DE1038276B - Process for the stabilization of synthetic resin compounds containing chlorine - Google Patents

Description

GERMAN

kl 39b 22/06

INTERNAT. KL. C 08 f

PATENT OFFICE

M 22269 IVb / 39b

REGISTRATION DATE: MARCH 10, 1954

NOTICE
THE REGISTRATION
AND ISSUE OF THE
LEGAL LETTERING:

SEPTEMBER 4, 1958

The invention relates to a. Process for stabilizing chlorine-containing synthetic resin compounds with antimony mercapto compounds, which are derived from the trivalent antimony.

The antimony mercapto compounds used according to the invention can generally be used as condensation products of antimony compounds with mercapto derivatives. In particular these are antimony mercaptides, antimony mercapto acids and antimony mercapto acid esters. These connections correspond to the following Structural formulas:

Sb (SR) ₃ ,
kyl, aryl

Sb (SR 'COOR ") ₃ ,

where R is an alkyl, aryl or aralkyl radical, and

where R ', an alkylene, arylene or aralkylene radical, which is either unsubstituted or has further COOR "groups as substituents Place carries one or more hydrogen atoms and R "is hydrogen or a substituted one or not substituted alkyl or aryl radical or a. Is aralkyl. So can. R methyl, ethyl, butyl, octyl, Lauryl, phenyl, propyl, phenylethyl, diphenylyl, etc., R 'can be from mercaptoacetic acid, mercaptopropionic acid, Mercaptoadipic acid, thio malic acid, thiosalicylic acid and R "of methanol, Ethanol, propanol, butanol, hexanol, octanol etc. or from glycerin, glycol monoesters, dihydroabietyl alcohol, Phenoxyethanol, etc. be derived.

The preparation of the antimony mercaptoveirbindungen used according to the invention can be according to any of the known methods take place, which have been described by various parties. One corresponding to Formula 1 Connection can e.g. B. by reacting antimony trioxide, or with antimony trihalide a mercaptan.

Antimony mercapto compounds according to formula 2 can in high yield and purity z. B. by Reaction of antimony trioxide or an antimony trihalide with a mercapto acid or a Mercapto acid ester and separation of the reaction product obtained with the desired Sb-S bond will.

Antimony mercapto derivatives of formula 1 or 2 are effective stabilizers for chlorine-containing synthetic resins, especially vinyl chloride polymers and copolymers, including those that contain plasticizers, such as. B. phthalates contain. If such antimony mercapto derivatives are incorporated into these synthetic resin compositions in finely divided form, plastic compositions result from high heat stabilization processes
synthetic resin compounds containing chlorine

Applicant:

Metal & Thermit Corporation,
Carteret, NJ (V.St.A.)

Representative: Dipl.-Ing. A. Bohr, Munich 5,
Dr.-Ing. H. Fincke, Berlin-Lichterfelde, Drakestr. 51,
and Dipl.-Ing. H. Bohr, Munich 5, patent attorneys

Elliott Lawrence Vineyard, Long Island City, N.Y., Clarence KennetlvEVnesi William Johnson,

Westfield, N.J.,

and Carl Robert Gloskey, Avenel, NJ (V. St. A.),
have been named as inventors

resistance. Films made from such plastic masses have a high degree of Persistence on. The amounts of stabilizer to be used for this purpose can be down to to be 0.5 percent by weight; However, a better stabilizing effect is achieved with larger additives reached on antimony mercapto derivative. Preferably about 2% of the stabilizer should be based based on the weight of the resin. Resin masses containing chlorine with this concentration of stabilizers result in stable plastic films that do not change at elevated temperatures color dark, which can be seen in the table below.

The resins used for the heat resistance test were polyvinyl chloride resins. In order to show that the stabilizing effect is independent of the way in which the resin is produced, polyvinyl chloride resins which were made by two different manufacturers and which are referred to as polyvinyl chloride resins 1 and 2 were used.

Each 2 parts of stabilizer was a mixture of 100 parts by weight of resin and 50 parts by weight Plasticizer added. With the exception of one case, dioctyl phthalate was used as the plasticizer.

809 600/49 *

Claims (1)

The mixture was then on a two-roll mill, whose rollers were rotated at different speeds rolled out into a film 1 mm thick. Samples of these films were then pressure polished. The aging tests were 2.5 cm wide, 10 cm long film strip carried out in an oven at 160 ° C. The duration of the experiment was Hours. Stabilizers Polyvinyl chloride resin plasticizer Appearance after aging None None Dibutyltin dilaurate Antimony trilauryl mercaptide ... the same Antimony triphenyl mercaptide .. the same Antimony trioctyl mercaptide the same Antimony-SS'S "-tri- (nonyl mercaptoacetate) the same 1
2 1
2 dioctyl phthalate
Dioctyl phthalate
Dioctyl phthalate
Dioctyl phthalate
Dioctyl phthalate
Dioctyl phthalate
Dioctyl phthalate
Dioctyl phthalate
Dioctyl phthalate Dioctyl phthalate Parts dioctyl phthalate. 10 parts
Alkyl aryl phosphate, 0.5 part
Calcium stearate black black black weak weak weak weak weak weak reddish yellow reddish yellow reddish yellow reddish yellow) reddish yellow reddish yellow Antimony SS'S "-tri- (dihydroabietyl mercaptoacetate) the same cloudy and reddish yellow cloudy and pale reddish yellow clear yellow This table clearly shows the stabilizing effect of the antimony mercapto compounds according to the invention compared to unstabilized films and films made with a well-known Stabilizers; d. H. Dibutyltin laurate. Further chlorine-containing synthetic resin compositions which, with the help of the compounds according to the invention, heat and made lightfast are, for example: Vinyl chloride polymers and vinyl resins which contain vinyl chloride as a copolymer, Copolymers of vinyl chloride and vinyl esters of aliphatic carboxylic acids, especially vinyl acetate, Copolymers of vinyl chloride and esters, nitriles and amides of unsaturated carboxylic acids, z. B. acrylic and methacrylic acid, Copolymers of vinyl chloride and diene compounds and unsaturated dicarboxylic acids or their anhydrides, such as vinyl chloride copolymers with diethyl maleate, diethyl fumarate or maleic anhydride, post-chlorinated polymers and copolymers of vinyl chloride, Vinylidene chloride polymers and copolymers with vinyl chloride and other polymerizable Links, Polymers of vinyl chloroacetate and dichlorodivinyl ether, chlorinated vinyl acetate polymers, chlorinated polymeric esters of the acrylic and α-substituted Acrylic acids, Polymers of chlorinated styrenes, for example chlorostyrene, chlorinated rubber, chlorinated ethylene polymers, Polymers and post-chlorinated polymers of chlorobutadienes and their copolymers with Vinyl chloride, Rubber hydrochloride and chlorinated rubber hydrochloride, also mixtures of those listed here Polymers with one another or with other polymerizable compounds. 35 40 45 Godfather s ρ i! r ι: Process for stabilizing chlorine-containing synthetic resin compositions, in particular resin compositions which contain polymers and copolymers of vinyl chloride, characterized in that organic antimony mercapto derivatives of the formula Sb (SR) ₃ , in which R is an alkyl, aryl or aralkyl radical, are added to the resins as stabilizers, or of the formula Sb (SR'COOR ") ₃ , in which R 'is an alkylene, arylene or aralkylene radical and R" is hydrogen or a substituted or unsubstituted alkyl or aryl radical or an aralkyl radical, in amounts of 0.5 to 10% and preferably in amounts of 2% based on the amount of the synthetic resin. Considered publications: British Patent Nos. 247,986, 258,973, 427; Swiss Patent No. 169 577; U.S. Patents Nos. 1,561,535, 2,060,181, 2 226 530, 2 510738, 2 606 201, 2556 420, 2 581915, 641588; Reports of the German Chemical Society, 39, pp. 737 and 1357 (1906); Zeitschrift für inorganic Chemie, 41, p. 246 (1904); Journal of the Chemical Society, 1932, p 1826, Chem. Abstracts, 26, p 934 ² (1932). ® 809 600/498 9.5 «