Efficient phosphorous stabilizers based on diphenylamine and heterocyclic diphenylamine derivatives

Patent metadata

Field	Value
Publication number	US-11634560-B2
Application number	US-201816488902-A
Country	US
Kind code	B2
Filing date	Feb 14, 2018
Priority date	Feb 27, 2017
Publication date	Apr 25, 2023
Grant date	Apr 25, 2023

Abstract

The present invention relates to the use of efficient phosphorous substances, in particular based on diphenylamine and heterocyclic diphenylamine derivatives as stabilizers for organic materials, in particular for plastic materials, against oxidative, thermal and/or actinic degradation. The present invention additionally relates to an organic material that has been correspondingly stabilized as described above. The invention further relates to a method of stabilizing organic materials and to specific stabilizers.

First claim

We claim:

1. A method of stabilizing an organic material comprising working into the organic material one or more compounds in accordance with general formula I,
A-B y ,  Formula I,

wherein A is:

and y=1, or
wherein A is:

and y=2, or
wherein A is:

and y=1,
and B is:

wherein, respectively independently of one another,
R 1 to R 10 are selected from hydrogen, alkyl residues, aryl residues, alky aryl residues, aryl alkyl residues, and heterocyclic residues.

2. The method of claim 1 , wherein the organic material is selected from plastics, coatings, lubricants, hydraulic oils, engine oils, turbine oils, transmission oils, metal machining liquids, chemicals, and monomers.

3. The method of claim 1 , wherein the compound or mixture of compounds of formula I is included in the organic material at a weight proportion of 0.01 to 10 wt. %.

4. The method of claim 1 , wherein the plastic is selected from
a) polymers of olefins or diolefins, polyalkylene carbon monoxide copolymers, and copolymers in the form of static structures or block structures, graft polymers, and blends thereof,
b) polystyrene, polymethylstyrene, poly-alpha-methyl styrene, polyvinyl naphthalene, polyvinyl biphenyl, polyvinyl toluol, styrene butadiene (SB), styrene butadiene styrene (SBS), styrene ethylene butylene styrene (SEBS), styrene ethylene propylene styrene, styrene isoprene, styrene isoprene styrene (SIS), styrene butadiene acrylonitrile (ABS), styrene acrylonitrile (SAN), styrene acrylonitrile acrylate (ASA), styrene ethylene, styrene maleic acid anhydride polymers, corresponding graft copolymers, and graft copolymers of methylmethacrylate, styrene butadiene, and ABS (MABS), and hydrated polystyrene derivatives,
c) halogen-containing polymers, copolymers of vinyl chloride and vinylidene chloride or of vinyl chloride and vinyl acetate, chlorinated polyethylene, polyvinylidene fluoride, epichlorohydrin homopolymers and copolymers thereof,
d) polymers of unsaturated esters, polyacrylonitrile, polyacrylamides, and polyacrylonitrile-poly alkyl acrylate,
e) polymers of unsaturated alcohols and derivatives,
f) polyacetates,
g) polyphenylene oxides and blends with polystyrene or polyamides,
h) polymers of cyclic ethers,
i) polyurethanes of hydroxy terminated polyethers or polyesters and aromatic or aliphatic isocyanates,
j) polyamides, blends of and blends of polyamides and polyolefins,
k) polyimides, polyamide imides, polyether imides, polyester imides, poly(ether)ketones, polysulfones, polyether sulfones, polyaryl sulfones, polyphenylene sulfides, polybenzimidazoles, polyhydantoins,
l) polyesters of aliphatic or aromatic dicarboxylic acids and diols or of hydroxy carboxylic acids,
m) polycarbonates, polyester carbonates, and blends,
n) cellulose derivatives,
o) epoxy resins comprising difunctional or polyfunctional epoxy compounds, optionally in combination with hardeners,
p) phenol resins, urea formaldehyde resins, melamine formaldehyde resins,
q) unsaturated polyester resins of unsaturated dicarboxylic acids and diols with vinyl compounds,
r) silicones,
s) and mixtures, combinations, or blends of two or more of the above-named polymers.

5. The method of claim 1 , wherein the plastic is selected from
a) polyethylene, polypropylene, polyisobutylene, poly-4-methyl-pentene-1, polybutadiene, polyisoprene, polycyclooctene, polyalkylene carbon monoxide copolymers, polypropylene-polyethylene copolymers (EP), EPM copolymer, EPDM copolymer, ethylene-vinyl acetate (EVA), ethylene-acrylic ester, ethylene-acrylic acid and their salts, ethylene-acrylic acid-glycidyl(meth)acrylate, polypropylene graft maleic acid anhydride, polypropylene graft acrylic acid, polyethylene graft acrylic acid, polyethylene polybutylacrylate graft maleic acid anhydride, and blends thereof,
b) polystyrene, polymethylstyrene, poly-alpha-methyl styrene, polyvinyl naphthalene, polyvinyl biphenyl, polyvinyl toluol, styrene butadiene (SB), styrene butadiene styrene (SBS), styrene ethylene butylene styrene (SEBS), styrene ethylene propylene styrene, styrene isoprene, styrene isoprene styrene (SIS), styrene butadiene acrylonitrile (ABS), styrene acrylonitrile (SAN), styrene acrylonitrile acrylate (ASA), styrene ethylene, styrene maleic acid anhydride polymers, graft copolymers of styrene on butadiene, graft copolymers of maleic acid anhydride on SBS or SEBS, and graft copolymers of methylmethacrylate, styrene butadiene, and ABS (MABS), and hydrated polystyrene derivatives,
c) polyvinyl chloride (PVC), polychloroprene, polyvinylidene chloride (PVDCl), copolymers of vinyl chloride and vinylidene chloride, copolymers of vinyl chloride and vinyl acetate, chlorinated polyethylene, polyvinylidene fluoride, epichlorohydrin homopolymers and copolymers thereof,
d) polymethyl methacrylate (PMMA), polybutyl acrylate, polylauryl acrylate, polystearyl acrylate, polyglycidyl acrylate, polyglycidyl methacrylate, polyacrylonitrile, polyacrylamides, and polyacrylonitrile-poly alkyl acrylate copolymers,
e) polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyallyl phthalate, and polyallyl melamine,
f) polyoxymethlyene (POM) or copolymers with butanal,
g) polyphenylene oxides and blends with polystyrene or polyamides,
h) polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide, or polytetrahydrofuran,
i) linear polyurethanes (TPU) and polyureas,
j) polyamide-6, 6.6, 6.10, 4.6, 4.10, 6.12, 10.10, 10.12, 12.12, polyamide 11, polyamide 12 and (partly) aromatic polyamides such as polyphthalamides, blends of PA-6 and PA 6.6 and blends of polyamides and blends of PA/PP,
k) polyimides, polyamide imides, polyether imides, polyester imides, poly(ether)ketones, polysulfones, polyether sulfones, polyaryl sulfones, polyphenylene sulfides, polybenzimidazoles, or polyhydantoins,
l) polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), polyethylene naphthalate (PEN), poly-1,4-dimethylol cyclohexane terephthalate, polyhydroxy benzoate, polyhydroxy napththalate, poly lactic acid (PLA), polyhydroxy butyrate (PHB), polyhydroxy valerate (PHV), polyethylene succinate, polytetramethylene succinate, or polycaprolactone,
m) polycarbonates, polyester carbonates, PC/ABS, PC/PBT, PC/PET/PBT, or PC/PA blends,
n) cellulose nitrate, cellulose acetate, cellulose propionate, or cellulose butyrate,
o) epoxy resins comprising difunctional or polyfunctional epoxy compounds in combination with a hardener based on amines, anhydrides, dicyandiamide, mercaptans, isocyanates or catalytically acting hardeners,
p) phenol formaldehyde resins, urea formaldehyde resins, or melamine formaldehyde resins,
q) unsaturated polyester resins of unsaturated dicarboxylic acids and diols with vinyl compounds,
r) silicones,
s) and mixtures, combinations, or blends of two or more of the above-named polymers.

6. The method of claim 1 , which includes adding at least one further additive selected from the group consisting of UV absorbers, light stabilizers, hydroxylamine based stabilizers, benzofuranone based stabilizers, nucleation agents, toughening agents, plasticizers, mold lubricants, rheology modifiers, chain extenders, processing aids, pigments, dyestuffs, optical brighteners, antimicrobial agents, antistatic agents, slip agents, anti-blocking agents, coup

Assignees

• Fraunhofer Ges Forschung

Inventors

• Ciesielski Michael
• Briesenick Max
• Pfaendner Rudolf

Classifications

• C07F9/247

  of aromatic amines (N-C aromatic linkage) · CPC title

• C07F9/4476

  of aromatic amines (N-C aromatic linkage) · CPC title

• C07F9/657163

  the ring phosphorus atom being bound to at least one carbon atom · CPC title

• C07F9/657154

  Cyclic esteramides of oxyacids of phosphorus · CPC title

• C08K5/5399 Primary

  Phosphorus bound to nitrogen · CPC title