JPH0433925A - Liquid crystal polyester ether imide and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject ether imide having excellent moldability and heat-resistance and low liquid-crystal initiation temperature and useful for film, fiber, etc., by using a specific imide monomer having ether group. CONSTITUTION:The objective ether imide having a glass transition temperature of >= 150 deg.C is composed of structural units of formula I to III (individual struc tural units are linked with each other through ester bond) wherein the structural units (I+II) accounts for 5-50 mol% of the total units, the structural unit of formula III accounts for 50-95 mol% and the molar ratio of the unit of formula I to formula II is 0.95<=I/II<=1.05. The ether imide can be produced by reacting compounds of formulas IV to VI [Y<1>, Y<2> and Y<3> are H or R<1>CO (R<1> is 1-6C hydrocarbon group); Z<1> to Z<3> are HO or R<2>O is 1-8C hydrocarbon group)] and eliminating the groups Y-Z (Y and Z are Y<1> to Y<3> and Z<1> to Z<3>).

Description

DETAILED DESCRIPTION OF THE INVENTION BACKGROUND OF THE INVENTION Field of Industrial Application The present invention relates to thermoplastic polyester etherimides. Specifically, the present invention relates to a wholly aromatic liquid crystalline polyester etherimide that exhibits optical anisotropy when melted and has excellent moldability and heat resistance, and a method for producing the same.

<Conventional technology> In recent years, with the development of the electrical/electronic field and the automobile field,
Demand for high performance plastics is also increasing, and a large number of plastics have been developed and provided to the market. Among these, thermotropic liquid crystalline polymers exhibit optical anisotropy when melted, molecular chains are arranged in parallel, and have improved mechanical properties of molded products as well as excellent moldability. A group of high-molecular compounds called

These liquid crystalline polymers include polyesters obtained from p-hydroxybenzoic acid, 4,4'-biphenol and terephthalic acid, polyesters obtained from p-hydroxybenzoic acid and hydroxynaphthoic acid,
Polyesters obtained from polyethylene terephthalate and p-hydroxybenzoic acid are well known.

Liquid crystalline polyesters having imide groups in the polymer main chain are also known. For example, polyesterimide (Mac
romol, Chem, 184.1223(1
983)), polyesterimide synthesized from trimellitic acid, aminophenol and hydroxynaphthoic acid (U.S. Pat. No. 4,383,105), or polyesterimide synthesized from polyethylene terephthalate, aminophenol and hydroxyphthalic acid (US Pat. No. 4,383,105)).
Japanese Unexamined Patent Publication No. 60-4531) is known. However, in the case of these polyesters, fully aromatic polyesterimide has a high melting temperature and is poor in moldability, and aliphatic polyesterimide cannot be said to have sufficient heat resistance.

[Summary of the invention]

<Problems to be Solved by the Invention> The purpose of the present invention is to solve the problems of the liquid crystalline polyesterimide and provide a novel wholly aromatic liquid crystalline polyesteretherimide with an excellent balance between moldability and heat resistance. It's about doing.

Means for Solving the Problems> The present invention provides a novel wholly aromatic liquid crystalline polyester etherimide obtained by using a specific imide monomer having an ether group, which has excellent moldability and heat resistance. This was done after discovering something excellent.

The present invention also provides fully aromatic liquid crystallinity by reacting an imide monomer having a specific ether group, a specific dicarboxylic acid functional derivative, and a specific hydroxycarboxylic acid functional derivative to form an ester bond and polymerize it. It was discovered that polyester etherimide could be produced.

That is, the liquid crystalline polyester ethyl imide according to the present invention has the following structural units [I], (II) and CIII.
) (However, each structural unit is connected to each other by an ester bond), and the structural unit (1”I) + [
II]) accounts for 5 to 50 mol% of the total, the structural unit [■] accounts for 50 to 95 mol% of the total, and the molar ratio of the structural units (1) and [II) is 0.95≦(I)/[ n)≦1.
05 and a glass transition temperature of 150°C or higher.

The method for producing etherimide is based on the following general formula (IV), (V
) and [VI] to form the following - general formula [■
] is characterized by eliminating the compound represented by.

・・・・・・Bori・・・・・・[I] Moreover, the above-mentioned liquid crystalline polyester according to the present invention (in the formula,
Y, Y and Y3 are the same or different H- or R1C0-, and R1 is a hydrocarbon group having 1 to 6 carbon atoms. zl, z2 and 2 are the same or different HO- or R20-, and R2 has 1 to 8 carbon atoms.
It is a hydrocarbon group up to. ) Y-Z...page (wherein, Y and Z are any of Y1 to Y3 used in the compounds of formulas [IV) to [VI) and 21 to Z3
Each indicates one of the following. ) Effects> The liquid crystalline polyester etherimide according to the present invention has excellent moldability and high heat resistance, although it is completely aromatic.

[Detailed description of the invention]

Polyester etherimide General description of molecular structure The liquid crystalline polyester etherimide according to the present invention is composed of the following structural units (I), (II) and [■], and each structural unit has an ester bond with each other. They are connected. That is, this polyester etherimide is a copolyester of a bisphenol compound having an aromatic etherimide bond (corresponding to [I]), phthalic acid (corresponding to [II]), and p-hydroxybenzoic acid.

...[1] This polyester etherimide according to the present invention has a structural unit ([11+ [II)] of 5 to 50 mol% of the total
, preferably 20 to 50 mol%, and the structural unit [III] is 50 to 95 mol% of the total, preferably 50 to 90 mol%
, which occupies the Also, structural unit [1] and l”
The molar ratio [I]/[■) with nl is 0.9 to 1.1, preferably 0.95 to 1.05.

In this way, the molar ratio of structural units [1] and [II] (1)
/ (n) is approximately 1, but this does not necessarily mean that this polyester polyetherimide is a block copolyester consisting of a polyester block consisting of (1) and [II] and a polyester block consisting of (m). does not mean. In other words, the polyester etherimide according to the present invention is a random copolyester in which each structural unit is bonded at random (even though it is called random, each structural unit is bonded through an ester bond) in addition to such a block copolyester. It goes without saying that there are limits to these arrays, given the fact that they are
This includes:

The liquid crystalline polyester etherimide according to the present invention should have a sufficiently large molecular weight. However, since this polyester etherimide is insoluble in commonly used organic solvents, it is impossible to measure its molecular weight. Therefore, as a measure of polymer properties, the polyester etherimide of the present invention is limited by the glass transition temperature, which is a property unique to polymers.

The molecular weight of this polyester etherimide is such that the glass transition temperature measured with a differential scanning calorimeter (DSC) is 150.
℃ or higher, preferably about 150 to 300℃.

Note that the structural units (1) and (II) have nok, meta, and ortho structural isomers, and isomers may coexist within these structural units.

Structural unit> Structural unit [I] is a residue from a bisphenol compound corresponding to bisimide of 4,4-oxycyphthalic acid and aminophenol.

As the structural unit (1), the aminophenol residue is para,
There are three types of structural isomers, meta and ortho, but preferred is an imide compound residue in which the aminophenol residue shown in the structure below contains an ether group with a para structure and/or a meta structure.

......(I a) ......(I b) Structural unit (II) is a phthalic acid residue, which also has rose, meta and ortho structural isomers, Specifically, terephthalic acid residues, isophthalic acid residues, and phthalic acid residues are preferred, and terephthalic acid residues and/or isophthalic acid residues are preferred.

The structural unit (m) is a p-hydroxybenzoic acid residue.

Production of polyester etherimide - Explanation for boat fishing The liquid crystalline polyester etherimide according to the present invention can be produced by any method suitable for the formation of polyester bonds, ether bonds, and/or imide bonds. .

This polyester etherimide is a bisphenol compound (corresponding to [I]) and phthalic acid (corresponding to [II]).
Considering that it corresponds to a copolyester with -hydroxybenzoic acid (corresponding to [■]), it can be said that a typical method is to react these compounds under ester-forming conditions.

In this case, "ester-forming conditions" refers to at least one of these reactants, in addition to direct esterification (including cases in which water produced by condensation is removed by azeotropy, etc., or cases in which an appropriate condensation agent is used). For example, when phthalic acid and p-hydroxybenzoic acid are reacted in the form of their functional derivatives, phthalic acid and p-hydroxybenzoic acid are reacted with acid halides (e.g. acid chlorides).
or when reacting with bisphenol compounds (corresponding to [I]) in the form of acid anhydrides (especially mixed anhydrides), and when bisphenol compounds are reacted in the form of their acyl derivatives with phthalic acid and p-hydroxybenzoic acid. case,
It includes others.

Bisphenol compounds (corresponding to [I]) are typically produced by first producing amic acid and then dehydrating it to form an imide ring, in accordance with the method commonly used for producing aromatic polyimides. .

Specific method> One specific method for producing liquid crystalline polyester etherimide according to the present invention is to eliminate compound [■] from the following compounds (IV), (V), and (V[). It consists of things.

......[Seki (in the formula, Yl, Y2 and Y3 are the same or different ■-
or RICo-, and R1 is a hydrocarbon group having 1 to 6 carbon atoms. zl, Z2 and Z3 are the same or different HO- or R20-, and R2 is a hydrocarbon group having 1 to 8 carbon atoms. ) Y-Z ...... [■] (wherein, Y and 2 are any of Y1 to Y3 used in the compounds of formulas [IV] to (Vl) and 21 to Z3 In the compound of formula [■] that is eliminated by the reaction of compounds [IV) to [■], Y and Z are Y1 to Y used in compounds (TV) to (VI), respectively.
3 and z1 to z3.

When the polycondensation reaction is direct esterification, Y1 to Y are H
, Z1 to Z3 are OH, and the compound [■] to be eliminated is H20. For example, in the case of a demonocarboxylic acid polycondensation reaction using a functional derivative, for example, Y −Y is RC
O, Z1 to Z3 are 0H, and the compound to be eliminated is of course RICOOH, and in the case of monoalcohol removal polycondensation reaction, for example, Y -Y is H, Z1 to Z3 are RO, and the compound to be eliminated is RICOOH. Of course, the compound that does this is R20H.

In addition, Y used in the compounds of formulas (IV) to (Vl)
When there are two or more types of each of -Y and 21 to z3, the elimination compounds of the formula [■] will theoretically exist in a number corresponding to their permutation combinations.

Specific examples of R1 when Y and Y2 of general formula (IV) are R'CO- include methyl, ethyl, n-
Propyl, i-propyl, n-butyl, t-butyl, n
Examples include -amyl, n-pentyl, n-hexyl, cyclohexyl, and phenyl groups. Particularly preferred as Yl and Y2 are hydrogen atoms and RIC
A group represented by O- in which R1 is a methyl, ethyl or phenyl group. Yl and Y2 are typically the same.

Specific examples of R2 when Zl and Z2 of general formula [v] are R20- include methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-amyl, n- -pentyl, n-hexyl, cyclohexyl,
Examples include phenyl group. Zl and Z2
Particularly preferred are a hydroxyl group and a group represented by R20- in which R2 is a phenyl, methyl or ethyl group. Z and Z2 are also typically the same.

Specific examples of Y and Z3 in general formula (VI) are the same as Y , Y , Z and z2 shown above,
Particularly preferable ones include Y3 being a hydrogen atom and RCo-
In the group represented by, R1 is methyl, group is hydroxyl group, and R2
A group represented by 0- in which R1 is a phenyl, methyl, or ethyl group.

The specific method for producing the compound (IVI) is as follows.

4,4-oxycyphthalic acid represented by the general formula [■]
First, an amic acid derivative represented by the general formula [X] is produced by a reaction between the dianhydride and the aminophenol derivative represented by the general formula (IX).

H2N+O-Y ......[IX] Subsequently, by dehydrating and ring-closing this amic acid derivative [X] by heating, a dihydroxyimide compound in which Y in the general formula CIV) is a hydrogen atom is obtained. .

The reaction between 4,4'-oxysiphthalic acid dianhydride and the aminophenol derivative described above proceeds in the container by simply mixing both components in a solvent to produce the amic acid derivative (X). Although the reaction proceeds satisfactorily at room temperature, the reaction temperature is preferably in the range of -20°C to 100°C, and is often carried out in the range of 0°C to 80°C. This reaction proceeds exothermically in a short time and usually does not require the presence of a special catalyst. The reaction solvent used is not particularly limited as long as it is an inert solvent that dissolves both components, and includes aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, ketone solvents, ether solvents, and non-reactive solvents. A protic polar solvent or the like is used. In particular, aprotic polar solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone are preferred from the viewpoint of solubility of raw material components and the amic acid compound as a product. For the dehydration ring closure of the amic acid derivative [X], the obtained amic acid derivative solution was
This is carried out by heating to 0°C, preferably 100 to 180°C.

Organic carboxylic acid (R
lCOOH) or its functional derivatives such as acid anhydrides, acid chlorides, etc., the general formula (
An imide compound in which Y in rV) is represented by R''CO- is obtained.

To produce an acyloxyimide compound in which Y in general formula (IV) is RICO- by reacting a hydroxyimide compound in which Y in general formula [IV) is a hydrogen atom with an organic carboxylic acid or a functional derivative thereof. , when using an organic carboxylic acid, an inorganic mineral acid such as sulfuric acid or hydrochloric acid or p-
It is sufficient to use an organic acid such as toluenesulfonic acid or benzenesulfonic acid as a catalyst and heat it while removing by-product water. When using an acid anhydride which is a functional derivative of an organic carboxylic acid, an organic base such as triethylamine or pyridine may be used. It is sufficient to heat it using as a catalyst or without a catalyst,
Further, when using acid chloride, in order to remove by-produced hydrochloric acid, an organic base such as triethylamine or pyridine may be present in the reaction. From the viewpoint of simplicity and economy of the manufacturing process, acylation using an acid anhydride is preferred.

The acylation in this case is carried out at a temperature between 0°C and the boiling point of the acid anhydride, preferably between room temperature and 150°C, and preferably in a reaction solvent; As the reaction solvent, aprotic polar solvents such as the above-mentioned dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferable in view of the solubility of the hydroxyimide compound and the acyloxyimide compound.

Furthermore, the acyloximide compound in which Y in the general formula (IV) is represented by R'CO- can also be directly produced by reacting the amic acid derivative [X] with a considerable amount of an acid anhydride.

The compound represented by the general formula (V) as one of the compounds to provide the carboxylic acid residue of the polyester according to the present invention is terephthalic acid, isophthalic acid, or a functional derivative thereof. Specific examples include terephthalic acid monoesters such as terephthalic acid, isophthalic acid, monomethyl terephthalate, monoethyl terephthalate, monopropyl terephthalate, monobutyl terephthalate, and monophenyl terephthalate, monomethyl isophthalate, monoethyl isophthalate, and isophthalic acid. Isophthalic acid monoesters such as monopropyl, monobutyl isophthalate, monophenyl isophthalate, terephthalic acid diesters such as dimethyl terephthalate, diethyl terephthalate, diphenyl terephthalate, dimethyl isophthalate, diethyl isophthalate, diphenyl isophthalate, etc. Examples include isophthalic acid diesters. Among these, terephthalic acid, isophthalic acid, dimethyl terephthalate, dimethyl isophthalate, diphenyl terephthalate, diphenyl isophthalate, and the like are preferred.

The other compound represented by the general formula (Vl) to provide the carboxylic acid residue of the polyester according to the present invention is hydroxybenzoic acid or a functional derivative thereof. Specific examples include 4-hydroxybenzoic acid, 4
-4-Hydroxybenzoic acid and its esters such as methyl hydroxybenzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, phenyl 4-hydroxybenzoate, etc. 4-acyloxybenzoic acid and its esters such as 4-acetoxybenzoic acid, methyl 4-acetoxybenzoate, ethyl 4-acetoxybenzoate, propyl 4-acetoxybenzoate, and phenyl 4-acetoxybenzoate. can. Among these, 4-hydroxybenzoic acid, 4-acetoxybenzoic acid, methyl 4-hydroxybenzoate, methyl 4-acetoxybenzoate, phenyl 4-hydroxybenzoate, 4-hydroxybenzoic acid,
-Phenyl acetoxybenzoate is preferred.

In addition, the compounds of general formulas (IV), (V) and [VI) may be used alone or in combination of two or more.

The liquid crystalline polyester etherimide of the present invention using these compounds can be produced by the following method.

(1) Cyasyloxyimide compound ([I]), phthalic acid ((II)) and acyloxybenzoic acid (Cm])
A method of manufacturing by polycondensation reaction using demonocarboxylic acid.

(2) A method for producing a dihydroxyimide compound ([1)), a diester of dicarboxylic acid ([II)] and a monoester of hydroxybenzoic acid ((II[)]) by polycondensation reaction by removal of monoalcohol.

In the monocarboxylic acid removal polycondensation reaction method (1), acetic acid is mainly used as the monocarboxylic acid to be eliminated. (2
) In the monoalcohol removal polycondensation reaction method, phenol is mainly used as the elimination component.

The demonocarboxylic acid polycondensation reaction of method (1) is a suitable polymerization method because it proceeds without a catalyst. (2) It is preferable to use a catalyst in the monoalcohol removal polycondensation reaction of method,
In this case, metal compounds such as stannous acetate, antimony oxide, tetrabutyl titanate, lead acetate, and sodium acetate are used as catalysts.

In the polycondensation reaction, polymerization conditions such as temperature, heating time, and pressure can be varied depending on the reactants used and the desired degree of polymerization;
When X is acetic acid, the polymerization is usually carried out under an inert gas while heating to about 400° C. to distill off the acetic acid.

Generally, at the end of the polymerization, it is preferable to bring the inside of the reaction system under reduced pressure to complete the reaction. It is also possible to stop the polycondensation reaction midway, take out the reactants, and then polymerize them in the solid phase to produce the final product.

Utilization of polyester etherimide The polyester etherimide of the present invention has a low liquid crystal initiation temperature of 400°C or less, and can be used for ordinary melt molding such as injection molding, extrusion molding, compression molding, and blow molding, and can be used for three-dimensional molding. Goods,
It can be processed into films, fibers, containers, etc. Moreover, it can also be made into a polymer alloy by mixing with other thermoplastic resins.

During molding, reinforcing agents such as glass fiber and carbon fiber, fillers,
Additives such as antioxidants, stabilizers, plasticizers, mold release agents, etc. can be added to impart desired properties to the molded article.

Experimental Example> Example 1 4,4-Oxyl(N
-(3-acetoxyphenyl)phthalimide) 46.1
g (0.08 mol), terephthalic acid 13°3 g (0
, 08 mol), and p-acetoxybenzoic acid 43.2
g (0.24 mol) was added, and vacuum and nitrogen introduction were repeated three times to purge the inside of the reaction system with nitrogen. 3 under nitrogen flow
heating to 50° C. for 2 hours with removal of acetic acid;
Heating was continued for 30 minutes at 350°C. Further, the pressure inside the reaction system was reduced and heating was continued for 30 minutes to complete the polymerization.

The inside of the reaction system was returned to normal pressure with nitrogen, and the polymer was taken out in a molten state.

The IR spectrum of the polymer is shown in Figure 1.
Using this data, it was confirmed that the polymer was the desired polymer.

The glass transition temperature was 180°C.

This polymer melted at temperatures above 250°C and exhibited good optical anisotropy. Note that optical anisotropy was observed using a polarizing microscope manufactured by Nikon Corporation equipped with a hot stage manufactured by Leitz Corporation.

Example 2 The charging molar ratio of Example 1 was changed to 4,4-oxyly(N-(3
-acetoxyphenyl)phthalimide) 46, 1g
(0,08 mol), terephthalic acid 13,3tr (0
, 08 mol), and p-acetoxybenzoic acid 115.
Polymerization was carried out in the same manner as in Example 1, except that the amount was changed to 3 g (0.64 mol).

This polymer has a glass transition temperature of 170°C and 2
It exhibited good optical anisotropy at temperatures of 60°C or higher.

Example 3 4,4-oxyly(N-(3-acetoxyphenyl)phthalimide) of Example 1 was converted to 4,4-oxyly(N-(
4-acetoxyphenyl)phthalimide) 46.1g
(0.08 mol), add terephthalic acid to isophthalic acid 13
．． Polymerization was carried out in the same manner as in Example 1 except that the amount was changed to 3tr (0.08 mol).

The IR spectrum of the obtained polymer was as shown in FIG. 2, and using this data, it was confirmed that the polymer was the desired polymer.

This polymer has a glass transition temperature of 190°C and 3
It exhibited good optical anisotropy at temperatures of 30°C or higher.

Comparative Example 1 The charging molar ratio of Example 1 was changed to 4,4-oxyly(N-(3
-acetoxyphenyl)phthalimide) 86, 6g
(0,15 mol), terephthalic acid 24.9 g (0,1
5 mol), and p-acetoxybenzoic acid 36. O
Polymerization was carried out in the same manner as in Example 1, except that the amount was changed to g (0.2 mol).

Although this polymer melts at temperatures above 245°C, it did not exhibit optical anisotropy.

Comparative Example 2 Polymerization was carried out in the same manner as in Example 1, except that 4.4-oxyly(N-(3-acetoxyphenyl)phthalimide) in Example 1 was changed to bis(N-(3-acetoxyphenyl))pyromellitimide. However, since the polymer solidified during the polymerization, the polymerization could not be completed.

This polymer did not flow up to 400°C.

[Brief explanation of the drawing]

1st v! J and FIG. 2 are IR spectra of the polymers obtained in Example 1 and Example 2, respectively.

Claims (1)

[Claims] 1. Consists of the following structural units [I], [II] and [III] (however, each structural unit is connected to each other by an ester bond), and the structural unit ([I] + [ II]) is 5 to 50 mol% of the total, and structural unit [III] is 50 to 9 of the total
5 mol%, the molar ratio of structural units [I] and [II] is in the range of 0.95≦[I]/[II]≦1.05, and the glass transition temperature is 150°C or higher. Characterized by liquid crystalline polyester etherimide. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[III] 2. The liquid crystalline polyester ether according to claim 1, characterized in that the compounds represented by the following general formulas [IV], [V] and [VI] are reacted to eliminate the compound represented by the following general formula [VII]. Imide production method. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[V] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[VI] (Formula In the formula, Y^1, Y^2 and Y^3 are the same or different H- or R^1CO-, and R^1 is a hydrocarbon group having 1 to 6 carbon atoms.Z^1, Z ^2 and Z
^3 is the same or different HO- or R^2O-, and R^2 is a hydrocarbon group having 1 to 8 carbon atoms. ) Y-Z...[VII] (wherein, Y and Z are any of Y^1 to Y^3 used in the compounds of formulas [IV] to [VI] and Z^1 to Z
Each indicates one of ^3. )