DE3041298A1 - Polycarbonate with improved hydrolytic stability - contains di:epoxy ether and opt. organo-phosphite colour stabiliser - Google Patents

Abstract

A polycarbonate compsn. with improved hydrolytic stability contains a stabilising amt. of a bis-epoxy ether of formula (I) (where R is alkylene esp. butylene; R1 and R2 are alkylene esp. methylene; R3-R8 are alkyl or esp. H and n and m are 0 or 1 esp. 1). Also claimed is a polycarbonate compsn. contg. (I) and an organophosphite colour stabiliser. The polycarbonates are transparent and colourless and are resistant to becoming opaque and brittle when exposed to elevated temps. and moisture. The compsn. can be for containers eg. bottles and baby bottles which can be sterilised.

Description

Polycarbonate preparation

With Improved Hydrolytic Stability The invention relates to an improved, transparent and colorless polycarbonate preparation which, if they are exposed to increased temperatures and humidity, against embrittlement and formation is resistant to turbidity. The improved polycarbonate feed) preparation of the present Invention contains an aliphatic in a mixture with an aromatic polycarbonate Bis (eloxy ether) as a stabilizer against hydrolysis.

Polycarbonas: - Resins have been used in many industries to manufacture Plastic parts found extensive use.

Your increased effort is due in part to toughness and transparency of the aromatic polycarbonate.

Polycarbonate resins have been used extensively as a substitute for glass used in its applications for glazing purposes.Transparent polycarbonates are also used for the manufacture of bottles that are compared to glass bottles have a superior breaking strength. As such, the Polycarbonate attracts versatile attention of use for found the manufacture of bottles.

When used for bottle production, they become transparent Polycarbonates are now used for molding baby feeding bottles because of their obvious Safety feature of superior breaking strength is used. Unfortunately this shows transparent baby feeding bottles the disadvantages that they are in after sterilization Consider water or moisture cloudy and somewhat brittle at elevated temperatures. When this happens, the goal becomes, namely, grazing the transparent polycarbonate Making it attractive for compression-molded baby feeding bottles is a failure. These problems, In particular that of clouding, are prevented by adding color stabilizers, such as the organophosphites, aggravated to polycarbonate resin. The addition of organophosphite stabilizers on polycarbonate resins is known to the person skilled in the art and in many patents, including U.S. Patent 4,138,379.

In general, the color stabilizers are used to create more transparent, colorless molded parts required Without these color stabilizers, the polycarbonate has a tendency generally used to provide pressed parts with a yellowish appearance. However leads the addition of color stabilizers to polycarbonate resin tends to be a disadvantage Influence of the hydrolic stability of the polycarbonate resin. lem according to the addition of color stabilizers to polycarbonate resin feels like a polycarbonate, which is generally colorless, but also to a polycarbonate resin, its hydrolytic Stability is inconceivable for a polycarbonate resin that does not contain any color stabilizers The prior art includes several patents referring to the use of epoxy compounds with polycarbonates are turned off. One such patent is the OS-PS 3,489,716, which the use of a cycloaliphatic Epoxy, which contains 1,2-cycloaliphatic rings, describes with polycarbonates. Another Patent is US Pat. No. 3,634,312, which discloses the use of a large number of of epoxy compounds that are used together with a CopolyearbJnat can be, and especially poly (bisphenol-A-carbonate-co-phosphite). The cycloaliphatic ] Spoxy compounds are useful in the practice of the present invention usually unsuitable as they are generally after steam treatment in the autoclave lead to a certain cloudiness. In addition, the phosphite-containing polycarbonates are generally unsuitable as they also lead to clouding of clear bottles the steam treatment in the autoclave.

The US-PS 839 247 teaches that the disadvantages of cloudiness (J and embrittlement of clear polycarbonate bottles when treated with water or moisture elevated temperatures can be overcome by either aromatic or clipatic epoxy compounds incorporated in a mixture with the polycalbonate. Even though the introduction of aromatic epoxy compounds the problems of clouding and embrittlement dissolves, the bottles pressed from this preparation generally tend to in most cases to show a pink hue, The use of the in aliphatic epoxy compounds described in U.S. Patent 3,839,247, although it solves the pink hue problem, usually to a material that tends to break after being in an environment of high humidity and temperature to be more brittle than the polycarbonate, which contains the aromatic epoxy compounds contains. There is, therefore, a need for polycarbonate bottles that linger no cloudiness in an environment of high humidity and high temperature show or become brittle, and which are transparent and colorless.

It has now been found that the disadvantages of clouding and embrittlement and the discoloration of transparent, for the production of containers, such as Polycarbonate used by bottles can be overcome by going into the Mixture with the polycarbonate, possibly a color stabilizer mixed with it it can hold smaller amounts of aliphatic bis (epoxy ether) compounds incorporated. It was found, after molding the resulting preparation into bottles, that it is transparent and colorless and has excellent resistance to Has cloudiness and embrittlement if the bottles are kept at elevated temperatures and Exposure to moisture such as those used in sterilization.

The aromatic polycarbonates that are used in practice of the present invention are homopolymers and copolymers and mixtures thereof obtained by reacting a dihydric phenol with a carbonate precursor have been manufactured. Typical of a number of the dihydric phenols found in the present invention can be used are bisphenol-A (2,2-bis (4-hydroxyphenyl) propane), Bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2- (3,5,3 ', 5'-tetrachloro-4,4'-dihydroxyphenyl) propane, 2,2- (3,5,3', 5'-tetrabromo-4,4'-dihydroxyphenyl )-propane, and (3,3'-dichloro-4'4'-dihydroxydiphenyl) methane. Other dihydric phenols les Bisphenol-type are also available and described in US Psen 2,999,835, 3,028,365 and 3,334,154.

It is of course possible to send two or more bivalent Phenols, or a copolymer of a ZWL1-valent phenol with a glycol, or with a polyester @ with terminal hydroxyl or acid groups, or with a dibasic Acid in the case where a carbonate copolymer or interpolymer, rather than a Homopolymer for use in making the aromatic carbonate polymers of the present invention is desired to use. In the practical implementation The present invention can also use mixtures of any of the above Materials used for the production of the aromatic Carbo-11 (1 t-polymers The carbonate precursor can either be a carbonyl halide, a carbonate ester or be a haloformate. The carbonyl halides that can be used here are carbonyl bromide, carbonyl chloride, and mixtures thereof. Typical carbonate esters, which can be used here are diphenyl carbonate, di (halophenyl) carbonates, such as di (chlorophenyl) carbonate, di (bromophenyl) carbonate, di (trichlorophenyl) carbonate, Di (tribromophenyl) carbonate, etc., di (alkylphenyl) carbonates, such as di (tolyl) carbonate, etc., di (naphthyl) carbonate, di (chloronaphthyl) carbonate, phenyl tolyl carbonate, Chlorophenyl chloronaphthyl carbonate, etc., or mixtures thereof. The one for one use Haloformates useful in the present invention include bis-haloformates of dihydric phenols (bischloroformates of ijydroquinone, etc.) or glycols (Bishalogen formates of ethylene glycol, neopentyl glycol, polyethylene glycol, etc.).

Although other carbonate precursors will occur to those skilled in the art, we will Carbonyl dichloride, also known as phosyen, I prefer.

Likewise, the polymeric derivatives of a dihydric phenol, one Dicarboxylic acid and carbonic acid included. These will be in the US Pat. No. 3,169,121, which is incorporated herein by reference.

The aromatic carbonate polymers of the present invention can using a molecular weight regulator, an acid acceptor and a catalyst can be produced. The molecular weight regulators that are used in the Performing the method of this invention can be used, close monohydric phenols such as phenol, chroman-l, p @ t rt.-butylphenol, p-bromophenol, primary and se @ undary amines, @tc., a. The preferred molecular weight regulator is Phenol used.

A suitable acid acceptor can either be organic, or be an inorganic acid acceptor. A suitable organic acid acceptor is a tertiary amine and umd @@@@ such materials as pyridine, triethylamine, dimethylantlin, Tributylamine, etc. The inorganic acid acceptor can be either a hydroxide, a Carbonate, a bicarbonate, or a phosphate of an alkali or alkaline earth metal The catalysts used here can be any of a number of suitable ones Catalyst agents, which support the polymerization of bisphenol-A with phosge:

Suitable catalysts include tertiary amines, for example Triethylamine, tripropylamine, N, N-dimethylaniline, quaternary ammonium compounds, such as tetraethylammoniumbronide, cetyl-triethyl-ammonium bromide, tetra-nheptyl-ammonium iodide, Tetra-n-propyl-ammonium bromide, tetramethylammonium chloride, tetramethylammonium hydroxide, Tetran-butylammonium iodide, benzyl-trimethyl-ammonium chloride and quaternary phosphonium compounds, such as n-butyl triphenyl phosphonium bromide and methyl triphenyl phosphonium bromide.

Also included here are branched polycarbonates, where a polyfunctional aromatic compound with the dihydric phenol and the Carbonate precursor to create a thermoplastic, randomly branched polycarbonate is implemented.

These polyfunctional aromatic compounds contain at least three functional groups, the carboxyl, carboxylic acid anhydride, haloformyl groups, or mixtures thereof. Examples of these polyfunctional aromatic compounds, used in practicing the prior invention can include; Trimellitic anhydride, trimellitic acid, trimellitic trichloride, -Chlol-formylphthalic anhydride, pyromellitic acid, pyromellitic dianhydride, Mellitic acid, mellitic anhydride, trimesic acid, benzophenone tetracarboxylic acid, Benzophenone tetracarboxylic anhydride, and the like. The vorzuyte polyfunctional, aromatic compounds are trimellitic anhydride or trimellitic acids, or their al ogenformyl derivatives, as well as mixtures of a linear Polycarbonate and a branched polycarbonate included.

Among the color stabilizers that are mixed with the polycarbonate resins. are the organophosphites of the general formula 9 10 11 in which 1, R - and R are independently selected from hydrogen, alkyl, aryl, cycloalkyl, aralkyl and alkaryl radicals, at least one of the radicals R9, R10 and R11 being a radical other than hydrogen. These radicals preferably contain from 1 to about 20 carbon atoms. The phosphite is present in an amount that stabilizes the color. This amount is usually in the range from 0.005 to about 1.0 percent by weight, and in particular in the range from 0.01 to about 0.2 percent by weight, based on the weight of the polycarbonate preparation. These phosphites and their use as color stabilizers are described in US Pat. No. 4,138,379, to which reference is expressly made here.

The aliphatic bis (epoxy ether) compounds can best be expressed by the following general formula 1 are reproduced, in which R is a divalent, saturated, aliphatic hydrocarbon radical, preferably with 1 to about 20 carbon atoms, bedded, R1 and R2 are independently selected from divalent, saturated, aliphatic hydrocarbon radicals, preferably from radicals with 1 Lis about 6 carbon atoms , the indices n and m independently represent an integer with a value of 0 or 1, and R3 R, R5, R6, R7 and R8 are independently selected from hydrogen and alkyl radicals, preferably from alkyl radicals having 1 to about 20 carbon atoms.

Preferred alkylene radicals which illustrate the radical R are -CH2-, -CH2-CH2-CH2-, -CH2- (CH2) 8-CH2-, and the same. Preferred alkylene radicals which illustrate the radicals R1 and R2 include -C112-, -CH2-CH2-, -CII2CH2-CH 2 ' -CH2CH2-CH -CH -, and the like.

Preferred compounds of general formula 1 are those in which both n and m are equal to 1. Very particularly preferred compounds of the general Formula I are those in which both n and m have the value 1, R1 and R2 one Methylene radical -CH2-, and the radicals R3 to R8 are hydrogen.

The amount of bis (epoxy ether) present in the polycarbonate formulation is one used to improve the hydrolytic stability of the preparation is effective. Usually this amount is in the range of 0.01 to about 0.50 percent by weight, based on the weight of the preparation, and preferably in the range of about 0.02 up to about 0.15 percent by weight.

The following examples serve for further explanation and clarification of the present invention. However, this is not intended to be restricted by the examples will. In the examples, all parts and percentages relate to weight, unless expressly stated otherwise.

B e 1 s p i e 1 1 An aromatic polycarbonate in solid form that from 2,2-bis (4-hydroxyphenyl) propane and phosgene in the presence of a stiureaceptor and a molecular weight regulator and had an intrinsic viscosity of about 0.57 dl / g was fed to an extruder located on a temperature of about 2740C (525 0F) and pelleted.

The pellets were then dried at about 121 ° C (250 ° F) for 16 hours. Test panels were then placed at a temperature of about 3160C (600 ° F) about 3.175 mm (1/8 inch) thick.

B e i s p i e 1 2 In a polymer that is essentially after the in the process described in Example 1 before pelletizing, 0.075 percent by weight tris (nonylphenyl) phosphite color stabilizer was mixed in and the mixture is then pelletized and, as in Example 1, into sheets by the injection molding process processed.

Example 3 11l a polymer which is essentially according to that in Example prior to pelletizing were made 0.075 Weight percent teis (nonylphenyl) phosphite and 0.051 weight percent butanedicl bis (glycidyl ether) mixed in and the mixture then pelletized unel as in Example 1 to form sheets processed by injection molding.

Example 4 In a polymer essentially made according to that in Example prior to pelletizing were made 0.075 Weight percent tris (nonylphenyl) phosphite and 0.102 weight percent butanediol bis (glycidyl ether) mixed in and the mixture then pelletized and as in Example 1 into sheets processed by injection molding.

Example 5 In a polymer essentially made according to that in Example 1 procedure described prior to pelletizing were 0.029 Percent by weight of butanediol bis (glycidyl ether) is mixed in and the mixture is then pelletized and processed as in Example 1 to sheets by the injection molding process. The plates were then examined for their light transmittance, with the following results obtained: 89.3% permeability before treatment in the autoclave; 87.2% transmission after 24 hours of treatment in the autoclave; 85.6% transmission after 48 hours Treatment in an autoclave; and 83.1% permeability after 72 hours of treatment in the Autoclave.

Each of these 7 test discs prepared above was then subjected to the ASTM test method D1003 for determining the light transmission rate in the samples before and after treatment autoclaved with steam at 1270C (2600F). The results are in the Table I laid down. The higher the percentage of light transmission, the more the clarity of the I-obe is better. The test plates prepared above were also subjected to ASTM Yellowness Index Test D1925-63T for determination of earbe, and the results are set out in Table II. The higher the yellowness index, the more so more unwanted color is present in the samples.

Table I. % Light transmission% light transmission% light transmission% light transmission Nonchalance Nonchalance Nonchalance play- before treatment after 24 hours after 48 hours after 72 hours No. in the autoclave treatment in the autoclave treatment in the autoclave treatment in the autoclave 1,88.8 72.2 51.3 37.2 2 89.5 77.4 59.2 47.0 3 89.7 85.8 77.9 66.4 4 89.8 85.5 74.6 58.0 T able II Yellowness index Example [Pressed at 316 ° C (600 ° F)] 1 7.0 2 4.9 3 4.7 4.8 As can be seen from Table I, those samples containing the bis (epoxyether) hydrolysis stabilizers of the present invention, even in the presence of a dijanophosphite color stabilizer (ie, Examples 3 and 4), have superior light transmission, indicating less haze and therefore indicates superior hydrolytic stability compared to the samples which do not contain a hydrolytic stabilizer (namely Examples 1 and 2).

Table II shows that the presence of the hydrolysis sterilizers of the present invention does not affect the color stability of the polycarbonate preparations adversely affected.

Essentially following the procedure of Example 1, Ls were further processed Specimens, with the exception that the test plates are at about 3600C (6800F) were manufactured by means of the injection molding process. These samples were the above yellowness index test described and the results in the following Table III laid down.

T able III Yellowness index Sample (additives) 360 ° C (680 ° F) @ (A) Control experiment, no additives 16.8 0.075 percent by weight tris (nonylphe- (B) nyl) phosphite 10.6 0.075 percent by weight tris (nonylphe- (Cj nyl) phosphite and 0.087 weight per cent. cent epoxidized soybean oil 0.075 percent by weight tris (nonylphe- (D) nyl) phosphite and 0.18 weight percent 34.7 cent bisphenol A diglycidyl ether 0.075 percent by weight tris (nonylphe- (E) nyl) phosphite and 0.102 weight percent 10.0 cent butanediol bis (glycidyl ether) 0.075 percent by weight tris (nonylphe- (F) nyl) phosphite and 0.051 weight percent 11.1 cent butanediol bis (glycidyl ether) As can be seen from Table III, the test plates pressed from polycarbonate blends containing organophosphorus color stabilizers and the hydrolysis stabilizers of the present invention (E and F) have a lower yellowness index - a yellowness index which corresponds to the Sample B is comparable, which was pressed from a polycarbonate mixture which contained only the color stabilizer and no hydrolysis stabilizer - as test plates, which were pressed from polycarbonate mixtures, which had the same color stabilizer, but hydrolysis stabilizers according to the state of the art eC and D) included.

It can be seen that the above, the present invention underlying problem was solved by the above description and it should, because of certain changes in the implementation of the above procedure and in the Composition made without departing from the subject of the present invention the present description is for illustrative purposes only and not be interpreted in a limiting sense.

Claims (1)

Polycarbonate preparation with improved hydrolytic stability, characterized in that it contains a mixture of a polycarbonate polymer and a stabilizing amount of a bis (epoxyether) of the general formula contains, in which R denotes an alkylene radical, R1 and R2 are independently selected from alkylene radicals, R3, R4, R5, R6, R7 and R8 are independently selected from hydrogen and alkyl radicals, and the indices n and m independently of one another are integers with a value from 0 or 1 snd 2. Preparation according to claim 1, characterized in that R is an alkylene radical having 1 to about 20 carbon atoms. 3. Preparation according to claim 2, d a d u r c h g e k e n n -z e i c Note that R1 and R2 are independently selected from alkylene radicals having 1 to about 6 carbon atoms are selected. 4. Preparation according to claim 3, d a d u r c h g e k e n n z e i c h S e t that the indices n and m have a value of 1. 5. Preparation according to claim 4, d a d u r c h g e k e n n z e i c Mr. e t that the radicals R3 to R8 are hydrogen. 6. Preparation according to claim 5, d a d u r c h g e k e n n z e i c Note that R1 and R2 are methylene radicals. 7. Preparation according to claim 5, d a d u r c h g e k e n n z e i c h n e tr that R is a butylene radical. 8. Improved polycarbonate preparation with improved hydrolytic stability containing in mixture (I) a polycarbonate polymer, and (II) an organophosphite color stabilizer, characterized in that it contains a stabilizing amount of a bis (epoxyether) of the general in mixture with the polycarbonate and the organophosphite formula contains, in which R is an alkylene radical having 1 to about 20 carbon atoms, R1 and R2 are independently selected from alkylene radicals having 1 to about 6 carbon atoms, the radicals R to R are independently selected from hydrogen or alkyl radicals, and the indices n and m are independently are integers of each other with a value of 0 or 1. 9. preparation according to claim 8, d a d u r c h g e k e n n z it is true that they contain from about 0.01 to about 0.5 percent by weight of the bis (epoxyether) contains. 10. Preparation according to claim 9, d a d u r c h g e -k e n n z e i c h n e t that they are from about 0.02 to about 0.15 percent by weight of the bis (epoxyether) contains. 11. Preparation according to claim 10, d a d b r c h <3 e k e n n z e i c h e t that the indices n and m have the value 1. 12. Preparation according to claim 11, d a d u r c h g e -k e n n z e i c h n e t that the radicals R3 Lis R8 are hydrogen.