# Patent

## Title
S-perfluoroalkyl substituted hydroxybenzylthioethers and derivatives as surface modifiers

## Abstract

The invention describes a process for reducing the surface energy of organic materials such as for example increasing the oil and water repellency and stain release of organic materials, which comprises treating the organic material with at least a compound of the formula I wherein the general symbols are as defined in claim 1; especially wherein at least one of the radicals R2, R3 or R4 is —CH(R11)—S(O)p—R12; R11 is hydrogen, C1-C8alkyl, unsubstituted or with C1-C4alkyl substituted phenyl; R12 is a monovalent perfluorinated alkyl or alkenyl, linear or branched organic radical having four to twenty fully fluorinated carbon atoms, and p is 0, 1 or 2.

## Background
The present invention relates to a process for reducing the surface energy of organic materials which comprises treating the organic material with at least a S-perfluoroalkyl substituted hydroxybenzylthioether and derivative thereof; to new S-perfluoroalkyl substituted hydroxybenzylthioethers and derivatives thereof; and to compositions comprising an organic material, for example a synthetic polymer, which is susceptible to oxidative, thermal or light-induced degradation and the new S-perfluoroalkyl substituted hydroxybenzylthioethers and derivatives thereof.
The use of various fluorochemical compositions on fibers and fibrous substrates, such as for example textiles, carpets, paper, leather and non-woven webs to impart oil and water repellency is known for example in U.S. Pat. No. 6,127,485. This reference discloses hydrophobic and oleophobic fibers, films and molded articles comprising synthetic organic polymer wherein dispersed within the fiber, fabric or molded article and present at the surface of the fiber, fabric or molded article are fluorochemical compounds.
The known fluorochemicals do not satisfy in every respect the high requirements which a melt additive is required to meet as reducers of surface energy for organic materials, for example, for increasing the oil and water repellency of organic materials.
It has now been found that S-perfluoroalkyl substituted hydroxybenzylthioethers are useful for various technical applications such as for example for increasing the oil and water repellency of organic materials like for example synthetic polymers. It has also now been found that S-perfluoroalkyl substituted hydroxybenzylthioethers are useful for various technical applications such as for example the making of improved electret articles. In general, a electret is defined as a dielectric material, which exhibits an external electric field in the absence of an applied field [see also G. M. Sessler in Electrets; Sessler, G. M., Ed.; Laplacian Press: Morgan Hill, Calif., 1998; Vol. 1, Chapter 1].
The present invention therefore provides a process for reducing the surface energy of organic materials which comprises treating the organic material with at least a compound of the formula I




wherein, when n is 1,

R1 is hydrogen, C1-C25alkyl, C2-C25alkenyl, —CO—R5, —CH(R10)CO—R5, —C(R10)2CO—R5, —CO—N(R6)—R7, —CH(R10)CO—N(R6)—R7, —C(R10)2CO—N(R6)—R7, —CH(R10)COOR5 or —C(R10)2CO—OR5;

when n is 2,

R1 is unsubstituted or with C1-C4alkyl, benzyl or phenyl substituted C1-C24alkylene; with oxygen or sulfur interrupted C2-C24alkylene; —CO—R8—CO—, —CH(R10)CO—R8—CO—CH(R10)—, —C(R10)2CO—R8—CO—C(R10)2—, —CO—N(R6)—R9—N(R6)—CO—, —CH(R10)CO—N(R6)—R9—N(R6)—CO—CH(R10)—, —C(R10)2CO—N(R6)—R9—N(R6)—CO—C(R10)2—, —CH(R10)CO—O—R9—O—CO—CH(R10)— or —C(R10)2CO—O—R9—O—CO—C(R10)2—;

when n is 3,

R1 is





R2, R3 and R4 independently of each other are hydrogen, C1-C25alkyl, C2-C25alkenyl, —CH(R11)—S(O)p—R12,





with the proviso that at least one of the radicals R2, R3 or R4 is —CH(R11)—S(O)p—R12; R5 is C1-C25alkyl, C2-C25alkenyl, unsubstituted or with C1-C4alkyl or halogen substituted phenyl; or C7-C12-phenylalkyl,

R6 is hydrogen or C1-C4alkyl,

R7 is hydrogen, C1-C25alkyl, unsubstituted or with C1-C4alkyl or halogen substituted phenyl;

R8 is phenylene, unsubstituted or with C1-C4alkyl, benzyl or phenyl substituted C1-C24alkylene; with oxygen or sulfur interrupted C2-C24alkylene;

R9 is a direct bond, unsubstituted or with C1-C4alkyl, benzyl or phenyl substituted C2-C24alkylene; or with oxygen or sulfur interrupted C2-C24alkylene;

R10 is hydrogen or C1-C8alkyl,

R11 is hydrogen, C1-C8alkyl, unsubstituted or with C1-C4alkyl substituted phenyl;

R12 is a monovalent perfluorinated alkyl or alkenyl, linear or branched organic radical having four to twenty fully fluorinated carbon atoms,

R13 is hydrogen, C1-C25alkyl, C2-C25alkenyl, —CO—R5, —CO—N(R6)—R7 or —CH2—CO—N(R6)—R7,

R14 is hydrogen, C1-C25alkyl, C2-C25alkenyl or —CH(R11)—S(O)p—R12,

R15 is hydrogen, C1-C25alkyl, C2-C25alkenyl or —CH(R11)—S(O)p—R12,

R16 is unsubstituted or with C1-C4alkyl substituted methylene, —S—, —S(O)—, —S(O)2— or —CO—;

R17 is C1-C4alkyl,

n is 1, 2 or 3, and

p is 0, 1 or 2.

Alkyl having up to 25 carbon atoms is a branched or unbranched radical, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, icosyl or docosyl.
Alkenyl having 2 to 25 carbon atoms is a branched or unbranched radical such as, for example, propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl.
Unsubstituted or with C1-C4alkyl, benzyl or phenyl substituted C1-C24alkylene is a branched or unbranched radical such as, for example methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, methylmethylene, ethylmethylene, 2-methylpropylene, 2-phenylpropylene, 2-benzylpropylene, benzylmethylene or phenylmethylene (benzylidene).
C2-C24Alkylene interrupted by oxygen or sulfur is, for example, —CH2—O—CH2—, —CH2—S—CH2—, —CH2—N(CH3)—CH2—, —CH2—O—CH2CH2—, —CH2CH2—O—CH2CH2—, —CH2CH2—O—CH2CH2—O—CH2CH2—, —CH2CH2—(O—CH2CH2—)2O—CH2CH2—, —CH2CH2—(O—CH2CH2—)3O—CH2CH2—, —CH2CH2—(O—CH2CH2—)4O—CH2CH2— or —CH2CH2—S—CH2CH2—.
C1-C4Alkyl or halogen substituted phenyl which contains preferably from 1 to 3, especially 1 or 2, alkyl or halogen groups, is, for example, o-, m- or p-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 2-chlorophenyl, 4-chlorophenyl or 2-methyl-4-chlorophenyl.
C7-C12Phenylalkyl unsubstituted or substituted on the phenyl radical by from 1 to 3 C1-C4alkyl groups is, for example, benzyl, α-methylbenzyl, α,α-dimethylbenzyl, 2-phenylethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl, 2,6-dimethylbenzyl or 4-tert-butylbenzyl. Preference is given to benzyl.
A monovalent perfluorinated alkyl or alkenyl, linear or branched organic radical having four to twenty fully fluorinated carbon atoms is for example —CH2CH2(CF2)mCF3 wherein m is 3 to 19, preferably 3 to 12. The perfluoroalkyl moieties represent also mixtures of perfluoroalkyl moieties which means that R12 usually concomitantly contains a small fraction of perfluoroalkyl groups with a lower number of carbon atoms and small fraction of perfluoroalkyl groups with a higher number of carbon atoms.
An interesting process comprises a compound of the formula I wherein, when n is 1, R1 is hydrogen, C1-C18alkyl, C2-C18alkenyl, —CO—R5, —CO—N(R6)—R7 or —CH2—CO—N(R6)—R7;
when n is 2,
R1 is unsubstituted or with C1-C4alkyl, benzyl or phenyl substituted C1-C18alkylene; with oxygen or sulfur interrupted C2-C18alkylene; —CO—R8—CO—, —CO—N(R6)—R9—N(R6)—CO— or —CH(R10)—CO—N(R6)—R9—N(R6)—CO—CH(R10)—;
when n is 3,
R1 is




R2, R3 and R4 independently of each other are hydrogen, C1-C18alkyl, C2-C18alkenyl, —CH(R11)—S(O)p—R12,





with the proviso that at least one of the radicals R2, R3 or R4 is —CH(R11)—S(O)p—R12;

R5 is C1-C18alkyl, C2-C18alkenyl, unsubstituted or with C1-C4alkyl or halogen substituted phenyl; or C7-C12phenylalkyl,

R6 is hydrogen or C1-C4alkyl,

R7 is hydrogen, C1-C18alkyl, unsubstituted or with C1-C4alkyl or halogen substituted phenyl;

R8 is phenylene, unsubstituted or with C1-C4alkyl, benzyl or phenyl substituted C1-C24alkylene; with oxygen or sulfur interrupted C2-C24alkylene;

R9 is a direct bond or unsubstituted or with C1-C4alkyl, benzyl or phenyl substituted C2-C18alkylene;

R10 is hydrogen or C1-C8alkyl,

R11 is hydrogen, C1-C8alkyl, unsubstituted or with C1-C4alkyl substituted phenyl;

R12 is a monovalent perfluorinated alkyl or alkenyl, linear or branched organic radical having four to twenty fully fluorinated carbon atoms,

R13 is hydrogen, C1-C18alkyl, C2-C18alkenyl, —CO—R5, —CO—N(R6)—R7 or —CH2—CO—N(R6)—R7,

R14 is hydrogen, C1-C18alkyl, C2-C18alkenyl or —CH(R11)—S(O)p—R12,

R15 is hydrogen, C1-C18alkyl, C2-C18alkenyl or —CH(R11)—S(O)p—R12,

R16 is unsubstituted or with C1-C4alkyl substituted methylene, —S—, —S(O)—, —S(O)2— or —CO—;

R17 is C1-C4alkyl,

n is 1, 2 or 3, and

p is 0, 1 or 2.

A preferred process comprises a compound of the formula I wherein R12 is saturated and contains 4-15 carbon atoms, is fully fluorinated and contains at least one terminal perfluoromethyl group.
Preference is also given to a process comprising a compound of the formula I wherein R2, R3 and R4 independently of each other are hydrogen, C1-C4alkyl, —CH(R11)—S(O)p—R12 or




with the proviso that at least one of the radicals R2, R3 or R4 is —CH(R11)—S(O)p—R12;

R11 is hydrogen, C1-C8alkyl, unsubstituted or with C1-C4alkyl substituted phenyl;

R12 is a monovalent perfluorinated alkyl or alkenyl, linear or branched organic radical having four to twenty fully fluorinated carbon atoms,

R13 is hydrogen, C1-C18alkyl, C2-C18alkenyl or acetyl,

R14 is hydrogen, C1-C18alkyl, C2-C18alkenyl or —CH(R11)—S(O)p—R12,

R15 is hydrogen, C1-C18alkyl, C2-C18alkenyl or —CH(R11)—S(O)p—R12,

R16 is unsubstituted or with C1-C4alkyl substituted methylene, —S—, —S(O)—, —S(O)2— or —CO—; and

p is 0, 1 or 2.

Particular preference is given to a process comprising a compound of the formula I wherein,
when n is 1,
R1 is hydrogen, C1-C18alkyl, —CO—R5, —CO—N(R6)—R7 or —CH2—CO—N(R6)—R7;
when n is 2,
R1 is unsubstituted or with C1-C4alkyl substituted C1-C8alkylene; —CO—R8—CO—, —CO—N(R6)—R9—N(R6)—CO— or —CH(R10)—CO—N(R6)—R9—N(R6)—CO—CH(R10)—,
when n is 3,
R1 is




R2, R3 and R4 independently of each other are hydrogen, C1-C8alkyl, —CH(R11)—S(O)p—R12,





with the proviso that at least one of the radicals

R2, R3 or R4 is —CH(R11)—S(O)p—R12;

R5 is C1-C18alkyl, unsubstituted or with C1-C4alkyl substituted phenyl; or C7-C12-phenylalkyl,

R6 is hydrogen or C1-C4alkyl,

R7 is hydrogen, C1-C8alkyl, unsubstituted or with C1-C4alkyl substituted phenyl;

R8 is phenylene, unsubstituted or with C1-C4alkyl substituted C1-C18alkylene;

R9 is unsubstituted or with C1-C4alkyl substituted C2-C18alkylene;

R10 is hydrogen or C1-C8alkyl,

R11 is hydrogen, C1-C8alkyl, unsubstituted or with C1-C4alkyl substituted phenyl;

R12 is saturated and contains 4-15 carbon atoms, is fully fluorinated and contains at least one terminal perfluoromethyl group,

R13 is hydrogen, C1-C12alkyl, —CO—R5, —CO—N(R6)—R7 or —CH2—CO—N(R6)—R7,

R14 is hydrogen, C1-C12alkyl or —CH(R11)—S(O)p—R12,

R15 is C1-C18alkyl or —CH(R11)—S(O)p—R12,

R16 is unsubstituted or with C1-C4alkyl substituted methylene;

n is 1, 2 or 3, and

p is 0.

Of interest is a process comprising a compound of the formula I wherein R1 is hydrogen, C1-C18alkyl, —CO—R5, —CO—N(R6)—R7 or —CH2—CO—N(R6)—R7,
when n is 2,
R1 is C1-C8alkylene, —CO—R8—CO—, —CO—N(R6)—R9—N(R6)—CO— or —CH(R10)—CO—N(R6)—R9—N(R6)—CO—CH(R10)—,
when n is 3,
R1 is




R2, R3 and R4 independently of each other are hydrogen, C1-C8alkyl, —CH(R11)—S(O)p—R12,





with the proviso that at least one of the radicals

R2, R3 or R4 is —CH(R11)—S(O)p—R12;

R5 is C1-C18alkyl, unsubstituted or with C1-C4alkyl substituted phenyl; or benzyl,

R6 is hydrogen,

R7 is hydrogen, C1-C8alkyl, unsubstituted or with C1-C4alkyl substituted phenyl;

R8 is phenylene or C1-C18alkylene,

R9 is C2-C18alkylene,

R10 is C1-C4alkyl,

R11 is hydrogen, C1-C8alkyl, unsubstituted or with C1-C4alkyl substituted phenyl;

R12 is —CH2CH2(CF2)mCF3,

R13 is hydrogen or —CO—R5,

R14 is hydrogen or C1-C8alkyl,

R15 is C1-C4alkyl or —CH(R11)—S(O)p—R12,

R16 is methylene,

m is 3 to 12,

n is 1, 2 or 3, and

p is 0.

Also of interest is a process comprising a compound of the formula I, wherein
when n is 1,
R1 is hydrogen, C1-C12alkyl, —CO—R5, —CO—N(R6)—R7 or —CH2—CO—N(R6)—R7;
when n is 2,
R1 is methylene, —CO—R8—CO— or —CH(R10)—CO—N(R6)—R9—N(R6)—CO—CH(R10)—;
when n is 3,
R1 is




R2, R3 and R4 independently of each other are hydrogen, C1-C4alkyl, —CH(R11)—S(O)p—R12 or





with the proviso that at least one of the radicals R2, R3 or R4 is —CH(R11)—S(O)p—R12;

R5 is C1-C18alkyl,

R6 is hydrogen,

R7 is hydrogen, C1-C6alkyl, unsubstituted or with C1-C4alkyl substituted phenyl;

R8 is phenylene,

R9 is ethylene,

R10 is methyl,

R11 is hydrogen, C1-C8alkyl, unsubstituted or with methyl substituted phenyl;

R12 is —CH2CH2(CF2)mCF3,

R13 is hydrogen or acetyl,

R14 is C1-C4alkyl,

R15 is —CH(R11)—S(O)p—R12,

R16 is methylene,

m is 3 to 12,

n is 1, 2 or 3, and

p is 0.

The compounds of the formula I can be prepared by methods known in the art or in analogy to the process disclosed for example in U.S. Pat. No. 4,874,885.
The compounds of the formula I are suitable as oil and water repellency agents for organic materials. Examples of organic materials which may be present in the compositions of the invention are following materials:
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:

    
    
        a) radical polymerisation (normally under high pressure and at elevated temperature.
        b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either π- or σ-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(III) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, IIa and/or IIIa of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
    
    


2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers (e.g. ethylene/norbornene like COC), ethylene/1-olefins copolymers, where the 1-olefin is generated in-situ; propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/vinylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.
4. Hydrocarbon resins (for example C5-C9) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.
Homopolymers and copolymers from 1.)-4.) may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).
6. Aromatic homopolymers and copolymers derived from vinyl aromatic monomers including styrene, α-methylstyrene, all isomers of vinyl toluene, especially p-vinyltoluene, all isomers of ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, and mixtures thereof. Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
6a. Copolymers including aforementioned vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/butadiene, styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.
6b. Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6.), especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).
6c. Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6a.).
Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
7. Graft copolymers of vinyl aromatic monomers such as styrene or α-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.
8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
9. Polymers derived from α,β-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.
12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethyllene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.
15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).
17. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
19. Polycarbonates and polyester carbonates.
20. Polysulfones, polyether sulfones and polyether ketones.
21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.
22. Drying and non-drying alkyd resins.
23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.
25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.
26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
27. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
28. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
29. Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emulsions of such materials.
30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carboxylated styrene/butadiene copolymers.
Preferred organic materials are natural, semi-synthetic or, preferably, synthetic polymers.
Particularly referred organic materials are synthetic polymers, most preferably thermoplastic polymers. Especially preferred organic materials are polyacetals, polyolefins such as polypropylene or polyethylene, polyether/polyurethanes, polyesters such as polybutylene terephthalate, polycarbonates or polyamides.
To be singled out for special mention is the efficacy of the compounds of the formula I as reducers of surface energy of the organic materials. Organic materials with low surface energy have intrinsically better properties like for example water and oil repellency, hydrophobicity, barrier properties, easy to clean, self cleaning, antigravity or solvent resistance.
The compounds of the formula I will preferably be added to the organic material in concentrations of 0.01 to 10%, preferably 0.01 to 2%, typically 0.1 to 2%, based on the weight of said material.
In addition to the compounds of the formula I, the process of the invention may comprise further additives, such as for example the following:
1. Antioxidants
1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol, 2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol, 2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.
1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.
1.3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).
1.5. Hydroxylated thiodiphenyl ethers, for example 2, 2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol), 4,4′-thiobis(6-tert-butyl-2-methylphenol), 4,4′-thiobis(3,6-di-sec-amylphenol), 4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.
1.6. Alkylidenebisphenols, for example 2, 2′-methylenebis(6-tert-butyl-4-methylphenol), 2,2′-methylenebis(6-tert-butyl-4-ethylphenol), 2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2′-methylenebis(4-methyl-6-cyclohexylphenol), 2,2′-methylenebis(6-nonyl-4-methylphenol), 2,2′-methylenebis(4,6-di-tert-butylphenol), 2,2′-ethylidenebis(4,6-di-tert-butylphenol), 2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4′-methyllenebis(2,6-di-tert-butylphenol), 4,4′-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene, bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methyl phenyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methyl phenyl)pentane.
1.7. O-, N- and S-benzyl compounds, for example 3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
1.9. Aromatic hydroxybenzyl compounds, for example 1, 3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
1.10. Triazine compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.
1.11. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methyl benzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
1.12. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane; 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]-undecane.
1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Naugard® XL-1, supplied by Uniroyal).
1.18. Ascorbic acid (vitamin C)
1.19. Aminic antioxidants, for example N,N′-di-isopropyl-p-phenylenediamine, N,N′-di-secbutyl-p-phenylenediamine, N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N′-bis(1-methylheptyl)-p-phenylenediamine, N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine, N,N′-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine, N-cyclohexyl-N′-phenyl-p-phenylenediamine, 4-(ptoluenesulfamoyl)diphenylamine, N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl/tert-octyl-phenothiazines, a mixture of mono- and dialkylated tert-octyl-phenothiazines, N-allylphenothiazine, N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene.
2. UV Absorbers and Light Stabilizers
2.1. 2-(2′-Hydroxyphenyl)benzotriazoles, for example 2-(2′-hydroxy-5′-methylphenyl)-benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole, 2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole, 2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole, 2-(3′,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3′-tert-butyl-5′-[2-(2-ethyl hexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenyl benzotriazole, 2,2′-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterification product of 2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300; [R—CH2CH2—COO—CH2CH2—]2, where R=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-yl phenyl, 2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazole; 2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)phenyl]benzotriazole.
2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxy derivatives.
2.3. Esters of substituted and unsubstituted benzoic acids, for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxy-cinnamate, methyl α-carbomethoxy-p-methoxycinnamate, N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline, neopentyl tetra(α-cyano-β,β-diphenylacrylate.
2.5. Nickel compounds, for example nickel complexes of 2,2′-thio-bis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
2.6. Sterically hindered amines, for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tertoctylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, 1,1′-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cyclic condensates of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); a condensate of 1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [192268-64-7]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide, N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9-tetramethyl-2-cyclounaecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, a diester of 4-methoxymethylenemalonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, a reaction product of maleic acid anhydride-α-olefin copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine, 2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-4-yl)-N-butylamino]-6-(2-hydroxyethyl)amino-1,3,5-triazine, 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, 5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, Sanduvor (Clariant; CAS Reg. No. 106917-31-1], 5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, the reaction product of 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidine-4-yl)butylamino]-6-chloro-s-triazine with N,N′-bis(3-aminopropyl)ethylenediamine), 1,3,5-tris(N-cyclohexyl-N-(2,2,6,6-tetramethylpiperazine-3-one-4-yl)amino)-s-triazine, 1,3,5-tris(N-cyclohexyl-N-(1,2,2,6,6-pentamethyl piperazine-3-one-4-yl)amino)-s-triazine.
2.7. Oxamides, for example 4, 4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with 2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- and p-methoxydisubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxyl-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(4-[2-ethylhexyloxy]-2-hydroxyphenyl)-6-(4-methoxyphenyl)-1,3,5-triazine.
3. Metal deactivators, for example N,N′-diphenyloxamide, N-salicylic-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyl dihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.
4. Phosphites and phosphonites, for example triphenyl phosphite, diphenylallyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphate, tetrakis(2,4-di-tert-butylphenyl) 4,4′-biphenylene diphosphonate, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin, 2,2′,2′′-nitrilo-[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite], 2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphinane.
5. Hydroxylamines, for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
6. Nitrones, for example, N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, Noctyl-alpha-heptylnitrone, N-lauryl-alpha-undecyInitrone, N-tetradecyl-alpha-tridecylnnitrone, N-hexadecyl-alpha-pentadecyInitrone, N-octadecyl-alpha-heptadecyInitrone, N-hexadecylalpha-heptadecyInitrone, N-ocatadecyl-alpha-pentadecyInitrone, N-heptadecyl-alpha-heptadecyInitrone, N-octadecyl-alpha-hexadecyInitrone, nitrone derived from N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
7. Thiosynergists, for example dilauryl thiodipropionate, dimistryl thiodipropionate, distearyl thiodipropionate or distearyl disulfide.
8. Peroxide scavengers, for example esters of P3-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(β-dodecylmercapto)propionate.
9. Polyamide stabilizers, for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
10. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
11. Nucleating agents, for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers). Especially preferred are 1,3:2,4-bis(3′,4′-dimethylbenzylidene)sorbitol, 1,3:2,4-di(paramethyldibenzylidene)sorbitol, and 1,3:2,4-di(benzylidene)sorbitol.
12. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibres, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
13. Other additives, for example plasticizers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
14. Benzofuranones and indolinones, for example those disclosed in U.S. Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No. 5,175,312; U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839, EP-A-0591102; EP-A-1291384 or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tertbutylbenzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2-acetyl-5-isooctyl phenyl)-5-isooctylbenzofuran-2-one.
The further additives are typically used in concentrations of 0.01 to 10%, based on the total weight of the material to be treated.
A preferred process of the invention comprises, as other additives phenolic antioxidants, light stabilizers and/or processing stabilizers.
Incorporation of the compounds of the formula I and, if desired, further additives into the synthetic polymers is carried out by known methods, for example before or during moulding or else by applying the dissolved or dispersed compounds to the synthetic polymer, if appropriate with subsequent slow evaporation of the solvent.
The present invention also relates to a composition comprising

    
    
        a) an organic material which is susceptible to oxidative, thermal or light-induced degradation, and
        b) a compound of the formula I
    
    






    
    
        
        
            wherein, when n is 1,
            R1 is hydrogen, C1-C25alkyl, C2-C25alkenyl, —CO—R5, —CH(R10)CO—R5, —C(R10)2CO—R5, —CO—N(R6)—R7, —CH(R10)CO—N(R6)—R7, —C(R10)2CO—N(R6)—R7, —CH(R10)COOR5 or —C(R10)2CO—OR5;
            when n is 2,
            R1 is unsubstituted or with C1-C4alkyl, benzyl or phenyl substituted C1-C24alkylene; with oxygen or sulfur interrupted C2-C24alkylene; —CO—R8—CO—, —CH(R10)CO—R8—CO—CH(R10)—, —C(R10)2CO—R8—CO—C(R10)2—, —CO—N(R6)—R9—N(R6)—CO—, —CH(R10)CO—N(R6)—R9—N(R6)—CO—CH(R10)—, —C(R10)2CO—N(R6)—R9—N(R6)—CO—C(R10)2—, —CH(R10)CO—O—R9—O—CO—CH(R10)— or —C(R10)2CO—O—R9—O—CO—C(R10)2—;
            when n is 3,
            R1 is
        
        
    
    






    
    
        
        
            R2, R3 and R4 independently of each other are hydrogen, C1-C25alkyl, C2-C25alkenyl, —CH(R11)—S(O)p—R12,
        
        
    
    






    
    
        
        
             with the proviso that at least one of the radicals R2, R3or R4 is —CH(R11)—S(O)p—R12;
            R5 is C1-C25alkyl, C2-C25alkenyl, unsubstituted or with C1-C4alkyl or halogen substituted phenyl; or C7-C12-phenylalkyl,
            R6 is hydrogen or C1-C4alkyl,
            R7 is hydrogen, C1-C25alkyl, unsubstituted or with C1-C4alkyl or halogen substituted phenyl;
            R8 is phenylene, unsubstituted or with C1-C4alkyl, benzyl or phenyl substituted C1-C24alkylene; with oxygen or sulfur interrupted C2-C24alkylene;
            R9 is a direct bond, unsubstituted or with C1-C4alkyl, benzyl or phenyl substituted C2-C24alkylene; or with oxygen or sulfur interrupted C2-C24alkylene;
            R10 is hydrogen or C1-C8alkyl,
            R11 is hydrogen, C1-C8alkyl, unsubstituted or with C1-C4alkyl substituted phenyl;
            R12 is a monovalent perfluorinated alkyl or alkenyl, linear or branched organic radical having four to twenty fully fluorinated carbon atoms,
            R13 is hydrogen, C1-C25alkyl, C2-C25alkenyl, —CO—R5, —CO—N(R6)—R7 or —CH2—CO—N(R6)—R7,
            R14 is hydrogen, C1-C25alkyl, C2-C25alkenyl or —CH(R11)—S(O)p—R12,
            R15 is hydrogen, C1-C25alkyl, C2-C25alkenyl or —CH(R11)—S(O)p—R12,
            R16 is unsubstituted or with C1-C4alkyl substituted methylene, —S—, —S(O)—, —S(O)2— or —CO—;
            R17 is C1-C4alkyl,
            n is 1, 2 or 3, and
            p is 0, 1 or 2; with the proviso that the compounds of the formula A and B
        
        
    
    






    
    
        
        
            are excluded.
        
        
    
    


The preferred compounds of the formula I in the composition are identical to those of the inventive process.
Preferably, component (b) is a compound of the formula I wherein,
when n is 1,
R1 is hydrogen, C1-C12alkyl, —CO—R5, —CO—N(R6)—R7 or —CH2—CO—N(R6)—R7;
when n is 2,
R1 is methylene, —CO—R8—CO— or —CH(R10)—CO—N(R6)—R9—N(R6)—CO—CH(R10)—;
when n is 3,
R1 is




R2, R3 and R4 independently of each other are hydrogen, C1-C4alkyl, —CH(R11)—S(O)p—R12 or





with the proviso that at least one of the radicals R2, R3 or R4 is —CH(R11)—S(O)p—R12;

R5 is C1-C18alkyl,

R6 is hydrogen,

R7 is hydrogen, C1-C6alkyl, unsubstituted or with C1-C4alkyl substituted phenyl;

R8 is phenylene,

R9 is ethylene,

R10 is methyl,

R11 is hydrogen, C1-C8alkyl, unsubstituted or with methyl substituted phenyl; is —CH2CH2(CF2)mCF3,

R13 is hydrogen or acetyl,

R14 is C1-C4alkyl,

R15 is —CH(R11)—S(O)p—R12,

R16 is methylene,

m is 3 to 12,

n is 1, 2 or 3, and

p is 0; with the proviso that the compounds of the formula A and B are excluded.

The present invention also relates to a composition in the form of a masterbatch or concentrate comprising component (a) in an amount of from 5 to 90% and component (b) in an amount of from 5 to 80% by weight.
Component (b) and, if desired, further additives, can also be added before or during polymerisation or before crosslinking.
Component (b), with or without further additives, can be incorporated in pure form or encapsulated in waxes, oils or polymers into the synthetic polymer.
Component (b), with or without further additives, can also be sprayed onto the synthetic polymer. It is able to dilute other additives (for example the conventional additives indicated above) or their melts so that they too can be sprayed together with these additives onto the polymer. Addition by spraying on during the deactivation of the polymerization catalysts is particularly advantageous, it being possible to carry out spraying using, for example, the steam used for deactivation.
In the case of spherically polymerized polyolefins it may, for example, be advantageous to apply component (b), with or without other additives, by spraying.
The synthetic polymers prepared in this way can be employed in a wide variety of forms, for example as foams, films, fibres, tapes, moulding compositions, as profiles or as binders for coating materials, especially powder coatings, adhesives, putties or especially as thick-layer polyolefin mouldings which are in long-term contact with extractive media, such as, for example, pipes for liquids or gases, films, fibres, geomembranes, tapes, profiles or tanks.
The preferred thick-layer polyolefin mouldings have a layer thickness of from 1 to 50 mm, in particular from 1 to 30 mm, for example from 2 to 10 mm.
The compositions according to the invention can be advantageously used for the preparation of various shaped articles. Examples are:
I-1) Floating devices, marine applications, pontoons, buoys, plastic lumber for decks, piers, boats, kayaks, oars, and beach reinforcements.
I-2) Automotive applications, in particular bumpers, dashboards, battery, rear and front linings, moldings parts under the hood, hat shelf, trunk linings, interior linings, air bag covers, electronic moldings for fittings (lights), panes for dashboards, headlamp glass, instrument panel, exterior linings, upholstery, automotive lights, head lights, parking lights, rear lights, stop lights, interior and exterior trims; door panels; gas tank; glazing front side; rear windows; seat backing, exterior panels, wire insulation, profile extrusion for sealing, cladding, pillar covers, chassis parts, exhaust systems, fuel filter/filler, fuel pumps, fuel tank, body side mouldings, convertible tops, exterior mirrors, exterior trim, fasteners/fixings, front end module, glass, hinges, lock systems, luggage/roof racks, pressed/stamped parts, seals, side impact protection, sound deadener/insulator and sunroof.
I-3) Road traffic devices, in particular sign postings, posts for road marking, car accessories, warning triangles, medical cases, helmets, tires.
I-4) Devices for plane, railway, motor car (car, motorbike) including furnishings.
I-5) Devices for space applications, in particular rockets and satellites, e.g. reentry shields.
I-6) Devices for architecture and design, mining applications, acoustic quietized systems, street refuges, and shelters.
II-1) Appliances, cases and coverings in general and electric/electronic devices (personal computer, telephone, portable phone, printer, television-sets, audio and video devices), flower pots, satellite TV bowl, and panel devices.
II-2) Jacketing for other materials such as steel or textiles.
II-3) Devices for the electronic industry, in particular insulation for plugs, especially computer plugs, cases for electric and electronic parts, printed boards, and materials for electronic data storage such as chips, check cards or credit cards.
II-4) Electric appliances, in particular washing machines, tumblers, ovens (microwave oven), dish-washers, mixers, and irons.
II-5) Covers for lights (e.g. street-lights, lamp-shades).
II-6) Applications in wire and cable (semi-conductor, insulation and cable-jacketing).
II-7) Foils for condensers, refrigerators, heating devices, air conditioners, encapsulating of electronics, semi-conductors, coffee machines, and vacuum cleaners.
III-1) Technical articles such as cogwheel (gear), slide fittings, spacers, screws, bolts, handles, and knobs.
III-2) Rotor blades, ventilators and windmill vanes, solar devices, swimming pools, swimming pool covers, pool liners, pond liners, closets, wardrobes, dividing walls, slat walls, folding walls, roofs, shutters (e.g. roller shutters), fittings, connections between pipes, sleeves, and conveyor belts.
III-3) Sanitary articles, in particular shower cubicles, lavatory seats, covers, and sinks.
III-4) Hygienic articles, in particular diapers (babies, adult incontinence), feminine hygiene articles, shower curtains, brushes, mats, tubs, mobile toilets, tooth brushes, and bed pans.
III-5) Pipes (cross-linked or not) for water, waste water and chemicals, pipes for wire and cable protection, pipes for gas, oil and sewage, guttering, down pipes, and drainage systems.
III-6) Profiles of any geometry (window panes) and siding.
III-7) Glass substitutes, in particular extruded plates, glazing for buildings (monolithic, twin or multiwall), aircraft, schools, extruded sheets, window film for architectural glazing, train, transportation, sanitary articles, and greenhouse.
III-8) Plates (walls, cutting board), extrusion-coating (photographic paper, tetrapack and pipe coating), silos, wood substitute, plastic lumber, wood composites, walls, surfaces, furniture, decorative foil, floor coverings (interior and exterior applications), flooring, duck boards, and tiles.
III-9) Intake and outlet manifolds.
III-10) Cement-, concrete-, composite-applications and covers, siding and cladding, hand rails, banisters, kitchen work tops, roofing, roofing sheets, tiles, and tarpaulins.
IV-1) Plates (walls and cutting board), trays, artificial grass, astroturf, artificial covering for stadium rings (athletics), artificial floor for stadium rings (athletics), and tapes.
IV-2) Woven fabrics continuous and staple, fibers (carpets/hygienic articles/geotextiles/monofilaments; filters; wipes/curtains (shades)/medical applications), bulk fibers (applications such as gown/protection clothes), nets, ropes, cables, strings, cords, threads, safety seat-belts, clothes, underwear, gloves; boots; rubber boots, intimate apparel, garments, swimwear, sportswear, umbrellas (parasol, sunshade), parachutes, paraglides, sails, “balloon-silk”, camping articles, tents, airbeds, sun beds, bulk bags, and bags.
IV-3) Membranes, insulation, covers and seals for roofs, tunnels, dumps, ponds, dumps, walls roofing membranes, geomembranes, swimming pools, curtains (shades)/sun-shields, awnings, canopies, wallpaper, food packing and wrapping (flexible and solid), medical packaging (flexible & solid), airbags/safety belts, arm- and head rests, carpets, centre console, dashboard, cockpits, door, overhead console module, door trim, headliners, interior lighting, interior mirrors, parcel shelf, rear luggage cover, seats, steering column, steering wheel, textiles, and trunk trim.
V) Films (packaging, dump, laminating, agriculture and horticulture, greenhouse, mulch, tunnel, silage), bale wrap, swimming pools, waste bags, wallpaper, stretch film, raffia, desalination film, batteries, and connectors.
VI-1) Food packing and wrapping (flexible and solid), bottles.
VI-2) Storage systems such as boxes (crates), luggage, chest, household boxes, pallets, shelves, tracks, screw boxes, packs, and cans.
VI-3) Cartridges, syringes, medical applications, containers for any transportation, waste baskets and waste bins, waste bags, bins, dust bins, bin liners, wheely bins, container in general, tanks for water/used water/chemistry/gas/oil/gasoline/diesel; tank liners, boxes, crates, battery cases, troughs, medical devices such as piston, ophthalmic applications, diagnostic devices, and packing for pharmaceuticals blister.
VII-1) Extrusion coating (photo paper, tetrapack, pipe coating), household articles of any kind (e.g. appliances, thermos bottle/clothes hanger), fastening systems such as plugs, wire and cable clamps, zippers, closures, locks, and snap-closures.
VII-2) Support devices, articles for the leisure time such as sports and fitness devices, gymnastics mats, ski-boots, inline-skates, skis, big foot, athletic surfaces (e.g. tennis grounds); screw tops, tops and stoppers for bottles, and cans.
VII-3) Furniture in general, foamed articles (cushions, impact absorbers), foams, sponges, dish clothes, mats, garden chairs, stadium seats, tables, couches, toys, building kits (boards/figures/balls), playhouses, slides, and play vehicles.
VII-4) Materials for optical and magnetic data storage.
VII-5) Kitchen ware (eating, drinking, cooking, storing).
VII-6) Boxes for CD's, cassettes and video tapes; DVD electronic articles, office supplies of any kind (ball-point pens, stamps and ink-pads, mouse, shelves, tracks), bottles of any volume and content (drinks, detergents, cosmetics including perfumes), and adhesive tapes.
VII-7) Footwear (shoes/shoe-soles), insoles, spats, adhesives, structural adhesives, food boxes (fruit, vegetables, meat, fish), synthetic paper, labels for bottles, couches, artificial joints (human), printing plates (flexographic), printed circuit boards, and display technologies.
VII-8) Devices of filled polymers (talc, chalk, china clay (kaolin), wollastonite, pigments, carbon black, TiO2, mica, nanocomposites, dolomite, silicates, glass, asbestos).
Of interest are compositions comprising as component (a) fibers and fabrics used in nonwoven medical fabric and related apparel (surgical gowns, drapes, bandages), contstruction fabrics (house wrapping, roofing, swimming-pool wrapping) and home furnishing (carpets, table linens, shower curtains).
Of special interest are compositions comprising as component (a) fibers and nonwovens.
Thus, a further embodiment of the present invention relates to a shaped article, in particular a film, pipe, profile, bottle, tank or container, fiber containing a composition as described above. Of special interest are fibers and nonwovens.
A further embodiment of the present invention relates to a molded article containing a composition as described above. The molding is in particular effected by injection, blow, compression, roto-molding or slush-molding or extrusion.
The present invention also relates to new compounds of the formula I




wherein, when n is 1,

R1 is hydrogen, C1-C25alkyl, C2-C25alkenyl, —CO—R5, —CH(R10)CO—R5, —C(R10)2CO—R5, —CO—N(R6)—R7, —CH(R10)CO—N(R6)—R7, —C(R10)2CO—N(R6)—R7, —CH(R10)COOR5 or —C(R10)2CO—OR5;

when n is 2,

R1 is unsubstituted or with C1-C4alkyl, benzyl or phenyl substituted C1-C24alkylene; with oxygen or sulfur interrupted C2-C24alkylene; —CO—R8—CO—, —CH(R10)CO—R8—CO—CH(R10)—, —C(R10)2CO—R8—CO—C(R10)2—, —CO—N(R6)—R9—N(R6)—CO—, —CH(R10)CO—N(R6)—R9—N(R6)—CO—CH(R10)—, —C(R10)2CO—N(R6)—R9—N(R6)—CO—C(R10)2—, —CH(R10)CO—O—R9—O—CO—CH(R10)— or —C(R10)2CO—O—R9—O—CO—C(R10)2—;

when n is 3,

R1 is





R2, R3 and R4 independently of each other are hydrogen, C1-C25alkyl, C2-C25alkenyl, —CH(R11)—S(O)p—R12,





with the proviso that at least one of the radicals R2, R3 or R4 is —CH(R11)—S(O)p—R12;

R5 is C1-C25alkyl, C2-C25alkenyl, unsubstituted or with C1-C4alkyl or halogen substituted phenyl; or C7-C12-phenylalkyl,

R6 is hydrogen or C1-C4alkyl,

R7 is hydrogen, C1-C25alkyl, unsubstituted or with C1-C4alkyl or halogen substituted phenyl;

R8 is phenylene, unsubstituted or with C1-C4alkyl, benzyl or phenyl substituted C1-C24alkylene; with oxygen or sulfur interrupted C2-C24alkylene;

R9 is a direct bond, unsubstituted or with C1-C4alkyl, benzyl or phenyl substituted C2-C24alkylene; or with oxygen or sulfur interrupted C2-C24alkylene;

R10 is hydrogen or C1-C8alkyl,

R11 is hydrogen, C1-C8alkyl, unsubstituted or with C1-C4alkyl substituted phenyl;

R12 is a monovalent perfluorinated alkyl or alkenyl, linear or branched organic radical having four to twenty fully fluorinated carbon atoms,

R13 is hydrogen, C1-C25alkyl, C2-C25alkenyl, —CO—R5, —CO—N(R6)—R7 or —CH2—CO—N(R6)—R7,

R14 is hydrogen, C1-C25alkyl, C2-C25alkenyl or —CH(R11)—S(O)p—R12,

R15 is hydrogen, C1-C25alkyl, C2-C25alkenyl or —CH(R11)—S(O)p—R12,

R16 is unsubstituted or with C1-C4alkyl substituted methylene, —S—, —S(O)—, —S(O)2— or —CO—;

R17 is C1-C4alkyl,

n is 1, 2 or 3, and

p is 0, 1 or 2; with the proviso that the compounds of the formula A and B





are excluded.

The preferred new compounds of the formula I [or component (b) respectively] are the same as those described for the composition and process.
Of special interest are the compounds of the formula I wherein,
when n is 1,
R1 is hydrogen, C1-C12alkyl, —CO—R5, —CO—N(R6)—R7 or —CH2—CO—N(R6)—R7;
when n is 2,
R1 is methylene, —CO—R8—CO— or —CH(R10)—CO—N(R6)—R9—N(R6)—CO—CH(R10)—;
when n is 3,
R1 is




R2, R3 and R4 independently of each other are hydrogen, C1-C4alkyl, —CH(R11)—S(O)p—R12 or





with the proviso that at least one of the radicals R2, R3 or R4 is —CH(R11)—S(O)p—R12;

R5 is C1-C18alkyl,

R6 is hydrogen,

R7 is hydrogen, C1-C6alkyl, unsubstituted or with C1-C4alkyl substituted phenyl;

R8 is phenylene,

R9 is ethylene,

R10 is methyl,

R11 is hydrogen, C1-C8alkyl, unsubstituted or with methyl substituted phenyl;

R12 is —CH2CH2(CF2)mCF3,

R13 is hydrogen or acetyl,

R14 is C1-C4alkyl,

R15 is —CH(R11)—S(O)p—R12, is methylene,

m is 3 to 12,

n is 1, 2 or 3, and

p is 0; with the proviso that the compounds of the formula A and B are excluded.

A preferred embodiment of the present invention is also the use of a compound of the formula I as reducer of surface energy [e.g. as oil and water repellency agent] for an organic material.
The preferred compounds of the formula I or component (b) respectively, and optionally further additives, in the use as reducer of surface energy [e.g. increasing the oil and water repellency] of organic materials are the same as those described for the process and composition.
The following examples illustrate the invention further. Parts or percentages relate to weight.


EXAMPLE 1
Preparation of Compound 101




6.59 g (38.1 mmol) of 4-tert-butyl-2-methylphenol, 18.3 g (38.1 mmol) of 1H,1H,2H,2H-perfluorodecane-1-thiol, 0.52 g (3.81 mmol) of dimethylamine (33% in EtOH), 2.30 g (76.2 mmol) of paraformaldehyde and 20 ml of N,N-dimethylformamide (DMF) are mixed and heated under reflux for 12 hours under nitrogen atmosphere. Ethyl acetate is added and the organic phase is washed repeatedly with water and brine until pH neutral. The organic phase is dried over magnesium sulfate, filtered and concentrated using a vacuum rotary evaporator to give 24.4 g of a red-brown liquid. The crude product is purified by flash chromatography (hexane/ethyl acetate: 10:1) to give 22.9 g of the compound 101, yellow solid, m.p. 60-61° C. 1H NMR: (300 MHz, CDCl3): δ=7.13 (d, J=2.4 Hz, ArH, 1H); 6.95 (d, J=2.4 Hz, ArH, 1H); 5.86 (s, OH, 1H); 3.85 (s, ArCH2, 2H); 2.70-2.60 (m, CH2CH2CF2, 2H); 2.40-2.15 (m, CH2CH2CF2, 2H); 2.24 (s, CH3, 3H); 1.29 (s, tert-butyl, 9H).
Starting from the corresponding phenols such as for example 2,6-dimethylphenol, 2-methylphenol, 4-methylphenol, phenol or 2-tert-butyl-6-(3-tert-butyl-2-hydroxybenzyl)-phenol and 1H,1H,2H,2H-perfluorodecane-1-thiol or 1H,1H,2H,2H-perfluorohexane-1-thiol compounds 102-108 are prepared in analogy to Example 1.




White solid; m.p. 55-57° C. 1H NMR: (300 MHz, CDCl3): δ=6.92 (s, ArH, 2H); 4.60 (s, OH, 1H); 3.66 (s, ArCH2, 2H); 2.70-2.60 (m, CH2CH2CF2, 2H); 2.40-2.20 (m, CH2CH2CF2, 2H); 2.25 (s, CH3, 6H).




White solid; m.p. 78-79° C. 1H NMR: (300 MHz, CDCl3): δ=7.06 (d, J=1.8 Hz, ArH, 1H); 6.92 (d, J=1.8 Hz, ArH, 1H); 6.04 (s, OH, 1H); 3.83 (s, ArCH2, 2H); 3.66 (s, ArCH2, 2H); 2.70-2.55 (m, CH2CH2CF2, 4H); 2.45-2.15 (m, CH2CH2CF2, 4H); 2.27 (s, CH3, 3H).




White solid; m.p. 77-79° C. 1H NMR: (300 MHz, CDCl3): δ=6.93 (s, ArH, 2H); 6.55 (s, OH, 1H); 3.82 (s, ArCH2, 2H); 3.66 (s, ArCH2, 2H); 2.75-2.55 (m, CH2CH2CF2, 4H); 2.50-2.20 (m, CH2CH2CF2, 4H); 2.26 (s, CH3, 3H).




White solid; m.p. 83° C. 1H NMR: (300 MHz, CDCl3): δ=7.10 (s, ArH, 2H); 6.83 (s, OH, 1H); (s, ArCH2, 4H); 3.67 (s, ArCH2, 2H); 2.70-2.55 (m, CH2CH2CF2, 6H); 2.50-2.20 (m, CH2CH2CF2, 6H).




Pale yellow solid; m.p. 52-55° C. 1H NMR: (300 MHz, CDCl3): δ=7.09 (s, ArH, 4H); 6.06 (br s, HO, 1H); 3.93 (s, ArCH2Ar, 2H); 3.68 (s, ArCH2 4H); 2.70-2.60 (m, CH2CH2CF2, 4H); 2.40-2.15 (m, CH2CH2CF2, 4H); 1.41 (s, tert-butyl, 18H).




Colourless liquid. 1H NMR: (300 MHz, CDCl3): δ=7.06 (s, ArH, 1H); 6.92 (s, ArH, 1H); 6.03 (s, OH, 1H); 3.83 (s, ArCH2, 2H); 3.66 (s, ArCH2, 2H); 2.70-2.55 (m, CH2CH2CF2, 4H); 2.45-2.15 (m, CH2CH2CF2, 4H); 2.27 (s, CH3, 3H).




Colourless oil. 1H NMR: (400 MHz, CDCl3): δ=7.10 (s, ArH, 2H); 6.82 (s, OH, 1H); 3.85 (s, ArCH2, 4H); 3.68 (s, ArCH2, 2H); 2.75-2.55 (m, CH2CH2CF2, 6H); 2.50-2.20 (m, CH2CH2CF2, 6H).
EXAMPLE 2
Preparation of Compound 109




A mixture of 1.99 g (3.03 mmol) of compound 101 [prepared according to Example 1], 0.78 g (3.03 mmol) of 1-bromododecane and 0.84 g (6.06 g) of pulverized K2CO3 in 30 ml of dry acetone is heated under reflux for 2 days. The reaction mixture is poured into ethyl acetate, washed with 1N NH4Cl, brine, dried over Na2SO4, filtered and concentrated using a vacuum rotary evaporator to give 2.40 g of a yellow oil. The crude material is purified by flash chromatography (hexane/ethyl acetate: 40:1) to give 1.30 g of the compound 109, colourless liquid. 1H NMR: (300 MHz, CDCl3): δ=7.15-7.05 (m, ArH, 2H); 5.86 (s, OH, 1H); 3.85-3.75 (m, ArCH2+ArOCH2; 4H); 2.75-2.65 (m, CH2CH2CF2, 2H); 2.45-2.20 (m, CH2CH2CF2, 2H); 2.30 (s, CH3, 3H); 1.95-1.70 (m, ArOCH2CH2, 2H); 1.60-1.10 (m, CH2+tert-butyl, 27H); 0.95-0.85 (m, CH3, 3H).
Starting from the corresponding phenols compounds 110, 111, 112, 113, 114 and 115 are prepared in analogy to Example 2.




Pale yellow solid; m.p. 117-124° C. 1H NMR: (300 MHz, acetone-d6): δ=7.85-7.75 (br s, NH, 2H); 7.28 (d, J=2.4 Hz, ArH, 2H); 7.19 (d, J=2.4 Hz, ArH, 2H); 4.60-4.50 (m, ArOCH, 2H); 4.00-3.90 (m, CH2NH; 4H); 3.55-3.45 (m, ArCH2, 4H); 2.80-2.70 (m, CH2CH2CF2, 4H); 2.65-2.35 (m, CH2CH2CF2, 4H); 2.29 (s, CH3, 6H); 1.42 (d, J=6.6 Hz, CH3CH, 6H); 1.29 (s, tert-butyl, 18H).




Orange oil. 1H NMR: (400 MHz, CDCl3): δ=7.75-7.65 (m, ArH, 1H); 7.60-7.50 (m, ArH, 2H); 7.40-7.20 (m, ArH, 4H); 5.70 (s, ArCH, 1H); 3.80-3.70 (m, OCHH, 1H); 3.60-3.50 (m, OCHH, 1H); 2.60-2.45 (m, CH2CH2CF2, 2H); 2.40-2.00 (m, CH2CH2CF2, 2H); 1.85-1.70 (m, OCH2CH2, 2H); 1.41 (s, tert-butyl, 9H); 1.34 (s, tert-butyl, 9H); 1.29 (br s, CH2, 18H).




Orange oil. 1H NMR: (300 MHz, CDCl3): δ=6.95 (s, ArH, 2H); 3.75 (t, J=6.6 Hz, ArOCH2, 2H); 3.66 (s, ArCH2, 2H); 2.70-2.60 (m, CH2CH2CF2, 2H); 2.40-2.15 (m, CH2CH2CF2, 2H); 2.27 (s, CH3, 6H); 2.40-2.25 (m, ArOCH2CH2, 2H); 1.60-1.20 (m, CH2, 18H); 1.00-0.80 (m, CH3, 3H).




Beige solid; m.p. 93-98° C. 1H NMR: (300 MHz, CDCl3): δ=7.55-7.40 (br s, NH, 2H); 7.00-6.90 (m, ArH, 2H); 4.47 (q, J=6.9 Hz, ArOCH, 2H); 3.66 (s, ArCH2, 4H); 3.70-3.55 (m, CH2NH; 4H); 2.70-2.60 (m, CH2CH2CF2, 4H); 2.40-2.20 (m, CH2CH2CF2, 4H); 2.23 (s, CH3, 12H); 1.45-1.35 (m, CH3CH, 6H).




Yellow oil. 1H NMR: (300 MHz, CDCl3): δ=7.15-7.05 (m, ArH, 1H); 7.05-7.00 (m, ArH, 1H); 3.81 (t, J=6.6 Hz, ArOCH2, 2H); 3.77 (s, ArCH2, 2H); 3.68 (s, ArCH2, 2H); 2.70-2.60 (m, CH2CH2CF2, 2H); 2.45-2.15 (m, CH2CH2CF2, 2H); 2.29 (s, CH3, 3H); 1.90-1.70 (m, ArOCH2CH2, 2H); 1.60-1.20 (m, CH2, 18H); 0.95-0.80 (m, CH3, 3H).




Off-white solid; m.p. 93-96° C. 1H NMR: (300 MHz, CDCl3): δ=8.67 (br s, NH, 1H); 7.55 (d, J=8.4 Hz, ArH, 2H); 7.19 (d, J=8.4 Hz, ArH, 2H); 7.20-7.05 (m, ArH, 2H); 4.52 (s, ArOCH2, 2H); 3.82 (s, ArCH2, 2H); 3.70 (s, ArCH2, 2H); 2.80-2.55 (m, CH2CH2CF2, 4H); 2.50-2.20 (m, CH2CH2CF2, 4H); 2.36 (s, CH3, 3H); 2.34 (s, CH3, 3H).
EXAMPLE 3
Preparation of Compound 116




1.50 g (2.29 mmol) of compound 101 [prepared according to Example 1] and 0.28 g (2.75 mmol) of triethylamine are dissolved in 10 ml of tetrahydrofuran. 0.69 g (2.29 mmol) of stearoyl chloride is added to the reaction mixture at room temperature under nitrogen atmosphere. The reaction mixture is stirred at room temperature for 12 hours. Ethyl acetate (80 ml) is added and the organic phase is washed repeatedly with water until pH neutral. The organic phase is dried over magnesium sulfate, filtered and concentrated using a vacuum rotary evaporator to give 2.05 g of a white wax. The crude product is purified by flash chromatography (hexane/ethyl acetate: 40:1) to give 1.75 g of compound 116, pale yellow solid, m.p. 35-36° C. 1H NMR: (300 MHz, CDCl3): δ=7.20-7.10 (m, ArH, 2H); 3.64 (s, ArCH2, 2H); 2.70-2.55 (m, CH2CH2CF2+CH2CO2, 4H); 2.60-2.15 (m, CH2CH2CF2, 2H); 2.15 (s, CH3, 3H); 1.90-1.70 (m, CH2CH2CO2, 2H); 1.50-1.20 (m, CH2+tert-butyl, 37H); 0.95-0.85 (m, CH3, 3H).
Starting from the corresponding phenols and acid chlorides, compounds 117-135 are prepared in analogy to Example 3.




M.p. 90-108° C. 1H NMR: (300 MHz, CDCl3): δ=8.40 (s, ArH, 4H); 7.30-7.15 (m, ArH, 4H); 3.71 (s, ArCH2, 4H); 2.70-2.60 (m, CH2CH2CF2, 4H); 2.35-2.10 (m, CH2CH2CF2, 4H); 2.22 (s, CH3, 6H); 1.35 (s, tert-butyl, 9H).




White solid; m.p. 112-113° C. 1H NMR: (300 MHz, CDCl3): δ=8.42 (s, ArH, 4H); 7.30-7.15 (m, ArH, 6H); 3.72 (s, ArCH2, 4H); 2.70-2.60 (m, CH2CH2CF2, 4H); 2.35-2.15 (m, CH2CH2CF2, 4H); 2.24 (s, CH3, 6H).




Colourless oil (compound 119).




White solid; m.p. 140-162° C.




White solid; m.p. 50-51° C. 1H NMR: (300 MHz, CDCl3): δ=7.00 (s, ArH, 2H); 3.68 (s, ArCH2, 2H); 2.75-2.55 (m, CH2CH2CF2+O2CCH2, 4H); 2.45-2.20 (m, CH2CH2CF2, 2H); 2.14 (s, CH3, 6H); 2.40-2.25 (m, O2CCH2CH2, 2H); 1.50-1.20 (m, CH2, 28H); 1.00-0.85 (m, CH3, 3H).




White solid; m.p. 124-130° C. 1H NMR: (300 MHz, CDCl3): δ=8.41 (s, ArH, 4H); 7.10 (s, ArH, 4H); 3.73 (s, ArCH2, 4H); 2.75-2.65 (m, CH2CH2CF2, 4H); 2.45-2.20 (m, CH2CH2CF2, 4H); (s, CH3, 12H).




White solid; m.p. 57-60° C. 1H NMR: (400 MHz, CDCl3): δ=7.20-7.10 (m ArH, 2H); 6.04 (s, OH, 1H); 3.71 (s, ArCH2, 2H); 3.65 (s, ArCH2, 2H); 2.70-2.60 (m, CH2CH2CF2, 4H); 2.40-2.20 (m, CH2CH2CF2, 4H); 2.37 (s, CH3, 3H); 2.17 (s, COCH3, 3H).




White solid; m.p. 62-63° C. 1H NMR: (300 MHz, CDCl3): δ=7.20-7.10 (m, ArH, 2H); 3.70 (s, ArCH2, 2H); 3.63 (s, ArCH2, 2H); 2.70-2.55 (m, CH2CH2CF2+O2CCH2, 4H); 2.45-2.15 (m, CH2CH2CF2, 2H); 2.15 (s, CH3, 3H); 1.90-1.70 (m, O2CCH2CH2, 2H); 1.50-1.20 (m, CH2, 28H); 0.95-0.85 (m, CH3, 3H).




White solid; m.p. 110-125° C. 1H NMR: (300 MHz, tetrahydrofuran-d8): δ=8.43 (s, ArH, 4H); (m, ArH, 2H); 7.30-7.20 (m, ArH, 2H); 3.84 (s, ArCH2, 4H); 3.80 (s, ArCH2, 4H); 2.80-2.60 (m, CH2CH2CF2, 8H); 2.60-2.20 (m, CH2CH2CF2, 8H); 2.21 (s, CH3, 6H).




White solid; m.p. 65-66° C. 1H NMR: (300 MHz, CDCl3): δ=7.13 (s, ArH, 2H); 3.62 (s, ArCH2, 4H); 2.70-2.55 (m, CH2CH2CF2, 4H); 2.40-2.15 (m, CH2CH2CF2, 4H); 2.37 (s, CH3, 3H); 2.34 (s, CH3, 3H).




Pale yellow wax. 1H NMR: (300 MHz, CDCl3): δ=7.12 (s, ArH, 2H); 3.61 (s, ArCH2, 4H); 2.70-2.55 (m, CH2CH2CF2+O2CCH2, 6H); 2.40-2.15 (m, CH2CH2CF2, 4H); 2.34 (s, CH3, 3H); 1.95-1.70 (m, O2CCH2CH2, 2H); 1.50-1.20 (m, CH2, 28H); 0.95-0.85 (m, CH3, 3H).




White solid; m.p. 155-157° C. 1H NMR: (300 MHz, tetrahydrofuran-d8): δ=8.39 (s, ArH, 4H); (s, ArH, 4H); 3.73 (s, ArCH2, 8H); 2.70-2.60 (m, CH2CH2CF2, 8H); 2.40-2.20 (m, CH2CH2CF2, 8H); 2.34 (s, CH3, 6H).




White solid; m.p. 74-75° C. 1H NMR: (400 MHz, CDCl3): δ=7.31 (s, ArH, 2H); 3.73 (s, ArCH2, 2H); 3.65 (s, ArCH2, 4H); 2.70-2.50 (m, CH2CH2CF2, 6H); 2.50-2.20 (m, CH2CH2CF2, 6H); 2.38 (s, COCH3, 3H).




White solid; m.p. 73-76° C. 1H NMR: (300 MHz, CDCl3): δ=7.31 (s, ArH, 2H); 3.73 (s, ArCH2, 2H); 3.63 (s, ArCH2, 4H); 2.70-2.50 (m, CH2CH2CF2, 6H); 2.70-2.55 (m, O2CCH2, 2H); 2.45-2.15 (m, CH2CH2CF2, 6H); 1.85-1.70 (m, O2CCH2CH2, 2H); 1.50-1.20 (m, CH2, 28H); 0.95-0.85 (m, CH3, 3H).




Colourless oil. 1H NMR: (300 MHz, CDCl3): δ=7.09 (d, J=1.8 Hz, ArH, 2H); 6.95-6.75 (br s, ArH, 2H); 3.67 (s, ArCH2, 4H); 3.70-3.40 (s, ArCH2Ar, 2H); 2.70-2.55 (m, CH2CH2CF2, 4H); 2.40-2.15 (m, CH2CH2CF2, 4H); 2.24 (s, COCH3, 6H); 1.35 (s, tert-butyl, 18H).




White solid; m.p. 35-37° C. 1H NMR: (400 MHz, CDCl3): δ=7.20-7.10 (m, ArH, 2H); 3.71 (s, ArCH2, 2H); 3.64 (s, ArCH2, 2H); 2.72-2.58 (m, CH2CH2CF2+CH2CO2, 6H); 2.42-2.20 (m, CH2CH2CF2, 4H); 2.16 (s, CH3, 3H); 1.90-1.75 (m, CH2CH2CO2, 2H); 1.52-1.20 (m, CH2, 28H); 0.95-0.85 (m, CH3, 3H).




White solid; m.p. 98-101° C. 1H NMR: (400 MHz, CDCl3): δ=8.41 (s, ArH, 4H); 7.35-7.15 (m, ArH, 4H); 3.76 (s, ArCH2, 4H); 3.71 (s, ArCH2, 4H); 2.90-2.60 (m, CH2CH2CF2, 8H); 2.55-2.15 (m, CH2CH2CF2, 8H); 2.23 (s, CH3, 6H).




Colourless resin. 1H NMR: (400 MHz, CDCl3): δ=9.33 (s, ArH, 3H); 7.30-7.15 (m, ArH, 6H); (m, ArCH2, 12H); 2.85-2.55 (m, CH2CH2CF2, 12H); 2.55-2.15 (m, CH2CH2CF2, 12H); 2.25 (s, CH3, 9H).




White solid; m.p. 35-37° C. 1H NMR: (300 MHz, CDCl3): δ=7.28 (s, ArH, 2H); 3.73 (s, ArCH2, 2H); 3.65 (s, ArCH2, 4H); 2.75-2.55 (m, CH2CH2CF2, 6H); 2.50-2.20 (m, CH2CH2CF2, 6H); 2.38 (s, COCH3, 3H).
EXAMPLE 4
Preparation of Compound 136




0.31 g (7.63 mmol) of pulverized sodium hydroxide is added to a mixture of 2.00 g (3.05 mmol) of compound 101 [prepared according to Example 1] and 6.21 g (73.1 mmol) of dichloromethane suspended in 8.0 ml of N-methylpyrrolidinone. The reaction mixture is heated under reflux for 4 hours. The reaction mixture is poured into ethyl acetate, tetrahydrofuran and washed with water. The organic phase is dried over sodium sulfate, filtered and concentrated using a vacuum rotary evaporator to give 2.00 g of a brown oil. The crude material is purified by flash chromatography (hexane as eluent) to give 1.30 g of compound 136 as pale yellow oil. 1H NMR: (300 MHz, CDCl3): δ=7.14 (br s, ArH, 4H); 5.36 (s, OCH2O, 2H); 3.90-3.81 (br s, ArCH2, 4H); 2.70-2.60 (m, CH2CH2CF2, 4H); 2.40-2.15 (m, CH2CH2CF2, 4H); 2.27 (s, CH3, 6H); 1.31 (s, tert-butyl, 18H).
Starting from the corresponding phenols [compounds 103 and 104], compounds 137 and 138 are prepared in analogy to Example 4.




White solid; m.p. 84-86° C. 1H NMR: (400 MHz, CDCl3): δ=7.20-7.05 (m, ArH, 4H); 5.35 (s, OCH2O, 2H); 3.78 (s, ArCH2, 4H); 3.69 (s, ArCH2, 4H); 2.75-2.55 (m, CH2CH2CF2, 8H); 2.50-2.15 (m, CH2CH2CF2, 8H); 2.27 (s, CH3, 6H). 13C NMR (100 MHz, CDCl3): 152.13; 134.25; 132.10; 131.83; 131.10; 128.68; 98.62; 35.67; 31.70; 31.63; 31.49; 30.81; 22.22; 21.78; 16.43.




White solid; m.p. 80-83° C. 1H NMR: (400 MHz, CDCl3): δ=7.08 (s, ArH, 4H); 5.51 (s, OCH2O, 2H); 3.80 (br s, ArCH2, 8H); 2.75-2.60 (m, CH2CH2CF2, 8H); 2.45-2.20 (m, CH2CH2CF2, 8H); 2.32 (s, CH3, 6H). 13C NMR (100 MHz, CDCl3): 150.83; 134.25; 135.22; 131.46; 130.80; 101.32; 31.95; 31.74; 31.52; 31.08; 22.53; 20.57.
EXAMPLE 5
Preparation of Compound 139




A mixture of 14.7 g (38.7 mmol) of 2,4-di-tert-butyl-6-(phenylpiperidin-1-yl-methyl)phenol and 37.2 g (77.4 mmol) of 1H,1H,2H,2H-perfluorodecane-1-thiol in 100 ml of toluene are heated under reflux for 18 hours under nitrogen atmosphere. Ethyl acetate is added and the organic phase is washed repeatedly with water, 1 N NH4Cl and brine until pH neutral. The organic phase is dried over magnesium sulfate, filtered and concentrated using a vacuum rotary evaporator to give 45.3 g of a pale yellow solid. The crude product is purified by flash chromatography (hexane as eluent) to give 19.2 g of the compound 139, white solid, m.p. 76-77° C. 1H NMR: (300 MHz, CDCl3): δ=7.50-7.20 (m, ArH, 6H); 6.90 (d, J=2.4 Hz, ArH, 1H); 6.77 (s, OH, 1H); 5.42 (s, ArCH, 1H); 2.72 (t, J=8.4 Hz, CH2CH2CF2, 2H); 2.35-2.10 (m, CH2CH2CF2, 2H); 1.45 (s, tert-butyl, 9H); 1.24 (s, tert-butyl, 9H).
Compound 140 is prepared in analogy to Example 5 from the corresponding phenol.




Colourless oil. 1H NMR: (300 MHz, CDCl3): δ=7.33 (d, J=2.4 Hz, ArH, 1H); 7.30-7.20 (m, ArH, 3H); 7.15-7.95 (m, ArH, 1H); 6.90 (d, J=2.4 Hz, ArH, 1H); 6.77 (s, OH, 1H); 5.38 (s, ArCH, 1H); 2.71 (t, J=8.4 Hz, CH2CH2CF2, 2H); 2.36 (s, CH3, 3H); 2.35-2.10 (m, CH2CH2CF2, 2H); 1.46 (s, tert-butyl, 9H); 1.25 (s, tert-butyl, 9H).
EXAMPLE 6
Preparation of Compound 141




0.01 g (0.10 mmol) of 1,4-diaza-bicyclo[2.2.2]octane (DABCO) dissolved in 10 ml of dioxane is added at room temperature to the mixture of 2.00 g (1.83 mmol) of compound 103 [prepared according to Example 1] and 0.24 g (1.83 mmol) of p-tolylisocyanate dissolved in 10 ml of dry dioxane. The reaction mixture is stirred at 50° C. for 18 hours. Ethyl acetate is added and the organic phase is washed repeatedly with water and brine until pH neutral. The organic phase is dried over magnesium sulfate, filtered and concentrated using a vacuum rotary evaporator to give 2.40 g of a yellow wax. The crude product is purified by recrystallization from acetonitrile to give 1.20 g of the compound 141 as white solid, m.p. 98-100° C. 1H NMR: (300 MHz, CDCl3): δ=7.45-7.25 (m, ArH, 2H); 7.25-7.10 (m, ArH, 4H); 7.05-6.85 (br s, NH, 1H); 3.72 (s, ArCH2, 4H); 2.70-2.60 (m, CH2CH2CF2, 4H); 2.50-2.20 (m, CH2CH2CF2, 4H); 2.34 (s, CH3, 3H); 2.26 (s, CH3, 3H).
EXAMPLE 7
Preparation of Compound 142




0.82 g (720.3 mmol) of pulverized sodium hydroxide is added to a mixture of 5.00 g (8.13 mmol) of compound 102 [prepared according to Example 1] and 16.6 g (195 mmol) of dichloromethane suspended in 22 ml of N-methylpyrrolidinone. The reaction mixture is heated under reflux for 4 hours. The reaction mixture is poured into ethyl acetate, tetrahydrofuran and washed with water. The organic phase is dried over sodium sulfate, filtered and concentrated using a vacuum rotary evaporator to give 8.90 g of a brown oil. The crude material is purified by flash chromatography (hexane/ethyl acetate: 5:1) to give 4.00 g of compound 142 as white solid, m.p. 55-58° C. 1H NMR: (400 MHz, CDCl3): δ=6.96 (s, ArH, 4H); 5.22 (s, OCH2O, 2H); 3.67 (s, ArCH2, 4H); 3.69 (s, ArCH2, 4H); 2.70-2.60 (m, CH2CH2CF2, 4H); 2.45-2.15 (m, CH2CH2CF2, 4H); 2.24 (s, CH3, 12H).
EXAMPLE 8
Preparation of Compound 143




0.015 g (0.14 mmol) of 1,4-diaza-bicyclo[2.2.2]octane (DABCO) dissolved in 10 ml of dioxane is added at room temperature to the mixture of 1.50 g (1.37 mmol) of compound 103 [prepared according to Example 1] and 0.18 g (1.37 mmol) of hexylisocyanate dissolved in 10 ml of dry dioxane. The reaction mixture is stirred at 50° C. for 4 hours. Ethyl acetate is added and the organic phase is washed repeatedly with water and brine until pH neutral. The organic phase is dried over magnesium sulfate, filtered and concentrated using a vacuum rotary evaporator to give 1.60 g of a yellow solid. The crude product is purified by recrystallization from hote acetonitrile to give 0.90 g of the compound 143 as white solid, m.p. 71-74° C.
EXAMPLE 9
Preparation of Compound 144




0.01 g (0.10 mmol) of 1,4-diaza-bicyclo[2.2.2]octane (DABCO) dissolved in 10 ml of dioxane is added at room temperature to the mixture of 1.50 g (1.37 mmol) of compound 104 [prepared according to Example 1] and 0.18 g (1.37 mmol) of hexylisocyanate dissolved in 10 ml of dry dioxane. The reaction mixture is stirred at 50° C. for 5 hours. Ethyl acetate is added and the organic phase is washed repeatedly with water and brine until pH neutral. The organic phase is dried over magnesium sulfate, filtered and concentrated using a vacuum rotary evaporator to give 1.60 g of a white solid. The crude product is purified by recrystallization from acetonitrile to give 1.25 g of the compound 144 as white solid, m.p. 109-111° C.
EXAMPLE 10
Preparation of Mixtures of Perfluorinated Compounds
Tel B is (CmF2m+1)—CH2CH2—I with fluoroalkyl (Rf)— distribution corresponding to Medium Distribution Cuts.
Tel BN is (CmF2m+1)—CH2CH2—I with fluoroalkyl (Rf)— distribution corresponding to Narrow Distribution Cuts.
Table 1 discloses the weight percentages of components in the products.










TABLE 1






Low Dist.
Medium Dist.
Narrow Dist.


Fluoroalkane Chain
(Avg. m = 7.3)
(Avg. m = 8.2)
(Avg. m = 9.0)







C4F9
4 max.
4 max.
—


C6F13
50
35
6 max.


C8F17
29
30
50


C10F21
11
17
29


C12F25
 4
 8
11


C14F29 and higher
2 max.
6 max.
4 max.









The following compounds 145-147 are prepared in analogy to Example 1:




Compound 145a derived from Tel B: pale yellow wax.
Compound 145b derived from Tel BN: yellow wax.




Compound 146a derived from Tel B: orange wax.
Compound 146b derived from Tel BN: off-white solid. M.p. 68-75° C.




Compound 147a derived from Tel B: white solid. M.p. 55-67° C.
Compound 147b derived from Tel BN: pale yellow solid. M.p. 92-100° C.
The following compounds 148-151 are prepared in analogy to Example 3:




Compound 148a derived from Tel B: white solid. M.p. 117-123° C.
Compound 148b derived from Tel BN: white solid. M.p. 129-140° C.




Compound 149a derived from Tel B: white waxy solid. M.p. 43-49° C.
Compound 149b derived from Tel BN: white solid. M.p. 53-57° C.




Compound 150a derived from Tel B: yellow wax.
Compound 150b derived from Tel BN: pale yellow solid. M.p. 90-99° C.




Compound 151a derived from Tel B: white wax.
Compound 151b derived from Tel BN: white solid. M.p. 73-83° C.
EXAMPLE 11
Water and Oil Repellency in Polypropylene
In order to determine the repellency properties of the compounds of the formula I, they are tested according to the following procedure. The sample preparation is a combination of polypropylene nonwovens and a thermal treatment (e.g. 130° C. for 10 minutes), which increases the migration of the additive to the surface and a proper surface rearrangement of the chemical groups. This extra heat cycle is recommended to melt the compounds of the formula I in order to obtain a homogeneous redistribution over the surface of the substrate. An industrial sample of polypropylene nonwoven, fabric weight: 40 g/m2, is dipped into a 1% isopropanol solution of the test compound, simultaneously applying ultrasonic energy for one minute. After that, the sample is dried overnight at room temperature and then two hours at 90° C. in an oven. A part of the sample is afterwards annealed for 10 minutes at 130° C.
The treated nonwoven samples are evaluated in the water repellency test similar to INDA test method 80.8 (99). The wetting behavior of the nonwovens is tested with a series of water/isopropanol mixtures. The observation of the wetting behavior is rated from 0 (water wetting, no repellency) to 10 (optimum water repellency). The results are summarized in Table 2.
The treated nonwoven samples are evaluated in the oil repellency test similar to AATCC test method 118-1997/ISO 14419. This test follows the same concepts of the already described for water repellency test method, but using, as test solvents, a series of hydrocarbons. The observation of the wetting behavior is rated from 0 (no repellency) to 8 (optimum repellency). The results are summarized in Table 3.










TABLE 2







Water repellency
Water repellency


Example
Compound
as received
after annealing


















11a
compound 105
9
9


11b
compound 115
7
8


11c
compound 117
7
8


11d
compound 118
8
9


11e
compound 122
7
9


11f
compound 123
8
8


11g
compound 124
10
9


11h
compound 125
8
10


11i
compound 127
8
8


11j
compound 129
10
10


11k
compound 130
9
9


11l
compound 133
8
8


11m
compound 137
10
10


11n
compound 138
10
10


11o
compound 141
7
9


11p
compound 142
9
8


11q
compound 143
8
9


11r
compound 144
8
8


11s
compound 134
8
8


11t
compound 146b
7
7


11u
compound 147a
9
8


11v
compound 147b
10
10


11w
compound 148a
8
10


11x
compound 148b
8
10


11y
compound 149a
10
9


11z
compound 149b
10
9


11za
compound 150a
10
10


11zb
compound 150b
10
10


11zc
compound 151a
10
10


11zd
compound 151b
10
10



















TABLE 3







Oil repellency
Oil repellency


Example
Compound
as received
after annealing







11ze
compound 105
5
6


11zf
compound 113
6
8


11zg
compound 115
4
5


11zh
compound 129
6
6


11zi
compound 137
6
6


11zj
compound 138
5
6


11zk
compound 141
5
7


11zl
compound 146b
6
5


11zm
compound 147a
6
5


11zn
compound 147b
6
5


11zo
compound 150a
7
6


11zp
compound 150b
7
8


11zq
compound 151a
8
6


11zr
compound 151b
8
6









EXAMPLE 12
Water and Oil Repellency in Polypropylene Nonwoven Fibers
Compounding: Samples of the compounds of formula I are heated in an oven at 70° C. until they are completely liquefied. The liquid is added at 10-20 ml/min to a twin-screw extrusion of polypropylene pellets via a heated graduated cylinder using a Leistritz MIC 27/GL-32D twin-screw extruder. The extruder zones are 150°-195° C. with the main screw at 500 RPM and the PP feeder at 200-250 RPM. The molten polymer and additive exit via a two orifice round die. The molten material is immediately cooled and solidified in a cold-water trough. The solidified strand is fed into a Conair/Jetro 304 Pelletizer. The polypropylene used for the spunbond processing is PP 3155 from ExxonMobil (melt flow rate 36 g/10 min) and PP 3546 from ExxonMobil (melt flow rate 1200 g/10 min) for the meltblown processing.
Alternatively, the compounds of formula I are made into masterbatches by those skilled in the technique. The masterbatch at the desired level is then tumble mixed with the appropriate polypropylene for making spunbond and meltblown nonwovens.
Tumble Mixing The concentrate pellets are let down with additional polypropylene pellets and are mixed with a Marion SPS 1224 mixer, resulting in a desired additive concentration by weight.
Meltblown Process: Meltblown polypropylene fabrics are prepared from the tumble-mixed additives pellets prepared as above using a custum-bilt 6-inch Melt Blowing Pilot Line under the following conditions: Extruder temperature of 175-240° C. Die and air temperature of 240° C. Throughput 0.479 g/h/m (22 kg/hour/meter). Collector belt speed is adjusted to produce a nonwoven with a basis weight of 40-45 gsm.
The produced nonwoven samples are evaluated on their water/alcohol repellency behaviour similar to INDA standards (International Nonwoven and Disposables Association) and their oil repellency behaviour similar to AATCC standards. The results are summarized in Tables 4 and 5.










TABLE 4







Water





repellency
Water repellency


Example
Compound
as received
after annealing


















12a
1.0% of compound 105
8
9


12b
1.0% of compound 122
9
9


12c
1.0% of compound 124
9
8


12d
0.5% of compound 125
9
10


12e
1.0% of compound 129
9
10


12f
1.0% of compound 137
10
10


12g
1.0% of compound 134
8
8


12h
0.5% of compound 148a
3
8


12i
1.0% of compound 148a
8
9


12j
0.5% of compound 148b
5
9


12k
1.0% of compound 148b
9
10


12l
0.25% of compound 150b
3
10


12m
0.5% of compound 150b
5
10


12n
1.0% of compound 150b
9
10



















TABLE 5







Oil repellency
Oil repellency


Example
Compound
as received
after annealing







12o
1.0% of compound 105
4
6


12p
1.0% of compound 125
4
7


12q
1.0% of compound 129
5
6


12r
1.0% of compound 137
3
6


12s
1.0% of compound 148a
1
5


12t
1.0% of compound 148b
1
5


12u
0.5% of compound 150b
0
7









EXAMPLE 13
Extrusion of TPO Tapes (Thermoplastic Olefin Elastomer Grade for Roofing Membranes)
In order to evaluate the surface properties of the new compounds of the formula I as surface modifier, the following procedure is used: TPO is dried in a vacuum oven for eight hours at 60° C. The compound of the formula I is added in an amount as indicated in Table 6 to the dried TPO. The formulations are mixed in a turbo mixer and extruded in a twin-screw extruder (MiniLab extruder from Thermo Fischer Scientific) equipped with a flat die. In this way, TPO tapes are produced with a width of 5 mm and a thickness of around 0.5 mm. The processing temperature is around 195° C. All produced tapes have a beige appearance.
The contact angle of the produced tapes are measured with a Dataphysics OCA 30 contact angle device, using the sessile drop method and water as measuring liquid. The bigger the contact angle, the better. The results are summarized in Table 6.









TABLE 6





Example
Compound
Contact Angle (°)







13a)
100% TPO
103


13b)
 95% TPO
116



5% of compound 134





a)Comparative Example.


b)Example according to the invention.






EXAMPLE 14
Water and Oil Repellency in Continuous Polypropylene Fibers
Compounding: The compounding of the compounds of formula I is prepared as described in Example 12. The polypropylene used for the fiber spinning processing is Moplen HP 552R from Basell (melt flow rate 25 g/10 min).
Fiber spinning process: Continuous polypropylene multifilament fibers are prepared using a fiber spinning line, under the following conditions: Extruder temperature of 175-240° C., die temperature of 280° C., 40 filaments. Spin pump speed is adjusted to produce fibers with a specific weight of 2 denier. The fibers are then knitted to socks.
The knitted PP samples are evaluated in the water/alcohol repellency and oil repellency, respectively, as described in Example 11. The results are summarized in Table 7.










TABLE 7








Water




Water repellency
repellency


Example
Compound
as received
after annealing







14a
1.0% of compound 148b
0
8

## Claims

1. A process for reducing the surface energy of a thermoplastic polymer selected from polyacetals, polypropylene, polyethylene, polyether/polyurethanes, polyesters, polycarbonates and polyamides,
which comprises incorporating into the thermoplastic polymer at least a compound of formula I




wherein, when n is 1,
R1 is hydrogen, C1-C25alkyl, C2-C25alkenyl, —CO—R5, —CH(R10)CO—R5, —C(R10)2CO—R5, —CO—N(R6)—R7, —CH(R10)CO—N(R6)—R7, —C(R10)2CO—N(R6)—R7, —CH(R10)COOR5 or —C(R10)2CO—OR5;
when n is 2,
R1 is unsubstituted or with C1-C4alkyl, benzyl or phenyl substituted C1-C24alkylene; with oxygen or sulfur interrupted C2-C24alkylene; —CO—R8—CO—, —CH(R10)CO—R8—CO—CH(R10)—, —C(R10)2CO—R8—CO—C(R10)2—, —CO—N(R6)—R9—N(R6)—CO—, —CH(R10)CO—N(R6)—R9—N(R6)—CO—CH(R10)—, —C(R10)2CO—N(R6)—R9—N(R6)—CO—C(R10)2—, —CH(R10)CO—O—R9—O—CO—CH(R10)— or —C(R10)2CO—O—R9—O—CO—C(R10)2—;
when n is 3,
R1 is




R2, R3 and R4 independently of each other are hydrogen, C1-C25alkyl, C2-C25alkenyl, —CH(R11)—S(O)p—R12,




with the proviso that at least one of the radicals R2, R3 or R4 is —CH(R11)—S(O)p—R12;
R5 is C1-C25alkyl, C2-C25alkenyl, unsubstituted or with C1-C4alkyl or halogen substituted phenyl; or C7-C12phenylalkyl,
R6 is hydrogen or C1-C4alkyl,
R7 is hydrogen, C1-C25alkyl, unsubstituted or with C1-C4alkyl or halogen substituted phenyl;
R8 is phenylene, unsubstituted or with C1-C4alkyl, benzyl or phenyl substituted C1-C24alkylene; with oxygen or sulfur interrupted C2-C24alkylene;
R9 is a direct bond; unsubstituted or with C1-C4alkyl, benzyl or phenyl substituted C2-C24alkylene; or with oxygen or sulfur interrupted C2-C24alkylene;
R10 is hydrogen or C1-C8alkyl,
R11 is hydrogen, C1-C8alkyl, unsubstituted or with C1-C4alkyl substituted phenyl;
R12 is a monovalent perfluorinated alkyl or alkenyl, linear or branched organic radical having four to twenty fully fluorinated carbon atoms,
R13 is hydrogen, C1-C25alkyl, C2-C25alkenyl, —CO—R5, —CO—N(R6)—R7 or —CH2—CO—N(R6)—R7,
R14 is hydrogen, C1-C25alkyl, C2-C25alkenyl or —CH(R11)—S(O)p—R12,
R15 is hydrogen, C1-C25alkyl, C2-C25alkenyl or —CH(R11)—S(O)p—R12,
R16 is unsubstituted or with C1-C4alkyl substituted methylene, —S—, —S(O)—, —S(O)2— or —CO—;
R17 is C1-C4alkyl,
n is 1, 2 or 3, and
p is 0, 1 or 2.

2. A process according to claim 1, wherein, when n is 1,
R1 is hydrogen, C1-C18alkyl, C2-C18alkenyl, —CO—R5, —CO—N(R6)—R7 or —CH2—CO—N(R6)—R7;
when n is 2,
R1 is unsubstituted or with C1-C4alkyl, benzyl or phenyl substituted C1-C18alkylene; with oxygen or sulfur interrupted C2-C18alkylene; —CO—R8—CO—, —CO—N(R6)—R9—N(R6)—CO— or —CH(R10)—CO—N(R8)—R9—N(R6)—CO—CH(R10)—;
when n is 3,
R1 is




R2, R3 and R4 independently of each other are hydrogen, C1-C1-C18alkyl, C2-C18alkenyl, —CH(R11)—S(O)p—R12,




with the proviso that at least one of the radicals R2, R3 or R4 is —CH(R11)—S(O)p—R12;
R5 is C1-C18alkyl, C2-C18alkenyl, unsubstituted or with C1-C4alkyl or halogen substituted phenyl; or C7-C12phenylalkyl,
R6 is hydrogen or C1-C4alkyl,
R7 is hydrogen, C1-C18alkyl, unsubstituted or with C1-C4alkyl or halogen substituted phenyl;
R8 is phenylene, unsubstituted or with C1-C4alkyl, benzyl or phenyl substituted C1-C24alkylene; with oxygen or sulfur interrupted C2-C24alkylene;
R9 is a direct bond or unsubstituted or with C1-C4alkyl, benzyl or phenyl substituted C2-C18alkylene;
R10 is hydrogen or C1-C8alkyl,
R11 is hydrogen, C1-C8alkyl, unsubstituted or with C1-C4alkyl substituted phenyl;
R12 is a monovalent perfluorinated alkyl or alkenyl, linear or branched organic radical having four to twenty fully fluorinated carbon atoms,
R13 is hydrogen, C1-C18alkyl, C2-C18alkenyl, —CO—R5, —CO—N(R6)—R7 or —CH2—CO—N(R6)—R7,
R14 is hydrogen, C1-C18alkyl, C2-C18alkenyl or —CH(R11)—S(O)p—R12,
R15 is hydrogen, C1-C18alkyl, C2-C18alkenyl or —CH(R11)—S(O)p—R12,
R16 is unsubstituted or with C1-C4alkyl substituted methylene, —S—, —S(O)—, —S(O)2— or —CO—;
R17 is C1-C4alkyl,
n is 1, 2 or 3, and
p is 0, 1 or 2.

3. A process according to claim 1, wherein R12 is saturated and contains 4-15 carbon atoms, is fully fluorinated and contains at least one terminal perfluoromethyl group.

4. A process according to claim 1, wherein
R2, R3 and R4 independently of each other are hydrogen, C1-C4alkyl, —CH(R11)—S(O)p—R12 or




with the proviso that at least one of the radicals R2, R3 or R4 is —CH(R11)—S(O)p—R12;
R11 is hydrogen, C1-C8alkyl, unsubstituted or with C1-C4alkyl substituted phenyl;
R12 is a monovalent perfluorinated alkyl or alkenyl, linear or branched organic radical having four to twenty fully fluorinated carbon atoms,
R13 is hydrogen, C1-C18alkyl, C2-C18alkenyl or acetyl,
R14 is hydrogen, C1-C18alkyl, C2-C18alkenyl or —CH(R11)—S(O)p—R12,
R15 is hydrogen, C1-C18alkyl, C2-C18alkenyl or —CH(R11)—S(O)p—R12,
R16 is unsubstituted or with C1-C4alkyl substituted methylene, —S—, —S(O)—, —S(O)2— or —CO—; and
p is 0, 1 or 2.

5. A process according to claim 1, wherein,
when n is 1,
R1 is hydrogen, C1-C18alkyl, —CO—R5, —CO—N(R6)—R7 or —CH2—CO—N(R6)—R7;
when n is 2,
R1 is unsubstituted or with C1-C4alkyl substituted C1-C8alkylene; —CO—R8—CO—, —CO—N(R6)—R9—N(R6)—CO— or —CH(R10)—CO—N(R6)—R9—N(R6)—CO—CH(R10)—,
when n is 3,
R1 is




R2, R3 and R4 independently of each other are hydrogen, C1-C8alkyl, —CH(R11)—S(O)p—R12,




with the proviso that at least one of the radicals R2, R3 or
R4 is —CH(R11)—S(O)p—R12;
R5 is C1-C18alkyl, unsubstituted or with C1-C4alkyl substituted phenyl; or C7-C12-phenylalkyl,
R6 is hydrogen or C1-C4alkyl,
R7 is hydrogen, C1-C8alkyl, unsubstituted or with C1-C4alkyl substituted phenyl;
R8 is phenylene, unsubstituted or with C1-C4alkyl substituted C1-C18alkylene;
R9 is unsubstituted or with C1-C4alkyl substituted C2-C18alkylene;
R10 is hydrogen or C1-C8alkyl,
R11 is hydrogen, C1-C8alkyl, unsubstituted or with C1-C4alkyl substituted phenyl;
R12 is saturated and contains 4-15 carbon atoms, is fully fluorinated and contains at least one terminal perfluoromethyl group,
R13 is hydrogen, C1-C12alkyl, —CO—R5, —CO—N(R6)—R7 or —CH2—CO—N(R6)—R7,
R14 is hydrogen, C1-C12alkyl or —CH(R11)—S(O)p—R12,
R15 is C1-C18alkyl or —CH(R11)—S(O)p—R12,
R16 is unsubstituted or with C1-C4alkyl substituted methylene;
n is 1, 2 or 3, and
p is 0.

6. A process according to claim 1, wherein
R1 is hydrogen, C1-C18alkyl, —CO—R5, —CO—N(R6)—R7 or —CH2—CO—N(R6)—R7,
when n is 2,
R1 is C1-C8alkylene, —CO—R8—CO—, —CO—N(R6)—R9—N(R6)—CO— or —CH(R10)—CO—N(R8)—R8—N(R8)—CO—CH(R10)—,
when n is 3,
R1 is




R2, R3 and R4 independently of each other are hydrogen, C1-C8alkyl, —CH(R11)—S(O)p—R12,




with the proviso that at least one of the radicals R2, R3 or
R4 is —CH(R11)—S(O)p—R12;
R5 is C1-C18alkyl, unsubstituted or with C1-C4alkyl substituted phenyl; or benzyl,
R6 is hydrogen,
R7 is hydrogen, C1-C8alkyl, unsubstituted or with C1-C4alkyl substituted phenyl;
R8 is phenylene or C1-C18alkylene,
R9 is C2-C18alkylene,
R10 is C1-C4alkyl,
R11 is hydrogen, C1-C8alkyl, unsubstituted or with C1-C4alkyl substituted phenyl;
R12 is —CH2CH2(CF2)mCF3,
R13 is hydrogen or —CO—R5,
R14 is hydrogen or C1-C8alkyl,
R15 is C1-C4alkyl or —CH(R11)—S(O)p—R12,
R16 is methylene,
m is 3 to 12,
n is 1, 2 or 3, and
p is 0.

7. A process according to claim 1, wherein
when n is 1,
R1 is hydrogen, C1-C12alkyl, —CO—R5, —CO—N(R6)—R7 or —CH2—CO—N(R6)—R7;
when n is 2,
R1 is methylene, —CO—R8—CO— or —CH(R10)—CO—N(R6)—R9—N(R6)—CO—CH(R10)—;
when n is 3,
R1 is




R2, R3 and R4 independently of each other are hydrogen, C1-C4alkyl, —CH(R11)—S(O)—R12 or




with the proviso that at least one of the radicals R2, R3 or R4 is —CH(R11)—S(O)p—R12;
R5 is C1-C18alkyl,
R6 is hydrogen,
R7 is hydrogen, C1-C6alkyl, unsubstituted or with C1-C4alkyl substituted phenyl;
R8 is phenylene,
R9 is ethylene,
R10 is methyl,
R11 is hydrogen, C1-C8alkyl, unsubstituted or with methyl substituted phenyl;
R12 is —CH2CH2(CF2)mCF3,
R13 is hydrogen or acetyl,
R14 is C1-C4alkyl,
R15 is —CH(R11)—S(O)p—R12,
R16 is methylene,
m is 3 to 12,
n is 1, 2 or 3, and
p is 0.

8. A process according to claim 1 wherein the thermoplastic polymer is polypropylene or polyethylene.

9. A process according to claim 1 wherein the thermoplastic polymer is polypropylene.

10. A process according to claim 9, wherein the polypropylene is in the form of a fiber or a nonwoven fabric.

11. A process according to claim 1 wherein the compound of the formula I is present in an amount of from 0.01 to 10%, based on the weight of the thermoplastic polymer.

12. A process according to claim 1, comprising the incorporation of further additives.

13. A process according to claim 12, comprising as further additives phenolic antioxidants, light-stabilizers and/or processing stabilizers.

14. A composition comprising
a) a thermoplastic polymer selected from polyacetals, polypropylene, polyethylene, polyether/polyurethanes, polyesters, polycarbonates and polyamides and incorporated therein
b) a compound of formula I





wherein, when n is 1,
R1 is hydrogen, C1-C25alkyl, C2-C25alkenyl, —CO—R5, —CH(R10)CO—R5, —C(R10)2CO—R5, —CO—N(R6)—R7, —CH(R10)CO—N(R6)—R7, —C(R10)2CO—N(R6)—R7, —CH(R10)COOR5 or —C(R10)2CO—OR5;
when n is 2,
R1 is unsubstituted or with C1-C4alkyl, benzyl or phenyl substituted C1-C24alkylene; with oxygen or sulfur interrupted C2-C24alkylene; —CO—R8—CO—, —CH(R10)CO—R8—CO—CH(R10)—, —C(R10)2CO—R8—CO—C(R10)2—, —CO—N(R6)—R9—N(R6)—CO—, —CH(R10)CO—N(R6)—R9—N(R6)—CO—CH(R10)—, —C(R10)2CO—N(R6)—R9—N(R6)—CO—C(R10)2—, —CH(R10)CO—O—R9—O—CO—CH(R10)— or —C(R10)2CO—O—R9—O—CO—C(R10)2—;
when n is 3,
R1 is






R2, R3 and R4 independently of each other are hydrogen, C1-C25alkyl, C2-C25alkenyl, —CH(R11)—S(O)p—R12,






with the proviso that at least one of the radicals R2, R3 or R4 is —CH(R11)—S(O)p—R12;
R5 is C1-C25alkyl, C2-C25alkenyl, unsubstituted or with C1-C4alkyl or halogen substituted phenyl; or C7-C12-phenylalkyl,
R6 is hydrogen or C1-C4alkyl,
R7 is hydrogen, C1-C25alkyl, unsubstituted or with C1-C4alkyl or halogen substituted phenyl;
R8 is phenylene, unsubstituted or with C1-C4alkyl, benzyl or phenyl substituted C1-C24alkylene; with oxygen or sulfur interrupted C2-C24alkylene;
R9 is a direct bond, unsubstituted or with C1-C4alkyl, benzyl or phenyl substituted C2-C24alkylene; or with oxygen or sulfur interrupted C2-C24alkylene;
R10 is hydrogen or C1-C8alkyl,
R11 is hydrogen, C1-C8alkyl, unsubstituted or with C1-C4alkyl substituted phenyl;
R12 is a monovalent perfluorinated alkyl or alkenyl, linear or branched organic radical having four to twenty fully fluorinated carbon atoms,
R13 is hydrogen, C1-C25alkyl, C2-C25alkenyl, —CO—R5, —CO—N(R6)—R7 or —CH2—CO—N(R6)—R7,
R14 is hydrogen, C1-C25alkyl, C2-C25alkenyl or —CH(R11)—S(O)p—R12,
R15 is hydrogen, C1-C25alkyl, C2-C25alkenyl or —CH(R11)—S(O)p—R12,
R16 is unsubstituted or with C1-C4alkyl substituted methylene, —S—, —S(O)—, —S(O)2— or —CO—;
R17 is C1-C4alkyl,
n is 1, 2 or 3, and
p is 0, 1 or 2; with the proviso that the compounds of the formula A and B






are excluded.

15. A composition according to claim 14, wherein,
when n is 1,
R1 is hydrogen, C1-C12alkyl, —CO—R5, —CO—N(R6)—R7 or —CH2—CO—N(R6)—R7;
when n is 2,
R1 is methylene, —CO—R8—CO— or —CH(R10)—CO—N(R6)—R9—N(R6)—CO—CH(R10)—;
when n is 3,
R1 is




R2, R3 and R4 independently of each other are hydrogen, C1-C4alkyl, —CH(R11)—S(O)p—R12 or




with the proviso that at least one of the radicals R2, R3 or R4 is —CH(R11)—S(O)p—R12;
R5 is C1-C18alkyl,
R6 is hydrogen,
R7 is hydrogen, C1-C6alkyl, unsubstituted or with C1-C4alkyl substituted phenyl;
R8 is phenylene,
R9 is ethylene,
R10 is methyl,
R11 is hydrogen, C1-C8alkyl, unsubstituted or with methyl substituted phenyl;
R12 is —CH2CH2(CF2)mCF3,
R13 is hydrogen or acetyl,
R14 is C1-C4alkyl,
R15 is —CH(R11)—S(O)p—R12,
R16 is methylene,
m is 3 to 12,
n is 1, 2 or 3, and
p is 0.