JPS599566B2 - Method for producing photochromic polycarbonate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing photochromic polycarbonate,
More specifically, the present invention relates to a method for producing a stable photochromic polycarbonate, which has not been previously known, by condensing a polycarbonate oligomer with paraquinone dioxime.

Conventionally, several polymer compositions that are colored or change color when irradiated with light are known.

However, many of these coloring phenomena are reversible, and although they become colored when irradiated with light, when the colored composition is left in a dark place, it returns to its pre-irradiation color. All such compositions are made by mixing a low molecular weight compound exhibiting photochromism (or phototropy, photochromism) with a polymer. It is also known that when polyester contains anthraquinone, it becomes colored when irradiated with light, and the color disappears when heated (Japanese Patent Publication No. 46-1106). Furthermore, it is known that when a compound represented by the general formula ●CH=N□Y is added to polyester, polycarbonate, etc., it becomes colored when irradiated with light and disappears in the dark (Japanese Patent Laid-Open No. 48-84
79).

However, since these are all mixtures of low-molecular compounds, uniform mixing and dispersion is difficult, and bleeding or fried occurs. In addition, colored compositions have various disadvantages in that they disappear from the crystalline state when they are dissolved or heated. 30 Therefore, the present inventors have conducted extensive research in order to eliminate the drawbacks of the above-mentioned conventional techniques and to develop a copolymerizable polycarbonate having uniform, long-term stable, and irreversible photochromic properties.

As a result, they discovered that the object could be achieved by condensing paraquinone dioxime with a polycarbonate oligomer, and completed the present invention. That is, the present invention provides a photochromic material characterized by condensing paraquinone dioxime or a mixture of paraquinone dioxime and an aromatic dioxy compound to a polycarbonate oligomer obtained by reacting an aromatic dioxy compound with phosgene. A method for producing polycarbonate is provided.

The polycarbonate oligomer used in the method of the present invention is, for example, bis-2-
While stirring a mixture of an aromatic dioxy compound such as (4-hydroxyphenyl)-propane (also known as bisphenol A) and an organic solvent such as methylene chloride, phosgene is blown into the mixture until the pH ranges from 9 to 12. At this point, the introduction of phosgene is stopped, and the aqueous layer and organic layer are separated by standing to obtain a solvent solution. At this time, by appropriately controlling the reaction conditions, the molecular weight of the oligomer and the ratio of hydroxyl groups to chloroformate groups in the molecule can be adjusted as desired. The novel polycarbonates according to the invention can be obtained by condensing paraquinone dioxime alone or in the form of a mixture with aromatic dioxy compounds onto such polycarbonate oligomers.

Here, there is no particular restriction on the amount of paraquinone dioxime blended, but usually the total amount of aromatic dioxy compounds used (
0.0 for the total amount of the aromatic dioxy compound constituting the oligomer and the aromatic dioxy compound added later)
It is preferable to range from about 1 to 1 times the mole. 0.0
If it is less than 1 mole, sufficient photochromic properties cannot be obtained, and if it is more than 1 mole, the physical properties will deteriorate.

Further, the composition of the mixture of paraquinone dioxime and aromatic dioxy compound to be condensed with the oligomer is not particularly limited. The aromatic dioxy compound that is the raw material for producing the copolymerized polycarbonate in the method of the present invention includes bis-
2-(4-hydroxyphenyl)-propane, bis(
4-hydroxyphenyl)-methane, bis-2-(4-
hydroxy-3,5-dimethylphenyl)-propane,
Bis-1-(4-hydroxyphenyl-butane) "Bis-3-(4-hydroxyphenyl)-pentane, bis-
Bis-(4-hydroxyphenyl)-alkanes such as 1-(4-hydroxyphenyl)-cyclohexane, 2
,2-(3,5,3',5'-tetrachlor-4,4'
-dihydroxydipheno(c)-propane (also known as tetrachlorbisphenol A), 2,2-(3,5,3
',5'-tetrabromo-4,4'-dihydroxydiphenynolypropane (also known as tetrabromo bisphenol A), 2,2-(3,3r-dichloro-4,4'-dihydroxydiphenol(c)) -propane, 2,2-(3
,5-dichloro-4,47-dihydroxydiphenyl)
-propane, 2,2-(3,3'-dichloro-5,5'
-dimethyl-4,41-dihydroxydiphenyl)-propane, 2,2-(3,3'-dibromo-4,41-dihydroxyphenyl)-propane, 3,5,3/,5'
-Tetrabromo-4,4'-dihydroxydiphenylsulfone (also known as tetrabromobisphenolsulfone)
halogen-containing bisphenols such as 4,
4'-dihydroxydiphenyl sulfone (also known as bisphenolsulfone), 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl sulfoxide,
Bisphenols such as 4,47-dihydroxydiphenyl ether, and hydroquinone are preferably used.

The compounds listed above are suitable not only as raw materials for the polycarbonate oligomer, but also as aromatic dioxy compounds that are mixed with paraquinonedioquim and added when condensing with the oligomer.

The aromatic dioxy compounds added after mixing with the oligomer raw material and paraquinone dioxime are preferably of the same type, but the reaction can proceed even if they are not necessarily of the same type. The condensation reaction in the present invention is polycondensation, and is carried out in the presence of a catalyst in an organic solvent capable of dissolving the polycarbonate oligomer and the polycarbonate produced.

As a catalyst, trimethylamine, triethylamine,
Tertiary amines such as tripropylamine and tributylamine are preferably used. Although the reaction proceeds with quaternary ammonium salts, the reaction rate is extremely slow and is not practical. Incidentally, during the condensation, a molecular weight regulator may be used in conjunction with the condensation if necessary. Examples of this molecular weight regulator include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and butyl alcohol, phenol, cresol, and butyl phenol. Phenols are suitable. Examples of solvents include chlorinated hydrocarbons such as tetrachloroethane, trichloroethane, dichloroethane, trichlorethylene, dichloroethylene, chloroform, methylene chloride, chlorobenzene, and dichlorobenzene, and cyclic oxy compounds such as dioxane and tetrahydrofuran. used. Furthermore, it is preferable to add an antioxidant such as hydrosulfide as necessary. In order to suitably carry out the present invention, a tubular reactor is used, into which the alkaline aqueous solution of the aromatic dioxy compound and the organic solvent for polycarbonate are continuously introduced to form a multiphase flow, and phosgeso is added to the reactor. The mixture is injected and reacted under external cooling while contacting cocurrently.

When the reaction is carried out in this way, the multiphase flow formed inside becomes a spray stream due to the reaction heat caused by the injection of phosgene, and contact with phosgene occurs in this spray stream, so that
Phosgeso reacts in almost the stoichiometric amount, and the reaction is completed in an extremely short time.

Further, due to the reaction heat generated at this time, a part of the organic solvent is vaporized and becomes vapor. On the other hand, the solvent in which oligomer 1 is dissolved and the aqueous solution containing alkali chloride form a spray, but these gradually condense toward the outlet of the reaction tube due to external cooling, and finally form an organic layer containing oligomer 1. It is extracted as a two-liquid multiphase flow consisting of aqueous layer containing alkali chloride, alkali chloride, and the remaining alkali. By leaving this item for a while, 2
Can be separated into phases. Introducing phosgeso into a multiphase flow of an alkaline aqueous solution of an aromatic dioxy compound and an organic solvent can be carried out using a single introduction port, but large-scale equipment may be used to slow down the progress of local reactions. It is advantageous to use two or more inlets, since this can prevent phosgene from being wasted.

In the tubular reactor, the length of the tube should be sufficiently long compared to the tube diameter (for example, tube length/tube length) so that the vaporized solvent can be completely condensed and the generated oligomers can be completely dissolved in the solvent. The diameter ratio is set to 8 or more) and a jacket or cooling tank is attached to the outside of the tube to enable external cooling. In this way, by using a tubular reactor and operating under predetermined reaction conditions, oligomers having a stable molecular weight range can be continuously obtained. For example, oligomers having a molecular weight of 450 to 500 can be obtained with good reproducibility by reacting bisphenol A and phosgene in a methylene chloride solvent and maintaining the final reaction product in a slightly alkaline state. Next, paraquinone dioxime or a mixture of an aromatic dioxy compound and paraquinone dioxime is added to the oligomer thus obtained in an alkaline aqueous solution, and a catalyst, such as a tertiary amine, and optionally a molecular weight regulator, such as Add along with branched alkyl-substituted phenol and allow to react with external cooling and stirring.

In this way, a solution of the target polycarbonate in an organic solvent is obtained.

To separate polycarbonate from this solution, add an organic solvent to this polycarbonate solution to make a solution with a concentration of 6 to 8%, wash with water to remove inorganic substances contained therein, and then add a precipitant. When the mixture is precipitated, polycarbonate powder can be obtained as a precipitate. In this case, precipitants include aliphatic hydrocarbons such as pentane, hexane, heptane, and cyclohexane, aliphatic alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol, and aliphatic hydrocarbons such as acetone and methyl ethyl ketone. are used alone or in combination of two or more. The polycarbonate obtained as described above has a completely new structure, and the color does not disappear when heated or placed in a dark place after being colored by one light irradiation.

2 No frieding or priming.

3 Transparency is not compromised.

It has excellent properties. Therefore, this polycarbonate can be suitably used for electrical parts, mechanical parts, building materials, miscellaneous goods, and the like. Next, examples of the present invention will be shown.

Example 1 Internal volume 1 fitted with stirrer, thermometer and reflux condenser
500 cc of 1.7 N aqueous sodium hydroxide solution was charged into a separable flask of
Add and dissolve 9l9, and then add 200C of methylene chloride.
C was added, and phosgene was bubbled in at a flow rate of 40 g/hour while stirring.

In this case, the reaction temperature was maintained at 20° C. by cooling from the outside of the flask. After 95 minutes, the pH of the reaction solution was 11.5.
At this point, the blowing of phosgene and stirring were stopped, and the reaction solution was allowed to stand still to separate into two layers.

The upper layer was an aqueous solution containing sodium chloride, which was removed by decanting to obtain a solution of bisphenol A polycarbonate oligomer in methylene chloride. This solution contains 0.3
It contained 99 equivalents of chloroformate groups. Next, add 250C of methylene chloride to this oligomer solution.
To this diluted solution, 160 cc of 2.0 N aqueous sodium hydroxide solution and 23 cc of paraquinone dioxime were added.
g and sodium hydrosulfide 0.5g dissolved, 48% sodium hydroxide aqueous solution 18.0eC,
3.2 f1 of paratertiary butylphenol and 0.19 g of triethylamine were added, and the mixture was stirred for 90 minutes while maintaining the temperature at 30°C.

By this operation, the chloroformate groups were completely reacted and a sticky emulsion solution was obtained. This solution was diluted with methylene chloride to give a polymer concentration of 7%, and washed with water until all inorganic salts were removed, to obtain a transparent methylene chloride solution of the copolymerized polycarbonate. When this is precipitated with methanol, a polymer powder of 1239 is obtained,
The intrinsic viscosity [η] measured in methylene chloride solvent at 20°C is 0.
．． It was 0510t/fl. Further, when the ultraviolet absorption vector (solvent: methylene chloride) of the polymer was measured, two strong absorptions with λu = 308 mμ were observed. In addition, the ultraviolet absorption spectrum of the raw material paraquinone oxime (
Solvent: methanol) was measured and λn = 319 mμ
It was hot. The obtained polymer powder was made into a methylene chloride solution with a concentration of 7.0%, and this solution was cast and heated at room temperature for 20 hours.
After leaving for a while to evaporate the methylene chloride,
It was dried under reduced pressure at 3 mmHg absolute pressure to obtain a yellow film.

This film turned red after 3 hours of sunlight exposure. Even when this red-colored film was heated at 120° C. for 50 hours or left in a dark place for one week, the color did not disappear. Also, when the film was immersed in methylene chloride, it dissolved, but the color of the solution did not disappear. Example 2
After diluting the methylene chloride solution of the bisphenol A polycarbonate oligomer obtained in Example 1 in the same manner as in Example 1, 12 g of paraquinone dioxime, 449 tetraprome bisphenol A, and sodium hydroxide were added to 160 cc of a 20N aqueous sodium hydroxide solution. Sulfide 0.
59 solution, 48% sodium hydroxide aqueous solution 1
8.0CC, paratertiary butylphenol 3.2
9 and triethylamine 0.19 were added, and the mixture was stirred for 90 minutes while being maintained at 30°C.

After post-treatment in the same manner as in Example 1, terpolymer polycarbonate 1509 was obtained, and the intrinsic viscosity [η] measured in a methylene chloride solvent at 20° C. was 0.0465 t/9. When the ultraviolet absorption spectrum of the polymer was measured (solvent: methylene chloride), absorption at λ = 308 mμ was observed. Furthermore, the bromine analysis result of the polymer is bromine%
=5.4%. Further, the film obtained in the same manner as in Example 1 was yellow in color, but turned red when exposed to sunlight. Furthermore, even if this red-colored film was heated, left in a dark place, or dissolved in methylene chloride, the color did not disappear.

Comparative Example 1 5 parts by weight of paraquinone dioxime was added to a melt of 100 parts by weight of bisphenol A polycarbonate produced according to a conventional method, and after kneading for 3 minutes, the polymer was taken out and melted according to a conventional method. A film was obtained.

Claims (1)

[Scope of Claims] 1. A photochromic method characterized by condensing paraquinone dioxime or a mixture of paraquinone dioxime and an aromatic dioxy compound with a polycarbonate oligomer obtained by reacting an aromatic dioxy compound with phosgene. method for producing polycarbonate. 2. The manufacturing method according to claim 1, wherein paraquinone dioxime is used in a molar ratio of 0.01 to 1 times the total amount of aromatic dioxy compounds. 3. The manufacturing method according to claim 1, wherein a tertiary amine is used as a catalyst in the condensation.