JPH06212043A - Polymer alloy composition - Google Patents

Abstract

PURPOSE:To obtain composition, consisting essentially of a fluororesin which is a crystalline polymer and a specific acrylic acid ester-based polymer which is an amorphous polymer and useful as a polymeric material excellent in compatibility and various characteristics in the automotive industry, etc. CONSTITUTION:This polymer alloy composition consists essentially of a fluororesin which is a crystalline polymer (preferably vinylidene fluoride polymer, etc.) and an acid acrylic ester-based polymer which is an amorphous polymer prepared by (co)polymerizing a monomer expressed by the formula {0.5<=(m+n)<=1; 0<=(p)<=0.5; R1 and R3 are H or methyl; R2 is CxH2x+1; R4 is CyG2y+1 [(1<=(x+y)<=5; (x) and (y) are 0-5]; A is unsaturated monomer unit other than two acrylic acid ester-based monomers constituting the polymer}. Furthermore, the blending ratio of both is suitably determined according to the characteristics to be obtained.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymer alloy composition which can be widely used as a high-performance and high-functional polymer material in various industrial fields such as the automobile industry.

[0002]

BACKGROUND ART Conventionally, a polymer alloy composition (polymer blend) has been developed for the purpose of improving various properties of polymer materials such as mechanical properties such as tensile strength and tensile elongation and electrical properties such as dielectric constant. Is very active,
By combining two or more kinds of known polymers (polymers or copolymers), high performance and high functionality of polymer materials have been achieved.

By the way, a polymer alloy composition has a synergistic effect (sy) by blending a plurality of polymers.
It is prepared for the purpose of expressing the nergistic effect) and obtaining a composition having the advantages of each single polymer. Ideally, as shown in FIG. 1, in the case of blending the polymer A and the polymer B, with respect to the average value of a certain characteristic represented by the line a, depending on the blending ratio. It is desirable that the characteristics be enhanced as indicated by the broken line. However, in reality, when different polymers are blended, in many cases, a phenomenon occurs in which various properties are pulled to be worse than the average, and the properties appear in the range shown by the shaded area in FIG. Is mostly.

It is believed that such a phenomenon is due to the fact that most of the blends of different polymers are incompatible systems. Therefore, in the development of the polymer alloy composition, how to bring polymers that are originally incompatible with each other into a compatible system to exert a synergistic effect and improve the overall properties has been a focus. For example, (1) modification of polymer, (2) addition of compatibilizer,
(3) Efforts to increase compatibility between polymers have been made by various methods such as improvement of kneading processing technology.

Under these circumstances, the present inventor has conducted a study with a focus on polymer modification regarding the formation of a composite of a crystalline polymer and an amorphous polymer. In a polymer alloy composition of an incompatible fluororesin (crystalline polymer) and an acrylic acid ester-based polymer (amorphous polymer), the crystal size (spherulites, etc.) of the fluororesin becomes uneven. It was inferred that there was a phenomenon in which the crystal size became smaller or the crystal size became smaller, and this had some relation with the incompatibility.

[0006]

The present invention has been made in view of such circumstances, and a problem to be solved by the present invention is that a fluororesin (crystalline polymer) and an acrylate polymer (amorphous polymer) are used. Incompatible blends with
By controlling the crystallization of the fluororesin, the obtained polymer alloy composition is brought close to a compatible system to effectively improve the characteristics.

[0007]

In order to solve the above problems, in the present invention, a polymer containing a fluoropolymer as a crystalline polymer and an acrylate ester polymer as an amorphous polymer as essential components, respectively. A gist of a polymer alloy composition, wherein the acrylic acid ester-based polymer satisfies the following unit structural formula as an alloy composition.

[0008]

[Chemical 2]

[However, 0.5 ≦ m + n ≦ 1, 0 ≦ p ≦
0.5, R ₁ , R ₃ : hydrogen atom or methyl group, R ₂ :
C _x H _{2x + 1} , R ₄ : C _y H _{2y + 1} , 1 ≦ x + y ≦ 5, x:
An integer of 0 to 5, y: an integer of 0 to 5, A: an unsaturated monomer unit other than the above-mentioned two acrylic acid ester-based monomers constituting the polymer]

[0010]

In effect, the present invention has an acrylic acid ester-based polymer as an essential component as an amorphous polymer that constitutes the polymer alloy composition, and the acrylic acid ester-based polymer is the R ₂ in the unit structural formula. , R ₄ are each a hydrogen atom or an alkyl group having not more than C ₅ .
50 mol% of low molecular weight acrylic acid ester monomer
It is characterized in that it is included in the above ratio. And, by using the polymer having such a structure, the crystallization of the fluororesin is effectively controlled and the uniform crystallization is promoted. Therefore, the phase of the acrylic ester-based polymer and the fluororesin is Solubility can be effectively improved. Therefore, in the polymer alloy composition according to the present invention, a synergistic effect due to blending can be advantageously exhibited, so that various properties such as mechanical properties and electrical properties can be effectively improved, and practical use can be achieved. As a typical polymer alloy composition, it has extremely high utility value in various industrial fields.

[0011]

SPECIFIC STRUCTURE By the way, the polymer alloy composition according to the present invention contains a fluoropolymer as a crystalline polymer and an acrylate polymer as an amorphous polymer as essential components. As the acrylic acid ester-based polymer, one satisfying the following unit structural formula is used in particular.

[0012]

[Chemical 3]

[However, 0.5≤m + n≤1, 0≤p≤
0.5, R ₁ , R ₃ : hydrogen atom or methyl group, R ₂ :
C _x H _{2x + 1} , R ₄ : C _y H _{2y + 1} , 1 ≦ x + y ≦ 5, x:
An integer of 0 to 5, y: an integer of 0 to 5, A: an unsaturated monomer unit other than the above-mentioned two acrylic acid ester-based monomers constituting the polymer]

That is, the acrylic acid ester-based polymer (homopolymer or copolymer) is obtained by polymerizing or copolymerizing 1 to 3 kinds of monomers at a ratio (mol%) defined by m, n and p. It is obtained by polymerizing. Specifically, in the case of p = 0 and m + n = 1, if two acrylic acid ester monomers are the same in the combination of R _{1 to} R ₄ , one kind is used, and if they are different, It will contain two types of monomers. Also, 0 <p ≦ 0.5,
In the case of 0.5 ≦ m + n <1, two kinds of monomers are included if the two acrylic acid ester monomers are the same, and three kinds of monomers are included if they are different. In any case, the ratio of the two acrylic acid ester-based monomers to the total monomer components is 50 mol% or more, which effectively improves the compatibility with the fluororesin. You can do it.

In the two acrylic acid ester-based monomers constituting the acrylic acid ester-based polymer, R ₁ and R ₃ are each a hydrogen atom or a methyl group,
₂ : C _x H _{2x + 1} and R ₄ : C _y H _{2y + 1} are each a hydrogen atom (when x and y are 0) or an alkyl group. Then, from the respective conditions of 1 ≦ x + y ≦ 5, x: an integer of 0 to 5 and y: an integer of 0 to 5, specific R ₂ and R
The combinations of ₄ are as shown in Table 1 below, except for the combinations that give the same polymer structure.

[0016]

[Table 1]

Further, when an unsaturated monomer unit: A other than the above-mentioned two acrylic acid ester-based monomers is introduced into the acrylic acid ester-based polymer, the mixing ratio is 50 mol% or less. (0 ≦ p ≦ 0.5). In addition, as the unsaturated monomer unit, any monomer copolymerizable with an acrylic acid ester-based monomer can be used, and for example, 2-chloroethyl vinyl ether, methyl vinyl ketone, acrylonitrile, butadiene, Examples thereof include ethylene.

The desired acrylic acid ester-based polymer can be obtained by blending the respective monomers at a predetermined ratio and polymerizing or copolymerizing them according to various known methods.

On the other hand, the fluororesin used as the crystalline polymer in the present invention is not particularly limited, and various commonly known fluororesins can be used. Thus, in order to exhibit good compatibility with the acrylic acid ester-based polymer, vinylidene fluoride polymer (PVF ₂ ), fluorinated alkoxyethylene polymer (PFA), tetrafluoroethylene polymer (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), trifluoroethylene chloride polymer (PC
TFE), vinylidene fluoride - tetrafluoroethylene copolymer [P (VF ₂ -TFE)], vinylidene fluoride - hexafluoride acetone copolymer [P (VF ₂ -HFA)], vinylidene fluoride - six Fluorinated propylene binary copolymer [P
(VF ₂ -HEP)] and vinylidene fluoride - hexafluoropropylene - tetrafluoroethylene terpolymer [P (V
F ₂ -HEP-TFE)] is desirable. Among them, the vinylidene fluoride polymer is most preferably used.

Then, the fluororesin and the acrylic acid ester-based polymer are blended in a predetermined ratio, and melted and kneaded according to a known method to obtain a desired polymer alloy composition (thermoplastic elastomer). Of. The blending ratio of the fluororesin and the acrylic ester-based polymer is appropriately determined according to the properties to be obtained, and in the case of improving the electrical properties such as dielectric constant and heat resistance, the fluororesin is used. In the case of increasing the tensile elongation and improving the tensile elongation, the proportion of the acrylic ester polymer is adjusted to be increased. Also,
If necessary, a polymer other than the fluororesin and the acrylic ester-based polymer can be further blended.

In the polymer alloy composition thus obtained, the crystallization of the fluororesin is well controlled, the compatibility between the polymers is high, and the synergistic effect of the blend can be advantageously exhibited. Therefore, it is possible to effectively improve various properties such as mechanical properties and electrical properties, and it becomes extremely useful in various industrial fields as a practical polymer alloy composition.

[0022]

EXAMPLES Hereinafter, representative examples of the present invention will be shown to clarify the present invention in more detail. However, the present invention is not limited by the description of such examples. Needless to say, it is not something to receive. Further, in addition to the following specific examples, in addition to the following embodiments, the present invention includes various modifications based on the knowledge of those skilled in the art without departing from the spirit of the present invention.
It should be understood that modifications, improvements, etc. may be made.

Examples 1 to 5 and Comparative Example 1 First, in the following unit structural formula, p = 0 and m = n =
0.5 (m + n = 1), R ₁ and R ₃ : conditions were defined as hydrogen atoms, and further R ₂ and R ₄ were defined as follows, and 6 types of acrylic acid ester polymers were prepared. Example 1 R ₂ : H, R ₄ : CH ₃ Example 2 R ₂ : H, R ₄ : C ₅ H ₁₁ Example 3 R ₂ : CH ₃ , R ₄ : CH ₃ Example 4 R ₂ : CH ₃ , R _4: C ₄ H ₉ example _{5 R 2: C 2 H 5} , R 4: C 3 H 7 Comparative example _{1 R 2: C 4 H 9} , R 4: C 4 H 9

[0024]

[Chemical 4]

Next, each of these six kinds of acrylic acid ester-based polymers (ACM) and a vinylidene fluoride polymer (PVF ₂ ) were added to PVF ₂ / A on a weight basis.
Various polymer alloy compositions were obtained by melting and kneading in the ratios of CM = 70/30, 50/50, 30/70. Then, the tensile strength (T _B ), the tensile elongation (E _B ), and the dielectric constant (ε) of each of the obtained polymer alloy compositions were measured, and the results are shown in Table 2 below. Further, the results of T _B (◯) and E _B (●) obtained in Example 1 are shown in FIG.
The results of T _B (◯) and E _B () obtained in Comparative Example 1 are shown in FIG.

[0026]

[Table 2]

As is clear from Table 2 and FIG.
The properties of the polymer alloy compositions of Examples 1 to 5 are higher than the average value of the properties of the respective single polymers, and the properties are advantageously improved by the synergistic effect. Be understood. On the other hand, the characteristics of the polymer alloy composition of Comparative Example 1 are considerably lower than the average value of the characteristics of each single polymer as shown in FIG.

Example 6 and Comparative Example 2 First, in the unit structural formula shown in Example 1, R ₁ ,
R _3: a hydrogen _{atom, R 2, R 4: CH} 3 as using one type of acrylic acid ester monomer, the unsaturated monomer unit A: -CH ₂ -CH ₂ - and a combination, in Example 6 p
= 0.5, m + n = 0.5, and in Comparative Example 2, p = 0.
7. Two types of acrylic acid ester-based polymers were prepared by defining 7, m + n = 0.3.

Then, in the same manner as in Example 1, the above 2
Each of the acrylic acid ester-based polymers (ACM) and vinylidene fluoride polymer (PVF ₂ ) are melted.
After kneading to obtain various polymer alloy compositions, various properties of each polymer alloy composition were measured, and the results are shown in Table 3 below. In addition, the T obtained in Example 6
The results of _B (○) and E _B (●) are shown in FIG.
The results of T _B (◯) and E _B () obtained in the above are shown in FIG.

[0030]

[Table 3]

As is clear from Table 3 and FIG. 4,
The properties of the polymer alloy composition of Example 6 are higher than the average value of the properties of the respective single polymers, and it can be seen that the properties are advantageously improved by the expression of the synergistic effect. . On the other hand, the characteristics of the polymer alloy composition of Comparative Example 2 are as shown in FIG.
It is much lower than the average value of the properties of each single polymer, which makes it impractical.

Examples 7 and 8 First, in the unit structural formula shown in Example 1, p =
0, m + n = 1, R ₁ , R ₃ : hydrogen atom, R ₂ : C
The conditions were set as H ₃ , R ₄ : C ₄ H ₉ , and further, Example 7 was used.
Then, m = 0.75, n = 0.25, and in Example 8, m =
Specified as 0.25 and n = 0.75, two kinds of acrylic acid ester polymers were prepared.

Then, in the same manner as in Example 1, the above 2
Each of the acrylic acid ester-based polymers (ACM) and vinylidene fluoride polymer (PVF ₂ ) are melted.
After kneading to obtain various polymer alloy compositions, various properties of each polymer alloy composition were measured, and the results are shown in Table 4 below. In addition, the T obtained in Example 7
The results of _B (◯) and E _B (●) are shown in FIG.
The results of T _B (∘) and E _B () obtained in Step 2 are shown in FIG.

[0034]

[Table 4]

As is clear from Table 4 and FIG. 6,
The properties of the polymer alloy composition of Example 7 are higher than the average value of the properties of the respective single polymers, and it can be seen that the properties are advantageously improved by the expression of the synergistic effect. . Further, as is clear from FIG. 7, the characteristics of the polymer alloy composition of Example 8 are also above the average although they are partially below the average, which is significantly higher than those of Comparative Examples 1 and 2. Improvements have been achieved.

[Brief description of drawings]

FIG. 1 is an explanatory diagram for explaining a synergistic effect of properties in a polymer alloy composition.

2 is a graph showing characteristics of the polymer alloy composition obtained in Example 1. FIG.

FIG. 3 is a graph showing characteristics of the polymer alloy composition obtained in Comparative Example 1.

4 is a graph showing characteristics of the polymer alloy composition obtained in Example 6. FIG.

5 is a graph showing characteristics of the polymer alloy composition obtained in Comparative Example 2. FIG.

6 is a graph showing characteristics of the polymer alloy composition obtained in Example 7. FIG.

7 is a graph showing characteristics of the polymer alloy composition obtained in Example 8. FIG.

Claims (2)

[Claims] 1. A polymer alloy composition comprising a fluoropolymer as a crystalline polymer and an acrylate polymer as an amorphous polymer as essential components, wherein the acrylate polymer has the following unit structure: A polymer alloy composition satisfying the formula. [Chemical 1] [However, 0.5 ≦ m + n ≦ 1, 0 ≦ p ≦ 0.5, R ₁ , R ₃ : hydrogen atom or methyl group, R ₂ : C _x H _{2x + 1} , R ₄ : C _y H _{2y + 1.} , 1 ≦ x + y ≦ 5, x: an integer of 0 to 5, y: an integer of 0 to 5, A: an unsaturated monomer unit other than the two acrylic acid ester-based monomers constituting the polymer] 2. The fluororesin is a vinylidene fluoride polymer, a fluoroalkoxyethylene polymer, a tetrafluoroethylene polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, or an ethylene-tetrafluoroethylene copolymer. Polymers, ethylene trifluoride chloride polymers, vinylidene fluoride-tetrafluoroethylene copolymers, vinylidene fluoride-acetone hexafluoride copolymers, vinylidene fluoride-propylene hexafluoride binary copolymers and fluorine The polymer alloy composition according to claim 1, wherein the polymer alloy composition is selected from vinylidene chloride-propylene hexafluoride-tetrafluoroethylene terpolymer.