DE1282933B - Coloring of polystyrene or polymethyl methacrylate - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

German class;

Number:
File number:
Registration date:
Display day:

C08f

C09b

39 b4- 33/02

39 M - 45/66; 39 b4 - 29/46;
22 b- 3/17

P 12 82 933.3-43 (A 50238)

September 14, 1965

November 14th 968

The subject of the invention is the use of a u-phenylthioanthraquinone of the formula

X O

Coloring of polystyrene or
Polymethyl methacrylate

XOX

wherein each radical X is hydrogen, alkylamino, anthraquinylamino or a phenylthio radical of the formula

X V ' ^Y »<

is. Y is hydrogen, halogen, alkyl or alkoxy. Z is hydrogen, halogen, alkyl or alkoxy and is in a, / - position of the anthraquinone molecule, in is 0, 1, 2 or 3 and /; is 0, 1, 2, 3 or 4. for coloring polystyrene or polymethyl methacrylate.

For the coloring of such polymers, and in particular _2S door making clear, vitreous colored products, is only a limited number of dyes available. Many of the dyes previously used for coloring plastics do not meet the current Vice end at such dyes to ^ ₀ Receivables more because during the processing of such polymers currently higher temperatures and pressures at which these dyes, lose their color authenticity or other desired properties, can be applied than before.

Most of the organic pigments are currently used in the processing of thermoplastic polymers applied conditions not stable, so that the introduction of thermoplastics inorganic substances such as carbon black. Iron oxides and Cudmiumsclcnidc. have been used. Inorganic pigments, however, do not give any coloration with the gloss and / or clarity desired for many purposes.

The number of organic pigments that are suitable for coloring such polymers is also increased also limited by the fact that they lead to reactions between the pigment and the catalysts. Antioxidants. Preservatives. Fungicides. Vulcanizing mills and other additives can react to form such polymers, with these also being all the more important Applicant:

Allied Chemical Corporation,

New York, N.Y. (V. St. A.)

Representative:

Dr. 1. Ruch, patent attorney,

8000 Munich 5, Reichenbachstr. 51

Named as inventor:

Chi Kang Dien, Buffalo, N.Y. (V. St. A.)

Claimed priority:
V. Sl. v. America September 14, 1964
(396376)

This decreases, the higher the temperatures and pressures are used during processing.

The color of the polymers colored according to the invention does not change when they are exposed to high temperatures for example up to 371 ° C. The polymers colored according to the invention are yellow in color. not only at the high temperatures used during deformation do not change, but are also lightfast.

The fi-phenylthioanthraquinones are surprising stable and do not change their color during normal processing when they touch the polymer or mixed with the monomers. In addition, the ii-phenylthioanthraquinones have no anti-catalytic effect on the monomers, for example methyl methacrylate. those in their presence are polymerized, and are in turn used by those used in such a polymerization Catalytic converters not attacked. According to the invention colored polymers have beautiful and clear tones of excellent authenticity and durability that retain their shine even under the influence of the weather. and the color is also at processing and deformation at high temperatures of, for example, up to 371 C, such as Compression molding. Spinning and extruding, and also in the presence of additives such as peroxides. stable.

It can be unsubstituted 1-phenylthioanthraquinone. 1.4-bis- (phcn> lthio) -anthraquinone, 1.5-bis-

aO9 637 12M

(phenylthio) anthraquinone, l, 8-bis (phenylthio) anthraquinone and l, 4,5,8-tetrakis (phenylthio) anthraquinone and substituted-phenylthioanthraquinones, in which a) one or more of the phenylthio radicals itself with 1 to 3 halogen atoms, alkyl or alkoxy radicals and / or b) the anthraquinone radical is also substituted in the -position 1 to 3 substituents, the 'substituted phenylthio radicals of the above class a), alkylamino radicals and / or

machine, an extruder or a thread spinning device are introduced. Alternatively, a aqueous paste or a solution of the phenylthioanthraquinone with the comminuted polymer mixed and the dried mixture after removal of water or solvent, if desired with further mixing, for example in a ribbon mixer, in a mold or a other deformation machine can be introduced.

the mixture can then be polymerized and shaped, which takes place in one or more process stages can, as is customary in this field.

Preferably, a mixture of the «-Phenylthioanthraquinone, preferably in a substantially pure and finely divided state with a polystyrene or polymethyl methacrylate granules. By circulating the mixture in known

Anthrachinylamino radicals are, bears and / or c) io The u-phenylthioanthraquinone can also be used in the anthraquinone nucleus in the / {positions 1 to the monomer or comonomer and bears 4 halogen atoms, alkyl or alkoxy radicals. The halogen atoms can be fluorine,
Be chlorine or bromine atoms, and the alkyl or
Alkoxy radicals usually contain 1 to 12 carbons each
material atoms.

Those connections in which at least
two of the radicals X and Y and all of the Z radicals are hydrogen
are and especially those in which each of the
Benzene nuclei of the anthraquinone molecule have a Phe- 20 way the plastic bears a surface nylthio radical, ie the 1,5- and 1,8-bisderivatives, provided with a coating of the pigment and then, because of its superior lightfastness, are preferred in a deformation apparatus, for example a press . Of these, in turn, the 1,8-bis (phenyl form, an extruder or a spinning machine or thio) -anthraquinone of the formula is a combination of such devices that are used in

25 is operated at a temperature between about 204 and about 316 ° C. The colored moldings obtained have a clear, bright yellow to reddish yellow hue which shows no signs of change.
30 Another method is that the -phenylthioanthraquinone in the monomethyl methacrylate, which contains a polymerization catalyst, for example benzoyl peroxide, dissolved or preferentially, since it is not only polystyrene and poly- and the solution is then suspended in the usual methyl methacrylate in clear yellow tones is heated by 35 ways in order to conduct the polymer with excellent heat resistance and lightfastness. The yellow-colored polymer formed thereby becomes colored, but also a surprisingly strong can then in any convenient way, has coloring power. That is, the same weight, for example, by extrusion, compression molding or quantities of 1,8-bis (phenylthio) anthraquinone and spinning, are deformed. The 1,5-bis- (phenylthio) -anthraquinone obtained in this way produce ahn- 40 objects have practically the same self-love of reddish-yellow tones of the same heat resistance as those produced by pigmenting the depth of color obtained with the 1,8-isomer is achieved; Polymer are obtained,
however, it is about twice as large as that used with the die used to color a polymer

1,5-jsoineren. The amount of α-phenylthioanthraquinone can be in one

Another advantage of the preferred class of 45 vary widely and depends on the ge-α-phenylthioanthraquinones is their solubility in the desired depth of color and it depends on which phenylene Polymers as well as a number of the common thioanthraquinones are used. That is, the organic solvents such as acetone, the amount used can be extremely small, Toluene and ethyl acetate. The invention and the upper limit for this amount result Use of these pigments for coloring 50 only from the compatibility of the u-Phe-polystyrene used and polymethyl methacrylate, clear, nylthioanthraquinones can be colored bright yellow with the poly to reddish yellow glass-like products. merisat.

the color of which can already change when they are processed in the case of tall moldings with light shades

Temperatures and when exposed to sunlight with a-phenylthioanthraquinones in an amount of not changed and which, even under the influence of weather, only flow 0.0001 part per 100 parts by weight of polymer retain their shine and clarity, be achieved. To achieve deeper tones you can be procreated. Quantities up to 5.0 or more parts per 100 parts by weight

The admixture of the a-phenylthioanthraquinone parts polymer can be used. For example, 0.5 to 5.0 parts and preferably 1.0 to mers or mixtures of monomers can be added to the preformed polymers or the monomers after 60 3.0 parts of α-phenylthioanthraquinone with 100 parts of known processes. For example, monomer or polymer can be mixed. Pellets, granules or rods, ie the usual products with a lighter yellow tone, can then be obtained from commercial forms from the polymer with a, if such a deep tone, provided in a surface coating of the pigment, is made according to the usual method by they are mixed in a mixing apparatus with processing and comminution with non-pigmendem comminuted pigment, and the polymerized material mixed with the polymer coated with a hole can then be further processed, for example by compression molding, extruding or molding into a compression molding machine, for example spun.

The α-PhenyIthioanthraquinones can according to different usual methods are produced. For example, 1-phenylthioanthraquinone, 1,4- and 1,5-bis (phenylthio) anthraquinone and their Alkyl and alkoxy substitution products are produced, as in German Patent 116 951, Annales de Chimie (12), 10, p. 716, and in the USA. - Patents 1,062,990, 2 109 464 and 3,018,154.

The H-phenylthioanthraquinones are preferred used in finely divided form and can easily in a known manner, for example by fine grinding or grinding with sand, can be obtained in this form.

Parts and percentages in the following examples relate to weight.

example 1

A number of mixtures of 100 parts each of polystyrene pellets and 0.05 parts of 1,8-bis (phenylthio) anthraquinone was subjected to the following treatment:

Each mixture was placed in a metal container, which was then sealed and 5 minutes was mechanically circulated so that the pellets were coated with the pigment. The one with the Coated pellets were then placed in a laboratory extruder, and the extruder was at various temperatures in the range of 160 to 316 C, as in the following Table indicated, operated. The mass was held in the extruder for 5 minutes and then with extruded at low speed into a rod 0.3 cm in diameter. The rods obtained were Colored in a clear, shiny reddish yellow and showed no change in color tone. The rods were chopped into pellets and the various masses of colored pellets were made placed in an injection molding machine, which was operated at about 204 C, and in this to plates 5 x 7.5 - 0.6 cm pressed. These plates were kept in the fade-ometer for 320 hours and then with Plates that were not held in the fade-ometer are compared. It turned out that the color was not noticeable was changed.

For comparison, colored polystyrene rods were prepared in the same way but using 0.05 part of the commercially available plastic dye Color Index Solvent Yellow 40 in place des 1. 8.-bis (phenylthio) -anthraquinone produced. The intensity of the color of the rods obtained was only about half of those with 1,8-bis- (phenylthio) -anthraquinone colored bars. In addition, the color of the bars was changed as indicated in the table.

Extrusion modification the color*) temperature I.8-bis4phenyl- Color Index C. thioanthraquinone) ' Solvent Yellow 40 160 no no 204 no no 260 no strong 288 no very strong 316 no very strong

55

60

*) The color change was rated according to the following scale: none, slight, noticeable, considerable, strong, very strong.

Example 2

The procedure of Example 1 was repeated, but the same instead of polystyrene Amount of polymethyl methacrylate was used. The polymer provided with the surface coating was extruded at about 177 ° C and deformed at about 163 ° C. Despite the applied in extrusion The pigmented polymer exhibited a relatively high temperature of 177 ° C. after extrusion no change in color. Even if the sheet obtained in the injection molding machine was 320 hours was held in the fade meter, the color did not change noticeably.

Example 3

A mixture of 100 parts of monomethyl methacrylate, 0.1 part benzoyl peroxide and 0.1 part 1,8-bis (phenylthio) anthraquinone was heated to a vigorous boil on the steam bath. Then the mixture was removed from the steam bath and, after the reaction had subsided, kept in a warm (60 C) oven for 16 hours. The polymerization was then terminated by leaving the mass on the steam bath for a further hour warmed. The pigmented polymer obtained in this way was eu as described in Example 2 Rods extruded, whereby clear, glass-like glossy reddish yellow colored rods were obtained. The polymerization was due to the presence of the 1,8-bis (phenylthio) anthraquinone in the Monomeremaese not noticeably affected, and the presence of the peroxide did not change the color of the pigmented polymer.

Example 4

A mixture of 100 parts of polystyrene pellets · and 0.05 parts of 1-Phenylthioanthrachinon was subjected to the procedure of Example 1 using an extrusion temperature of 316 "C and a Spriti gubtemperatur of about 204 ¹ C. This gave a clear, bright yellow colored polystyrene whose color somewhat greenish yellow but less intense than that obtained under the same conditions in example 1. Despite the high temperatures used, no change in color could be detected.

Example 5

If, instead of the 1-phenylthioanthraquinone used in Example 4, an equal amount of 1,5-bis (phenylthio) anthraquinone was used, a bright reddish yellow colored polystyrene was obtained, its color tone was similar to that obtained under the same conditions in example 1, its color intensity however, was considerably less. Despite the high temperatures used, there was no change the color detectable.

B «i s ρ i e 1 6

A mixture of 100 parts of polystyrene pellets and 0.05 part of 4-methylamino-1-phenylthioanthraquinone was subjected to the procedure of Example 1 using an extrusion temperature of 288 ° C and an injection molding temperature of about 204 ° C. Clear, bright purple-colored polystyrene was obtained. Despite the high temperatures used, no change in color was noticeable.

Even if the details of the above examples are slightly modified, the same results are obtained. For example, the temperatures can be changed. When using polystyrene, temperatures from 149 to 316 ° C and when using polymethyl methacrylate temperatures from 149 to about 204 ° C can be used. If /, the colored polymers are produced by polymerizing the monomeric compounds, then - when using monomeric, ( ₀ styrene. Temperatures between about 49 and about 149.degree. C.; and when using monomethyl methacrylate temperatures between about 38 and about 12! C should be applied.

Instead of the -phenyllhioanthraquinones used in the examples, the same amounts of the following n-phenylthioanthraquinones can be used: i.4-bis (phenylthio) anthraquinone. 1 - (. Or or, m- or p-Methyl-phenylthio) -anthraquinone. l- (o- or m- or p-chlorophenylthio) -anthraquinone, l- (o- or m- or p-metho, xyphenylthioj-anthraquinone. l- (o ~ or m- or p-ethoxy-, phertylthio) - anthraquinone. 1- (4'-Butyiphenylthio) -anthraquinone. 1- (4'-Nonylphenyltbio) -antnrachinone.1 - (4'-Dodecylphenylthio) -anthraquinone.1 - (Diinethylphenylthioi-antnrachinone. l- (6'-Isopropyl- 3'-nTe "thylphenylthio) - anthraquinone. The corresponding 1.4-, 1,5- and 1.8-bis- (subst. Phenylthio) -anthraquinones, the corresponding 1.4.5.8-tetriikis- (subst.- ^v phenylthio) -anthraquinones.4.4-bis- (phcnylthio) -1.1 -dianthnniid and brominated 1,4-bis- or 1,5-bis- or IS-bis- (phenylthio) -anthraquinones.

Claims (1)

Claim: Use, of a H-phenylthioanthraquinone, the. Formula ..- ■ -, '. . .-,, - .. X Q S i / ± m ". X ₁ O. X, wherein each X is hydrogen. Acylamino .. -. Anthrachinylamino or a phenylthiprest of the formula V, is. Y hydrogen. Halogen. Alkyl or alkoxy _; is. Z is hydrogen ". Halogen. Alkyl or alkoxy and is in a ί position of the anlhraquinone molecule. / ;; is 0. L is 2 or 3" and /; is equal to 0. 1. 2. 3 or 4., for the display of polystyrene or polvmcthvlmethacniat .. Documents considered: Swiss Patent No. 374 964.. 809 637-1214 Il 6ö Ö H .. ro, kt