JP2591056B2 - Aromatic polyester and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an aromatic polyester containing

This polyester exhibits liquid crystallinity when melted, so it has good fluidity and excellent moldability, and also has high elastic modulus and impact strength, and it has high heat resistance, so it is used for precision parts, electric / electronic materials, automobile parts, etc. Can be used as molded articles, films, fibers, etc.

[Conventional technology and problems]

As polyesters containing USP 4,237,259 and USP
(1) in P4,268,647 However, there is no description such as showing liquid crystallinity or mechanical property values.

As a typical example of polyester using
-Polymer There is. This is (6) Is a polymer with excellent impact resistance
However, this is not only amorphous but also in the molecular chain.
Lopylidene groupIt seems to contain.

However, (9) is very flexible and has no liquid crystallinity due to kink properties. On the contrary, since the polymer chains are entangled with each other, a polyester having a very high melt viscosity can be obtained, and a polymer having difficulty in moldability can be obtained. Become.

On the other hand, polyesters exhibiting liquid crystallinity during molding have attracted much attention in recent years because of their excellent moldability.

As such a liquid crystalline polyester, (i) a flexible component such as an alkylene chain is introduced into a rigid component, And (iii) a substituent is introduced into an aromatic ring.

Among them, there are many examples using the method according to (ii),
inside that As an example of studying a liquid crystal polymer using the component of (1), for example, Macromolecules 14 1405 ('8
1)) there is. This document is of type (2) (so-called 4,4 '
(Functional group type) and (3) type are being studied. Among them, especially when (9) is used, the addition of a small amount greatly reduces the liquid crystallinity. Not shown.

According to JP-A-61-73730, flexibility is imparted by using (9). In this case, the liquid crystallinity is lowered due to the description of relaxation of anisotropy and a large decrease in the elastic modulus in Examples. Obviously, it has dropped significantly.

[Means for solving the problem]

As a result of intensive studies on liquid crystal polyesters that impart flexibility and enhance liquid crystallinity and have heat resistance, very surprisingly, (1) having a 3,4'-functional group, It has been found that an aromatic polyester using the above achieves the above object, and has reached the present invention.

That is, the present invention relates to (1) (A) 1 to 35 equivalent% of 2,2 represented by the formula (1).
-(3,4'-dihydroxydiphenyl) propane residue (B) 1 to 20 equivalent% of at least one of the diol compound residues represented by the formulas (2), (3) and (4), (Here, X represents a hydrocarbon group, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group or an ester group, R represents a hydrocarbon group, and n represents an integer of 1 to 4.) 35 equivalent% of 4,4'-dihydroxydiphenyl represented by the formula (5) and / or hydroquinone residue represented by the formula (6) (D) 5 to 45 equivalent% of terephthalic acid residues and / or isophthalic acid residues represented by the formula (7) (E) 15 to 90 equivalent% of the p-oxycarboxylic acid residue and / or m-oxycarboxylic acid residue represented by the formula (5) An aromatic polyester consisting of (1), (2),
When the equivalent number of (3), (4), (5), (6), and (7) is represented by [1] [2] [3] [4] [5] [6] [7], 0.9 ([ 1] + [2] + [3] + [4] + [5] +
(6)) / [7] 1.1 aromatic polyester having a melt viscosity of 30 poise or more at 320 ° C. and 100 sec ⁻¹ , and (f) 1 to 35 mol% of the formula (10 2,2-
(3,4'-dihydroxydiphenyl) propane (G) 1 to 20 mol% of at least one of dihydroxy compounds represented by formulas (11), (12) and (13), (Where X represents a hydrocarbon group, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an ester group, R represents a hydrocarbon group, and n represents an integer of 1 to 4). Mol% of 4,4'- represented by the formula (14)
Dihydroxydiphenyl and / or hydroquinone represented by the formula (15), (I) 5-45 mol% of terephthalic acid and / or isophthalic acid represented by the formula (16), (Nu) 15-90 mol% of p-hydroxybenzoic acid and / or m-hydroxybenzoic acid represented by the formula (17), Or using these derivatives, reacting by adding an acid anhydride in the system, and reacting while distilling off the acid and the acid anhydride at a temperature of 100 to 400 ° C. Lies in the manufacturing method.

 The present invention will be described in more detail.

In the aromatic polyester of the present invention, it is essential that the aromatic polyester of the present invention contains the 2,2- (3,4'-dihydroxydiphenyl) propane residue of the above-mentioned (A), and the content ratio is the entire content. 1-3 assuming that the total amount of ingredients is 100 equivalent%
It has a surprising feature that the liquid crystallinity is enhanced only by the presence of 1 equivalent% or more, and as a result, the elastic modulus is improved and the moldability is improved. Preferably 2 equivalent%
Not less than 30 equivalent%, more preferably not less than 4 equivalent%,
% Or less. If it exceeds 35 equivalent%, it is not preferable from the viewpoint of cost.

Further, in the aromatic polyester of the present invention, at least one of the compound residues of the above (b), that is, at least one of the diol compound residues represented by the following formulas (2), (3) and (4) seed, (Where X represents a hydrocarbon group, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group or an ester group, R represents a hydrocarbon group, and n represents an integer of 1 to 4). This is a mandatory requirement.

The content ratio is 1 to 20 with the total amount of all components being 100 equivalent%.
%, And surprisingly, without adding such a component, without reducing the liquid crystallinity,
The heat resistance and the impact resistance can be improved without significantly lowering the elastic modulus and without significantly lowering the moldability.

The content ratio of the diol compound residue is preferably from 2 to
It is 10 equivalent%, more preferably 3 to 8 equivalent%. If it exceeds 20 equivalent%, the liquid crystallinity is undesirably reduced. These may be used alone or as a mixture, but are preferably used alone.

As the residue of (2), 2,2- (bis-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl)
Methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) sulfide, bis (4-
(Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ether, (4-hydroxyphenyl) -4
Residues such as -hydroxybenzoate.

The residue of (3) includes a residue of resorcinol.

As the residue of (4), methylhydroquinone, 2,3,5
-Trimethylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, phenylhydroquinone and the like.

Of these, the residues of 2,2- (bis-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, resorcinol and t-butylhydroquinone are particularly preferred.

The aromatic polyester of the present invention has a compound residue of the above-mentioned (c), that is, a 4,4′-dihydroxydiphenyl represented by the formula (5) and / or a hydroquinone residue represented by the formula (6) as a constituent component thereof. , May be contained.

The addition of these components is preferable because the heat resistance can be increased, but liquid crystallinity (high elastic modulus, good moldability) can be imparted without introducing this component.

The content ratio of (c) is 0 when the total amount of all components is 100 equivalent%.
-35 equivalent%, preferably 0-30 equivalent%, more preferably 0-20 equivalent%.

When it is desired to increase heat resistance, the content is preferably 2 to 30 equivalent%, more preferably 5 to 20 equivalent%.

 If it exceeds 35 equivalent%, moldability deteriorates, which is not preferable.

 These may be used alone or as a mixture.

The aromatic polyester of the present invention further contains a terephthalic acid residue and / or an isophthalic acid residue represented by the formula (7) in (d) above.

The content ratio of (d) is 5 with the total of all components being 100 equivalent%.
~ 45 equivalent%, preferably 10-40 equivalent%, more preferably
It is 15 to 35 equivalent%.

If it is less than 5 equivalent% or more than 45 equivalent%, the moldability deteriorates, which is not preferable.

The equivalent number of each component of (a), (b), (c), and (d) is 0.9 ([1] + [2] + [3] + [4] + [5] +
[6]) / [7] 1.1 is preferable, especially 0.95 ([1] + [2] + [3] + [4] + [5] +
[6]) / [7] 1.05 is preferred.

The terephthalic acid residue and the isophthalic acid residue may be used alone or in combination. When used in combination, the amount of terephthalic acid residues is preferably larger than the amount of isophthalic acid residues.

The aromatic polyester of the present invention further contains, as a constituent component thereof, an aromatic oxycarboxylic acid residue represented by the above formula (8) (8).

Specific examples of the aromatic oxycarboxylic acid residue represented by the formula (8) include p-hydroxybenzoic acid and m-hydroxybenzoic acid residues.

These residues may be used alone or in combination. When a p-hydroxybenzoic acid residue and an m-hydroxybenzoic acid residue are used in combination, it is preferable to increase the amount of the p-hydroxybenzoic acid residue.

The content ratio of (e) is 15 with the total sum of all components as 100 equivalent%.
-90 equivalent%, preferably 20-80 equivalent%, more preferably 20-70 equivalent%.

It may be no problem to slightly contain components (usually about 3 equivalent% or less) other than the components listed here.

Surprisingly, by containing these components, the resulting polymer is optically anisotropic in the molten phase (has liquid crystallinity), and therefore has excellent moldability and high elastic modulus, It has also been found that a wholly aromatic polyester having excellent impact resistance and good heat resistance can be obtained and can be produced by a conventional apparatus.

In particular, by containing the 2,2- (3,4'-dihydroxydiphenyl) propane residue of the above (1), a conventional polyester production apparatus (for example, a vertical polyethylene terephthalate production apparatus) can be used. It was also found that there was a great merit that the polymer could be extracted from the bottom of the tank. (Hereinafter referred to as pull-out property) It is possible to reduce the flow onset temperature by combining 2,2- (3,4'-dihydroxydiphenyl) propane residue of (1) with the components of (7) and (8). It is thought that it becomes.

On the other hand, a polymer having excellent heat resistance can be obtained. For example, 40 ° C, 150 ° C measured with Vibron (110Hz)
The complex elastic modulus / E ^* / at / E ^* / ₄₀ and / E ^* / _{150 respectively}
Then And / E ^* / ₁₅₀ 4.0 × 10 ¹⁰ dyne / cm ² / E ^* / ₄₀ 8.0 × 10 ¹⁰ dyne / cm ² . If you choose the composition / E ^* / ₁₅₀ 8.0 × 10 ¹⁰ dyne / cm ² and / E ^* / ₄₀ 12.0 × 10 ¹⁰ dyne / cm ² .

Also, it has excellent impact resistance. When an impact resistance test (Izod impact test) is measured using a Mitsubishi Chemical dumbbell, the Izod impact value is 7 kg · cm / cm, and if the composition is selected, it is 15 kg · cm / cm.

Further, from a rheological point of view, the melt viscosity is low and the moldability is good.

These results are derived from the unique structure of the 2,2- (3,4'-dihydroxydiphenyl) propane residue.

When (1) is used, the molecular chain is Rather than (kink) (Crankshaft), which greatly contributes to liquid crystallinity, and it is considered that the use of such a crankshaft component is very effective for a liquid crystal polymer. ((6)
Is (It becomes kink and is accompanied by twisting.) From this, it is expected that the wholly aromatic polyester using (1) is more rigid and less entangled,
It can be seen that the structure (1) greatly contributes to the liquid crystallinity.

Also, in the molecule of the compound having the residue (1) In the main chain of the polyester It is presumed that a group can be introduced, thereby increasing the impact resistance value.

Further, in the present invention, the 2,2- (3,4'-dihydroxydiphenyl) propane residue of (1) is (2), (3),
Surprisingly, it has been found that by adding at least one residue of (4), heat resistance and impact resistance can be improved while maintaining liquid crystallinity.

In this case, improvement of the flow start temperature can be mentioned as heat resistance.

In order to produce the aromatic polyester of the present invention, a predetermined ratio of (A) 2,2- (3,4'-dihydroxydiphenyl) propane residue represented by (1), (B) (2),
(3) at least one compound residue of (4), if necessary, at least one compound residue of (5) and (6) of (c), and further a terephthalic acid residue and / or isophthalic acid of (d) Well-known polymerization methods, such as a melt polymerization method and a solution polymerization method, using an acid residue, a p-oxybenzoic acid residue and / or an m-oxybenzoic acid residue of (e), or a derivative thereof as a raw material Alternatively, the treatment may be performed according to an interfacial polymerization method or the like. In particular, the melt polymerization method is advantageous in industrial production because post-treatment after the polymerization reaction is unnecessary, and the solution polymerization method and the interfacial polymerization method have an advantage that the polymerization reaction can be carried out at a relatively low temperature.

In the case of the melt polymerization method, a method in which a part of the raw material components are used as an acylated product or an ester and polymerized at a temperature of 200 to 400 ° C, or a method in which an acylating agent is added to the raw material components to perform polymerization. Taken.

In the solution polymerization method or the interfacial polymerization method, an acid halide, particularly an acid chloride, is generally used as a raw material monomer corresponding to the carboxylic acid residue. In the interfacial polymerization method, the oxy residue of the raw material needs to be converted into a salt.

It is essential that the wholly aromatic polyester of the present invention has a melt viscosity at 320 ° C. of 100 sec ⁻¹ of 30 poise or more, and if it is less than 30 poise, sufficient strength cannot be obtained. 320 ℃, 100sec
The preferred melt viscosity at ^-1 is 100 poise or more, especially 100 to 1
0,000 poise is preferred in terms of moldability.

If it does not melt at 320 ° C, the melt viscosity shall be ∞, and in that case, it shall fall within this range.

In particular, the production method of the present invention is excellent in terms of cost, workability, and the like. That is, the production method of the present invention comprises, as a starting material, (f) 1 to 35 mol% of 2,2-- represented by the formula (10).
(3,4'-dihydroxydiphenyl) propane, (G) 1 to 20 mol% of at least one of dihydroxy compounds represented by formulas (11), (12) and (13), (Here, X represents a hydrocarbon group, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an ester group, R represents a hydrocarbon group, and n represents an integer of 1 to 4.) 35 mol% of 4,4'- represented by the formula (14)
Dihydroxydiphenyl and / or hydroquinone represented by the formula (15), (I) 5-45 mol% of terephthalic acid and / or isophthalic acid represented by the formula (16), (Nu) 15-90 mol% of p-hydroxybenzoic acid and / or m-hydroxybenzoic acid represented by the formula (17), Alternatively, using these derivatives, an acid anhydride is added and reacted in the system, and the reaction is carried out at a temperature of 100 to 400 ° C. while distilling off the acid and the acid anhydride.

Since the composition of the produced polyester is equivalent to the composition of the charged raw material, the composition of the charged raw material may be determined so as to have a desired polyester composition.

Catalysts such as BuSnOOH, Bu ₂ SnO, Ti (OiPr) ₄ , Zn (OAc)
₂ , Sn (OAc) ₂ or the like is used, but need not be used.

Examples of the acid anhydride (18) include acetic anhydride, propionic anhydride, and benzoic anhydride. Particularly, acetic anhydride (19) is preferable. The number of moles of the acid anhydride used is [1
9], 0.8 [19] / (2 [10] +2 [11] +2 [12] +2 [1
3] +2 [14] +2 [15] + [17]) 2.0 Particularly preferably 1.0 or more and 1.5 or less.

As the reaction temperature, any temperature of 100 ° C. to 400 ° C. can be used, but when an acid anhydride is added and acylation is mainly performed, about 100 to 200 ° C., and then condensation is mainly performed At this time, it is preferable to raise the temperature and use a temperature of 250 to 400 ° C. It is possible to flow an inert gas such as N ₂ or Ar or to apply a reduced pressure to remove the acid or the acid anhydride.

By adopting the above manufacturing method, even when using a vertical stirrer having a conventional helical blade or squirrel blade for the production of polyester, especially polyethylene terephthalate,
The polymers of the present invention have been found to have the operational advantage of being able to be removed from the reactor.

When it is desired to further increase the degree of polymerization, solid-state polymerization can be applied.

Since the copolymerized polyester of the present invention can show an optically anisotropic phase in the molten phase, it has very good fluidity, and therefore has good moldability and can be subjected to general melt molding such as extrusion molding, injection molding, and compression molding. It can be processed into molded articles, films, fibers and the like.

In particular, it is suitable for precision molded products due to its high fluidity.

Further, at the time of molding, for the copolymerized polyester of the present invention, glass fibers, fibers such as carbon fibers, talc, mica, fillers such as calcium carbonate, nucleic acids, pigments, antioxidants,
Fillers and additives such as lubricants, other stabilizers, flame retardants and the like, thermoplastic resins and the like can be added to impart desired properties to molded articles.

It is also possible to create a composition that combines both the characteristics of the other polymer and the advantages of the aromatic polyester of the present invention by blending or alloying with the other polymer.

〔Example〕

Now, the present invention will be described in further detail with reference to Examples.
The present invention is not limited to the following examples unless it exceeds the gist.

The melt viscosity in the examples was measured using a capillary rheometer (manufactured by Intesco Corporation) at a temperature of 320 ° C.
A shear rate () of 100 sec ^-1 and a cylinder nozzle length / diameter of 30 was used.

As the infrared spectrophotometer, 20DXBFT-IR manufactured by Nicolet was used. The polymer was dissolved in hexafluoroisopropanol or used as a test sample on a KBr disk.

Molding is performed using a 0.1oz injection molding machine manufactured by Nippon Steel Corporation.
Molded pieces were made.

As the vibron, the above molded piece was used at 110 Hz under Leo Vibron manufactured by Toyo Baldwin.

The impact strength was measured using the above molded piece with an Isod impact tester.

Optical anisotropy was performed using a polarizing microscope equipped with a hot stage.

 The flow onset temperature was determined from Vibron data.

Example 1 71.6 g (0.52 mol) of p-hydroxybenzoic acid, 21.5 g (0.13 mol) of terephthalic acid, 2,2- (3,4'-) were placed in a glass polymerization tube equipped with a stirring blade, a nitrogen inlet, and a vacuum port. 7.4 g (0.03 mol) of dihydroxydiphenyl) propane, 2,2- (4,4 '
-Dihydroxydiphenyl) propane (7.4 g, 0.03 mol) and 4,4'-dihydroxydiphenyl (12.1 g, 0.06 mol) were charged, and vacuum-nitrogen substitution was repeated three times to finally fill with nitrogen.

87.3 g of acetic anhydride was added dropwise thereto, stirring was started, the polymerization tube was immersed in an oil bath at 150 ° C., and stirring was continued for 1 hour to perform acetylation. Thereafter, the temperature of the oil bath is raised to 320 ° C. in 90 minutes under a nitrogen stream at a flow rate of 0.5 / min.

 Here, the pressure was gradually applied, and polymerization was performed for 25 minutes.

The polymer flowed under its own weight and could be removed from the bottom of the reactor. After the removal, this polymer was subjected to solid-state polymerization at 240 ° C. for 3 hours. The melt viscosity (320 ° C., 100 sec ⁻¹ ) of the polymer thus obtained was 470 poise.

Further, this polymer was molded with a 0.1 oz injection molding machine, and the vibron of the molded piece was measured.

Vibron than _{^{/ E * / 40 = 14.3GPa /}} E * / 150 = was 8.2GPa.

 The impact strength was 24.5 kg · cm / cm.

The polymer started to flow at about 310 ° C. or higher and showed optical anisotropy. FIG. 1 shows the IR chart of this polymer.

The composition of this polymer is (1) / (2) / (5) / (7) / (8) = 4.2 / 4.2 / 8.
4 / 16.8 / 63.4.

Examples 2 to 13 Polymers were produced in the same manner as in Example 1 except that the composition of each component was changed as shown in Table 1. Table 1 summarizes the measurement results of various physical properties.

Comparative Example 1 In Example 1, 2,3- (3,4'-dihydroxydiphenyl) propane and 2,2- (bis-4-hydroxyphenyl) propane were used in an amount of 0.03 mol each. Instead of using 2- (3,4'-dihydroxydiphenyl) propane, 0.06 mol of 2,2- (bis-4-hydroxyphenyl) propane was used.

 Otherwise, the procedure was the same as in Example 1.

Performed molded in the same manner as in Example 1, was measured Vibron, the polymer was / E ^* / ₄₀ = 4.8GPa.

Comparative Example 2 4 equivalents of residue When the same procedure was performed as in Example 6 except that the residue was changed,
5.2 / E ^* / ₄₀ by vibron of molded product of the produced polymer
GPa.

(Effect of the Invention) The aromatic polyester of the present invention has excellent heat resistance,
In addition, since it has liquid crystallinity in the molten phase, it has excellent fluidity, and thus has excellent moldability. In addition, it has a high elastic modulus as a mechanical property, and is very excellent in impact resistance. Further, the aromatic polyester of the present invention has a feature that it can be molded at a temperature of 350 ° C. or less.

Based on the above properties, the aromatic polyester of the present invention is used for applications such as injection molded articles, films, and fibers.

Further, the wholly aromatic polyester of the present invention generally contains 330
Since it shows a molten state at a temperature of ℃ or less, when it is manufactured by a melt polymerization method, it has an operational advantage that the produced polymer can be easily taken out of the reaction vessel by applying pressure or by its own weight after the reaction. Have.

[Brief description of the drawings]

FIG. 1 is an IR chart of the aromatic polyester obtained in Example 1 of the present invention.

Claims (2)

(57) [Claims] (1) a 1,2- (3,4'-dihydroxydiphenyl) propane residue represented by the formula (1) in an amount of 1 to 35 equivalent%; (B) 1 to 20 equivalent% of at least one of the diol compound residues represented by the formulas (2), (3) and (4), (Here, X represents a hydrocarbon group, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group or an ester group, R represents a hydrocarbon group, and n represents an integer of 1 to 4.) 35 equivalent% of a 4,4'-dihydroxydiphenyl represented by the formula (5) and / or a hydroquinone residue represented by the formula (6), (D) 5-45 equivalent% of a terephthalic acid residue and / or isophthalic acid residue represented by the formula (7), (E) 15-90 equivalent% of a p-oxycarboxylic acid residue represented by the formula (5) and / or an m-oxycarboxylic acid residue, An aromatic polyester consisting of (1), (2),
When the equivalent number of (3), (4), (5), (6), and (7) is represented by [1] [2] [3] [4] [5] [6] [7], 0.9 ([ 1] + [2] + [3] + [4] + [5] +
[6]) / [7] An aromatic polyester having a melt viscosity at 1.1 ° C. and 30 poise or more at 320 ° C. and 100 sec ⁻¹ . (2) As starting materials, (f) 1 to 35 mol% of the 2,2-formula represented by the formula (10)
(3,4'-dihydroxydiphenyl) propane, (G) 1 to 20 mol% of at least one of dihydroxy compounds represented by formulas (11), (12) and (13), (Here, X represents a hydrocarbon group, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an ester group, R represents a hydrocarbon group, and n represents an integer of 1 to 4.) 35 mol% of 4,4'- represented by the formula (14)
Dihydroxydiphenyl and / or hydroquinone represented by the formula (15), (I) 5-45 mol% of terephthalic acid and / or isophthalic acid represented by the formula (16), (Nu) 15-90 mol% of p-hydroxybenzoic acid and / or m-hydroxybenzoic acid represented by the formula (17), Or using these derivatives, reacting by adding an acid anhydride in the system, and reacting while distilling off the acid and the acid anhydride at a temperature of 100 to 400 ° C. Production method.