JP2011148999A - Polycarbonate resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate resin having a high Tg and a high molecular weight. <P>SOLUTION: The polycarbonate resin is produced by carbonate-coupling of 1, 4-cyclohexane dimethanol with diphenyl carbonate. The resin is produced by a multi-stage melt-polycondensation process including two or more stages applied to 1, 4-cyclohexane dimethanol and diphenyl carbonate in the presence of a basic compound catalyst, a transesterification catalyst or a mixture catalyst of the two catalysts, with a charging molar ratio of the diphenyl carbonate to 1, 4-cyclohexane dimethanol of from 0.97 to 1.01. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a polycarbonate resin.

  Polycarbonate resins are used for optical materials such as CD or DVD substrates, optical films, optical sheets, various lenses or prisms because of their excellent transparency, heat resistance, low water absorption, chemical resistance, mechanical properties and dimensional stability. Widely used. Various polycarbonates using cyclohexanedimethanol are known (see Patent Documents 1 to 3). However, they are used as raw materials for polyurethane, and are low temperature, low Tg, room temperature liquids.

JP-A-6-145336 JP-A-55-56124 JP-A-5-077841

  It is an object of the present invention to provide a high Tg, high molecular weight polycarbonate resin using cyclohexanedimethanol.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have completed the present invention. That is, the present invention relates to a polycarbonate resin having a terminal OH group amount of 500 ppm or less obtained by carbonate-bonding 1,4-cyclohexanedimethanol with diphenyl carbonate.

  The polycarbonate resin of the present invention can be suitably used as a wide variety of optical materials such as optical materials, spectacle lenses, in-vehicle lenses, covers, window glass, touch panels, etc. by blending with other polycarbonates.

  For the polycarbonate resin of the present invention, a known melt polycondensation method in which 1,4-cyclohexanedimethanol and diphenyl carbonate are reacted in the presence of a basic compound catalyst, a transesterification catalyst, or a mixed catalyst composed of both is suitably used. .

  The 1,4-cyclohexanedimethanol used in the present invention is the most common production method, that is, obtained by distilling 1,4-cyclohexanedicarboxylic acid dimethyl ester after hydrogenation. It contains 30 to 40 wt% of cis isomer.

  The terminal OH group amount (terminal OH group concentration) of the polycarbonate resin of the present invention is 500 ppm or less, preferably 100 ppm or less. If the amount of terminal OH groups is too large, it reacts during blending, causing a decrease in molecular weight and coloring. These terminal OH group amounts can be achieved by adjusting the molar ratio of diphenyl carbonate and 1,4-cyclohexanedimethanol at the time of melt polymerization. Specifically, it is preferable that the charged molar ratio of diphenyl carbonate and 1,4-cyclohexanedimethanol at the time of melt polymerization is 0.97 to 1.01.

  Examples of the basic compound catalyst include alkali metal compounds and / or alkaline earth metal compounds, nitrogen-containing compounds, and the like. Examples of such compounds include organic acid salts such as alkali metal and alkaline earth metal compounds, inorganic salts, oxides, hydroxides, hydrides or alkoxides, quaternary ammonium hydroxides and salts thereof, amines, and the like. These compounds are preferably used, and these compounds can be used alone or in combination.

  Specific examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, acetic acid. Cesium, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenyl borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, hydrogen phosphate Disodium, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenyl phosphate, disodium salt of bisphenol A, 2 potassium salt, 2 cesium salt, 2 lithium salt, sodium salt of phenol, potassium salt Cesium salt, lithium salt or the like is used.

  Specific examples of the alkaline earth metal compound include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen carbonate, magnesium carbonate, calcium carbonate. Strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenyl phosphate, and the like are used.

  Specific examples of nitrogen-containing compounds include alkyl, aryl, groups, etc. such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. Secondary ammoniums such as quaternary ammonium hydroxides, triethylamine, dimethylbenzylamine and triphenylamine, secondary amines such as diethylamine and dibutylamine, primary amines such as propylamine and butylamine, 2-methylimidazole, 2 -Imidazoles such as phenylimidazole and benzimidazole, or ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, Tetrabutylammonium tetraphenylborate, basic or basic salts such as tetraphenyl ammonium tetraphenylborate, or the like is used.

As the transesterification catalyst, zinc, tin, zirconium and lead salts are preferably used, and these can be used alone or in combination. Specifically, zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin Dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead (II) acetate, lead (IV) acetate and the like are used. These catalysts are used in a ratio of 10 ⁻⁹ to 10 ⁻³ mol, preferably 10 ⁻⁷ to 10 ⁻⁴ mol, per 1 mol of the total of dihydroxy compounds.

  The melt polycondensation method according to the present invention is a method in which melt polycondensation is performed using the above-mentioned raw materials and catalyst while removing by-products by a transesterification reaction under normal pressure or reduced pressure. The reaction is generally carried out in a multistage process of two or more stages.

  Specifically, the reaction at the first stage is performed at a temperature of 120 to 220 ° C., preferably 160 to 200 ° C. for 0.1 to 5 hours, preferably 0.5 to 3 hours, at a pressure of normal pressure to 200 Torr. Let Next, the temperature is gradually raised to the final temperature of 230 to 260 ° C. over 1 to 3 hours, and the pressure is gradually reduced to 1 Torr or less of the final pressure, and the reaction is continued. Finally, the polycondensation reaction proceeds at a temperature of 230 to 260 ° C. under a reduced pressure of 1 Torr or less. When a predetermined viscosity is reached, the pressure is restored with nitrogen, and the reaction is completed. The reaction time of 1 Torr or less is 0.1 to 2 hours, and the total reaction time is 1 to 6 hours, usually 2 to 5 hours.

  Such a reaction may be carried out continuously or batchwise. The reaction apparatus used for carrying out the above reaction is equipped with paddle blades, lattice blades, glasses blades, etc. It may be a horizontal type or an extruder type equipped with a screw, and it is preferable to use a reaction apparatus in which these are appropriately combined in consideration of the viscosity of the polymer.

  After completion of the polymerization reaction, the catalyst is removed or deactivated in order to maintain thermal stability and hydrolysis stability. In general, a method of deactivating a catalyst by adding a known acidic substance is preferably performed. Specific examples of these substances include aromatic sulfonic acids such as p-toluenesulfonic acid, aromatic sulfonic acid esters such as p-toluenesulfonic acid butyl and p-toluenesulfonic acid hexyl, dodecylbenzenesulfonic acid tetra Aromatic sulfonates such as butylphosphonium salts, organic halides such as stearic acid chloride, benzoyl chloride and p-toluenesulfonic acid chloride, alkyl sulfuric acids such as dimethyl sulfate, and organic halides such as benzyl chloride are preferably used. .

  Examples of the catalyst deactivator used in the present invention include phosphoric acid, phosphorous acid, hypophosphorous acid, phenyl phosphoric acid, phenylphosphine, phenylphosphinic acid, phenylphosphonic acid, diphenyl phosphate, diphenyl phosphite, and diphenyl. Phosphine, diphenylphosphine oxide, diphenylphosphinic acid, monomethyl acid phosphate, monomethyl acid phosphite, dimethyl acid phosphate, dimethyl acid phosphite, monobutyl acid phosphate, monobutyl acid phosphite, dibutyl acid phosphate, dibutyl acid phosphite, monostearyl Phosphorus-containing acidic compounds such as acid phosphate and distearyl acid phosphate, p-toluenesulfonic acid, p-toluenesulfonic acid P-toluenesulfonate ethyl, p-toluenesulfonate propyl, p-toluenesulfonate butyl, p-toluenesulfonate pentyl, p-toluenesulfonate hexyl, p-toluenesulfonate octyl, p-toluenesulfonate phenyl And aromatic sulfonic acid compounds such as phenethyl p-toluenesulfonate and naphthyl p-toluenesulfonate.

  The addition amount of the phosphorus-containing acidic compound and aromatic sulfonic acid compound is 1/5 to 20 times the neutralization equivalent to the alkali metal compound and / or alkaline earth metal compound catalyst, preferably 1/2 to 15 Double the amount. If the amount added is too small, the desired effect cannot be obtained, and if it is excessive, the heat resistance and mechanical properties may be deteriorated, which may not be appropriate.

  Aromatic sulfonic acid phosphonium salts can also be suitably used. For example, benzenesulfonic acid tetrabutylphosphonium salt, p-toluenesulfonic acid tetrabutylphosphonium salt, butylbenzenesulfonic acid tetrabutylphosphonium salt, octylbenzenesulfonic acid tetra Examples thereof include butylphosphonium salt, tetrabutylphosphonium dodecylbenzenesulfonate, tetramethylphosphonium dodecylbenzenesulfonate, tetraethylphosphonium dodecylbenzenesulfonate, tetrahexylphosphonium dodecylbenzenesulfonate, and the like.

  The amount of the aromatic sulfonic acid phosphonium salt added is 1 to 300 ppm, preferably 10 to 100 ppm, based on the polycarbonate resin. If the amount added is too small, the desired effect cannot be obtained, and if it is excessive, the heat resistance and mechanical properties may be deteriorated, which may not be appropriate.

  After deactivation of the catalyst, a step of devolatilizing and removing low boiling point compounds in the polymer at a pressure of 0.1 to 1 Torr and a temperature of 200 to 350 ° C. may be provided. For this purpose, paddle blades, lattice blades, glasses A horizontal apparatus provided with a stirring blade having excellent surface renewability such as a blade or a thin film evaporator is preferably used. In this way, the polycarbonate resin of the present invention can be obtained.

  The weight average molecular weight (Mw) in terms of polystyrene of the polycarbonate resin of the present invention is preferably 10,000 to 200,000, more preferably 15,000 to 150,000. When Mw is smaller than 10,000, a polycarbonate resin composition obtained by blending (hereinafter sometimes referred to as “blend resin composition”) may become brittle. When Mw is larger than 200,000, the melt viscosity becomes high and the conditions for blending may become severe, and the injection molding conditions of the blend resin composition become severe, and silver may occur in the molded product.

  The MFR (260 ° C., 2.16 kg load) of the polycarbonate resin of the present invention is not particularly limited, but is preferably 10 to 100 g / 10 minutes, more preferably 20 to 80 g / 10 minutes.

  Various known additives can be added to the polycarbonate resin of the present invention depending on the purpose within a range that does not impair the physical properties thereof. For example, heat stabilizer, hydrolysis stabilizer, antioxidant, pigment, dye, reinforcing agent, filler, ultraviolet absorber, lubricant, mold release agent, crystal nucleating agent, plasticizer, fluidity improver, antistatic It is preferable to add an agent, an antibacterial agent and the like.

The blend resin of the present invention can be formed into a molded article by injection molding, compression molding, extrusion molding, hollow molding or the like after being pelletized. A conventionally known method can be used as the molding method.
Specific examples of the molded product thus obtained include flat plates, discs (injection and compression molding) pellets, films (extrusion molding), bottles (hollow molding), and the like.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition, the measured value of the Example was measured using the following method or apparatus.
1) Weight average molecular weight (Mw): Using GPC (Shodex GPC system 11), it was measured as a polystyrene equivalent molecular weight (weight average molecular weight: Mw). THF was used as a developing solvent.
2) Glass transition temperature (Tg): Measured at 10 ° C./min by SSC-5200 (DSC) of a differential thermal scanning calorimeter (manufactured by Seiko Denshi Kogyo).
3) Terminal OH group determination: 0.25 g of resin was dissolved in 10 mL of dry methylene chloride, then 40 μL of triethylamine was added and reacted with 0.04 g of anthraquinone carboxylic anhydride at room temperature, followed by washing with water and excess anthraquinone carboxyl. The acid anhydride was removed, methylene chloride was further removed from the organic layer, and the obtained solid was analyzed by GPC. The OH concentration was determined from the peak area by a one-inspection curve method using OH-end known samples (detector UV; 325 nm).

Example 1
10.600 kg (73.5 mol) of cyclohexanedimethanol (Eastman Chemical Co., Ltd.), 15.431 kg (72.0 mol) of diphenyl carbonate, and 0.0152 g (1.81 × 10 ⁻⁴ mol) of sodium hydrogen carbonate The mixture was placed in a 50 liter reactor equipped with a stirrer and a distillation apparatus, and heated to 215 ° C. and stirred for 1 hour under a nitrogen atmosphere of 760 Torr.

  Thereafter, the degree of vacuum was adjusted to 150 Torr over 15 minutes, and the transesterification reaction was carried out by maintaining for 20 minutes under the conditions of 215 ° C. and 150 Torr. Further, the temperature was raised to 240 ° C. at a rate of 37.5 ° C./hr, and maintained at 240 ° C. and 150 Torr for 10 minutes. Thereafter, the pressure was adjusted to 120 Torr over 10 minutes and maintained at 240 ° C. and 120 Torr for 70 minutes. Thereafter, the pressure was adjusted to 100 Torr over 10 minutes and held at 240 ° C. and 100 Torr for 10 minutes. Furthermore, the polymerization reaction was carried out with stirring for 10 minutes under the conditions of 240 ° C. and 1 Torr or less at 1 Torr or less over 40 minutes.

  After completion of the reaction, nitrogen was blown into the reactor to increase the pressure, and the produced polycarbonate resin was extracted while being pelletized. Mw of the obtained polycarbonate resin was 63,300, MFR was 53.0 g / 10 min, Tg = 48 ° C., and the amount of terminal OH groups was 55 ppm.

Example 2
Polymerization was carried out in the same manner as in Synthesis Example 1 except that the amount charged was 10.136 kg (70.3 mol) of cyclohexanedimethanol and 14.622 kg (68.3 mol) of diphenyl carbonate. Mw of the obtained polycarbonate resin (A2) was 160,000, MFR (260 ° C., 2.16 kg load) was 5.0 g / 10 min, Tg = 49 ° C., and the amount of terminal OH group = 49 ppm.

Comparative Example 1
Polymerization was carried out in the same manner as in Synthesis Example 1 except that the charged amount was 9.844 kg (68.3 mol) of cyclohexanedimethanol and 14.699 kg (68.6 mol) of diphenyl carbonate. Mw of the obtained polycarbonate resin (A3) was 14,500, MFR (260 ° C., 2.16 kg load) was as low as 140.0 g / 10 min, Tg = 41 ° C., and the amount of terminal OH groups was 65 ppm.

Comparative Example 2
Polymerization was carried out in the same manner as in Synthesis Example 1 except that the amount charged was 10.344 kg (71.73 mol) of cyclohexanedimethanol and 14.724 kg (68.7 mol) of diphenyl carbonate. The obtained polycarbonate resin (A4) has an Mw of 62,000, an MFR of 44.0 g / 10 min, a low Tg = 45 ° C., and a large amount of terminal OH of 1050 ppm, which is not preferable for melt kneading for resin modification. Causes side reactions.

  The polycarbonate resin of the present invention can be suitably used as a wide variety of optical materials such as optical materials, spectacle lenses, in-vehicle lenses, covers, window glass, touch panels, etc. by blending with other polycarbonates.

Claims (2)

  A polycarbonate resin having a terminal OH group amount of 500 ppm or less obtained by carbonate-bonding 1,4-cyclohexanedimethanol with diphenyl carbonate. The 1,4-cyclohexanedimethanol and diphenyl carbonate are polymerized by a melt polycondensation method, and the charged molar ratio of diphenyl carbonate and 1,4-cyclohexanedimethanol is 0.97 to 1.01. Polycarbonate resin.