JP2002146006A - Linear polycarbonate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a linear polycarbonate with improved flowability, without leaving any adhered material to a mold on injection molding, and the molded article has a good appearance. SOLUTION: This linear polycarbonate is produced using as a terminator a long chain monoalkyl phenol having an alkyl group containing 19 to 35 carbon atoms on the average, and has an un-reacted long chain monoalkyl phenol content of <=300 ppm and a viscosity-average mol.wt. of 14,000 to 30,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a linear polycarbonate, and more particularly, to a molded product having improved fluidity, free from deposits on a mold during injection molding, and having a good appearance. It relates to a linear polycarbonate.

[0002]

2. Description of the Related Art Polycarbonate resins are excellent in mechanical properties (particularly, impact resistance), electrical properties, transparency and the like.
It is widely used in various fields such as A equipment, electric / electronic equipment, and construction.

[0003] In recent years, in response to demands such as thinning and enlargement of molded articles and improvement of molding cycles, it has become necessary to further improve fluidity. It is known to use long-chain alkylphenols as terminators to improve their flow properties. For example, the claims of JP-B-52-50078 disclose that an alkyl phenol, carboxylic acid or acid halide having an alkyl group having 8 to 20 carbon atoms is used as a terminal stopper. However, in the examples, there is only a description of an acid chloride having 9 to 17 carbon atoms in the alkyl group.
When the polymerization solution is washed with water, it is described that the system is emulsified to make the washing difficult, and that the heat distortion temperature of the obtained polycarbonate resin is remarkably lowered. 7-258
The claims of JP-A No. 71 disclose that an alkyl phenol having an alkyl group having 8 to 30 carbon atoms is used as a terminal stopper. However, the examples only describe alkylphenols having 18 carbon atoms in the alkyl group.

On the other hand, when injection molding is performed on a polycarbonate obtained by using a long-chain alkylphenol as a terminal terminator, deposits are found on a mold, and the molded product tends to have uneven surface.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made under such circumstances, and has improved fluidity, shows no deposits on a mold when injection-molded, and shows the appearance of a molded article. Also provides a good linear polycarbonate.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have used long-chain monoalkylphenol having a specific number of carbon atoms as a terminal terminator and obtained polycarbonate. It has been found that the object of the present invention can be met by adjusting the amount of unreacted long-chain monoalkylphenol therein. The present invention has been completed based on such findings.

That is, the gist of the present invention is as follows. 1. A viscosity average molecular weight of 14,000 to 1, which is produced using a long-chain monoalkylphenol having an alkyl group having an average carbon number of 19 to 35 as a terminal terminator and has an unreacted long-chain monoalkylphenol amount of 300 ppm or less.
30,000 linear polycarbonates. 2. 2. The linear polycarbonate according to the above 1, wherein the average carbon number of the alkyl group of the long-chain monoalkylphenol is 21 to 25.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. As the linear polycarbonate of the present invention, various ones can be mentioned.

[0009]

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A polymer having a repeating unit having a structure represented by the following formula is preferred. In the above general formula (I), X ¹ and X ² each represent a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and specific examples include a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-amyl group, isoamyl group, n-hexyl group, isohexyl group,
Examples thereof include a cyclopentyl group and a cyclohexyl group. X ¹ and X ² may be the same or different. a and b are X ¹ and X, respectively.
² represents the number of substitutions, and is an integer of 0 to 4. When plural X ^1, a plurality of X ¹ may be the same as or different from each other, if X ² is plural, X ² may be the same with or different from each other.

Y is a single bond, an alkylene group having 1 to 8 carbon atoms (eg, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylylene group, a hexylene group), an alkylidene group having 2 to 8 carbon atoms (eg, an ethylidene group) , Isopropylidene group, etc.), a cycloalkylene group having 5 to 15 carbon atoms (eg, cyclopentylene group, cyclohexylene group, etc.), a cycloalkylidene group having 5 to 15 carbon atoms (eg, cyclopentylidene group, cyclohexylidene group, etc.) ), - S -, - SO -, - SO 2 -, - O -, - CO
-Bond or formula (II-1) or formula (II-2)

[0012]

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[0013] The bond represented by Here, the linear polycarbonate refers to a polycarbonate produced without using a branching agent. The polymer is usually represented by the general formula (III)

[0014]

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(Where X ¹ , X ² , a, b and Y are
Same as above. ) And a carbonate precursor such as phosgene or a carbonate compound. That is, for example, in a solvent such as methylene chloride, in the presence of a known acid acceptor or molecular weight regulator, by the reaction of a dihydric phenol with a carbonate precursor such as phosgene, or in the presence or absence of a solvent, It can be produced by a transesterification reaction between a polyhydric phenol and a carbonate precursor such as a carbonate compound.

As the dihydric phenol represented by the general formula (III), various ones can be mentioned. Especially 2,
2-bis (4-hydroxyphenyl) propane [commonly known as
Bisphenol A] is preferred. Examples of the dihydric phenol other than bisphenol A include bis (4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; and bis (4 such as 1,2-bis (4-hydroxyphenyl) ethane. -Hydroxyphenyl) alkane, 1,1-bis (4-hydroxyphenyl) cyclohexane; bis (4-hydroxyphenyl) cycloalkane such as 1,1-bis (4-hydroxyphenyl) cyclodecane, 4,4′-dihydroxydiphenyl , Bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ether (Hydroxyphenyl) ketone etc. be able to. In addition, examples of the dihydric phenol include hydroquinone. These dihydric phenols may be used alone or in combination of two or more.

Examples of the carbonic acid ester include diaryl carbonates such as diphenyl carbonate and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate. In the present invention, when a polycarbonate is produced by reacting the dihydric phenol with a carbonate precursor, an average carbon number of 19 to 19 is used as a terminal terminator (also referred to as a molecular weight regulator).
It is essential to use a long-chain monoalkylphenol having 35 alkyl groups. If it is less than 19,
If the flowability is insufficiently improved, and if it exceeds 35, the reactivity will be poor, and the loss of long-chain monoalkylphenol will increase accordingly. Preferably, it has an average carbon number of 21 to 35, and more preferably, it has an average carbon number of 21 to 25.

The average number of carbon atoms of the alkyl group is the sum of [product of (number of carbon atoms of alkyl group) and (molar fraction)]. The above long-chain monoalkylphenols may be used alone or in combination of two or more. When two or more kinds are used in combination, the carbon number of the alkyl group is represented by the average carbon number.

Further, the long-chain monoalkylphenol has an isomer, an ortho-form, a meta-form and a para-form as isomers. The long-chain alkyl group is linear,
It may be branched. The linear polycarbonate of the present invention needs to have a viscosity average molecular weight in the range of 14,000 to 30,000 from the viewpoint of mechanical strength and moldability. Preferably, it is in the range of 15,000 to 25,000, more preferably 15,000 to 21,000. The viscosity average molecular weight (Mv) of the methylene chloride solution at 20 ° C. was measured using an Ubbelohde viscometer, and the intrinsic viscosity [η] was determined from this.
= 1.23 × 10 ⁻⁵ Mv ^0.83 .

Further, the unreacted long-chain monoalkylphenol of the linear polycarbonate of the present invention needs to be 300 ppm or less. The method for reducing the concentration to 300 ppm or less is not particularly limited. For example, in a solution method, a precipitate of polycarbonate generated in a poor solvent may be separated by filtration. If it exceeds 300 ppm, deposits are observed on the injection mold and the appearance of the molded product is not good, which is not preferable.

In the linear polycarbonate of the present invention, various additives such as an antioxidant, a lightness improver, a lubricant (release agent), a flame retardant, and the like may be used as long as the object of the present invention is not impaired. An anti-drip agent and other inorganic fillers may be appropriately contained. A composition can be prepared by blending and kneading various additives with the polycarbonate of the present invention. As the compounding and kneading method, a method applied to a usual resin composition can be applied as it is, and a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw or a multi-screw extruder having two or more screws, a co-kneader and the like can be used. The method used is preferred. The kneading temperature is not particularly limited, but is usually 240 to 34.
It is suitably selected from the range of 0 ° C.

The resin composition thus obtained can be molded by a usual molding method, for example, an injection molding method or a compression molding method to obtain a molded product.

[0023]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. (1) Preparation of long-chain monoalkylphenol [Preparation of alkylphenol (a)] In a reactor equipped with a baffle and a stirring blade, a mixture of 300 parts by mass of phenol and 1-eicosene, 1-docosene and 1-tetracosene [composition ratio ( 53.3: 40.2: 6.5] 1
The reaction raw materials and the reaction raw materials were prepared at a charge ratio of 05 parts by mass (phenol / olefin = 9/1 (molar ratio)) and 10.5 parts by mass of a strongly acidic polystyrene sulfonic acid type cationic resin (Amberlyst 15; manufactured by Rohm and Haas Co.) as a catalyst. The catalyst was charged and reacted at 120 ° C. for 3 hours with stirring. After the completion of the reaction, purification by distillation under reduced pressure,
A long-chain monoalkylphenol (a) was obtained. The average carbon number of the alkyl group of the obtained long-chain monoalkylphenol (a) was 21.

[Preparation of Alkylphenol (b)] In the preparation of the alkylphenol (a), 110 parts by mass of 1-docosene (phenol / olefin = 9/1 (molar ratio)) was used as the olefin, and the amount of catalyst was 1
An alkylphenol (b) was obtained in the same manner except that the amount was 1 part by mass. The obtained alkylphenol (b)
The average carbon number of the alkyl group was 22.

(2) Preparation of Polycarbonate Oligomer Bisphenol A is dissolved in a 5.6% by mass aqueous sodium hydroxide solution so that the bisphenol A concentration becomes 13.5% by mass to prepare a sodium hydroxide aqueous solution of bisphenol A. did.

At a flow rate of 41 l / hr of an aqueous sodium hydroxide solution of bisphenol A and 15 l / hr of methylene chloride, phosgene is continuously fed into a tubular reactor having an inner diameter of 6 mm and a length of 30 m at a flow rate of 4.0 kg / hr. Supplied. The tubular reactor had a jacket portion, and the temperature of the reaction solution was kept at 40 ° C. or lower by passing cooling water through the jacket.

The reaction solution exiting the tubular reactor is continuously introduced into a tank reactor having a baffle equipped with a swept wing and having an inner volume of 40 liters, and 2.8 liters of an aqueous sodium hydroxide solution of bisphenol A is further added thereto. / Hr, 25% by weight aqueous sodium hydroxide solution 0.07 L / hr, water 17 L / hr, 1% by weight aqueous triethylamine solution 0.32
The reaction was carried out by adding liter / hr.

The reaction solution overflowing from the tank reactor was continuously withdrawn, and the aqueous phase was separated and removed by standing, and the methylene chloride phase was collected. The concentration of the polycarbonate oligomer thus obtained was 355 g / l,
The chloroformate group concentration was 0.80 mol / liter.

(3) Production of Polycarbonate [Example 1] 12 liters of the above oligomer solution, 9.3 liters of methylene chloride were placed in a 50 liter tank-type reactor equipped with baffles, two paddle-type stirring blades and a cooling jacket.
A solution in which 587 g of alkylphenol (a), 1.35 ml of triethylamine, and an aqueous solution of bisphenol A in sodium hydroxide (580 g of NaOH and 1.98 g of sodium dithionite dissolved in 9.78 liters of water) are dissolved with 992 g of bisphenol A. ) Was added and the polymerization reaction was carried out at 300 rpm for 1 hour.

Then, after adding 10 liters of methylene chloride for dilution, the mixture is allowed to stand and separated into an organic phase containing polycarbonate and an aqueous phase containing excess bisphenol A and sodium hydroxide. And isolated. The thus obtained methylene chloride solution of the polycarbonate was successively added to a solution of 15% by volume of 0.03 mol / L sodium hydroxide aqueous solution,
After washing with 0.2 N hydrochloric acid, washing with pure water was repeated until the electric conductivity in the aqueous phase after washing became 0.1 μS / m or less.

After completion of the washing, the methylene chloride solution of the polycarbonate is concentrated to a concentration of 150 to 170 g / l, 20% by volume of n-hexane is added, and the resulting precipitate is filtered and dried to obtain a polycarbonate flake. Was. The viscosity average molecular weight, the Q value, and the amount of unreacted long-chain monoalkylphenol were measured for the flakes in the following manner, and the results are shown in Table 1.

Method for measuring physical properties of polycarbonate flakes (a) Viscosity average molecular weight (Mv) The viscosity of a methylene chloride solution at 20 ° C. was measured using an Ubbelohde viscometer, and the intrinsic viscosity [η] was determined from this. ] = 1.23 × 10 ⁻⁵ Mv ^0.83 . (B) Q value (flow value) The melt viscosity measured by an elevated flow tester was 280
The amount of molten resin flowing out of a 1 mmφ × 10 mmL nozzle under a pressure of 15.7 MPa and a pressure of 15.7 MPa is expressed in units of cc / sec.
The value increases. (C) Amount of unreacted long-chain monoalkylphenol 2 g of polycarbonate flake was dissolved in 50 ml of methylene chloride, and 250 ml of acetone was added little by little to precipitate a polymer. This was suction-filtered and concentrated, and the concentrated solution was quantified by gas chromatography (GC) after being made constant in volume with 20 ml of n-hexane. The measurement conditions are as follows.

GC body: HEWLETT PACKAR
D HP 6890 Column: DB-1 manufactured by J & W SCIENTIFIC
(15m × 0.53mmφ × 0.15μm) Temperature pattern: 40 ° C / 1 minute hold → 40 ° C / minute temperature rise → 1
Hold at 20 ° C. for 7 minutes → Raise temperature for 10 minutes / minute → Hold at 330 ° C./5 minutes Carrier gas: Helium (40 cm ³ / sec, constant flow) Injection: Splitless (2.0 μl) Injection temperature: 350 ° C. FID Detector Temperature: 350 ° C

Example 2 A polycarbonate flake was prepared in the same manner as in Example 1, except that the addition amount of the alkylphenol (a) was changed to 450 g. The viscosity average molecular weight, the Q value, and the amount of unreacted long-chain monoalkylphenol were measured in the same manner as in Example 1. The result is
It is shown in the table.

Example 3 A polycarbonate flake was prepared in the same manner as in Example 1 except that the amount of the alkylphenol (a) was changed to 392 g. The viscosity average molecular weight, the Q value, and the amount of unreacted long-chain monoalkylphenol were measured in the same manner as in Example 1. The result is
It is shown in the table.

Example 4 A polycarbonate flake was prepared in the same manner as in Example 1, except that the addition amount of the alkylphenol (b) was changed to 590 g. The viscosity average molecular weight, the Q value, and the amount of unreacted long-chain monoalkylphenol were measured in the same manner as in Example 1. The result is
It is shown in the table.

Example 5 A polycarbonate flake was prepared in the same manner as in Example 1 except that the amount of the alkylphenol (b) was changed to 455 g. The viscosity average molecular weight, the Q value, and the amount of unreacted long-chain monoalkylphenol were measured in the same manner as in Example 1. The result is
It is shown in the table.

Example 6 A polycarbonate flake was prepared in the same manner as in Example 1 except that the addition amount of the alkylphenol (b) was changed to 400 g. The viscosity average molecular weight, the Q value, and the amount of unreacted long-chain monoalkylphenol were measured in the same manner as in Example 1. The result is
It is shown in the table.

Comparative Example 1 A polycarbonate flake was prepared in the same manner as in Example 1, except that 240 g of lauric chloride was used instead of the long-chain monoalkylphenol (a). The viscosity average molecular weight and Q value were measured in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 2 A polycarbonate flake was prepared in the same manner as in Example 1, except that 302 g of palmitic acid chloride was used instead of the long-chain monoalkylphenol (a). Its viscosity average molecular weight, Q
The values were measured as in Example 1. Table 1 shows the results.

Comparative Example 3 A polycarbonate flake was prepared in the same manner as in Example 1, except that 329 g of stearic acid chloride was used instead of the long-chain monoalkylphenol (a). Its viscosity average molecular weight, Q
The values were measured as in Example 1. Table 1 shows the results.

Comparative Example 4 A polycarbonate flake was prepared in the same manner as in Example 1, except that 594 g of octadecylphenol was used instead of the long-chain monoalkylphenol (a). Its viscosity average molecular weight, Q
The values were measured as in Example 1. Table 1 shows the results.

Comparative Example 5 A polycarbonate flake was prepared in the same manner as in Example 1 except that 234 g of dodecyl p-hydroxybenzoate was used instead of the long-chain monoalkylphenol (a). The viscosity average molecular weight and Q value were measured in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 6 A polycarbonate flake was prepared in the same manner as in Example 1, except that 210 g of palmitic acid chloride was used instead of the long-chain monoalkylphenol (a). Its viscosity average molecular weight, Q
The values were measured as in Example 1. Table 1 shows the results.

Comparative Example 7 A polycarbonate flake was prepared in the same manner as in Example 1, except that 422 g of octadecylphenol was used instead of the long-chain monoalkylphenol (a). Its viscosity average molecular weight, Q
The values were measured as in Example 1. Table 1 shows the results.

Comparative Example 8 A polycarbonate flake was prepared in the same manner as in Example 1, except that 146 g of lauric chloride was used instead of the long-chain monoalkylphenol (a). The viscosity average molecular weight and Q value were measured in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 9 A polycarbonate flake was prepared in the same manner as in Example 1, except that 184 g of palmitic acid chloride was used instead of the long-chain monoalkylphenol (a). Its viscosity average molecular weight, Q
The values were measured as in Example 1. Table 1 shows the results.

Comparative Example 10 A polycarbonate flake was prepared in the same manner as in Example 1, except that 199 g of stearic acid chloride was used instead of the long-chain monoalkylphenol (a). Its viscosity average molecular weight,
The Q value was measured as in Example 1. Table 1 shows the results.

[Comparative Example 11] A polycarbonate flake was prepared in the same manner as in Example 1, except that after adding n-hexane, the mixture was concentrated without filtration and the obtained solid was dried. The viscosity average molecular weight, the Q value, and the amount of unreacted long-chain monoalkylphenol were measured in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 12 A polycarbonate flake was prepared in the same manner as in Comparative Example 1, except that after adding n-hexane, the mixture was concentrated without filtration and the obtained solid was dried. The viscosity average molecular weight, the Q value, and the amount of unreacted long-chain monoalkylphenol were measured in the same manner as in Example 1. Table 1 shows the results.

[0051]

[Table 1]

(4) Injection molding of polycarbonate Irgafos 168 (manufactured by Ciba Specialty Chemicals) as a phosphorus-based antioxidant was added to the polycarbonate flakes obtained in Examples 1 to 6 and Comparative Examples 11 and 12.
Was added and granulated at 270 ° C. to obtain pellets. The obtained pellets were heated at a cylinder temperature using a 45-ton injection molding machine (manufactured by Toshiba Machine Co., Ltd., IS45PV);
320 ° C, mold temperature; 50 ° C, injection pressure; 7.84MP
Injection molding under the conditions of a, 35 of 300 shots continuously
A molded piece having a size of 25 mm and a thickness of 3 mm was obtained. Thereafter, the presence or absence of the adhesion to the mold and the appearance of the molded product were observed.

When the pellets obtained from the polycarbonate flakes obtained in Examples 1 to 6 were used, there was no deposit on the mold and the appearance of the molded product was good. When pellets made from the polycarbonate flakes obtained in Steps 12 and 12 are used, oil-like deposits are observed in the mold, and the molded product has a surface unevenness and a uniform and smooth appearance. did not become.

[0054]

According to the present invention, it is possible to obtain a linear polycarbonate having improved fluidity, no deposit on the mold when injection molding is performed, and a good appearance of the molded product.

Continued on the front page F term (reference) 4J029 AA09 AA10 AB02 AD10 AE01 BB10A BB10B BB12A BB12B BB12C BB13A BB13B BB13C BB16A BB16B BB16C BD09A BD09B BD09C BE05A BE05B BF13 JB01B03J01 HC13

Claims (2)

[Claims] 1. A viscosity average molecular weight of 1 produced by using a long-chain monoalkylphenol having an alkyl group having an average carbon number of 19 to 35 as a terminal terminator and having an unreacted long-chain monoalkylphenol content of 300 ppm or less.
4,000-30,000 linear polycarbonates. 2. The linear polycarbonate according to claim 1, wherein the alkyl group of the long-chain monoalkylphenol has an average carbon number of 21 to 25.