CH678331A5 - - Google Patents

Description

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CH 678 331 A5

description

It has been found that polymeric, organic compounds can be stabilized very effectively, in particular against yellowing and the subsequent degradation, if they are stabilized in the mass from 30 to 80 percent by weight of a compound of the formula I.

tert-butyl -

tert-butyl

(I),

where fit

Hydrogen, methyl, unsubstituted phenyl or a group of the formula ai tert-butyl tert-butyl <y-

!.

P

(31) J

wherein n is zero or 1, and admixes 20 to 70 percent by weight of an organic phosphite compound.

Preferred phosphites correspond to the formula II or III,

[0-R2):

(II)

/ 0 — cb> s ^ xh -— 0 \

R2 "° - \" TX ^ P-O-R,

o CH £ ^ XCH2 0 ^ 2

wherein all Rz independently of one another are linear or branched Ci-22-alkyl or optionally up to 3 linear or branched Ci-4-alkyl groups, preferably phenyl bearing methyl and / or tert-butyl.

Particularly preferred organic phosphites are e.g. Tris (2,4-di-tert-butylenephenyl) phosphite, tris (nonyIphenyl) phosphite, trilauryl phosphite, bis- (2,6-di-tert-butyl-4-methylphenyl) -pentaerythryI-di- phosphite, bis (2,4-di-tert.butylphenyl) pentaerythryl diphosphite and distearyl pentaerythryl diphosphite

These stabilizer mixtures are generally used in amounts of 0.01 to 1.0, preferably 0.05 to 0.3 percent by weight, based on the polymeric organic compounds to be stabilized.

The stabilizers preferably consist of 40 to 70, in particular 40 to 60 percent by weight of a compound of the formula I and 60 to 30, in particular 60 to 40 percent by weight of an organic phosphite compound.

The stabilizers according to the invention can additionally contain antioxidants, e.g. sterically hindered

2nd

CH 678 331 AS

phenolic antioxidants, sulfur-containing or aminoaryl antioxidants. The latter compounds are generally present in amounts between 0.5 and 2 parts by weight per part by weight of phosphorus-containing stabilizers.

Preferred phenolic antioxidants are, for example: octadecyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxy-5 phenyl) propionate, pentaerythryl tetrakis-3- (3', 5'-di- tert-butyl-4'-hydroxyphenyl) propionate, 1,3,5-tris (3 ', 5', di-tert-butyl-4'-hydroxyphenyl) isocyanurate, 1,1,3-tris - (5'-tert-butyl-4'-hydroxy-2-methylphenyl) butane, 1,3,5-tris- (tris- (3'I5'-di-tert-butyl-4 ' -hydroxybenzyl) mesitylene and ethylene glycol bis- [3,3- (3'-tert-butyl-4'-hydroxyphenyl) butyrate].

Preferred aminoaryl antioxidants include: N, N'-dinaphthyl-para-phenylenediamine and N, N-10 hexamethylene-bis- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide.

Preferred sulfur-containing antioxidants are, for example: di-tridecyI-3,3-thiodipropionate, di-lauryl-3,3'-thiodipropionate, di-lauryl-3,3'-thiodipropionate, di-stearyI-3,3'-thiodipropionate , Methane tetrakis (methylene-3-hexylthiopropionate) and di-octadecyl disulfide.

Another additive to the stabilizers according to the invention is e.g. a-tocopherol (vitamin E) 15 into consideration.

The stabilizers according to the invention are preferably suitable for all polyolefins (e.g. high and low pressure polyethylene, polypropylene), polyisobutylene, poly-4-methylpentene and the copolymers of these plastics. Furthermore, they are also effective for stabilizing polystyrene (and its copolymers), ABS, polyvinyl acetate, polyvinyl alcohol oil, polyacetate (POM), polyacrylates, polyacrylni-20 tril, polyacrylamide, PVC, polyvinylidene chloride, polyamides, polyesters, polyethers, polythioethers and thioplasts, polycarbonates , Polyurethane, cellulose derivatives, maleic acid, melamine, phenol, aniline, furan, carbamide, epoxy and silicone resins.

The polymeric organic materials modified according to the invention can also e.g. contain flame retardants, antistatic agents, UV absorbers, UV stabilizers, plasticizers, nucleic agents, metal deactivators, biocides, fillers and pigments.

The stabilizers used according to the invention can be added to the polymeric organic compounds at any stage of processing; before, during and after the polymerization or polycondensation. They can be tel quel, solid or melted, in solution (preferably as 10 to 80 weight percent solutions), e.g. 10 to 90 percent by weight concentrate (Master-30 batch) can be used with the plastic to be stabilized or with a plastic that is compatible with it.

In general, the stabilizers used according to the invention are introduced into the melt of the material to be stabilized, which e.g. is carried out in an extruder or in a melt spinning machine. Then the plastics are e.g. processed into foils, tubes, fibers, threads, foams and other fittings. The stabilizers used according to the invention are particularly suitable for fibers and films made of polypropylene.

example 1

A solution is being prepared by

40

1.0 g calcium stearate,

1.0 g of pentaerythryl tetrakis-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate, 0.4 g of tetrakis (2,4-di-tert-butylphenyl) -4 , 4'-diphenylene diphosphonite, 0.4 g tris (2,4-di-tert-butylphenyl) phosphite and 45 0.2 g bis- (2,4-di-tert-butylphenyl) diphenyl -phosphonite in 25 ml acetone. This solution is added to 1000 g of polypropylene powder and treated in a mixer at 400 revolutions per minute for 5 minutes. The mixture is then dried at 50 ° C. for 30 minutes, introduced into a Göttfert extrusiometer (with a 20 mm screw, compression 1: 3, diameter / length ratio = 1:20) and heated to 270 ° C. extruded several times. After each extrusion, the Helt Flow Index (MFl) is measured at 230 ° C / 2.16 Kp and evaluated as a characteristic for the stabilizing effect.

Examples 2 to 4

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Instead of the 0.4 g of tris (2,4-di-tert-butylenephenyl) phosphite, only 0.2 g of this compound and (Ex. 2) 0.2 g of tris (nonylphenyl) phosphite are used, (Ex. 3) 0.2 g of a 4: 6 - (parts by weight) mixture of a-tocopherol and tris (nonylphenyl) phosphite and (Ex. 4) 0.2 g of a 2: 4: 4 (parts by weight) mixture of a-tocopherol, di-tridecyl-3,3'-thiodipropionate and trilauryl phosphite.

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Claims (6)

Claims 1. Stabilizers for polymeric organic compounds containing 30 to 80 percent by weight of a compound of formula I. 65 3rd 5 10th 15 20th 25th 30th 35 40 45 50 55 fin CH 678 331 A5 tert-butyl - & tert-butyl Rt CD, where Ri Hydrogen, methyl, unsubstituted phenyl or a group of the formula ai (ai). wherein n is zero or 1, and contain 20 to 70 weight percent of an organic phosphite compound. 2. Stabilizers for polymeric organic compounds according to claim 1, wherein the organic phosphite compound corresponds to the formula II or III (0-R2): (II) / Û / CH- (K Rg-Q-P c 2 ^ .P-O-R (III), X0 VCH2 0 ^ 2 where all R2 independently of one another are linear or branched Ci-22-alkyl or optionally up to 3 linear or branched Ci_4-alkyl groups, preferably phenyl bearing methyl and / or tert-butyl. 3. Stabilizers for polymeric organic compounds according to claim 1 or 2, which contain 40 to 70, preferably 40 to 60 percent by weight of a compound of formula I and 60 to 30, preferably 60 to 40 percent by weight of an organic phosphite compound. 4. Stabilizers for polymeric organic compounds according to one of claims 1 to 3, which additionally contain 0.5 to 2 parts by weight of one or more antioxidants per part by weight of the stabilizer mixture. 5. stabilizers for polymeric organic compounds, according to one of claims 1 to 4, which are present as a concentrate, the 10 to 80 percent by weight of a mixture of the stabilizers, and additionally 90 to 20 percent by weight of one or more solvents for the polymeric, organic compounds to be stabilized, or a compound compatible with these and optionally contains antioxidants. 6. The at least one stabilizer mixture according to one of claims 1 to 3, in amounts of 0.01 to 1.0 percent by weight, based on the polymeric organic compounds to be stabilized, containing non-textile polymeric organic compounds. 4th