HUT54380A - Stabilizing composition utilizable with workong up polymere products - Google Patents

Description

BACKGROUND OF THE INVENTION The present invention relates to a novel stabilizer composition for use in the processing of polymeric products

a) 50-99.9% by weight of one or more phosphonite compounds of the formula I as component I, and

b) II. as component, 0.1 to 50% by weight of one or more phosphite compounds of formula II

68902-2703-PT-tm, wherein in formulas I and II m is 0 or 1;

π is 0 or 1;

Y is -O-, -S- or -CH (R 1 -) - or 1,4-phenylene, where R 1 is hydrogen, C 1 -C 8 alkyl, or -CO 0 R 6 - ₍ R 6) wherein R 1 is C 1-8 alkyl;

each R-O group is independently an aliphatic, alicyclic or aromatic alcohol group containing from 1 to 3 hydroxy groups, provided that two hydroxyl groups cannot be present in the position to form a phosphorus ring (hereinafter: R-0 monovalent) /;

or two R-O groups taken together are aliphatic, alicyclic or aromatic alcohols containing at least two hydroxy groups, wherein at least two hydroxyl groups are in the appropriate position to form a cyclic group with a single phosphorus atom, as follows: R-O- bivalent (bivalent);

R 1 -O- have the same meaning as R-O; and each R 1 -O- group is independently an aliphatic, alicyclic or aromatic alcohol group containing from 1 to 3 hydroxy groups, provided that two hydroxy groups in the position suitable for the formation of a phosphorus ring may not be monovalent ( monovalent) meanings /;

or two R 4 -O- groups taken together containing at least two hydroxyl groups which are aliphatic, alicyclic or aromatic

an alcohol-derived group wherein at least two hydroxyl groups are in the appropriate position to form a cyclic group with a single phosphorus atom: R 1 -O- is bivalent (i 7);

with the proviso that

1) Compounds of formula I are different from tetrakis / 2,4-di-tert-butylphenyl-7-biphenylene diphosphonite; and preferably

2) at least one R 0 -O group and at least one R 1 -O-group derived from a phenol containing at least one spherically inhibiting group at the 2-position.

When the R-O and / or R ^ -O- groups are bivalent, the alcohols from which they are derived preferably contain two or three hydroxy groups.

R is preferably R 'wherein R' is alkyl, aralkyl, aryl or alkylaryl (hereinafter referred to as R 'monovalent); or R 'is a group of the formula (o <) in which the groups A and B may themselves be substituted; and Y 'is -O-, -S-, or -CHCR () - wherein R ^ is hydrogen, (C 1 -C 8) -alkyl or -C (C 1 -C 8) R 8 (hereinafter: R) 'bivalent reports); and n is 0 or 1.

More preferably, R is R where R is

C 1 -C 22 alkyl; unsubstituted phenyl; or C 1 -C 22 alkyl, C 1 -C 22 alkoxy, benzyl, phenyl, 2,2,6,6-tetramethyl-4-piperidyl, -C C 8 alkyl, phenyl, and carboxyl, -CO 2 - (C 1 -C 22 alkyl), -Ch 2 -Ch 2 -C 4 R 4, cyano, or -O 2 -C- (1). Phenyl mono-, di-, or tri-substituted with -C 22 alkyl; or R (i) to (vii); or two R groups taken together may also represent a group of formula (viii) wherein R5 is hydrogen or C1-C22 alkyl;

Y * n

is oxygen or sulfur or -CH (R 1 -) -;

0 or 1;

is hydrogen, (C 1 -C 8) -alkyl or -CO (C 1 -C 8) -alkyl;

is hydrogen or C 1-22 alkyl;

is hydrogen, (C 1 -C 22) -alkyl, (C 1 -C 22) -alkoxy, benzyl, -C (CH 2) 2 -C 8 H 6, -phenyl, hydroxy, -Cl 1 -Ch 2 -CO 2 ^R 15, ( C1-C8-alkyl) -phenyl, -CO2- (C1-C22-alkyl), cyano, -CH2-S-C1-C2-alkyl or 2,2, 6,6-tetramethyl-4-piperidyl; and hydrogen, (C 1 -C 22) -alkyl, hydroxy or (C 1 -C 22) -alkoxy.

Most preferably, R is R ', wherein R' may be any of the groups (a) to (g) in which

R10 is hydrogen, (C1-C8) alkyl, (C1-C8) alkoxy, phenyl (C1-C4) alkyl, phenyl or (C1-C8) alkyl-phenyl;

R11 and R12 are independently hydrogen,

C 1 -C 22 alkyl, C 1 -C 8 alkylphenyl or phenyl;

R _{13 is} hydrogen or C 1-8 alkyl; and

R 14 is cyano or -CO 2 R 16.

Preferably the group (a) is 2- (tert-butyl) phenyl, 2-phenylphenyl, 2- (1 ', 1'-dimethylpropyl) phenyl, 2-cyclohexylphenyl, 2- (tert-butyl) -4-methylphenyl, 2,4-di (tert-amyl) phenyl, 2,4-di (tert-butyl) phenyl, 2,4-diphenylphenyl -, 2,4-di (tert-octyl) phenyl, 2- (t-butyl) -4-phenyl-phenyl, 2,4-bis (l ', 1 ^{1-dimethyl-propyl)} -phenyl- , 2- (1-phenyl-1-methylethyl) phenyl, 2,4-bis (1-phenyl-1-methylethyl) phenyl or 2,4-di-tert-butyl-6 methyl-phenyl.

R ^ is preferably R ^ ', wherein R ^' has the same meaning as one of R 'but independently of R'. More preferably, R 1 is R 1 a group wherein R 4, independently of R, is one of R 2 's. Most preferably, R ^ is a R ^ 'group wherein R' 'independently of R' has the same meaning as any of R '.

preferably R 1 'is where R 4' is independently monovalent R '; more preferably, R 4 is R 4, wherein R 6 is, independently of R, a monovalent value of R; most preferably, R ^ is R '', wherein R '' independently of R 'is one of the monovalent values of R'.

m is preferably 1.

A preferred stabilizing composition of the invention

(a) a diphosphonite of formula (I) as defined above (hereinafter component (a));

(b) a phosphite of formula II as defined above

Component 11); and

c) a monophosphonite of formula I as defined above (hereinafter component c).

In addition, the stabilizing compositions of the present invention have the general formula (IV)

R _? (0H) (IV) or a compound of formula (V)

Rg (OH) (V) phenol may also be included in component d) below. In formula (IV), R? has the same meaning as any one of R; in the formula (V), Rg is a bivalent value of R.

For the avoidance of doubt, it is to be noted that, unless a contrary statement is made, when a letter symbol is used more than once in one formula or once in two different formulas in the components of a stabilizing composition of the invention, their meanings are independent. However, when a letter symbol appears in both the formulas (I) and (II) and optionally in formulas (IV) and (V) in a stabilizing composition of the invention, this symbol preferably has the same meaning in all formulas.

In the stabilizing compositions of the invention, preferably R 1 is the same as R 1.

The amount of component I in the stabilizing compositions of the present invention is preferably 50-95% (more preferably greater than 70-90%); II. The amount of component A is from 5 to 50 weight percent (more preferably 10-30 parts by weight ^{of 5} »).

A highly preferred stabilizing composition of the present invention comprises the following components (% by weight refers to the weight of the composition):

a) 60-80% by weight of component a) as defined above;

(b) 5 to 20% by weight of II. component;

c) 10-20% by weight of component c) as defined above; and

d) 0-5% by weight of component d) as defined above.

Another highly preferred stabilizing composition of the present invention has the following composition:

a) 20-50% by weight of component a);

b) 20-55% by weight of II. component;

c) 3-20% by weight of component c); and

d) 0-5% by weight of component d).

The compounds of formula (I) may be prepared at elevated temperatures (preferably in the range of 40-140 ° C).

a) 2 moles of formula (X)

Compound (X) wherein R 1b is the same as R 1 and optionally 2 moles of formula (XI)

Compound (XI), wherein R 1 = R 1 is one of the monovalent values, is reacted with 1 mol of compound (XIV), wherein in formula (XIV), Y,

m and n are as defined above; obsession

b) 1 mol of formula XII

R ₃₂ - (O H) ₂ (XII) wherein R 1 is R 2 is as defined above and optionally 2 moles of the above compound (X) is reacted with 1 mole of the above compound XIV ; obsession

c) 1 mole of the compound of formula XII as defined above and 1 mole of the compound ^r 33- ^(oh) 2 (XIII) of the formula XIII wherein X is the same as one of the bivalent values of R above; With a compound of formula XIV.

The invention further relates to new compounds of formula XV wherein n is 0 or 1 (preferably n is 0);

d is 1 or 2;

each ^R 21 is independently hydrogen,

C 1 -C 4 alkyl (preferably tert-butyl or methyl) or -C 1 H 2 -C 6 -C 8 H 2; and each ^R 22 is independently selected from the group ^{consisting of R} 21 and ^R 21;

with the proviso that

i) at least one of R 21 or at least one of R 22 is -CXCH 2 - C 8 H 8; and ii) at least one of R21 is not spherically inhibited.

As used herein, a spherically hindered group is any tertiary alkyl or alkylaryl group; preferably any C 4 -C 22 tertiary alkyl group, which means that the C 4 -C 22 alkyl group has a tertiary carbon atom.

The invention also relates to novel compounds of formula XVI, wherein in formula XVI, d is 1 or 2, preferably 2.

The invention further encompasses stabilizing compositions which

a) 50-95% by weight of a compound of formula XV or XVI as defined above; and

b) 5 to 50% by weight of a phosphite compound of the formula II as defined above.

The invention also relates to polymeric compositions comprising a polymeric material in a stabilizing amount of a stabilizing composition of the invention or a stabilizing amount of a compound of formula (XV) or (XVI), optionally mixed with a phosphite of formula (II).

In such polymeric compositions, the stabilizing composition of the present invention is characterized by the use of the compounds I and II. The component is preferably present in an amount of 0.01 to 2% by weight, more preferably 0.05 to 0.3% by weight (based on the polymeric material).

It has now been found that compounds I and II in the stabilizing composition of the invention are present. The combination of the components has a synergistic effect on the processing and aging stability of the polymeric composition in which it is used. The properties of these polymeric compositions, such as their yellowing (as measured by the yellowness index) and melt flow index (hereinafter sometimes referred to as MFI), are significantly better than those of the polymeric formulations which are only obtained in Table I or II. component.

For example, homopolymers, copolymers, and blends of polymers such as the following may be stabilized with the stabilizing composition of the present invention:

cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cresol formaldehyde resin, carboxymethyl cellulose, »·

cellulose nitrate, cellulose propionate, casein plastics, casein formaldehyde resin, cellulose triacetate, ethyl cellulose, epoxy resins, methyl cellulose, melamine formaldehyde resins, polyamide, poly (amide), polyacrylonitrile , poly (1-butene), poly (butyl acrylate), poly (butylene terephthalate), polycarbonate, polychlorotrifluoroethylene, poly (diallyl phthalate), polyethylene, chlorinated polyethylene, poly ether ether ketone ), polyetheretherimide, polyethylene oxide, polyethersulfone, polyethylene terephthalate, polytetrafluoroethylene, phenol formaldehyde resins, polyimide, polyisobutylene, polyisocyanurate, poly (methacrylamide), poly (methyl methacrylate), poly (4-methyl-1-pentene), poly (c-methylstyrene), poly (oxymethylene), polyacetal, polypropylene, poly (phenylene) ether), poly (phenylene sulfide), poly (phenylene sulfone), polystyrene, polysulfone, polyurethane, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, chlorinated polyvinyl chloride ), polyvinylidene chloride, polyvinyl denofluoride), polyvinyl fluoride, polyvinylformaldehyde, polyvinylcarbazole, polyvinylpyrrolidone, silicone polymers, saturated polyesters, urea formaldehyde resins, unsaturated polyester, polyacrylate , polymethacrylate, polyacrylamide, maleate resins, phenolic resins, aniling resins, furan resins and urea resins.

For example, the stabilizing composition of the present invention may be used to stabilize copolymers of the following monomeric components: acrylonitrile / butadiene / acrylate; acrylonitrile / butadiene / styrene; acrylonitrile / methyl methacrylate; acrylonitrile / styrene / acrylic ester; acrylonitrile / ethylene-propylene-diene / styrene; acrylonitrile / chlorinated polyethylene / styrene; ethylene / ethyl acrylate; ethylene / methacrylic acid; an ethylene / propylene; ethylene / propylene diene; ethylene / vinyl acetate; ethylene / vinyl alcohol; ethylene / tetrafluoroethylene; tetrafluoroethylene / hexafluoropropylene; methacrylate / butadiene / styrene; melamine / phenol-formaldehyde; polyester blockamide; perfluoroalkoxy-alkane; styrene / acrylonitrile; styrene / butadiene; styrene / maleic anhydride;

styrene / c-methylstyrene: vinyl chloride / ethylene; vinyl chloride / ethylene / methacrylate; vinyl chloride / ethylene / vinyl acetate; vinyl chloride / methyl methacrylate; vinyl chloride / octyl acrylate; vinyl chloride / vinyl acetate; and vinyl chloride / vinylidene chloride.

Advantageously, the stabilizing composition of the present invention can stabilize polyolefins such as polypropylene, polyethylene (e.g., high density polyethylene, low density polyethylene, low density or medium density linear polyethylene), polyisobutylene, poly (4-methylene) and poly (4-methylpentene).

Additional additives may be added to the stabilizing composition or polymer composition of the present invention. Examples include antioxidants such as spherically inhibited phenols, secondary aromatic amines, or thioethers, as described in Gáchter and Müller, Plastics Additives 1985, 8-12. side.

Additionally, UV-stabilizing agents such as N-unsubstituted, N-alkyl- or N-acyl-substituted 2,2,6,6-tetramethylpiperidine derivatives, which are inhibited by amine-like light, may also be used as additives. also known as opacifying agents); and UV-absorbers such as 2- (2'-hydroxyphenyl) benzothiazoles, 2-hydroxybenzophenone derivatives, 1,3-bis (2'-hydroxybenzoyl) benzene salicylates, cinnamates and oxalic diamide derivatives; UV light extinguishing agents such as benzoates and substituted benzoates; and antistatic agents, refractory agents, plasticizers, metal deactivators, biocidal agents, impact modifiers, fillers, pigments and fungicides.

The stabilizing compositions of the present invention are characterized in that the polymer ·· · «

- it can be added to the material 12 before, during or after the polymerization step in solid or molten form; the addition is preferably in solution, for example in the form of a concentrated solution consisting of 10-80% by weight of the composition and 90-20% by weight of the solvent or 10-80% (more preferably 40-70%) of the composition and 90-20% (even more preferably 30%). -60% by weight) in the form of a solid premix consisting of a solid polymeric material. In the latter case, a solid polymeric material is used which is identical to or compatible with the material to be stabilized.

The compositions of the invention may be incorporated into the polymeric material to be stabilized in a known manner. In a particularly important method in this regard, the compounds are blended with the thermoplastic polymers in a melt state such as a melt-mixer; or combined during extrusion forming of molded articles such as foils, tubes, fibers or foams, and injection molding, blow molding, spinning or cable wrapping. The compositions of the invention are particularly useful for stabilizing polyolefins.

It should be noted that in this specification, the figures indicating the boundaries of a domain also belong to the domain. Any group which may be linear or branched in principle may be straight or branched unless otherwise noted.

For the avoidance of doubt, tert-butyl in this specification is -C (CH2) - j.

The invention is further illustrated by the following non-limiting examples. In the examples, unless otherwise noted, parts are parts by weight, percentages are by weight; temperature values are given in degrees Celsius.

·· ♦ · • ο • ο

- 13 · ♦ · • · · · · · ·

Example 1

The reactions described in this example are carried out in an airtight space under dry nitrogen gas, protected from moisture.

16.9 g of biphenyl with 38.5 g of aluminum trichloride and 58 g of phosphorus trichloride are heated under reflux at 72-74 ° C for 6 hours. During this time, 5.6 g of hydrogen chloride gas (73% of theory) is removed from the reaction mixture.

After the heating is complete, excess phosphorus trichloride is distilled off in vacuo at 55-60 ° C until the vapor pressure of the reaction mixture is reduced from 100 kPa to 8 kPa. At this time, the clear red reaction mixture was added dropwise at 80 ° C over a period of 1 hour to a solution of 145 g of 2,4-bis (1-phenyl-1-methylethyl) phenol in 230 g of toluene and 69 g of pyridine. The resulting mixture was heated at 80 [deg.] C. for 4 hours with stirring, and the resulting 156 g complex was isolated and further filtered through low temperature filtration (-10 [deg.] C.) to isolate another 5 g of pyridine and aluminum trichloride. The solvent was removed by distillation; This leaves 155 g of a yellow, transparent product which, at room temperature, is converted to a glassy solid.

The product thus obtained contains the following compounds of formula (Ia) to (ld), depending on the size of the apparatus (1 liter flask in the above case) and the speed of stirring (300 rpm in the above case):

0-5 mol%

R-OH (Ia) phenol of formula (Ia);

10-25 mol%

P (OR) ₃ (1b) (1b) phosphite;

·· ··

14 10-25 mol% of monophosphite of formula Le; and

55-75 mol% of diphosphonite of formula (ld) wherein all R in the above formulas (la) to (ld) are of formula (f). The product thus obtained melts at 83-88 ° C and has a drop point of 93 ° C.

If desired, the above compounds may be isolated by known methods (for example, recrystallization from an inert solvent such as dioxane or hexane).

2-22nd examples

Similar products to the compounds of formula (Ia), (lb), (le) and (ld) obtained in Example 1 can be prepared by reacting the appropriate reagents in the same manner as in Example 1. The R-values of the products thus obtained are given in Table 1 below.

Table 1

example serial number R Second 2- (tert-octyl) -4-methyl-phenyl Third 2,4-di (tert-butyl) -6-methylphenyl 4th 2- (tert-butyl) phenyl 5th 2-phenylphenyl 6th 2- (l-dimethylamino-propyl) phenyl 7th 2-cyclohexyl-phenyl 8th 2- (tert-butyl) -4-phenyl-phenyl 9th 2- (tert-butyl) -4-methyl-phenyl 10th 2,4-di (t-amyl) phenyl 11th 2,4-di (tert-butyl) -6-ethylphenyl 12th Diphenyl-2,4-phenyl 13th 2,4-di (tert-octyl) phenyl 14th 2- (l-phenyl-l-methylethyl) phenyl 15th 2,4-bis (l, l-dimethylpropyl) phenyl

»* ♦ ·· ♦ • ·

16th

a group of formula (h)

17th

a group of formula (i)

18th

a group of formula (j)

19th

a group of formula (k)

20th

A group of formula (1)

21st

a group of formula (m)

22nd

a group of formula (n)

23-26th examples

0-5 mol%

Phenol of formula R ₁ - (H) ₂ (23a) (23a),

5-20 mol% phosphite of formula 23b

10-20 moles of ⁹ »monophosphonite of formula (23c) and

60-80 mol% of diphosphonite 23d

- wherein R is as given in Table 2 below - can be prepared from the appropriate starting materials as in Example 1; if desired, the above compounds may be isolated by conventional means (e.g., by recrystallization).

Table 2 i serial number R 23rd a group of the formula (o) 24th a group of formula (p) 25th a group of formula (q) 26th a group of formula (r)

Example 27

The reactions described in this example are carried out in an atmosphere free of air and moisture under dry nitrogen.

* · <· · *

a) 11.1 g of biphenyl are heated under reflux for 6 hours at 72-74 ° C with vigorous stirring of 25.4 g of aluminum trichloride and 37.7 g of phosphorus trichloride. During this time, 4.1 g of hydrogen chloride gas (82% of the theoretical amount) were removed from the reaction mixture.

After heating, excess phosphorus trichloride

The mixture is distilled under vacuum at 55-60 ° C until the vapor pressure of the reaction mixture is reduced from 100 kPa to 8 kPa.

b)

5.5 g of phosphorus were obtained at room temperature

trichloride is added.

c) The red reaction mixture was added dropwise to a solution of 3-methyl-6-tert-butylphenol (66.8 g), chlorobenzene (160 g) and pyridine (54.4 g) at 80 ° C for one hour. The resulting mixture was heated at 80 ° C for 4 hours with stirring. After isolation of the complex thus formed, an additional 2 g of pyridine aluminum trichloride complex was isolated by filtration at low temperature (-10 ° C). The solvent was distilled off to give 81 g of a yellow transparent product, which was converted to a glassy solid at room temperature, m.p. 51-60 ° C with a drop point of 71 ° C.

The product thus obtained is of the following general formula (Ia) to (ld) depending on the size of the apparatus (in this case a 1 liter flask) and the speed of stirring (300 rpm depending on

0-5 mol%

R-OH (27a) Phenol (27a);

35-45 mol%

P (OR) ₃ (27b) • γ:. * · .. ··. . ·· .. · • · · '*. ♦ * * ·; : · '· »·« -T ·. Phosphite of formula 27b;

10-20 mol% of monophosphonite 27c; and

30 to 40 mol% of the formula (27d) contains diphosphonite, wherein in the above formulas (27a) to (27d) all R (s) groups.

If desired, the above compounds may be isolated by known methods (for example, recrystallization from an inert solvent such as dioxane or hexane). The above ratio of compounds of formulas 27a to 27d may vary depending on the amount of phosphorus trichloride used.

28th-37th examples

Similar products to the compounds of formulas 27a, 27b, 27c and 27d obtained in Example 27 can be prepared.

that the appropriate reagents a In Example 27 described procedure like reacted. Yeah got R products below Table 3 below a. Table 3 The example Product behavior during bulk Weight% A (27a) - (27d) number Lp. Op. Cp. R groups ° C ° C C supplying phenol R 0H 28th 51 69 72.7 6.82 2- (tert-butyl) phenol 29th 51 66 70.8 7.0 6- (tert-butyl) -3-methyl- -phenol 30th 60 90 94.3 6.93 6- (tert-butyl) -2,4-di- methylphenol 31st resinous 67.0 5.95 2,6-di (sec-butyl) phenol 32nd resinous 66.7 5.22 2- (sec-butyl) -4- (tere- butyl) phenol 33rd 46 55 72.8 4.85 2,4-di (t-amyl) phenol 34th resinous 30.0 7.1 2- (sec-butyl) phenol

♦ · 4> · «·» · 9 • · · · · · · · · · ····································································· »

35th resinous 30.3 7.49 2-isopropyl-phenol 36th resinous 34.9 3.29 2,4-dinonyl phenol 37th 45 60 66 5.83 2- (tert-butyl) -4-methylphenol

Abbreviations: Lp: softening point; M.p., Cp. : drop point

Application example

Polypropylene formulations are prepared from the following components

Components A B parts c in D Polypropylene · * · 100 100 100 100 Calcium stearate 0.1 0.1 0.1 2 Irganox 1010 0.1 0.1 0.1 Example 1 Product - - 0.1 - Sandostab P-EPCp - - 0.1

1: Hostalen PPK 0160P was used as polypropylene.

. Tetrakis / ^- 3, 5-di (tert-butyl) -4-hydroxyphenyl _ / - pentaerythritol.

3. Sandostab P-EPQ is a processing stabilizer available from SANDOZ AG (Basel, Switzerland).

Polypropylene was extruded on a 20 mm Göttfert screw extruder (1: 3 compression ratio, 1:20 diameter to length ratio) at 270 ° C. Repeat extrusion is performed under the same conditions. After each extrusion, the melt flow index (MFI) at 230 ° C / 2.16 kp and the yellowing index (YI) were measured.

The flow index and yellowing index of samples A, B, C, and D are shown in Table 4 below.

·· *; * · ·· ·· ··, * ♦. * · · · · · - - · ·. * * · Ί! ··.

........ * .. ·

Table 4

The sample was MFI (g polypropylene / 10 min) Yellowing index

After flow After flow

1 3 5 1 3 ' THE 2.8 4.7 6.9 3.8 7.2 9.8 B 1.8 2.7 4.1 3.5 9.3 12.4 C 0.9 1.1 1.4 4.6 8.0 10.2 D 1.0 1.5 2.0 2.6 10.7 17.0

From the above results, sample C containing the phosphorus stabilizer compositions of the present invention is a polypropylene which exhibits excellent resistance to heat and degradation during polymer processing.

The procedure described in the Application Examples was repeated by using in Example C one of the products obtained in Examples 2 to 37 instead of the product of Example 1.

Polypropylene is thus obtained which has excellent resistance to heat and decomposition.

Claims (19)

Claims CLAIMS 1. A stabilizing composition for use in the processing of polymeric products, characterized in that: a) component I is 50 to 99.9 mass ⁹ »of one or more (I), preference is given formula and b) II. as component, 0.1 to 50% by weight of one or more phosphite compounds of formula II wherein m in formulas I and II are 0 or 1; n is 0 or 1; Y is -O-, -S-, -CH (R ^) - or a 1,4-phenylene group, wherein R 1 is hydrogen, C 1 -C 8 alkyl, or -CC 1 -R 8, wherein R 1 is 1; -C8 alkyl; each R-Q group is independently an aliphatic, alicyclic or aromatic alcohol group containing from 1 to 3 hydroxy groups, with the proviso that two hydroxy groups cannot be present in the position to form a phosphorus ring; or two R-O groups taken together are aliphatic, alicyclic or aromatic alcohols containing at least two hydroxy groups, wherein at least two hydroxyl groups are in the appropriate position to form a ring group with a single phosphorus atom (hereinafter: R-bivalent); R 1 -O- have the same meaning as R 1 -O-; and each R 4 -O- group is independently an aliphatic, alicyclic or aromatic alcohol containing from 1 to 3 hydroxy groups, with the proviso that two hydroxy groups in the position suitable for the formation of a phosphorus ring are as follows: (monovalent) meanings /; or two R 4 -O- groups taken together are aliphatic, alicyclic or aromatic alcohols containing at least two hydroxy groups, wherein at least two hydroxyl groups are in the appropriate position to form a cyclic group with a single phosphorus atom. ^ /; with the proviso that 1) The compounds of formula I are different from tetrakis / 2,4-di-tert-butylphenylZ-biphenylene diphosphonite. Composition according to claim 1, characterized in that at least one R and at least one R 1 group are derived from phenol having at least one spherically hindered group in position 2. A composition according to claim 1 or 2, wherein R is R ', wherein R' is alkyl, aralkyl, aryl or alkylaryl (hereinafter referred to as R 'monovalent); or R 'is a group of the formula (<X) in which the A and B groups may themselves be substituted; Y 'is -O- or -S- or -Cl-KR ^) - wherein R 1 is hydrogen, C 1 -C 8 alkyl, or -CO 1 -R 8 where R 1 is C 1 -C 8 alkyl (a). hereinafter referred to as R bivalent values); and n is 0 or 1. Composition according to Claim 3, characterized in that R represents an R group, wherein R represents C 1 -C 22 alkyl; unsubstituted phenyl; or C 1 -C 22 alkyl, C 1 -C 22 alkoxy, benzyl, phenyl, 2,2,6,6-tetramethyl-4-piperidyl, -C (CH-CH, hydroxy) -unsubstituted (C 1 -C 8) alkyl) phenyl, and carboxyl, -CO 2 - (C 1 -C 22 alkyl), -C 1 -C 4 -C 1 -C 4 R 4, cyano, or -CH 2 -S- (1-22). phenyl, mono-, di- or trisubstituted with C 1 -C 4 alkyl; or R (i) to (vii), or two R groups taken together may represent a group of formula (viii) wherein R ??? represents 5 hydrogen or C 1 -C 22 alkyl groups; Y 'is -O- or -S- or -CH (R 1) - -; n is 0 or 1; is hydrogen, (C 1 -C 8) -alkyl or -CO (C 1 -C 8) -alkyl; is hydrogen or C 1-22 alkyl; is hydrogen, (C 1 -C 22) -alkyl, (C 1 -C 22) -alkoxy, benzyl, -C 1 H 2 -C 3 -C 8 H 4, -phenyl, hydroxy, -Ch 2 C 1 -C 22 alkyl, phenyl, -CO 2 -C 22 -alkyl), cyano, -Ch 2 -C 4 -C 1 -C 4 R 4, -CH 2 -S- (C 1 -C 22 alkyl) -, or 2,2,6,6-tetramethyl-4-piperidyl; and ^R 24 is hydrogen, C 1 -C 22 alkyl, hydroxy, or C 1 -C 22 alkoxy. The composition of claim 4, wherein R is a group R ¹ , wherein R 'can be any of the groups of general formula (a) to (g) in which R g is hydrogen, (C 1 -C 8) alkyl, (C 1 -C 8) alkoxy, phenyl (C 1 -C 4) alkyl, phenyl or (C 1 -C 8) alkyl-phenyl; R 1 and R 2 are independently hydrogen, C 1 -C 22 alkyl, C 1 -C 8 alkylphenyl or phenyl; R1 is hydrogen or (C1-C8) -alkyl; and R &lt; 3 &gt; is cyano or -C1R &lt; 1 &gt; 6. A composition according to any one of claims 1 to 5, wherein R 1 is R 1 group where R | R ', independently of R', has the meaning given in claim 3. The composition of claim 6, wherein R 1 is R 6, wherein R 6 is, independently of R, as defined in claim 3. A composition according to claim 7, wherein R 1 is R 6 ', wherein R 6' is independently of one of R 1 as defined in claim 4. 9. A composition according to any one of claims 1 to 3, wherein n is 1. 10. The stabilizing composition of claim 1, wherein: (a) one of the tables 1 to 9; diphosphonite of the formula I as defined in any one of claims 1 to 5 (hereinafter referred to as component a); b) a phosphite of the formula II as defined in claim 1 (hereinafter referred to as "component II"); and c. A monophosphonite of the formula (I) as defined in any one of claims 1 to 6, hereinafter referred to as component (c). 11. A stabilizing composition according to claim 10, characterized in that, as a further component d), r ₇ - (oh) (arc) of formula (IV) or r ₈ - (oh) ₂ (V) of formula (V) it also contains phenol, wherein in formula (IV), R 1 is equal to one of the monovalent values of R 1 as defined in claim 1, and in formula (V), R 8 is as defined in any one of R 2; 12. Composition according to any one of claims 1 to 3, characterized in that component I is present in an amount of 50-95%. 13. A composition according to any one of claims 1 to 3, characterized in that containing from 5% to 50%. A stabilizing composition according to claim 11, characterized in that a) 60-80% of component I as defined in claim 1, b) 5% to 20% of II. component, c) 10-20% of component c) as defined in claim 10; and d) 0-5% of component d) as defined in claim 11. 15. A compound of formula XV wherein n is 0 or 1; d is 1 or 2; each R _{2 '} is independently hydrogen, C 1 -C 4 alkyl, or -C 1 H ₂ -C ₂ -C ₈ H ₂ -; and each R ₂₂ is independently selected from the group consisting of R ₂₁ and independently of one another; with the proviso that i) at least one of R 4 or at least one of R ₂₂ is -C (CH ₂ ) ₂ -C ₈ H ₃ ; and ii) at least one of R 1 is non-spherically inhibited. 16. A compound of formula XVI wherein d is 1 or 2. 17. A polymer composition, wherein a polymeric material according to any one of claims 1-14. A stabilizing composition according to any one of claims 1 to 6, or a It comprises a stabilizing amount of a compound of formula (XV) as defined in claim 15 or a stabilizing amount of a compound of formula (XVI) as defined in claim 16. 18. A stabilizing composition, characterized in that a) 50-95¾ of a compound of formula (XV) as defined in claim 15 or of formula (XVI) as defined in claim 16; and b) 5-50 ¾ of a phosphite compound of the formula II as defined in claim 1. • u 19. A polymer composition comprising Components a) and b) are present in an amount of 0.01 to 2%.