DE1141789B - Process for the production of high molecular weight polycarbonates. - Google Patents

Description

nSTERNAT.KL. C 08 g

GERMAN

PATENT OFFICE

G29498IVd / 39c

REGISTRATION DATE: 21 A P R I L 1960

NOTICE
THE REGISTRATION
ANDOUTPUTE
EDITORIAL: DECEMBER 27, 1962

It is known that high molecular weight polycarbonates can be obtained by converting diphenols into aqueous alkaline solutions To prepare a solution or suspension with phosgene or with bischlorocarbonic acid esters of diphenols. It is also known to use small amounts of quaternary ammonium compounds as catalysts in this condensation to be used in the form of the free bases or as salts.

It is also known to use tertiary amines as catalysts for polycarbonate formation.

A process for the production of polymethylene terephthalates by polycondensation is also known of terephthalic acid esters with glycols in the melt using onium compounds of the elements nitrogen, phosphorus, oxygen and sulfur.

All of these known catalysts have the disadvantage of not being very effective. You condition therefore very long response times that prohibit continuous work. Some of them must be used in high concentrations, including the electrical properties of the polyester To suffer.

The invention relates to a process for the production of high molecular weight polycarbonates by reacting Diphenols in aqueous alkaline solution or suspension with phosphene and / or with bis-chlorocarbonic acid esters of diphenols and / or with bis-chlorocarbonic acid esters of aliphatic or cycloaliphatic glycols in the presence of small amounts quaternary onium compounds as catalysts, which is characterized in that the reactions in the presence of small amounts of quaternary arsonium compounds in the form of the free bases or performs as salts.

Surprisingly, it has been shown that arsonium compounds in contrast to the known Catalysts are characterized by high activity and in a short time in low concentration lead to technically valuable polycarbonates. With these catalysts is therefore the continuous Production of polycarbonates possible.

Quaternary arsonium compounds are preferably used, which in water and in the for Solvents used to carry out the polycondensation are soluble.

Useful quaternary arsonium compounds are, for example, triphenylmethylarsonium iodide, triphenylbenzylarsonium bromide, Triphenyl-p-nitrobenzylarsonium bromide, Triphenylbenzylarsonium chloride, octyltrimethylarsonium iodide, benzyltriethylarsonium iodide, Benzyldiphenyl-oc-naphthylarsonium iodide and Process for the production of high molecular weight polycarbonates

Applicant:

Gevaert Photo-Producten N.V., Mortsel, Antwerp (Belgium)

Representative: Dr. W. Muller-Bore

and Dipl.-Ing. H. Gralfs, patent attorneys,

Braunschweig, Am Bürgerpark 8

Dr. Andre Jan Conix, Wilrijk, Antwerp (Belgium), has been named as the inventor

Triphenyl bromarsonium malonate, as described, for example, by A. Michaelis in Annalen der Chemie, Vol. 321, pp. 141-248 (1902).

The advantages of using quaternary arsonium compounds can be found in the table below, in which comparative viscosity numbers [η] of polycarbonates are given. This is the polycarbonate produced by reacting 2,2-bis- (4-oxyphenyl) -propane-bis-chlorocarbonic acid ester with 2,2'-bis- (4-oxyphenyl) propane.

Reaction time

5 minutes..
30 minutes..

Triphenylmethylarsonium iodide concentration

catalyst

0.05%
M.

0.68

2 ° o

In]

0.96
1.65

Triethylbenzyl

ammonium chloride

concentration

0.05 0 ₀

0.26

2 ° "

0.1 0.70

The reaction time is calculated from the point in time at which all reagents have been mixed with one another are mixed.

This table shows the following:

1. The arsonium compounds accelerate the polycondensation much more than ammonium compounds. Just 5 minutes after the reagents have been combined, the

209 749/354

Arsonium compounds achieve the rather high viscosity number of 0.96, while ammonium compounds give a polycarbonate that has too low a viscosity number. Such a shortening of the polycondensation time is important because it makes it possible to produce the polycarbonates in a continuous process. 2. If arsonium compounds are used, 15 cm ^{3 of} methylene chloride are added. After the dropping funnel has ^{been rinsed with 5 cm 3 of} methylene chloride, stirring is continued for 30 minutes. The concentration of the polycarbonate in methylene chloride is 40%.

During the polycondensation, the reaction mixture separates into two layers. From the received, very viscous organic layer, the water is poured off. The organic layer will

the finally reached viscosity number noticeably ¹⁰ washed repeatedly with large amounts of water, the hl bi dd Ai is then decanted afterwards

higher than when using ammonium compounds, e.g. B. 1.65 versus 0.7.

3. The catalyst can optionally be used in very low concentrations. This allows the electrical properties of the polycarbonates obtained to be influenced because possible catalyst residues can be kept to a minimum.

Suitable diphenols are e.g. B .:

Bis (4-oxyphenyl) methane,

Bis (4-oxy-3-chlorophenyl) methane, bis (4-oxy-3,5-dichlorophenyl) methane, Bis (4-oxy-3,5-dibromophenyl) methane, bis (4-oxy-3,5-difluorophenyl) methane, Bis (4-oxyphenyl) ketone,

Bis (4-oxyphenyl) sulfide,

Bis (4-oxyphenyl) sulfone,

4,4'-dioxydiphenyl ether,

1,1 bis (4-oxyphenyl) ethane,

2,2-bis (4-oxyphenyl) propane,

2,2-bis- (4-oxy-3-methylphenyl) -propane, 2,2-bis- (4-oxy-3-methylphenyl) -propane, 2,2-bis- (4-oxy-3,5-dichlorophenyl) propane, 2,2-bis (4-oxynaphthyl) propane, Bis- (4-oxyphenyl) -phenylmethane, bis- (4-oxyphenyl) -diphenylmethane, bis- (4-oxyphenyl) -4'-methylphenylmethane, l, l-bis- (4-oxyphenyl) -2,2,2-trichloroethane, bis- (4-oxyphenyl) -4- (chlorophenyl) methane, 1,1 -Bis- (4-oxyphenyl) -cyclohexane, bis- (4-oxyphenyl) -cyclohexylmethane, 4,4'-dioxydiphenyl and

2,2'-dioxydiphenyl.

The polycarbonates produced according to the invention are soluble in a number of organic solvents, such as methylene chloride, chloroform, and some also in benzene, toluene; they can come from solutions too shaped bodies such as films and fibers.

The polycarbonates can be melted without decomposition and can therefore be closed by pressing and injection molding Moldings or coatings are processed.

The following examples illustrate the invention.

example 1

^{In a 250 cm 3 three-} necked flask equipped with a stirrer and dropping funnel, 4.56 g of 2,2-bis- (4-oxyphenyl) propane (0.02 mol), 200 mg of triphenylmethylarsonium iodide (2%, based on the polycarbonate) , 40.8 cm ^{3 of} normal aqueous sodium hydroxide (in 2% excess) and 5 cm ^{3 of} methylene chloride.

In the course of 5 minutes, a solution of 7.13 g of 2,2-bis (4-oxyphenyl) propane-bis-chlorkohlensäureester is (0.02 mol, ig ^em in 1% excess) then decanted in each case. The polycarbonate is then precipitated by pouring it into boiling water. The flakes formed are then dried at HO ⁰ C. Yield: 10 g.

The viscosity number measured in tetrachloroethane is 1.65 dl / g.

Example 2

The procedure is as in Example 1, but with the difference that stirring is only continued for 5 minutes.
The viscosity number is 0.96 dl / g.

Example 3

It is as the procedure in Example 1, but with the difference that instead of 200 mg are used only 5 mg Triphenylmethylarsoniumjodid (0.05 ° / _0, based on the polycarbonate). As in Example 1, stirring is continued for 30 minutes.

The viscosity number measured in tetrachloroethane is 0.68 dl / g.

Example 4

70 g of sodium hydroxide, 145 g of 2,2-bis- (4-oxyphenyl) propane, 700 cm ^{3 of} water and 400 cm ^{3 of} methylene chloride are placed in a 3-1 three-necked flask equipped with a stirrer, dropping funnel and thermometer.
In the course of 1'V ₂ hours 73 g of phosgene are introduced, it being understood that the temperature never exceeds 25 ⁰ C by cooling. 5 minutes after the addition of the phosgene, 3 g of triphenylmethylarsonium iodide are introduced into the flask. The mixture is then stirred for 45 minutes.

The resulting stiff slurry is diluted with methylene chloride. The organic layer is repeated with washed large amounts of water, each of which is then decanted. Finally the polycarbonate precipitated in boiling water.

The viscosity number measured in tetrachloroethane is 1.32 dl / g.

Example 5

^{In a 250 cm 3 three-} necked flask equipped with a stirrer and dropping funnel, 4.56 g of 2,2-bis- (4-oxyphenyl) propane (0.02 mol), 200 mg of triphenylbenzylarsonium bromide (2%> based on the polycarbonate) , 40.8 cm ^{3 of} normal aqueous sodium hydroxide (in 2% excess) and 5 cm ^{3 of} methylene chloride.

In the course of 5 minutes, a solution of 7.13 g of 2,2-bis (4-oxyphenyl) propane-bis-chlorkohlensäureester (0.02 mole, l ° / oig ^em excess) in 15 cm ³ of methylene chloride is added . After the dropping funnel has ^{been rinsed out with 5 cm 3 of} methylene chloride, stirring is continued for a further 30 minutes. During the polycondensation, the reaction mixture separates into two layers. From the

The very viscous organic layer that holds the water is poured off. The organic layer will washed repeatedly with large amounts of water, each of which is then decanted. Then it will be the polycarbonate is precipitated by pouring it into boiling water. The flakes formed are then dried at 110 ° C.

The viscosity number measured in tetrachloroethane is 1.30 dl / g.

Example 6

Into a reactor equipped with a stirrer and dropping funnel, 250 cm ³ necked flask is 3.66 g of 2,2-bis (4-oxy-3,5-dichlorophenyl) propane (0.01 mol), 120 mg Triphenylmethylarsoniumjodid, 20, 4 cm ^{3 of} 1 normal aqueous sodium hydroxide and 3 cm ^{3 of} methylene chloride brought.

In the course of 5 minutes a solution of 3.565 g of 2,2-bis (4-oxyphenyl) -propanbis-chlorkohlensäureester (0.01 mole, m in l% ig ^e excess) in 7 cm ³ Metylenchlorid is added to the mixture. After the dropping funnel has ^{been rinsed with 5 cm 3 of} methylene chloride, stirring is continued for 30 minutes.

During the polycondensation, the reaction mixture separates into two layers. From the received, very viscous organic layer, the water is poured off. The organic layer will washed repeatedly with large amounts of water, each of which is then decanted. Then it will be the polycarbonate is precipitated by pouring it into boiling water.

The flakes formed are then dried at HO ⁰ C. Yield: 6.5 g.

The viscosity number measured in tetrachloroethane is 1.41 dl / g.

Example 7

2.28 g of bis (4-oxy-3-methylphenyl) methane (0.01 mol), 120 mg of triphenylmethylarsonium ^{iodide, 20.4 cm 3 of} normal aqueous ^{solution are placed in a 250 cm 3 three-} necked flask equipped with a stirrer and dropping funnel Brought sodium hydroxide and 3 cm ^{3 of} methylene chloride.

In the course of 5 minutes to the mixture, a solution of 3.565 g of 2,2-bis (4-oxyphenyl) -propane - bis - chlorkohlensäureester (0.01 mol, in l ^o / _o sodium excess) in 7 cm ³ of methylene chloride added. After the dropping funnel has ^{been rinsed with 5 cm 3 of} methylene chloride, stirring is continued for 30 minutes.

During the polycondensation, the reaction mixture separates into two layers. From the received, very viscous organic layer, the water is poured off. The organic layer will washed repeatedly with large amounts of water, each of which is then decanted. Then it will be the polycarbonate is precipitated by pouring it into boiling water. The flakes formed are at Dried at 110 ° C. Yield: 5 g.

The viscosity number measured in tetrachloroethane is 1.16 dl / g.

Example 8

3.175 g of 1,1-bis (4-oxyphenyl) -2,2,2-trichloroethane (0.01 mol) and 120 mg of triphenylmethylarsonium iodide are placed in a ^{250 cm 3 three-} necked flask equipped with a stirrer and dropping funnel.

Under cooling in an ice-acetone bath of -5 ° C are slowly 20.4 cm ³ lnormales aqueous sodium hydroxide and 3 cm ³ of methylene chloride are added in succession (in 2 ° / ₀ sodium excess).

In the course of 5 minutes, a solution of 3.565 g of 2,2-bis- (4-oxyphenyl) propane-bis-chlorocarbonic acid ester (0.01 mol, in 1% Excess) in 7 cm ^{3 of} methylene chloride was added. After the dropping funnel has ^{been rinsed with 5 cm 3 of} methylene chloride, cooling is interrupted and stirring is continued for 30 minutes.

The water is poured off from the very viscous organic layer obtained. The organic Layer is repeatedly washed with large amounts of water, which is then decanted in each case. The polycarbonate is then precipitated by pouring it into boiling water. The formed flakes are dried at 110 ° C.

The viscosity number measured in tetrachloroethane is 1.06 dl / g.

Claims (1)

PATENT CLAIM: Process for the production of high molecular weight polycarbonates by reacting diphenols in aqueous alkaline solution or suspension with phosgene and / or with bis-chlorocarbonic acid esters of diphenols and / or with bis-chlorocarbonic acid esters of aliphatic or cycloaliphatic glycols in the presence of small amounts of quaternary onium compounds as catalysts, characterized in that the reactions are carried out in the presence of small amounts of quaternary arsonium compounds in the form of the free bases or as salts. Considered publications:
German Auslegeschrift No. 1 046 311;
Dutch patent specification No. 90 066. © 209 749/354 12.