JPS6020415B2 - Aromatic polyester copolymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aromatic polyester copolymer composition with excellent stability. The present invention relates to an aromatic polyester copolymer composition with excellent stability.

Aromatic polyester copolymers made of a mixture of terephthalic acid and isophthalic acid or their functional derivatives (however, the molar ratio of terephthalic acid groups to isophthalic acid groups is 9:1, 1:9) and bisphenols have long been reported. better known.

A method for producing such an aromatic polyester copolymer is the so-called interfacial polymerization method (W.M. Earecks) in which an alkaline aqueous solution of bisphenols and aromatic dicarboxylic acid chloride dissolved in an organic solvent that is incompatible with water are mixed.
on;J. poly. Sci. 40 399 (1959
), Japanese Patent Publication No. 35-35, Japanese Patent Publication No. 401-1959), solution polymerization method in which bisphenols and acid chloride are heated in an organic solvent (A.Conix:lnd.En)
g. Chem. 51 147 (1959), Special Publication No. 37
-5599 Publication), a melt polymerization method of heating phenyl ester of aromatic dicarboxylic acid and bisphenol (Special Publication Shoichi No. 15247, Special Publication Sho Madaraichi No. 2629y, Hakama Kosho No. 431-28119), etc. method is known.

The aromatic polyester copolymer made of an aromatic dicarboxylic acid and a pisphyl alcohol obtained in this way has superior properties compared to a polyester made of an aromatic dicarboxylic acid and an aliphatic alkylene glycol. This is also well known.

In other words, it has many excellent properties in terms of mechanical properties such as tensile strength and elongation, bending strength, bending recovery rate, and impact strength, heat distortion temperature, dimensional stability, electrical properties, and flame retardancy. Therefore, it is known that it can be used in a wide range of fields as various extrusion molded, injection molded, etc. molded products, films, fibers, and coating materials. On the other hand, it has been found that the aromatic polyester copolymer obtained by the above-mentioned method is already yellow or brown when it is finally produced, or becomes colored while left standing.

Further, when the aromatic polyester copolymer is molded into a general molded article or film by injection molding, extrusion molding, or other methods, it is recognized that the aromatic polyester copolymer becomes colored during heating. Such coloring is very inconvenient when it is important that the product be colorless, and when pigments are mixed in to obtain the desired color, the resulting coloration is often completely different from what was expected. So I don't like it. Furthermore, such coloring is thought to be accompanied by decomposition of the polymer, which irregularly reduces the viscosity of the molded product and reduces the physical properties of these polymers, which have useful properties. is also extremely disadvantageous. There are few known attempts to improve such drawbacks.

Slight amount of sodium dithionite (Special Publication No. 381112
Although it has been proposed to add polyphenylene or activated anthracene (Japanese Patent Publication No. 45-23418), the addition of polyphenylene or activated anthracene (Japanese Patent Publication No. 45-23418) has been proposed. No good results have been obtained. As a result of intensive research to solve the above-mentioned drawbacks of aromatic polyester copolymers, the present inventors have found that by adding a specific amount of a specific phosphorus compound as a stabilizer, the above-mentioned disadvantages of aromatic polyester copolymers can be improved. Undesirable coloration or thermal decomposition such as
The present invention was achieved based on the discovery that an extremely stable aromatic polyester copolymer composition can be obtained.

That is, the present invention provides a mixture of terephthalic acid and isophthalic acid or functional derivatives thereof (provided that the molar ratio of terephthalic acid groups to isophthalic acid groups is 9:1 to 1:9) and bisphenols represented by the general formula [however, 1×1 is 101, 1S1, 1S021, 1CO-, alkylene group and alkylidene group (if necessary, the hydrogen atom of the alkylene group or alkylidene group can be one or more hydrocarbon group, halogen atom or substituted with a halogenated hydrocarbon group), R,, R2, R3, R4, R',, R'2, R
'3, R'4 are selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group] and 0.01% by weight based on the aromatic polyester copolymer obtained. The above general formula (where n is 1 to 2
is an integer represented by C, ~C. o is a halogenated alkyl group.

) is an aromatic polyester copolymer composition consisting of a phosphorus compound 'B-'. Conventionally, amine compounds such as naphthylamine, diphenylamine, ethylenediamine, and aromatic amines have been used as antioxidants for rubber, but when these amine compounds are used as antioxidants for plastics, Although it is possible to reduce thermal decomposition of plastics, the deterioration of the color tone cannot be avoided and only extremely colored molded products can be obtained. However, by adding a specific phosphorus compound as shown in the present invention, It is possible to obtain molded products with excellent color tone and no coloration.

Various types of aromatic polyester copolymers used in the present invention can be obtained by changing the ratio of terephthalic acid groups to isophthalic acid groups and the type and ratio of bisphenols.

Examples of the pisphenols used in the present invention include 2,2-bis(4-hydroxyphenyl)-propane (hereinafter referred to as bisphenol A), 2,2-bis(4-hydroxyphenyl)-propane (hereinafter referred to as bisphenol A),
-hydroxy-3,5-dibromophenyl)propane,
2,2-bis(4-hydroxy-3,5-dicoo phenyl)-pro/dine, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl Ketone, 4,
4-dihydroxydiphenylmethane, 2,2-pis(4
-hydroxy-3,5-dimethylphenyl)-propane, 1-1-bis(4-hydroxyphenyl)-ethane,
Examples include 1,1-bis(4-hydroxyphenyl-cyclohexane and 4,4'-dihydroxydiphenyl-methyl-isobutyl-methane).

As a method for producing the aromatic polyester copolymer used in the present invention, any of the aforementioned interfacial polymerization methods, solution polymerization methods, and melt polymerization methods may be used, but in particular, organic solvent solutions of terephthalic acid dichloride and isophthalic acid dichloride are used. The interfacial polymerization method in which bisphenols are mixed with an alkaline aqueous solution is advantageous because it provides an aromatic polyester copolymer with relatively little coloring.

The phosphorus compound used in the present invention has the general formula (where n is an integer of 1 to 2, and R is C. to C
, o is a halogenated alkyl group.

). Such phosphorus compounds include, for example, di(2-chloroethyl)-acidophosphate, (B) di-(2-furomoethyl)-acidophosphate, {C' di(3-chloropropyl)-acidophosphate, dish phosphate, etc. (3-promopropyl)
One acid phosphate, (2,3-bromopropyl-2-furomo-3-chloropropyl) one acid phosphate, (F'(2,3-dichloropropyl-2-furomo-3-chloropropyl) one acid phosphate ,(
G) Mono(2-chloroethyl)-acidophosphate, (H) Mono(2-furomoethyl)-acidophosphate, (1) Mono-(3-chloropropyl)-acidophosphate, (J) Mono(3-bromopropyl) )-acydophos-to, (K)di(2-methyl-
Examples include 3-chloropropyl)-acid phosphate. (However, these phosphorus compounds are
It is represented by the structural formula (K). ) These phosphorus compounds may be used alone or in combination.

Among them, the addition of a phosphorus compound represented by the formula or is particularly effective.
The effect is particularly remarkable when di(2-chloroethyl)-acid phosphate and mono(2-chloroethyl)-acid phosphate are added alone or in combination.

The amount of the phosphorus compound added to the aromatic polyester copolymer varies depending on the type of phosphorus compound used, but it needs to be 0.01% by weight or more based on the aromatic polyester copolymer, preferably 0. .05~2. weight%,
Particularly preferably 1.1 to 1. It is used in a range of % by weight.

In this case, a content of 0.01% by weight is not suitable because it has no effect of preventing coloration or thermal decomposition. Moreover, if it exceeds 5% by weight, mechanical properties deteriorate, which is not preferable. The method of adding the phosphorus compound to the aromatic polyester copolymer is not particularly limited, and various methods can be used.

When producing an aromatic polyester copolymer, for example, in an interfacial polymerization method in which an organic solvent in which dicarboxylic acid chloride is dissolved and an alkaline solution of bisphenols are concentrated, a phosphorus compound is added before polymerization of the aromatic polyester copolymer, i.e. It can also be added in advance to any of the monomer components.
Furthermore, when the polymer solution is isolated after completion of polymerization, it is also possible to add a previously dissolved phosphorus compound to the polymer solution. When the aromatic polyester copolymer is isolated as a solid, the phosphorus compound can be present in the aromatic polyester copolymer composition in the following manner instead of simply being added. That is, the polymer is immersed in a solution in which a phosphorus compound is dissolved or suspended in a solvent such as methanol or acetone, and after immersion, the solvent is evaporated off. Furthermore, in melt polymerization, it may be supplied together with the monomer during polymerization. In addition, it may be added to chips of aromatic polyester copolymer during molding, for example, during injection molding. In particular, if it is added to powder or chips and then molded, a molded product with uniform color tone and uniform properties can be obtained. In addition to the phosphorus compound, the composition of the present invention may contain various antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, etc. in combination as appropriate depending on the purpose of use.

For example, in the present invention, it is possible to further increase the effects of the present invention by adding a phosphorus compound and an antioxidant in combination. These antioxidants include:
Examples include conventional phenolic antioxidants, phosphite antioxidants, amine antioxidants, impregnated yellow compounds, organometallic compounds, epoxy compounds, and the like. Also,
In the present invention, plasticizers, pigments, lubricants, etc. can also be used, and glass fibers can also be added for reinforcement. The composition of the present invention may also be applied to polyalkylene terephthalates such as polyethylene terephthalate and polybutylene terephthalate, polyethylene oxybenzoate, polycarbonate, polyethylene, polypropylene, polyamide, polyurethane, polystyrene, ABS, EVA, polyacrylic acid ester, and polytetrafluorocarbon. It may contain one or more types of polymers such as tyrene, methyl methacrylate, polyphenylene sulfide, rubber, etc. depending on the purpose.

That is, in the present invention, a mixture of an aromatic polyester copolymer and other polymers such as those mentioned above can be used, and the phosphorus compound used in the present invention also exhibits remarkable effects in this case. The aromatic polyester copolymer composition of the present invention has excellent stability and moldability while retaining the advantages of conventional aromatic polyester copolymers.

Next, the present invention will be explained with reference to examples, but the present invention is not limited to these examples.

In addition, in the examples, the logarithmic viscosity inh is phenol/
This is a value measured at 25 qo (C=1 night/d') using a mixed solvent of tetrachloroethane (6/4) (weight ratio).
The color tone of the molded product and the presence or absence of craze were determined visually, and the markings were as follows. Color tone display No craze occurrence Color 1 No craze occurrence
○Pale yellow 3 Slight crease occurrence △Yellow 5
Small amount of craze occurrence × Brown 7 Medium amount of craze occurrence × × Brown 9 Large amount of craze occurrence It was measured using

In the high temperature retention test, the test piece was molded using injection molding, and the molded product was molded after being retained at 380°C for 5 minutes, and the performance of the molded product was evaluated. Example 1 Caustic soda aqueous solution 450k9 in which bisphenol A22.5k9 was dissolved, isophthalic acid dichloride 10k9,
After mixing with 292 kg of methylene chloride solution in which 10k9 of terephthalic acid dichloride was dissolved and undergoing a vigorous clearing reaction,
The organic phase was separated.

After washing this organic phase four times with pure water, methylene chloride was concentrated and distilled off to obtain a powdery polymer. This powder paste i blood was 0.70. Various additives shown in Table 1 were added to this powder at a concentration of 0.1% by weight based on the powder, and after blending with a super mixer, sufficient vacuum drying was carried out.
Next, I made chips using an extruder. After sufficiently drying the obtained chip, a test piece was molded using an injection molding machine.

After thoroughly drying the test piece, it was exposed to air at 170 pm for 24 hours. The test pieces were examined for changes in color tone, changes in viscosity, and the presence or absence of craze, and the results are shown in Table 1. Note that the molding temperature of the test piece was 360 qo.

As is clear from Table 1, the test piece prepared from the aromatic polyester copolymer composition to which the IJ compound was added as a stabilizer was different from the aromatic polyester copolymer composition to which no stabilizer was added. Control Example) and Comparative Example were superior in terms of post-treatment viscosity reduction, coloration prevention, craze generation, and viscosity reduction and coloration prevention effects in high-temperature retention tests. Among them, di(2-chloroethyl)-acidophosphate and mono(2-chloroethyl)-acidophosphate are excellent, especially di(2-chloroethyl)-acidophosphate and mono(2-chloroethyl)-acidophosphate. - The effect was remarkable when both were used in a 1:1 ratio (weight ratio). Example
2 An aromatic polyester copolymer powder was obtained in the same manner as in Example 1.

To this powder, an additive made by mixing di(2-chloroethyl)-acid phosphate and mono-(2-chloroethyl)-acid phosphate in a 1:1 ratio (weight ratio) was added to the powder. .01, 0.1, 1.0, 2. After adding the powder to a weight percent of After molding each test piece and drying it thoroughly,
The feeding time was exposed to air atmosphere. The results of examining changes in color tone and viscosity of the test pieces are shown in Table 2. As is clear from Table 2, di-(2-chloroethyl)
-Acidophosite and mono-(2-chloroethyl)
- A test piece prepared from an aromatic polyester copolymer composition containing acid phosphate in a 1:1 ratio (weight ratio) was better than an aromatic polyester copolymer composition to which no stabilizer was added. Compared to the prepared test piece, the effect of preventing viscosity reduction, the effect of preventing coloration, and the Izod impact strength were significantly superior, especially when the addition amount was 0.1 to 1. Significant differences were shown in the weight percent range.

Example 3 5.5 kg of caustic soda aqueous solution in which 2.75k9 of bisphenol A was dissolved, 1.21k9 of isophthalic acid dichloride
, terephthalic acid dichloride 1.21 [9, methylene chloride 25
A suspension of 0.55 ml of methylene chloride containing 21.0 ml of bromo-3-3-chloropropyl)-acid phosphate was added and mixed.

After gradually evaporating methylene chloride, the aromatic polyester copolymer composition containing (2,3-dichloropropyl-2-furomo-3-chloropropyl)-acid phosphate as a stabilizer was prepared by crushing it with a kneader. Granules were obtained.
The obtained granular aromatic polyester copolymer composition was sufficiently dried, and a test piece was prepared in the same manner as in Example 1. This test piece was exposed to an air atmosphere at 170 oo for 24 days. The results of examining changes in viscosity and color tone of the test pieces at that time are shown in Table 3. Table 3 As is clear from Table 3, the aromatic polyester copolymer composition containing a phosphorus compound obtained by adding a methylene chloride solution containing a stabilizer to a polymer solution also has the effect of preventing viscosity reduction. , coloration prevention effect is recognized.

Example 4 An aromatic polyester copolymer powder was obtained in the same manner as in Example 1.

Add 95 parts by weight of this powder to polyethylene terephthalate powder [glue in phenol/tetrachloroethane (5'5)].
el1. *] Added 5 parts by weight, and further added 0.5 parts by weight of di(3-chloropropyl)-acid phosphate. After adding part by weight of the mixture and blending with a spar mixer, the mixture was thoroughly dried in vacuum, chipped with an extruder, and a test piece was molded using an injection molding machine in the same manner as in Example 1. The obtained test pieces were exposed to an atmosphere of 85° C. and 95% RH for 240 hours, and changes in color tone, changes in viscosity, and the presence or absence of craze generation were investigated. The results are shown in Table 4. Table 4 As is clear from Table 4, it is recognized that the addition of a phosphorus compound significantly improves the prevention of viscosity reduction and coloration even when polytethylene terephthalate is added, and in this case, craze It has been found that this can also be prevented.

Example 5 An aromatic polyester copolymer powder was obtained in the same manner as in Example 1.

Add polyethylene terephthalate powder [glue in phenol/tetrachloroethane (5/5)] to the weight part of this powder 6.
40 parts by weight of el=1.38] was added, and further g(2
-chloroethyl)-acid phosphate (1/2) and mono-(2-chloroethyl)-acid phosphate (1/2)
After adding 0.1 part by weight of a mixture (weight ratio) of 1/2) and blending with a super mixer, sufficient vacuum drying was performed and the mixture was formed into chips using an extruder. After thoroughly drying this chip, a test piece was molded using an injection molding machine. The color tone and viscosity of the obtained test piece were as shown in Table 5.

Note that the molding temperature was 280 oo.

As is clear from Table 5, it was observed that even in the case of compositions containing polyethylene terephthalate, addition of a phosphorus compound significantly improved prevention of viscosity reduction and prevention of discoloration.

Claims (1)

[Claims] 1. A mixture of terephthalic acid and isophthalic acid or their functional derivatives (however, the molar ratio of terephthalic acid groups and isophthalic acid groups is 9:1 to 1:9) and a general formula ▲ mathematical formula, chemical formula, table etc. ▼ Bisphenols represented by [However, -X- is -O
-, -S-, -SO_2-, -CO-, alkylene groups and alkylidene groups (if necessary, the hydrogen atoms of the alkylene and alkylidene groups may be one or more hydrocarbon groups, halogen atoms, or halogenated hydrocarbon groups) ) is selected from the group consisting of
R_1, R_2, R_3, R_4, R'_1, R'_2
, R'_3, R'_4 are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group]; and the aromatic polyester copolymer (A) 0.01% by weight or more of general formula ▲
There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, n is an integer from 1 to 2, and R is C_1
~C_1_0 is a halogenated alkyl group. ) An aromatic polyester copolymer composition comprising a phosphorus compound (B) represented by: