DE2117510A1 - Polycarbonate preparations stable against thermal oxidation and process for their production - Google Patents

Description

Polycarbonate preparations stable against thermal oxidation and process for their production

The present invention relates to polycarbonate preparations, which are stable to oxidation when heated, and especially polycarbonate preparations which contain small amounts of phosphorus Contain compounds linked to the polymer chain. The invention also relates to manufacture the polymers stable to oxidation when heated, which are described below.

Although the incorporation of phosphorus into polymer chains has already been described has been disclosed, for example, in U.S. Patent 3,378,523 and in

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of publication by G.S. Kolesnikov et al in Vysokomolsoyed A 9; No. 10, pages 2246-2249, 1947, does not include any of these Publications the incorporation of small amounts of phosphorus-containing substances in polymer chains to a strongly increased thermal To maintain stability.

Because of the use of elevated deformation temperatures for polycarbonates and because of the use of deformed polycarbonate bodies at higher temperatures it becomes increasingly important to find polycarbonates which have an increased stability against thermal Possess decomposition or discoloration at elevated temperatures.

It has surprisingly been found that by incorporating small amounts of phosphorus-containing substances into the polymer chains thermally stable polycarbonates can be obtained.

According to the method according to the invention, a bivalent reacts Phenol, such as 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol-A) with a carbonate precursor and a small amount of an ester of a phosphoric acid halide from the shape

R. Π - P

where X is in each case identical or different halogen atoms selected from the group consisting of fluorine, ChIOr _5, bromine and iodine, and R represents an organic radical having t to 25 carbon atoms; R can be an aryl, haloaryl, alkyl, cycloalkyl, aralkyl or alkaryl radical. In addition, the polymer described above can contain an admixture of an epoxy compound.

The following examples serve to illustrate the principle and practice of OCE invention, "Unless otherwise specified, data denote In parts

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or percentages by weight or parts by weight.

Example I.

In a reaction vessel, which is equipped with a reflux condenser and mechanical stirrer, JB kg of methylene chloride, 953 kg of 2,2-bis- (M-hydroxyphenyl) propane, 8.5 kg of calcium hydroxide, 0.188 kg of p-tert-butylphenol and 4.7 ml of triethylamine given. The slurry is stirred and phosgene is added at a rate of 6 kg per hour. The phosgene addition is ended after ^ 8 minutes. The solid polycarbonate is recovered by filtering and evaporating the solvent. The polycarbonate is extruded overnight at 125 ⁰ C and dried at 27 ¹ I ⁰ C (525 ° P). The pressed product is crushed into pellets. These pellets are denoted by A.

Example II

7β kg methylene chloride, 9.53 kg 2.2 ~ bis (* l-hydroxphenyl) propane, 8.5 kg calcium hydroxide, 0.188 kg p-tert-butylphenol, * J, 7 ml of triethylamine and 7.1 ml of phenylphosphorus dichloridite were added. The slurry is stirred and phosgene is added at a rate of about 6 kg per hour. After 43 minutes, the phosgene addition is ended and the polycarbonate is obtained as in Example I and pelletized.

The elementary phosphorus content of the polycarbonate is determined by means of the Schoninger combustion method, which is described in "Identification and Analysis of Plastics "by Haslum and Willis, Iliffe Books, London, 1965» page 8. Der Elemental phosphorus content was found to be 0.0086 percent by weight. The polycarbonate pellets thus obtained are labeled with B designated.

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Example III

Example II is made with 28 ^ 1 ml of phenyl phosphorodichloridite instead of 7jl ml. The elementary phosphorus content found to be 0.0185 percent by weight. The polycarbonate pellets obtained in this way are designated with C.

Example IV

From the polycarbonate pellets of Examples I to III are in the temperatures given in Table 1 test specimen molded. The thermal stability, based on discoloration, is under Use of the IDL Color Eye Colorimeter indicated in the form of APHA (American Public Health Association) numbers. The following results will get:

Gev.% V phosphorus Table 1 ° C (550 APHA ⁰ C (600 ⁰ F) 0 62 ⁰ F) 316 se sample 0 , 0086 288 " 23 23 A. 0 , 0185 20th 20th B. C. example

Example IV is repeated with the difference that 0.1 % 3, ^ - Epoxycyclohexylmethy1-3,4-epoxycyclohexane-carboxylate are mixed with the polycarbonate pellets. Samples B and C are molded at the temperatures shown in Table 2. The samples are aged for 7 days at IO I ^{1 0} C by heat. The thermal stability of these samples, based on discoloration, is then investigated in the same way as for sample IV. The following results were found:

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Weight % Table 2 the one in heat aged samples 0
0 APHA ° C (550 ⁰ F) 316 ⁰ C (600 ⁰ F) sample Phosphorus 288 117
37
32 152
ill
35 A.
B.
C. 0
, 0086
, 0185

The present invention deals with a thermally stable polymer composition, specifically a thermally stable polycarbonate, in the polymer structure of which an amount from 0.0005 to 1.0 Percentage by weight of elemental phosphorus - based on the total amount of the polymer - were incorporated.

The polymer according to the invention is the residue of the condensation reaction a dihydric phenol, a carbonate precursor and a small amount of an ester of phosphoric acid dihalide the formula:

where X is in each case identical or different halogen atoms selected from the group consisting of fluorine, iodine, bromine and chlorine and R represents an organic radical having 1 to 25 carbon atoms; R can be an aryl, haloaryl, alkyl, cycloalkyl, Be aralkyl or alkaryl. The invention also relates to an improved method for the preparation of the invention Polycarbonate preparations. This procedure consists of the preparation of polymers that are stable to thermal oxidation by reacting a dihydric phenol, a Carbonate precursor and a small amount of an ester of phosphoric acid dihalide in an organic medium such as methylene chloride and in the presence of a catalyst, a molecular weight regulator and an acid acceptor. Per mole of dihydric phenol there will be 0.000015 to about 0.05 moles of phosphoric acid ester dihalide used.

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In the ester of phosphoric acid dihalide - see above Formula - R can be an alkyl, such as methyl, ethyl, n-propyl, isopropyl, η-butyl, sec-butyl, tertiary-butyl, n-amyl, Isoamyl, tertiary amyl, n-hexyl, dodecyl and nonyl; further Cycloalkyl, such as cyclohexyl, 2-methyl-cyclohexyl, 4-methylcyclohexyl, 2-ethyl-cyclohexyl, 4-ethyl-cyclohexyl and 4-isopropyl-cyclohexyl; also aryl, such as phenyl, naphthyl, 1-naphthyl, 2-naphthyl, biphenyl and terphenyl; also aralkyl, such as benzyl, phenylethyl, 2-phenylethyl, 1-phenylpropyl and 2-phenylpropyl; also alkaryl, p-tolyl, o-tolyl, 2,6-XyIyI, para-cumyl, m-cumyl, o-cumyl, mesityl and p-tert-butylphenyl; also halogenaryl, such as 2-chlorophenyl, 2,4,6-trichlorophenyl and 2,4,6-tribromophenyl.

The novel polycarbonate can be mixed with epoxy compounds represented by the following formula:

and Rj, are independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, substituted aryl and heteroxyclic organic radicals, the organic radicals having 1 to 2k carbon atoms. sen. Although the number of hydrogen atoms can vary, the volatility of the epoxy compound depends on it. The number of hydrogen atoms should be chosen so that the tendency of the epoxy compound to volatilize at low temperatures is kept as small as possible, otherwise the benefit of the polymers of this invention would be lost at the molding temperatures which are used in the manufacture of molded articles from the polymeric material were applied.

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The amount of the epoxy compound used can be practical To practice this invention vary from 0.01 to 1.0 weight percent based on the weight of the polymeric material; it is preferably 0.03 to 0.50 percent by weight. Although greater than 1 percent by weight epoxy compounds can be used, it has been shown that larger amounts tend to reduce the physical properties of the To worsen copolycarbonate phosphite and thereby the usefulness of the polymer for producing tough, flexible, deformed objects.

In practicing this invention, instead of 3 ^ -epoxycyclohexylmethyl-3j ¹ * -epoxycyclohexane carboxylate, as in the examples, other epoxy compounds are used with essentially the same results. Such epoxy compounds are: 3 ^ - epoxy-6-methylcyclohexylmethyl-3, ^I -epoxy-6-methylcyclohexane carboxylate, 2,3-epoxycyclomethyl-3, i | -epoxycyclohexane carboxylate, 4- (3,4-epoxy-5-methylcyclohexyl ) butyl-3, ¹ t-epoxycyclohexane carboxylate, 3,4-Epoxycyclohexyläthylenoxld-di-3, ^ - epoxy-6-methylcyclohexylmethyladipat, cyclohexylmethyl-3, ⁱ i-epoxycyclohexanecarboxylate, 3, A-epoxy-ö-methylcyclohexylmethyl-ö-methylcyclohexyl carboxylate , bisphenol-A-diglycidylather, tetrabromobisphenol-A-diglycidylather, Diglyöidylester of phthalic acid, diglycidyl esters of Hexahydrophthaisäure, Bisepoxydicyclopentadienyläther of ethylene glycol, epoxidized Saubohnenöl, Bisepoxycyclohexyladipat, butadiene diepoxide, Tetraphenyläthylenepoxid, indene oxide, octyl epoxytallate, epoxidized polybutadiene and cyclododecene epoxide. The preferred epoxy compound used in the practice of this invention is 3 »4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate.

The dihydric phenols which can be used to prepare the copolymer in this invention are bisphenols such as bis (1 | -lydroxyphenyl) methane, 2,2-bis (1-hydroxyphenyl) propane, 2,2-bis (4-hydroxy -3-methylphenyl) propane, M, 4-Bls ( k- hydroxyphenyl) heptane, 2,2-Bls ( ¹ »-hydroxy-3,5-dichlorophenyl) propane, 2,2-BIs ( ¹ J-hydroxy-3 , 5-dibroinphenyl) propane etc., also divalent

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Phenol esters, such as bis (4-hydroxyphenyl) ether, bis (3,5-dichloro-4-hydroxyphenyl) ether, etc., and also dihydroxydiphenple, such as p, p-dihydroxyphenyl, 3,3'-dichloro-4, i! ^l -dihydroxydipheny, etc., also dihydroxyarylsulfones, such as bis (4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, etc., also dihydroxybenzenes, resorcinol, hydroquinone, halogen- and alkyl-substituted dihydroxybenzenes, such as 1,4-dihydroxy-2-chlorobenzene, 1,4-dihydroxy-2,5-dichlorobenzene, 1,4-dihydroxy-3-methylbenzene etc., also dihydroxydiphenyl sulfoxides, such as bis (4-hydroxyphenyl) sulfoxide, bis (3, 5-dibromo-4-hydroxyphenyl) sulfoxide, etc. A number of additional dihydric phenols which are used to obtain the carbonate polymers are disclosed in U.S. Patent 2,999,835, 3028 36 ^ 3 and I53 008th It is of course possible to use two or more different dihydric phenols or a copolymer of a dihydric phenol with glycol or with a polyester which has a terminal hydroxyl or acid group, or with a dibasic acid if more of a carbonate copolymer or interpolymer than a homopolymer is desired to make aromatic polymers of this invention.

The carbonate precursors involved in practical implementation Applied to this invention can be either a carbonyl halide or a bishalogen format. The carbonyl halides, which can be used here are carbonyl chloride, carbonyl bromide and mixtures thereof; the bis-halogen formats dihydric phenols (bishloro formats of hydroquinone, etc.) or glycols (bishalogen formats of ethylene glycol, Neepentyl glycol, polyethylene glycol, etc.). Even if other carbonate precursors are known to the person skilled in the art, carbonyl chloride, also known as phosgene, is preferred.

As already mentioned, the reaction can take place in the presence of an acid acceptor which can be either an organic or inorganic compound. A useful organic one Acid acceptor is a tertiary amine included

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such substances as pyridine, triethylamine, dimethylaniline, Tributylamine, etc. Either a hydroxide, a carbonate, a bicarbonate or a is used as the inorganic acid acceptor Phosphate of an alkali or alkaline earth metal.

As molecular weight regulators used in the manufacturing process of aromatic polycarbonate resins, serve phenol, cyclohexanol, methanol, para-tertiary butylphenol, para-bromophenol, etc. Para-tertiary butyphenol is preferred used as a molecular weight regulator.

The above examples are only intended to illustrate the present invention.

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Claims (8)

21175T0 - ίο - claims 1. Polymer preparations stable against thermal oxidation, characterized in that they Residue from the condensation reaction of a dihydric phenol, a carbonate precursor and a small amount an ester of a phosphoric acid dihalide having the formula R-O-P ^ X are »where for X identical or different halogen atoms, which are selected from the group consisting of fluorine, chlorine, bromine, iodine, and R is an organic radical from aryl, Haloaryl, alkyl, cycloalkyl, aralkyl or alkaryl radicals having 1 to 25 carbon atoms. 2. Polymer preparation according to claim 1, characterized that it contains 0.0005 to 1.0 weight percent elemental phosphorus. 3. Polymer preparation according to claim 1 or 2, characterized characterized in that the ester of phosphoric acid dihalide is a phenyl phosphorus dichloride. k. Polymer preparation according to Claims 1 to 3, characterized in that the dihydric phenol is bisphenol-A. 5. Polymer preparation according to claims 1 to ή, characterized in that it has a Contains the addition of 0.01 to about 1.0 weight sprout of an epoxy compound with the following formula: ORIGINALINSPECTED 109844/1815 - li - O
^R 3. wherein R ₁ , R «, R, and R _{11 are} independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl and heterocyclic radicals having 1 to 24 carbon atoms and mixtures thereof. 6. Polymer preparation according to claim 5 »characterized that the epoxy compound is an epoxidized cycloaliphatic compound. 7. Polymer preparation according to claim 5 »characterized in that the epoxy compound 3 * 4- hexyl
Is epoxycyclohexanyl-JjH-epoxycyclohexane carboxylate. 8th]. A process for preparing a stable against thermal oxidation polymer preparation according to claims 1 to 7 by reacting a dihydric phenol with a carbonyl natvorstufe in the presence of an acid acceptor, a catalyst and a regulator of the molecular weight, characterized in that per mole of dihydric phenol 0.000015 to 0.05 mol of an ester of a phosphoric acid dihalide having the formula R-O-P are reacted, in which X are identical or different halogen atoms fluorine, chlorine, bromine and iodine are selected from the group and R is an organic radical 109844/1815 21175 ι ö is made from aryl, haloaryl, alkyl, aralkyl or · kllz & ry radicals with 1 to 25 carbon atoms. 9- The method according to claim 8, characterized in that the ester of the phosphoric acid dihalide is phenylphosphorus dichloride. 1 0 9 8 U Ll 1 8 1 B bad original