KR980009320A - Method for producing polycarbonate resin - Google Patents

Abstract

The present invention relates to a process for producing a polycarbonate resin, and more particularly, to a process for producing polycarbonate resin, which comprises mixing an aromatic phenol compound and an aliphatic dihydric alcohol and reacting them with phosgene under the catalyst of tertiary amines, To a method for producing a polycarbonate resin suitable as a member.

Description

Method for producing polycarbonate resin

The present invention relates to a process for producing a polycarbonate resin, and more particularly, to a process for producing a polycarbonate resin by mixing an aromatic phenol compound and an aliphatic dihydric alcohol and reacting them with phosgene in the presence of a tertiary amine catalyst, And a method for producing a carbonate resin.

In general, polycarbonate resins are excellent in strength, heat resistance, transparency, impact resistance, and electrical characteristics because of their glass transition temperature (T _g ) near 150 ° C., Is the material.

Therefore, the polycarbonate resin is widely used in various fields such as a light cover, a windshield glass, a safety glass, a safety cap, an instrument panel, an electric and electronic field such as a copying machine, a CD, a TV, a radio, , Pump parts, mechanical parts such as power tools, eyeglasses, dentures. Medical devices such as medical containers, oxygen generators, sterilizers, and artificial kidneys, milk bottles, artillery, and optical instruments such as tableware and miscellaneous goods.

However, a general polycarbonate resin is selectively infiltrated into a specific solvent, has no resistance, and has good creep resistance against a static load. However, when the temperature and various environmental conditions are mated, the polycarbonate resin is relatively easily broken and the resistance to dynamic load is complicated.

Accordingly, researches for increasing the heat resistance, workability and mechanical strength have been continuously carried out. As a result, high heat-resistant polycarbonate resins have been commercialized (U.S. Patent Nos. 5,070,177, 4,918,149, 3,269,986, and 52-36554).

Generally, such high-heat-resistant polycarbonate has modified bisphenol A to introduce a stereosubstituted substituent at the ortho position to increase the hydrolyzability and increase the heat distortion temperature and impact resistance. In addition, Schnell et al. Proposed a method for preparing a modified bisphenol A having a specific bond between aromatics and using the same to prepare a heat-resistant polycarbonate having a high transition point.

The conventional polycarbonate resin produced by the above-mentioned method has a problem in the process of synthesizing new monomer by modifying bisphenol A which is an aromatic monomer. In addition, there is a problem that the produced resin has poor color appearance and thus has poor appearance.

Accordingly, the present inventors have made efforts to solve the problems of the polycarbonate resin by a method different from the above methods. As a result, they have found that when an aromatic phenol compound and an aliphatic dihydric alcohol are mixed and reacted with phosgene, they have excellent heat resistance, color, workability and mechanical strength A polycarbonate resin, and the like, thereby completing the present invention.

The present invention relates to a process for producing a polycarbonate resin from a dihydric alcohol, phosgene and a molecular weight modifier, wherein the aromatic divalent alcohol is a mixture of 70 to 95% by weight of an aromatic phenol compound and 5 to 30% by weight of an aliphatic dihydric alcohol And is characterized in that it is used.

Hereinafter, the present invention will be described in detail.

The present invention relates to a process for producing a polycarbonate resin having excellent color by mixing an aromatic phenol compound and an aliphatic dihydric alcohol.

In the present invention, an aromatic phenol compound and an aliphatic bivalent alcohol compound are added as a dihydric alcohol compound, and the aromatic divalent phenol compound generally used is a molecule of the following form.

In Formula 1, Ar ¹ and Ar ² are unsubstituted phenylene groups or substituted phenylene groups. Examples of the substituent include a hydrocarbon, a halogen group, a nitro group, an alkoxy group, a cycloalkyl group, an alkyl group, an alkenyl group and an aryl group.

Preferably, both of Ar ¹ and Ar ² are ρ-phenylene groups, or ο- or m-phenylene groups.

In the above formula (1), X is usually a monovalent hydrocarbon group, and the groups other than carbon and hydrogen include -O-, -S-, -SO ₂ -, -CO-, and the like.

Typical aromatic dihydric phenolic compounds include 1,1-bis (4'-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2- -Propane, bis (3,5-dimethyl-4-hydroxyphenyl) -methane, 2,2-bis Bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxydiphenyl) Hydroxyphenol) -cyclohexane, 4,4'-dihydroxydiphenol, 2,4-bis (4-hydroxyphenol) Phenol) -p-diisopropylbenzene, 2,2-bis (3-methyl-4-hydroxyphenyl) -propane, 2,2- (3,5-dimethyl-4-hydroxyphenyl) -cyclohexane,?,? '- bis (3,5- Bis (3,5-dichloro-4-hydroxyphe Propane, and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) -propane

In particular, preferred aromatic divalent phenolic compounds are 2,2-bis (4-hydroxyphenol) -propane (aka bisphenol A), 2,2-bis (3,5-dichloro- Propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) -propane, 2,2-bis Phenyl) -propane, and 1,1,1-bis (4-hydroxyphenyl) cyclohexane-propane.

On the other hand, commonly used aliphatic dihydric alcohols include 1,3-propanediol. 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol and their structural isomers, 2,2-dimethyl-1,3-propanediol, Methyl-2'-isopropyl-1,3-propanediol, 2,2-bis (4-cyclohexanol) propane, 1,4-dimethylene Diol cyclohexane, 2,2-bis (3,3'-dimethyl-4,4'-hydroxycyclohexane) -propane, 2,2-bis (3-methyl-4'-hydroxycyclohexane- -Hydroxycyclohexane) -propane, 2,2-bis (3,5'-dimethyl-4,4'-hydroxycyclohexane) -propane and the like.

Particularly preferred among these are 2,2-bis (4-cyclohexanol) propane, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2- -Dimethyl-4,4'-hydroxycyclohexane) -propane, 2,2-bis (3-methyl-4'-hydroxycyclohexane-4-hydroxycyclohexane) (3,5'-dimetal-4,4'-hydroxycyclohexane) -propane.

The reaction in the present invention proceeds largely in two steps. In the first step reaction, the aromatic dihydric phenols and the aliphatic dihydric alcohols are formed into a salt in an appropriate molar ratio with an alkaline aqueous solution, and a phosgene gas The mixture is placed in a solvent such as methylene chloride (MC, Methylenechloride) or 1,2-dichloroethane, and the mixture is stirred with a molecular weight controlled by a monovalent phenol as a molecular weight regulator. At this time, when the aromatic phenols and the aliphatic dihydric alcohol compound are mixed, 70 to 75% by weight of the aromatic phenol compound and 5 to 30% by weight of the aliphatic dihydric alcohol are mixed.

If the content of the aromatic phenol compound is less than 70% by weight, there is a problem that the degree of thermal decomposition is lowered, and when it exceeds 95% by weight, there is a problem in workability. If the content of the aliphatic dihydric alcohol compound is less than 5% by weight, there is a problem in workability. If the content is more than 30% by weight, the pyrolysis temperature is lowered and there is a problem in color. As the monovalent phenol used as a molecular weight modifier, phenol, p-tetra-butylphenol, isopropylphenol and the like can be used to adjust the molecular weight to a desired level. The number of n is usually 20 or less, , The number of n is 5 to 10, which is more effective. The molecular weight of the oligomer, polycarbonate, is about 1,500 to 2,500.

In the second-step reaction, the oligomer polycarbonate prepared in the first-step reaction was subjected to interfacial polycondensation using an aqueous alkaline solution (water ratio: 15 to 25 ± 1%) and tertiary amines as catalysts, I make it.

Examples of the tertiary amine compound used as the phase transfer catalyst used in the present invention include triethylamine [(CH ₃ CH ₂ ) ₃ N] triisopropylamine {[(CH ₃ ) ₂ CH ₃ ] N }, and the like tripropylamine _{[(CH 3 CH 2 CH 2} ) 3 N].

In the reaction of the present invention, there are various reaction conditions, but generally, the reaction temperature is room temperature, and the reaction time is usually from 10 to 180 minutes.

The condensation reaction at the interface is usually at 10 to 40 ° C for about 1 hour and 30 minutes. The reaction is carried out at a stirring speed of 250 to 500 rpm (revolutions per minute), more preferably about 30 minutes at 25 ° C and stirring speed of 500 rpm to produce a desired polycarbonate.

The polycarbonate synthesized in the present invention has a viscosity molecular weight of 20,000 or more and is well soluble in a solvent for dissolving an ordinary polycarbonate.

The polycarbonate resin prepared as described above is excellent in heat resistance, color, workability, and mechanical strength and can be usefully used in the relevant fields.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the following Examples.

[Example 1]

45 g of 2,2-bis (4-hydroxyphenyl) -propane as an aromatic phenol compound and 2,2-bis (3.3'-dimethyl-4,4'-hydroxycyclohexane) g was added to 273 ml of a 6 wt% caustic soda aqueous solution, and 25.6 g of carbonyldichloride gas was added to a 1 L round flask and stirred for 10 to 20 minutes. Subsequently, 0.111 g of a molecular weight modifier phenol, 15 wt% Is added and stirred for 30 minutes to obtain an oligomer of about n = 5 to 10. Then, the aqueous solution layer and the organic solvent layer were separated, and the aqueous solution layer was discarded. 95 ml of 6% caustic soda was added to the organic solvent layer, the catalyst triethylamine and organic solvent were added thereto, and the reaction was completed by stirring for 1 to 2 hours.

After completion of the reaction, pure water and 1,2-dichloroethanol are added to dilute the reaction solution, followed by washing with alkali, acid, and pure water.

Polycarbonate was granulated using acetone and pure water.

[Examples 2 to 3]

The content of aromatic phenol compound and aliphatic dihydric alcohol was varied as shown in the following table.

[Examples 4 to 5]

The procedure of Example 1 was repeated. But using 2,2-bis (3-methyl-4'-hydroxycyclohexane-4-hydroxycyclohexane-4-carboxylic acid instead of 2,2- Hexane) -propane, the contents of aromatic phenol compounds and aliphatic 2-alcohols were varied as shown in Table 1 below.

[Examples 7 to 9]

Except that 2,2'-bis (3,5'-dimethyl-thiazol-2-yl) propane was used in place of 2,2-bis (3,3'-dimethyl-4,4'-hydroxycyclohexane) 4,4'-hydroxycyclohexane) -propane, the contents of aromatic phenol compounds and aliphatic dihydric alcohols were varied as shown in Table 1 below. ,

[Comparative Examples 1 and 2]

Except that 2,2-bis (3 (3'-dimethyl-4,4'-hydroxycyclohexane) -propane was used in place of aromatic phenol The contents of the compounds and aliphatic dihydric alcohols were varied.

[Comparative Examples 3 to 4]

Except that 2,2-bis (3'-methyl-4'-hydroxycyclohexane-4-hydroxycyclohexane) -propane was used in the same manner as in Example 1, The contents of aromatic phenolic compounds and aliphatic dihydric alcohols were different.

[Comparative Examples 5 to 6]

The procedure of Example 1 was repeated. However, the content of the aromatic phenolate and the aliphatic dihydric alcohol was varied using 2,2-bis (3,5'-dimethyl-4 (4'-hydroxycyclohexane) Respectively.

[Experimental Example]

The viscosity average molecular weight, pyrolysis temperature, melt flow rate and color index (Yellow Index, YI) of polycarbonate prepared according to the above Examples and Comparative Examples were measured, and the results are shown in Table 1 below.

Here, the viscosity average molecular weight was measured by the ASTM D2857-87 method, the pyrolysis temperature was measured by KS M3048, and the melt flow ratio was measured by the ASTM D1238-38 method. The color value (YI) was measured using a Sigma 90 colorimeter.

[Table 1]

As described above, the polycarbonate resin prepared by mixing an aromatic phenol compound and an aliphatic dihydric alcoholol and reacting it with phosgene under the catalyst of tertiary amines has excellent color rendering and is excellent in appearance. Therefore, And can be usefully used as an industrial member.

Claims (3)

A method for producing a polycarbonate resin from a dihydric alcohol, phosgene and a molecular weight modifier, wherein the dihydric alcohol is a mixture of 70 to 95% by weight of aromatic phenol and 5 to 30% by weight of an aliphatic dihydric alcohol compound By weight based on the total weight of the polycarbonate resin. The aromatic phenol according to claim 1, wherein the aromatic phenol is at least one selected from the group consisting of 2,2-bis (4-hydroxyphenol) -propane, 2,2-bis (3,5-dichloro- . Bis (3,5-dibromo-4-hydroxyphenyl) -propane, 2,2-bis And 1,1,1-bis (4-hydroxyphenyl) cyclohexane-propane are used as the polycarbonate resin. The aromatic divalent alcohol according to claim 1, wherein the aromatic divalent alcohol is at least one selected from the group consisting of 2,2-bis (4-cyclohexanol) propane, 1,4-butanediol, 1,5- (3,3'-dimethyl-4,4'-hydroxycyclohexane) -propane, 2,2-bis (3-methyl-4'-hydroxycyclohexane-4-hydroxycyclohexane) And 2,2-bis (3,5'-dimethyl-4,4'-hydroxycyclohexane) -propane are used as the polycarbonate resin. ※ Note: It is disclosed by the contents of the first application.