DE2729485A1 - THERMOPLASTIC COMPRESSION COMPOUND - Google Patents

Description

Dr. rer. near Horst Schüler ⁶⁰⁰⁰ Frankfurt / Main ι, June 29, 1977

PATENT Attorney Kaiserstrasse 41 Dr. Sch / Boe / Hk

Telephone (0611) 235555 2 7 29 A 85 Telex: 04-16 / 59 mapal d

Postal check account: 282420-602 Fiankfurt / M. 7 bank account: 225/0389

Deutsche Bank AG, Frankfurt / M

4303-8CH-2277

GENERAL ELECTRIC COMPANY

1, River Road
Schenectady, NY, USA

Thermoplastic molding compound

The invention relates to a thermoplastic molding composition comprising an aromatic carbonate polymer and 0.1 to about 3.0 % By weight of an ester based on the weight of the polycarbonate composition, contains.

Thermoplastic compositions that contain a release agent to remove (disjoining) a to facilitate molded article that is in contact with a molding and cooling surface, e.g. a die are known in the art. In particular, it is known from ÜS-PSs 3 784 595 and 3 836 499 that the addition of esters of certain alcohols and acids to polycarbonates the separation of these polymeric products easier when molded by injection molding.

However, in order to be an effective mold release agent, an additive should not only remove the article from the mold should also be compatible with the physical properties of the end product during processing does not adversely affect, no unwanted color

8CH-2277 709881/1 171

or cause color mismatch, can be easily added to the resin, and in many cases FDA approval (the health authority) if it comes into contact with food in its eventual use. It is also important that the mold release agent not settle on the surface of the mold or molded part enriches (plate out).

According to the invention, certain well-defined esters can be used incorporate certain organic acids and certain alcohols into a thermoplastic aromatic carbonate polymer, whereby a composition is obtained which is easily removed from the after molding of molded articles Can detach the mold. Furthermore, the composition according to the invention is compatible with the polycarbonate melt. Furthermore, there is no visible degradation of the polymer properties by the ester additive according to the invention. The ester additives according to the invention also help in processing the aromatic polycarbonate polymer composition by they lower their apparent melt viscosity, which results in improved farmability. Furthermore, with these additives there is no accumulation of any kind (plate out) either on the surface of the mold or of the molded part visible, whereby the original surface properties of the molding compound are retained. Further the additives according to the invention work synergistically together with known UV stabilizers for polycarbonates and improve the UV stability.

Esters effective in accordance with the invention are by known working methods available reaction products of saturated aliphatic mono- and dicarboxylic acids with the following Formulas:

(a) C _n H _{2n + 1} -COOH, and

(b) HOOO-C _n H _2n -COOH,

where η is about 5 to about 34, such as valeric acid, caproic acid, Capric acid, lauric acid, arachidic acid, behinic acid, lignoceric acid, cerotic acid, melissic acid, tetratriacontoic acid (tetratriacontoic acid), glutaric acid, adipic acid and

709881/1171

ORIGINAL INSPECTED

~ \ ~ 2729A - I5

Azelaic acid, with polyhydric alcohols that do not contain a hydrogen atom on a carbon atom in ß-position to the hydroxyl group and have the following general formulas:

where η is 1 to 20;

(d) R ₁ CH ₂ OH

where R ^ and Hp independently of one another denote alkyl radicals and substituted alkyl radicals having 1 to 10 carbon atoms or B .. together with R ₂ denotes a radical which forms a five- or six-membered ring;

(e) HIGH ₂ CH ₂ OH

H/

CIl ₂ OIl

(f) CH ₂ OH CH ₂ OH

i I

CH ₂ OH CH ₂ OH

where R, and R, - independently of one another are alkyl radicals and substituted alkyl radicals having 1 to 4 carbon atoms and R, is an alkylene radical having 1 to 4 carbon atoms or a - (ClLO-O- (CH ₀ ) .- radical, where a is a whole Number is from 1 to 4;

709881/1171

ORIGINAL INSPECTED

(ο

(κ) CH ₀ OH CH ₇ OH

I I

HO-CH ₉ C R, C CHo

2.4,

CH ₂ OH CH ₂ OH

where R. denotes an alkylene radical having 1 to 4 carbon atoms or a - (CH ₀ ) -0- (CH _n ) -Resb, where a is an integer

C-O. £ approx

is from 1 to 4, and with their mixtures. The alcohols include, for example, alpha, alpha-dihydroperfluoropropanol, Neopentylene glycol, pentaerythritol, ditrimethylolpropane and Dipentaerythritol.

Esters useful in the present invention include, for example Pentaerythrityl tetrastearate and neopentylene glycol distearate a. Mixtures of such esters of naturally occurring acids are also effective and included in the present invention.

The esters are used in amounts of from 0.1 to about 3.0% by weight on the weight of the composition.

The ester can be incorporated into the polycarbonate composition by mixing it with grains of the polycarbonate composition mixed and then extruded through an extruder under standard conditions. Further you can incorporate the esters if you make the polycarbonate by dissolving them in a solvent, in which the polycarbonate is dissolved, and then the polymer composition from the solvent by known Recovers working methods.

The aromatic carbonate polymers used in the practice of the invention are homopolymers and interpolymers and mixtures thereof made by reacting a dihydric phenol with a carbonate precursor.

The dihydric phenols that can be used are bisphenols, such as bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) -

709881/1171

- ^ - 2729 / ^ 5

propane (hereinafter referred to as bisphenol-A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis ( 4-hydroxy-3,5-dichlorophenyl) propane and 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane; ζwe iwertige phenol ethers, such as bis (4-hydroxyphenyl) ethers and bis (3,5-dichloro-4-hydroxyphenyl) ethers; Hydroxydiphenyls, such as, for example, ρ, ρ'-dihydroxydiphenyl and 3,3'-dichloro-4,4 ^l -dihydroxydiphenyl; Dihydroxyarylsulfones, such as, for example, bis (4-hydroxyphenyl) sulfone and bis (3,5-dimethyl-4-hydroxyphenyl) sulfone; Dihydroxybenzenes, resorcinol, hydroquinone, halogen- and alkyl-substituted dihydroxybenzenes, such as 1,4-dihydroxy-2,5-dichlorobenzene and 1,4-dihydroxy-3-methylbenzene; and dihydroxydiphenyl sulfoxides such as bis (4-hydroxyphenyl) sulfoxide and bis (3,5-dibromo-4-hydroxyphenyl) sulfoxide. A number of other dihydric phenols are also useful in making carbonate polymers and are described in U.S. Patents 2,999,335, 3,023,365 and 3,153,003. For the preparation of the aromatic carbonate polymers, copolymers are also suitable which have been prepared from any of the above by copolymerization with halogen-containing dihydric phenols, such as 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) propane and 2, 2-bis (3,5-dibromo-4-hydroxyphenyl) propane. It is of course possible to use two or more different dihydric phenols or a copolymer of a dihydric phenol with a glycol or with a polyester which carries a hydroxyl or acid group at the end, or with a dibasic acid when using a carbonate copolymer or interpolymer instead of as a homopolymer in the preparation of the aromatic carbonate polymers according to the invention. In the practice of the invention, one can also use mixtures of any of the above materials to make the aromatic carbonate polymer.

The carbonate Vorstule can either be a carbonyl halide, be a carbonic acid ester or a halogen formate. According to the invention Usable carbonyl halides are carbonyl bromide, carbonyl chloride and their mixtures. Typical for the carbonic acid esters which can be used according to the invention are diphenyl

709881/1171

ORIGINAL INSPECTED

- ^ y "2729435

carbonate, T) i- (halophenyl) carbonates, such as di- (chlorophenyl) carbonate, Di (bromophenyl) carbonate, di (trichlorophenyl) carbonate and I> i- (tribroraphenyl) carbonate; Di (alkylphenyl) carbonate, wi ·? e.g., di (tolyl) carbonate; Di (naphthyl) carbonate, Di (chloronaphthyl) carbonate, phenyltolyl carbonate and chlorophenylchloronaphthyl carbonate, or their mixtures. The halogen formates suitable for use according to the invention include bishaloformates of dihydric phenols (e.g., bischloroformates of hydroquinone) or glycols (e.g. bis-halogen formates of ethylene glycol, neopentyl glycol and polyethylene glycol). While other carbonate precursors for It may be obvious to the person skilled in the art that carbonyl chloride, also known as phosgene, is preferred.

The invention also includes the polymeric derivatives of a dihydric phenol, a dicarboxylic acid and carbonic acid a. These are described in US Pat. No. 3,169,121, the disclosure of which is incorporated herein by reference Registration is recorded.

The aromatic carbonate polymers according to the invention using a molecular weight regulator, an acid acceptor and a catalyst. The molecular weight regulators, which can be used in carrying out the method of operation of the invention include, for example monohydric phenols such as phenol, chroman-I, p-t-butylphenol and p-bromophenol and primary and secondary amines. Preferably phenol is used as a molecular weight regulator.

A suitable acid acceptor can be either an organic or an inorganic acid acceptor. A suitable one organic acid acceptor is a tertiary amine and includes substances such as pyridine, triethylamine, dimethylaniline and tributylamine. The inorganic acid acceptor can be either a hydroxide, a carbonate, a bicarbonate or a Be phosphate of an alkali or alkaline earth metal.

The catalysts usable in the present invention can be any suitable catalysts that facilitate the polymerization support of bisphenol-A with phosgene. Suitable catalyst

709881/1171

-Y- 27 29 U ^ 5

Sators include, for example, tertiary amines such as triethylamine, tripropylamine and Ν, Ν-dimethylaniline, quaternary Ammonium compounds such as tetraethylammonium bromide, Cetyltriethylammonium bromide, tetra-n-heptylammonium iodine, Tetra-n-propylammonium bromide, tetramethylammonium chloride, Tetramethylammonium hydroxide, tetra-n-butylammonium iodide, and benzyl trimethyl ammonium chloride, and quaternary phosphonium compounds such as n-butyl triphenylphosphonium bromide and methyltriphenylphosphonium bromide.

The invention further includes branched polycarbonates, one having a polyfunctional aromatic compound with converts the dihydric phenol and the carbonate precursor and produces a thermoplastic polycarbonate with any branching.

These polyfunctional aromatic compounds contain at least three functional groups representing the carboxyl, carboxylic anhydride or haloformyl group or mixtures thereof. Examples of these polyfunctional aromatic Compounds that can be used in the practice of the invention include, for example: trimellitic anhydride, Trimellitic acid, trimellityl trichloride, 4-chloroformylphthalic anhydride, Pyromellitic acid, pyromellitic acid dianhydride, Mellitic acid, mellitic anhydride, trimesic acid, benzophenone tetracarboxylic acid, Benzophenone tetracarboxylic acid anhydride and diphenoleic acid.

Of course, you can also use other substances in the invention use aromatic carbonate polymer composition and substances such as antistatic agents, other mold release agents, thermal stabilizers, such as phosphites, UV light stabilizers, such as hydroxyarylbenzotriazoles, and reinforcing fillers such as glass and other inert fillers, Include foaming agents, dyes and flame retardants.

The invention thus relates to a thermoplastic molding composition, which consists of an aromatic carbonate polymer and 0.1 to about

709881/1171

ORIGINAL INSPECTED

3.0 wt .- ^ of an ester, based on the weight of the polycarbonate composition _/ consists.

The invention is explained in more detail below by means of examples, with parts and percentages being parts by weight and percentages by weight mean unless otherwise stated.

Example I.

A polycarbonate molding compound was prepared by extruding a homopolymer of 2,2-bis- (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol-A), which was obtained by reacting essentially equimolar amounts of bisphenol-A and Phosgene in an organic medium with triethylamine, sodium hydroxide and phenol under standard conditions. The polymers were introduced to an extruder operating at a temperature of about 265 ⁰ G, and chopping the extrudate into pellets. The pellet was molded by injection molding under standard conditions in test pattern of about 76.2 50.3 χ χ 3.17 mm (3 x 2 1/3 in χ) at 315 ⁰ C (600 ⁰ F) and 371 ⁰ C (700 ⁰ P). The sample was named Sample A (comparative). One measure of the thermal stability to discoloration in accordance with the ASTM-D1925 test yellowness index of samples that were molded at 315 ⁰ C (600 ⁰ F) and 371 ° C (700 ⁰ F). The results are shown in Table I.

Example II

Example I was repeated with the exception that 0.3% by weight of the following additives were added to the polycarbonate mixed:

Sample B: pentaerythrityl tetrastearate Sample C: poly (neopentylene azelate) Sample D: Organopolysiloxane Fluid Sample E: glycol tristearate

Sample F: Loxiol G 47 (stearylphenic acid ester with C ₂₀ fatty acids)

Sample G: stearic acid.

709881/1171

Each of the compositions was processed and molded into test specimens as in Example I. The test specimens were subjected the test is carried out as described in Example I and the results are shown in Table I.

Table I.

Yellow index according to example Shaping at sample 315 ⁰ C 371 ⁰ C Δ 371-315 ⁰ C. (600 ⁰ P) (700 ⁰ F) (7OO ° -6OO ° F) A (comparison) 0.1 10.4 10.5 B. -, 2 6.9 7.1 C. -,1 6.3 6.9 D. -, 4 6.7 7.1 E. -, 3 9.2 9.5 F. -.6 3.7 9.3 G -, 5 10.4 10.9 III

Example I was repeated with the exception that 0.3% by weight of the following additives were added to the polycarbonate:

Sample H: Pentaerythrityl tetrastearate Sample I: Organopolysiloxane fluid Sample J: Glycerol tristearate
Sample K: Loxiol G 47

Each of the compositions was pelletized as in Example I. The pellets were injection molded into test specimens in the form of open boxes measuring 7.62 χ 7.62 cm (3x3 in) with a depth of 2.54 cm (1 in) and a side wall thickness 0.25 cm (0.1 in) in a low draft mold with a pressure-transmitting ejector system (pressure transducing ejector system), which measures the force required to move the molded part of the Detach the mold, and that records this force with a writing instrument. The results are shown in Table II.

709881/1171

2729A85

Table II

sample Peel force in kg / cm (psi) A (comparison) did not come off that Nozzle pins (injector pins) broke the part H 679 (9700) I. 363 (12 400) J 707 (10 100) K 340 (12,000) Example IV

Example I was repeated with the exception that 0.35% by weight of pentaerythrityl tetrastearate was admixed with the polycarbonate. This was referred to as Sample L. The processability of the pellets was determined by their apparent melt viscosity - determined by melt flow as measured by ASTM D1238 at Condition 0. The molecular weight of the composition was determined by measuring the intrinsic viscosity using a standard method, where a polymer solution of 0.4 volume /% by weight in dioxane at 30 ^° C. was used. The results are shown in Table III.

(Comparison) Tabel III Basic viscosity (I.V.) Melt flow 0.496 sample 13.3 0.503 A. 17.3 L. example V

Repeating BeiBpiel I except that 0.3 percent -. $> A Hydroxyphenylbenzotriazoles commercially (Tinuvin P) zumischte the polycarbonate. The polymer was formed into pellets and injection molded into test specimens as described in Example I. The r test samples were exposed to a 4000 W mercury vapor lamp for 7 days and 14 days, respectively. The discoloration is measured according to the ASTM binding test D1925

709881/1171

Samples molded at 315 ⁰ G (600 ⁰ P). The test samples were designated Sample M. The results are shown in Table IV.

Example VI

Example V was repeated with the exception that 0.3 wt. Organopolysiloxane fluid added to the polymer. One processed the composition, shaped into test specimens and subjected to the test as described in Example V. The test patterns were designated as sample N. The results are shown in Table IV.

Example VII

Example V was repeated with the exception that 0.3% by weight Pentaerythrityl tetrastearate added to the polymer. The composition was processed, shaped into test samples, and subjected them to the test as described in Example V. The test samples were named Sample 0. The results are listed in Table IV.

Table IV

Yellow index
Sample 7 days 14 days

9 ,1 33 , 6 11 36 ,8th 3 ,1 29 , 3

The data in Table I show that a polycarbonate composition which contains an additive according to the invention (Pro ben B and C), shows a smaller change in the Gelbiudex number, i.e. less discoloration of the polymer and therefore a better thermal stability than the polymer without additive (sample A) and polymers with in the trade » available additives (samples D, E, P and G). The data in Table II show that a polymer composition

709881/1171

Etching molded article containing the additive of the invention contains (Sample H), a lower pressure to peel off the molded part than commercially available additives needed (samples I, J, K). The comparative sample (sample A) without an additive did not peel off.

The data in Table III shows the processability of a Composition containing an additive according to the invention (sample L) because the melt flow increased while the intrinsic viscosity did not change significantly, indicating that there was no degradation in molecular weight compared to the control which contained no additive.

The data in Table IV shows the synergistic effect when adding an additive according to the invention to the polycarbonate composition which contains a commercially available UV stabilizer (sample O) compared to a composition that contains only a UV stabilizer (sample M) and a composition that contains a UV stabilizer and contains a commercially available mold release agent (Sample N). This is shown by the lower yellow index number.

30 & 88 1/1171

Claims (4)

Dr. rer. nat. Horst Schüler 6000 Frankfurt / Main ι, June 29, 1977 PATENTANWALT Kaiserstrasse 41 Dr. Sch / Boe / HJ Telephone (0611) 235555 2 7 2 9 A 8 5 Telex: ° * -i6759 moPa »d Postal check account: 282420-602 Frankfurt / M. Bank account: 225/0389 Deutsche Bank AG, Frankfurt / M. 43Q3-8CH-2277 GENERAL ELECTRIC COMPANY 1, River Road Schenectady, N.Y., U.S.A. claims 1. Thermoplastic molding compound, characterized by an aromatic carbonate polymer and 0.1 to 3.0 wt .- ^ of an ester (based on the weight of the polycarbonate composition) from an acid from the group of saturated aliphatic mono- and dicarboxylic acids with the the following formulas: (a) C _n H _{2n + 1} -COOH and (b) HOOC-C _n H _2n -OOOH wherein η is 5 to 34, and their mixtures with an alcohol from the group with the following general formulas: (c) (C ,,? - ,.) -CH _o 0H where η is 1 to 20; W) «i CH ₂ OH * 2 CH ₂ OH where R ₁ and R ₂ independently of one another denote alkyl radicals and substituted alkyl radicals having 1 to 10 carbon atoms, or R ₁ together with R ₂ denotes a radical which forms a five- or six-membered ring; 709881/1171 ORIGINAL INSPECTED (e) UU CH ₂ CH ₂ OH HIGH ₂ / "CH ₂ OH (f) CH ₂ OH CB ₂ QH -C- R ₃ CR ₄ CR _{5 2} 0H CH ₂ QH wherein R, and R, - are independently alkyl radicals and substituted alkyl radicals having 1 to 4 carbon atoms, and R. is an alkylene radical having 1 to 4 carbon atoms or a - (CHg) -O- (CHp) ₃ radical, wherein a is a is an integer from 1 to 4; (g) CH ₂ OH CH ₂ OH ΗΠ-.ΓΗ r * τ> ο n \ ir \\ i l \\ J 1> I1 * J ^>"AO w Π Uli I ₂ OH CH ₂ OH wherein R. denotes an alkylene radical having 1 to 4 carbon atoms or a - (CH ₀ ) -0- (CH ₀ ) radical, where a is an integer from 1 to 4, and mixtures thereof. 2. Composition according to claim 1, characterized by pentaerythrityl tetrastearate as ester. 3. Composition according to claim 1, characterized by a stabilizing amount of a UV light stabilizer. 4. Composition according to claim 3, characterized by hydroxyphenylbenzotriazole as a UV light stabilizer. 709881/1171