JPS59140251A - Composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION BACKGROUND OF THE INVENTION The present invention relates to novel copolyester carbonate compositions.
It is related to.

Aromatic polycarbonates are thermally stabilized by phosphorous esters of various structures. However, the effectiveness of using stabilizers effective for aromatic polycarbonates with copolyester carbonates, which are polymers containing repeating ester units along with carbonate repeating units, has not yet been fully demonstrated. It has now been discovered that certain phosphite stabilizers provide unique effects (especially thermal and hydrolytic stabilization) on certain copolyester carbonates.

SUMMARY OF THE INVENTION In accordance with the present invention, (a) a copolyester carbonate and (b) an effective amount of tris(2,
4-di-t-butylphenyl).

Particularly preferred are compositions as described above which additionally contain an effective amount of aromatic sulfonate for flame retardation. When such a salt is present in the composition, the heat stabilizing effect of the phosphite becomes even more pronounced.

Copolyester carbonates useful in the present invention and methods of making them are known in the art and are disclosed in U.S. Pat.
38.4156069.4238596 and 4238
No. 597.

A copolyester carbonate generally refers to a copolyester carbonate containing a carbonate ester group, a carboxylic ester group, and an aromatic carbocyclic group, with at least some carboxylic ester groups and at least some carboxylic ester groups. It can be defined as a polymer in which the groups and at least some of the carbonate groups are bonded directly to aromatic carbocyclic groups. Such copolyestercarbonates are generally prepared by reacting (1) a dihydric phenol, (2) a difunctional carboxylic acid or its reactive conductor (e.g., an acid dihalide), and (3) a carbonate precursor. Manufactured by

The dihydric phenols useful in making the copolyester carbonates used in the practice of this invention are represented by the general formula. In the formula, A is an aromatic group such as a phenylene group, a biphenylene group, a naphthylene group, etc.

E is an alkylene group or an alkylidene group (e.g. methylene group, ethylene group, propylene group, glopylidene group,
(isopropylidene group, butylene group, butylidene group, isobutylidene group, amidino group, isoamylene group, amylidene group, isobutylidene group, etc.). When E is an alkylene or alkylidene group, it is a non-alkylene or non-alkylidene group (e.g. an aromatic group,
It may consist of two or more alkylene or alkylidene groups linked by a tertiary amino group, an ether group, a carbonyl group, a silicon-containing group, or a sulfur-containing group such as a sulfide group, a sulfoxide group, or a sulfone group.

Furthermore, E can be a cycloaliphatic group (e.g. cyclopentyl, cyclohexyl, etc.), a sulfur-containing group (e.g. sulfide, sulfoxide or sulfone), an ether group, a carbonyl group, a tertiary nitrogen group or a silicon-containing group. (for example, a silane group or a siloxy group). R is a hydrogen atom or a monovalent hydrocarbon group such as an alkyl group (methyl group, ethyl group, propyl group, etc.),
An aryl group (such as a rhenyl group or a naphthyl group), an aralkyl group (such as a benzyl group or an ethylphenyl group), an alkaryl group or a cycloaliphatic group (such as a cyclopentyl group or a cyclohexyl group). Y can be an inorganic atom such as a halogen (fluorine, bromine, chlorine or iodine), an inorganic group such as a nitro group, a group as described above for R, or an oxy group as in OR. In short, Y need only be inert to and unaffected by the reactants and reaction conditions. m is an integer from 0 to the number of substitutable positions present in the A matrix, p is an integer from 0 to the number of substitutable positions present in the E matrix, t is an integer at least equal to 1, S is an integer An integer equal to 0 or 1, and U is any integer including 0.

In the dihydric phenol represented by the above formula (1), 2
If more than one Y group is present, they may be the same or different. The same is true for the R group. In formula (1), when day is 0 and U is not 0, the aromatic rings are directly bonded to each other without intervening an alkylene group or other bridging group. When two or more ring carbon atoms of aromatic group A are substituted by a Y group and a hydroxyl group, the positions of the hydroxyl group and Y group on the aromatic group A may be any of the ortho, meta or para positions. Also, the positional relationship between the substituents may be adjacent,
It can be either symmetrical or asymmetrical.

Non-limiting examples of dihydric phenols included within the scope of formula (1) include 2-bis(4-hydroxyphenyl)furopane (bisphenol A), 2,4'-dihydroxydiphenylmethane, bis(2- hydroxyphenyl)methane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane, bis(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)methane, 1,1-bis (4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxy-2-chlorophenyl)ethane, 2,2-his(3-phenyl-
Examples include 4-hydroxyphenyl)furopane, bis(4-hydroxyphenyl)cyclohexylmethane, and 2,2-bis(4-hydroxyphenyl)-1-phenylpropane.

These dihydric phenols can be used alone or in a mixture of two or more.

To prepare the copolyester carbonates useful in the compositions of this invention, generally any difunctional carboxylic acid or reactive derivative thereof (e.g., acid dichloride) conventionally used in making polyesters is used. can be used. Generally speaking, the carboxylic acids that can be used are aliphatic carboxylic acids, aliphatic-aromatic carboxylic acids or aromatic carboxylic acids. From the viewpoint of providing the most useful aromatic copolyester carbonate in carrying out the present invention, aromatic dicarboxylic acids or reactive derivatives thereof (eg, acid dihalides) are preferred.

Such carboxylic acids can be represented by the general formula %. In the formula, R1 is an alkylene group, an alkylidene group or a cycloaliphatic group as described above for E in formula (1), an alkylene group containing an ethylenically unsaturated bond, an alkylidene group or a cycloaliphatic group. Aromatic groups such as phenylene groups, naphthylene groups, biphenylene groups, substituted phenylene groups, etc., formula (1
) with two or more aromatic groups linked through a non-aromatic group, such as those defined by E in ), or a divalent aralkyl group, such as tolylene group, xylylene group, etc. R2 is a carboxyl group or a hydroxyl group. If R2 is a hydroxyl group, q is 1; if R2 is a carboxyl group, q is 0 or 1. That is, the difunctional carboxylic acid can be a monohydroxy monocarboxylic acid or a dicarboxylic acid. For the purposes of the present invention, dicarboxylic acids or their reactive derivatives (eg acid dihalides) are preferred, especially aromatic dicarboxylic acids or their dihalides. That is, in the more preferred dicarboxylic acid, R2 is a carboxyl group, and R1 is a divalent aromatic group such as a phenylene group, a naphthylene group, a biphenylene group, a substituted phenylene group, or a non-aromatic group. two or more aromatic groups bonded via
It is a divalent aralkyl group. Suitable aromatic and aliphatic/aromatic dicarboxylic acids that may be used to prepare the copolyestercarbonates useful in the practice of this invention include phthalic acid, inphthalic acid, terephthalic acid, homophthalic acid, o-lm- Mention may be made of hydrophenylene diacetic acid and polycyclic aromatic dicarboxylic acids such as diphenic acid and 1,4-naphthalic acid.

These carboxylic acids can be used alone or
Alternatively, they can also be used as a mixture of two or more.

The carbonate precursor may be a carbonyl halide, carbonate or haloformate. Carbonyl halides that can be used in the present invention are carbonyl chloride, carbonyl bromide and mixtures thereof. Representative examples of carbonate esters that can be used in the present invention include:
Diphenyl carbonate, di(halophenyl carbonate) such as di(chlorophenyl) carbonate, bromophenyl carbonate, di(trichlorophenyl) carbonate, di(tribromophenyl) carbonate, di(alkylphenyl carbonate) such as ditril carbonate, etc. Examples include dinaphthyl carbonate, di(chloronaphthyl) carbonate, phenyltolyl carbonate, chlorophenylchloronaphthyl carbonate, and mixtures thereof. Haloformates suitable for use in the present invention include bishaloformates of dihydric phenols (such as hydroquinone) and bisshaloformates of glycols (such as ethylene glycol, neopentyl glycol, polyethylene glycol, etc.). acid esters). Among them, carbonyl chloride known as phosgene is preferred.

In reacting (]) dihydric phenol, (2) dicarboxylic acid or reactive derivative thereof and (3) carbonate precursor, catalysts, molecular weight regulators and acid acceptors are additionally used. Examples of suitable molecular weight modifiers include:
Examples include phenol and pt-butylphenol. Examples of suitable catalysts include tertiary amines, quaternary ammonium compounds, quaternary phosphonium compounds, and the like. Examples of suitable acid acceptors include tertiary amines, alkali metal hydroxides, alkaline earth metal hydroxides, and the like.

Copolyestercarbonates that are particularly useful in the practice of this invention include (1) dihydric phenols, (2) aromatic dicarboxylic acids or reactive derivatives thereof (e.g., acid dihalides and dichlorides), and (3) dihydric phenols. ) derived from carbonate precursors (e.g. phosgene). In particular, aromatic copolyester carbonates derived from (1) bisphenol A, (2) terephthalic acid, inphthalic acid or mixtures thereof or terephthaloyl dichloride, inphthaloyl dichloride or mixtures thereof and (3) phosgene are extremely useful. be. In addition, when a mixture of terephthaloyl dichloride and isophthaloyl dichloride is used, the weight ratio of terephthaloyl dichloride and inphthaloyl dichloride is approximately 10:90 to 9.
It is within the range of up to 5:5.

In such copolyester carbonates, from about 25 to about 9
There is 0 (mol)% ester bond present, thus about 75 to
There are approximately 10 (mole) carbonate bonds present. The preferred content range of ester bonds is about 35 to about 80 (mol)%
It is. If 5 moles of bisphenol A are completely reacted with 4 moles of isophthaloyl dichloride and 1 mmole of phosgene, an aromatic copolyester carbonate containing 80 (mol) of ester bonds is obtained.

The phosphite used in the compositions of the present invention is tris(2,4-di-t-butylphenyl) phosphite, represented by the structural formula. This phosphorous ester is Ciba
It is commercially available from C1ba Aeigy under the name Irgafos 168. Hereinafter, this phosphorous acid ester will be referred to as TBPP.

Any amount of TBPP that is effective for thermal stabilization of the copolyester carbonate can be used.

Generally about 0.01 to about 0.05 (by weight), preferably 0.01 to about 0.05 (by weight).
Amounts of 0.03% to about 0.1% (by weight) are used. If the amount used is less than about 0.001% (by weight), sufficient thermal stabilization will usually not be obtained. Usage amount is approximately 1.0% (weight)
Beyond this, there is little or no increase in the thermal stabilizing effect, and even some deterioration of the desirable properties of the copolyester carbonate. The degree of thermal stabilization is determined by melt viscosity. For a given resin, the magnitude of melt viscosity is an indicator of the degree of deterioration that occurs during thermal processing. Alongside this increase in thermal stability, an increase in hydrolytic stability is also observed, as indicated by the light transmittance and intrinsic viscosity of the molded articles before and after autoclaving at elevated temperatures. This is unusual considering that stabilization with phosphites often significantly reduces the hydrolytic stability of the resin.

The composition of the present invention can be manufactured by compounding according to conventional methods. For example, a dry (eg, powdered or granular) copolyester carbonate may be mixed with a phosphite and the mixture may then be extruded.

Such compositions may also contain conventional additives such as antioxidants, antistatic agents, glass fibers, impact modifiers, fillers (e.g. mica, talc, etc.), colorants, UV stabilizers, hydrolysis stabilizers. and can also be mixed with flame retardants. Particularly useful as flame retardants are the alkali metal and alkaline earth metal salts of sulfonic acids (particularly aromatic sulfonic acids and perfluoroalkylsulfonic acids), which are described, for example, in U.S. Pat.
．． 393,1100.3978024.3948851
．． 592690B, 3919167.3909490X
3953396.3953399.3917559.
See US Pat. Nos. 3,951,910 and 3,940,366. In addition, when a sulfonate salt (particularly a potassium salt of diphenylsulfone-6-sulfonic acid) is present in such a composition, the stabilizer TBPP for the thermal stability of the composition
It is interesting to note that the effect of is found to be substantially greater than in the absence of the sulfonate.

The present invention will be explained in more detail by the following examples.
The scope of the present invention is not limited thereby.

Preparation Example 1 In a reactor equipped with a pA-like stirrer, 10 t of deionized water, 16 t of methylene chloride, 1910 f (&36 mol) of bisphenol A124-triethylamine, '5.
4f sodium gluconate and 6s y (0,4
3 mol) of pt-butylphenol was charged. While stirring the reaction mixture, a 25% solids (wt) solution of a mixture of 92.6% terephthaloyl dichloride and 1621% isophthaloyl dichloride dissolved in methylene chloride was added over 15 minutes. During addition,
pH'(il-8,5
-11.5. After all the acid chloride has been added, the pH is brought to 9 by the addition of aqueous sodium hydroxide.
．． Phosgene was introduced over a period of 15 minutes at a rate of 36 f7 minutes, adjusting the temperature between 5 and 12 minutes.

After the completion of phosgene introduction, 6t of methylene chloride was added,
The brine layer was centrifuged and the resin solution was washed with aqueous acid and then water. After the resin was vapor precipitated, it was dried at about 240° C. in a nitrogen flow, moving bed dryer. The resin product was fed into an extruder operating at a temperature of about 600 ℃ below and extruded into strands, which were then shredded into pellets. The pellets thus obtained were injection molded under about 620 to 650 mm to form test specimens measuring approximately 2 inches by 3 inches.

The Kasha index (K-K) is a measure of melt viscosity. The Kasha index was measured as follows. 72 resin dried at 125° C. for at least 90 minutes to a modified Tinius-Olesen (T
in1 u melon - o1 day en) Introduced into a T3 type melt index measuring device. Keep the temperature inside the device at 300℃,
The resin is then heated to this temperature for 6 minutes. 6
After 1 minute, use a 0.1865 inch radius plunger to
By applying a force of 7.7 bonds, the resin has a radius of 0.
04 j Extrude through 25 inch orifice. Then, the time required for the plunger to move by 2 inches is measured in units of 1/ioo seconds, and this value is taken as the Kacha index.

For each test system used, the intrinsic viscosity (I.

(2)) were measured at 25°C in methylene chloride.

In addition, the light transmittance (%T
) was measured. Transmittance measurements were made at #OkaKani in the early stage.
After the molded product is subjected to autoclave treatment for a certain period of time, 7
I also did this after leaving it for 2 hours.

Yellowness index (Y, 1.) is ASTM D-1825
Measured according to

The phosphorous ester used in the comparative example was diphosphorous his(2,4-di-t-butylphenyl)pentae IJ).
It was Little. Its structural formula is as follows.

The molecular weight of this phosphorous acid ester (hereinafter referred to as BPBT) is 604. Note that the molecular weight of TBPP is 647. Therefore, it can easily be seen that in order to obtain phosphorous esters having the same number of phosphorus atoms, approximately twice the amount of TBPP (-2) as compared to BPKT is required.

In the above test examples, the same weight of phosphite stabilizer was used. As a result, TBPP is more effective than the near-green compound BPBT in imparting hydrolytic stability as indicated by a reduction in permeability and intrinsic viscosity after autoclaving. Moreover, some changes are observed in the yellowness index.

In the above table, even if the same weight of phosphorous ester is added, and in Example 2, 1.5 times the weight of TBPP is added, the melt viscosity, which is a measure of thermal stabilization, is hardly affected. do not have. However, in the second batch of Preparation Example 1, a polymer with a higher melt viscosity as indicated by the Cassis index was obtained. The test results regarding this are as follows.
It is.

Table 2 Comparative Example 5N 0.03 BPBT 667
80 5.0 Example 4 a O,03TBP
P 76410 6.3 Comparative Example 4 a
0.06BPTjT 534B5 4
．． 4 Example 5 a G, 06 TBPP
84495 B, Oa) These compositions also contained 0.10% (by weight) cyclohexyl epoxide.

As evidenced by the above data, the melt viscosity as indicated by the Cassis index is significantly higher with the phosphorous ester of the present invention, TBPP, than with BPKT. These results indicate that the amount of phosphorous acid or phosphite bonds present in the TBPP composition is
This is observed even though the amount is only about half that of the ET composition. If equal amounts of phosphite linkages are present in the composition, the difference in melt viscosity will be even greater. That is, the melt viscosity provided by TBPP in Example 5 is much higher than that in Comparative Example 3. In contrast, doubling the amount of BPETO actually causes a decrease in thermal stability. Note that the yellowness index when using TBPP is not as good as when using BPKT.

The difference in thermal stabilization effect is even greater in the presence of aromatic sulfonate flame retardants. Please refer to the table below in this regard.

Table 5 Comparative Example 5 c 0.03 BPET
62340 Example 6 c O,03TBPP
82870C) These compositions also contain 0
10% (by weight) cyclohexyl epoxide and 50%
It also contained ppm of aromatic sulfonic acid potassium salt.

As shown by the data above, the thermal stabilization provided by TBPP in the presence of sulfonate flame retardants is
The problem is also noticeable when PET is used. Furthermore, T.B.
The heating strain temperature under load when using PP was also significantly higher than when using BPET.

In the table below, the same copolyester carbonates were used in each test group, but they belonged to different batches of Preparation Example 1.

These tests show the results of comparing three types: no addition of phosphite, addition of BPET, and addition of TBPP.

Table 4 Comparative Example 5d -53580508756,7 Comparative Example baQ, 03 BPBT 44070 4
0B80 0.1 real 7jai example SeL [103TB
PP 51430 50330 5.8 Comparative Example 7° -3886036470-Comparative Example 880
．． 03 BPFiT 34410 31860
Example 7° 0.03 TBPP 44
250 41570.

d) These compositions also contained olo (by weight) % cyclohexyl epoxide, silicone oil, aromatic sulfonate flame retardant and an additive package for blue coloring.

e) As in case d above, but the blue coloring additive package was replaced by a brown coloring additive package with a much higher concentration.

As shown by the above data, TBPP is far superior to BPET in preventing heat-induced decreases in melt viscosity in all test runs of 12 minutes, 6 minutes, and 12 minutes. The yellowness index of the BPBT system is better than that of the TBPP system, but the yellowness index of the TBPP system is also better than the case without phosphorous acid ester.

Preparation Example 2 326 deionized water in a reactor equipped with a mechanical stirrer,
65't methylene chloride, 7.6 kg (554 moles)
bisphenol A, '100-triethylamine,
17y sodium gluconate and 125f (0,8
3 mol) of p,-t-butylphenol was charged.

While stirring the reaction mixture, add 5.08 kli (2
A 30% (by weight) solids solution of 5 mol) of inphthaloyl dichloride in methylene chloride was added over a period of 10 minutes. During the acid chloride addition, the pH was kept within the range 9-10 by addition of 25% aqueous sodium hydroxide. The mixture thus obtained is hydroxylated) IJ
Phosgene was introduced at a rate of 1202/min over a period of about 15 minutes while the pH was adjusted to 10-12 by addition of an aqueous solution of aluminum. After the end of the phosgene introduction, 10 t of methylene chloride was added, the brine layer was centrifuged off, and then the resin solution was washed with an aqueous acid solution and then with water. After total resin vapor precipitation, it was dried in a nitrogen fluidized bed dryer at about 240 ℃. This resin mixture was fed into an extruder operating at a temperature of about 600 ℃ below and extruded into strands, which were then shredded into pellets. Approximately 620 pellets were obtained in this way. Test specimens having dimensions of approximately 2 inches by 3 inches by inches were formed by injection molding. The following compositions were prepared and tested as described above. The results are as follows.

Table 5 Phosphite ester test example (% by weight) Kashiju index Yellowness index Comparative example 9a-' 48050 9.6 Comparative example 10a 0.03 BPET 559
55 8.7 Example 8 ao, 03 TBP
P 58810 6.7 Example 9 a
O, []6 TBPP 60240
6.4a) These compositions are 1, 0.10 (by weight)
% of cyclohexyl peroxide.

As shown in the table above, TBPP provides better thermal stabilization than when it does not contain a phosphite or when it contains the closely related phosphite BPBT. Moreover, the yellowness index of compositions containing TBPP is better than other compositions.

This good color quality means that compared to BPET, T
This is in contrast to the previous results, which show that the color is slightly inferior when using BPP.

The hydrolytic stability test results, as shown below, demonstrate that a unique improvement in hydrolytic stability is obtained alongside an improvement in melt viscosity. In addition, the time in the table represents the autoclave treatment time under 250℃.

Table 6 Comparative Example 9 0 84,7 72,5
54.6 (5 Comparative Example 10 0.03BPET, 8
5.2 71.644.7 (5 Example 8 0.
03TBPP 85.6 81.4 77.0
51.7 Example 9 0.06TBPP 86,6
82.3 80,4 64.4 In summary, TBPP is clearly effective in providing thermal stabilization of copolyestercarbonates as indicated by changes in melt viscosity, an effect that The effect is not inferior to that of BPET, which is a phosphorous ester.

Additionally, TBPP
Hydrolytic stabilizing properties are also clearly present.

Furthermore, the increased stability shown in the presence of various additive packages in the resin, and especially in the presence of aromatic sulfonates, demonstrates the unique effectiveness of TBPP.

Claims (1)

Claims: 1. A composition comprising a copolyester carbonate mixed with an effective amount of tris(2,4-di-t-butylphenyl) phosphite for thermal stabilization. 2. The composition according to claim 1, wherein the copolyester carbonate is an aromatic copolyester carbonate. 5. The copolyester carbonate is derived from (1) a dihydric phenol, (2) an acid selected from terephthalic acid, isophthalic acid, reactive derivatives of each acid and mixtures thereof, and (3) a carbonate precursor. A composition according to claim 2. 4. The composition according to claim 3, wherein the reactive derivative is an acid dichloride. 5. The composition according to claim 4, wherein the dihydric phenol is bisphenol A. 6. The composition of claim 1, wherein the amount of tris(2,4-di-t-butylphenyl) phosphite is from about 101 to about 50% (by weight) based on the copolyester carbonate. . 7. The composition of claim 6, wherein the amount of tris(2,4-di-t-butylphenyl) phosphite is from about 0.03 to about 0.3o. & The composition according to claim 5, which contains an effective amount of an alkali metal salt or an alkaline earth metal salt of an aromatic sulfonic acid for flame retardation.