is reduced, and the absorption peak of Zn ionization -000- is also reduced. At the same time, a new method based on ammonium ionization (
A peak (1550 to 1500 cm-') appears in which the -000-〇 absorption and the 1aOO- absorption estimated to be based on zn++ ionization of amine coordination overlap.

This suggests that the coordination ionic copolymer of the present invention may simply form either an ammonium ion/carboxylic acid ion complex structure or a structure in which an amine is coordinately bonded to a metal ion. This shows that a structure is formed in which both coexist.

Such a coordination ionic copolymer can be used in combination with other thermoplastic resins or thermosetting resins within a range that does not substantially impair its physical properties, and if necessary,
Antioxidants, stabilizers, lubricants, adhesives, thickeners, colorants, and the like are appropriately added and used.

〔Effect of the invention〕

The coordinated ionic co-claw assembly according to the present invention is excellent in mechanical properties (particularly rigidity), flowability, and thermal stability.

In terms of mechanical properties, ionomer resin itself has relatively high rigidity, and this characteristic can be used to make moldings for automobiles, the outer skin of golf balls, ski boots, ski windshield glasses, and tools such as screwdrivers. It is used for uses such as handles and pencil cases, but for example, optical moldings require higher rigidity due to toughness, and golf balls require even higher rigidity due to distance. The coordination ionic copolymer according to the invention fully satisfies these requirements.

There is almost no change in flowability as indicated by the melting index compared to that of ionomer resins, and this ensures that the coordination ionic copolymer of the present invention can be used in a sufficient range as a thermoplastic resin. It can be said that

1. Coordination ionic co-polymer has excellent thermal stability in terms of smoke generation, odor, and coloration of molded products during molding process, and therefore it has a good effect on the working environment and the quality of molded products. Also, no amine bleed-out phenomenon was observed on the surface of the molded product.

The coordination ionic copolymer of the present invention having these favorable properties at the same time can be produced by extrusion molding, injection molding, etc.
It can be suitably used for various purposes such as films and sheets as mentioned above.

〔Example〕

Next, the present invention will be explained with reference to examples.

Example 1 Single screw extruder (screw diameter 30 recommended, L/D
= 32), 5.6% by weight (24.0 mol% based on the amount of carboxylic acid in the copolymer) of 1,3-bisaminomethylcyclohexane was added to the ionomer resin A shown in Table 2 below. After blending by injecting into the extruder with a pump, the melting temperature was 220°C and the screw rotation speed was 45.
rpm, and the average residence time of the resin was about 3 minutes.

Go no 1. The coordinated ionic ethyl 1/one copolymer was pressure-molded into a predetermined shape, and its melting index and mechanical properties were determined as follows.
(Measurement was carried out using the zero constant method, and the processing and forming conditions were also investigated.

Bending rigidity: Based on ASTM D-747-70; Test piece 100 x 20 4.81i1% (21.3 mol% m
-Xylylene diamine was used.

Comparative Examples 1 to 13 In Example 1, 1,3-bisaminomethylcyclohexane was replaced with various amines shown in Table 1 below in the amount of 4.R.

Table 1 W4 Gold 1 1 Hexamethylene diamine 5.0 2
6.0 Triblend 2 Hexamethylenetetramine // 21.6 p3 Ethylenediamine 5.4 54.5
Pump 4 Piperazine
5.0 15.6 Triblend 5
Iminobispropylamine 4.0 18.2
Pump 6 Methyliminobispripylamine 3,8 15,6 tt8 Aminoethylpiperazine 5.2 24,4
tt9 bisaminopropylpiperazine
5,0 15.110 p-phenylenediamine N 27.9 Triblend 1
1 bis(4-aminophenyl)methane //
15,2 p12 m-hexylamine 5.4 32.4 Pumped 13 (none) 0
- The measurement results of each of the above Examples and Comparative Examples are shown in Table 2 below.

Examples 3 to 4 In Example 2, the amount of m-xylylenediamine was variously changed. The results of similar measurements are shown in Table 4 below.
is shown.

Example 5 In Example 2, ionomer resin B shown in Table 3 below was used as ionomer resin AC1 generation r), and m-
The amount of xylylenediamine blended was 5.9% by weight (26.4% by weight).
(mol%).

Comparative Example 14 In Example 5, m-xylylenediamine was not used.

Comparative Example 15 In Example 2, ionomer resin 0 shown in Table 3 below was used instead of ionomer resin A, and the m-xylylenediamine compounding lid was adjusted to 6.2% by weight (27.9 mol%). changed.

Comparative Example 16 In Comparative Example 15, xylylene diamine df was not used.

Comparative Example 17 In Example 2, the acid copolymer shown in Table 3 below was used instead of ionomer resin A, and the amount of m-xylylenediamine was 7.5)][% (34.2 mol). %
) was changed.

Comparative Example 18 In Comparative Example 17, no chirari 1 nondiaminka was used.

Table 3 Acid copolymer 95.3 4.7 - -
-60 9・Ionomer resin A #
tt Zn” 10
20 14 9 Ionomer resin B IF
The measurement results for #Mg++IF Example 5 and Comparative Examples 14 to 18 are also shown in Table 4 below.

Examples 6-7 Eyemenomer I & J greasiness and E each had τ゛10,
14% (44.9 mol%) of 1,3-bisaminomethylcyclohegisane was blended, and melt-kneaded at 220°C for 10 minutes using a Laboplast Mill.

When the resulting coordination ionic copolymer was pressure molded, a molded article with improved transparency and mechanical properties was obtained compared to Ionomer W fat or ordinary pressure molded articles.

Claims (1)

[Claims] 1. (1) Ethylene-unsaturated carboxylic acid copolymer, (
2) a metal compound capable of supplying divalent cations of zinc, cobalt, nickel, copper, lead or magnesium;
) A coordination ionic ethylene copolymer obtained from an aromatic or alicyclic compound having a bisaminoalkyl group. 2. The coordination ionic ethylene copolymer according to claim 1 obtained by melt-kneading each component (1) to (3). 3. The coordination ionic ethylene copolymer according to claim 1 or 2, in which the metal compound is used in an amount of 5 to 45 mol% based on the amount of carboxylic acid in the copolymer. . 4. The coordination ionic ethylene copolymer according to claim 1 or 2, wherein the bisaminoalkyl compound is used in an amount of 8 to 100 mol% based on the amount of carboxylic acid in the copolymer. Polymer.