JPH03210329A - Block copolymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an aromatic polyester-polyorganosiloxane block copolymer, and more specifically, it has excellent weather resistance, heat resistance, cold resistance, and impact resistance, and has excellent mechanical properties. Aromatic polyester-polyorganosiloxane block copolymerization (HC-related) with high mechanical strength.

[Prior Art and Problems to be Solved by the Invention] Block copolymers consisting of hard segments and soft segments are known as thermoplastic elastomers, and are widely used mainly in the field of replacing vulcanized rubber. Thermoplastic elastomers are classified into various types depending on their constituent components and block configurations, and the main ones include styrene, olefin, vinyl chloride, polyurethane, polyester, and polyamide. Among them, polyester thermoplastic elastomers have good heat resistance and are widely used as high-performance thermoplastic elastomers.

This polyester-based thermoplastic elastomer can be divided into polyether type and polyester type depending on the soft segment that it consists of, but the polyether type has a problem with weather resistance, and the improved polyester type also has poor melt stability.・There are problems with cold resistance, flexibility, and hydrolysis resistance.

An object of the present invention is to provide a polyester-based thermoplastic elastomer that solves the above problems, that is, a thermoplastic elastomer that has excellent heat resistance, cold resistance, and weather resistance.

[Means for solving problems]

As a result of intensive studies to achieve the above object, the present inventors have discovered that a block copolymer consisting of aromatic polyester and polyorganosiloxane exhibiting liquid crystallinity has excellent weather resistance, heat resistance, cold resistance, and impact resistance. The inventors have discovered that this polymer has excellent properties and high mechanical strength, and have arrived at the present invention.

That is, in the present invention, the polyester segment is (a)
Aromatic polyester consisting of aromatic dicarboxylic acid and dihydric phenol, (b) aromatic polyester consisting of aromatic hydroxycarboxylic acid, or (c) copolymer consisting of (a) and (b) as main constituent components. A polyester exhibiting liquid crystallinity, the polyorganosiloxane segment is represented by the formula (1) (4, where R1 and R6 each independently represent a methyl group or a phenyl group, and n represents an integer of 10 or more). The present invention relates to an aromatic polyester-polyorganosiloxane block copolymer characterized in that it has a repeating unit.

Congratulations on the present invention, the polyester segment includes (a) an aromatic polyester consisting of an aromatic dicarboxylic acid and a dihydric phenol, (b) an aromatic polyester consisting of an aromatic hydroxycarboxylic acid, or (C) (- and ( It is a polyester exhibiting liquid crystallinity, whose main constituent is the copolymer shown in 'b).

The aromatic dicarboxylic acid used in the present invention has the formula (El) aTi-a-R, -c-oFl (T) [In the formula, R3 is a substituted or unsubstituted phenylene group, and the following formula: (In the formula, 2 represents a direct bond or -C-) or a naphthylene group], where substituents of the phenylene group include, for example, chlorine,
Examples include bromine and methyl groups, and substituted phenylene groups include 1-
Can be substituted with 4 substituents.

Examples of such aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, diphenyl-m,m'-dicarboxylic acid, diphenyl-p,p'-dicarboxylic acid, diphenylmethane-m,m'-dicarboxylic acid, diphenylmethane-p , p'-dicarboxylic acid, benzophenone-4,4
'-dicarboxylic acid, naphthalene dicarboxylic acid, etc., and these can be used alone or in combination of two or more. Further, aliphatic dicarboxylic acids such as adipic acid and sebacic acid may also be used in small amounts as long as they do not substantially impair the liquid crystallinity of the polyester.

Next, the dihydric phenol is represented by the formula [1] % formula % ([[) [wherein R4 represents a substituted or unsubstituted phenylene group, naphthylene group, or anthraquinone group]], and its For example, two phenols such as
Hydroquinone, resorcinol, dihydroxynaphthalene,
Biphenol (biphenyl diol), 1,8-dihydroxyanthraquinone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-cyhydroxydiphenyl ether, 4,4'-diphenyl sulfide, 4,4'-
Examples include dihydroxydiphenylketone, and these can be used alone or in a mixture of two or more. Also, within a range that does not impair the liquid crystallinity of polyester, 2.2-(4
Aromatic diols containing lower alkylene groups, such as -hydroxyphenyl)propane and 4,4'-dihydroxyphenylmethane, may also be used in small amounts.

The aromatic hydroxycarboxylic acid used in the present invention is represented by the following formula: ) % formula % (wherein R5ki represents a phenylene group, a biphenylene group, or a naphthylene group).

Examples of such aromatic hydroxycarboxylic acids include o-, b-, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, etc. These may be used alone or in combination of two or more. Preferred polyester segments include copolymers of p- and droxybenzoic acid and 2,6-natsuta-1/dicarboxylic acid tohydroquinone, p-hydroquinone benzoic acid and 4-dicarboxylic acid tohydroquinone copolymers,
Copolymer of 6-Natsuta 1/2 dicarboxylic acid, isophthalic acid and hydroquinone, p-hydroxybenzoic acid - Hydroxy? - copolymer of naphthoic acid, p-hydroxybenzoic acid, 2,6-naphthalene dicarboxylic acid and 2,
It is a copolymer of 6-naphthalenediol.

t & polyorganosiloxane segment has a repeating unit represented by the following formula: i? Among them, polydimethylsiloxane is preferred.

In the block copolymer of the present invention, the composition ratio of the polyester segment and the polyorganosiloxane segment is preferably 90:10 to 10:90 by weight, and if it deviates from this range, the original performance as a block polymer will deteriorate. is on a declining trend. In other words, the properties of polyester and polyorganosiloxane are no longer utilized. Note that when the ratio of polyester segments is large, the properties as a resin become strong, and when the ratio of polyorganosiloxane is large, the properties as an elastomer become strong.

The aromatic polyester-polyorganosiloxane block copolymer of the present invention preferably has a number average molecular weight of 10
．． Of:) 0 or more, more preferably 15,
000 or more. When the number average molecular weight is small, the mechanical strength of the polymer tends to decrease.

Next, the aromatic polyester-polyorganosiloxane block copolymer Ua of the present invention can be produced using the reaction conditions used in conventional polyester production, and can be created, for example, as follows.

1. ■ A method of reacting an aromatic polyester with a polyorganosiloxane having amino groups at both ends represented by the formula [tera] (wherein R1, R, and n are the same as above) in the presence of a transesterification catalyst.

■ Monomers constituting aromatic polyester and the above formula [
A method of melting and condensing a polyorganosiloxane with amino groups at both terminals in the presence of a transesterification catalyst.

■ Melt polymerization of the compound constituting the aromatic polyester and the polyorganosiloxane with a carboxylic acid at both terminals represented by the formula [bone] (wherein R1* R1 and n are the same as above) in the presence of a transesterification catalyst. How to do it.

There is no particular problem in using any method, and it goes without saying that the method is not limited to these methods.

Note that polyorganosiloxanes, such as polydimethylsiloxane, are described in J. Polym, Polymerp.
hysics l! fa,, 23.2319 (198
It can be manufactured by the known method described in 5).

The thus obtained block copolymer of the present invention may contain a heat stabilizer, an antioxidant, an ultraviolet absorber, a flame retardant, a flame retardant, a waste retardant aid, etc., and/or a pigment, a dye, etc. can.

Further, the block copolymer of the present invention can be pelletized by a normal extrusion process and then molded into a desired shape by extrusion molding, injection molding, pressure molding, or the like.

Preferred embodiments of the present invention are as follows.

(1) Claim 1 whose number average molecular weight is IQ, 000 or more
The aromatic polyester-polyorganosiloxane block copolymer described above.

(2) The aromatic polyester-polyorganosiloxane block copolymer according to claim 1, wherein the composition ratio of the aromatic polyester to the polyorganosiloxane is from 90:10 to 10:90 by weight.

(3) The aromatic dicarboxylic acid constituting the aromatic polyester is represented by the following f (11), and the -valent phenol is represented by the following formula (1). The aromatic polyester-1 organosiloxane block copolymer according to claim 1.

0 0 ]i HO0-R3-00H1:11) [In the formula, R3 represents a substituted or unsubstituted phenylene group, a group represented by the following formula: or -〇-), or a naphthylene group] 0-14 OH [111) [In the formula, R4 is a substituted or unsubstituted phenylene group or naphthylene group, or the formula: 1 (4) The aromatic polyester is a copolymer of p-hydroxy7benzoic acid, 2,6-naphthalene dicarboxylic acid, and hydroquinone. The aromatic polyester-polyorganosiloxane block copolymer described above.

(5) The aromatic polyester-polyorganosiloxane block copolymer according to claim 1, wherein the aromatic polyester is a copolymer of p-hydroxybenzoic acid, 2,6-naphthalene dicarboxylic acid, isophthalic acid, and hydroquinone.

(6) The aromatic polyester-polyorganosiloxane block copolymer according to claim 1, wherein the aromatic polyester is a copolymer of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid.

(iii) The aromatic polyester is p-hydroxybenzoic acid and 2
．． The aromatic polyester-polyorganosiloxane block copolymer according to claim 1, which is a copolymer of 6-naphthalene dicarboxylic acid and 6-naphthalene diol.

2. The aromatically extended polyester-polyorgano V-loxane block copolymer according to claim 1, wherein (B) R and R2 are both methyl groups.

[Effect]

The aromatic polyester-polyorganosiloxane block copolymer of the present invention has a fully aromatic polyester exhibiting high heat resistance and liquid crystallinity in the hard segment, so it has excellent weather resistance compared to conventional thermoplastic elastomers. It can be a useful thermoplastic elastomer that exhibits properties such as hardness, heat resistance, cold resistance, and impact resistance, and also has high mechanical strength.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.

Synthesis Examples 1 to 6 Polydimethylsiloxane having aminopropyl groups at both ends, naphthalene dicarboxylic acid (NDA), hydroquinone diacetate (A-HQ') and p-hydroxybenzoic acid (A-POB') are shown in Table 1. The composition shown was charged into a reaction vessel equipped with a stirrer, and heated from 20[)℃ to 3℃ under a nitrogen atmosphere.
The reaction was carried out for 3 hours at [ ) O''ct, and the pressure was reduced to 15 J over 30 minutes at 300°C.
After heating for 30 minutes, further reduce the pressure with CL5■Hg t.
After heating for a period of time, the product is taken out and a highly viscous polymer (
S-1 ~ Ministry) was obtained.

Table 1 Examples 1 to 6 The polymers (S-1 to 6) obtained in Synthesis Examples 1 to 6 were injection molded into test pieces with predetermined dimensions using a conventional method, and the test pieces were subjected to tensile tests and thermal deformation tests. Tested. The tensile test was conducted in accordance with ABTMD636, and the thermal deformation test was conducted in accordance with A8.
According to TMD648. The results are shown in Table 2.

Comparative Examples 1 to 3 Commercially available polyester thermoplastic elastomers Perbrene p-aaH (Comparative Example 1), Perbrene P-70B (Comparative Example 2) and Perbrene P-150B (Comparative Example 3) (all manufactured by Toyobo ■) Each test piece was injection molded to a predetermined size using a conventional method and evaluated in the same manner as in the Examples, and the results are shown in Table 2.

Table [Effects of the Invention] The aromatic polyester-polyorganosiloxane block copolymer of the present invention has excellent weather resistance, heat resistance, cold resistance, and impact resistance, and has high mechanical strength and moldability. Because of its excellent properties, it can be used as a thermoplastic resin or thermoplastic elastomer that can be used under harsher conditions than conventional ones and can be used for a wider range of applications.

Claims (1)

[Scope of Claims] 1) The polyester segment is (a) an aromatic polyester consisting of an aromatic dicarboxylic acid and a dihydric phenol, (b) an aromatic polyester consisting of an aromatic hydroxycarboxylic acid, or (c) (a) ) and (b), and the polyorganosiloxane segment has the formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I ] (In the formula, R_1 and R_2 each independently represent a methyl group or a phenyl group, and n represents an integer of 10 or more.) An aromatic polyester-polyorganosiloxane block characterized by having a repeating unit represented by Copolymer.