JPH05239203A - Aromatic polycarbonate and its production - Google Patents

Abstract

PURPOSE:To improve low-temp. impact resistance, transparency, flowability, etc., by reacting an aromatic dihydroxy compound with a carbonate precursor in the presence of a specific mol.wt. regulator. CONSTITUTION:An aromatic dihydroxy compound is reacted with a carbonate precursor in the presence of a mol.wt. regulator consisting of a monohydric phenol represented by formula I (wherein R1 and R2 each is H, an alkyl, a cycloalkyl, an aryl, or a halogen) to obtain an aromatic polycarbonate which has a backbone comprising a repeating unit represented by formula II (wherein Ar is a divalent aromatic group), with 5-100mol% of the terminal groups each being an (un)substituted menthanylphenyl group represented by formula III and 95-0mol% thereof being at least one of hydroxy, arylcacbonate, and alkylcarbonate groups. The polymer has a weight-average mol.wt. of 2,000-300,000.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an aromatic polycarbonate and a method for producing the same. More specifically, the present invention relates to an aromatic polycarbonate having an improved balance of fluidity and impact resistance as compared with conventional aromatic polycarbonates, and an efficient production method thereof.

[0002]

2. Description of the Related Art Aromatic polycarbonate is used in many applications because it is a resin having excellent heat resistance, impact resistance and transparency. However, the aromatic polycarbonate has a drawback that the fluidity at the time of molding is inferior, and the fluidity has been improved from the past.

For example, the fluidity has been improved by lowering the molecular weight of aromatic polycarbonate such as disc grade. However, in this case, although the fluidity is improved, there is a drawback that the greatest characteristic of the aromatic polycarbonate, the impact resistance is lowered and the application range is limited. Further, attempts have been made to improve the impact resistance of an aromatic polycarbonate having a relatively low molecular weight and good fluidity by forming the terminal group of the aromatic polycarbonate into a specific structure. For example, as a terminal group,
Method using phenoxy group, pt-butylphenoxy group, p-cumylphenoxy group (JP-A-1-24501)
6), a phenoxy group, a pt-butylphenoxy group,
A method using a p-cumylphenoxy group or a chromanyl group (JP-A-3-231919) has been tried. However, even with these methods, the improvement of the balance between fluidity and impact resistance is still insufficient, and it cannot be used in specific applications.

[0004]

In view of the above situation, the present inventors have found that an aromatic polycarbonate having an excellent balance of fluidity and impact resistance, and particularly having excellent impact resistance even in a low molecular weight region and having a flowability. We have conducted intensive research to develop aromatic polycarbonate that is well balanced with properties. As a result, surprisingly, when the substituted or unsubstituted mentanylphenyl group represented by the formula (2) is used as the terminal group, an aromatic polycarbonate having an excellent balance of fluidity and impact resistance can be obtained. They have found the present invention and reached the present invention.

[0005]

That is, the present invention has a main chain composed of a repeating unit represented by the formula (1),

[0006]

[Chemical 4]

5 to 100 mol% of the terminal group is a substituted or unsubstituted mentanylphenyl group represented by the formula (2),

[0008]

[Chemical 5]

95 to 0 mol% of the terminal groups consist of one or more kinds of terminal groups selected from a hydroxyl group, an aryl carbonate group and an alkyl carbonate group, and a weight average molecular weight of 2,000 to 300,000. And an aromatic polycarbonate and a method for producing the same. The aromatic polycarbonate of the present invention comprises a repeating unit represented by the following formula.

[0010]

[Chemical 6]

It has a main chain of In the formula, Ar is a divalent aromatic residue, and examples thereof include phenylene, naphthylene, biphenylene, pyridylene, and those represented by the formula (A).

[0012]

[Chemical 7]

[In the formula, Ar ⁵ and Ar ⁶ are each an arylene group, for example, phenylene, naphthylene,
It represents a group such as biphenylene or pyridylene, and Y is an alkylene group or a substituted alkylene group represented by the following general formula. ]

[0014]

[Chemical 8]

Further, the divalent aromatic residue represented by the formula (5) may be contained as a copolymerization component.

[0016]

[Chemical 9]

[Wherein Ar ³ and Ar ⁴ are the same as defined above, Z is a mere bond, or —O—, —CO—, —S
_{-, - SO 2 -, -} CO 2 -, - CON (R 1)
A divalent group such as (R ² )-, (R ¹ and R ² are the same as the above). Examples of these divalent aromatic residues include those represented by Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3.

[0018]

[Chemical 10]

[0019]

[Chemical 11]

[0020]

[Chemical 12]

Among them, the one represented by the following formula is a preferable example.

[0022]

[Chemical 13]

Particularly, those containing 85 mol% or more of the repeating unit in which the chemical formula 4 is Ar are preferable. The aromatic polycarbonate of the present invention has a substituted or unsubstituted menthanylphenyl group represented by the formula (2) at its molecular end.

[0024]

[Chemical 14]

In the formula (2), R ₁ and R ₂ are hydrogen, an alkyl group, a cycloalkyl group, an aryl group and halogen. The bonding position to the benzene ring is ortho, meta,
It may be at any position in the para position or a mixture thereof. The configuration of the cyclohexyl ring, the benzene ring, and the methyl group may be either cis or trans, or a mixture thereof. Specifically, the following examples can be given.

[0026]

[Chemical 15]

The cis-form, trans-form, and mixture thereof are preferably used. To the aromatic polycarbonate of the present invention, one or more terminal groups selected from a hydroxyl group, an aryl carbonate group and an alkyl carbonate group can be bonded together with the terminal of the formula (2). The aryl carbonate group end is

[0028]

[Chemical 16]

It is represented by, and as a concrete example, for example,

[0030]

[Chemical 17]

And the like. The alkyl carbonate group terminal is represented by —O—R ³ (wherein R ³ is a linear or branched alkyl group having 8 to 20 carbon atoms), and specific examples include, for example,

[0032]

[Chemical 18]

And the like. Of these, a phenyl carbonate group, a pt-butylphenyl carbonate group, a p-cumylphenylphenyl carbonate group and the like are preferably used. Since the hydroxyl group end lowers heat resistance and hot water resistance, it is preferable that the number of hydroxyl group ends is as small as possible. The ratio of the terminal of formula (2) to all the terminals of the aromatic polycarbonate of the present invention is in the range of 5 to 100 mol%. 5 mol%
If it is less than [1572, the effect of improving impact resistance is small, which is not preferable. It is preferably in the range of 10 to 100 mol%, and more preferably in the range of 20 to 100 mol%.

Further, the molecular weight of the aromatic polycarbonate of the present invention has a weight average molecular weight of 2,000 to 300,000.
0, preferably 10,000-100,
000, more preferably 15,000-60,00
It is in the range of 0. Next, the manufacturing method according to the present invention will be described. The aromatic polycarbonate of the present invention can be produced by a known method using the monophenol represented by the formula (3) as a molecular weight modifier. Specifically, a known method of reacting an aromatic dihydroxy compound and a carbonate precursor, for example, an interfacial polymerization method of reacting an aromatic dihydroxy compound and phosgene (phosgene method), an ester of reacting an aromatic dihydroxy compound and diphenyl carbonate It can be produced by a method such as an exchange method (melting method) or a method of solid-phase polymerizing the crystallized carbonate prepolymer.

The monophenol of the formula (3) used in the present invention is

[0036]

[Chemical 19]

In the formula, R ₁ and R ₂ are hydrogen, an alkyl group, a cycloalkyl group, an aryl group and halogen. The bonding position to the benzene ring is ortho, meta,
It may be at any position in the para position or a mixture thereof. The configuration of the cyclohexyl ring, the benzene ring, and the methyl group may be either cis or trans, or a mixture thereof. Specific examples include the following.

[0038]

[Chemical 20]

The cis-form, trans-form, and mixture thereof of
It is preferably used. In the present invention, other molecular weights
Modulators can also be used. For example, R ³-OH (formula
Medium, R³Is a straight-chain or branched alkyl having 8 to 20 carbon atoms
Group) and Ar²-OH (in the formula, Ar²Is a monovalent aromatic residue
Basis. The aromatic ring may be substituted. )
Rucols and phenols can be used. An example
For example, as a specific example,

[0040]

[Chemical 21]

And the like. Usually, phenol, p-
T-butylphenol, p-cumylphenol and the like are often used. The amount of these molecular weight regulators used is determined by the desired molecular weight and the ratio of the terminal structure. The aromatic dihydroxy compound used for producing the aromatic polycarbonate of the present invention is not particularly limited, and examples thereof include those represented by the formula (6).

[0042]

[Chemical formula 22]

In the formula, Ar is a divalent aromatic residue, and examples thereof include phenylene, naphthylene, biphenylene, pyridylene, and those represented by the formula (7).

[0044]

[Chemical formula 23]

Further, the aromatic dihydroxy compound represented by the formula (8) may be used as a copolymerization component.

[0046]

[Chemical formula 24]

Examples of Ar of these aromatic dihydroxy compounds include those represented by Chemical formulas 11, 12, and 13.

[0048]

[Chemical 25]

[0049]

[Chemical formula 26]

[0050]

[Chemical 27]

Of these, 2,2-bis (4'-hydroxyphenyl) propane, bisphenol A and substituted bisphenol A's are preferable, and these are particularly preferable.
It is preferable to use mol% or more. It is also possible to use a trifunctional or higher functional monomer in order to introduce a branched structure.

When the aromatic polycarbonate of the present invention is used, it is desirable to add a phosphorus-based heat stabilizer as in the case of ordinary polycarbonate. Examples of the phosphorus-based heat-resistant stabilizer used include diphenyl hydrogen phosphite, bis (nonylphenyl) hydrogen phosphite, phosphite diesters such as bis (2,4-di-t-butylphenyl) hydrogen phosphite, Tris (2,4-di-t-butylphenyl) phosphite,
Trisnonylphenylphosphite, trisdinonylphenylphosphite, triphenylphosphite, bis (nonylphenyl) pentaerythritol-diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite, Phosphite triesters such as bis (2,4-di-t-butylphenyl) pentaerythritol-diphosphite,
Organic phosphites such as tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenylenediphosphinate can be mentioned. These may be used alone or in combination. Above all, a combination of phosphite diesters and phosphite triesters is preferably used.

Further, the aromatic polycarbonate of the present invention may be blended with a usual polycarbonate in order to adjust the ratio of end groups, fluidity, balance of physical properties and the like. In the present invention, other heat stabilizers, phenolic antioxidants and additives such as flame retardants, weather resistance agents, lubricants, UV absorbers, dyes, colorants such as pigments, fillers, GF, C
Fillers such as F may be added.

The present invention will be described in detail below with reference to examples. Measurement of weight average molecular weight (Mw) 0.8w with GPC (HLC8020 manufactured by Toso Corporation)
Measured with t% methylene chloride solution. Create a calibration curve using polystyrene standards. It was calculated by the following formula. (Polycarbonate Mw) = 0.3519 × (Polystyrene Mw) ^1.0388 Developing solvent is THF. Column is Toso-made TSK-GEL
A combination of G5000HXL and G4000HXL was used. NMR measurement using 270 MHz (GX270 manufactured by JEOL Ltd.)
It measured by S standard and a deuterated chloroform solvent. SFD molding temperature 300 ° C, mold temperature 90 ° C, injection pressure 1000
The flow length [mm] was measured under the condition of kg / cm ² using a mold of 2 mm thickness × 10 mm width × Archimedes spiral. IZOD Impact Strength Performed at 3.2 mm thickness according to ASTM D-256. For the low temperature IZOD, a test piece left at a predetermined temperature for 24 hours in a refrigerator was taken out and rapidly measured. The evaluation results were expressed by the number of ductile fractures during the measurement of 10.

[0055]

【Example】

[0056]

Example 1 1.71 kg of bisphenol A (7.5 m
ol) dissolved in a 12.3% NaOH aqueous solution (5.9 L) and methylene chloride (5.7 L) into a 30 L reactor equipped with a charging port, a phosgene blowing tube, a thermometer and a stirrer.
Phosgene 1.04 while stirring at a temperature of ~ 25 ° C
kg (10.5 mol) was bubbled in in about 2 hours. Then, p-menthanylphenol of Chemical formula 10 (cis / trans mixture = 7/3)

[0057]

[Chemical 28]

150 mL of a 10% NaOH aqueous solution in which 0.1 kg (0.45 mol) was dissolved was added, and after 10 minutes,
3.5 g (0.035 mol) of triethylamine was added. Then, an aqueous solution 24 in which 180 g of NaOH was dissolved
0 mL was added and stirred for about 3 hours to complete the reaction. After the reaction was completed, the aqueous phase was separated. The organic phase was diluted with methylene chloride, washed with a 5% aqueous hydrochloric acid solution, and then washed several times with water to remove the electrolyte. Then, methylene chloride was removed to give Mw 23,0.
00 aromatic polycarbonate was obtained. When the obtained aromatic polycarbonate was analyzed by NMR, it was found to be bisphenol-A polycarbonate having approximately 100% p-menthanylphenoxy group terminal of Chemical formula 11.

[0059]

[Chemical 29]

[0060]¹Chemical shift in H-NMR (TMS
(Standard) has a main chain benzene ring of 7.26 ppm, 7.1
6 ppm, propylidene group proton 1.68 pp
m, isopropyl terminal p-menthanylphenoxy group
The methyl proton of the group is 0.78 ppm (trans form),
It was confirmed at 0.91 ppm (cis form). Carbonate group
Is ¹³It was confirmed by C-NMR at 152.1 ppm.

To 100 parts by weight of the obtained aromatic polycarbonate was added trisnonylphenyl phosphite.
After adding 02 parts by weight, pelletizing by extrusion at 270 ° C.,
Test pieces were prepared by injection molding at 300 ° C. to evaluate the physical properties. The evaluation results are shown in Table-1.

[0062]

[Example 2] The same procedure as in Example 1 was repeated except that p-cumylphenol and p-menthanylphenol were used instead of 0.1 kg of p-menthanylphenol.
22,800, the ratio of end groups is p-cumylphenoxy group:
An aromatic polycarbonate having a p-menthanylphenoxy group of 12:88 was obtained.

Physical properties of the obtained aromatic polycarbonate were evaluated in the same manner as in Example 1. Table the evaluation results
-1.

[0064]

[Example 3] The same procedure as in Example 1 was repeated except that pt-butylphenol and p-menthanylphenol were used instead of 0.1 kg of p-menthanylphenol.
An aromatic polycarbonate having an Mw of 22,700 and a terminal group ratio of p-t-butylphenoxy group: p-menthanylphenoxy group = 21: 79 was obtained.

Physical properties of the obtained aromatic polycarbonate were evaluated in the same manner as in Example 1. Table the evaluation results
-1.

[0066]

Example 4 In a 30 L reactor having a stirrer, a thermometer, a nitrogen inlet, an exhaust port, a vacuum port and a lower outlet, 11.4 kg (53.3 mol) of diphenyl carbonate,
Bisphenol A 11.4 kg (50 mol), p-menthanylphenol (cis / trans mixture = 7/3)
Charge 0.6 kg (2.6 mol), under a nitrogen stream 23
After reacting at 0 ° C. for 3 hours, the pressure was switched to reduced pressure, and the degree of vacuum was increased stepwise from normal pressure over 1 hour to carry out reaction at 1 mmHg for 1 hour. Then, the mixture was poured into 20 L of acetone through the lower outlet and crystallized overnight. Filter this,
The crystallized aromatic polycarbonate powder was obtained by vacuum drying (80 ° C. × 5 hours).

The crystalline aromatic polycarbonate powder was placed in a turnbull dryer and rotated while flowing 10 NL / Hr of nitrogen gas to reduce the pressure to 2-3 mmHg, gradually raise the temperature, and solidify at 220 ° C. Polymerization was carried out for 12 hours to obtain an aromatic polycarbonate having Mw22500.
When analyzed by NMR, the main chain was a polycarbonate derived from bisphenol A, and the end groups had a ratio of hydroxyl group: phenoxy group: p-menthanylphenoxy group of 3:28:69, respectively.

With respect to 100 parts by weight of the obtained aromatic polycarbonate, 0.001 part by weight of bis (nonylphenyl) hydrogenphosphite and tris (2,4-di-) were used.
After adding 0.025 parts by weight of t-butylphenyl) phosphite, extrusion pelletization was performed at 270 ° C., and a test piece was prepared by injection molding at 300 ° C. to evaluate the physical properties. The evaluation results are shown in Table-1.

[0069]

Comparative Example 1 Diphenyl carbonate 12.0 kg (5
6.1 mol), 11.4 kg of bisphenol A (50
mol) and use the same procedure as in Example 4, except that Mw
22,000 aromatic polycarbonates were obtained. It was a bisphenol A polycarbonate having an end group ratio of hydroxyl group: phenoxy group = 2: 98.

To 100 parts by weight of the obtained aromatic polycarbonate, 0.002 parts by weight of diphenyl hydrogen phosphite and 0.02 parts by weight of trisnonylphenyl phosphite were added, and then extrusion pelletized at 270 ° C. and 300 ° C. A test piece was prepared by injection molding and the physical properties were evaluated. The evaluation results are shown in Table-1.

[0071]

[Comparative Examples 2 and 3] Aromatic polycarbonate A (Mw 22,300, terminal group ratio hydroxyl group: t
-Butylphenoxy group = 1: 99, Comparative Example 2), and aromatic polycarbonate B (Mw22,100, ratio of end group hydroxy group: p-cumylphenoxy group = 1: 99,
A test piece of Comparative Example 3) was injection-molded at 300 ° C. to evaluate the physical properties. Evaluation result. Shown in Table-1.

[0072]

Example 5 11.6 kg of diphenyl carbonate (5
4.3 mol), bisphenol A 11.4 kg (50
mol) and p-menthanylphenol (cis, trans mixture = 7/3) 0.53 kg (2.3 mol) were used in the same manner as in Example 4 to obtain an aromatic polycarbonate with Mw18,600.

When analyzed by NMR, the main chain was a polycarbonate derived from bisphenol A, and the end groups were
The ratio of hydroxyl group: phenoxy group: p-menthanylphenoxy group was 2:40:58, respectively. Physical properties of the obtained aromatic polycarbonate were evaluated in the same manner as in Example 4. The evaluation results are shown in Table-1.

[0074]

Comparative Example 4 12.1 kg of diphenyl carbonate (5
6.8 mol), bisphenol A 11.4 kg (50
mol), and using M in the same manner as in Example 4.
An aromatic polycarbonate having w18,500 and a terminal group ratio of hydroxyl group: phenoxy group = 2: 98 was obtained.

Physical properties of the obtained aromatic polycarbonate were evaluated in the same manner as in Example 4. Table the evaluation results
-1.

[0076]

Comparative Example 5 12.1 kg of diphenyl carbonate (5
4.3 mol), bisphenol A 11.4 kg (50
mol), 0.5 kg of cumylphenol (2.4 mo
Mw1 in the same manner as in Example 4 except that l) is used.
An aromatic polycarbonate having a terminal group ratio of 8,300 and a hydroxyl group: phenoxy group: p-cumylphenoxy group = 2: 40: 58 was obtained.

The physical properties of the obtained aromatic polycarbonate were evaluated in the same manner as in Example 4. Table the evaluation results
-1.

[0078]

[Table 1]

[0079]

INDUSTRIAL APPLICABILITY As described above, the aromatic polycarbonate of the present invention is excellent in the balance between fluidity and impact resistance, and is particularly excellent in low temperature impact resistance and impact resistance at low molecular weight. Further, since it is also excellent in color, transparency, heat resistance, etc., it can be suitably used for applications requiring high fluidity, for example, precision parts such as cameras.

Claims (2)

[Claims] 1. A main chain comprising a repeating unit represented by the following formula (1): 5 to 100 mol% of the terminal group is a substituted or unsubstituted mentanylphenyl group represented by the following formula (2): 95 to 0 mol% of the end groups are composed of one or more end groups selected from a hydroxyl group, an aryl carbonate group and an alkyl carbonate group, and have a weight average molecular weight of 2,000.
An aromatic polycarbonate, which is 0 to 300,000. 2. A method for producing an aromatic polycarbonate, which comprises using a monophenol represented by the following formula (3) as a molecular weight modifier in producing the aromatic polycarbonate. [Chemical 3]