阅读说明：本技术 具有稳定作用的化合物，该化合物的制备方法，含有该稳定化化合物的组合物，使有机成分稳定的方法以及稳定化化合物的用途 (Compound with stabilizing effect, preparation method of compound, composition containing stabilizing compound, method for stabilizing organic component and application of stabilizing compound ) 是由 约翰内斯·费舍尔 埃尔克·梅奇-齐利根 鲁道夫·芬德尔 于 2018-11-14 设计创作，主要内容包括：本发明涉及具有稳定作用,特别是对于有机材料的氧化、热和/或光化降解或破坏提供稳定作用的新型化合物。这些化合物表示为下面指定的通式I。本发明还涉及制备这种化合物的方法,涉及含有所述化合物的组合物,涉及通过所述稳定化化合物使有机化合物稳定的方法,并且涉及所述稳定化化合物使有机材料稳定的用途。(The present invention relates to novel compounds having a stabilizing effect, in particular with respect to oxidative, thermal and/or photochemical degradation or destruction of organic materials. These compounds are represented by the general formula I indicated below. The invention also relates to a method for producing such a compound, to a composition containing said compound, to a method for stabilizing an organic compound by means of said stabilizing compound, and to the use of said stabilizing compound for stabilizing an organic material.)

1. A compound according to formula I

Wherein the variables A, B, D, R, B, x, y, z independently of one another have the following definitions:

a is an aromatic, unsaturated or saturated residue;

b is O or NH;

d is a straight or branched aliphatic residue having 1 to 12 carbon atoms;

r is a residue having at least one steric hindering group and at least one hydroxyl group;

b is 0 or 1;

x is 0 to 12;

y is 1 to 4; and

z is 1 to 6.

2. A compound according to the preceding claim, characterized in that the variable a is selected from the individual z-valent cyanuric acid residues, wherein z has the meaning given in claim 1; a triazine residue; a cyclic aliphatic hydrocarbon residue having 5 to 36 carbon atoms, particularly cyclohexyl; aromatic hydrocarbon residues, in particular phenyl; and a straight or branched chain aliphatic hydrocarbon residue having 2 to 36 carbon atoms.

3. Compound according to any one of the preceding claims, characterized in that the variable R represents a group having at least one sterically hindered hydroxyphenyl residue, and in particular has the following meaning

Wherein

E is identical or different on each occurrence and denotes a straight-chain aliphatic, branched aliphatic or cycloaliphatic alkyl residue having from 1 to 18 carbon atoms or an aromatic residue having from 6 to 36 carbon atoms or hydrogen, in particular tert-butyl or methyl;

a is 1 or 0; and

c is 0,1, 2,3 or 4.

4. A compound according to any one of the preceding claims, characterized in that the variables x, y and z have the following meanings, independently of one another:

x is 0 or 1;

y is 1 or 2; and

z is 1,2,3 or 4.

5. A compound according to any one of the preceding claims, wherein the compound of formula I is selected from:

wherein Z has the following meaning;

the variables B, D, R, B, x, y and z are as defined in claim 1.

6. A compound according to any one of the preceding claims, wherein D is selected from-CH₂-or a 1,2, 3-propynyl residue.

7. The compound according to any one of the preceding claims, selected from:

wherein the residues Y have the following meanings independently of one another at each occurrence:

or

Among the above residues, the tBu residue may be replaced with a methyl group and/or hydrogen in whole or in part.

8. A process for the preparation of a compound of formula I according to any one of the preceding claims, wherein a compound of formula ii is reacted

With a thiol according to one of the formulae IIIa or IIIb

And, in the case of using the thiol of the formula IIIa, the reaction product obtained by reacting the compounds of the formulae II and IIIa is subsequently reacted with the compound of the formula IV

X-R

Formula IV

Wherein

X is a leaving group; and

the meanings of the variables A, B, D, R, B, x, y and z in the compounds of the formulae IIa, IIb and III are as defined in claim 1.

9. Process according to the preceding claim, characterized in that X is a hydrocarbyloxy group, a halogen, a trifluoromethanesulfonate group, a tosylate group, a mesylate group, a fluorosulfonate group or a perfluorobutanesulfonate group.

10. The process according to either of the two preceding claims, characterized in that the reaction of the compound according to formula II with the thiol is carried out in the presence of an excess of thiol according to one of the formulae IIIa or IIIb with respect to the unsaturated function of the compound according to formula II.

11. A composition comprising or consisting of at least one organic component to be stabilized; and at least one compound according to any one of claims 1 to 7.

12. Composition according to the preceding claim, characterized in that the component to be stabilized is chosen from plastics, oils, lubricants and fats.

13. The composition according to any one of the two preceding claims, comprising or consisting of

95.00 to 99.99% by weight, preferably 97.00 to 99.95% by weight, particularly preferably 98.00 to 99.90% by weight, of at least one component to be stabilized; and

0.01 to 5.00 wt.%, preferably 0.05 to 3.00 wt.%, particularly preferably 0.10 to 2.00 wt.% of at least one compound according to any one of claims 1 to 7.

14. The composition according to any one of claims 11 to 13, characterized in that the further at least one additive is selected from the group consisting of UV absorbers, light stabilizers, antioxidants, hydroxylamines, benzofurans, metal deactivators, filler deactivators, antiozonants, nucleating agents, impact strength improvers, plasticizers, lubricants, rheology modifiers, thixotropic agents, chain extenders, processing aids, mold release aids, flame retardants, pigments, dyes, optical brighteners, biocides, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anticrosslinking agents, hydrophilic agents, hydrophobic agents, binders, dispersants, degradation additives, antifoaming aids, odor traps, marking agents, antifogging agents, fillers and reinforcing agents.

15. A composition according to any one of claims 11 to 14, characterised in that the at least one further additive included is selected from phosphites, phosphonites, hydroxylamines or nitrones.

16. A method for stabilizing organic components to be stabilized, in particular against oxidative, thermal or photochemical degradation or destruction, wherein at least one compound according to any of claims 1 to 7 is mixed with or added to the organic component to be stabilized.

17. Use of a compound according to any one of claims 1 to 7 to stabilize an organic material against oxidative, thermal or photochemical degradation or destruction.

Preferred embodiments:

the method comprises the following steps:

the conversion of the allyl compound or vinyl compound or michael acceptor is preferably carried out in a first reaction step with a thiol compound additionally comprising an alcohol group by means of a catalyst, and in a second reaction step the alcohol group is transesterified with an ester compound comprising a sterically hindered phenol group. Mercaptoethanol, 3-mercaptopropanol, 2-mercaptopropanol and 1-mercaptobutanol and thioglycerol are particularly preferred as thiol compounds. Another preferred process is the conversion of thiopropyl compounds comprising a sterically hindered phenol group, for example of the formula

The reaction is preferably carried out in the presence of a catalyst; preferred catalysts are free-radical-generating compounds, such as photoinitiators, azo initiators or peroxides, and for Michael acceptors, preferred catalysts are bases, such as sodium methoxide, triethylamine, or nucleophiles, such as 1-methylimidazolyl imide, or alkyl phosphines, such as dimethylphenyl phosphine.

The reaction can be carried out either in bulk or in a solvent. Preferred solvents are inert solvents, such as toluene, N-methyl-2-pyrrolidone or N, N-dimethylformamide. In addition, methanol was used as a solvent. Particular preference is given to the reaction being carried out in bulk, preferably with an excess of the thiol component as solvent/diluent.

The second reaction step is preferably carried out, if desired, by transesterification of the alcohol group formed in the middle with an ester having a sterically hindered phenol group. Corresponding processes and catalysts for transesterification are familiar to the skilled worker and are described, for example, in J.Otera, chem.Rev.1993,93,1449-1470 (cf. annex) or WO 86/00301 (cf. annex) or WO2004/033699 (cf. annex). Preferred catalysts are metal compounds such as tin organyl groups or titanates.

The application is as follows:

plastics and oils and fats are preferred organic materials which can be stabilized by the stabilizers according to the invention.

If the organic materials are greases, they may be based on mineral oils, vegetable or animal fats, or also on oils, fats or waxes, for example based on synthetic esters. Vegetable oils and fats such as palm oil, olive oil, rapeseed oil, linseed oil, soybean oil, sunflower seed oil, castor oil; animal fat such as fish oil or sheep oil.

The compounds according to the invention can also be used as stabilizers for lubricants, hydraulic oils, engine oils, turbine oils, transmission oils, metal working fluids, or as greases. These mineral or synthetic lubricants are mainly based on hydrocarbons.