DE2064599C3 - Mixture containing brominated polycarbonate - Google Patents

Description

homopolymeric, non-halogenated polycarbonates

with copolymers of tetrabromobisphenol-A and

25 other phenols, glycols, carboxylic acids and the like.

Aromatic polycarbonates are known, as described in US Pat. No. 3,334,514 common materials with a variety of uses and various other mixtures of homopoly- genization possibilities in the plastics industry. You meren. halogenated bisphenol A polycarbonates, can by reacting a dihydric phenol, have already been used to remedy the above be for example 2,2-bis- (4-hydroxyphenyl) propane (all writing difficulties suggested. It was common and referred to below as "bisphenol-A") but found that mixtures of bisphenol-A with a derivative of carbonic acid, for example polycarbonates with tetrahalo-bisphenol-A-polyPhosgene, in the presence of an acid binder, carbonates are also produced due to their high processing properties will. Polycarbonates turned out to be ungeneral temperatures for thermoforming advantageous for the production of fibers, 35 are suitable and only for the production of foils by Sheets and moldings, since they can be used in general casting a solution. It have high resistance to mineral acids, it was also found that copolymers of can be easily deformed and both physiolo- bisphenol-A and halogenated bisphenols even for Gisch harmless as well as resistant to the production of foils after the solution casting soiling are. 40 drives are unsuitable as they have poor flexibility

Polycarbonates show excellent physical properties.

and mechanical properties, such as high tensile strength and If a mixture of homo- and copolymers,

Impact resistance, heat resistance and dimensionally halogenated polycarbonates are used that Stability similar to that of any other less active halogen than chlorine, for example Thermoplastics by far exceeding 45 bromine, are not so highly processed. In addition, polycarbonates are generally required at temperatures such as those used for processing considered self-extinguishing, d. H. they delete chlorine-containing homo- and copolymers. Himself within about 20 s after removing the opposite, the less firmly adhering bromine atom becomes Pilot light. Nonetheless, various grain sizes remain under the processing conditions of the polycarbomeric Uses in which the heat is easily split off and the polymer degrades strongly durability of the polymer while preserving the and makes it even in the cases of commercially unusable excellence physical and mechanical bar in which the concentration of halogenated Properties the above-described self-copolymer in the mixture is very low, i.e. H. self clearing ranking must surpass. if it is in a way to achieve an effective

Insufficient concentration to create a polycarbonate of improved flame resistance Flai ^ m'resistance has been suggested as an addition. Accordingly, it was a satisfactory one inorganic flame retardants, for example agents to improve flame resistance Antimony oxide, to use. However, it has been found that polycarbonates without adversely affecting anything Such additives up the polycarbonate during one of the other desirable properties Overly degrading deformation treatments like 60 fro not available. With the specified in claim 1 this also occurs with halogen-containing additives and the like. benen molding compounds, the task is achieved, eir In addition, such additives must be used in large quantities of a mixture containing brominated polycarbonate shares are used, and even then their creation is the disadvantage described above « The effect is not sufficient to be resistant to resistance and, for example, with the use of: ability of the polymer against high ignition temperatures 65 conventional deformation processes to form enough to improve. bodies can process that under preservation

Alternatively, it has been proposed that the flame-exacerbating physical, chemical and mechanical resistance of deformable polycarbonate resins under properties improved flame resistance against

³ ί 4

have high ignition temperatures and under the conditions for polymer 3 of the examples with and without bariura

working conditions do not emit bromine. carbonate additive, show. Although the carbonate stabil

o 7? λ α Ei ^D ι, u · I u * ~ 7 ", ^{SM 65 4} ^ 'sators in the mixture according to the invention in any!

S. 1) that halogen-containing ^ high molecular weight substances can be used in the additional amount, it has sfch

Hitee split off hydrogen halide, which has generally shown that the most effective concentration

Damage to the polymer itself as well as from tration in the range of 0.01 to 5 percent by weight,

Metal parts of the equipment used for production are based on the total weight of polycarbonate,

or processing of these polymers used This concentration range is effective even when

The addition of basic substances _{reduces the} concentration of halogenated poly-

in the case of halogen-containing polymers, the mixture should be very high in temperature when io carbonate or if 100 °, i

stabilize, namely by the fact that a halogenated polycarbonate homopolymer is removed in the heat.

split hydrogen halide are absorbed and neutral. Although higher concentrations de.

is siert (US-PS 23 65 400 p. 1, left column, lines carbonate stabilizers in the inventive Ge

19 to 26 and right column, lines 18 to 24). _M can be used if desired, as

ProblematisA oil yew this case, however, on the one hand the i _S to hydrogen halide from halogen-containing polymers, the properties of the polymer does not adversely Tafsache that basic agents will affect the elimination of and therefore used with impunity, it was found that higher Konzentrationer still favor (Ub-PS 23 65 400), on the other hand, which are not much more effective. The effect is different! The fact that basic agents, for example concentrations of the carbonate stabilizer, for example ester bonds, are known to cleave and so break down barium carbonate to the high molecular weight polyesters according to the invention, in particular as a mixture, is shown in FIG. 2 shown graphically,
high molecular weight polycarbonates. While with the mixture according to the invention

LS-PS 32 74 156 describes aliphatically bound achievable results that are really surprising.

Aromatic polycarbonates containing chlorine, so the mechanism and theory of the

those containing Cl-CHj ₈ - and ClgCH groups. a ₅ effect of the disclosed teaching cannot be explained

To improve the heat stability of these poly- The results achieved are also particularly un-

carbonate, that is, waiting for Neutrahsierung in the heat, since the carbonates of other members of the same

split off HCl can include tin- Group of the periodic table, in which barium,

Organic compounds or calcium carbonate, strontium and calcium, are not the same

be turned. _{30 oc} ] _{it will} show a similar effect. In this relationship

In contrast, suppress calcium carbonate, is shown in FIG. 1 graphically corroborates the fact that strontium carbonate or barium carbonate in the molding compositions containing brominated polycarbonates during barium, strontium and calcium carbonate actually give the unique stabilizer described here the early sizing effect of converting sodium carbonate (i.e. when processing the molding compositions at 35% increase in temperature) Melt viscosity of 1.51 to 2.351O ¹ P temperatures around 30O ⁰ C) splitting off of bromine, measured after 5 and 35 mm in the "Instron" device at 300 C according to the invention, which results during the entire test duration Polycarbonate molding compositions is improved in the event of fire, remained unchanged at this high value. Obviously, what with the tin-borne suitable as heat stabilizers, sodium carbonate stimulates chain extension or organic compounds, such as tetra-crosslinking, from which the high viscosity results, phenyltin, does not succeed. This effect of example. Magnesium carbonate, on the other hand, completely degrade the polymer calcium carbonate in brominated, aromatic ones. The halogenated polymer without the er polycarbonates was, in view of the two United States stabilizer additions according to the invention, decomposed during patents 23 65 400 and 32 74 156 not to be obtained from the test as demonstrated by the. 45 broken line connected points appears

The statements on US Pat. No. 3,274,156 apply meaningfully. The same result is shown in FIG. 6 shows which of the

according to British patent specification 11 00 382. Stabilizing influence of barium carbonate aui

The surprising with the inventive polymer 3 of the examples shows.

Mixtures achievable results are in the drawing It has been found that with the inventive

The results are shown graphically, in which 50% mixture, whether it is now a brominated homo odei

F i g. 1 the influence of various alkaline earth metal copolycarbonate, a mixture of homopoly-

carbonate to the »Instrone melt viscosity of the carbonate or of homo- and copolycarbonates

Polymers 1 of the examples, contain, the degradation, which under the processing

F i g. 2 the influence of different concentrations conditions of polycarbonate inevitable aul

from barium carbonate to the "Instron" melt viscosity

tat of polymer 1 of the examples is avoided. In addition, the carbonate

F i g. 3 the influence of varying amounts of stabilizers added the advantageous properties of the poly

Stabilizers on the "Instron" melt viscosity of carbonate do not detrimentally and also reduce them

Not cloudy, opaque molded bodies made of polymer 1, but rather exert a synergistic effect!

of Examples, 60 halogenated polycarbonate blends and in particular

F i g. 4 shows the influence of varying amounts of addition on brominated polycarbonates when they are combined

Stabilizers to the "Instron" melt viscosity of with phosphite stabilizers, for example in the

cloudy, opaque moldings made from polymer 1 USA.-Patents 32 05 269; 33 05 520; 33 42 767

of Examples, 33 98 115; 28 67 594; 33 98 115; 35 09 091 and dei

F i g. 5 describes the effect of varying additions from 65 Canadian Patent 6 46 424, ver

Stabilizers to the "Instron" melt viscosity are applied.

Polymer 2 of the examples, It was found that when using a stabili

F i g. 6 the »Instrone melt resistance values setting amount of a phosphite, for example«

5,5-dimethyl-1,3,2-dioxaphosphorindene, an orga- for example in US-PS 32 90 261 and 32 77 029 niche ester of phosphorous acid, a trialkyl described. In addition, brominated poly-triaryl or mixed tri (alkylaryl) phosphite can be used. Like. Carbonate-containing mixtures containing halogenated, in particular triphenyl, tri- (nonylphenyl), phenyl additives, such as, for example, in US-PS didecyl-phosphite, pentite, the neopentyl phosphites, 5 33 34 154; 33 65 517; 33 57 942 and the like, diisodecyl-pentaerythrityl-diphosphite, dipentite through use in the mixtures according to the invention and the like, together with one of those also stabilized in the invention. Even if the mixture of carbonate stabilizers to be used, ins- polycarbonate mixture of a mixture of no particular barium carbonate, an improvement in the bromine-containing polycarbonate with a bromine properties of the polycarbonate is achieved, which homo- or copolymers containing io or completely the sum of each of these both stabilizers made from a bromine-containing polycarbonate, as aHein's deducible effect far exceeds. For example, in US Pat. No. 3,422,065; 33 40 229 and especially the synergistic results in 33 26 854 are described, produced, the carbonate stabilizers in the mixture according to the invention, especially at high temperatures and under severe conditions, exert their unique effect anyway. It has been found to be more complicated ever-shear stress in compression molding, although the carbonate stabilization moldings, especially of thin spots thereof. If results in the mixture according to the invention are superior and the carbonate stabilizers together with phosphite give extremely unexpected results with regard to the degradation stabilizers, in particular phenylneopentyl phosphite effect of bromine or diisodecylpentaerythrityl diphosphite contained in the polycarbonate itself, such results are not achieved, a polycarbonate mixture will be achieved that if the halogen is not passed through the polymer itself without a change in color or degradation of the molecular. For example, the polymer is not weight stabilized against the degradation action of bromine, which can be processed, even under very severe deformation. The fact that this is based on a synergistic effect via an additive, for example phosphorus tri-result, results in 25 bromide and the like.
The carbonate stabilizers can also be found in the following examples from the fact that phosphites are added as a heat mixture in any way, stabilizers for polycarbonate mixtures are known which have their thorough distribution throughout the region and here that the im guaranteed by the invention. For example, powdery mixture of carbonates to be used can be shaped or granulated polycarbonates with which are suitable for stabilizing a polycarbonate against the degradation effect of carbonate stabilizers on any of the various bromine. If, however, the phosphites are used together with the carbonates to incorporate plasticizers and fillers, methods used in thermoplastic polymers stabilize the mixture according to the invention . "Banbury" mixers, extruders, and any bromine, but they give the polycarbonate mix other suitable facilities. The resulting color stability and processability, even when mixed, can then be processed further in the conventional, in the strictest conditions of high temperature processing of thermoplastic plastics and shear stress, which the polymer was otherwise familiar with. Destroy the mixture. Since neither the phosphite nor the 40 can be deformed in any trusion by means of injection molding, rolling, casting or ex-carbonate additives. In addition, the polymers, and much less a polycarbonate, carbonate stabilizers, can impart such stability properties to a solution of the polycarbonate when it is absolutely unexpected that the phosphites and carbonates are added to the melt during their manufacture or to a polycarbonate. You can also give the components for the production of the polycarbonate mixture in the stabilization system of the inventive gel actually greatly improved coloring and processing properties during its production at any time, as has been added up to now. If in the invention was not possible. It is therefore clear that the carbonate mixture contains the above-described stabilizer in the mixture according to the invention, in addition to the system of the carbonate stabilizer and a prevention of the large post-neopentyl phosphite or diisodecyl-pentaerythrityl which occurs when using halogen-based phosphorus stabilizers, for example phenyl-containing polycarbonate mixtures. If the components are capable of being contained in combination with phosphites, insphosphite or the like, this special diisodecyl-pentaerythrityl-diphosphite, No-System, can be added to the polycarbonate mixture such as benylneopentyl-phosphite and dipentite, a synergistic one, as above the usable, see effect. SS phosphorus-containing compounds in general as well

In addition to the above, it is also clear that they are soluble in polycarbonates.

The carbonates in the mixture according to the invention have their It should be noted that the Ge according to the invention is unique Effect on brominated polycarbonates mixed except for the carbonate stabilizer or the foregoing the presence of other stabilizers, the stabilizer system described above and others such as UV stabilizers, as in US-PS 60 may contain additives, for example lubricants, 33 67 958 described; Hydrolysis stabilizers, such as in antioxidants, dyes, pigments, fillers and the like. the US-PS 34 04 122 describes η; modified poly- any of these known additives, for example carbonate mixtures, as described in US Pat. No. 3,294,871. Pigments, such as white opacity pigments, such as lead writing; and the like. It is also clear that the zinc, titanium and antimony oxides; red, brownish red and Carbonates in the mixture according to the invention are their only brown inorganic pigments from different exert a similar effect, whether the polycarbonate is not liisenoxiden; Cadmium gdb. -red and -brown-red, wi < is cellular, for example in US Pat. No. 3,028,365 cadmium sulfosdenides, cadmium sulfides, the like; green pigments and 29 99 835, or be foamed, such as blue pigment, such as iron and ultramarine blue; soot

<o

Iron oxide black and the like can be used. that this absorbs 109 T. of it within 80 min. Particularly suitable pigments are, for example. The temperature is kept at 25 ° C. during the phosgenation "pigment blue" 15 CI 74160, "solvent violet" 13 C. 1. reaction by external cooling. 60725, yellow 37 CI 77199, cadmium red CI 77196, After phosgenation is complete, the reaction phthalocyanine pigments, such as copper slurry, are transferred to a mixer, where non-phthalocyanine, chlorinated copper phthalocyanines, sulphate 2 parts of triethylamine are added and the concentrated Copper phthalocyanine, metal-free phthalo- mically processed to form a heavy dough, cyanine and phthalocyanine derivatives in which an or is. The dough obtained is washed out to remove several of the external hydrogen atoms by other electrolytes with phosphoric acid and then with groups such as halogen, alkyl, aryl, amino, nitro, ίο water. The thus obtained polycarbonate-substituted amino, sulfo, carboxy, alkoxy, aryloxy, is separated as a dry powder and shows a thiocyano and the like, are replaced. relative viscosity of 1.3, determined at 25 ° C with Anything in any of the known ways. A solution of 0.5 T. Polymer in 100 ml of methylene-made polycarbonate can be used in the chloride according to the invention. The copolymer contains 5 to 5.3% bromine. Mixtures can be used. The polycarbonate can 15 As polymer 2, a copolycarbonate was produced from a dihydroxy-di-arylalkane and phosgene or 10 mol percent tetrabromo-bisphenol-A and 90 mol percent of a diester of a carboxylic acid, such as percent bisphenol-A, as follows:
Canadian Patents 5,78,585; 5 78 795; The preparation process for Polymer 1 is 5 94 805 and U.S. Patents 30 28 365 and repeated with the exception that 464.3 T. Bisphe-

29 99 835 described, be produced. Other hennol-A (2.03 moles), 125.1 T. tetrabromo-bisphenol-A position process for in the invention (0.23 mol) and 3.38 T. p-tert-butylphenol in 1958 T. Mixable polycarbonates are, for example, suspended in water.

in "Polycarbonate" by William F. Christopher The polymer obtained has a relative viscosity

and Daniel W. F ο χ described and also disclosed by 1.28, determined as described above, and

in the above and following as a content of 11 to 12% bromine.

U.S. Patents: 29,99846; 31 53 008; 32 15 668; A copolycarbonate was selected as polymer 3

3,187,065; 29 70 131; 29 64 794; 29 91 273; 30 94 508; 19 mole percent tetrabromo-bisphenol-A and 81 mol-

32 15 667; 32 27 740; 32 48 414; 31 48 172; 33 80 965; percent bisphenol-A produced as follows:

30 14 891; 33 20 211; 32 77 054; 32 80 078; 32 71 368; The manufacturing process for polymer 1 is 32 71 367; 32 61 808 and 32 51 803. 30 repeated with the exception that 417.2 T. Bisphe-

The mixtures according to the invention are extremely nol-A (183 mol) and 233.9 T. tetrabromo-bisphenol-A

suitable for application for any use (0.43 mol) suspended in 1958 T. water,

purpose for which polycarbonates are suitable The polymer obtained has a relative viscosity

and especially where increased flame resistance - of 1.25, determined as described above and

is required. For example, the invention contains 18 to 19% bromine.

mixtures according to the invention for the production of masks; Polymer 4 was made as follows:

Interior decorative panels; Structural components for 454T. 4,4'-dihydroxydiphenyl-2,2-propane and 9.5T.

Interior lining of aircraft; electrical p-tert-bulylphenol are suspended in 1.5 liters of water

Equipment such as terminal blocks; Helmets; and stirred well in a three-necked flask, while-

Wall coverings and the like are used. 40 rend by purging nitrogen during

In the following, for example, the heart is 15 min the oxygen is removed from the mixture, Preparation of four different polycarbonates, then 355 parts of a 45% aqueous solution are drawn as polymer 1 to 4. The addition of sodium hydroxide and 1000 parts of methylene to the parts (parts) and percentages given below, chloride added. The mixture is drawn off to 25 ° C where nothing else is stated, cools to 45 and maintains this temperature the weight. Cooling within 120 min 237 T. phosgene equal-

As polymer 1, a copolycarbonate of 4.5 was introduced moderately. 15 or 30 minutes after the start of the

Mol percent of tetrabromobisphenol-A and 95.5 mol of phosgene introduction are each 75 parts of a 45% strength

percent bisphenol-A prepared as follows: aqueous solution of sodium hydroxide added. Of the

492.5 T. 2.2-bis (4-hydroxyphenyl) propane (bis 50 obtained solution are 1.6 T. triethylamine added

phenol-A) (2.16 mol and 55.5 T. give 2,2-bis (3,5-dibromo- and the mixture for a further 15 min.

4-hydroxyphenyl) propane (tetrabromo-bisphenol-A) stirs. A highly viscous solution forms, whose

(0.102 mol) and 3.4 T. p-tert.-butylphenol, are increased in viscosity by adding Meihylenciik> rid

1958 T. water was suspended and placed in a three-necked tube and the aqueous phase was then separated off

flask with gas inlet tube and drip tube for 55 becomes. The organic phase is salt and water

Introduction of liquid well stirred. Washed through alkali free. From the washed solution

Blowing nitrogen through for 15 minutes, the polycarbonate is recovered and dried. That

Oxygen from the polycarbonate obtained from the suspended slurry shows a relative viscosity

removed and thereafter strength 361.6 T. a 50% aqueous of 1.32, measured at 20 ⁰ C to a 0.5% solu-

Solution of sodium hydroxide added. Then 60 solution of the polymer in methylene chloride, what a

the reaction flask cooled from the outside to 25X corresponds to a molecular weight of approximately 34 * 000,

and then with stirring 1149 T. methylene chloride With the prepared as described above

introduced. With stirring, polymers 1 to 4 and from them according to the following

Phosgene introduced into the reaction mixture that the Tables I to III prepared polymer mixtures

this within 100 min 268.5 T. (2.71 mol) COCl, 65 were attempts to determine rheological and

records. Simultaneously with the beginning of the phos- physical properties and the flame resistance

Generation a 50% aqueous sodium hydroxide solution is carried out in digkeit, the results of which are also in the

dripped into the reaction mixture to such an extent, Tables I to 111 are listed.

ίο

Rheological and physical properties and flame resistance data of stabilized and not stabilized polycarbonate of Example 1

Table I.

Stabilizer system colour Melt stability at
3OO ° C / 72 s- ¹ »Instron« -
Rheometer
(P 10-)
S min 35 min 0.90 65 min Relative viscosity
65 min
From extru-
gang-dated
granulate strand 1.259 "Izod" -Bash-
strength
mkg / cm
Notch depth, mm
3.18 6.36 0.103 U. L.
Flame
resistant
speed
Check
template
1.6 mm
thick
class 1
% 0.05% TNPP natural
lich 1.02 1.23 0.67 1.296 1.290 0.926 0.125 20th 0.05% TNPP +
0.01% TOP natural
lich 1.46 0.58 0.29 to 0.14 1.329 1.244 0.908 0.114 90 0.05% TNPP +
0.01% TIOP natural
lich 1.32 1.25 0.23 to 0.12 1.322 - 0.897 - 65 0.05% TNPP +
0.01% TIOP natural
lich 1.51 1.20 0.20 to 0.10 1,332 - - - 90 0.2% TNPP beige
(1) 1.20 1.03 0.63 to 0.36 - 1.308 - - - None V * /
Avoca
do (3) 1.11 1.06 1.03 1.326 - - - - None Avoca
do (3) 1.20 0.92 1.06 - - - - - 0.2% TNPP beige
(2) 1.23 0.62 0.18 1,316 1.276 - 0.087 - None beige
(2) 0.72 1.28 0.48 1.323 0.114 _ 20th None green (4) 1.51 0.99 to 0.84 0.48 - - - _ None black
(5) 1.50 0.91 to 0.84 0.48 to 0.34 - - - None by
shit
ending
white (6) 1.44 1.56 0.31 to 0.23 1,345 - 0.2% tetra
phenyltin natural
lich 1.44 1.27 1.66 1,332 1,342 - - 0 0.1% tetra
phenyltin natural
lich 1.22 1.33 1.30 1.334 1,339 - - - 0.05% tetra
phenyltin natural
lich 1.34 1.15 1.27 1.341 1.317 - - - 0.01% tetra
phenyltin natural
lich 1.30 0.62 0.74 1.327 1.271 - - - 0.3% Ba-Cd-
Carboxylate natural
lich 0.73 0.53 0.53 1.318 1.265 - - - 0.3% Ba-Cd-Zn-
Carboxylate natural
lich 0.58 0.58 0.42 1.289 U72 - - - 0.3% Ba-Cd-La »-
advice natural
lich 0.67 0.53 0.48 1,310 U65 - - - 0.3% Ba-Cd-Zn-
Laurate natural
lich 0.53 0.87 0.53 1.291 1,299 - 0.103 - 0.3% barium
metaborate natural
lich 1.13 0.82 1,324 0.169 50

The experiments performed on the various polymers and mixtures thereof were as follows executed:

Determining melt stability at 300 ⁰ C. The "Instrone check determines the melt viscosity (P x 10" ⁴⁾ after 5, 35 and 65 min residence time in the cylinder of the "Instron" -Geräts at 300 ° C under a shear stress of 72s ~ ' The extent of the change in the determined viscosity between 5 and 65 min in this test is a good indication of the stability of the polymer tested considered stable.

The relative viscosities of the test samples were determined on the original granulate and on a strand after extrusion for 65 min by dissolving 0.5 g of the polymer in 100 ml of methylene chloride and measuring determined at 25 ° C.

The "Izod" impact strength was determined in accordance with ASTM test standard D-256 with notch depths of 3.18 and 6.36 mm certainly.

The percentage of equivalent in the U.L. flame resistance requirements under Class 1 Materials were prepared using the methods described in the U. L. memorandum bulletin, Subject 94, “Burning Tests of Plastics ", December 9, 1959, of Underwriter's Laboratories, Inc., was determined. In this test, pressed test specimens 1.6 12.7 χ 152 mm are arranged vertically so that its lower end is 9.5 mm above the upper end of a Bunsen burner, and the flame of the burner is adjusted to a blue flame 19 mm high. This pilot flame becomes central placed under the lower end of the test specimen and left there for 10 s, then removed and the The duration of the burning and afterglow of the test object after removing the pilot flame is noted. if After burning and afterglow cease within 30 s after removing the pilot flame, the pilot flame becomes Immediately thereafter placed under the test item for another 10 s, then removed again and the The duration of the afterburning and / or afterglow is again noted.

The duration of the afterburning or afterglow of each individual test item should be 30 s and the average of 3 test objects (6 ignition processes) should not exceed 25 s. In addition, the examinee may during cannot be used up completely during the test. In other words, everyone must (100%) DUTs pass the 30 s test. Materials that meet the requirements described above do not comply or give off burning particles or droplets, which also nui during the test burn for a short time, were not listed under class 1 below.

Abbreviations used in the tables:

TNPP = Tris (mixed mono- and di-nonylphenyl) phosphite.

TlOP = triisooctyl phosphate. PNPP = phenyl neopentyl phosphite.

DIPD = diisodecyl pentaerythrityl diphosphite. ao dw = translucent white.

The in table I with the index numbers (1) to (6) be dyes were drawn by admixture de; the following color pigment proportions per kg of polycarbonate keep

additive

(1) titanium dioxide 0.883%

Diluted black pigment 0.013% Cadmium Orange 0.004% Cadmium yellow 0.0018%

TNPP 0.208%

(2) titanium dioxide 0.438%

Diluted black pigment 0.0053% Cadmium Orange 0.0017% Cadmium Yellow 0.0009%

TNPP 0.208%

(3) titanium dioxide 0.402%

Diluted black pigment 0.358% Cadmium yellow 0.124% Phthalo green 0.0025%

(4) Phthalo Green 0.0044%

(5) Diluted black pigment 0.33%

(6) barium sulfate 0.33%

Rheological and physical properties and flame resistance data of with Alkaline earth metal carbonates stabilized flame retardant polycarbonates

Table II

Poly Stabilizer system colour Melt stability at Relative 300 ° C / 72s - »» Instron «- Ans- , 35 1.323 viscosity "Izod" punch 6.36 U. L. Flamm mer Rheomcter fflllftS * 1.35 1.330 strength persistence (P 10- «) 35 min 65 min granules 1.318 tnkg / cm - Test sample 1.25 1.337 - 1.6 rom 1.10 1 1,342 0.087 thick 1.20 1.328 - massel 1.39 65 min 0.103 5 min 1.30 1 extmdicr- 0.098 1.39 1.17 1 the strand 0.108 % 1 0.33% CaCO ₃ dw 1.20 1.27! 0.092 1 0.165% CaCO, dw 1.37 1.02 1,310 - - 1 0.825% CaCO, dw 1.39 , 05 1.308 - 1 0.3% BaCO, dw U7 , 05 1.322 70 1 0.2% BaCO ₈ dw 1.49 , 39 1,335 Notch depth, mm - 1 0.1% BaCO ₃ dw 1.47 , 30 1.326 3.18 100 1 0.05% BaCO, dw 1.54 1.20 1 1.325 100 1 0.01% BaCO, dw 1.42 1.15 - - 90 1 0.3% SrCO, dw 1.51 1.10 0.67 - - - 1 0.3% Na ₁ CO, dw 1.35 - 0.131 - 2.35: - 0.136 0.381 0.125 0.152 -

13th

14th

Table II continued

Poly Stabilizer sysicm RiAe Melt stability at s- ¹ "Instron" - 35 min 65 min Relative viscosity 65 min
extruding 35 min 65 min Relative viscosity 65 min
extruding "Izod" punch 6.36 6.36 U.L. Flame mer 300 ° C / 72 Rheometer ab ab the strand the strand strength resistance (P 10-) builds builds mkg / cm Test sample 1.34 1.34 0.11 1.6 mm
thick 1.32 1.32 1,324 0.103 class 1 S min 1.42 1.32 the end
gangly 1.331 0.103 0.36 granules 1.325 the end
gangly % 1 0.3% MgCO ₃ dw 1.15 1.15 granules 0.103 1.46 0.65 0.65 1,314 - 1 0.3% BaCO ₃ dw 1.48 1,332 - Notch depth, mm 80 1 0.3% BaCO ₃ dw 1.48 1.347 3.18 80 1 0.3% BaCO, dw 0.91 0.91 1.329 . - 60 1 0.2% PNPP + 1.30 0.14 ab - - 0.3% BaCO ₃ dw 1.01 builds 1.326 - 0.13 8C 4th None n / A 0.60 0.60 - 0.13 0.052 - door 1.254 0.11 lich 0.94 0.46 0.45 0.059 4th 0.3% BaCO ₃ dw 0.43 - 1,232 0.942 - 4th 0.3% Na ₄ CO ₃ dw 0.51 0.51 - - 0.038 - 0.55 0.36 ab 1,237 0.092 2 0.3% BaCO ₃ dw builds 1.253 1,232 100 2 0.2% PNPP + 0.55 - 0.3% BaCO ₃ dw 1.253 - 100 2 0.2% PNPP + 0.54 made of polymer 1 0.5% BaCO ₃ dw 0.84 1.253 opaque beige (') - 8-colored products 0.08 • Izod «strike 100 2 None n / A 1.276 Melt stability at strength 87 door 300 ° C / 72 s- ¹ »Instron« - 0.081 mkg / cm lich Rheometer Table III Values at ι (P · 10- «) 0.054 Identified stabilizer system 0.103 U. L. Flamm resistance 5 min Test sample 1.6 mm thick Notch depth, mm class 1 3.18 O/

0.33% CaCO ₃ ² ) 1.20

0.33% BaCO ₃ *) 1.10

0.2% TNPP 1.23

0.3% BaCO ₃ 1.10

0.3% BaCO ₃ 1.15

0.2% PNPP 1.25

0.2% PNPP + 0.3% BaCO ₃ 1.25

0.1% PNPP + 0.5% BaCO ₃ 1.35

0.1% PNPP + 0.1% BaCO ₃ 1.39

0.3% PNPP + 0.5% BaCO ₃ 1.15

0.3% PNPP + 0.1% BaCO ₃ 1.11

0.2% DIPD + 0.3% BaCO ₃ 1.42

0.1% DIPD + 0.5% BaCO ₁ 1.42

0.1% DIPD + 0.1% BaCO ₃ 1.42

0.3% DIPD + 0.5% BaCO ₃ 1.25

0.3% DIPD + 0.1% BaCO ₃ 1.15

0.2% TNPP + 0.3% BaCO ₃ 1.27

0.2% DIPD + 0.3% BaCO ₃ 1.32

0.1% PNPP + 0.1% SrCO ₃ 1.49

0.1% PNPP + 0.5% SrCO ₃ 1.49

0.3% PNPP + 0.5% SrCO ₃ 1.20

0.2% PNPP + 0.3% SrCO ₃ 1.30

0.2% PNPP + 0.3% BaCO ₃ 1.32

0.91 1.06 0.92 1.10 1.15 0.60 1.08 1.22 1.22 0.98 0.84 1.19 1.32 1.18 0.89 0.87 1.20 1.10 1.20 1.08 0.72 0.94 1.13

0.74 1.10 0.18 1.10 1.15 0.41 1.03 1.15 0.98 0.87 0.62 1.12 1.25 1.06 0.89 0.77 1.20 1 .03 0.98 1.01 0.65 0.74 1.03

1.312 1.313 1.316 1.325 1.323

1.332 1.331 1.324 1.324

1.325 1.325 1.324 1.334

1.335 1.321 1.340 1.344 1.334

1,311
1.309

1,324
1.328

1,311
1.302
1.296
1.283

1,314
1.303
1.296
1.290

1.403
1.308
1.283
1,280
1,310

0.147 0.147

0.136 0.136 0.131 0.131

0.103 0.125 0.141 0.125 0.147 0.158 0.098 0.125 0.131 0.158 0.103

0.098 0.098

0.087 0.131 0.136 0.125

0.087 0.098 0.092 0.125 0.076 0.092 0.092 0.114 0.092 0.087 0.087

100 60 90 80

100

100

100

100

100

The beige coloring (1) of the products listed in Table III was carried out according to the above with respect to the Coloring of the products in the recipe given in Table I under index (2).

(2) The calcium or barium carbonate was in the mixing drum on the surface of colored Brought Polynaergranulat and reextruded this.

example

To demonstrate the synergistic effect of the combination of phosphite heat stabilizers with the carbonate stabilizers contained in the mixture according to the invention to achieve better Color stability of colored products, a sample of an opaque beige colored product was made Polymer 1 produced which contains the following color pigments in the specified percentage concentrations contained

Titanium dioxide 0.438

Diluted black pigment 0.0053

Cadmium Orange 0.0017

Cadmium Yellow 0.0009

Samples of the colored product thus obtained were dissolved in methylene chloride to prepare a 5% polymer solution. The pigments were filtered off using a pressure filter apparatus and the solids-free filtrate was analyzed spectrophotoetrically. The yellow index (YI) was calculated from the analysis results. The Yellowness Index is a measure for comparison wipe in the degree of yellowing ^e different, being compared ι

Inspect. The higher the yellow index, the higher the degree of yellowing.

The yellow index was calculated according to the following formula

Y. L =

128X-106Z

where X, Y and Z represent the tristimulus values which are obtained from the integrator on the writing GE ίο spectrophotometer and are used to localize a color in the color space. The following values were obtained:

Stabilizer system Y. I.

None 106.8

0.2% barium carbonate 205.9

0.3% barium carbonate 180.6

0.2% phenyl neopentyl phosphite 71.9

0.1% PNPP + 0.1% BaCO ₃ 17.6

0.1% DIPD: 0.1% BaCO ₃ 19.6

The same synergistic effect was not obtained when the same stabilizer ^{systems were used in a 1} polycarbonate which did not contain bromine.

Additional data obtained using that described in the present example from Polymer 1 produced, opaque beige colored mixture were obtained, the F i g. 3 and 4 can be taken while the effect of the stabilizer in the invention, using Polymer 2 prepared mixture, in F i g. 5 is shown graphically.

For this purpose 3 sheets of drawings

Claims (3)

Use of halogen-substituted divalent Phe claims: to increase nols for the production of the polymer. Unfortunately, however, such polycarbonates require such high levels 1. Thermoplastic molding compound, consisting of processing temperatures that they are commercially available for (A) one or more homo- and / or copoly- 5 the use for the production of moldings carbonates, at least one brominated, out of the question. It has also been suggested It contains romatic polycarbonate, (B) 0.01 carbonate copolymers from tetrahalobisphenol-A up to 5 percent by weight - based on the total and bisphenol-A. However, if the molar weight of the polycarbonates - barium, strontium part of the halogenated bisphenol in the copolymer or calcium carbonate, as well as optionally (Q io is not very low, cause the copoly more usual additives. mere such high processing temperatures that 2. Molding composition according to claim I, marked they are not suitable for the deformation. Another sign an additional content on the one hand makes the flame resistance of copolymers organic phosphite as a stabilizer. with only a small proportion of halogenated bisphenol 3. Use of the molding composition according to claim 15 units no better than that of a homopoly-1 or 2 for the production of flame-resistant moldings of bisphenol A polycarbonate. Also show co-bodies. polymers of tetrahalobisphenol-A and bisphenol-A have poor flexibility properties. Mixtures of homopolymeric, non-halogenated ao polycarbonates and homopolymeric tetrachloride bis- phenol-A-polycarbonates, as in the USA. Schnft 30 38 874 and mixtures of