DE1495483A1 - Process for the production of polycarbonates - Google Patents

Description

Process for making polycarbonates The invention relates to a new process for the manufacture of polymeric material, in particular for manufacture solid polycarbonate.

The polycarbonates belong to the newer major synthetic ones Plastic polymers and are condensation polymers in which the organic components are linked together by carbonate bonds. Polycarbonate and excellent Pre # mass, as the products made from it have high poetiness, toughness and Have original stability. However, the poly carbonates are difficult to manufacture. A common technique for making polycarbonate materials is that of Phosgenation of an organic dihydroxy compound in a herterogeneous two-phase system, welohes Contains aqueous sodium hydroxide and an organic solvent. Oit forms rioh an emulsion or a gel and thick mixtures are formed that are difficult to stir, wash and handle su. It also requires the use of very strong alkaline sodium hydroxide the use of highly corrosion-resistant @ eaction vessels, and a yellowish polycarbonate is sucked up.

The present invention provides an improved method for the production of solid polycarbonates by condensation polymerization of monochloroformate an aromatic dihydroxy compound accessible in the presence of a solvent made. The condensation reaction becomes an essential feature of the process in the presence of the hydroxide or oxide of at least one alkaline earth metal or the hydroxide of a strongly basic ion exchange resin or a combination carried out of it. It may be desirable to have wine that contains oxides or hydroxides in a porn to use aqueous slurry. The condensation reaction becomes advantageous carried out in the presence of a catalyst.

The condensation polymerization process of the invention is in particular two-kilometer for the polymerization of the monochlororriate of a di (hydroxyaryl) sulfone, a di (hydroxyaryl) alkane or a combination thereof. Good results are obtained if the strongly basic ion exchange resin used has a crosslinked polymeric structure with a large number of uaternary ammonium hydroxide radicals of the formula where the radical is bonded to an aromatic nucleus of the polymer via an aliphatic carbon atom, n is 1 to 4 and B1, R2 and R3 represent monovalent hydrocarbon radicals, preferably methyl radicals.

The monochloroformate used in the process of the invention can made from a fairly wide variety of aromatic dihydroxy compounds will. Typical representatives of such aromatic dihydroxy compounds are hydroquinone, Resorcinol, catechol, 4,4'-dihydroxydiphenyl, 2,2'-dihydroxydiphenyl, 1,4-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,2-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, Dihydroxyanthraoene, 2,2'-dihydroxydinaphthyl-1,1 'and o-, 1- and p-hydroxybenzyl alcohol.

Among the monochloroformates of the aromatic dihydroxy compounds the monochloroformates of di (hydroxyaryl) -a @ ane and di (hydroxyaryl) sulfones have been found as particularly satisfactory. Examples of this class of compounds are the Monochloroformates of di (4-hydroxyphenyl) methane, 1,1-di (4-hydroxyphenyl) ethane, 1,1-di (4-hydroxyphenyl) propane, 1,1-di (4-hydroxyphenyl) butane, 1,1-di (4-hydroxyphenyl) -2-methylpropane, 1,1-di (4-hydroxyphenyl) -heptane, 1,1-di (2-hydroxyphenyl) -1 -phenylmethane, di (4-hydroxyphenyl) -4-methylphenylmethane, Di (4-hydroxyphenyl) -4-ethylphenylmethane, di (4-hydroxyphenyl) -4-isopropylphenylmethane, Di (4-hydroxyphenyl) -4-butylphenylmethane, di (4-hydroxyphenyl) -benzymethane, di (4-hydroxyphenyl) -r-furfurglmethane, 2,2-di (4-hydroxyphenyl) propane, 2,2-di (4-hydroxyphenyl) butane, 2 2-di (4-hydroxyphenyl ) pentane, 2,2-di (4-hydroxyphenyl) -4-methylpentane, 2,2-di (4-hydroxyphenyl) heptane, 2,2-di (4-hydroxyphenyl) ootane, 2,2-di (4-hydroxyphenyl) nonane, 1,1-di (4-hydroxyphenyl) -1-phenylethane, 3,3-di (4-hydroxyphenyl) pentane, 4,4-die (4-hydroxyphenyl) heptane, 1,1-di (4-hydroxyphenyl) cyclcpentane, 1,1-di (4-hydroxyphenyl) -cyclchexane, 2,2-di (4-hydroxyphenyl) -decahydronaphthal @ n, 2,2-di- (4-hydroxyoyclohexyl) propane, 2- (4-hydroxy-3-methylphenyl) -2- (4-hydroxyphenyl) propane, 2- (4-hydroxy-3-isopropylphenyl) -2- (4-hydroxyphenyl) -butane, 1,1-di (4-hydroxy-3-methylphenyl) -cyclchexane, 2,2-di (4-hydroxy-3-butylphenyl) propane, 2,2-di (4-hydroxy-3-phenylphenyl) propane, 2,2-di (4-hydroxy-2-methylphenyl) propane, 1,1-di (4-hydroxy-3-reth3l-6-butylphenyl) butaa, 1,1-di (4-hydroxy-3-methyl-6-tert-butylphenyl) -ethane, 1,1-di (4-hydroxy-3-methyl-6-tert. butylphenyl) propane, 1,1-di (4-hydroxy-3-methyl-6-tert. @utylphenyl) butane, 1,1-di (4-hydroxy-3-methyl-6-tert-butylphenyl) isobutane, l, l-di (4-hyaroxy-3-ethyl-6-tert-butylphonyl) -heptane, 1,1-di (4-hydroxy-3-methyl-6-tert-butylphenyl) -1-phenylethane, 1,1-di (4-hydroxy-3-methyl-6-tert-butylphenyl) -2-methyl-pentane, 1,1-di (4-hydropy-3-methyl-6-tert. butylphonyl) -2 ethylhexane, 1,1-di (4-hydroxy-3-methyl-6-tert-amylphenyl) butane, di (4-hydroxyphenyl) sulfone, Di (2-hydroxyphenyl) sulfone, di (3-hydroryphenyl) sulfone, di (4-hydroxy-2-methylphenyl) sulfone, Di (4-hydroxy-3-methylphenyl) sulfone, di (2-hydroxy-4-methylphenyl) eulion, di (-4-hydroxy-2-ethylphenyl) sulfone, Di (4-hydroxy-3-ethylphenyl) sulfone, di (4-hydroxy-2-tert-butylphenyl) sulfone, di (4-hydroxy-3-tert-butylphenyl) sulfone and di (2-hydroxynaphthyl) sulfone.

Among the above-mentioned monochloroformates of the di (hydroxyaryl) alkanes the di (4-hydroxyphenyl) alkanes should be used, especially the monochloroformate of 2,2-di (4-hydroxyphonyl) propane. A mixture of two or more monochloroformates aromatic dihydroxy compounds can be polymers with special properties getting produced.

The monochloroformates listed above can be phoegenerated an aqueous solution or suspension obtained which ii essential equimolar proportions of an alkali or potassium hydroxide and the aromatic dihydroxy compound contains according to the desired Xonoohlorformiat.

The above-mentioned strongly basic hydroxide ion exchange resin has an insoluble resinous quaternary bond of a large number of quaternary groups bonded to the crosslinked ammonium hydroxide with a crosslinked Hars. is preferably a Hars made from a mixture of a mixed polymer, aromatic and monovinyl hydrocarbon of an aromatic, divinyl hydrocarbon, the mixture being an amount of predominantly monovinyl carbons - preferably an amount of 60 hydrogen, 99.9 to%,% on a molar basis, contains. The quaternary groups attached to the aromatic nuclei of the copolymer preferably have the following formula in which n is a value from 1 to 4 and II, R2 and R3 are monovalent hydrocarbon radicals. The number of quaternary ammonium hydroxide groups can range from one for every 15 aromatic to 3 to 6 for every 4 aromatic nuclei in the mixed polymers. The typical representatives of the class of aromatic xonovinyl hydrocarbons include the following compounds @styrene, o-, i- and p-methylstyrene, o-, @@ and p-ethylstyrene, vinyl @ phthalene, vinyl anthracene and the homologues of these compounds. While divinylbenzene is the initially selected divinyl hydrocarbon, others can also be used, including divinyltoluene, divinylnaphthalene, divinylethylbenzene, and divinylxylene.

As indicated above, each of R1, 12 and 23 is monovalent Hydrogen residue which has no aliphatic unsaturation. Everyone Hydrocarbon radical can be an alkyl radical, aryl radical, cyoloalkyl radical or an aaltyl radical be. The hydrocarbon radicals can all be the same, two of the same and the third difference will be me or three different leftovers. Typical explanatory Examples of suitable hydrocarbon radicals are methyl, ethyl, propyl, isopropyl, Butyl, isobutyl, tert-butyl, pentyl, hexyl, oyolohexyl, phenyl and benzyl. A specific one Example of a copolymer suitable for the process according to the invention is an insoluble resinous, crosslinked quaternary ammonium copolymer in one 99% styrene and 1 benzene-containing mixture, with copolymers on the aromatic Core contains substituents of the following formula -CH2 - @ (CH3) 3OH and the number of these groups between 3 and 6 for each @ 4 aromatic nuclei in the Mixed polymers lies. The insoluble mixed polymer is preferably smaller in size Pieces, spheres or pearls, the size of which ranges from 1.5 to 0.03 mm in diameter lies. Extremely fine particles of approximately 0.03 to 0.125 mm in diameter are also possible suitable for the method according to the invention.

According to a preferred embodiment of the invention, the Yonoohlorioruiat is used the aromatic dihydroxy compound into a water-immiscible organic Solvent that is a solvent for the polycarbonate to be formed, dissolved, and the resulting solution is nit an aqueous suspension of an alkaline earth oxide @ or Hydroxyds, a strongly basic hydroxide ion exchange resin, or a combination brought into contact with it. The suspension and the solution are then mixed together mixed and agitated by stirring or shaking until the polycarbonate forms Has. The organic solvent layer containing the polycarbonate is separated from the aqueous layer and any insoluble material. That Polycarbonate is obtained from its solutions in any suitable manner, e.g. by precipitation, in which the solution is immersed in a large volume of a nonsolvent for the polymer and then filtered and dried or e.g. by evaporation the solvent medium under the influence of heat and or vacuum. b @as during implementation solvents used in the invention should be a solvent both for the yono-chloroformate of the aromatic dihydroxy compound and also for be the polycarbonate, but it must not react with any of these compounds, i.e. it should not react with hydroxyl or chloroformoxy groups. Many such solvents are known; among these can be the class of chlorinated Alternative connections can be used, @@@ can also be used for other purposes can. Typical examples of chlorinated aliphatic liquids used in the invention Methods to be used are chloroform, methylene chloride, symmetric Tetrachlorethylene, cis-1,2-dichloroethylene, 1,1,2-triohloroethane and 1,2-dichloroethane. Thiophene can also be used.

The method of the invention can be used at room temperature or below be performed. However, at slightly elevated temperatures, it is advantageous to e.g. at around 2500. Lan should make sure that the temperature is low su rises high, e.g. not above about 50 ° C. There should be enough time for the polycarbonate are available to achieve the desired molecular weight su. The time @@ nn vary from a few minutes to a few hours.

A suitable amount of solvent should be used to create a polycarbonate solution get a reasonable viscosity @u so that the polycarbonate of the quaternary @@@ onium - @@ ehpoly @ eren can be separated. The hydroxide ion @@ ustau @ herhars or the alkaline earth oxide or hydroxide is converted into the chloride by the reaction and should be in at least stoichiometric amount, based on the Amount of monochloroformate used. Preferably an excess # used on hydroxide or oxide. Since quaternary ammonium copolymers can be mixed with aqueous Sodium hydroxide can be regenerated to pure original hydroxide. The @experienced the invention serves to form both homopolymers and copolymers, the former being made by applying a solution of a single Yonoohloriormiate and the latter from mixtures of two or more Mon @ chloroformates is more aromatic Dihydroxy compounds.

The polymers produced by the process according to the invention can using conventional molding techniques such as compression molding, injection molding, extrusion and calenders are processed into usable products, e.g. B su foils, pipes, Rods, @@ l @ en, fibers and overlays.

Preparation of mono-chloroformate One gram-mole of 2,2-di- (4-hydroxyphenyl) propane is combined with one gram-mole of sodium hydroxide to form an aqueous solution dissolved at a temperature of about 9000.

Phosgene is blown into the solution until it becomes neutral @ and about 1 gram-mole of phosgene gas is needed. The one formed during the reaction Precipitate is filtered off, washed with water until it is free of balls and air dried to a white low density powder.

On the basis of the analysis, the product turned out to be a yono-chloroformate of 2,2-di (4-hydroxyphenyl) propane.

Similarly, monochloroformates of other aromatic dihydroxy compounds can be used be obtained by converting the 2,2-di (4-hydroxyphenyl) prepane through an equimolar Amount of an aromatic dihydroxy compound corresponding to the desired monochloroformate replaced.

Preparation of the polycarbonate Example 1 5 g of monochloroformate des 2,2-Di (4-h @ droxyphenyl) propane is dissolved in 50 ml of methylene chloride. Then 1 ml of 80% aqueous solution of benzyltrimethylammonium chloride was added as a catalyst and 20 ml of water and 5 g of magnesium hydroxide. The whole mixture is 6 hours touched. The pH of the mixture remains between 7 and 9 during the reaction. No gel forms. The polycarbonate is obtained by adding the Xethylene chloride layer (after washing with water) poured into hot water, filtered and the remaining methylene chloride guts. The polycarbonate is beautifully white and has a Fikentscher t-value (K - 1 000 k) from 40.

For comparison, the procedure of Example 1 has been used of 1 g of sodium hydroxide instead of 5 g of magnesium hydroxide. The pH of the mixture remained during the reaction for over 14. After about half an hour of At the beginning of the reaction a thick gel formed which was difficult to stir and difficult clay is to be washed free of alkali. That obtained polycarbonate is light yellow and has a K value naoh Fikentscher of 42.

Similarly to where in the previous example dae can be used in it Magnesium hydroxide by any magnesium oxide, calcium oxide or calcium hydroxide replaced with similar results. In the same way you can solid polycarbonates can be made by using those in the example Yonoohlorforsiatmonohydroxyverbindungen by any compound of the class of aromatic Monochloroformate monohydroxy compounds or mixtures thereof, as indicated above, replaced. Similarly, methylene chloride can be used in place of dep in the example any suitable solvent from the above with good results insert given class.

The use of a catalyst in the process according to the invention is desirable because the condensation reaction is thereby accelerated and the generation supported by high molecular weight polymers. It can be different Catalysts are used advantageously, which are water-soluble are. Quaternary ammonium compounds, especially quaternary ammonium salts suitable, for example tetramethylammonium chloride, tetrab @ tylammonium chloride, Tetramethylammonium iodide, di @ ethyldioetade @ ylammonium chloride and styrene / vinylbenzyl tri @ ethylammonium chloride copolymers.

Example 2 5 g of monochloroformate of 2,2-di (4-hydroxyphenyl) propane is dissolved in 40 ml of methylene chloride and placed in a 4 ounce flask. Then bring 30 ml of trookene pearls of an insoluble, cross-linked, resinous, tuaternary ammonium polymer as a mixture of 99% Btyrene and 1% divinylbenzene with substituents of the formula -CH2-N (CH3) 3OH on the aromatic nucleus, where the number of such substituents is one for each benzene ring of the copolymer. Of the The flask is then closed and shaken for 6 hours. The solution becomes more viscous, however, no gel forms. The solution of the polycarbonate is separated from the insoluble one quaternary ammonium milk polymer decanted and the polycarbonate by evaporation of methylene chloride obtained. The polycarbonate has a K value (t = 1,000 k) according to Fikentscher of 59 and a molecular weight of about 70,000.

Claims (9)

Claims 1. A method for producing solid polycarbonates by condensation polymerization of monochloroformate of an aromatic dihydroxy compound in the presence of a solvent, characterized in that the condensation reaction in the presence of the hydroxide or oxide of at least one alkaline earth metal or the hydroxide of a strongly basic ion exchange resin or a combination of which carries out. 2. The method according to claim 1, characterized in that the Oxide or hydroxide used in the form of an aqueous slurry. 3. The method according to claim 1 or 2, characterized in that one carries out the condensation reaction in the presence of a catalyst. 4. The method according to claim 1 to 3, characterized in that the to be polymerized monochloroformate the monochloroformate of a di - (@ ydroxyaryl) sulfone, Is di (hydroxyaryl) alka @ s or a combination thereof. 5. The method according to claim 1 to 4, characterized in that # the strongly basic ion exchange resin has a crosslinked polymeric structure with a large number of equatorial ammonium hydroxide groups of the formula the group being connected to an aromatic core of the polymer by an aliphatic carbon atom, 1 being 1 to 4 and R1, R2 and R3 being monovalent hydrocarbon radicals. 6. Method @@ ch claim 5, characterized in that # the monovalent ones Carbon dioxide radicals of the quaternary ammonium hydroxide groups are methyl radicals. 7. Process for the production of molded objects by pres- @@ n, drawing or @ or @@ n of the polycarbonate resins obtained by the process of Claims 1 to 6. 8. @ orobjects received after the procedure de @ claim @ 7 became. 9. @ olye @ rbomatharse, produced according to the method of the claims 1 bi @ 6.