JPS6016452B2 - Manufacturing method of aromatic polyester - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an aromatic polyester whose main components are bisphenols and aromatic dicarboxylic acid.

More specifically, the present invention relates to a method for producing an aromatic polyester whose main constituents are pisphenols and an aromatic dicarboxylic acid by subjecting a polycarbonate to a polyjet ester containing an aromatic dicarboxylic acid as its main constituents.
Polyethylene terephthalate is widely used industrially due to its excellent mechanical properties and chemical resistance, but its relatively low heat distortion temperature (heat resistance) and fast crystallization rate make it difficult to maintain dimensional stability and transparency. It has the disadvantage of lacking in

As a method for producing polymers that improves these drawbacks, a method has been proposed in which an aromatic dicarboxylic acid derivative and an aromatic dihydroxy compound undergo a military condensation reaction.

For example, 'a} A method in which an aromatic dicarboxylic acid chloride and an aromatic dihydroxy compound are reacted in a solution, 'b} A method in which a diarylester of an aromatic dicarboxylic acid and an aromatic dihydroxy compound are melt-polymerized, {c' A method of reacting an aromatic dicarboxylic acid, an aromatic dihydroxy compound, and a diaryl carbonate is known.
However, method 'a} requires steps such as solvent removal and purification because it uses a reaction solvent, and has many manufacturing steps, which poses problems in productivity, and methods [b} and 'c} There are problems as an industrial method because expensive raw materials such as diarylester of aromatic dicarboxylic acid and diaryl carbonate are used. As a result of repeated studies to find a method for producing fully aromatic polyester that does not have these drawbacks, the present inventors have found that by reacting polycarbonate derived from bisphenols with polyester containing ethylene glycol, it is possible to easily produce fully aromatic polyester. It was discovered that a wholly aromatic polyester can be obtained, leading to the present invention.

That is, the present invention uses a bisphenol polycarbonate (1) and a polyester (0) consisting of an aromatic dicarboxylic acid component and an ethylene glycol component in a molar ratio of bisphenols as the component (1) to aromatic dicarboxylic acid as the component (0). In the presence of a catalyst, 80% of the ethylene glycol in the component (b) that can be substituted with bisphenols in a ratio of 20:80 to 80:20.
This is a method for producing aromatic polyester, which is characterized by carrying out a melt reaction until % or more of the aromatic polyester is distilled out.

Bisphenol polycarbonate used in the present invention (1
) may be any polycarbonate derived from bisphenols.

Examples of the bisphenols include the following. That is, as these bisphenols, for example, 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], 1,1-bis(4-hydroxyphenyl)cyclohexane [bisphenol Z]
, 1,1-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)methane, 1,2-bis(
4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)cyclohexylmethane, 3,3-bis(4
-hydroxyphenyl)pentane, bis(4-hydroxyphenyl)ether, and the like. Among these, bisphenol A and bisphenol Z are preferred. Polycarbonate using bisphenol A or bisphenol Z is generally widely used as a molding material and is preferable from the viewpoint of stability and the like.

Although this polycarbonate may have a large or small molecular weight, it does not pose a problem in the reaction, but polycarbonate having a melt viscosity that is generally used for injection molding is preferably used.

On the other hand, the polyester (0) comprising an ethylene glycol component and an aromatic dicarboxylic component is a polyester obtained by reacting an aromatic dicarboxylic acid or an ester-forming derivative thereof with ethylene glycol or an ester-forming derivative thereof. Examples of the aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid,
・6-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 3,3'-dimethyldiphenyl-4,4
Examples include '-dicarboxylic acid, 4,4-diphenylsulfonedicarboxylic acid, and 4,4'-diphenoxyethanedicarboxylic acid. Examples of these ester-forming derivatives include lower alkyl esters such as methyl ester and ethyl ester, substituted aliphatic esters such as 2-hydroxyethyl ester, aryl esters such as phenyl ester, carbonic acid esters, and acid halogen compounds. is exemplified. In addition, ethylene glycol may be used alone or less than 30 mol% thereof may be substituted with other glycol components such as propylene glycol, tetramethylene glycol, hexamethylene glycol, neobentyl glycol, cyclohexane dimethylol, etc. Furthermore, bisphenols, Aromatic diols such as hydroquinone may also be included.

The polycarbonate (1) and polyester (0) may be copolymerized, respectively, but when an aliphatic or alicyclic dicarboxylic acid is used as the dicarboxylic acid, the amount is less than 30 mol% of the dicarboxylic acid. This is preferable in order to maintain a high heat distortion temperature of the resulting aromatic polyester.

Examples of the copolymerizable aliphatic or alicyclic dicarboxylic acids include oxalic acid, adipic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, decahydronaphthalene-
2,6-dicarboxylic acid, decamethylene dicarboxylic acid, 1
Examples include 04-cyclohexanedicarboxylic acid. The polyester used in the present invention can be produced by a conventional melt polymerization method, interfacial polymerization method, or solution polymerization method.

Furthermore, low molecular weight polyesters are not preferred, and polyesters with an intrinsic viscosity of at least 0.1, preferably 0.2 or more are effective. This is because if the intrinsic viscosity is lower than 0.1, a high molecular weight polymer cannot be obtained even if the polycarbonate reaction is carried out for a long time. In the present invention, polymer carbonate (
1) and polyester (0) are caused to undergo a melting reaction, and this melting reaction occurs in the periodic table 1^, Plate^, W^, V^.
, OB, B, skin B, and salts of related metals are preferably carried out.

These metal salts include carboxylates, phosphates and carbonates of Group 1 metals of the periodic table, Group 1 metals, Group 1 metals, DB metals,
Metal salts selected from the group consisting of carboxylates of WB, skin B and skin group metals, and nitrates of group V metals are preferred, and one or more of these may be used. Examples of Group 1 metals include lithium, sodium, potassium, and ribidium. Among these, lithium, sodium and potassium are preferred. Examples of the m^ group metal include aluminum, gallium, etc., and aluminum is particularly preferred. The WA group metals include germanium, tin, lead, etc., with tin and lead being particularly preferred. Examples of group V^ metals include antimony and bismuth, with bismuth being particularly preferred. Examples of Group DB metals include zinc, cadmium, mercury, etc., and zinc is particularly preferred. WB group metals include chromium, molybdenum,
Examples include tungsten, but chromium is particularly preferred. Examples of the Group B metal include manganese and rhenium, with manganese being particularly preferred. Examples of blood group metals include iron, cobalt, nickel, palladium, etc., and cobalt is particularly preferred. Examples of carboxylic acid salts include salts of formic acid, acetic acid, propionic acid, benzoic acid, phthalic acid, and the like. Among these, acetate is preferred. The metal salt may be anhydrous;
It may also contain crystal water.

Further, the salt may be an acid salt, a neutral salt, or a basic salt, but a neutral salt or an acid salt is preferable. Only one type of metal salt may be used, or two or more types may be used in combination. Specific examples of metal salts include sodium phosphate, sodium dihydrogen phosphate, sodium acetate trihydrate, sodium acetate, sodium tungstate, lithium carbonate, lithium acetate, dipotassium hydrogen phosphate, manganese acetate, zinc acetate 2 Examples include hydrate, acetate, cobalt acetate, aluminum acetate, chromium (m) acetate, and bismuth nitrate.

The amount of metal salt added is preferably 0.1 to 5 parts by weight per 10 parts by weight of the sum of polycarbonate (1) and polyester (0) as raw materials.

In the present invention, the above-mentioned polycarbonate (1) and polyester (0) are melt-reacted, and the reaction temperature at that time is 220 to 35,000, preferably 250 to 32,000.
It is pi 0.

Furthermore, since the reaction involves the generation of carbon dioxide gas, ethylene glycol of polyester (0) and its derivatives, care must be taken and the reaction must be carried out in an apparatus capable of distilling these. In particular, a large amount of ethylene carbonate needs to be extracted and distilled, so after the generation of carbon dioxide gas has substantially finished, 1
It is necessary to create a vacuum of less than 1 side Hg, preferably less than 1 side Hg. Although the degree of vacuum varies depending on the reaction temperature, a degree of vacuum of 0.05 to 1 foot Hg is used at a reaction temperature of 270 to 30,000 °C. In the present invention, after the melting reaction as shown in JP-A-48-7091 is carried out, ethylene glycol and its derivatives, such as ethylene carbonate, are further discharged under high vacuum as described above. It is characterized by the fact that it is carried out. That is, in the present invention, it is necessary to extract at least 80%, preferably 95% or more of the ethylene glycol contained in the polyester (b) used, which can be substituted with bisphenols. Here, the ethylene glycol that can be substituted with bisphenols is a theoretical value that assumes that while both the ethylene glycol component and bisphenols are present in the system, all ethylene glycol is extracted and replaced with bisphenols. be. If the amount of crab release is less than 80%, the resulting aromatic polyester will have a low heat deformation temperature and low rigidity, which is not preferable. In the present invention, the charging ratio (mole ratio) of polycarbonate (1) and polyester (0) is 2 to 8.
0-8 seals 20, preferably 3 pairs 70-7 arm sizes 30.

If the amount of polycarbonate (1) exceeds this ratio, the resulting polymer will be substantially the same as polycarbonate, which is not preferable. Moreover, if polyester (0) is present in a large amount, the resulting polymer will have a low heat deformation temperature, which is not preferable. The aromatic polyester thus obtained generally has a high melt viscosity, and it is often difficult to obtain one with a high degree of polymerization.

In this case, a preferred method is to obtain a polymer with a low degree of polymerization and then further solid-phase polymerize it to obtain a high degree of polymerization. Solid phase polymerization produces polymers in the form of powder or pellets,
It is preferable to carry out the process in a vacuum or in an inert gas stream while increasing the temperature to an extent that no stickiness occurs. The aromatic polyester obtained by the method of the present invention is a polymer that has a higher heat distortion temperature and lower gas permeability than polycarbonate, and has improved solvent resistance. It has a high heat deformation temperature and high rigidity.

Transparent molded articles can generally be obtained from these aromatic polyesters. In addition, the method of the present invention has easier raw materials to obtain than conventional melt polymerization methods, and can produce polymers with various properties by adjusting the degree of reaction and the mixing ratio of raw materials. have the advantages that can be obtained. The present invention will be explained in detail below with reference to Examples.

In addition, "part" in the examples means "part by weight", and the reduced specific viscosity (resp/c) is phenol/tetrachloroethane: 6
Using a mixed solvent of 0/40 (weight ratio), C= at 3500
This is a value measured as 1.2. In addition, the carboxyl group value can be determined using the Conix method (MacroMolecular
．． Chem, 2022019), and the heat distortion temperature was measured by the method of ASTM D-648. Example 1 Intrinsic viscosity 0.65 containing 0.08% calcium acetate
33.5 parts of polyethylene terephthalate and Teijin Kasei△
Polycarbonate manufactured by Teijin Panlite L-125o
■, polycarbonate using bisphenol A) 66
．． 5 parts of dipotassium hydrogen phosphate and 0.5 parts of dipotassium hydrogen phosphate were placed in a vacuum-enabled reaction layer, and reacted under a high vacuum of 0.2 Hg for 80 minutes at 270°C while moving. I got a gift.

Analysis of this crabmeat revealed that ethylene carbonate 6
% by weight, triethylene glycol 2nd base weight%, and 4% by weight of other components. This indicates that about 99% of the ethylene glycol in the polyethylene terephthalate was distilled off. Obtained aromatic polyester beam sp/c=0
．． The molded piece obtained by injection molding this polymer was transparent.

The heat distortion temperature of this material was 264 psi and 148 qo. Comparative Example 1 The same procedure as in Example 1 was carried out except that dipotassium hydrogen phosphate was not used.

Observations during the reaction showed that polyethylene terephthalate and polycarbonate were simply melt-mixed, and there was almost no foaming or distillate observed in Example 1. The resulting polymer had a sp/c of 0.92, but the injection molded pieces were opaque and had a heat distortion temperature of 10
It was 600.

Examples 2 and 3 The same procedure as in Example 1 was carried out except that the catalyst shown in Table 1 was used instead of dipotassium hydrogen phosphate.

The results are shown in Table 1. Table 1 Example 4 Transesterification of an acid component comprising 7% by weight of dimethyl terephthalate and 3% by weight of dimethyl isophthalate and ethylene glycol in the presence of a catalyst of 0.05% by weight of manganese acetate and germanium oxide. reaction, then adding phosphorous acid, followed by polycondensation reaction, or sp.
/co. 77 polyethylene terephthalate/isophthalate copolymer 4 parts and polycarbonate derived from bisphenol A (Teijin Panlite L-1250) 6
$ parts and 0.6 parts of dipotassium hydrogen phosphate were charged into a reaction tank capable of being vacuumed, and reacted for 270,009 minutes.

The distillate during the reaction was received in a sufficiently cooled receiver, and after the reaction was completed, it was weighed and found to be 14.3 parts.

The composition of the distillate was 77.5% by weight ethylene carbonate, 19.1% by weight triethylene glycol and 3.4% by weight of other components. This indicates that 99.9% of ethylene glycol was extracted from the polyethylene terephthalate copolymer. The obtained polymer had an sp/c value of 0.95, and a molded piece obtained by injection molding this polymer was transparent and had a heat distortion temperature of 264 psj and 44 oo.

Example 5 66.5 parts of polyethylene terephthalate and polycarbonate (Teijin Panlite L-1250) derived from bisphenol A were used. 24. The reaction was carried out in exactly the same manner as in Example 1, except that the amount was 5 parts. A $0.00 portion of distillate was obtained.

As a result of analysis, the composition of the distillate was 70% of ethylene carbonate.
．． 7% by weight, triethylene glycol 26.5% by weight,
Others 2. It was % by weight of Tsuru. This indicates that 99.7% of the ethylene glycol in the polyethylene terephthalate was distilled out. The obtained polymer has a sword sp/c=0.
91 and injection molded pieces of this polymer were transparent.

The heat distortion temperature of this material was 14,600 at 2 mouse psi. Examples 6 to 15 and Comparative Row 2 The reaction was carried out in the same manner as in Example 1, except that 2 parts of the catalyst shown in Table 2 was used in place of dipotassium hydrogen phosphate.

The results are shown in Table-2.

Claims (1)

[Scope of Claims] 1. A bisphenol polycarbonate (I) and a polyester (II) consisting of an aromatic dicarboxylic acid component and an ethylene glycol component, and a bisphenol as the component (I) and an aromatic dicarbonate as the component (II). The molar ratio of acid is 20:
(II) in the presence of a catalyst in a ratio of 80 to 80:20
A method for producing an aromatic polyester, which comprises carrying out a melt reaction until 80% or more of the ethylene glycol in the components that can be substituted with bisphenols is distilled off. 2. The catalyst is a carboxylate of a group I_A metal of the periodic table,
Phosphates and carbonates, chapters III_A, IV_A, II_B, VI
_B, carboxylates of group VII_B and VIII metals, Chapter V_A
2. The method for producing an aromatic polyester according to claim 1, wherein the metal salt is at least one metal salt selected from group metal nitrates.