JPS5930727B2 - Aromatic polyester carbonate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel aromatic polyester carbonates.

An object of the present invention is to provide an aromatic polyester carbonate which can be molded into a molded article having excellent heat resistance, chemical resistance, and extremely excellent mechanical performance by melt molding, and a method for producing the same.

Conventionally, polyethylene terephthalate has excellent chemical resistance and mechanical properties, and has been widely used as a molding material for fibers, films, plastics, and the like.

However, polyethylene terephthalate has a relatively low heat distortion temperature, and it cannot be said that it has sufficient strength especially when used as an engineering plastic. be. The present inventor has focused on this point, and has arrived at the present invention as a result of intensive research to find a polyester that has sufficiently high heat resistance and mechanical strength without using reinforcing materials such as glass fibers.

That is, the present invention provides residues (1) of aromatic oxycarboxylic acids mainly consisting of p-oxybenzoic acid, represented by the following formulas (I), (■), and (■), aromatic acids mainly consisting of hydroquinone, Residues of group dihydroxy compounds () and residues of carbonic acid (
), consisting of '8. 88)
′! ~ [However, Ar and Ar' are each an aromatic group mainly composed of p-phenylene] and the above three components in the polymer have the following formulas (1), (2) (40/6
0)≦MI/M≦(95/5)・・・・・・(1) Ml
I+M・・・・・・・・・(2)
However, MI is the mol% of the residue (1) in the polymer, M is the mol% of the residue (1) in the polymer, and M is the mol% of the residue (1) in the polymer.
), and MI+M+M=100 (mol%)] is an aromatic polyester carbonate having an intrinsic viscosity of 0.3 or more.

Such an aromatic polyester carbonate preferably comprises an aromatic oxycarboxylic acid mainly consisting of p-oxybenzoic acid and/or an ester-forming derivative thereof (A) and an aromatic dihydroxy compound mainly consisting of hydroquinone (B). Diaryl carbonate (C) and the following formula 40/60
≦MA/MB≦95/5, Mc≧MB [However, in the formula, MA, MB, and MC are MA+MB+Mc=10
It represents the number of moles of the components (A), (B), and (C), respectively, when the number is 0.

] is reacted in a molten state in a satisfactory ratio, and further reacted in a solid state if necessary.

The aromatic oxycarboxylic acid used as component (A) in the present invention is mainly p-oxybenzoic acid, but a portion (for example, a proportion of 30 mol% or less) of p-oxybenzoic acid is
Nuclear substituted derivatives of oxybenzoic acid (for example, halogen atoms such as chlorine, bromine, iodine, etc.; lower alkyl groups such as methyl, ethyl, etc.; alkoxy groups such as methoxy, ethoxy, etc.) p-oxybenzoic acid derivatives in which at least one nuclear hydrogen atom is substituted); m-oxybenzoic acid, oxynaphthoic acid,
Oxydiphenylcarboxylic acid and nuclear substituted derivatives thereof; substitution may be made with aliphatic oxycarboxylic acids such as ε-oxycaproic acid or alicyclic oxycarboxylic acids such as cyclohexaneoxycarboxylic acid.

Specific examples of the above-mentioned nuclear-substituted derivatives of p-oxybenzoic acid include p-oxybenzoic acid, 3-chloro-4-oxybenzoic acid, 3-bromo4oxybenzoic acid, 3-methyl-4oxybenzoic acid, -methoxy-4oxybenzoic acid, 3,
Examples include 5-dichloro-4-oxybenzoic acid and 3,5-dibromo-4-oxybenzoic acid. In the present invention, ester-forming derivatives of aromatic oxycarboxylic acids can be used similarly to the aromatic oxycarboxylic acids described above.

Examples of the ester-forming derivative include lower aliphatic carboxylic acid esters, acid halides, and aryl esters of the aromatic oxybenzoic acids. More specifically, p-acetoxybenzoic acid, p-oxybenzoic acid chloride, p-oxybenzoic acid phenyl, m-acetoxybenzoic acid, m-oxybenzoic acid chloride, m-oxybenzoic acid phenyl, oxynaphthoic acid phenyl, etc. is exemplified. Ester-forming derivatives of aliphatic oxybenzoic acid and alicyclic oxybenzoic acid are used in the same manner as the above-mentioned ester-forming derivatives of aromatic oxybenzoic acid, and their lower aliphatic carboxylic acid esters, aryl esters, acid halides, etc. can be mentioned. The aromatic dihydroxy compound used as component (B) in the present invention is a compound in which two hydroxy groups are directly bonded to an aromatic nucleus, and mainly targets hydroquinone, but some of it (e.g.
0 mol % or less) and other aromatic dihydroxy compounds such as nuclear substituted derivatives of hydroquinone (e.g. halogen atoms such as chlorine, bromine, iodine, etc.; methyl,
lower alkyl groups such as ethyl; hydroquinone derivatives in which at least one hydrogen atom of the benzene nucleus is substituted with an atom or group such as an alkoxy group such as methoxy group, ethoxy group, etc.), resorcinol, dioxynaphthalene, dioxydiphthalene, etc. enyl, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, and their nuclear substituted derivatives, etc.), or for example, ethylene glycol, neopentylene glycol, etc. It may be substituted with one or more types of other diols such as aliphatic diols, alicyclic diols such as cyclohexane dimethylol, and cyclohexane diol.

The above-mentioned nuclear-substituted derivatives of hydroquinone include hydroquinone chloride, hydroquinone bromide, hydroquinone iodide,
Examples include methylhydroquinone and methoxyhydroquinone. In the present invention, similar to the aromatic dihydroxy compounds described above, ester-forming derivatives of aromatic dihydroxy compounds can be used.

Examples of such ester-forming derivatives include hydroquinone, esters of aliphatic or aromatic carboxylic acids such as p-diacetoxybenzene and p-dibenzoyloxybenzene, or carbonate compounds with aromatic hydroxy compounds. be done. Furthermore, in the present invention,
Diaryl carbonate is used as component (C),
Specific examples include diphenyl carbonate, di-p-
Tolyl carbonate, dinaphthyl carbonate, di-p
Examples include -chlorophenyl carbonate and phenyl p-tolyl carbonate. Among these, diphenyl carbonate is particularly preferred. In the present invention, the above (A) component and (B) component are used in a molar ratio of 40:60 to 95:5, and the (C) component is used in a ratio of 1 mole or more of the (B) component. Make it react.

That is, the number of moles of components (A), (B), and (C) is MA,
When MB, MC and MA+MB+MO=100, 40/60≦MA/MB≦95/5...
(3) Mc≧MB Components (A), (B), and (C) are reacted in a ratio that satisfies the two equations (4).

If formula (3) is not satisfied, the melting point of the obtained polymer will become too high, making melt molding difficult, which is not preferable. Further, if the formula (4) is not satisfied, the degree of polymerization is difficult to increase, which is not preferable. In addition, when using free oxycarfonic acid as component (A), the number of moles thereof is M
As A, Mc≧(MA'+MB) is satisfied (C
) It is preferable to use the component in excess because the reaction progresses more easily.

The reaction is carried out by mixing the above components (A), (B), and (C) in predetermined amounts in a molten state.

Further, if necessary, a solid phase reaction can be performed after the melt reaction.
The reaction temperature is generally 180°C or higher, preferably 200°C
Above, the temperature is particularly preferably 250°C or more and 400°C or less. Although any reaction pressure can be used, it is preferable to reduce the pressure as the reaction progresses. It is also possible to carry out a solution reaction by melting the above three components and in the presence of an organic solvent inert to the reaction. In the reaction, the order of addition of each component is arbitrary. Moreover, what is generally known as a polyester polymerization catalyst can be used as a reaction catalyst. Examples of such reaction catalysts include simple substances such as sodium, potassium, calcium, magnesium, zinc, manganese, cobalt, titanium, tin, lead, antimony, and germanium, as well as compounds thereof (for example, oxides,
hydride, hydrogen oxide, halide, alcoholade,
phenolade, organic acid salts, complex salts, double salts, etc.). The aromatic polyester carbonate of the present invention can be produced by the method described above, and includes aromatic oxycarboxylic acid residues (1) represented by the following formulas (1), (), and (), aromatic dihydroxy compound residues ( ) and carbonic acid residues (), +0-Ar-CO→ ・・・・・・・・・
・(lノ+0−Ar!−0+ ・・・・・・・・・
...() [However, Ar and Ar' are each the same as defined above] and the above three components in the polymer are represented by the following formula (1)
, (2) (40/60)≦MI/M≦(95/5) ・
・・・(1) MIII+M ・・・・・・・・・・・・
...(2) [However, MI, M, M are the same as defined above], and its intrinsic viscosity is 0.3 or more, preferably 0.5 or more, especially Preferably it is 0.8 or more.

Incidentally, the symbol "satisfaction" in the above formula (2) means that the amounts are substantially the same. M/M ratio is (95/5)
If it is larger, the melting point of the polymer becomes too high, making melt molding difficult, and if it is smaller than (40/60), it will not have the property of being oriented by shear, which is not preferable.
The aromatic polyester carbonate has the property of being oriented by shear, and has melt moldability,
This determines extremely excellent performance in terms of heat resistance, chemical resistance, mechanical properties, etc.

In the present invention, various additives such as stabilizers such as antioxidants and ultraviolet absorbers; pigments; fluorescent brighteners, etc. may be added. The present invention will be described in detail below with reference to Examples.

Note that "parts" in the examples mean parts by weight. In addition, the heat distortion temperature is ASTM D-648, and the tensile property is ASTM D-6.
38, bending properties were measured by ASTM D-790, and impact strength was measured by ASTM D-250. In addition, the intrinsic viscosity in the text and examples is a value calculated from the solution viscosity measured at 35°C in a mixed solvent of 2,4,6-trichlorophenol/0-chlorophenol = 70/30 (weight ratio). be. Examples 1 to 3 and Comparative Example 1 In a Mitsuro flask equipped with a stirrer, a nitrogen gas inlet, and a distillation outlet, p-oxybenzoic acid, hydroquinone, and diphenyl carbonate were added in the amounts shown in Table 1, and stannous acetate. After charging 0.12 parts, the inside of the system was sufficiently replaced with nitrogen gas, and then heated to 250° C. while slowly flowing nitrogen gas.

After about 30 minutes, the reaction temperature was raised to 280°C, and the pressure inside the system was gradually reduced to an absolute pressure of about 0.5 degrees H9 over about 30 minutes.Then, the reaction temperature was raised to 300°C, and the reaction was continued for an additional 90 minutes. . Table 1 shows the intrinsic viscosity of the obtained polymer.

Furthermore, the polymer was crushed and dried at a cylinder temperature of 260°C.
Table 1 shows the physical properties of the molded product obtained by injection molding at a mold temperature of 140°C. Example 4 171.2 parts of phenyl p-oxybenzoate, 22.0 parts of hydroquinone, 291.4 parts of diphenyl carbonate and 0.10 parts of titanium tetrabutoxide were charged into the same reactor as in Example 1. Polymerization was carried out in the same manner to obtain a polymer.

The intrinsic viscosity of this polymer is 1.65. In addition, this polymer was used at a cylinder temperature of 310°C and a mold temperature of 110°C.
The heat distortion temperature of the molded product obtained by injection molding is 194℃, and the tensile strength is 1,220Kf/0! IL, flexural modulus is 51,
It was 000Kf/Md. The above polymers are p-oxybenzoic acid residues (MA), hydroquinone residues (MB
) and the ratio of carbonic acid residues (Mc) is MA:MB:Mc=6
The ratio was 6:17:17 (mol% ratio). Example 5 90.0 parts of p-acetoxybenzoic acid, 5 parts of hydroquinone
When 5.0 parts of diphenyl carbonate, 128.4 parts of diphenyl carbonate, and 0.10 parts of dibutyltin oxide were charged into the same reactor as in Example 1 and reacted in the same manner as in Example 1, the absolute pressure was approximately 0.5 nHf1. The polymer solidified when it reached .

Next, this polymer was pulverized to a size of about 10 to 20 meshes, and then reacted at 300° C. for 3 hours under reduced pressure of about 0.5 mmH9 absolute pressure.

The intrinsic viscosity of the obtained polymer is 1.73. A molded product made by injection molding this polymer at a cylinder temperature of 350°C and a mold temperature of 140°C has a heat distortion temperature of 172°C and a tensile strength of 9.
The flexural modulus was 87 Kg/Cd and the flexural modulus was 47,300 Kg/Cd. The above polymer is a residue of p-oxybenzoic acid (M
A), hydroquinone residues (MB) and carbonic acid residues (M
The ratio of c) was MA:MB:Mc=34:33:33 (mol% ratio). Example 6 96.6 parts of p-oxybenzoic acid, 33 parts of hydroquinone.
0 parts and 256.8 parts of diphenyl carbonate in the presence of 0.12 parts of stannous acetate at a temperature of 260 to 320°C, 7
A polymer having an intrinsic viscosity of 1.29 was obtained by melt polymerization under a pressure of 60-0.3 nHg.

The composition of this polymer is p-oxybenzoic acid residue (A)
, hydroquinone residue (B) and carbonate residue (C) are MA
:MB:Mc=54:23:23 (mol% ratio). Next, the polymer was pulverized and dried, and then extruded from a T-die into a rotating drum heated to 150°C using a Luder type film molding machine at a cylinder temperature of 340°C.

The thickness of the obtained film was 101μ, the tensile strength in the extrusion direction was 36.1~/Md) and the Young's modulus was 882~/Md.

Claims (1)

[Claims] 1 p represented by the following formulas (I), (II), and (III)
- Consisting of residues of aromatic oxycarbophonic acid (I) mainly consisting of oxybenzoic acid, residues of aromatic dihydroxy compounds (II) mainly consisting of hydroquinone, and residues of carbonic acid (III), ▲Math. , chemical formulas, tables, etc.▼...
・・・・・・(I)▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・(II)▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・......(III) [However, Ar and Ar' are each an aromatic group mainly composed of p-phenylene] and the above three components in the polymer have the following formulas (1), (2) (40 /60)≦M I /MII≦(95
/5)・・・・・・(1)MIII≒MII・・・・・・・
...(2) [However, M I is the residue in the polymer (
I), MII is the mol% of residue (II) in the polymer
, MIII is the mole percent of residue (III) in the polymer, M
An aromatic polyester carbonate having an intrinsic viscosity of 0.3 or more, which satisfies the following ratio: I + MII + MIII = 100 (mol %). 2. The aromatic polyester carbonate according to claim 1, wherein the aromatic oxycarboxylic acid residue (I) is a p-oxybenzoic acid residue. 3. The aromatic polyester carbonate according to claim 1, wherein the residue (II) of the aromatic dihydroxy compound is a residue of hydroquinone.