FR2627185A1 - STABILIZING COMPOSITIONS OF POLYMERIC MATERIALS - Google Patents

Abstract

The subject of the present invention is a composition comprising: a) from 30 to 80% by weight of one or more compounds of formula I: (CF DRAWING IN BOPI) in which R1 signifies hydrogen, a methyl group, a non-phenyl group. substituted or a residue of formula a1): (CF DRAWING IN BOPI) in which n signifies 0 or 1, and b) from 20 to 70% by weight of one or more organic phosphites. These compositions are used as stabilizers for polymeric materials during their processing.

Description

The subject of the present invention is compositions based on a

  phosphonite and a phosphite and their use as stabilizers for the

  transformation of polymeric materials.

  In particular, the invention relates to a composition comprising a) from 30 to 80% by weight of one or more compounds of Formula I tert.-Butyl. tert.Butyle-C O R I)

  in which R1 signifies hydrogen, a methyl group

  thyl, unsubstituted phenyl or a radical of formula a) tert.Butyl-tert.-Butl - (a1), wherein n is 0 or 1, and b) 20 to 70% by weight of one or more phosphites organic. The compounds of formulas I and II are

antioxidants.

  The compositions according to the invention can be used to stabilize the polymeric materials during their transformation. The subject of the invention is therefore also the use of these compositions as stabilizing agents for the transformation of polymeric materials and stabilizing compositions

  for the processing of polymeric materials

  components a) and b) defined above. Linen-

  The invention also comprises a process for stabilizing the polymeric materials during their conversion, which method comprises incorporating into the polymeric material a composition comprising component a) and

  component b) previously defined.

  The compositions of the invention preferably contain one or more additional antioxidants (e.g., sterically hindered phenols, aminoaryl compounds, or

anti-oxidants containing sulfur).

  The preferred phosphites are those corresponding to formula II or III

P (-O-R) 3 (II)

  R -0-p? - cH. ## STR5 ##

O-CH --- H '\ CH, ---- O

2 2

  wherein R is independently a linear or branched C1-C22 alkyl group or a phenyl group unsubstituted or substituted by 1 to 3 linear or branched C1-C12 alkyl groups, preferably C1 to 3 C1-C6 alkyl groups; C4, in particular

methyl or tert-butyl groups.

  Particularly preferred phosphites are tris- (2,4di-tert.-butylphenyl) phosphite,

  tris phosphite (nonylphenyl), the phosphite of -

  trilauryl, pentaerythrityldiphasphite bis (2,6-

  di-tert.-butyl-4-methylphenyl), pentaerythrityldi

  bis (2,4-di-tert.-butylphenyl) phosphite, and the

  pentaerythrityldiphosphite of distearyl.

  The preferred phenolic antioxidants are

  selected from 3- (3,5-di-tert.-butyl-4-hydroxy-

  phenyl) -propionate of octadecyl, tetrakis [3- (3,5-

  di-tert.-butyl-4-hydroxyphenyl) propionyloxy-methyl] -

  methane, the isocyanurate of 1,3,5-tris- (3,5-di-tert.-

  butyl-4-hydroxy-phenyl), 1,1,3-tris (5-tert.n.

  butyl-4-hydroxy-2-methylphenyl) butane, 1,3,5-tri-

  methyl-2,4,6-tris- (3,5-di-tert-butyl-4-hydroxy-

  benzyl) benzene and diester 3,3-bis (4-hydroxy-3-

  tert.-butylphenyl) -butyric acid ethylene glycol.

  The preferred aminoaryl antioxidants are N, N'-dinaphthyl-p-phenylenediamine and the

  N, N'-hexamethylene-bis-3- (3,5-di-tert-butyl-4-hydro

  xy-phenyl) -propionamide. The preferred sulfur-containing antioxidants are tridecyl thio-3,3'-dipropionate,

  lauryl thio-3,3'-dipropionate, thio-3,3'-di-

  stearyl propionate, tetrakis (3-hexylthio)

  propionyloxymethyl) methane and diocta disulphide

decyl.

  Another preferred additive for a composition

  stabilizer according to the invention is α-tocopherol

(Vitamin E).

  In the composition of the invention, the

  quantity of component a) present is preferably included

  between 70 and 40% by weight and the amount of

  b) present is preferably between 30 and% by weight of the composition. In the composition of the invention, the amount of component a) is more preferably between 40 and 60% by weight and the amount of component b) is more preferably

  between 60 and 40% by weight of the composition.

  When an antioxidant (or vitamin E) is present, it is preferably 50 to

% by weight of components a) and b).

  In addition, the invention relates to a

  polymer composition comprising a polymeric material and a

  sufficient amount of a composition according to the invention.

  to obtain stability in the transformation of

the polymeric material.

  The amount of components a) and b) present is such that they preferably represent from 0.01 to 1% by weight, more preferably from 0.05 to 0.3% by weight.

relative to the polymeric material.

  The Applicant has now found that a combination of component a) and component b) produces

  a synergistic effect on the stability at processing

  of the polymer composition to which the combination

  sound is applied. Properties such as yellowing (measured by yellowness index) and

  the Melt Flow Index of such composi-

  polymer concentrations are significantly improved over those containing only component a)

or component b).

  Preferred polymeric materials that can be stabilized are polyolefins such as

  polypropylene, polyethylene (for example, poly-

  high density ethylene, low density polyethylene, linear low density polyethylene or medium density polyethylene), polyisobutylene, poly-4-methylpentene and copolymers such as

  ethylene-vinyl acetate copolymers.

  As other polymeric materials which can be stabilized with the composition of the invention, it is possible to

  polystyrene and its copolymers and its

  nappes, ABS, polyvinyl acetate, polyalcohol

  vinylacrylate, polyacetates (POM), polyacrylates and

  polymethacrylates, polyacrylonitrile, poly-

  acrylamides, PVC, polyvinylidene chloride, polyamides, polyesters, for example polybutylene terephthalate and polyethylene terephthalate, polyethers (for example polyphenylene oxide PPO),

  polythioethers and thioplasts, polycarboxylic

  polyurethanes, cellulose derivatives, maleic resins, melamine resins, phenolic resins, aniline resins, furan resins, carbamide resins, resins

epoxy and silicone resins.

  Other additives may be added to the stabilizing composition or the polymer composition of the invention, for example flame retardants, antistatic agents, ultraviolet stabilizers such as sterically hindered amines used as stabilizers against the effects of light and UV absorbers (eg 2- (2'-hydroxyphenyl) benzotriazoles,

  2-hydroxybenzophenones, 1,3-bis- (2'-hydroxybenzenes)

  zoyl) benzenes, salicylates, cinnamates and

  diamides of oxalic acid), U.V.

  such as substituted benzoates and benzoates, sterically hindered amines (for example nitrogenless or N-alkylated or N-acylated 2,2,6,6-tetramethylpiperidines), softeners, nucleating agents, metal deactivators, biocides, impact modifiers, fillers,

pigments and fungicides.

  Stabilizing compositions of the invention

  may be added to the polymeric material before, during or after polymerization; they can be

  added in the solid or molten state, in the form of

  preferably in the form of a liquid concentrate containing 10 to 80% by weight of the composition and 20% by weight of a solvent, or in the form of a solid composition (master batch) containing from 10 to % by weight (more preferably from 40 to 70%) of the

  composition and from 90 to 20% by weight (more preferably

  from 60 to 30%) of a solid polymeric material

  tick or compatible with the material to be stabilized.

  The compositions of the invention can be incorporated into the polymeric material & stabilize according to

  known methods. A particularly important aspect

  both of the invention is the mixture of the composition of the invention with thermoplastic polymers in the molten state, for example in a mixer for mass

  melt, or during the manufacture of fashionable articles

  born, for example sheets, tubes, fibers or

  foam, obtained by extrusion, injection molding

  blow molding, spinning or coating of

  cables. The compositions of the invention are

  especially useful for polypropylene fibers or sheets. The following examples illustrate the present invention without in any way limiting its scope. In these examples, parts and percentages are by weight and temperatures are given in degrees

Celsius, unless otherwise indicated.

EXAMPLE i

  In 25 ml of acetone are dissolved: 1 g of calcium stearate,

  1 g of tetrakis- [3- (3,5-di-tert.-butyl-4-hydroxy)

  phenyl) propionyloxymethyl] methane,

  0.4 g of biphenyl-4,4'-diphosphonite from tetrakis

(2,4-di-tert-butyl-phenyl),

  0.4 g of tris- (2,4-di-tert.-butyl) phosphite

phenyl), and

  0.2 g of biphenyl-4-phosphonite bis (2,4-di-tert)

  butylphenyl). This solution is added to 1000 g of polypropylene powder and mixed for 5 minutes at 400 rpm. The powder is dried for 30 minutes at 50 in an oven and compressed to 270 in an extruder (Gottom) having a screw diameter of 20 mm.

  (1: 3 compression, diameter to length [d: 1] - 1:20).

  Several extrusions are carried out under the same conditions.

  tions. For each extrusion, the Melt Flow Index (MFI) is determined at 230 / 2.16 kp and

  uses these values to characterize the stabilizing effect

transformation.

EXAMPLES 2 TO 4

  The procedure is as described in Example 1, but

  replacing 0.4 g of tris- (2,4-di-tertiary) phosphite

  butylphenyl) with 0.2 g of tris- (2,4-di-

  tert.-butyl-phenyl) and 0.2 g of one of the following compounds: Example 2: Tris (nonylphenyl) phosphite, Example 3: A 40:60 mixture of tocopherol (vitamin E) and phosphite of tris- (nonylphenyl), and Example 4: a 20:40:40 mixture of α-tocopherol (vitamin E), thio-3,3'dipropionate

  tridecyl and tri-lauryl phosphite.

Claims (15)

  1. A composition comprising a) from 30 to 80% by weight of one or more compounds of the formula tert.-Butyl tert.-Butyl - - 0 P - R1),   in which R1 signifies hydrogen, a methyl group   thyl, unsubstituted phenyl or a radical of formula a) tert. Butyl tert.-butyl O-O wherein n is 0 or 1, and b) 20 to 70% by weight of one or more organic phosphites. 2. A composition according to claim 1, characterized in that component b) is chosen from one or more compounds of formula II or III P (-O-R) 3 (II) 0 CH% CHH O- R.-O-PNo CH '' R.P-O-R (III), 0-CH - "'CH2 ---- o 2 2   wherein R is independently a linear or branched C1-C22 alkyl group or a phenyl group unsubstituted or substituted with 1 to 3 groups   Linear or branched C 1 -C 12 alkyl.   3. A composition according to claim 2, characterized in that component b) is chosen from tris (2,4-di-tert.butylphenyl) phosphite,   phosphite tris (nonylphenyl), the phosphite tris   lauryl, pentaerythrityldiphosphite bis (2,6-di-   tert.-butyl-4-methylphenyl), pentaerythrityldi   bis (2,4-di-tert.-butylphenyl) phosphite, and the   pentaerythrityldiphosphite of distearyl.   4. A composition according to any one   Claims 1 to 3, characterized in that   contains one or more additional antioxidant   selected from sterically hindered phenols   aminoaryl compounds and anti- oxidants containing sulfur.   5. A composition according to claim 4, characterized in that the phenolic antioxidant agent   is 3- (3,5-di-tert-butyl-4-hydroxy-phenyl) -propionic   octadecyl nate, tetraki- [3- (3,5-di-tert.-butyl)   4-hydroxyphenyl) propionyloxy-methyl] -methane, the iso-   1,3,5-tris (3,5-di-tert-butyl-4-hydroxy) cyanurate   phenyl), 1,1,3-tris- (5-tert-butyl-4-hydroxy-2-   methylphenyl) -butane, 1,3,5-trimethyl-2,4,6-tris   (3,5-di-tert-butyl-4-hydroxy-benzyl) benzene or   3,3-bis (4-hydroxy-3-tert.-butylphenyl) butyl diester Ethylene Glycol.   6. A composition according to claim 4,   characterized in that the aminoary antioxidant agent   is N, N'-dinaphthyl-p-phenylenediamine or   N, N'-hexamethylene-bis-3- (3,5-ditert-butyl-4-hydroxy-   phenyl) -propionamide. 7. A composition according to claim 4, characterized in that the sulfur-containing antioxidant is tridecyl thio-3,3'-dipropionate,   lauryl thio-3,3'-dipropionate, thio-3,3'-di-   stearyl propionate, tetrakis (3-hexylthio)   propionyloxymethyl) -methane or diocta disulphide   decyl. 8. A composition according to any one   Claims 1 to 7, characterized in that   contains as an additional additive the-tocopherol (Vitamin E).   9. A composition according to any one   Claims 1 to 8, characterized in that the   amount of component a) present is between 70 and 40% by weight and the amount of component b) present   is between 30 and 60% by weight of the composition   tion. 10. A composition according to any one   Claims 4 to 9, characterized in that   the additional antioxidant or vitamin E is present in an amount of between 50 and 200%   weight of components a) and b) of the composition.   11. Use of a composition according to   any of claims 1 to 10 as an agent   stabilizer for the processing of poly-   mothers. 12. A stabilizing composition for the transformation of polymeric materials, characterized in that it comprises from 30 to 80% by weight of one or more components a) and from 20 to 70% by weight of one or more components b) such that defined in one   any of claims 1 to 3 and optionally   one or more antioxidant agents as defined in   any of claims 4 to 8.   13. A polymer composition, characterized in that it comprises a polymeric material and a sufficient amount of a composition according to one of   any of claims 1 to 10 to obtain the   stability to the transformation of the polymeric material.   14. A polymer composition according to claim 13, characterized in that the amount of components a) and b) is between 0.01 and 1% by weight.   weight relative to the weight of the polymeric material.   15. A process for stabilizing polymeric materials during their transformation, characterized in   what is incorporated in the polymer material a composition   according to any one of claims 1 to 10.