JPS5930728B2 - Aromatic polyester carbonate - Google Patents

Description

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

The object is to provide an aromatic polyester carbonate which has excellent heat resistance and chemical resistance and can be molded into molded articles exhibiting extremely excellent mechanical performance by melt molding. Conventionally, polyethylene terephthalate has excellent chemical resistance and mechanical properties, and has been widely used in fibers, films, plastics, and the like.

However, polyethylene terephthalate has a relatively low heat deformation temperature strength, and it cannot be said that it has sufficient strength especially when used as an engineering plastic. I am in a situation where I am The present inventor focused on this point,
As a result of intensive research into polyester that has sufficiently high heat resistance and mechanical strength even without reinforcement with reinforcing materials such as glass fibers, the present invention has been arrived at. ), (), (l), AV) residues of aromatic oxycarboxylic acids mainly consisting of p-oxybenzoic acid (1), residues of aromatic dicarboxylic acids mainly consisting of terephthalic acid or isophthalic acid. group ( ), a residue (4) of an aromatic dihydroxy compound mainly containing hydroquinone, and a carbonic acid residue (1V), [However, Ar, Ar'5
are aromatic groups mainly consisting of p-phenylene,
Is Ar′ an aromatic group consisting mainly of p-phenylene or m-phenylene? and the residues (1), (), (1) and 0
The ratio of V) is expressed by the following formulas (1), (2), (3) and (4).
40/60≦(MI+M)AMI-Ml)≦95/5・
...(1) 40/60≦MI/M≦82/18...(
2) MlV=-(M-M)...(3)M
l>M...(4) [However, in the formula,
MI, M, Ml, MlV is MI+M+Ml+MIV=
100 (mole (F6)), each of the above residues (1
), residue (), residue (1), residue 0V)].

Such an aromatic polyester carbonate preferably contains an aromatic oxycarboxylic acid and/or its ester-forming derivative (4), an aromatic dicarboxylic acid and/or its ester-forming derivative (B), and an aromatic polyester carbonate mainly containing hydroquinone. Dihydroxy compound (0 and diaryl carbonate (to)) are combined using the following formula 40/60≦(MA+MB)/(M
c-MB)≦95/5...(1)″40/60≦MA
/MB≦82/18...(4YMD≧(Mc-MB)
...(3YM0>MB...(4)'' [However, in the formula, MA, MB, MC, and MD are (A) and (B), respectively.
), (0, the number of moles of component (D)) are reacted at a ratio that satisfies the following.

The aromatic oxycarboxylic acid used as a captive component in the present invention is mainly p-oxybenzoic acid, but a portion (for example, 30 mol% or less) of it is a nuclear substituted derivative of p-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. (substituted p-oxybenzoic acid derivatives); m-oxybenzoic acid, oxynaphthoic acid, oxydiphenylcarboxylic acid and their nuclear substituted derivatives; ε
- It may be replaced with an aliphatic oxycarboxylic acid such as oxycaproic acid or an alicyclic oxycarboxylic acid such as cyclohexaneoxycarboxylic acid.

Specific examples of the nuclear substituted derivatives of p-oxybenzoic acid include 3-chloro-4-oxybenzoic acid, 3-bromo-4
Oxybenzoic acid, 3-methyl-4oxybenzoic acid, 3-
Methoxy-4oxybenzoic acid, 3,5-dichloro-4-
Examples include 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. The aromatic dicarboxylic acid used as a component in the present invention is mainly terephthalic acid or isophthalic acid, but a portion (for example, 30 mol% or less) of the aromatic dicarboxylic acid used as a component is naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, etc. other aromatic dicarboxylic acids such as methyl terephthalic acid, methyl isophthalic acid, diphenoxyethane dicarboxylic acid, etc.; aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, etc.; alicyclic acids such as cyclohexane dicarboxylic acid; One or more types of other dicarboxylic acids such as dicarboxylic acids may be substituted.

Examples of the ester-forming derivatives of aromatic dicarboxylic acids that can be used in the same manner as the aromatic dicarboxylic acids include alkyl esters, aryl esters, and acid halides of the aromatic dicarboxylic acids.

More specific examples include dimethyl terephthalate, diphenyl terephthalate, dimethyl isophthalate, diphenyl isophthalate, and the like. Among these, terephthalic acid diphenyl ester and isophthalic acid diphenyl ester are particularly preferred. In the present invention, the aromatic dihydroxy compound used as the O component (O component) is a compound in which two hydroxy groups are directly bonded to the aromatic nucleus, and the main target is hydroquinone, but a portion of it (for example, 30 mol% The following proportions) are added to other aromatic dihydroxy compounds such as nuclear-substituted derivatives of hydroquinone (e.g. halogen atoms such as chlorine, bromine, iodine, etc.; lower alkyl groups such as methyl, ethyl, etc.; methoxy, ethoxy, etc.). (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), resorcinol, dioxynaphthalene, dioxydiphenyl,
2,2-bis(4-hydroxyphenyl)propane, 1
, 1-bis(4-hydroxyphenyl)cyclohexane and their nuclear substituted derivatives, etc.), or aliphatic diols such as ethylene glycol, neopentylene glycol, etc., and alicyclic diols such as cyclohexane dimethylol, cyclohexane diol, etc. It may be substituted with one or two or more of various diols such as.

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

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 the component, and specific examples include diphenyl carbonate, di-p-tolyl carbonate, dinaphthyl carbonate, di-p-
Tolyl carbonate, dinaphthyl carbonate, di-p
Examples include -chlorophenyl carbonate, phenyl-p-tolyl carbonate, and the like. Among these, diphenyl carbonate is particularly preferred. The usage ratio of component (4), component (B), component (O) and component (1) is determined by the following formula (1Y,
(2Y, (3y and (4Y40/60≦(MA+MB)
AMc-MB)≦95/5...(1)″40/60≦
MA/MB≦82/18...(2YMD≧(Mc-M
B) ...(3yM0>MB...(4Y[
However, in the formula, MA, MB, MC, and MD are respectively CA), (
number of moles of components B), (C), and (D)].

If (MA+MB)/(Mc-MB) is larger than 95/5, the melting point of the obtained polymer will be too high, making melt molding difficult.If it is smaller than 40/60, the polymer will not have the property of being oriented by shear, and This is not preferred because the physical properties deteriorate. Moreover, if MA/MB is smaller than 40/60, the physical properties of the polymer, particularly the elastic modulus, will deteriorate, which is not preferable. Furthermore, if the formula (3f) is not satisfied, the degree of polymerization will be difficult to increase, which is undesirable.In addition, component (4), (B)
When using 1 free oxycarboxylic acid and 1 free dicarboxylic acid as components, and assuming that the amounts used are MA' mol and MB' mol, MD≧(MA'+MB'+M
It is better to use an excess of component (9) to satisfy c).
The preferred reactions are the above (A) and (B) because the reaction progresses easily.
), (D) and (component) in predetermined amounts are mixed in a molten state. Furthermore, if necessary, a solid phase reaction can be performed after the melt reaction. In that case, the reaction temperature should be 180°C or higher, or even 2°C.
The temperature is preferably 00°C or higher, particularly 250°C or higher and 400°C or lower. Any pressure can be used as the reaction pressure, but
It is preferable to reduce the pressure as the reaction progresses. Also,
The reaction can also be carried out in an organic solvent that can dissolve each component and is inert to the reaction. In the reaction, the order of addition of each component is arbitrary. A polyester polymerization catalyst can be used in the above reaction.

Such catalysts include, for example, sodium, potassium, calcium, magnesium, zinc, manganese, cobalt,
List metals such as titanium, tin, zinc, antimony, germanium, etc. and their compounds (e.g. oxides, hydrides, hydroxides, halides, alcoholades, phenolades, organic acid salts, complex salts, double salts, etc.). I can do it. The aromatic polyester carbonate of the present invention can be produced by the method described above and has the following formula (1), (), (), Av)
Residues of aromatic oxycarboxylic acids mainly composed of p-oxybenzoic acid (1), residues of aromatic dicarboxylic acids mainly composed of terephthalic acid or isophthalic acid (), represented by
-FO-
Ar-CO-+ ・・・・・・(1)+0
C-Ar'-CO-1- ・・・・・・()
+O-Ar'2-0-3-...
・(l) [However, Ar, Ar″ and Ar′″ are the same as the above definition] and the ratio of the residues (1), (), (l) and AV) is the following formula (1), (2) , (3) and (4) 40/
60≦(MI+Mll)AMI-M)≦95/5...
(1) 40/60≦MI/M≦82/18...(2)
MlV+(M-M)...(3) Ml>M
...(4) [However, in the formula, MI,
M, M, and MlV are the same as defined above] and have an intrinsic viscosity of 0.3 or more.

The preferable intrinsic viscosity of the polymer is 0.5 or more, especially 0.8
That's all. Note that the symbol = in the above formula (3) means that they are substantially the same. (MI+M)/(M
l-MlV) larger than 95/5, the melting point of the polymer becomes too high, making melt molding difficult;
If it is smaller, it is not preferable because there is no property of orientation by shear and the physical properties of the polymer deteriorate. Also MI/M is 4
If it is less than 0/60, the physical properties of the polymer, especially the elastic modulus, will deteriorate, which is not preferable. Such polymers have extremely excellent heat resistance, chemical resistance, and mechanical properties, and can be easily produced into molded articles by melt molding.

In the present invention, various additives such as antioxidants, stabilizers such as ultraviolet absorbers, pigments, optical brighteners, etc. may be added.

Hereinafter, the present invention will be explained in detail 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 ASTMD-790, impact strength is AST
Measured by the MD25O method.

Furthermore, the intrinsic viscosity in the text and examples is 2,4,6,1-trichlorophenol/0-chlorophenol=70/
This is a value measured at 35°C in a mixed solvent of 30 (weight ratio). Examples 1 to 3 and Comparative Example 1 In a three-tube flask equipped with a stirrer, a nitrogen gas inlet, and a distillation port, p-oxybenzoic acid, isophthalic acid, and hydroquinone were added in the amounts shown in Table 1, and diephenyl carbonate was added. 257 parts and 0.12 parts of stannous acetate were charged.
After the inside of the system was sufficiently replaced with nitrogen gas, the system was 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 increased to 300°C, and then the temperature was increased to 90°C.
It reacted for a minute. Table 1 shows the intrinsic viscosity of the obtained polymer. Table 1 shows the physical properties of the molded product obtained by pulverizing and drying the polymer and then injection molding it at a cylinder temperature of 260°C and a mold temperature of 140°C. Example 4 Phenyl p-oxybenzoate 160.5 parts, diphenyl terephthalate 39.8 parts, diphenyl isophthalate 39.8 parts
Example 1
The mixture was charged into a reactor similar to that of Example 1, and polymerized in the same manner as in Example 1 to obtain a polymer.

The intrinsic viscosity of this polymer is 1.17, and the molded product obtained by injection molding the polymer at a cylinder temperature of 330°C and a mold temperature of 110°C has a heat distortion temperature of 175°C and a tensile strength of 1200 kg/d1 or Flexural modulus is 47,700
kg/Cd. In the above polymer, the ratio of p-oxybenzoic acid residue MAl terephthalic acid residue MBl isophthalic acid residue MCl hydroquinone residue MD and carbonic acid residue ME = 34: 8
:8:33:17 (mol% ratio). Example 5 37.8 parts of p-acetoxybenzoic acid, 24 parts of isophthalic acid
．． 9 parts of hydroquinone, 42.9 parts of diphenyl carbonate, and 0.102 parts of titanium tetrabutoxide were placed in the same reactor as in Example 1 and reacted in the same manner as in Example 1. When the absolute pressure was 0.5 mmH9 It solidified at the stage below.

Next, the polymer was crushed to a size of about 20 meshes, and
The reaction was carried out at 0° C. for 3 hours under reduced pressure of absolute pressure 0.5 mmH9. The intrinsic viscosity of the obtained polymer was 1.87,
Furthermore, the heat distortion temperature of a molded product made by injection molding this polymer at a cylinder temperature of 360°C and a mold temperature of 140°C is 177°C.
℃, the tensile strength was 1020 kg/(1-JMoV11), and the flexural modulus was 45,800 kg/Cd.

In the above polymer, the ratio of p-oxybenzoic acid residue MA, isophthalic acid residue MB, hydroquinone residue Mc, and carbonic acid residue MD is MA:MB:MC:MD22:15:
The ratio was 39:24 (mol% ratio). Example 6 89.7 parts of p-oxybenzoic acid, 49.8 parts of isophthalic acid, 38.5 parts of hydroquinone and 34 parts of diphenyl carbonate
2.4 parts of stannous acetate in the presence of 0.12 parts of stannous acetate at a temperature of 250-2800C and 760-0.3 parts as in Example 5.
Melt reaction and solid phase reaction were carried out under reduced pressure of 9 mmH9 for 7 hours to obtain a polymer with an intrinsic viscosity of 1.73.

The composition of this polymer is p-oxybenzoic acid residue MA,
Hydroquinone residue MB, isophthalic acid residue Mc and carbonate residue MD are MA:MB:MC:MD=48:26:2
The ratio was 2:4 (mol% ratio). After drying, this polymer was extruded from a T-die onto a rotating drum heated to 150°C using a Luder type film molding machine at a cylinder temperature of 330°C.

The resulting film was 0.02m7! LH9 under reduced pressure 250
Heat treatment was performed at ℃ for 3 hours. The thickness of this film is 52μ,
Tensile strength is 56.8k9Am2, Young's modulus is 2368.
It was 8k9Am2. Example 7 After drying the polymer obtained in Example 6, it was injection molded at a cylinder temperature of 330°C and a mold temperature of 140°C, and the physical properties of the molded product obtained were as follows.

Heat distortion temperature 181℃ Tensile strength 1170kg/CTil Flexural modulus 47500kg/C! ! l Impact strength (with 1/4” notch) 19kg・-/1

Claims (1)

[Scope of Claims] 1. Residues of aromatic oxycarboxylic acids mainly consisting of p-oxybenzoic acid represented by the following formulas (I), (II), (III), and (IV) (I), terephthalic acid or residues of aromatic dicarboxylic acids mainly containing isophthalic acid (II), residues of aromatic dihydroxy compounds mainly containing hydroquinone (I
II) and carbonic acid residues (IV), ▲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)▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(IV) [However, A
r and Ar'' are each an aromatic group mainly composed of p-phenylene, and Ar' is an aromatic group mainly composed of p-phenylene or m-phenylene.] and the residues (I) and (II) , (III) and (IV) are expressed by the following formulas (1), (2), (3) and (4) 40/6
0≦(M I + MII)/(MIII-MII)≦95/5...
・(1) 40/60≦M I /MII≦82/18...
(2) MIV≒(MIII-MII)...(3) MIII>MI
I...(4) [However, in the formula, M I , MII, MIII, MIV are M I +M
When II + MIII + MIV = 100 (mol%), the above residue (I), residue (II), residue (III), and residue (
IV) An aromatic polyester carbonate having an intrinsic viscosity of 0.3 or more that satisfies the following. 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 aromatic dicarboxylic acid residue (II) is a terephthalic acid residue or an isophthalic acid residue. 4. Claim 1, wherein the aromatic dioxy compound residue (III) is a hydroquinone residue.
Aromatic polyester carbonate described in .