DE1162079B - Process for the production of thermoplastic high molecular weight polycarbonates. - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school Class: C 08 g

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German class: 39 c-16

G 29246 IVd / 39 c
March 16, 1960
January 30, 1964

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 bis-chlorocarbonic acid esters of diphenols. It is also known to use small amounts of quaternary ammonium compounds in this condensation to be used as catalysts in the form of the free bases or as salts.

Such ammonium compounds are better catalysts for the production of polycarbonates ίο than the tertiary amines also known for this purpose, but leave their accelerating Influence on the polycondensation, the properties of the polycarbonates and the minimum quantities required still much to be desired.

It has now been found that the process of the invention leads to high molecular weights much faster Polycarbonates are obtained if small amounts of quaternary phosphonium salts are used instead of the ammonium compounds used as catalysts. This superiority of the phosphonium salts over the ammonium compounds is all the more striking Ammonium and phosphonium compounds are used as catalysts in transesterification and polycondensation of terephthalic acid esters and glycols to polymethylene terephthalates behave in the same way. However, this polycondensation takes place in the melt, i.e. a single-phase system is, as an equilibrium reaction according to a different mechanism than the polycarbonate formation investigated here, so that conclusions by analogy are forbidden.

Accordingly, the invention relates to a method for producing thermoplastic high molecular weight polycarbonates by reacting diphenols in aqueous alkaline solution or suspension with Phosgene and / or bis-chlorocarbonic acid esters of diphenols and / or bis-chlorocarbonic acid esters of aliphatic or cycloaliphatic glycols in the presence of small amounts of onium compounds than Catalyst, which is characterized in that the reaction is carried out in the presence of small amounts quaternary phosphonium salts.

Suitable quaternary phosphonium salts are, for example, triphenylmethylphosphonium iodide, triphenylbenzylphosphonium chloride, p-xylylene-bis- (triphenylphosphonium chloride), tetraethylphosphonium- 1,

bromide, triethyloctadecylphosphonium iodide, phenylethylpentamethylene - phosphonium acetate, ρ - xylylene bis (diethylphosphonium bromide) and bis (triethylphosphonium acetate) 1,4-butane.

The advantages of using quaternary phosphonium salts are shown in the table below, Methods of Making Thermoplastic
high molecular weight polycarbonates

Applicant:

Gevaert Photo-Producten N.V.,

Mortsel, Antwerp (Belgium)

Representative:

Dr. W. Müller-Bore and Dipl.-Ing. H. Gralfs,
Patent attorneys, Braunschweig, Am Bürgerpark 8

Named as inventor:

Dr. Andre Jan Conix, Antwerp (Belgium)

can be found in the comparative viscosity numbers [η] of polycarbonates are given. This is the polycarbonate produced by the reaction of 2,2-bis- (4-oxyphenyl) -propane-bis-chlorocarbonic acid ester with 2,2'-bis- (4-oxyphenyl) -propane.

Triphenyl
benzyl
phosphonium
chloride 2%
M. catalyst
Triphenyl
methyl-
phosphonium
iodide tration
2%
ätszahl Triethyl
benzyl
ammonium-
chloride 2%
ω 0.05 »A, 0.90 Conc
0.05 »/ 0
Viscose
[η] 0.9 0.05% 0.1 Reaction
duration
5 minutes 0.41 1.36 0.40 1.2 0.7 30 minutes 0.65 0.80 0.26

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

All in all:
The phosphonium salts accelerate the polycondensation much more than ammonium compounds. Just 5 minutes after the reactants have been brought together, the rather high viscosity number of 0.9 is achieved with the help of the phosphonium salts, while ammonium compounds result in a polycarbonate,

309 807/467

3 4

That is what will be a very viscous organic layer which is too low for practical purposes

Has viscosity number. Such a shortening water is poured off. After watering the organic

The polycondensation time is therefore important, the polycarbonate is poured into the layer

because this makes it possible to make the boiling water like it. The formed flakes Polycarbonates in the continuous process 5 are then dried at 110.degree. Yield: 10 g.

perform. The viscosity number measured in tetrachloroethane

2. If phosphonium salts are used, this is 1.2 dl / g.

the final viscosity reached noticeably B is η ie 1 2
higher than when using ammonium compounds, e.g. B. 1.36 versus 0.7. io The procedure is as in example 1, but with

3. The catalyst can, if necessary, differ greatly from the fact that stirring is continued for only 5 minutes, low concentrations are used. The viscosity number is 0.9 dl / g.

This allows the electrical properties

of the polycarbonates obtained, because Example 3

possible catalyst residues to a minimum 15

can be restricted. The procedure is as in Example 1, but with

Suitable diphenols are ζ B · ^{the difference} > ^{that instead of 20} ° ^m S ^{only 5 m} S ^Tri "

Bis (4-oxyphenyJ) methane / "phenylmethylphosphonium iodide (0.05%, based on

Bis- (4-oxy-3-methylphenyl) methane, ^the polycarbonate) can be used. It w _e d as

Bis- (4-oxy-3,5-dichlorophen> 1) methane, ^ao ™ «first example, stirred for 30 minutes.

Bis (4-oxy-3,5-dibromophenyl) methane,. ^The viscosity number measured by tetrachloroethane

Bis- (4-oxy-3,5-difluorophenyl) methane, amounts U, S dl / g.

l, l-bis- (4-oxyphenylj-ethane, example 4

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

2,2-bis (4-oxy-3-methylphenyl) - _P ropan, ^{25th Es} ™ ^rd ™. ™ Example 1 followed, but with

2,2-bis- (4-oxy-3-chlorophenyl) propane, the difference being that it is only stirred for 5 minutes

2,2-bis- (4-oxy-3,5-dichlorophenyl) propane, ÄiÄ * ⁵ ™ ^{S T} "phenylmethylphosphonium iodide

Bis (4-oxyphene _y l) -phen _y lm _e than, <° ^'05 \ ^inscribed ° gf ^{on the} polycarbonate) instead of 200 mg

Are bis (4-ox _{y P} henyl) diphenylmethane used

Bis (4-oxyphenyl) -4'-methylphenylmethane, ³ °. ^D i ^{e a} . Viscosity number measured by tetrachloroethane

1,1-bis (4-oxyphenyl) -2,2,2-trichloroethane, amounts to U.4 di / g.

Bis- (4-oxyphenyl) -4- (chlorophenyl) methane, Example 5

l, l-bis (4-oxyphenyl) cyclohexane,. , _. . ,,.

Bis- (4-oxyphenyl) -cyclohexylmethane, ^{In emen mt} Ruhrwerk Tropftnchter and Jhermo

4 4'-dioxydiphenyl and ^{35 meter} 3-1 three-necked flasks are 70 g

2'2'-DioxvdiDhenvl sodium hydroxide, 145 g 2,2-bis- (4-oxyphenyl) -propane,

' ^ypy 700 cm ^{3 of} water and 400 cm ^{3 of} methylene chloride brought.

The inventively produced polycarbonates Over 1V ₂ hours 73 g of phosgene

are soluble in a number of organic solutions, whereby it should be noted that

medium, such as methylene chloride and chloroform, and cooling the temperature never ^{exceeds 25 0} C,

some also in benzene and toluene; they can be in from 5 minutes after adding the phosgene

Solutions to molded bodies such as films and the flask 3 g triphenylbenzylphosphonium chloride

Fibers. brought in. The mixture is then stirred for 45 minutes.

The Polycarbonates Preparable According to the Invention The stiff slurry formed is treated with methylene chloride

can be melted without decomposition and can therefore be diluted and then mixed with water; in the end

by pressing or injection molding to form moldings, or the polycarbonate is precipitated in boiling water.

Coatings are processed. The viscosity number measured in tetrachloroethane

The following examples illustrate the Er- is 1.18 dL / g.

^findun S- _o example 6

Example] j _ne j _{nen with} j _t stirrer and dropping funnel equipped

^{In a 250 cm 3 three-} necked flask equipped with a stirrer and dropping funnel, 4.56 g of 2,2-bisarmet 250 cm ^{3 three-} necked flask are placed in 4.56 g of 2,2-bis- (4-oxyphenyl) propane ( 0.02 mol), 200 mg triphenyl- (4-oxyphenyl) -propane (0.02 mol), 200 mg triphenylbenzylphosphonium chloride (2%> based on the methylphosphonium iodide (2% based on the 55 polycarbonate), 40, 8 cm ^{3 of} 1 normal aqueous sodium polycarbonate), 40.8 cm ^{3 of} normal aqueous sodium hydroxide (in 2% excess) and 5 cm ^{3 of} methylene hydroxide (in 2% excess) and 5 cm ^{3 of} methylene chloride.

chloride brought. A solution of

In the course of 5 minutes, a solution of 7.13 g of 2,2-bis- (4-oxyphenyl) -propane-bis-carbon-7.13 g of 2,2-bis- (4-oxyphenyl) -propane-bis -chlorkohlen- 60 säureester (0.02 mol, in 1 ° / _a sodium excess) in 15 cm ³ säureester (0.02 mole, l ° / _o sodium excess) in 15 cm ³ of methylene chloride. After adding methylene chloride to the dropping funnel. After the dropping funnel has ^{been rinsed with 5 cm 3 of} methylene chloride and rinsed with 5 cm ^{3 of} methylene chloride, stirring is continued for a further 30 minutes.
is stirred for another 30 minutes. The concentration During the polycondensation, the separates

of the polycarbonate in methylene chloride is here 65 reaction mixture in two layers. From the received 40% very viscous organic layer

During the polycondensation, the water separates and is poured off. After watering the organic Reaction mixture in two layers. The polycarbonate is poured from the receiving layer into

5 6

like boiling water. The flakes of bis-chlorocarbonic acid ester formed (0.01 mol, in 1% excess are dried at 110 ° C. The shot in tetrachloroethane) in 7 cm ^{3 of} methylene chloride was added. The viscosity number measured is 1.36 dl / g. the dropping funnel is ^{filled with 5 cm 3 of} methylene chloride

has been rinsed, stirring is continued for 30 minutes.

B is ρ ie 1 7 ⁵ During the polycondensation, the separates

Reaction mixture in two layers. From the received

This is done in the same way as in Example 6, the very viscous organic layer, but with the difference that water is poured off as catalysis. After soaking the organic sator instead of 200 mg only 5 mg triphenylbenzylphos layer, the polycarbonate is used by pouring it into phonium chloride (0.05%> based on the poly- io boiling water. The flake carbonate formed) can be used. The viscosity reached dried ⁰ C at HO. Yield: 5 g.
number is 0.65 dl / g. The viscosity number measured in tetrachloroethane

is 1.35 dl / g.
Example"

The procedure is the same as in Example 6

went, but is only stirred for 5 minutes. In one equipped with a stirrer and dropping funnel

Viscosity number is 0.9 dl / g. Equipped 250 cm ^{3 three-} necked flasks are 3.175 g

l, l-bis (4-oxyphenyl) -2,2,2-trichloroethane (0.01 mol) Example 9 ^and 120 mg triphenylbenzylphosphonium chloride ge

20 brings.

It is superiors in the same manner as in Example 6 under cooling in an ice-acetone bath at -5 ⁰ C

walked; however, instead of 200 mg of triphenylbenzyl, 20.4 cm ^{3 of} normal phosphonium chloride, 200 mg of p-xylylene-bis- (triphenyl-aqueous sodium hydroxide (in 2% excess) phosphonium chloride) are slowly used one after the other. The added in tetrachloride and 3 cm ^{3 of} methylene chloride,
Viscosity number measured in ethane is 1.19 dl / g. 25 Over the course of 5 minutes becomes this mixture

at a temperature of -5 ° C a solution of

Example 10 3.565 g of 2,2-bis- (4-oxyphenyl) -propane-bis-chlorocarbons-

acid ester (0.01 mol, in 1% excess) in 7 cm ³

Methylene chloride is added in the same way as in Example 6. After the dropping funnel has gone, but instead of 200 mg triphenylbenzyl 30 has ^{been rinsed with 5 cm 3 of} methylene chloride, phosphonium chloride 200 mg triphenyloxyäthylphos- the cooling is interrupted and phonium chloride is used for another 30 minutes. The stirred in tetrachloroethane.

measured viscosity number is 1.1 dl / g. From the obtained, very viscous organic

Layer is poured off the water; after watering

If the organic layer is 1 11 35, the polycarbonate is through

Pouring into boiling water like. The educated

Flakes are then dried at 110 ° C. in a funnel with a stirrer and dropping funnel. The viscosity number measured in armed 250 cm ^{3 three-} necked flasks is 3.66 g of 2,2-bis-tetrachloroethane (4-oxy-3,5-dichlorodiphenyl) propane (0.01 mol), 120 mg, 0.84 dl /G.

Triphenylbenzylphosphonium chloride, 20.4cm ³ standard 40 Example 14

males aqueous sodium hydroxide and 3 cm ^{3 of} methylene chloride brought. In a stirrer and dropping funnel, over the course of 5 minutes, a 250 cm ³ three-necked flask is added successively to 2.28 g of a solution of 3.565 g of 2,2-bis- (4-oxyphenyl) -propane-bis-2,2 -Bis- (4-oxyphenyl) -propane (0.01 mol), 20.4 cm ³ chlorocarbonic acid ester (0.01 mol, in 1% excess - 45 normal aqueous sodium hydroxide (in 2% shot) in 7 cm ³ Methylene chloride was added. After excess), 100 mg of triphenylbenzylphosphonium were added to the dropping funnel with 5 cm ^{3 of} methylene chloride and 3 cm ^{3 of} methylene chloride,
has been rinsed, stirring is continued for 30 minutes. During the polycondensation, the solution of 2.72 g of 1,4-cyclohexanedimethylol-bis reaction mixture separates into two layers. The shot of the chlorocarbonic acid ester obtained (0.01 mol, in 1% excess, very thin organic layer) is poured off drop by drop in water ^{in 7 cm 3 of methylene chloride.} After watering the organic sets. Thereafter, the mixture is still another layer, the polycarbonate is stirred by pouring out in 30 minutes at room temperature, whereupon the boiling water is precipitated. organic layer becomes very viscous. The aqueous flakes formed are then ^{decanted at HO 0} C 55 and the residue is dried twice. Yield: 6.5 g. watered and decanted while stirring vigorously. The viscosity number measured in tetrachloroethane Then the polycarbonate by pouring in is 1.28 dl / g. Boiling water is precipitated, and the flakes formed, Example 12, are dried at 110.degree. The yield is close

60 quantitative, and the polycarbonate has a limit in a with stirrer and dropping funnel viscosity number of 0.93 dl / g, measured in symmetrical 250 cm ^{3 three-} necked flasks 2.28 g of bis-tetrachloroethane at 25 ° C.
(4-oxy-3-methylphenyl) methane (0.01 mol), 120 mg

Triphenylbenzylphosphonium chloride 20.4cm ³ lnor- Example 15

males aqueous sodium hydroxide and 3 cm ³ methylene 65

chloride brought. In one equipped with a stirrer and dropping funnel

Over the course of 5 minutes, 250 cm ^{3 three-} necked flasks are added successively to 4.56 g of a solution of 3.565 g of 2,2-bis (4-oxyphenyl) propane-2,2-bis (4-oxyphenyl) ) propane (0.02 moles), 40.8 cm ³

Normal aqueous sodium hydroxide (in a 2% excess), 160 mg of triphenylbenzylphosphonium chloride and 5 cm ^{3 of} methylene chloride were added.

Within 5 minutes, a solution of 3.78 g of ethylene glycol-bis-chlorkohlensäureester (0.02 mol% strength in l ^e m excess) was added dropwise in 15 cm ³ of methylene chloride. After the addition of the solution, the mixture is stirred for a further 30 minutes at room temperature, the organic layer becoming very viscous. The aqueous layer is decanted and the residue is washed twice with vigorous stirring and decanted. Then, the polycarbonate is precipitated by pouring into boiling water, and the flocs formed are dried at 110 ⁰ C. The yield is almost quantitative, and the polycarbonate has an intrinsic viscosity of 0.90 dl / g as measured in sym-tetrachloroethane at 25 ⁰ C.

Claims (1)

Claim: Process for the production of thermoplastic high molecular weight polycarbonates by reaction of diphenols in aqueous alkaline solution or suspension with phosgene and / or bis-chlorocarbonic acid esters of diphenols and / or bischlorocarbonic acid esters of aliphatic and cycloaliphatic glycols in the presence of small amounts of onium compounds as catalysts, characterized in that the reaction is carried out in the presence of small amounts quaternary phosphonium salts. Considered publications:
German Auslegeschrift No. 1 046 311;
Dutch Patent No. 90 066;
Industrial and Engineering Chemistry, Vol. 51, 1959, pp. 147-150. 309 807/467 1.64 © Bundesdruckerei Berlin