CH552407A - Bicyclic phosphorus cpds - used as stabilisers for organic materials - Google Patents

Abstract

Cpds. of formula (I) (where X is a 1-19C alkane residue in which is not >3 bonds exist between one C-atom and the carboxyl- and the phenol-gps. or it may be the residue of an aralkane, alkene, oxaalkane or thiaalkane (with not >3 bonds from the same C-atom to the carboxyl- and phenol-gps) or it may be a direct bond; R1 and R2 are independently 1-8c alkyl, 6-8C cycloalkyl or 7-9C aralkyl, R3 is H or CH3, Y is O or S; p and q are, independently, 1 or 2, n is 0 or 1). A prefd. cpd. is 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-(2,2,2)-octane-3,(3- ,5-ditertbutyl-4-hydroxyphenyl)-propionate. Claimed cpds. are more efficient than known synergistic mixts. of phenolic and P-cpds. as stabilisers for org. cpds.

Description

  

  
 



   It is known that derivatives of sterically hindered phenols can be used as stabilizers for plastics against thermo-oxidative or light-induced degradation. It is also known. Use phosphorus compounds as co-stabilizers together with phenolic antioxidants for stabilization. such mixtures often showing a synergistic effect. It is also known to use bicyclic phosphites as phosphorus compounds in such mixtures in which the phosphorus represents the bridgehead atom.



   Surprisingly, it has now been found that the new compounds of the general formula I
EMI1.1
 wherein
X is the (p + q) -valent radical of an alkane with 1-19 carbon atoms. in which no more than three bonds to the carbonyloxyl and phenol groups proceed from the same carbon atoms, an aralkane, alkene, oxaalkane or thiaalkane each with 2-19 carbon atoms. where from the same carbon atom no more than three bonds to the carbonyloxy and phenyl groups emanate, or the direct bond.



   R1 and R2 independently of one another are hydrogen, alkyl with 1-8 carbon atoms, cycloalkyl with 6-8 carbon atoms or aralkyl with 7-9 carbon atoms, preferred for R1 is alkyl, cycloalkyl or aralkyl with the abovementioned numbers of carbon atoms,
R3 is hydrogen or methyl. preferably hydrogen,
Y is oxygen or sulfur, p and q are independently 1 or 2 and n is 0 or 1.



  Represent stabilizers whose action is significantly better than the action of the above-mentioned synergistic mixtures of phenolic antioxidants with phosphorus-containing compounds. The compounds mentioned in the patent claim of patent no. 542 652 are excluded. Preferred compounds of the formula I are in which
X is the (p + cl) -valent radical of an alkane with 1-9, preferably 1-6, particularly preferably 1-3 carbon atoms.



  an alkene with 2-9, preferably 2-5 carbon atoms, particularly preferably -CH = CH-, an oxaalkane or a thiaalkane each with 2-9, preferably 2-5 carbon atoms, particularly preferably -CH2-S-CH2-, in which Residues from the same carbon atom do not have more than two bonds to the carbonyloxyl and phenyl groups, or the direct bond,
R1 alkyl with 1-5, preferably 1-4 carbon atoms, or cycloalkyl with 6-8 carbon atoms,
R2 is hydrogen, alkyl with 1-5 carbon atoms or cycloalkyl with 6-8 carbon atoms, preferably R2 is alkyl with 14 carbon atoms.



   R3 is hydrogen, p and q are independently 1 or 2 and n is 0 or 1.



   Particularly preferred are compounds of the formula I in which
X is the direct bond or one of the radicals
EMI1.2
 R1 methyl. iso-propyl or tert-butyl,
R2 hydrogen, methyl, iso-propyl or tert.-butyl,
R3 is hydrogen, p and q independently of one another are 1 or 2 and nO.



   If X in formula I is the radical of a (p + q) -valent alkane, it can be -CH2-.



     -CH, -CH2, -CH2-CH2-CH2-,
EMI1.3
 act.



   If X in formula I is the radical of a (pt) -valent alkene, it can be -CH =CH- or -CH2-1-CH2-CHCH2.



   If X in formula I is the radical of a (p + q) -valent aralkane, it can
EMI1.4
 be.
If X in formula I is the radical of a (p + q) -valent oxa- or thiaalkane, it can be
EMI1.5
 act.



   If R1 and / or R2 are alkyl, they can be methyl, ethyl, iso-propyl, tert-butyl, sec-butyl, t-pentyl or t-octyl. If R1 and / or R2 are cycloalkyl, they can be cyclohexyl, α-methylcyclohexyl or cyclooctyl. If R1 and / or R2 are aralkyl, they can mean benzyl, α-methylbenzyl or α, α-dimethylbenzyl.



   The compounds of the formula I can be prepared in various ways: For example, by reacting 1 mol of a compound of the general formula II
EMI2.1
 wherein R4 is a lower alkyl group, in particular the methyl or ethyl group, with q moles of a compound of the formula III
EMI2.2
 in the presence of catalytic amounts of a basic catalyst. During this reaction, q moles of R4OH are split off.



   The preparation of the compounds of the formula III is described in J. Amer. Chem. Soc., 84, 610 (1962).



   The preparation of the compound of the formula I is also possible by first adding 1 mol of a trialkyl phosphite, such as trimethyl or triethyl phosphite, or a triaryl phosphite, such as triphenyl phosphite, or a corresponding phosphate or thiophosphate of the formula IV
EMI2.3
 wherein
R is alkyl, such as methyl or ethyl, or aryl, such as phenyl, and
Y and n have the meaning given under formula I, are reacted with 1 mole of pentaerythritol in the presence of a basic catalyst to form the compound of formula III and this is then reacted in situ with 1/2 or 1 mole of a compound of formula II in the presence of the same or another basic one Transesterified catalyst.



   The compounds of the formula I can also be prepared in good yields in such a way that 1 mol of a compound of the formula IV and pentaerythritol and 1 or 1/2 mol of the compound of the formula II are initially taken together.



  In the presence of a basic catalyst, the reaction leads directly to the compounds of the formula I.



   Another possibility for the preparation of compounds of the formula I is the reaction of 1 mole of a compound of the general formula II with 1 or 2 moles of pentaerythritol in the presence of a basic catalyst, a compound of the formula V being formed:
EMI2.4
 in which R1, R2, R3, X, p and q have the meaning given under formula I.



   The compound of the formula V is reacted directly with q moles of a compound of the formula IV in the presence of the same or another basic catalyst to give the compounds of the formula I, without intermediate work-up.



   The basic catalysts used are, for example, alkali amides such as sodium or lithium amide, alkali hydroxides such as lithium, sodium or potassium hydroxide, alcoholates such as sodium and magnesium alcoholates of methanol, ethanol or tert-butanol or tertiary amines such as triethylamine. Preferred basic catalysts are sodium methylate, sodium hydride and lithium amide.



   Aliphatic or aromatic hydrocarbons such as special boiling point spirit, benzene, toluene or xylene can be used as solvents. However, preference is given to working without a solvent.



   Compounds of the formula I where n = 1 can be prepared by subsequent reaction of the compounds of the formula I where n = O with oxidizing agents such as hydrogen peroxide, cumene hydroperoxide, sulfur, disulfides or mercaptans. However, they can also be prepared by reacting a compound of the formula III, in which n = 1, with a compound of the formula II or VI.



   Compounds of the formula I can also be prepared by reacting a compound of the general formula VI
EMI2.5
 with 1 or 2 moles of a compound of formula III in the presence of a base to neutralize the hydrochloric acid formed.

 

   The compounds of the formula I are used as stabilizers for organic substrates. For example, the following are possible:
1. Polymers derived from mono- or doubly unsaturated hydrocarbons, such as polyolefins such. B.



  Polyethylene, which may optionally be crosslinked, polypropylene, polyisobutylene, polymethylbutene-1, polymethylpentene-1, polybutene-1, polyisoprene, polybutadiene, polystyrene, polyisobutylene, copolymers of the monomers on which the homopolymers mentioned are based, such as ethylene-propylene copolymers-1-propylene-butylene Copolymers, propylene-isobutylene copolymers, styrene-butadiene copolymers, and terpolymers of ethylene and propylene with a diene, such as. B. hexadiene, dicyclopentadiene or ethylidene norbomene; Mixtures of the above homopolymers, such as mixtures of polypropylene and polyethylene, polypropylene and polybutene-1, polypropylene and polyisobutylene, for example.



   2. Halogen-containing vinyl polymers such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene and chlorinated rubbers.



   3. Polymers derived from α, ß-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitrile, and their copolymers with other vinyl compounds, such as acrylonitrile / butadiene / styrene, acrylonitrile / styrene and acrylonitrile / styrene / Acrylic ester copolymers.



   4. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine and their copolymers with other vinyl compounds such as ethylene / vinyl acetate Copolymers.



   5. Homopolymers and copolymers derived from epoxides, such as polyethylene oxide or the polymers derived from bisglycidyl ethers.



   6. Polyacetals, such as polyoxymethylene and polyoxyethylene, and those polyoxymethylenes which contain ethylene oxide as a comonomer.



   7. Polyphenylene oxides.



   8. Polyurethanes and polyureas.



   9. Polycarbonates.



   10. Polysulfones.



   11. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams, such as polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 11, polyamide 12.



   12. Polyesters derived from dicarboxylic acids and dialcohols and / or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene glycol terephthalate, poly-1,4-dimethylol-cyclohexane terephthalate, and their starting materials, such as lower alkyl terephthalate.



   13. Crosslinked polymers which are derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins.



   14. Alkyl resins, such as glycerol-phthalic acid resins and their mixtures with melamine-formaldehyde resins.



   15. Unsaturated polyester resins, which are derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols, and vinyl compounds as crosslinking agents, as well as their halogen-containing, flame-retardant modifications.



   16. Natural polymers such as cellulose, rubber, proteins and their polymer homologous chemically modified derivatives such as cellulose acetates, cellulose propionates and cellulose butyrates or the cellulose ethers such as methyl cellulose.



   The compounds of the formula I are incorporated into the substrates in a concentration of 0.005 to 5% by weight, calculated on the material to be stabilized.



   Preferably 0.05 to 2.0, particularly preferably 0.1 to 1.0% by weight of the compounds, calculated on the material to be stabilized, are incorporated into it. The incorporation can take place before, during or after the polymerization, for example by mixing in at least one of the compounds of the formula I and, if appropriate, further additives by the methods customary in the art, before or during the shaping, or by applying the dissolved or dispersed compounds the polymer, optionally with subsequent evaporation of the solvent.



   In the case of crosslinked polyethylene, the compounds are added before crosslinking.



   Further additives with which the stabilizers can be used together include:
1. Antioxidants of the amino and hydroxyaryl series. In the latter case, the sterically hindered phenolic compounds should be mentioned, e.g. B: 2,2'-thiobis- (4-methyl-6-tert-butylphenol), 4,4'-thiobis- (3-methyl-6-tert-butylphenol), 2,2'-methylene-bis (4-methyl-6 tert.

   -tert.-butylphenol), 2,2'-methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4'-methylene-bis- (2-methyl-6-tert.-butylphenol) , 4,4'-butylidene-bis- (3-methyl-6-tert-butylphenol), 2,2'-methylene-bis [4-methyl-6- (a-methylcyclohexyl) phenol], 2 , 6-Di (2-hydroxy-3-tert-butyl-5-methylbenzyl) -4-methyl-phenol, 2,6-di-tert-butyl-4-methylphenol, 1,1,3 -Tris -2-methyl- (4-hydroxy-5-tert.

   -butyl-phenyl) -butane, 1,3, 5-trimethyl-2,4,6 -tri- (3, 5 -di-tert-butyl-4-hydroxy-benzyl) -benzene, ester of, ss- 4-Hydroxy-3, 5-di-tert-butylphenyl-propionic acid with mono- or polyhydric alcohols, such as methanol, ethanol, octadecanol, hexanediol, nonanediol, trimethyl hexanediol, thiodiethylene glycol, trimethylolethane or
Pentaerythritol, 2,4-bis-octylmercapto -6 - (4-hydroxy-3, 5 -di-tert-butylanilino) -3-triazine, 2,4-bis- (4-hydroxy-3 -di tert-butylphenoxy) -6-octylmer capto-s-triazine, 1,1 -Bis- (4-hydroxy-2-methyl-5-tert-butyl-phenyl) -3-dodecyl-mercapto-butane, 4 -Hydroxy-3,5-di-tert-butylbenzyl-phosphonic acid ester, such as the dimethyl, diethyl or dioctadecyl ester, (3-methyl-4-hydroxy-5-tert.

   -butylbenzyl) malonic acid di octadecyl ester, S- (3,5-dimethyl-4-hydroxyphenyl) -thioglycolic acid octadecyl ester, esters of bis (3,5 -dütert.-butyl4-hydroxybenzyl) malonic acid, such as the didodecyl ester, the dioctadecyl ester, the 2-dodecyl mercaptoethyl ester and the p-tert-octylphenyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate.



   The aminoaryl derivatives include aniline and naphthylamine derivatives and their heterocyclic derivatives, for example: phenyl-1-naphthylamine, phenyl-2-naphthylamine, N, N'-diphenyl-p-phenylenediamine, N, N'-di-2-naphthyl -p-phenylenediamine, N, N'-D i-sec.-butyl-p-phenylenediamine, 6 -ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 6 -dodecyl-2,2,4- trimethyl-1,2-dihydroquinoline, mono- and dioctyliminodibenzyl, polymerized 2,2,4-trimethyl-1,2-dihydroquinoline, although when the compounds of formula I are used in combination with the amine compounds mentioned above, the stabilized polymer is due to the discoloration tendency of the latter no longer has such good color properties.

 

   2. UV absorbers and light stabilizers, such as: a) 2- ('-Hydroxyphenyl) -benztriazoles, for example the
5'-methyl-, 3 ', 5'-di-tert-butyl-, 5'-tert-butyl-, 5th
Chloro-3'-, 5'-tert-butyl-, 5-chloro-3'-tert-butyl-5 'methyl-, 3'-sec-butyl-5'-tert-butyl-, 3 '- methylbenzyl] -5'-methyl-, 3'-h-methylbenzyl] -5'-methyl-5-chloro-. 4'-octoxy, 3 ', 5'-di-tert-amyl-, 3'-methyl-5' carbomethoxyethyl-, 5-chloro-3 ', 5' -di-tert-amyl derivative, b) 2.4- Bis (2'-hydroxyphenyl) -6-alkyl-s-triazines, e.g. B. the 6-ethyl or 6-undecyl derivative, c) 2-hydroxy-benzophenone, z. B. that
4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy,
4-dodecyloxy-1, 4,2 ', 4'-tri-hydroxy or 2'-hydroxy
4,4'-dimethoxy derivative, d) 1,3-bis (2'-hydroxy-benzoyl) -benzenes, e.g.

  B. 1,2 bis (2'-hydroxy-4 '-hexyloxy-benzoyl) -benzene, 1,3 bis- (2'-hydroxy-4' -octoxy-benzoyl) -benzene, 1,3
Bis- (2'-hydroxy-4'-dodecyloxy-benzoyl) -benzene.



  e) aryl esters of optionally substituted benzoic acids, such as. B.



   Phenyl salicylate, octylphenyl salicylate, di-benzoylresorcinol, bis- (tert -butylbenzoyl) -resorcinol, benzoylresorcinol, 3, 5 -
Di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butyl phenyl ester, octadecyl ester or -2-methyl-4,6 -ditered. - butylphenyl ester.



  f) acrylates, e.g. B.



     a-Cyano-ss, ss-diphenylacrylic acid ethyl or isooctyl ester, a-carbomethoxy-cinnamic acid methyl ester, a-cyano-ss -methyl p-methoxy-cinnamic acid methyl or. butyl ester, N- (ss-carbo methoxy-vinyl) -2-methyl-indoline.



  g) nickel compounds, e.g. B.



   Nickel complexes of 2,2'-thiobis (4-tert-octylphenol), such as the 1: 1 and 1: 2 complex, optionally with other ligands such as n-butylamine,
Nickel complexes of bis (4-tert-octylphenyl) sulfone, such as the 2: 1 complex, optionally with other ligands such as 2-ethylcaproic acid,
Nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy 3,5-di-tert. -butylbenzyl-phosphonic acid monoalkyl esters, such as methyl, ethyl or butyl esters, the nickel complex of 2-hydroxy-4-methyl-phenyl-undecyl ketone oxime, h) oxalic acid diamides, e.g. B.



     
4,4'-di-octyloxyoxanilide,
2,2'-di-octyloxy-5,5'-di-tert. -butyl-oxanilide,
2,2'-di-dodecyloxy-5, 5 '-di-tert-butyl-oxanilide, i) 2,2,6,6-tetramethylpiperidines, such as
2,2,6,6-tetramethyl-4-steaoryloxyperidin,
Bis (2,2,6,6-tetramethyl-4-hydroxypiperidine) sebacate.



   3. Phosphites, such as triphenyl phosphite, diphenylalkyl phosphites, phenyl dialkyl phosphites, trinonylphenyl phosphite, trilauryl phosphite, trioctadecyl phosphite, 3, 9-di-isodecyloxy-2,4,8,10-tetraoxa-3, 9 -diphosphaspiro- (5,5) -undecane, tri-phosphaspiro- (5,5) -undecane - (4-hydroxy-3-di-tert-butylphenyl) -phosphite.



   4. Peroxide-destroying compounds, such as esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, salts of 2-mercaptobenzimidazole, for example the zinc salt and diphenylthiourea for polyolefins.



   5. Polyamide stabilizers, such as copper salts in combination with iodides and / or other phosphorus compounds and salts of divalent manganese.



   6. Basic costabilizers, such as polyvinylpyrrolidone, melamine, benzoguanamine, Triallylcyanu rat, dicyandiamide, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth salts of higher saturated or unsaturated fatty acids such. B.



  the laurates, myristates, palmitates, stearates, oleates or ricinoleates of calcium, magnesium, zinc, sodium or potassium. Such salts are advantageously added to the stabilizer according to the invention in concentrations of 0.1-40% by weight, preferably 1-10% by weight, before being incorporated into the material to be protected.



   7. PVC stabilizers such as organic tin compounds, organic lead compounds and Ba / Cd salts of fatty acids.



   8. Nucleating agents, such as 4-tert.-butylbenzoic acid, adipic acid, diphenylacetic acid,
9. Other additives such as plasticizers, lubricants, e.g. B.



  Glycerine monostearate, emulsifiers, antistatic agents, flame retardants, pigments, carbon black, asbestos, glass fibers, kaolin, talc.



   The invention is illustrated in more detail in the following examples. Percentages (%) therein mean percentages by weight and parts mean parts by weight.



   example 1
EMI4.1


<tb> <SEP> tert <SEP> butyl
<tb> <SEP> / CH2O \
<tb> HO <SEP> Q <SEP> CH2CH2-COO-CH2-% 0H2-O-P
<tb> <SEP> tert <SEP>. <SEP> butyl
<tb>
13.6 g (0.1 mol) of pentaerythritol and 13.6 g (0.11 mol) of trimethyl phosphite are placed in a reaction vessel connected to a descending cooler and downstream cold trap as well as a vacuum unit, with 0.25 g (4.6 mol) Sodium methylate is added and the mixture is heated to 1100.degree. The methanol formed during the reaction distills off continuously. After the theoretical amount (12 ml) of methanol has passed over, the mixture is briefly heated to 140 ° C., then with 32.2 g (0.11 mol) of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) under nitrogen -propionic acid methyl ester added, whereby a homogeneous melt is formed.

  A further 0.2 g of sodium methylate are added with stirring and the reaction vessel is evacuated. The methanol formed during the reaction is distilled into the cold trap. The temperature is left at 140 ° C. for 60 minutes, then brought to 1600 ° C. and held for a further hour.



  The homogeneous melt is cooled to 100 ° C. After releasing the pressure with nitrogen, 30 ml of ethanol and 0.5 ml of glacial acetic acid are added all at once and the warm solution is cooled, the product crystallizing. After suctioning off, washing with a little ice-cold ethanol and drying At 60 "C, 34 g of 4-hydroxymethyl-1-phospha-2,6,7-trioxa bicyclo [2.2.2] octane-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate are obtained (Stabilizer No. 1) with a melting point of 154-155 "C. The compound can be recrystallized from ethanol or ligroin.

 

   If, in the present example, the methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is replaced by the corresponding alkyl-substituted methyl 4-hydroxyphenylpropionate, the corresponding esters of 4-hydroxymethyl-1-phospha- 2,6,7-trioxabicyclo [2.2.2] octane of Table 1 with the given melting points:
EMI4.2
   Table 1
EMI5.1


<tb> <SEP> melting point <SEP> stabilizer
<tb> <SEP> No.
<tb>



   <SEP> tert <SEP> butyl
<tb> H0- <SEP> yt <SEP> - <SEP> R <SEP> 78 "C <SEP> 2
<tb> <SEP> CH3
<tb> <SEP> iso-propyl
<tb> R <SEP> ss <SEP> R <SEP> 102 "C <SEP> 3
<tb> <SEP> iso-propyl
<tb> <SEP> term <SEP> butyl
<tb> HO - R <SEP> 1500C <SEP> 4
<tb> <SEP> H
<tb> <SEP> tert <SEP> butyl
<tb> HO-YY
<tb> <SEP> C113 <SEP> CH3
<tb> <SEP> example <SEP> 2
<tb> <SEP> tert-butyl
<tb> / C112 <SEP> O \
<tb> H0 <SEP> $ <SEP> / <SEP> 2 <SEP> \
<tb> <SEP> LL <SEP> L \ <SEP> /
<tb> <SEP> te.rt.I5utyl
<tb>
13.6 g (0.1 mol) of pentaerythritol, 13.6 g (0.11 mol) of trimethyl phosphite and 32.2 g (0.11 mol) of 3 are placed in a reaction vessel connected to a descending cooler and a downstream cold trap as well as a vacuum unit. 3.5 -d itert.-butyl-4-hydroxyphenyl) propionic acid methyl ester,

   the mixture is heated to 70 ° C. and 0.5 g of sodium methylate is added with slow stirring. The internal temperature is brought to 110 ° C., the methanol formed during the reaction being distilled off. The evolution of methanol subsides when about 12 ml have passed over. The temperature the reaction mixture is then brought to 160 ° C. for 30 minutes, the reaction vessel is evacuated and the temperature is maintained for a further hour.



   The homogeneous melt is cooled to 100 ° C. After releasing the pressure with nitrogen, 30 ml of ethanol and 0.5 ml of glacial acetic acid are added all at once and the warm solution is cooled, the product crystallizing. After suctioning off, washing with a little ice-cold ethanol and drying At 60 "C, 36 g of 4-hydroxymethyl-1-phospha-2,6,7-trioxa-bicyclo [2,2.2] octane-3 - (3,5-di-tert-butyl-4-hydroxyphenyl) propionate are obtained (Stabilizer No. 1) with a melting point of 154-155 "C. The compound can be recrystallized from ethanol or ligroin.



   Example 3
EMI5.2


<tb> <SEP> tert <SEP> Butyl <SEP> 0.
<tb>



  HO, <SEP> ¯CH2CH2COO <SEP> CKZ <SEP>, CH, <SEP> 0.
<tb>



  HO <SEP> 9 <SEP> CH2Cll2: COO-CH2 <SEP> g
<tb> <SEP> tert-butyl <SEP> CH2
13.6 g (0.1 mol) of pentaerythritol and 32.2 g (0.11 mol) of 3- (3.5 -ditert.-butyl-4-) are placed in a reaction vessel connected to a descending cooler and a downstream cold trap as well as a vacuum unit. methyl hydroxyphenyl) propionate, the mixture is heated to 100 ° C. and 0.25 g of sodium methylate is added. After evacuating the reaction vessel, it is heated to 1500 ° C., with methanol distilling into the cold trap. After the theoretical amount (4 ml) has passed, the mixture becomes cooled to 90 ° C. and admixed with 13.6 g (0.11 mol) of trimethyl phosphite and a further 0.25 g of sodium methylate, the internal temperature being brought to 1100 ° C., with a further 12 ml of methanol distilling into the cold trap for about 3 hours.



  This second stage of the reaction is carried out at normal pressure. Finally, it is briefly evacuated, the temperature is brought to 100 ° C. and a mixture of 30 ml of ethanol and 0.5 ml of glacial acetic acid is added all at once. The warm solution is cooled, the product crystallizing.



   After filtering off with suction, washing with a little ice-cold ethanol and drying at 600 ° C., 30 g of 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane-3 - (3, 5-ditered) are obtained. -butyl-4-hydroxyphenyl) propionate (stabilizer no. 1) with a
Melting point of 154-155 C. The compound can be recrystallized from ethanol or ligroin.



   Example 4
EMI5.3


<tb> <SEP> tert-butyl
<tb> / CH2 <SEP> C <SEP> .CH2 <SEP> - <SEP> 0,
<tb> HG- <SEP> v <SEP> CH2CH2-C00-CH2-C-CH2-0-P
<tb> <SEP> tert-butyl <SEP> CH2-O
<tb> 16.4 g of 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo- [2.2.2] octane are dissolved in 100 ml of dimethylacetamide. A solution of 33 g of 3- (3.5 di-tert-butyl-4-hydroxyphenyl) propionic acid chloride in 100 ml of dimethylacetamide is added dropwise with vigorous stirring, the temperature rising to 45 "C. The mixture is kept at 80" C. for one hour stirred, cooled and poured into 2 liters of water. The product, which initially precipitated as an oily product, crystallized in the course of a few hours. After suctioning off, 4 times the amount of alcohol is recrystallized.

  The 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane-3 - (3,5 - di-tert-butyl-4-hydroxyphenyl) propionate (stabilizer no . 1), which shows a melting point of 156 "C.



  Example 5
EMI6.1


<tb> <SEP> tert <SEP> Butyl <SEP> / cm2 <SEP> 0 \
<tb> HO <SEP> 9 <SEP> CH <SEP> = <SEP> CM-C00-CM2-C-C112-O-P
<tb> <SEP> tert-butyl <SEP> CM2 <SEP> -o
<tb>
30.4 g of ethyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) acrylic acid and 16.4 g of 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2 ] octane are heated together to 1500 C, a homogeneous melt being formed. 0.4 g of lithium amide are added with stirring, then heated to 1600 ° C. and kept at this temperature for 12 hours.



  After cooling, it is mixed with 250 ml of toluene, filtered and evaporated. The product is obtained in crystalline form by adding hexane. The 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane-3 - (3,5-di-tert-butyl4-hydroxyphenyl) acrylate (stabilizer no. 5) obtained in this way melts afterwards repeated recrystallization from toluene at 197 C.



   Example 6
EMI6.2


<tb> <SEP> tert-butyl
<tb> <SEP> / C112 <SEP> O \
<tb> 110 <SEP> CH2-C00-CH2-C \ C <SEP> 2
<tb> <SEP> CH3
<tb>
23.6 g of 3-tert. -Butyl-4-hydroxy-5-methyl-phenylacetic acid methyl ester and 16.4 g of 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane are heated together to 1300 C and the 0.4 g of lithium amide were added to the homogeneous melt while stirring. The reaction vessel is evacuated and the temperature is kept at 1300 ° C. for 2 hours.



  After releasing the pressure with nitrogen and cooling, 150 ml of toluene are added, the mixture is filtered and evaporated. The product is obtained in crystalline form by adding hexane to the evaporation residue and can be recrystallized from a mixture of toluene and hexane. The 4-hydroxymethyl-1phospha-2,6,7-trioxabicyclo [2.2.2] octane-3-tert-butyl-4 hydroxy-5-methyl-phenyl acetate (stabilizer no. 6) thus obtained shows a Melting point of 99 "C.



   If, in this example, the 3-tert-butyl-4-hydroxy-5-methyl-phenyl-acetic acid methyl ester is replaced by an equivalent amount of 3,5-dimethyl-4-hydroxyphenylacetic acid methyl ester, this is obtained with otherwise the same procedure 4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane-3,5-dimethyl-4-hydroxyphenyl acetate (stabilizer No. 7) with a melting point of 1500 C.



   Example 7
EMI6.3


<tb> <SEP> tert <SEP> butyl
<tb> <SEP> / CH20 \
<tb> HO <SEP> gOf <SEP> - <SEP> C00-CH2-C-CE12,0-P
<tb> <SEP> tert-butyl <SEP> CM2-0
<tb>
26.4 g of 3.5 liters. -butyl-4-hydroxybenzoic acid methyl ester and 16.4 g of 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo- [2.2.2] octane are heated together to 1200 ° C. and the homogeneous 0.2 g lithium amide was added to the melt.



  The flask is evacuated, the temperature is brought to 1500 C and held for 2 hours. After releasing the pressure and cooling, 150 ml of toluene are added, the solution is boiled and filtered. The product crystallizes out on evaporation. It can be recrystallized from toluene. The 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane-3,5-di-tert-butyl-4-hydroxybenzoate (stabilizer no. 8) thus obtained melts at 200 ° C.



  Example 8
EMI6.4


<tb> <SEP> / <SEP> CH2 <SEP> Ox
<tb> <SEP> COO-CH <SEP> -C-CH <SEP> O-P
<tb> <SEP> tert-butyl <SEP> 2 <SEP> \ <SEP> 2 <SEP> /
<tb> <SEP> CM2-0 <SEP> Aert.Butyl
<tb> HO <SEP> - <SEP> C <SEP> -CH2- (<SEP>, -CH2 <SEP> 011
<tb> <SEP> to <SEP> / C112 <SEP> -o
<tb> <SEP> tert-butyl
<tb> <SEP> C00-CM2 <SEP> C \ CM2 <SEP> \ <SEP> 2
<tb> <SEP> CM2-0 '
<tb>
56.8 g of bis (3,5-di-tert-butyl-4-hydroxybenzyl) -malonic acid dimethyl ester and 32.8 g of 4-hydroxymethyl-1-phospha 2,6,7-trioxabicyclo [2.2.2] octane are placed in 100 ml of toluene and the mixture is heated to boiling. The resulting homogeneous solution is cooled to 90 ° C. and 0.3 g of lithium amide is added.

  The reaction vessel is carefully evacuated, the methanol formed and the toluene completely distilling off at an outside temperature of 105-120 ° C. 100 ml of toluene are added to the melt, and the solution is boiled and filtered. The viscous residue which remains after evaporation is triturated with 150 ml of hexane, whereupon it becomes solid and crystalline. The bis (4-hydroxymethyl-1-phospha-2,6,7 -trioxabicyclo [2.2.2] octane) bis - (3,5-di-tert-butyl-4-hydroxybenzyl) - is obtained in this way malon at (stabilizer No. 9) with a melting point of 70 C.



   If, in this example, the bis- (3,5-di-tert-butyl-4-hydroxybenzyl) -malonic acid dimethyl ester is replaced by an equivalent amount of a 3,5-dialkyl-4-hydroxybenzyl-malonic acid dialkyl ester from Table 2 below, otherwise the result is the same procedure, the corresponding bis (4hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane) 3,5-dialkyl-4-hydroxybenzylmalonates as slightly yellowish oils.



  Table 2
EMI7.1


<tb> <SEP> dialkyl hydroxybenzyl malonate <SEP> reaction product
<tb> <SEP> sec.butyl <SEP> COOC3 <SEP> sec.butyl
<tb> HO <SEP> CR2- <SEP> ¯CH <SEP> ----- C-- <SEP> CH <SEP> - <SEP> X <SEP> OH <SEP> yellowish <SEP> oil
<tb> <SEP> sec.butyl <SEP> 3 <SEP> sec.butyl
<tb> <SEP> tert <SEP> Butyl <SEP> COOCH3
<tb> <SEP> 3
<tb> HO <SEP> t <SEP> CH2 <SEP> - <SEP> CM <SEP> oil,
<tb> J <SEP> 2 <SEP> Stabilizer <SEP> No.

  <SEP> 10
<tb> <SEP> fiert.bu <SEP> COOCH
<tb> <SEP> tert.butyl <SEP> COOCH3
<tb> <SEP> Cyclooctyl <SEP> COOCK3 <SEP> Cyclooctyl
<tb> <SEP> C112-O11
<tb> HO <SEP> CH2 <SEP> - <SEP> C <SEP> - <SEP> wastksantiirer
<tb> <SEP> Cyclooctyl <SEP> COOCH3 <SEP> Cyclooctyl
<tb> <SEP> 3
<tb> <SEP> t <SEP> COOC2H5
<tb> HO <SEP> - <SEP> CM2 <SEP> - <SEP> CH <SEP> oil
<tb> <SEP> CH3 <SEP> COOC2H5
<tb> <SEP> füM / CM3 <SEP> COOC2M
<tb> <SEP> 5
<tb> 110 <SEP> C7 <SEP> CH2 <SEP> - <SEP> CM <SEP> ö1
<tb> <SEP> CH3 <SEP> COOC2H5
<tb> <SEP> CM3 <SEP> CM
<tb> C11 <SEP> CH <SEP> COOCH3 <SEP> CM
<tb> <SEP> 110 <SEP> - <SEP> to <SEP> CH2 <SEP> - <SEP> C <SEP> ¯ <SEP> CH2 <SEP> oil
<tb> <SEP> H <SEP> COOCH,

   <SEP> CH
<tb> <SEP> 1 <SEP> I
<tb> <SEP> CM3 <SEP> CH3
<tb> Table 2 (continued)
EMI8.1


<tb> D <SEP> ialkyl-hydroxybenzyl-malonate <SEP> reaction product
<tb> <SEP> reaction product
<tb> <SEP> CM3 <SEP> OOCH <SEP> C <SEP> H3 <SEP> t
<tb> <SEP> OH3 <SEP> Ci <SEP> i <SEP> 3 <SEP> / -oCH3
<tb> RO <SEP> t <SEP> CM2 <SEP> - <SEP> g <SEP> CH2 <SEP> CM2O <SEP> 011 <SEP> ö1
<tb> <SEP> ($ 30113 <SEP> CO <SEP> OC <SEP> H3 <SEP> C <SEP> H3 <SEP> X
<tb> Example 9
EMI8.2


<tb> <SEP> tert <SEP> Butyl <SEP> / CH20 \
<tb> H <SEP> CH2-S-CM2-C00-C2-C-CM2-0-P
<tb> <SEP> t <SEP> er <SEP> t <SEP>, Bu <SEP> ty <SEP> l <SEP> CH2-0
<tb>
16.4 g of 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and 32.4 g of S- (3,5-di-tert-butyl-4-hydroxybenzyl) thioglycolic acid methyl ester are heated together to 70 "C, creating a homogeneous melt.

  After adding 0.4 g of lithium amide, the melt is heated to 1200 ° C., with methanol distilling off. After cooling, 200 ml of toluene are added, the solution is boiled, filtered and evaporated. The viscous oil that remains is triturated with 100 ml of ligroin, whereupon crystallization occurs. After filtering and drying, 4-hydroxymethyl-1-phospha-2,6,7 -trioxabicyclo [2.2.2] octane-S - (3,5 -ditert-butyl-4-hydroxy-benzyl) is obtained thioglycolate (stabilizer no. 11), which sinters at 70 "C.



  Example 10
EMI8.3


<tb> <SEP> tert-butyl <SEP> C1120
<tb> 110
<tb> <SEP> CM2CM2C00-CH2 <SEP> -CCM2 <SEP> -0-P = 0
<tb> <SEP> C1120
<tb> <SEP> tert-butyl
<tb> 1st stage:
8.2 g of 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane are in 160 ml of absol. Alcohol dissolved.



  While stirring, 15 g of a 70% solution of cumene hydroxyperoxide in cumene are added. The mixture warms up to about 55 ° C. The precipitate which separates out on cooling is filtered off and dried. This gives 4-hydroxymethyl-1-oxophospha-2,6,7-trioxabicyclo- [2.2.2] octane from Melting point 220 C.



  2nd stage:
32.2 g of methyl 3 - (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 18.0 g of 4-hydroxymethyl-1-oxophospha-2,6,7-trioxabicyclo [2, 2.2] octane are heated together to 1500 C. 0.4 g of sodium methylate are added with stirring, then heated to 1600 ° C. and kept at this temperature for 12 hours. After cooling, 250 ml of toluene are added and the mixture is filtered while hot. The crystals separated out after cooling are filtered off with suction and dried. This gives 4-hydroxymethyl-1-oxophospha-2,6,7-trioxabicyclo [2.2.2] octane-3 - (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (stabilizer no. 12) with a melting point of 183 "C.



  Example 11
EMI8.4


<tb> <SEP> tert-butyl <SEP> l
<tb> <SEP> \ <SEP> C <SEP> H <SEP> 2- <SEP> O
<tb> 110 <SEP> O <SEP> <<SEP> CH2 <SEP> C <SEP> H2 <SEP> -C <SEP> OO-C <SEP> H2 <SEP> -C <SEP> \ CH < SEP> 2 <SEP>
<tb> <SEP> tert-butyl <SEP> CM20
<tb>
42.4 g of 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane-3 - (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (stabilizer no. 1, example 1) are dissolved in 500 ml of dry ether by briefly boiling. 25 g of a 70% strength solution of cumene hydroperoxide in cumene are added to the solution, and the resulting mixture is stirred for 3 hours at room temperature. The product slowly falls out as a white precipitate.

  After filtration and recrystallization from alcohol, 4-hydroxymethyl-1-oxophospha n, 6,7 -trioxabicyclo [2,2,2] octane-3 - (3,5 -ditert-butyl-4-hydroxyphenyl) is obtained Propionate (stabilizer No. 12) with a melting point of 183 C.



  Example 12
EMI9.1


<tb> <SEP> tert-butyl <SEP> CH2 <SEP> -O
<tb> 110 <SEP> O <SEP> ss <SEP> CH <SEP> 2CH <SEP> 2 <SEP> ¯ <SEP> -C- ± M-0-P = S
<tb> <SEP> t <SEP> e <SEP> rt <SEP> .Bu <SEP> ty <SEP> l <SEP> CM2 <SEP>
<tb> 42.4 g of 4-hydroxymethyl-1-phospha-2.6,7-trioxabicyclo- [2.2.2] octane -3 - (3,5-di-tert-butyl4-hydroxyphenyl) propinnate (stabilizer no. 1 example 1) are refluxed for 4 hours with 3.2 g of sulfur and 0.2 g of sodium sulfide in 100 ml of toluene. The solid that separates out on cooling is filtered off with suction and recrystallized from toluene.

  After filtration and drying, 4-hydroxymethyl-1-thiophospha 2.6,7 -trioxabicyclo [2.2.2] octane -3 - (3.5-di-tert-butyl-4-hydroxyphenyl) propionate (stabilizer no. 13) with a melting point of 188 "C.



   In the following application examples, the previously known stabilizers listed in Table 3 were also tested as comparison compounds:
Table 3 Stabilizer No. Chemical name 14 Pentaerythritol tetrakis [3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl)] propionate 15 Tris-nonylphenyl-phosphite 16 l, 3,5-tris- ( 3'.5'-di-tert-butyl-4'-hydroxy-benzyl) -2,4,6-trimethylbenzene 17 diethyl (3,5-di-tert-butyl-4-hydroxy-benzyl) phosphonate
18 thiodiglycol-bis- [3- (3 ', 5'-di-tert-butyl-
4-hydroxyphenyl)] propionate 19 1,1 -bis- (5-tert-butyl-4-hydroxy-2-methyl-phenyl) -butane 20 2.2'-methylene-bis (4-ethyl-6-t- butyl) phenol 21 <RTI

    ID = 9.18> Nickel-bis- (3,5-di-tert-butyl-4-hydroxy-henzyl) -ethyl-phosphonate 22 2- (2'-hydroxy-5 '-methylphenyl) -benz-triazole 23 4-hydroxymethyl -1-phospha-2,6,7-trioxabicyclo [2.2.2] octane stearate (mp 49 "C) 24 octadecyl-3- (3 ', 5'-di-tert-butyl-4'- hydroxyphenyl) propionate 25 Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate
Example 13
The additives listed in Table 4 are each incorporated homogeneously using Labor-Gelimat (Draiswerke) in a concentration of 1.9% in polyamide 12 (relative viscosity = 1.9, 0.5 Icig in m-cresol) and these mixtures are added 260 C pressed into 1 mm plates.

  Test strips 1 cm wide are punched out of the press plates. The test specimens required for comparison purposes without the addition of additives are produced in an analogous manner.



   The effectiveness of the additives added to the test strips is tested by heat aging in a convection oven at 1500 C. The end product is defined as the time to reach the brittle point, which is reached when breakage occurs when the test specimen is manually bent by 1800 (table 4, column 3).



   Table 4, column 2 contains information on discolouration of the polyamide test specimens caused by the additives in the delivery state before heat aging, an empirical color scale being used in which 5 is colorless, 4 is just noticeable, slight discoloration, 3, 2, 1 gradually stronger Mean discoloration.



   Table 4 Stabilizer color of the test pieces Heat aging at No. im 1500C
Delivery condition days to Brittle Point without additive 5 1
1 5 30
2 5 28
3 5 27
4 5 21
9 5 30 11 5 13 13 5 14
Comparative products 14 3 10 14 + 15 (0.5%) 3 10 16 3 8 16 + 15 (0.5%) 5 9 17 5 6 18 3 11
Example 14
The additives listed in Table 5 are coated dry in the specified concentrations on a polyamide 12 granulate (relative viscosity = 1.9, 0.5% in m-cresol) and the breadcrumbs are each regranulated on a single-screw extruder at 2600C. On an injection molding machine (from Arburg), 1 mm thick tensile rods are injected from the granules at 240 ° C. (dimension of the web: 30 × 6 mm).

 

   The testing of the effectiveness of the additives added to the test items is carried out by heat aging in a forced air oven at 150 ° C. The thermo-oxidative degradation of the material during heat aging is monitored in three different ways: a) Periodic measurement of the relative viscosity of a
0.5% solution in m-cresol (Table 5, columns 2-6).



  b) Determining the time to reach the Brittle
Point as described in Example 13 (Table 5 Column 7).



  c) Periodic determination of the tensile strength and determination of the time until the yield stress drops to 80%
Initial value (Table 5, column 8).



   Table 5 Stabilizer No. a) Relat. Solution viscosity after b) days to c) days to (conc.) Days, heat aging at 150 C Brittle 80% remainder
0 5 10 20 30 point yield stress without additive 1.90 1.4 - - - 1 1 1 (0.5%) 1.85 1.80 1.68 1.58 - 17 21 1 (1.0%) 1 .85 1.82 1.78 1.70 1.62 30 27 9 (1.0%) 1.90 1.84 1.79 1.72 1.61 31 28 Comparative products 14 (1.0%) 1, 84 1.75 1.61 1.50 - 10 12 14 (1.0%) + 15 (0.5%) 1.85 1.76 1.63 1.55 - 11 13 17 (1.0%) 1.87 1.61 1.42 - - 6 6 23 (0.5%) + 24 (0.5%) 1.85 1.51 - - - 4 4 As can be seen in Table 5, the stabilizers according to the invention achieved a higher thermostabilizing effect according to all 3 criteria than with a commercial stabilizer.



   Example 15
The additives listed in Table 6 are incorporated homogeneously in a concentration of 1.0% using Labor-Gelimat (Draiswerke) in polyamide 12 (relative viscosity = 1.9, 0.5% in m-cresol) and these mixtures are added 260 C pressed into 1 mm thick plates. Test strips 1 cm wide are punched out of the press plates. The test specimens required for comparison purposes without the addition of additives were produced in an analogous manner.



   The test for color stability (yellowing tendency) of the additives added to the test strips is carried out by exposure in a Xenotest device. An empirical color scale was used to assess the intensity of discoloration, in which 5 colorlessness, 4 a just perceptible, slight discoloration, 3, 2, 1 successively stronger discoloration. Table 6 contains the color values immediately after incorporation and after an exposure time of 1000 hours.



   Table 6 Stabilizer color assessment no. After incorporation after 1000 hours.



   Xenotest
1 5 5
2 5 5
3 5 5
4 5 5
5 5 5
6 5 5
7 5 5
8 5 5
9 5 5 10 5 5 11 5 5 12 5 5 13 5 5
Comparative products 14 3 2 14 + 15 (0.5%) 4 3 16 3 3 18 3 1 19 4 2 20 3 2 21 2 2
Example 16
The additives listed in Table 7 are coated dry in a concentration of 1% on a polyamide 12 granulate (relative viscosity = 1.9, 0.5% in m-cresol) and the breading mixes are each placed on a single-screw Extruder re-granulated. On an injection molding machine (from Arburg), 1 mm thick tensile rods are injected from the granules at 240 ° C. (dimension of the web: 30 × 6 mm).



   The effectiveness of the additives added to the test items is tested by heat aging in a convection oven at 1600 C. The thermo-oxidative degradation of the material during heat aging is monitored in two different ways: a) Periodic measurement of the relative viscosity of a
0.5% solution in m-cresol (Table 7. Columns 2-7).



  b) Periodic determination of the tensile strength and determination of the time until the yield stress drops to 80% of its initial value (Table 7, column 8).



   Table 7 Stabilizer No. a) Relative solution viscosity after days b) Days up to 80% rest concentration: 1to heat aging at 160 "C yield stress
0 3 5 7 9 12 without additive 1.95 1.5 - - - - 0.5 1 1.90 1.84 1.80 1.76 1.72 1.66 20 4 1.95 1.84 1, 77 1.74 1.70 1.65 18
Example 17
The additives listed in Table 8 are coated dry in a concentration of 0.5% on dried polyamide 6 granulate (relative viscosity = 2.9, 1% in concentrated sulfuric acid) and the breadcrumbs are granulated on a single-screw extruder at 2600 ° C. 0.3 mm press foils are then produced from the granules, likewise at 260 ° C., and test strips 1 cm wide are punched out of these press foils.



   The effectiveness of the additives added to the test items is tested by heat aging in a forced-air oven at 165 ° C. The thermo-oxidative degradation of the material during heat aging is monitored by periodically measuring the relative viscosity of a 1% solution in 96% sulfuric acid, the time after which the relative viscosity drops from 2.9 to a value of 2.0 is determined (Table 8).



   Table 8 Stabilizer heat aging time at 1650 C for waste No. of the solution viscosity device rel. from 2.9 to 2.0 in hours without additive 5 1 50 Comparative products 14 12 16 40 17 30 19 40 21 20 25 12
Example 18
100 parts of polypropylene (melt index 3.2 g / 10 min., 230 ° C./2160 g) are mixed intensively in a shaker with 0.2 parts of an additive listed in Table 9 below for 10 minutes.



   The mixture obtained is kneaded in a Brabender plastograph at 200 ° C. for 10 minutes, and the resulting mass is then pressed in a plate press at a plate temperature of 2600 ° C. to form 1 mm thick plates, from which strips 1 cm wide and 17 cm long are punched .



   The effectiveness of the additives added to the test strips is tested by heat aging in a convection oven at 135 and 149 ° C., with an additive-free test strip serving as a comparison. For this purpose, 3 test strips are used from each formulation. The beginning, easily visible decomposition of the test strip is defined as the end point. The results are given in days.



   Table 9 Stabilizer days until decomposition begins No. 149 "C 135" C without additive t / 2 1
1 8 52
9 15 98
Comparative products 20 5 40 17 2 10
Example 19
The test specimens described in Example 18 were also tested for their color stability, namely: a) After incorporation (Tab. 10, column 2).

 

  b) After 500 hours of exposure in a Xenotest device from Hanau (Tab. 10, column 3).



  c) After 1 week of treatment with boiling water (Tab. 10, column 4).



   For table 10 an empirical color scale was used, in which 5 colorless, 4 one even. perceptible, slight discoloration, 3, 2, 1 and 1 denote successively stronger discoloration.



   Table 10
Stabilizer color assessment according to scale 1-5 no. After exposure to boiling water for 1 week
1 4 5 4
9 4 5 4
Comparative products 20 2 3 1
17 4 4 4
Example 20
100 parts of polypropylene (melt index 3.2 g / 10 min., 230 C / 2160 g) are thoroughly mixed in a shaker with 0.1 part of an additive listed in Table 11 below and 0.3 part of dilauryl thiodipropionate for 10 minutes.



   The resulting mixture is kneaded in a Brabender plastograph at 200 "C for 10 minutes, the resulting mass is then pressed in a platen press at 260" C to give 1 mm thick plates, from which strips 1 cm wide and 17 cm long are punched will.



   The testing of the effectiveness of the additives added to the test strips is carried out by heat aging in a forced-air oven at 135 and 149 ° C., a test strip which contains only 0.3 part of dilauryl thiodipropionate being used as a comparison. For this purpose, three test strips are applied from each formulation. The beginning, easily visible decomposition of the test strip is defined as the end point; the results are given in days.



   Table 11 Stabilizer days until decomposition begins No. 149 "C 135" C without additive 5 11
1 20 95
9 28 115
Comparable products 20 13 65 17 8 37
Example 21
0.25 parts of each of the additives in Table 12 are used in 100
Share a 25% polyurethane solution (ESTANE 5707 der
Goodrich) dissolved cold.



   On a glass plate from these solutions with a film puller about 400kl thick films are drawn, which dry out after about 10 minutes of forced air drying at 140C to films with a final thickness of 100μ. The stabilizers are therefore present in the films in a concentration of 1.0%. Samples of these films are exposed to visually perceptible yellowing in a Xenotest device on a white cardboard base. The results of the table
12 are given in hours.



   Table 12
Stabilizer Exposure time in Remarks No. Xenotest device until clearly visible yellowing (in hours) without additive 100 1 (0.5%) 300
1,400
1 + 22 700
Comparison products
14 250
14 + 22 500
15 + 22 300
17 200
Table 12 (continued) Stabilizer Exposure time in Comments No. Xenotest device until the yellowing is clearly not visible (in hours) 17 + 22 400 19 150 19 + 22 250 24 200 incompatible 24 + 22 400 incompatible 16 150 incompatible 16 + 22 250 incompatible 25 + 22 250 incompatible 22 200
As can be seen from Table 12, the stabilizer according to the invention provides excellent protection against yellowing of polyurethane films, both when it is used alone and when it is used with co-additives.



   Example 22
Yellowing protection of polyacrylonitrile (PAN)
0.5 part of stabilizer 1 is dissolved for 4 hours together with 25 parts of PAN in 75 parts of dimethylformamide (DMF) at 70 ° C. In a visual comparison, the stabilized solution already shows a significantly lighter color than the additive-free solution about 500, t <thick films drawn on a glass plate and these
Dried 10 minutes at 125 ° C.



   The dried films are visually assessed for their degree of yellowing on a white background as follows:
Table 13
Discoloration Additional free comparison color yellow 0.5% Stabilizer 1 white with a very slight yellow tinge
The same results are obtained if, instead of dimethylformamide, other solvents such as. B.



  Ethylene carbonate-water mixture (80:20) used.



   Example 23
Stabilization of ABS
0.3% of stabilizer 1 is applied to unstabilized ABS resin and the breading mixture is granulated at 240 ° C. on a single-screw extruder. For comparison, granules without the addition of stabilizer 1 are produced in the same way. The granules are in the usual way on a
Injection molding machine molded into platelets at 250 C. The plates are aged in a convection oven at 80 ° C. for 10 days and the color behavior is assessed.



   Table 14
Color of the panels.



   Delivery after 10 days 80 "C without stabilizer yellow-beige yellow-brownish
0.3% stabilizer 1 light beige light beige
The addition of 0.3% Stabilizer 1 improves the color of ABS in the delivery condition and prevents discoloration during oven aging.



   Example 24
Stabilization against degradation of polypropylene in the
processing
The stabilizers in Table 15 below are mixed homogeneously in the specified concentrations with polypropylene powder (Propathene HF 20 from ICI) and mixed 5 times in a single-screw extruder at a maximum of 260 ° C. and 100 rpm. re-granulated one after the other. After the 1st, 3rd and 5th extrusion, the melt index (MI) of the material is measured (2160 g load at 230 ° C., g / 10 min).



  A degradation of the polymer manifests itself in a rapid increase in the melt index.



   Table 15 Stabilizer MI / 2160 g at 230 C in g / 10 min.



  No. Delivery 1. Extrusion 3. Extrusion 5. Extrusion (concentration) state without stable. 2.50 5.30 27.2 38.5 1 (0.1%) 2.50 3.16 4.80 6.55 (0.05 2.50 3.95 6.34 9.40 14 (0 .05%) + (0.05 2.50 3.58 4.90 6.94 24 (0.05%) + (0.05 2.50 2.50 4.64 7.05 16 (0.05 %) + 1 (0.05%) 2.50 2.50 4.36 6.46 19 (0.05%) + (0.05 2.50 2.92 4.96 7.54 25 (0. 05%) +
1 (0.05%) 2.50 4.11 5.22 8.25
Comparative products 14 (0.1%) 2.50 4.10 7.37 10.7 24 (0.1%) 2.50 4.44 8.26 13.40 16 (0.1%) 2.50 3 .87 6.82 10.4 19 (0.1%) 2.50 4.26 8.10 12.76 25 (0.1%) 2.50 5.95 8.10 10.45
As from the values in Table 15

   As can be seen, the stabilizer 1 according to the invention improves the processing stability of the polymer not only as such, but also in combination with conventional phenolic antioxidants.



   In addition to keeping the melt index constant, Stabilizer 1 brings about a clear color improvement compared to unstabilized material, even after multiple extrusions.



   Example 25
Stabilization of EPDM a) Production of the test items
100 parts of unstabilized ethylene-propylene rubber are mixed with 0.1 part of each of the stabilizers given in Table 16 in the Brabender plastograph, equipped with a roller kneader type 50 EC, at 150 ° C. and 60 rpm. homogenized for 10 minutes. The mixtures stabilized in this way are pressed in a plate press at 120 ° C. for 5 minutes to give 1 mm thick plates. The non-stabilized rubber plate used as a comparison is produced in the same way.



  b) examination
The criterion for the protective effect of the incorporated stabilizers is the gel content determined after storage in air at elevated temperatures. For this purpose, the test samples obtained as above are kept on an aluminum base in a convection oven at 1000 C and examined for their gel content after 5 and 10 days, which is determined as follows:
About 1 g of the samples are cut into pieces of about 3 × 3 × 1 mm and dissolved in 100 ml of n-hexane at room temperature overnight. These solutions are filtered through glass wool, the gel particles retained by the glass wool are washed with 3 times 20 ml of n-hexane, the filtered solutions are evaporated to dryness and dried to constant weight.

  The gel content of a sample is then obtained using the following calculation:
Gel content in% = E-A 100
E.
E = total weight of the examined
sample
A = weight of the dissolved portion of the sample examined.



   The following table 16 summarizes the results of the gel determination after oven aging:
Table 16 Stabilizer gel content in% after aging in air, 1000 C No. 5 days 10 days 15 days 20 days without stabilizer. 2 84 83 81
1 0 0 1 1 11 0 1 1 2
Comparable products 15 4 65 85 85 23 5 85 84 80 24 0 3 10 15
Example 26
Stabilization of impact-resistant polystyrene
100 parts of impact-resistant polystyrene, which contains about 8 parts of polybutadiene, are mixed dry with 0.1 parts of each of the stabilizers given in Table 17 in a mixer and these mixtures are then mixed in a Brabender plastograph (roller kneader 50 EC) at 220 ° C. for 30 minutes The material is then pressed at 220 ° C. to form 1 mm plates and visually assessed for the discoloration caused by the Brabender treatment.

  For comparison purposes, unstabilized polymer is subjected to the same treatment. The results are shown in Table 17 below.



   Table 17 Stabilizer color after Brabender treatment No. 30 minutes / 220 C without stabilizer brown-yellow, opaque
1 white, opaque (no change in color compared to a sample without Brabender treatment)
Example 27
Stabilization of polystyrene
100 parts of crystal clear polystyrene granulate are mixed dry in a mixer with the following additives:
Mixture I: No additive
Mixture II: 0.25 part of stabilizer No. 22 (light stabilizer)
Mixture III: 0.25 part of stabilizer No. 1
Mixture IV: 0.15 part of stabilizer # 22
0.1 part Stabilizer No. 1
These mixtures are granulated in an extruder and then injected in an injection molding machine at 280 C to form sheets about 1.5 mm thick.



   The plates obtained are exposed for 1500 h in a Xenotest device (type 150) and their yellowing is determined by the yellowing factor VF as follows:
EMI14.1

Significant here are the transmission losses that occurred as a result of exposure, measured at wavelengths 420 or 680 nm and T560 the transmission value as a percentage of an unexposed sample, measured at a wavelength of 560 nm.



   The yellowing factors calculated from the transmission measurements of the exposed samples are summarized in Table No. 18 below.



   Table 18 Mixture yellowing factor after 15 hours No. Xenotest 150 I 20.6 II 3.3 III 12.4 IV 1.7
The results show that the partial replacement of the light stabilizer (stabilizer No. 22) with stabilizer No. 1 results in better protection against yellowing than any of the individual components.



   Example 28
Stabilization against crosslinking of high molecular weight
Low-pressure polyethylene during processing 0.05% stabilizer 1 is mixed homogeneously with the polyethylene powder (MG¯250 000) and placed in a single-screw extruder at max. 200 C and 100 rpm re-granulated.



  For comparison, granules are produced in the same way without the addition of stabilizer 1. The melt index (MI) was determined on the starting material and on the extruder pellets.



   The oxidative damage to the polymer material due to the thermal stress during extrusion causes crosslinking of the polymer and is manifested by a greatly increased viscosity of the polymer melt and thus a greatly reduced melt index (Table 19).



   Table 19 MI (10 kg at 230 ° C) g / 10 minutes
Delivery condition After extrusion without stabilizer 0.5 0.1 0.05% stabilizer 1 0.5 0.5
In addition to keeping the melt index constant, Stabilizer 1 brings about a clear color improvement after re-granulation compared to the unstabilized material.



   Example 29
Stabilization of very high molecular weight polyethylene against crosslinking under thermal-mechanical stress
0.3 parts of stabilizer no. 1 are mixed dry with 100 parts of high molecular weight polyethylene (Min1,000,000) and then in a Brabender plastograph at 2400 ° C. and 40 rpm. kneaded for a total of 7 minutes.



  The mixture treated in this way is pressed into a plate and examined for its gel content. For this purpose, the material is extracted in the form of fine chips with xylene for 10 h and the residue remaining after the extraction is determined, which represents the cross-linked, insoluble gel fraction. For comparison, a stabilizer-free mixture is treated in the same way. The results are summarized in the following table 20:
Table 20
Stabilizer gel content according to No. Brabender treatment;
7 min./240 C, 40 rpm.



  without addition not kneaded 0 without addition kneaded 44 with 0.3% stabilizer 1 kneaded 0 with 0.3% stabilizer 14 kneaded 8
Example 30
Stabilization of polyvinyl chloride
70 parts by weight of PVC (Solvic 239) produced by the suspension process were added with 30 parts by weight of dioctyl phthalate, 0.44 part by weight of cadmium laurate, 0.66 part by weight of barium laurate and 0.3 part by weight of a costabilizer 165 "C for 5 minutes on a laboratory roller. The films obtained in this way were subjected to a heat test in a constant temperature oven at 1800 C by taking samples from the oven at 15 minute intervals and determining the degree of decomposition the stabilizer 1 or bisphenol A are used.

  The following table 21 contains the visually recognizable degree of decomposition in the stabilizer according to the invention and the comparative stabilizer bisphenol A:
Table 21 Co-stabilizer rolled film 15 '30' 45 '60' 75 '90' 105 '120' 135 'Stabilizer 1 colorless colorless colorless colorless colorless weak weak weak yellow-black yellow yellow yellow brown bisphenol A colorless colorless colorless weak weak weak yellow-black yellow yellow yellow brown
As can be seen from the table, the stabilizer according to the invention achieves a significantly higher thermostabilizing effect than a commercially available stabilizer.



   Example 31
Stabilization of polyethylene terephthalate
In a stirred autoclave 235 parts of dimethyl tere phthalate in the presence of 0.04 parts of zinc acetate and 0.06
Parts of antimony trioxide with 170 parts of ethylene glycol
Temperatures of 150 to 210 "C, the released methanol is distilled off via a suitable column. For the subsequent polycondensation, the transesterification product is gradually heated to 285" C with stirring, the pressure at the same time gradually reduced to 0.5 Torr and these conditions maintained for 5 h. This gives a polyester with a relative viscosity of 1.65 (1% in m-cresol, 25 ° C.) and a yellowish inherent color.



   If the process described above is repeated and, however, approximately in the middle of the polycondensation time, 0.26 part of stabilizer 1 (dissolved in ethylene glycol) is obtained after the usual reaction time has elapsed a polyester with a relative viscosity of 1.60, its However, its own color is considerably lighter than that of the comparison sample that does not contain any additives. The same applies to the filaments spun from the two polyester samples.



   Example 32
Yellowing protection of dimethyl terephthalate
The dimethyl terephthalate with the additives listed in Table 22 is kept in a concentration of 0.01% for 20 hours at 200 ° C. in a glass tube under nitrogen. The values that occurred during this treatment
Yellowing is judged according to an empirical color scale, in which 5 colorlessness, 4 just noticeable slight yellowing, 3, 2, 1 successively stronger yellowing.



   Table 22 Additions Yellowing grade without additive 1 Tris-nonylphenyl phosphite 2 4-Hydroxy-3,5-di-tert-butylbenzyl-phosphoric acid diethyl ester 3-4 Stabilizer 1 5
Example 33
100 parts of polypropylene (melt index 20 g / 10 min., 230 C / 2160 g) are mixed intensively in a shaker with 0.2 parts of stabilizer No. 24 and 0.5 part of stabilizer No. 8 for 10 minutes.



   The resulting mixture is kneaded in a Brabender plastograph at 200 "C for 10 minutes, the resulting mass is then pressed in a precision press at a plate temperature of 260" C to give 0.1 mm thick films, which are then placed in an oven for one hour kept at exactly 1500 C and then quenched in tap water (temperature about 13 C). Test specimens measuring 44 × 60 mm are punched out of the foils obtained in this way.



   The testing of stabilizer no. 8 for its effectiveness as a stabilizer against damaging influences when the polymer is exposed is carried out in a Xenotest 150 exposure device from Hanau, a film which only contains stabilizer no. 24 being used as a comparison.



  To determine the end point, dumbbell-shaped tensile bars 40 mm in length are punched out of the exposed films and are periodically examined for their elongation. The end point is reached as soon as the residual elongation has dropped to 50% of its initial value.



   Table 23 Stabilizer No. hours to 50% residual elongation 24 (0.2%) 800 24 (0.2%) +
8 (0.5%) 2070 The results show that the addition of 0.5 of stabilizer No. 8 causes the polypropylene to have a light resistance which corresponds to approximately 2.6 times that of an unstabilized sample.



   Example 34
100 parts of polycarbonate powder (Lexan 145-111 "from General Electric, which had previously been dried in a vacuum oven for 12 hours at 1200 ° C.) are intensified in a shaker with 0.1 part of stabilizer No. 1 for 10 minutes mixed.



   The mixture obtained is extruded in a laboratory single-screw extruder (Killion) at a nozzle temperature of 290 ° C. and 110 rpm and then granulated. The granules required for comparison purposes without the addition of stabilizer No. 1 are produced in an analogous manner After further processing, the granules are dried in a vacuum oven at 120 ° C. for 12 hours.

 

   The effectiveness of the added stabilizer No. 1 as a stabilizer against yellowing of the material under extreme heat loads is tested in a laboratory injection molding machine at 315 "C. The yellowing is measured according to the Hunter scale (Wyszecki-Stiles, Color Science, John Wiley, NY , Page 460) judged according to increasing residence times in the injection cylinder on the resulting spray platelets.Yellowing is represented by falling values on the Hunter scale (Table 24).



   Table 24 Stabilizer Hunter values after the specified residence times in cylinder No. 2 min. 5 min. 10 min. 15 min. 20 min. 25 min.



  without stabilizer 64 59 48 41 35 34 1 (0.1%) 81 81 80 82 80 80
The results show that stabilizer no. 1 practically completely suppresses the yellowing tendency of polycarbonate at the high temperatures required for processing.



   Example 35
Stabilization of styrene-butadiene copolymers (SBR) a) Production of the test items
100 parts of an unstabilized styrene-butadiene rubber (Emulsion-SBR Synpol 1500 from Texas U. S.



  Chem. Corp.) are each with 0.125 parts of the stabilizers given in Table 25 in the Brabender plastograph at 1500 C and 60 rpm. homogenized for 10 minutes. The mixtures stabilized in this way are pressed in a plate press at 1200 C for 5 minutes to give 1 mm thick plates. The non-stabilized rubber sheet used as a comparison is produced in the same way.



  b) examination
The criterion for the protective effect of the incorporated stabilizers is the gel content determined after storage in air at elevated temperatures. For this purpose, the test samples obtained above are kept on an aluminum base in a convection oven at 100 ° C and periodically (approximately every 10 hours) their gel content is examined, which is determined as follows:
About 1 g of the samples are cut into pieces of about 3 × 3 × 1 mm and dissolved in 100 ml of n-hexane at room temperature overnight. These solutions are filtered through glass wool, the gel particles retained by the glass wool are washed with 3 times 20 ml of n-hexane, the filtered solutions are evaporated to dryness and dried to constant weight.

  The gel content of a sample is then obtained using the following calculation: Gel content in% = E-A 100
E means E = total weight of the examined
sample
A = weight of the dissolved portion of the sample examined.



   The end point is defined as the time after which a sudden increase in the gel content occurs after an induction period that is characteristic of the additive under investigation (Table 25).



   Table 25 Stabilizer No. Induction period up to the rapid (0.125%) appearance of a high gel content without stabilizer 5 hours
1 40 hours
2 35 hours 24 20 hours

 

Claims (1)

PATENT CLAIM Use of compounds of general formula I. EMI16.1 wherein X is the (p + q) -valent radical of an alkane with 1-19 carbon atoms, in which no more than three bonds to the carbonyloxy and phenyl groups emanate from the same carbon atom, an aralkane, alkene, oxaalkane or thiaalkane with 2-19 carbon atoms each, in which no more than three bonds to the carbonyloxy and phenyl groups emanate from the same carbon atom, or the direct bond, R1 and R2 independently of one another are hydrogen, alkyl with 1-8 carbon atoms, cycloalkyl with 6-8 carbon atoms or aralkyl with 7-9 carbon atoms, R3 hydrogen or methyl, Y is oxygen or sulfur, p and q are independently 1 or 2 and n is 0 or 1. For stabilizing organic material, with the exception of the use mentioned in claim of patent no. 542 652. 2. Use according to claim, wherein in formula I R3 is hydrogen. 3. Use according to patent claim, wherein in formula I R, alkyl having 1-4 carbon atoms and R3 is hydrogen. 3. Use according to claim, characterized in that the organic material is a polymer. 4. Use according to claim, characterized in that the polymer is a polyamide. 5. Use according to claim, characterized in that the polymer is a polyolefin. 6. Use according to claim, characterized in that the polyolefin is polypropylene. 7. Use according to claim, characterized in that the polyolefin is polystyrene. 8. Use according to patent claim, characterized in that the polyolefin is a terpolymer of ethylene, propylene and a diene. 9. Use according to claim, characterized in that the polymer is polyacrylonitrile. 10. Use according to claim, characterized in that the polymer is an acrylonitrile-butadiene-styrene copolymer. 11. Use according to claim, characterized in that the polymer is a halogen-containing vinyl polymer. 12. Use according to claim, characterized in that the polymer is a polyester. 13. Use according to claim, characterized in that the polymer is a polyurethane. 14. Use according to claim, characterized in that the polymer is a styrene-butadiene copolymer. 15. Use according to claim, characterized in that the polyolefin is polyethylene.