JPS61261320A - Polyarylate - Google Patents

Abstract

PURPOSE:To increase the heat resistance and flame retardancy of a polyarylate so as to adapt it for use in plasma spray coating or a molding used at high temperatures, by forming the polyarylate from specified P-containing repeating units. CONSTITUTION:The titled polyarylate consists of repeating units of formula I (wherein n is an average degree of polymerization and is an integer of 10-300, R1 and R2 are each H, a halogen, a 1-6C lower alkyl, Ar is an aromatic residue having at least two aromatic rings, n1 and n2 are each an integer of 1-4) and has an average degree of polymerization of 10-300. The polyarylate having the above structure can be obtained by reacting an aromatic dicarboxylic acid or its esterifiable derivative with an aromatic diol group-containing phosphinic acid or its esterifiable derivative. As the aromatic dicarboxylic acid, terephthalic or isophthalic acid is preferable. Examples of the aromatic diol group-containing phosphinic acids include compounds of formula II (wherein R1, R2, Ar, n1 and n2 are as defined in formula I). As the aromatic diol residue of formula III, 1,4-dihydroxynaphthalene residue for example is preferable.

Description

Detailed Description of the Invention (・Field of Industrial Application) The present invention relates to a novel polyarylate with excellent heat resistance, and more specifically relates to a polyarylate containing an aromatic diol containing a phosphorus atom and an aromatic dicarboxylic acid. The present invention relates to a novel polyarylate with excellent heat resistance and flame retardancy obtained from.

(Prior Art) Polyarylates have been known as heat-resistant polymers. For example, 4-hydroxybenzoic acid homopolymer or copolymer (Sumitomo Chemical, trade name Econol), or a polymer consisting of bisphenol A, terephthalic acid, and isophthalic acid (Unitika, trade name U Polymer)
was once proposed and is now commercially available.

(Problems to be Solved by the Invention) However, such polymers inherently have (1) a relatively high melting point or a decomposition temperature lower than the melting point or softening point, and therefore have poor moldability.

(2) Heat resistance is insufficient.

(3) Poor flame retardancy.

It had such drawbacks.

Therefore, a principal object of the present invention is to provide a heat-resistant polyarylate particularly suitable for plasma spray coatings and molded articles used at high temperatures, which has good resistance and also has a high degree of flame retardancy. The object of the present invention is to provide a new heat-resistant polyarylate.

(Means for Solving the Problems) The present inventors have conducted extensive research into a new heat-resistant polyarylate that does not have the above-mentioned problems.

The present invention was achieved by discovering that polyarylates having repeating units with a specific structure containing phosphorus atoms have extremely excellent properties.

That is, the present invention is a heat-resistant polyarylate consisting of a repeating unit represented by the following structural formula (1) and having an average degree of polymerization of 10 (1 to 300).

(However, n is an integer of 10 to 300 and indicates the average degree of polymerization.

In addition, R1 and R2 are selected from a hydrogen atom, a halogen atom, and a lower alkyl group having 1 to 6 carbon atoms, and A
r is an aromatic residue having two or more aromatic rings. Also g
nl y-"n'j° each represents an integer of 1 to 4.) The average degree of polymerization of the polyarylate of the present invention (Xun is 10 to 30
0. Preferably 30-200, optimally 50-150
It must be. When the average degree of polymerization is less than 10, there are various physical problems including heat resistance as described above.

Poor mechanical and chemical properties. On the other hand, the average degree of polymerization is 30
If it is larger than 0°, the melt viscosity becomes too high and fluidity etc. are impaired.

R1 and R2 are chlorine atom, bromine atom, etc.), rogene atom, methyl group, ethyl group, propyl group.

Examples thereof include a lower alkyl group having 1 to 6 carbon atoms such as a hexyl group, and a hydrogen atom, and among them, a hydrogen atom and a halogen atom are preferred.

As a method for producing polyarylate of the present invention.

Reacting an aromatic dicarboxylic acid or an ester-forming derivative thereof having an appropriate functional group capable of forming a repeating unit having a predetermined structure by condensation with a phosphinic acid having an aromatic diol group or an ester-forming derivative thereof. This can be done by utilizing various ester formation methods.

Aromatic dicarboxylic acids or ester-forming derivatives thereof effective in such ester-forming reactions include:

For example, free dicarboxylic acid groups9. A dicarboxylic acid ester group or a dicarboxylic acid halide group, on the other hand.

As the phosphinic acid having an aromatic di-redundant group or its ester-forming derivative, for example, a phosphinic acid compound having a free dihydroxyl group, diacyloxy group, etc. is preferably used.

An example of an aromatic dicarboxylic acid used in the production of the polyarylate of the present invention is terephthalic acid.

Examples include isophthalic acid and phthalic acid, among which terephthalic acid (hereinafter abbreviated as TPA), in-7thalic acid (
Hereinafter, it will be abbreviated as IPA. ) is particularly preferably used. A mixture of the above aromatic dicarboxylic acids may be used if necessary.

On the other hand, as the phosphinic acid (hereinafter abbreviated as HCA) having an aromatic diol group used in the production of the polyarylate of the present invention, a compound represented by the following formula (It) is exemplified.

HO-Ar-OH (However, R1 and R2 are selected from hydrogen atoms, halogen atoms, and lower alkyl groups having 1 to 6 carbon atoms, and A
r is an aromatic residue having two or more aromatic rings. Also,
fil and fi2 each represent an integer from 1 to 4. ) In formula (■), examples of aromatic diol residues represented by HO-Ar-OH include 1.2-dihydroxynaphthalene, 1.3-dihydroxynaphthalene, 1.4-dihydroxynaphthalene, 1.5 -dihydroxynaphthalene,
1.6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2.
3-dihydroxynaphthalene, 2゜6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene I 21
2'-diphenyl, 4.4'-diphenyl, 1.1
'-Binaphthyl-2,2'-diol.

2-methyl-1,4-dihydroxynaphthalene, 3゜3
',5,5'-tetramethoxypiphenyl-4,4'-
Diol, 4,4'-dihydroxy-diphenyl ether, bis(4-hydroxy-2-methylphenyl)-ether, his(4-hydroxy-3-/lorophenyl)
-ether, bis(4-hydroxyphenyl)-sulfide, bis(4-hydroxyphenyl)-sulfone,
Bis(4-hydroxyphenyl)-ketone, bis(4-
hydroxyphenyl)-methane, bis(4-hydroxy-3-methylphenyl)-meta/, bis(4-hydroxy-3,5-dichlorophenyl)-methane, bis(4-
Hydroxy-3,5-cyfromophenyl)-methane.

Bis(4-hydroxy-3,5-difluorophenyl)
-methane, 1,1-bis(4-dihydroxyphenyl)
-ethane, 2,2-his(4'-hydroxy-13'-methylphenyl)propane, 2,2-bis(4'-hydroxy-3'-/lorophenyl)-furopane.

2.2-bis(4'-hydroxy-37-dichlorophenyl)-furopane, 2.2-bis(4'-hydroxyphenyl)-furopane, 2.2-bis(4'-hydroxy-37S/-dichlorophenyl) ) - propane.

1.1-bis(4'-hydroxyphenyl)-n-butane, bis(4-hydroxyphenyl)-phenylmethane, bis(4-hydroxyphenyl)-diphenylmethane, bis(4-hydroxyphenyl)-4'-methyl Phenylmethane, 1,1-bis(4'-hydroxyphenyl)-2,2,2-trichloroethane, bis('4-hydroxyphenyl)-(4'-10lophenyl)-methane, 1,1-bis(4 '-hydroxyphenyl)-cyclohexane, his(4'-hydroxyphenyl)-cyclohexylmethane, 2°2-bis(4'-hydroxynaphthyl)-propane.

Bis(4'-hydroxy-3,5-dimethylphenyl)
-methane, bis(4-hydroxy-3,5-dimethylphenyl)-ketone, his(4-hydroxy-3,5-dichlorophenyl)-ketone, bis(4-hydroxy-3
-10lophenyl)-sulfite.

Bis(4-hydroxy-3,5-dichlorobuphenyl)
-sulfide, bis(4-hydroxy-3,5-cis(
3-hydroxyphenyl) sulfite, bis(3-hydroxyphenyl) sulfone, bis(3-hydroxyphenyl) ether, 3-hydroxyphenyl-4-hydroxyphenyl ether.

3.4-bis(4'-hydroxyphenyl)hexane.

1,5-dihydroxyanthracene, 1,2-dihydroxyphenanthrene, 1,4-dihydroxyphenanthrene, x,6-dihydroxyphenanthrene.

1,7-dihydroxyphenanthrene, 2.3--/
Hydroxyphenanthrene, 2,5-dihydroxyphenanthrene, 2,6-dihydroxyphenanthrene 7.2
．． 7-dihydroxyphenanthrene, 3.4-dihydroxyphenanthrene, 3.6-dihydroxyphenanthrene, 3.10-dihydroxyphenanthrene,
9.10-Dihydroxyphenanthrene.

1.1-dithiodi-2-naphthol, retin-3,8-
Diol, 3,4-dihydroxyanthrone, 1°8-
Dihydroxy-3-methylanthraquinone, 1.2-dihydroxyanthraquinone, 1.8-dihydroxy-3-methylanthraquinone, 1.2-dihydroxy-3-nitroanthraquinone, 1.8-dihydroxy-2,4,5
, 7-tetranitroanthraquinone, 5,6-cyhydroxy-2-anthraquinone carbo/acid, 3,4-dihydroxya/traquinone-2-sulfonic acid, 3,7-cyoxy-10-methylxanthedi, dioxyacridone,
1,3-dioxyxanthone, 2,7-cyoxy9-
Residues such as phenylxanthine and methylene-di-β-naphthol are mentioned, among which 1,4-dihydroxynaphthalene residue and 4,47-bisphenol residue are particularly preferably used.

The polyarylate of the present invention is a carboxyl group of 9, for example, a compound represented by the following formula (i) (hereinafter abbreviated as P-HCA) derived from phosphinic acid represented by the following formula (V) and 1,4-naphthoquinone. An acid ester derivative, that is, a derivative represented by the following formula ([V)].

It can be produced by condensing an aromatic dicarboxylic acid such as TPA and/or IPA at high temperature and under high vacuum.

(However, R3 and R4 are the same or different groups.

Each is a lower alkyl group having 1 to 6 carbon atoms.

In addition, a carboxylic acid ester derivative of P-H, CA represented by the formula (IV) [for example, diacetate (hereinafter referred to as P
It is abbreviated as -HCA-2A. ) can be produced by esterifying P-HCA represented by the above formula (1) in a corresponding carboxylic acid anhydride (eg, acetic anhydride) under reflux.

To produce HCA represented by the above formula ((■)).

A phosphinic acid represented by the following formula (v) and a corresponding cyclic conjugated diketone (hereinafter abbreviated as quinone) may be reacted in a suitable solvent such as ethyl cellosolve.

Such quinones include 2.6-naphthoquinone, 1°4
-naphthoquinone, 1.2-naphthoquinone, 4.4'-diphenoquinone, 2.2'-diphenoquinone, 3.1
0-perylenequinone and the like are preferably used.

When producing the heat-resistant polyarylate of the present invention, the molar ratio of the aromatic dicarboxylic acid and the carboxylic acid ester derivative of HCA is usually 0.8 to 1.2. Preferably 0.9
~1.1. The optimum ratio is equimolar.

Although a catalyst is usually used in the polycondensation reaction, one or more compounds selected from, for example, various metal compounds or organic sulfonic acid compounds are used to obtain the polyarylate of the present invention. Such a metal compound is antimony.

Compounds such as titanium, germanium, tin, zinc, aluminum, magnesium, calcium, manganese and hycobalt are used, while as the organic sulfonic acid compound, compounds such as sulfosalicylic acid and 0-sulfobenzoic anhydride are used.

Dimethyltin malate (hereinafter abbreviated as C8) is particularly preferably used.

In addition, the temperature conditions and reaction times for the transesterification reaction and the polycondensation reaction are as follows:
1 to 12 hours at 0 to 400°C, preferably 150 to 3
2 to 10 hours at 40°C, optimally 2 to 200°C to 300°C.
It is preferred to transesterify for ~6 hours. After that, as a second step, the pressure is further reduced (usually 0.01 to 10 torr).
r) 1-12 hours at 250-400°C.

Especially at 300-340℃ for 2-10 hours, optimally 30
Preferably, the polycondensation is carried out at 0 to 330°C for 6 to 8 hours.

(Examples) Hereinafter, the present invention will be explained in more detail by giving examples. 9 The average degree of polymerization (n) of the polymer referred to in the present invention was determined using gel permeation chromatography (manufactured by Toyo Soda Co., Ltd., HL; Model C801A) in a chloroform solution containing 2.5% hexafluoroisopropanol. It was determined by dividing the number average molecular weight measured at a temperature of 39° C. by the molecular weight of the repeating unit. Moreover, the glass transition temperature and melting point were measured using a differential calorimeter (manufactured by PerkinElmer, Model DSC-2).

on the other hand.

The limiting oxygen index (LOI) was determined using a combustion test device (Suga Test Machinery Co., Ltd., 0N-1), using JISK7201.
It was measured by the method.

On the other hand, the novel polyarylate according to the present invention is.

Identification was made by infrared absorption spectrum, NMR spectrum, glass transition temperature, and elemental analysis.

Example 1 P-HCA represented by the above formula (1) was produced by reacting the phosphinic acid represented by the above formula (V) with 1,4-naphthoquinone at a temperature of 90°C in an ethyl cellosolve solvent.
was manufactured. Next, this P-H is added to the esterification reactor.
A diacetate, ie, PF (CA-2A), was produced by charging CA and acetic anhydride in a ratio of 1:4 and esterifying the mixture under reflux in acetic anhydride.

P-HCA-2 in the polycondensation reactor (vacuum type twin-screw kneader)
A and IPA were charged in a molar ratio of 1:1, and C8 was added as a catalyst in an amount of 4×10 mol per mol of the polyarylate structural unit, and the mixture was reacted with kneading at 280° C. under nitrogen atmosphere for 8 hours. The transesterification rate determined from the weight of the distilled acetic acid was 95%.

This reaction product was further heated at 320°C under a reduced pressure of 0.1 torr.
The reaction was carried out, and the temperature was finally raised to 340° C. for polycondensation for a total of 10 hours.

In addition, during the reduced pressure reaction, the raw materials P-HCA-2A and IPA
No sublimation was observed.

The obtained polyarylate had an average degree of polymerization (n) of 73° and a glass transition point of 225°C, and was found to have good heat resistance. Furthermore, the LOI was 62, which was the highest level of flame retardant performance among organic polymers.

In addition, this polyarylate has an infrared absorption spectrum, N
As analyzed by MR spectrum and elemental analysis, 9
The following results were obtained, and it was confirmed that this was a polyarylate having a repeating unit with the following structure.

In other words, in the infrared absorption spectrum, 1+780
791 is the absorption based on C=0 of aromatic dicarboxylic acid esters, and 791 is the absorption of rose-substituted aromatics.

At 1200, absorption based on P=0 of phosphinic acid was observed.

In addition, in the NMR spectrum, the absorption of hydrogen atoms of methyl groups based on the raw material acetate (1.5 ppm and 2.3 ppm)
ppm) was not observed.

As a result of elemental analysis, C=71.3% (theoretical value 7164
%), H= 3.3% (theoretical value 3.496')
, P = 6.0% (W theoretical value 6.1).

Examples 2-18 In Example 1, 1,4-naphthoquinone and IPA
An experiment was carried out in the same manner as in Example 1, except that the quinone and aromatic dicarboxylic acid shown in Table 1 were used instead of the quinone and aromatic dicarboxylic acid shown in Table 1, and the results shown in Table 1 were obtained. Note that all of the obtained polyarylates have excellent heat resistance with a Tg of 150° C. or higher, are amorphous or have a melting point temperature range that is not too high, and are expected to have excellent moldability.

Moreover, the LOI was 63 to 68 inches, indicating that the polymers had good flame retardancy.

However, the compound shown in the column of diol group indicates that the diol component is a reaction product of the compound and the phosphinic acid represented by formula (v).

Comparative examples 1 to 3 As a comparative example, polyethylene terephthalate.

Table 2 shows the characteristic values of U polymer (Unitika, trade name U-100) and Econol (Sumitomo Chemical, trade name E-2000).

Although polyethylene terephthalate has good color tone and transparency, its LOI is 23, and its Tg is significantly lower than that of the polymer of the present invention, indicating that it has poor flame retardancy and heat resistance.

Further, the U polymer T and 9 are slightly inferior to the polymer of the present invention, but the LOI is only 36 inches.

It can be seen that the flame retardance is still significantly inferior to that of the polymer of the present invention.

It should be noted that although Econol has a Tg of about 300° C. and is excellent in heat resistance, its LOI is 37, which clearly shows that it is significantly inferior in flame retardancy to the polymer of the present invention.

Reference Example 1 The tensile strength of an unstretched film with a thickness of 80μ obtained by press-molding the polymer obtained in Example 1 at 390°C is 140
MP&, tensile modulus is 3,900 MPa.

It had sufficient strength.

(Effect of the invention) The boaryarylate of the present invention is.

(1) No decomposition occurs even when used at high temperatures.

(2) Preferred glass transition temperature range (150-230℃
) and/or preferred melting point temperature range (280-420
) and has excellent heat resistance.

(3) Excellent flame retardancy.

This is a new polyarylate that has excellent physical properties as a heat-resistant polymer. Furthermore, the polyarylate of the present invention is particularly useful as a material for films, fibers, and molded products used in applications requiring heat resistance and flame retardancy.

Claims (1)

[Claims] (1) A polyarylate consisting of repeating units represented by the following structural formula (I) and having an average degree of polymerization of 10 to 300. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (However, n is an integer of 10 to 300 and indicates the average degree of polymerization. In addition, R1 and R2 are hydrogen atoms, halogen atoms, and lower alkyl having 1 to 6 carbon atoms. Ar
is an aromatic residue having two or more aromatic rings. Also, n
1 and n2 each represent an integer of 1 to 4. )