DE3922496A1 - Thermally-stable, gas-permeable co-polycarbonate(s) - based on 1,1-bis-4-hydroxyphenyl -cycloalkane(s) phenolphthalein-like bisphenol(s) and other bisphenol(s), pref. bisphenol=A - Google Patents

Abstract

Copolycarbonates (I) are based on (a) 5-90 pts.wt. bisphenol of formula (II), (b) 1-90 pts.wt. bisphenol of formula (III) and (c) 0-30 pts.wt. other known bisphenols of formula HO-Z-OH (IV); R1, R2 = H, Hal (pref. Cl or Br), 1-8C alkyl, 5-6C cycloalkyl, 6-10C aryl (pref. Ph), 7-12C aralkyl (pref. (1-4C alkyl)-phenyl, esp. pref. benzyl) or 1-7C alkoxy, pref. OMe; in (III), R1, R2 pref. = H; R3, R4 = H or 1-6C alkyl (can be different for each X, but at least one, pref. both = alkyl on at least one X atom); X = carbon; m = 4-7, pref. 4-5; Z = 6-30C aromatic residue with 1 or more aromatic nuclei, opt. substd. and opt. contg. aliphatic residues, cycloaliphatic residues other than (II) or (III), or heteroatoms as bridging units. USE/ADVANTAGE - (I) are useful for the prodn. of injection moulded and extruded prods., fibre, etc. and esp. film of thickness 5-2000 microns. Moulded parts, film, fibres and laminated film contg. (I) are claimed as such. They have good thermal dimensional stability, good permeability w.r.t. a range of gases, and good UV stability and fire resistance.

Description

The present invention relates to copolycarbonates Base of

• a) 5 to 90 parts by weight, preferably 10 to 85 parts by weight, in particular 15 to 80 parts by weight of bisphenol of the formula (I) wherein
  R₁ and R₂ independently of one another are hydrogen, halogen, preferably chlorine or bromine, C₁-C₈-alkyl, C₅-C₆-cycloalkyl, C₆-C₁₀-aryl, preferably phenyl, C₇-C₁₂-aralkyl, preferably phenyl-C₁-C₄-alkyl, in particular benzyl, and C₁-C₇ alkoxy, preferably methoxy,
  m is an integer from 4 to 7, preferably 4 or 5,
  R₃ and R₄ individually selectable for each X, independently of one another hydrogen or C₁-C₆ alkyl and
  X is carbon,
  with the proviso that at least one atom X means at least one of the substituents R₃ or R₄, preferably both at the same time, alkyl and
• b) 1 to 90 parts by weight, preferably 5 to 80 parts by weight, in particular 10 to 50 parts by weight of bisphenol of the formula (II) wherein
  R₁ and R₂ have the same meaning as in formula (I), preferably represent hydrogen, and
• c) 0 to 30 parts by weight, preferably 0 to 25 Parts by weight, in particular 0 to 20 parts by weight other known bisphenols of the general formula (III) HO-Z-OH (III) in which Z for an aromatic radical with 6 to 30 carbon atoms, one or more aromatic May contain cores, may be substituted and aliphatic or other cycloaliphatic Residues as those of formula (I) or residues (II) or can contain heteroatoms as bridge members.

Preferred bisphenol compounds of the formula (I) are

Preferred bisphenols of the formula (II) are

Suitable other bisphenols of the formula (III) are, for example

Hydroquinone,
Resorcinol,
Dihydroxybiphenyls,
Bis (hydroxyphenyl) alkanes,
Bis (hydroxyphenyl) cycloalkanes,
Bis (hydroxyphenyl) sulfides,
Bis (hydroxyphenyl) ether,
Bis (hydroxyphenyl) ketones,
Bis (hydroxyphenyl) sulfones,
Bis (hydroxyphenyl) sulfoxides,
α, α′-bis (hydroxyphenyl) diisopropylbenzenes
and their nuclear alkylated and nuclear halogenated compounds.

These and other suitable other diphenols (III) are e.g. B. in US-PS 30 28 365, 29 99 835, 31 48 172, 32 75 601, 29 91 273, 32 71 367, 30 62 781, 29 70 131 and 29 99 846, in German Offenlegungsschriften 15 70 703, 20 63 050, 20 63 052, 2 21 10 956, the French Patent 15 61 518 and in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964 ".  

Preferred other diphenols are, for example:

4,4'-dihydroxybiphenyl,
2,2-bis (4-hydroxyphenyl) propane,
2,4-bis (4-hydroxyphenyl) -2-methylbutane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
α, α′-bis (4-hydroxyphenyl) -p-diisopropylbenzene,
2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-chloro-4-hydroxyphenyl) propane,
Bis (3,5-dimethyl-4-hydroxyphenyl) methane,
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane,
Bis (3,5-dimethyl-4-hydroxyphenyl) sulfone,
2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane,
1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane,
α, α′-bis- (3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene,
2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane and
2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.

Diphenols of the formula (III) are particularly preferred for example:

2,2-bis (4-hydroxyphenyl) propane,
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane,
2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane,
2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and
1,1-bis (4-hydroxyphenyl) cyclohexane.

In particular, 2,2-bis (4-hydroxyphenyl) propane is preferred.  

The high molecular copolycarbonates from the diphenols of the formulas (I), (II) and (III) can be according to the known Polycarbonate manufacturing processes are produced. The different diphenols can be both statistical as well as linked together in blocks be.

The polycarbonates can be branched in a manner known per se be. If branching is desired, it can in a known manner by condensing in small amounts, preferably amounts between 0.05 and 2.0 mol% (based on diphenols used), on three or more than trifunctional compounds, especially those with three or more than three phenolic hydroxyl groups can be achieved. Some branches with three or more than three phenolic hydroxyl groups

Phloroglucin,
4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2,
4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) heptane,
1,3,5-tri- (4-hydroxyphenyl) benzene,
1,1,1-tri- (4-hydroxyphenyl) ethane,
Tri- (4-hydroxyphenyl) phenylmethane,
2,2-bis (4,4-bis (4-hydroxyphenyl) cyclohexyl) propane,
2,4-bis (4-hydroxyphenyl-isopropyl) phenol,
2,6-bis (2-hydroxy-5'-methylbenzyl) -4-methylphenol,
2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane,
Hexa- (4- (4-hydroxyphenyl-isopropyl) phenyl) orthoterephthalic acid ester,
Tetra- (4-hydroxyphenyl) methane,
Tetra- (4- (4-hydroxyphenyl-isopropyl) phenoxy) methane and
1,4-bis - ((4 '-, 4''- dihydroxytriphenyl) methyl) benzene.

Some of the other tri-functional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.

As a chain terminator for the known regulation of the Molecular weight of the copolycarbonates serve monofunctional Compounds in usual concentrations. Suitable Connections are e.g. B. phenol, tert-butylphenols or other alkyl-C₁-C₇-substituted phenols. To Regulation of the molecular weight is particularly small Amounts of phenols of formula (IV) are suitable

wherein R represents a branched C₈ and / or C₉ alkyl radical. The proportion of CH₃- in the alkyl radical R is preferred. Protons between 47 and 89% and the proportion of CH and CH₂ protons between 53 and 11%; also preferred R is in the o- and / or p-position to the OH group, and the upper limit of the ortho component is particularly preferred 20%. The chain terminators are generally in Amounts of 0.5 to 10, preferably 1.5 to 8 mol%, based on diphenols used.  

The copolycarbonates can preferably after Phase boundary method (see H. Schnell, "Chemistry and Physics of Polycarbonates ", Polymer Reviews, Vol. IX, pages 33 ff., Interscience Publ., 1964) in itself be made in a known manner. Here, the Diphenols of the formulas (I), (II) and (III) with the specified Parts by weight in the aqueous alkaline phase solved. To regulate the molecular weight can Chain breaker z. B. the formula (IV) are added. Then in the presence of an inert, preferably Polycarbonate dissolving organic phase with phosgene according to the method of phase interface condensation implemented. The reaction temperature is between 0 ° C and 40 ° C.

The branching agents which may be used (preferred 0.05 to 2 mol%) can either with the diphenols in be submitted to the aqueous alkaline phase or in the organic solvent dissolved before phosgenation be added.

In addition to the diphenols of the formulas (I), (II) and (III) can also their mono- and / or bis-chlorocarbonic acid esters be used, these in organic Solvents are added dissolved. The amount of Chain breakers and branches are then aimed according to the molar amount of diphenolate residues Formulas (I), (II) and (III), when used of chlorocarbonic acid esters the amount of phosgene in known manner can be reduced accordingly.  

Suitable organic solvents for the chain terminators as well as for the branching and the Chlorocarbonic acid esters are, for example, methylene chloride, Chlorobenzene, acetone, acetonitrile and mixtures these solvents, especially mixtures of Methylene chloride and chlorobenzene. If necessary, the used chain breakers and splitters in the same Solvent can be solved.

As an organic phase for interfacial polycondensation is used for example methylene chloride, chlorobenzene and mixtures of methylene chloride and chlorobenzene.

For example, serves as the aqueous alkaline phase aqueous NaOH solution.

The production of the co-polycarbonates after Phase boundary processes can be carried out in the usual way Catalysts such as tertiary amines, especially tertiary ones aliphatic amines such as tributylamine or triethylamine be catalyzed; the catalysts can be used in quantities from 0.05 to 10 mol%, based on moles, of Diphenols can be used. The catalysts can before the start of phosgenation or during or after be added to the phosgenation.  

The copolycarbonates can also according to the known Process in homogeneous phase, the so-called "pyridine process" as well as the known melt transesterification process using, for example, diphenyl carbonate instead of phosgene.

The copolycarbonates preferably have molecular weights w (weight average, determined by gel chromatography after prior verification) of at least 10,000, especially preferably from 10,000 to 200,000 and in particular from 20,000 to 80,000. They can be linear or branched be, they are copolycarbonates based on the diphenols of the formulas (I), (II) and (III).

The invention also relates to the production the copolycarbonates based on the diphenols of the formula (I), (II) and (III) in the parts by weight mentioned the phase boundary method.

The copolycarbonates according to the invention are thermally stable and quite permeable to a number of gases. They are still UV stable and have a good one Flame resistance.

From them, molded parts such. B. fibers, foils, Filaments and three-dimensional molded parts will. The copolycarbonates are preferred Injection molded articles, extrusion articles and in particular Films between 5 and 2000 microns thick.  

The production of films from the copolycarbonates mentioned can be done using conventional techniques, for example by pouring the individual polymer solution, preferably mixtures of CH₂Cl₂ as solvent and CHCl₃ can be used. As a casting machine can both used a drum as well as a belt casting machine will. Another way of making films consists in extrusion, whereby the polymers are melted and the melt is expressed through a nozzle becomes.

Composite films with other polymers can also be produced will. The production of plastic composite films can be done in different ways. requirement is that they have a joint liability that for example in the thermoforming of composite films withstands occurring shear stresses. Under Thermoforming of foils is the production of To understand molded articles from films, the to deforming plastic film to temperatures above the Softening point of the respective plastic is heated and with the help of vacuum or compressed air to a corresponding one Formling is reared, which in the present Fall in general temperatures between 180 ° C and 370 ° C are required.

A particularly good bond is achieved through use suitable adhesive based on polyurethane achieved, wherein in particular thermally stable adhesives are used, the one during the thermoforming due to crosslinking achieve optimal stability.  

The films can also be cold stretched getting produced.

The cold stretching process corresponds to the deep-drawing forming process known from the metal sheet and cardboard processing industry. Here, the composite film is pressed into a corresponding shape at high speed by means of a drawing punch, as is shown schematically in FIGS. 15 to 18. This process is particularly economical when simple geometric containers are formed.

Preferred electronic components for which according to the present Invention containers are made for example capacitors, coils, rectifiers, Thermocouples, complex components such as high-voltage cascades and amplifier circuits.

The films can also be made from solutions.

A concentrated solution of the polymer is poured out in a suitable solvent on one level Pad, evaporates the solvent and lifts the formed film from the base. The slides can in a conventional manner at temperatures between Room temperature and the softening point of the foils, if necessary also beyond this temperature, as far as the viscosity of the polymer is not too strong is lowered, stretched on known devices will.  

The copolycarbonates can be made before or during manufacture additives common to moldings such as anti-aging agents, Reinforcing materials, flame retardants or UV stabilizers are added.

Examples 1. Preparation of the bisphenol (Ia)

7.5 mol (705 g) of phenol and 0.15 mol (30.3 g) of dodecylthiol are placed in a 1 liter round-bottom flask equipped with a stirrer, dropping funnel, thermometer, reflux condenser and gas inlet tube and at 28 to 30 ° C. with dry HCl -Gas saturated. A solution of 1.5 mol (210 g) of dihydroisophorone (3,3,5-trimethylcyclohexan-1-one) and 1.5 mol (151 g) of phenol are added dropwise to this solution over the course of 3 hours, with further HCl gas is fed through the reaction solution. When the addition has ended, HCl gas is passed in for a further 5 hours. The mixture is left to react for 8 hours at room temperature. The excess phenol is then removed by steam distillation. The remaining residue is extracted twice with petroleum ether (60-90) and once with methylene chloride and filtered off.
Yield: 370 g.
Melting point: 205 to 207 ° C.

2. Production of copolycarbonates A) Not according to the invention Substance 1a

3523.9 g (11 mol) of bisphenol are placed in a reactor of the formula (IIa) 528 g (13.2 mol) of NaOH and 15.1 ml (1 mol%) of N-ethylpiperidine in 55.7 kg Water dissolved. 18.71 kg of methylene chloride, 15.57 kg chlorobenzene and 15.528 g (1.5 mol%) Phenol added. Then phosgene is introduced, the pH of the aqueous phase being added dropwise is kept from 45% NaOH to pH 7-8. The reaction is complete when the aqueous phase no longer contains bisphenol of the formula (IIa). A total of About 2938 g (29.7 mol) of phosgene are introduced. After the initiation will be completed a further 15.1 ml of N-ethylpiperidine were added and 45 Stirred minutes at pH 7-8. The reaction temperature was 20-25 ° C. The phases are then separated, the organic phase with phosphoric acid washed and then with water washed free of electrolyte; relative viscosity, together in 52 g / l polymer in methylene chloride 25 ° C, from 1293.  

Substance 1b

1483.9 g (6.5 mol) of bisphenol are placed in a reactor A, 1121.2 g (3.5 mol) of bisphenol of the formula (IIa) 1067 g (12 moles) 45% NaOH and 13.75 ml (1 mol%) N-ethylpiperidine dissolved in 50.63 kg water. There will be 35.34 kg of methylene chloride and 18.822 g (2 mol%) of phenol added. Then it will be Phosgene introduced, the pH of the aqueous Phase by dropping 45% NaOH pH 7-8 is maintained. The reaction is over when the aqueous phase no longer contains bisphenols contains. A total of approx. 2671 g (27 moles) Phosgene introduced. At the end of the introduction a further 13.75 ml of N-ethylpiperidine are added and stirred for 45 minutes at pH 7-8. The reaction temperature was 20-25 ° C. The phases are then separated, using the organic phase Washed phosphoric acid and then with water washed free of electrolyte; relative viscosity = 1,266.

Substance 1c

684.9 g (3 mol) of bisphenol are placed in a reactor A, 2242.5 g (7 moles) of bisphenol of the formula (IIa) 480 g (12 mol) NaOH and 13.75 ml (1 mol%) N-ethylpiperidine dissolved in 50.63 kg of water. It 39.31 kg of methylene chloride and 16.94 g (1.8 mol%) phenol added. Then phosgene  initiated, the pH of the aqueous phase kept at pH 7-8 by dropwise addition of 45% NaOH becomes. The reaction is over when the aqueous phase no longer contains bisphenols. A total of About 2671 g (27 mol) of phosgene are introduced. After the initiation will be completed a further 13.75 ml of N-ethylpiperidine were added and 45 Stirred minutes at pH 7-8. The reaction temperature was 20-25 ° C. The phases are then separated, the organic phase with Washed phosphoric acid and then with water washed free of electrolyte; relative viscosity = 1.28.

B) According to the invention Substance 1d

15.5 g (50 mmol) of bisphenol are placed in a flask of the formula (Ia), 16 g (50 mmol) of bisphenol of the formula (IIa), 4.8 g (120 mmol%) NaOH and 0.15 ml (1 mol%) N-ethylpiperidine dissolved in 506 g of water. It will 230 ml methylene chloride and 141 mg (1.5 mol%) phenol admitted. Then phosgene is introduced, whereby the pH of the aqueous phase by dropping 45% NaOH is kept at pH 7-8. The reaction is finished when the aqueous phase is none Bisphenols contains more. In total, approx. 26.7 g (270 mol) of phosgene introduced. To Completion of the introduction will be another 0.15 ml N-ethylpiperidine was added and 45 minutes  stirred at pH 7-8. The reaction temperature was 20-25 ° C. The phases are then separated, the organic phase with phosphoric acid washed and then electrolyte-free with water washed; relative viscosity = 1.205.

3. Production of the foils

Films were in each case from the substances 1a-1d prepared in which the substances in methylene chloride were dissolved, the solution concentrated was and from the thickened solution on a Foil drawing bench a film was made.

4. Determination of gas permeability

The passage of a gas through a dense polymer membrane is through a solution diffusion process described. The characteristic constant is the permeation coefficient for this process P, which indicates the gas volume V for a given Pressure difference Δp in a certain time t by a film of known area F and thickness d passes through. For the steady state, the differential equations of the permeation process derive:

In addition, the permeation depends on the Temperature and gas humidity.

The measuring arrangement consists of a thermostatted Two-chamber system. One chamber is for the Designed to accept the permeate. The chambers are separated by the polymer membrane to be measured.

Before the gas supply, both chambers are opened 0.001 mbar evacuated and then the specification chamber with Gas filled. The permeated gas - inert gases - then causes in the permeate chamber at constant Volume a pressure increase with a pressure transducer - Baratron from MKS - depending from time to steady gas passage is registered. This turns V into NTP according to (1) calculated, t is known. The specified pressure difference taking into account the external air pressure Δp is set to 100 kilo-Pascals. The membrane area F is known. The membrane thickness d is measured using a micrometer screw Average of 10 independent, across the membrane surface distributed thickness measurements determined.

The permeation coefficient is from these quantities P to be determined according to (1) in dimension

referring to a membrane thickness of 1 mm.

Other measurement parameters are:
Temperature 25 ± 1 ° C,
rel. Gas humidity 0%.

Results of the permeation coefficients for the films the following table shows:

5. Assessment of heat resistance

The heat resistance was due to the dimensional stability of the respective co-polycarbonate 245 ° C assessed under mechanical stress. As A measure of good heat resistance can Example a high shear modulus at a high temperature be used. As long as the thrust module is higher than 40 MPa, the molded parts are in the Usually quite stable and do not melt.  

Assessment of substances 1a to 1d

Claims (2)

1. Copolycarbonate based on

• a) 5 to 90 parts by weight of bisphenol of the formula (I) wherein
  R₁ and R₂ independently of one another are hydrogen, halogen, preferably chlorine or bromine, C₁-C₈-alkyl, C₅-C₆-cycloalkyl, C₆-C₁₀-aryl, preferably phenyl, C₇-C₁₂-aralkyl, preferably phenyl-C₁-C₄-alkyl, in particular benzyl, and C₁-C₇ alkoxy, preferably methoxy,
  m is an integer from 4 to 7, preferably 4 or 5,
  R₃ and R₄ individually selectable for each X, independently of one another hydrogen or C₁-C₆-alkyl and
  X is carbon,
  with the proviso that at least one atom X means at least one of the substituents R₃ or R₄, preferably both at the same time, alkyl,
• b) 1 to 90 parts by weight of bisphenol of the formula (II) wherein
  R₁ and R₂ have the same meaning as in formula (I), preferably represent hydrogen, and
• c) 0 to 30 parts by weight of other known bisphenols of the general formula (III) HO-Z-OH (III) in which Z represents an aromatic radical having 6 to 30 C atoms, which may contain one or more aromatic nuclei may and may contain aliphatic radicals or cycloaliphatic radicals other than that of the formula (I) or radicals (II) or heteroatoms as bridge members.

2. Molded parts, foils, fibers, composite foils, the co Polycarbonates according to claim 1 included.