DE3423864A1 - Polycarbonate copolycondensates, and process for their preparation - Google Patents

Abstract

The invention relates to a process for the preparation of polycarbonate copolycondensates by reacting from 99 to 10 % by weight of 1,1-bis(4-hydroxyphenyl)-1-phenylethane and from 1 to 90 % by weight of 2,2-bis(4-hydroxyphenyl)propane with phosgene or diphenyl carbonate. The resultant polycarbonate copolycondensates have high heat resistance and very good flow properties and processing properties.

Description

Polycarbonate is the only one of the so-called aromatic polycarbonates from 2,2-bis- (4-hydroxyphenyl) -propane and phosgene or diphenyl carbonate in the trade available. This polycarbonate is hereinafter referred to as pCt. The heat resistance from, for example, Upiron S2000, a product of Nitsubishi Gas Chemical Co., Ltd. 13500. There is a need for polymers with significantly higher thermal stability.

A polycarbonate made from 1,1-bis- (4-hydroxyphenyl) -1-phenylethane and phosgene or diphenyl carbonate has a heat resistance of 17400 and it can with it can be referred to as heat-resistant. This type of polycarbonate will be briefly described below labeled "NPC". However, NPC has the disadvantage that its fluidity, i. its processability is poor compared to PC.

The invention is therefore based on the object of producing new polycarbonate polycondensates which develop due to a higher thermal stability than PC as well as a considerably distinguish improved pourability or processability as NPC. This task is achieved by the invention.

The invention thus relates to what is characterized in the claims Object.

The invention thus relates to polycarbonate copolycondensates, which are obtainable by reacting 99 to 10 percent by weight 1,1-bis (4-hydroxyphenyl ) -1-phenylethane and 1 to 90 percent by weight of 2,2-bis (4-hydroxyphenyl) propane with Phosgene or diphenyl carbonate.

The proportion of 1,1-bis (4-hydroxyphenyl) -1 -phenylethane and 2,2-bis (4-hydroxyphenyl) propane should be in the range given above. If the proportion of 1,1-bis (4-hydroxyphenyl) -1-phenylethane is less than 10 percent by weight no significant improvement in heat resistance is achieved. At more than 99 percent by weight, the processing temperature of the obtained Polycarbonate, which leads to a deterioration in processability.

The proportion of 1,1-bis (4-hydroxyphenyl) -1-phenylethane is preferably in the range from 97 to 20 percent by weight.

In the production of the polycarbonate copolycondensates from 1,1-bis- (4-hydroxyphenyl) -1-phenylethane and 2, 2-bis (4-hydroxyphenyl) propane, which are briefly referred to below as dihydric phenols and phosgene, the dihydric phenols are inert in one Solvent, such as methylene chloride or 1,2-dichloroethane, in the presence of an acid acceptor, e.g. an aqueous-alkaline solution or pyridine, with the introduction of gaseous Phosgene implemented. When using an aqueous-alkaline solution as the acid acceptor and when a quaternary ammonium salt or a tertiary amine is added as a catalyst the speed of reaction increases.

The reaction temperature is in the range from 0 to 100.degree.

The dihydric phenols can be used simultaneously with phosgene, for example implemented. Alternatively, one of the dihydric phenols can be mixed with phosgene implemented. Once the condensation reaction reaches a certain extent the other dihydric phenol is added and, at the same time, the gaseous one continues Phosgene passed in until the reaction has ended.

The catalyst can be added at the beginning of the reaction.

Alternatively, the catalyst can also be used after the preparation of a prepolymer may be added to obtain a high molecular weight polycarbonate.

The polycarbonate obtained can be solidified by the customary methods Conventional polycarbonates are solidified, for example using a precipitating, non-dissolving solvent, by steam distillation or by separation of the solvent by means of a vented extruder.

For the preparation of the polycarbonate copolycondensates of the invention from the dihydric phenols and diphenyl carbonate, the reaction takes place in two stages carried out. The reaction in the first stage is preferred among such Conditions carried out that a rapid condensation reaction occurs and that Phenol formed as a by-product, but not the dihydric phenols distilled off will.

Usually this takes place at temperatures of 130 to 2200C and pressures from 60 to 15 mm Hg. When the initial condensation reaction under these conditions is carried out for 1 to 3 hours and the amount of phenol distilled off has reached about 80 to 90% of the theoretical value, i.e. when the further distilling off of the phenol becomes difficult, the first condensation reaction is practically over. In the second stage, the reaction is at elevated temperatures and greatly reduced Pressure carried out until a high degree of polymerization is obtained. Preferably the reaction is carried out under a protective gas such as nitrogen or argon. When using a catalyst, transesterification catalysts are preferably used, like metallic lithium or potassium or manganese acetate.

In the process according to the invention, the reaction mixture can also contain further Dihydric phenols are added within a range in which the properties of the polycarbonate copolycondensates obtained do not deteriorate. Typical Examples of such dihydric phenols are resorcinol, hydroquinone and nuclear chlorinated or core Brominated 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxy phenyl) sulfone and biphenol.

The polyamide copolycondensates of the invention can contain further additives contain, such as dyes, pigments, fillers, light stabilizers and antioxidants, how they are used in plastics. The proportions are calculated in such a way that that the properties of the copolycondensates do not deteriorate.

The mechanical strength of the polycarbonate copolycondensates of the invention can be improved by adding glass fibers. Their proportion is also there in a range in which the properties of the copolycondensates do not deteriorate.

The polycarbonate copolycondensates of the invention can be prepared according to conventional methods Methods such as compression molding, extrusion or injection molding, into sheets, foils and other molded parts used in the plastics processing industry electrical devices, in automobile construction, for containers, as packaging material and the like are suitable.

The examples illustrate the invention.

The heat resistance is determined according to ASTM test standard D648.

The flow temperature (° C) is the temperature at which the flowability, determines the value in a Koka flow tester at a load of 100 kg / cm2 10-3 ml / sec reached.

The reduced viscosity (sp / C) of the polycarbonates is at 25 ° C Determined in chloroform (c = 0.5 g polymer / 100 ml siksmittel).

Ex. 1 e 1 to 3 and Comparative Examples 1 and 2 A mixture from 14.5 g (0.05 mol) 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 11.4 g (0.05 mol) 2,2-bis- (4-hydroxyphenyl) propane and 0.45 g of p-tert-butylphenol are in a solution of 11.2 g of sodium hydroxide dissolved in 200 ml of water. Then there are 67 g of methylene chloride admitted. The mixture is kept at a temperature of 20 ° C. or less. 12.2 g of phosgene are passed into the mixture over the course of 1 hour.

Then an aqueous solution of 3 g of sodium hydroxide in 25 ml of water and 0.078 g of triethylamine were added. The resulting mixture is another 4 hours Polymerized with vigorous stirring at 250C. Thereafter, the reaction mixture diluted with methylene chloride, washed thoroughly with acid and then with water and precipitated with methanol. The yield is 97% of theory. # sp / C = 0.60 dl / g. The polymer powder obtained is dried in a stream of hot air at 120 ° C. for 6 hours and then shaped into test specimens for 10 minutes at 290 ° C. and a pressure of 100 kg / cm2. The physical properties of the copolymer are summarized in Table I.

The procedure described above is repeated, however changes the amounts of dihydric phenols.

The physical properties of the copolymers obtained are also summarized in Table I.

Table I 1,1-bis- (4-hydroxyphenyl) - heat resistance- flowed-1-phenylethane / 2,2-bis- (4-polymer strength, temperature, example hydroxyphenyl) propane yield,% n sp / C ° C ° C 1 21.8 (g) 0.075 (mol) = 97 0.59 167 280 5.7 (g) 0.025 (mol) 2 14.5 (g) 0.05 (mol) = 96 0.60 158 271 11.4 (g) 0.05 (mol) 3 7.3 (g) 0.025 (mol) = 97 0.62 150 263 17.1 (g) 0.075 (mol) comparative 29 (g) 0.10 (mol) = 96 0.62 174 288 example 1 0 0 comparative 0 0 97 0.63 138 255 example 2 22.8 (g) 0.10 (mol) example 4 A mixture of 14.5 g 1,1-bis- (4-hydroxyphenyl) -1-phenyl ethane, 11.4 g 2,2-bis- (4-hydroxyphenyl) propane, 34.5 g of diphenyl carbonate and 0.07 g of manganese acetate are brought to 1900 ° C. in a stream of nitrogen heated. The pressure is reduced to 50 mm Hg. It instantly sets an evaporation of phenol. Once the distillation of phenol is over, the temperature will increase increased to 205 0C. At this temperature, phenol evaporates again. The free phenol produced in the first stage is obtained by further reducing the Pressure to 15 mm Hg sufficiently distilled off. This transesterification reaction is within finished about 4 hours.

The pressure is then reduced to 1 mm Hg and at this Pressure will gradually increase the temperature. The reaction is carried out for 30 minutes at 2250C, Continued for 2 hours at 2600C and 1 hour at 2950C. The polymer yield is 95%; t sp / C = 0.67. The heat resistance is 1560C and the flow temperature 2680C.

Example 5 A mixture of 14.5 g (0.05 mol) of 1,1-bis (4-hydroxyphenyl) -1-phenylethane and 0.225 g of p-tert-butylphenol is dissolved in an aqueous solution of 5.6 g of sodium hydroxide dissolved in 110 ml of water. 93 g of methylene chloride are then added. At a At a temperature of 200C or less, 6.1 g of phosgene are poured into the Mixture initiated. The reaction mixture obtained is called reaction mixture A designated.

Similarly, a mixture of 11.4 g of 2,2-bis (4-hydroxyphenyl) propane is made and 0.225 g of p-tert-butylphenol in an aqueous solution of 5.6 g of sodium hydroxide dissolved in 90 ml of water, and then treated with 74 g of methylene chloride. At a Temperature of 20 ° C or less 6.1 g of phosgene in the Mixture initiated. This reaction mixture is referred to as reaction mixture B.

Reaction mixture B is added to reaction mixture A.

A uniform reaction mixture is obtained, which with a aqueous solution of 3 g of sodium hydroxide in 25 g of water and 0.078 g of triethylamine is moved. The resulting mixture is stirred for 4 hours at 25 0C polymerized. The polymerization mixture is then diluted with methylene chloride, washed thoroughly with acid and then with water and coagulated with methanol. The polymer yield is 98%, t sp / C = 0.60 dl / g. The powder obtained becomes 6 Hours dried at 1400C in a stream of hot air and then 10 minutes at 2900C and pressed to test specimens at a pressure of 100 kg / cm2. The thermal stability of the obtained copolymer is 1570C and the flow temperature 2600C.

EXAMPLES 1 e 6 to 8 and Comparative Examples 3 and 4 The procedures Examples 1 to 3 are repeated, but the amount is ten times as large elevated. The polymer powders obtained are thoroughly dried and then others Dried 6 hours at 1500C in a stream of hot air.

The polymers are then subjected to the same conditions as in Example 1 to 3 pressed and their physical properties examined. the Results are summarized in Table II.

Table II 1,1-bis (4-hydroxyphenyl) -1 tensile strength Izod notched phenyl ethane / 2,2-bis- (4-hydroxylity, impact strength example elongation,% phenyl) propane, molar ratio kg / cm2 (6.4 mm t), kg-cm / cm2 6 3/1 725 30 8.5 7 1/1 690 45 10.0 8 1/3 650 52 11.0 Comparative 1/0 740 17 6.5 example 3 Comparative 0/1 595 55 11.5 example 4 Tensile strength: Test specimen in the form of a JIS No. 3 dumbbell, drawing speed 10 mm / min. Notched impact strength: according to ASTM test standard D256

Claims (9)

"Polycarbonate Copolycondensates and Process for Their Production" Process for the production of polycarbonate copolycondensates, d it is not stated that 99 to 10 percent by weight of 1,1-bis- (4-hydroxyphenyl) -1-phenylethane is used and 1 to 90 percent by weight of 2,2-bis (4-hydroxyphenyl) propane with phosgene or diphenyl carbonate implements. 2. The method according to claim 1, characterized in that 97 up to 20 percent by weight 1,1-bis (4-hydroxyphenyl) -1-phenylethane and 3 to 80 percent by weight Reacts 2,2-bis (4-hyaroxyphenyl) propane with phosgene or diphenyl carbonate 3. Procedure according to claim 1, characterized in that the reaction with phosgene is carried out in the presence an acid acceptor and in the presence of an inert solvent. 4. The method according to claim 3, characterized in that as Acid acceptor an aqueous alkaline solution or pyridine is used. 5. The method according to claim 3, characterized in that the Implementation at temperatures from 0 to 1000C. 6. The method according to claim 1, characterized in that the Implementation with diphenyl carbonate in two stages. 7. The method according to claim 6, characterized in that the the first stage is carried out as a condensation reaction. 8. The method according to claim 6, characterized in that the second stage is carried out as a polymerization reaction. 9. Polycarbonate copolycondensates, obtainable by one process according to any one of claims 1 to 8.