JP2003313276A - Polyarylate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polyarylate having extremely high heat resistance and elastic modulus. <P>SOLUTION: This polyarylate contains 10-90% repeating unit of formula (1) (wherein A is at least one kind selected from an aliphatic hydrocarbon group which may have a 4-15C branch and an alicyclic hydrocarbon group which may have a 4-15C branch; and R<SP>1</SP>to R<SP>8</SP>are the same or different and are each hydrogen or a 1-6C hydrocarbon group). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to polyarylate. More specifically, it relates to a polyarylate having extremely high heat resistance and elastic modulus.

[0002]

2. Description of the Related Art Polyarylate, which is a wholly aromatic polyester, is widely used as an engineering plastic having excellent heat resistance and toughness. As one of the performance enhancements of polyarylate, studies are under way to further increase the heat resistance of polyarylate. Conventionally, as a method for increasing heat resistance, a method of introducing a bisphenol component having a cardo type structure has been used. For example, Macromolecules Vol. 3,53
The fluorenylidene-introduced arylate on page 6 (1970) and the tetrahydrodicyclopentadienylidene-introduced arylate in U.S. Pat. In 166849, an arylate having a cyclohexylidene derivative introduced therein is exemplified. On the other hand, as the carboxylic acid component, although many of the exemplified compounds are used, actually, a component derived from terephthalic acid and isophthalic acid was mainly used. Carboxylic acids other than these components have hardly been used, and their effects on various properties of the carboxylic acid component have not been clarified.

On the other hand, improvement studies of various properties of polyarylate have hitherto been focused on heat resistance, and almost no studies have been made on mechanical properties. For example, regarding the elastic modulus, reduction of warpage etc. of various molded products,
Although it is important as a characteristic that has an important influence on the thinning of the film, few examples have been studied for the purpose of improving it.

[0004]

As is apparent from the prior art, the object of the present invention is to provide a polyarylate having high heat resistance and improved elastic modulus.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to solve the above problems. As a result, when a 2,6-naphthalenedicarboxylic acid component was introduced as the carboxylic acid component, the heat resistance was high and the elasticity was high. They have found that polyarylate having a high rate can be obtained, and have completed the present invention. That is, the present invention provides the following formulas (I) and (II)

[0006]

[Chemical 2]

(In the formulas (I) and (II), A has 1 carbon atom)
To at least one substituent selected from an aliphatic hydrocarbon group having 16 to 16 branches and an alicyclic hydrocarbon group having 5 to 16 carbon atoms, and B is 6 to 6 carbon atoms. 1
2 aromatic hydrocarbon groups, R ^{1 to} R ⁸ are the same or different,
Hydrogen or a hydrocarbon group having 1 to 6 carbon atoms) and a molar ratio of (I) to (II) is (I) / (II) =
The amorphous polyarylate is 1/9 to 9/1.

Further, A in the formulas (I) and (II) preferably comprises an alicyclic hydrocarbon group having 5 to 16 carbon atoms and which may have a branch. Further, the A is 1,1 -(3
3,5-trimethylcyclohexylidene) group and 4,
It is preferably at least one selected from a 4- (octahydro-4,7-methano-5H-indene-5-ylidene) group.

Further, in the formulas (I) and (II), R ¹ to
R ⁸ is preferably a hydrogen atom. Also, the formula (II)
B in is preferably one selected from paraphenylene and metaphenylene, and more preferably B is paraphenylene.

The present invention will be described in detail below. The polyarylate in the present invention has the following formulas (I) and (II)

[0011]

[Chemical 3]

(In the formulas (I) and (II), A has 1 carbon atom.
To at least one selected from the group consisting of an aliphatic hydrocarbon group which may have 16 to 16 branches and an alicyclic hydrocarbon group having 5 to 16 carbon atoms, B is an aromatic hydrocarbon group, and R ^{1 to} R ⁸ are the same or Differently, hydrogen or a hydrocarbon group having 1 to 6 carbon atoms).

Here, as the group suitable as A in the formulas (I) and (II), isopropylidene, 1,1-ethylmethyl-methylene, 1,1-diethyl-methylene,
Cyclopentylidene, cyclohexylidene, 1,1-
(3,3,5-trimethylcyclohexylidene), cycloheptylidene, cyclooctylidene, 2,2-norbornylidene, 4,4- (octahydro-4,7-methano-5H-indene-5-ylidene), etc. Can be mentioned. Among them, 1,1- (3,3,5-trimethylcyclohexylidene) and 4,4- (octahydro-) are preferable because polyarylate has high transparency and little coloring.
4,7-Methano-5H-indene-5-ylidene) is preferred. These may be used alone or in combination of two or more.

Preferred examples of B in the formula (II) include orthophenylene, metaphenylene, paraphenylene, 1,7-naphthalenylene, 2,5-naphthalenylene and 2,7-naphthalenylene. it can. Among these, metaphenylene and paraphenylene are preferable, and paraphenylene is particularly preferable, from the viewpoint of easy availability. These may be used alone or in combination of two or more.

Preferable examples of R ^{1 to} R ⁸ include hydrogen atom, methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, hexyl, cyclohexyl,
Examples thereof include phenyl and the like. Of these, a hydrogen atom and methyl are preferable, and a hydrogen atom is particularly preferable. These may be used alone or in combination of two or more.

Regarding the polyarylate of the present invention, the molar ratio of the above formulas (I) and (II) is (I) / (II) = 1 / 9-
It is 9/1. When the molar ratio is less than 1/9, 2,6-
The effect of improving the elastic modulus by introducing a naphthylene group is not exhibited,
Not preferable. Further, if it is larger than 9/1, the moldability is deteriorated, which is not preferable. A preferable range of the molar ratio is (I) / (II) = 1/9 to 8/2, more preferably 1/9 to 7/3.

More specifically, the following structures can be mentioned as suitable polyarylate in the present invention.

[0018]

[Chemical 4]

(In the above structural formula, x and y represent composition ratios, 10≤x≤90, 10≤y≤90, and x + y = 100.
Is)

The molecular weight of the polyarylate in the present invention is not particularly limited, but a polymer solution of 0.6 g / dL (solvent: phenol / tetrachloroethane = 60/40)
(Weight ratio)) of diluted solution viscosity (ηsp /
The value of c) is preferably 0.2 to 3.0,
More preferably 0.3 to 2.5, 0.4 to
It is more preferably 2.0.

The method for producing the polyarylate in the present invention is not particularly limited, and a conventionally known polymerization method may be used. Preferred methods include a reaction between an aromatic carboxylic acid and an aromatic hydroxyacetate, and an aromatic compound. Examples thereof include a reaction between a carboxylic acid ester and an aromatic hydroxy compound, a reaction between an aromatic carboxylic acid and an aromatic hydroxy compound, and a reaction between an aromatic carboxylic acid halide and an aromatic hydroxy compound.

[0022]

EXAMPLES The present invention will be described in detail below with reference to examples. However, the present invention is not limited to these examples. 1- (3,3,5-trimethylcyclohexylidene) bisphenol (the following formula): JP-A-9-13254
It was synthesized according to JP-A-4.

[0023]

[Chemical 5]

4,4- (Octahydro-4,7-methano-5H-indene-5-ylidene) bisphenol (the following formula): purchased from Acros Co., Ltd. and used as it was.

[0025]

[Chemical 6]

Isophoronylene bisphthalimide (the following formula): Synthesized according to JP-A-9-132544.

[0027]

[Chemical 7]

Dilute solution viscosity: 0.6 g / dL polymer solution (solvent: phenol / tetrachloroethane = 60 /
40 (weight ratio)) at 35 ° C. was measured. Glass transition point: DSC TA- manufactured by TA Instruments
It was measured using 2920. 350 ° C at 10 ° C / min
Up to 10 ℃ / mi
The temperature was raised to 350 ° C. with n. From the second measurement result,
The glass transition point was determined. Elastic Modulus: A & D / Orientec RTC-1225A
Was used to measure the elastic modulus in the tensile test.

[Example 1] 47.9 g of terephthalic acid diphenyl ester was placed in a flask which was sufficiently dried and purged with nitrogen.
(151 mmol), naphthalenedicarboxylic acid diphenyl ester 23.8 g (64.5 mmol), 1,1-
66.7 g (215 mmol) of (3,3,5-trimethylcyclohexylidene) bisphenol and 22 mg (65 μmol) of tetrabutoxytitanium were added, 100 g of isophoronylene bisphthalimide was further added as a plasticizer, and the mixture was stirred at 280 ° C. The pressure inside the flask was gradually reduced, and finally polymerization was carried out at 0.3 mmHg for 7 hours. The mixture remained homogeneous during the polymerization. The reaction mixture was dissolved in dichloromethane and poured into acetone to reprecipitate only the allylate. Isophoronylene bisphthalimide was removed by filtering off the arylate and drying to obtain polyarylate. The polyarylate had the following repeating units and their compositional ratio.

[0030]

[Chemical 8]

The glass transition point of polyarylate is 295.
The diluted solution viscosity was 0.89 dL / g at 0 ° C.

The polyarylate was dissolved in methylene chloride to prepare a 15 wt% dope. Using this, 7
A 0 μm thick polyarylate film was prepared. The elastic modulus of the polyarylate film was 2.2 GPa.

Example 2 20.5 g (64.5 mmol) of terephthalic acid diphenyl ester and 55.6 g (151 m) of naphthalenedicarboxylic acid diphenyl ester.
mol) was used to obtain polyarylate by the same operation as in Example 1. The polyarylate had the following repeating units and composition ratios.

[0034]

[Chemical 9]

The glass transition point of polyarylate is 299.
C., the diluted solution viscosity was 0.85 dL / g.

The polyarylate was dissolved in methylene chloride to prepare a 13 wt% dope. Using this, 6
A 4 μm thick polyarylate film was prepared. The elastic modulus of the polyarylate film was 2.4 GPa.

Example 3 66.7 g of 1,1- (3,3,5-trimethylcyclohexylidene) bisphenol
The following operation was repeated by the same operation as in Example 1 except that 68.8 g (215 mol) of 4,4- (octahydro-4,7-methano-5H-indene-5-ylidene) bisphenol was used instead of (215 mmol). A polyarylate having units and composition ratio was obtained.

[0038]

[Chemical 10]

The glass transition point of the polyarylate is 320.
C., the diluted solution viscosity was 0.82 dL / g. The polyarylate was dissolved in methylene chloride to prepare a 13 wt% dope. Using this, a polyarylate film having a thickness of 60 μm was prepared. The elastic modulus of the polyarylate film was 2.6 GPa.

[Comparative Example 1] 47.9 g of terephthalic acid diphenyl ester was placed in a flask which was sufficiently dried and purged with nitrogen.
(151 mmol), isophthalic acid diphenyl ester 20.5 g (64.5 mmol), 1,1- (3,3,
5-trimethylcyclohexylidene) bisphenol 6
6.7 g (215 mmol), tetrabutoxy titanium 2
2 mg (65 μmol) and 100 g of isophoronylene bisphthalimide were added and stirred at 280 ° C. The pressure inside the flask was gradually reduced, and finally polymerization was carried out at 0.3 mmHg for 7 hours. The mixture remained homogeneous during the polymerization. The reaction mixture was dissolved in dichloromethane and poured into acetone to reprecipitate only the allylate. The arylate was filtered off and dried to obtain a polyarylate containing no isophoronylene bisphthalimide. The polyarylate had the following repeating units and their compositional ratio.

[0041]

[Chemical 11]

The glass transition point of polyarylate is 273.
C., the diluted solution viscosity was 0.83 dL / g.

The polyarylate was dissolved in methylene chloride to prepare a 15 wt% dope. Using this, 7
An 8 μm thick polyarylate film was prepared. The elastic modulus of the polyarylate film was 1.8 GPa.

Comparative Example 2 69.0 g of terephthalic acid diphenyl ester was placed in a flask which had been sufficiently dried and purged with nitrogen.
(217 mmol), 4,4- (octahydro-4,7
-Methano-5H-indene-5-ylidene) bisphenol 68.8 g (215 mmol), tetrabutoxy titanium 22 mg (65 μmol) and isophoronylene bisphthalimide 100 g were added and stirred at 280 ° C. The pressure inside the flask was gradually reduced to 7 mm with a final pressure of 0.3 mmHg.
Polymerization was carried out for a time. The mixture remained homogeneous during the polymerization. The reaction mixture was dissolved in dichloromethane and poured into acetone to reprecipitate only the allylate. The arylate was filtered off and dried to obtain a polyarylate containing no isophoronylene bisphthalimide. The polyarylate had the following repeating units:

[0045]

[Chemical 12]

The glass transition point of polyarylate is 314.
C., the diluted solution viscosity was 0.85 dL / g.

The polyarylate was dissolved in methylene chloride to prepare a 12 wt% dope. Using this, 7
A 2 μm thick polyarylate film was prepared. The elastic modulus of the polyarylate film was 2.2 GPa.

[0048]

According to the present invention, by introducing a 2,6-naphthalenedicarboxylic acid component, high heat resistance,
A polyarylate having a high elastic modulus can be preferably obtained.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J029 AA06 AB01 AC03 AE03 BD09C                       CB04A CC05A JB131 JC253                       JC751 KE05

Claims (6)

[Claims] 1. The following formulas (I) and (II): (In the formulas (I) and (II), A is an aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a branch and 5 to 16 carbon atoms.
At least one selected from alicyclic hydrocarbon groups which may have a branch, B is an aromatic hydrocarbon group having 6 to 12 carbon atoms, R ^{1 to} R ⁸ are the same or different, and are hydrogen or 1 carbon atoms.
.About.6 hydrocarbon groups), and the molar ratio of (I) to (II) is (I) / (II) = 1/9 to 9/1. 2. The polyarylate according to claim 1, wherein A in the formulas (I) and (II) is an alicyclic hydrocarbon group having 4 to 15 carbon atoms and optionally having a branch. 3. A in formula (I) and formula (II) is 1,1.
At least one selected from a cyclohexylidene group, a 1,1- (3,3,5-trimethylcyclohexylidene) group and a 4,4- (octahydro-4,7-methano-5H-indene-5-ylidene) group. The polyarylate according to claim 2, which is one kind. 4. The polyarylate according to claim 1, wherein R ^{1 to} R ⁸ in formulas (I) and (II) are hydrogen atoms. 5. The polyarylate according to claim 1, wherein B in the formula (II) is at least one selected from paraphenylene and metaphenylene. 6. The polyarylate according to claim 5, wherein B in the formula (II) comprises paraphenylene.