Rheological modification of polymers with free radical initiators and thiourethanes

Abstract

The present invention relates to a process for modifying the rheology of a polymeric material, the process comprising the step of incorporating a modifier blend into the polymeric material, the modifier blend comprising a) a free radical initiator selected from the group consisting of peroxides, carbon-based free radical generators, bisazo compounds, or stable nitroxyl compounds, and b) a thiourethane having formula (1). The invention also relates to a modified polymeric material obtainable by incorporating a modifier blend into a polymeric material; and to a modifier blend.

Description

[0001] The present invention relates to a method for modifying the rheology of a polymer material, the method comprising the step of incorporating into the polymer material a modifier blend, the modifier blend comprising a) a free radical initiator selected from peroxides, carbon-based free radical generators, bis-azo compounds, or stable nitroxyl compounds, and b) a thiourethane having formula (1). The present invention also relates to a modified polymer material obtainable by incorporating the modifier blend into the polymer material; and to the modifier blend.

[0002] The controlled preparation of polymer types (polymer types with different molar masses, melt viscosities, densities, molar mass distributions, etc.) by conventional compounding methods (e.g. by extrusion or injection molding) is a conventional method used by polymer manufacturers and polymer processors / compounders. The setting of the desired parameters (e.g. melt viscosity) by such polymer processing steps depends largely on the controlled reactivity and mode of action of the additives used. Free radical formers, especially peroxides, are often used to modify the melt viscosity and rheology of polymer materials.

[0003] Various problems are known: high concentrations of free radical initiators are required to provide the expected properties; market and regulatory trends drive a general reduction in the amount of additives, e.g. to meet safety and sustainability requirements; peroxides in particular are often hazardous, quite unstable, sensitive to heat, shock or friction, and prone to reaction, with fire and explosion hazards being the main concerns.

[0004] Due to the low decomposition temperature of many free radical formers (e.g., peroxides), which is usually below the conventional temperature of polymer processing, the use of peroxides allows working only within a restricted "processing temperature window". Although the industry has developed reliable methods to ensure their safe use, there is still a need to optimize their performance as free radical initiators to promote rheological modification of polymeric materials.

[0005] These objects are solved by a method for modifying the rheology of a polymeric material, comprising the step of incorporating into the polymeric material a modifier blend comprising

[0006] a) a free radical initiator selected from peroxides, carbon-based free radical generators, disazo compounds, or stable nitroxyl compounds, and

[0007] b) Thiourethane having the formula (1)

[0008]

[0009] in

[0010] Ra Based on organic isocyanates,

[0011] One or more groups -SR a Introduced by reaction with isocyanate groups,

[0012] R b is optionally substituted and / or interrupted by C2-C 40 Alkyl, and

[0013] n is equal to or greater than 1.

[0014] These objects are solved by a modified polymer material obtainable by incorporating a modifier blend into a polymer material, wherein the modifier blend comprises

[0015] a) the free radical initiator, the free radical initiator being selected from peroxides, carbon-based free radical generators, disazo compounds, or stable nitroxyl compounds, and

[0016] b) the thiourethane of formula (1)

[0017]

[0018] in

[0019] R a Based on organic isocyanates,

[0020] One or more groups -SR a Introduced by reaction with isocyanate groups,

[0021] R b is optionally substituted and / or interrupted by C2-C 40 Alkyl, and

[0022] n is equal to or greater than 1.

[0023] These objects are solved by a modifier blend, wherein the modifier blend comprises

[0024] a) the free radical initiator, the free radical initiator being selected from peroxides, carbon-based free radical generators, disazo compounds, or stable nitroxyl compounds, and

[0025] b) the thiourethane of formula (1)

[0026]

[0027] in

[0028] R a Based on organic isocyanates,

[0029] One or more groups -SR a Introduced by reaction with isocyanate groups,

[0030] R b is optionally substituted and / or interrupted by C2-C 40 Alkyl, and

[0031] n is equal to or greater than 1.

[0032] Thiourethane has the formula (1)

[0033]

[0034] in

[0035] R a Based on organic isocyanates,

[0036] One or more groups -SR a Introduced by reaction with isocyanate groups,

[0037] R b is optionally substituted and / or interrupted by C2-C 40 Alkyl, and

[0038] n is equal to or greater than 1.

[0039] Residue R a Preferably based on an organic isocyanate, which is cyclohexyl diisocyanate, methylene bis(cyclohexyl) diisocyanate, isophorone diisocyanate, phenyl diisocyanate, diphenylmethane diisocyanate or naphthyl diisocyanate, each of which is unsubstituted or substituted by C1-C4 alkyl or di(C1-C4 alkyl)amino groups, or a C4-C4 alkyl 20 Alkyl diisocyanates, or oligomeric or polymeric products obtained by reaction of the above diisocyanates with themselves and / or with polyols.

[0040] More preferably, the residue R a Based on organic isocyanates, they are phenyl diisocyanate, diphenylmethane diisocyanate or naphthyl diisocyanate, each of which is unsubstituted or substituted by C1-C4 alkyl or di(C1-C4 alkyl)amino groups, or oligomeric or polymeric products obtained by reaction of the above diisocyanates with themselves and / or with polyols.

[0041] Highly preferred is R a Based on organic isocyanates, these are unsubstituted or C1-C4-alkyl-substituted phenyl diisocyanates, or oligomeric or polymeric products obtained by reaction of the above diisocyanates with themselves and / or with polyols.

[0042] The most preferred is Ra Based on toluene-2,4-diisocyanate or toluene-2,6-diisocyanate, or oligomeric or polymeric products obtained by reaction of the above diisocyanates with themselves and / or with polyols.

[0043] Examples of products obtained by reaction of the above diisocyanates with themselves are the following reaction products of three equivalents of toluene-2,4-diisocyanate or toluene-2,6-diisocyanate, respectively, having formulae (2) and (3):

[0044]

[0045] Examples of products obtained by the reaction of the above-mentioned diisocyanates with polyols are the following reaction products of toluene-2,4-diisocyanate or toluene-2,6-diisocyanate with a polyol having the formula HO—CH2—C(CH2—OH)2—CH2—CH3, respectively, having formulas (4) and (5):

[0046]

[0047] The polyol is preferably a C1-C 10 Alkanol, or poly-C2-C 10 Alkylene glycol.

[0048] For polyols, as C1-C 10 Alkanols are preferably those substituted by two to four, especially two or three, hydroxyl groups. Particularly preferred are C2-C 10 Alkanols, especially C2-C6-alkanols, which are correspondingly substituted with hydroxyl groups. Highly preferred are polyols having the formula HO-CH2-C(CH2-OH)2-CH2-CH3.

[0049] As poly-C2-C 10 Alkylene glycols, preferably poly-C2-C6 alkylene glycols, especially those having formula (7)

[0050]

[0051] wherein y is a number from 2 to 600, especially from 2 to 200 and most preferably from 2 to 100. Highly preferred are numbers from 2 to 50, especially from 2 to 20. As for formula (7), preferred are the corresponding polyethylene glycols or polypropylene glycols. Preferably, the polyol is a C2-C6 alkanol substituted with two to four hydroxyl groups, or a poly-C2-C6 alkylene glycol, especially of the type having formula (7).

[0052] In the case of the reaction of diisocyanates with themselves or of different types of diisocyanates with themselves, this can give rise to mixtures of different oligomers or polymers, and in the case of additional reactions with polyols, even more complex mixtures can be obtained. The corresponding organic isocyanates are known or can be obtained according to known methods, for example from WO 05 / 070987.

[0053] Residue R b It may be interrupted, for example, by -O-, -NH-, -S- and / or carbonyl groups. b A possible substituent is -SH. The corresponding C8-C 40 Alkyl, especially C8-C 20 Alkyl groups are preferred.

[0054] R b Preferably, the C2-C 40 The alkyl radical is, in particular, interrupted by -O- and / or carbonyl radicals.

[0055] Particularly preferably, R b It is a C8-C 40 Alkyl, especially C8-C 20 alkyl.

[0056] n is equal to or greater than 1, such as 1 to 10, preferably 1 to 5, or especially 1 to 3. In another form, n can be 1, 2, 3, 4 or 5.

[0057] Thiourea can be reacted with organic isocyanate to form HSR b The reaction of thiols can be obtained, where for R b The above definitions and preferences apply.

[0058] One or more groups -SR b The isocyanate group of an organic isocyanate is introduced by reaction and is bonded in the reaction product as a group having the formula (8)

[0059]

[0060] Where R b is as defined above.

[0061] In view of the above, the term "isocyanate functionalized with a thio compound" relates to the corresponding thiourethane.

[0062] The above method for preparing thiourethane is usually carried out in the presence of a catalyst (like a tertiary amine, for example triethylenediamine, dimethylpiperazine, dimethylethanolamine, 1,4-diazabicyclo[2.2.2]octane or 1,8-diazabicyclo[5,4,0]undec-7-ene), or with a tin compound (for example dibutyltin dilaurate) as a catalyst. Triethylamine is preferred. The catalyst is used, for example, in an amount of 0.1 to 10% by weight, based on the weight of the organic isocyanate. The reaction is usually carried out in the presence of an organic solvent (like tetrahydrofuran or ethyl acetate) and at a temperature of, for example, 30°C to 80°C.

[0063] Suitable thiourethanes have the formula (9), (10) or (11)

[0064]

[0065] In each of the formulas (9) and (10), R b is as defined above and for which the above preferences apply, or

[0066]

[0067] For formula (11), R b It is a C8-C 40 alkyl, and for which the above for R b Preferred are compounds of formula (9) and (10), especially those of formula (10).

[0068] In another form, the preferred thiourethane has the formula (12)

[0069]

[0070] The free radical initiator can be selected from peroxides, carbon-based free radical generators, disazo compounds, or stable nitroxyl compounds, wherein peroxides and carbon-based free radical generators are preferred. In one form, the free radical initiator is a peroxide. In another form, the free radical initiator is a carbon-based free radical generator.

[0071] Suitable peroxides are organic or inorganic peroxides, preferably organic peroxides. Typical examples of suitable organic peroxides include 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,3,6,6,9,9-pentamethyl-3-(ethyl acetate)-1,2,4,5-tetraoxycyclononane, tert-butyl hydroperoxide, hydrogen peroxide, dicumyl peroxide, tert-butyl peroxyisopropyl carbonate, di-tert-butyl peroxide, p-chlorobenzoyl peroxide, dibenzoyl diperoxide, tert-butylcumyl peroxide; tert-butyl hydroxyethyl peroxide, di-tert-pentyl peroxide, Peroxide and 2,5-dimethylhexene-2,5-diperisononanoate, acetyl cyclohexanesulfonyl peroxide, diisopropyl peroxydicarbonate, tert-amyl perneodecanoate, tert-butyl perneodecanoate, tert-butyl perpivalate, tert-amyl perpivalate, bis(2,4-dichlorobenzoyl) peroxide, diisononanoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, bis(2-methylbenzoyl) peroxide, disuccinyl peroxide, diacetyl peroxide, dibenzoyl peroxide, tert-butyl per-2-ethylhexanoate Ester, bis(4-chlorobenzoyl) peroxide, tert-butyl perisobutyrate, tert-butyl permaleate, 1,1-bis(tert-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, tert-butylperoxyisopropyl carbonate, tert-butyl perisononanoate, 2,5-dimethylhexane 2,5-dibenzoate, tert-butyl peracetate, tert-amyl perbenzoate, tert-butyl perbenzoate, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)propane, dicumyl peroxide, 2,5-dimethylhexane 2,5-dibenzoate tert-butyl peroxide, 3-tert-butylperoxy-3-phenylphthalide, di-tert-amyl peroxide, α,α'-bis(tert-butylperoxyisopropyl)benzene, 3,5-bis(tert-butylperoxy)-3,5-dimethyl-1,2-dioxolane, di-tert-butyl peroxide, 2,5-dimethylhexyne 2,5-di-tert-butyl peroxide, 3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxacyclononane, p-menthane hydroperoxide, pinane hydroperoxide, diisopropylbenzene mono-α-hydroperoxide, cumene hydroperoxide or tert-butyl hydroperoxide.

[0072] In another form, suitable peroxides are 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (DHBP), 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3 (DYBP), dicumyl-peroxide (DCUP), di-tert-butyl-peroxide (DTBP), tert-butyl-cumyl-peroxide (BCUP), bis(tert-butylperoxyisopropyl)benzene (DIPP), 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxanonane, di(tert-butylperoxyisopropyl)benzene, dicetyl peroxydicarbonate, and tert-butyl monoperoxymaleate.

[0073] Preferred peroxides are 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (DHBP), tert-butylcumyl-peroxide (BCUP) and 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxanonane, especially 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (DHBP) and 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxanonane. The peroxide is particularly 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane.

[0074] Suitable bisazo compounds are, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis(1-cyclohexanecarbonitrile), 2,2'-azobis(isobutyramide) dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-azobisisobutyric acid dimethyl ester, 2-(carbamoylazo)isobutyronitrile , 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methyl-propane), 2,2'-azobis(N,N'-dimethyleneisobutyramidine) in the form of a free base or a hydrochloride salt, 2,2'-azobis(2-amidinopropane) in the form of a free base or a hydrochloride salt, 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} or 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}.

[0075] Suitable stable nitroxyl compounds have the general formula (13)

[0076]

[0077] or a compound containing one or more groups of formula (14)

[0078]

[0079] wherein each R is an alkyl group and T is a group required to complete the 5-membered or 6-membered ring. Two or more nitroxyl groups may be present in the same molecule by being linked via a T moiety as exemplified below, wherein E is a linking group in formula (15):

[0080]

[0081] Suitable stable nitroxyl compounds include bis(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 4-hydroxy-1-oxy-2,2,6,6-tetramethylpiperidine, 4-ethoxy-1-oxy-2,2,6,6-tetramethylpiperidine, 4-propoxy-1-oxy-2,2,6,6-tetramethylpiperidine, 4-acetamido-1-oxy-2,2,6,6-tetramethylpiperidine, 1-oxy-2,2,6,6-tetramethylpiperidin-4-one, 1-oxy-2,2,6,6-tetramethylpiperidin-4-one, and 1-oxy-2,2,6,6-tetramethylpiperidin-4-one. 1-Oxy-2,2,6,6-tetramethylpiperidin-4-yl ester, 1-Oxy-2,2,6,6-tetramethylpiperidin-4-yl 2-ethyl hexanoate, 1-Oxy-2,2,6,6-tetramethylpiperidin-4-yl stearate, 1-Oxy-2,2,6,6-tetramethylpiperidin-4-yl benzoate, 1-Oxy-2,2,6,6-tetramethylpiperidin-4-yl 4-tert-butyl benzoate, bis(1-Oxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis(1-Oxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis(1-Oxy-2,2,6, 6-tetramethylpiperidin-4-yl) n-butylmalonate, bis(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl) o-phthalate, bis(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate, bis(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl) terephthalate, bis(-oxy-2,2,6,6-tetramethyl-piperidin-4-yl) hexahydroterephthalate, N,N'-bis(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl) adipamide, N-(1-oxy-2,2,6, 6-tetramethylpiperidin-4-yl)caprolactam, N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)dodecylsuccinimide, 2,4,6-tri-[N-butyl-N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)]-s-triazine, 4,4'-ethylenebis(1-oxyl-2,2,6,6-tetramethylpiperazin-3-one), 2-oxyl-1,1,3,3-tetramethyl-2-isobenzoxazole, 1-oxyl-2,2,5,5-tetramethylpyrrolidine and N,N-bis-(1,1,3,3-tetramethylbutyl)nitroxide.

[0082] Suitable carbon-based free radical generators have the formula (16)

[0083]

[0084] Where R 1 , R 3 , R 4 and R 6 Each of R is independently selected from the group consisting of hydrogen, substituted and unsubstituted linear, branched and cyclic hydrocarbons having 1 to 12 carbon atoms, and substituted and unsubstituted aromatic hydrocarbons having 6 to 12 carbon atoms, and R 2 and R 5 Each of the R is independently selected from the group consisting of substituted and unsubstituted linear, branched, and cyclic hydrocarbons having 1 to 12 carbon atoms and substituted and unsubstituted aromatic hydrocarbons having 6 to 12 carbon atoms, and wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 At least one of the is a substituted or unsubstituted aromatic hydrocarbon having 6 to 12 carbon atoms.

[0085] The carbon-based free radical generator having formula (16) can have symmetrical as well as asymmetrical structures. 2 and R 5 Each of which may be independently selected from a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R 1 , R 3 , R 4 and R 6 Each of is independently selected from the group consisting of hydrogen and C1-C6 alkyl.

[0086] In another embodiment, the carbon-based free radical generator has the formula (17)

[0087]

[0088] Where R 7 , R 8 , R 9 and R 10 Each of which is independently selected from the group consisting of a hydrogen atom, a C1-6 alkyl group, a C1-2 alkoxy group, a nitrile group and a halogen atom, and wherein R 1 , R 3 , R 4 and R 6 Each of is independently selected from the group consisting of hydrogen and C1-6 alkyl.

[0089] In yet another embodiment, the carbon-based free radical generator is selected from the group consisting of 2,3-dimethyl-2,3-diphenylbutane, 2,3-dipropyl-2,3-diphenylbutane, 2,3-dibutyl-2,3-diphenylbutane, 2,3-dihexyl-2,3-diphenylbutane, 2-methyl-3-ethyl-2,3-diphenylbutane, 2-methyl-2,3-diphenylbutane, 2,3-diphenylbutane, 2,3-dimethyl-2,3-di-(p-methoxyphenyl)-butane, 2,3-dimethyl-2,3-di-(p-methylphenyl)-butane, 2,3-dimethyl-2-methylphenyl-3-(p-2'3'-dimethyl-3'-methylphenyl-butyl)-phenyl-butane, 3,4-dimethyl-3,4-diphenylhexane, 3,4-diethyl-3,4-diphenylhexane, 3,4-dipropyl-3,4-diphenylhexane, 4,5-dipropyl-4,5-diphenyloctane, 2,3-diisobutyl-2,3-diphenylbutane, 3,4-diisobutyl-3,4-diphenylhexane, 2,3-dimethyl-2,3-di-(p-tert-butylphenyl)butane, 5,6-dimethyl-5,6-diphenyldecane, 6,7-dimethyl-6,7-diphenyldodecane, 7,8-dimethyl-7,8-di(methoxyphenyl)-tetradecane, 2,3-diethyl-2,3-diphenylbutane, 2,3-dimethyl-2,3-di(p-chlorophenyl)butane, 2,3-dimethyl-2,3-di(p-iodophenyl)butane and 2,3-dimethyl-2,3-di(p-nitrophenyl)butane.

[0090] In another embodiment, the carbon-based free radical generator is selected from the group consisting of 2,3-dimethyl-2,3-diphenylbutane and 3,4-dimethyl-3,4-diphenylhexane, preferably 2,3-dimethyl-2,3-diphenylbutane.

[0091] The free radical initiator can be added to a polymer material such as a polyolefin in an amount of 0.0001% to 5% by weight, especially 0.001% to 5% by weight and more preferably 0.01% to 5% by weight. In another form, the free radical initiator can be added to a polymer material such as a polyolefin in an amount of 0.01% to 2% by weight, especially 0.01% to 1% by weight.

[0092] Thiourethane can be added to a polymer material such as polyolefin in an amount of 0.0001% to 5% by weight, especially 0.001% to 5% by weight and more preferably 0.01% to 5% by weight. In another form, the free radical initiator can be added to a polymer material such as polyolefin in an amount of 0.01% to 2% by weight, especially 0.01% to 1% by weight.

[0093] The weight ratio of the free radical initiator to the thiourethane is generally 1:2 to 30:1, preferably 1:1 to 20:1, and particularly 1.2:1 to 15:1. In another form, the weight ratio of the free radical initiator to the thiourethane may be 1:1 to 10:1, preferably 1.5:1 to 5:1, and particularly 2:1 to 4:1. In another form, the weight ratio of the free radical initiator to the thiourethane is 1:2 to 30:1, preferably 1:1 to 20:1, and particularly 1.5:1 to 5:1.

[0094] In another form, the polymeric material is a polyolefin, the free radical initiator is a peroxide, and the weight ratio of free radical initiator to thiourethane is from 1:1 to 20:1.

[0095] In another form, the polymer material is a polyolefin, the free radical initiator is a peroxide, wherein the peroxide is 2,5-dimethyl-2,5-bis(tert-butyl-peroxy)hexane (DHBP), 2,5-dimethyl-2,5-bis(tert-butyl-peroxy)hexyne-3 (DYBP), dicumyl-peroxide (DCUP), di-tert-butyl-peroxide (DTBP), tert-butyl-cumyl-peroxide (BCUP), bis(tert-butylperoxyisopropyl)benzene (DIPP), 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxanonane, di(tert-butylperoxyisopropyl)benzene, dicetyl peroxydicarbonate, or tert-butyl monoperoxymaleate, and the weight ratio of the free radical initiator to the thiourethane is 1:1 to 20:1.

[0096] In another form, the polymeric material is a polyolefin, the free radical initiator is a carbon-based free radical generator, and the weight ratio of the free radical initiator to the thiourethane is from 1:1 to 20:1.

[0097] In another form, the polymeric material is a polyolefin, the free radical initiator is a carbon-based free radical generator, wherein the carbon-based free radical generator has formula (17), and the weight ratio of the free radical initiator to the thiourethane is 1:1 to 20:1.

[0098] In another form, the polymeric material is a polyolefin, the free radical initiator is a peroxide, and the weight ratio of free radical initiator to thiourethane is from 1.5:1 to 5:1.

[0099] In another form, the polymeric material is a polyolefin, the free radical initiator is a carbon-based free radical generator, and the weight ratio of the free radical initiator to the thiourethane is from 1.5:1 to 5:1.

[0100] In another form, the polymeric material is a polyolefin, the free radical initiator is a carbon-based free radical generator, wherein the carbon-based free radical generator has formula (17), and the weight ratio of the free radical initiator to the thiourethane is from 1.5:1 to 5:1.

[0101] In another form, the polymer material is a polyolefin, the free radical initiator is a peroxide, the weight ratio of the free radical initiator to the thiourethane is 1:1 to 20:1, and R a Based on an organic isocyanate, it is cyclohexyl diisocyanate, methylenebis(cyclohexyl) diisocyanate, isophorone diisocyanate, phenyl diisocyanate, diphenylmethane diisocyanate or naphthyl diisocyanate, each of which is unsubstituted or substituted by a C1-C4 alkyl group or a di(C1-C4 alkyl)amino group, or is a C4-C20 alkyl diisocyanate, or an oligomeric or polymeric product obtained by reacting the above diisocyanates with themselves and / or with a polyol.

[0102] In another form, the polymer material is a polyolefin, the free radical initiator is a peroxide, wherein the peroxide is 2,5-dimethyl-2,5-bis(tert-butyl-peroxy)hexane (DHBP), 2,5-dimethyl-2,5-bis(tert-butyl-peroxy)hexyne-3 (DYBP), dicumyl-peroxide (DCUP), di-tert-butyl-peroxide (DTBP), tert-butyl-cumyl-peroxide (BCUP), bis(tert-butylperoxyisopropyl)benzene (DIPP), 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxanonane, di(tert-butylperoxyisopropyl)benzene, dicetyl peroxydicarbonate, or tert-butyl monoperoxymaleate, the weight ratio of the free radical initiator to the thiourethane is 1:1 to 20:1, and R a Based on an organic isocyanate, it is cyclohexyl diisocyanate, methylenebis(cyclohexyl) diisocyanate, isophorone diisocyanate, phenyl diisocyanate, diphenylmethane diisocyanate or naphthyl diisocyanate, each of which is unsubstituted or substituted by a C1-C4 alkyl group or a di(C1-C4 alkyl)amino group, or is a C4-C20 alkyl diisocyanate, or an oligomeric or polymeric product obtained by reacting the above diisocyanates with themselves and / or with a polyol.

[0103] In another form, the polymer material is a polyolefin, the free radical initiator is a carbon-based free radical generator, the weight ratio of the free radical initiator to the thiourethane is 1:1 to 20:1, and R aBased on an organic isocyanate, which is cyclohexyl diisocyanate, methylene bis(cyclohexyl) diisocyanate, isophorone diisocyanate, phenyl diisocyanate, diphenylmethane diisocyanate or naphthyl diisocyanate, each of which is unsubstituted or substituted by C1-C4 alkyl or di(C1-C4 alkyl)amino groups, or is C4-C 20 Alkyl diisocyanates, or oligomeric or polymeric products obtained by reaction of the above diisocyanates with themselves and / or with polyols.

[0104] In another form, the polymer material is a polyolefin, the free radical initiator is a carbon-based free radical generator, wherein the carbon-based free radical generator has formula (17), the weight ratio of the free radical initiator to the thiourethane is 1:1 to 20:1, and R a Based on an organic isocyanate, which is cyclohexyl diisocyanate, methylene bis(cyclohexyl) diisocyanate, isophorone diisocyanate, phenyl diisocyanate, diphenylmethane diisocyanate or naphthyl diisocyanate, each of which is unsubstituted or substituted by C1-C4 alkyl or di(C1-C4 alkyl)amino groups, or is C4-C 20 Alkyl diisocyanates, or oligomeric or polymeric products obtained by reaction of the above diisocyanates with themselves and / or with polyols.

[0105] In another form, the polymer material is a polyolefin, the free radical initiator is a peroxide, the weight ratio of the free radical initiator to the thiourethane is 1:1 to 20:1, and R a Based on organic isocyanates, these are unsubstituted or C1-C4-alkyl-substituted phenyl diisocyanates, or oligomeric or polymeric products obtained by reaction of the above diisocyanates with themselves and / or with polyols.

[0106] In another form, the polymer material is a polyolefin, the free radical initiator is a carbon-based free radical generator, the weight ratio of the free radical initiator to the thiourethane is 1.5:1 to 5:1, and R a Based on organic isocyanates, these are unsubstituted or C1-C4-alkyl-substituted phenyl diisocyanates, or oligomeric or polymeric products obtained by reaction of the above diisocyanates with themselves and / or with polyols.

[0107] In another form, the polymer material is a polyolefin, the free radical initiator is a peroxide, the weight ratio of the free radical initiator to the thiourethane is 1.5:1 to 5:1, and R a Based on organic isocyanates, these are unsubstituted or C1-C4-alkyl-substituted phenyl diisocyanates, or oligomeric or polymeric products obtained by reaction of the above diisocyanates with themselves and / or with polyols.

[0108] In another form, the polymer material is a polyolefin, the free radical initiator is a carbon-based free radical generator, the weight ratio of the free radical initiator to the thiourethane is 1:1 to 20:1, and R a Based on organic isocyanates, these are unsubstituted or C1-C4-alkyl-substituted phenyl diisocyanates, or oligomeric or polymeric products obtained by reaction of the above diisocyanates with themselves and / or with polyols.

[0109] In another form, the polymer material is a polyolefin, the free radical initiator is a peroxide, the weight ratio of the free radical initiator to the thiourethane is 1:1 to 20:1, and the thiourethane is a compound having formula (9) and formula (10).

[0110] In another form, the polymer material is a polyolefin, the free radical initiator is a peroxide, wherein the peroxide is 2,5-dimethyl-2,5-bis(tert-butyl-peroxy)hexane (DHBP), 2,5-dimethyl-2,5-bis(tert-butyl-peroxy)hexyne-3 (DYBP), dicumyl-peroxide (DCUP), di-tert-butyl-peroxide (DTBP), tert-butyl-cumyl-peroxide (BCUP), bis(tert-butylperoxyisopropyl)benzene (DIPP), 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxanonane, di(tert-butylperoxyisopropyl)benzene, dicetyl peroxydicarbonate, or tert-butyl monoperoxymaleate, the weight ratio of the free radical initiator to the thiourethane is 1:1 to 20:1, and the thiourethane is a compound having formula (9) and formula (10).

[0111] In another form, the polymer material is a polyolefin, the free radical initiator is a carbon-based free radical generator, the weight ratio of the free radical initiator to the thiourethane is 1:1 to 20:1, and the thiourethane is a compound having formula (9) and formula (10).

[0112] In another form, the polymer material is a polyolefin, the free radical initiator is a carbon-based free radical generator, wherein the carbon-based free radical generator has formula (17), the weight ratio of the free radical initiator to the thiourethane is 1:1 to 20:1, and the thiourethane is a compound having formula (9) and formula (10).

[0113] In another form, the modifier blend comprises a free radical initiator selected from peroxides and a thiourethane, wherein R aBased on organic isocyanate, it is unsubstituted or C1-C4 alkyl-substituted phenyl diisocyanate, or oligomeric or polymeric products obtained by reaction of the above diisocyanates with themselves and / or with polyols, and the weight ratio of free radical initiator to thiourethane is 1:2 to 30:1, preferably 1:1 to 20:1, in particular 1.5:1 to 5:1.

[0114] In another form, the modifier blend comprises a free radical initiator selected from a peroxide, wherein the peroxide is 2,5-dimethyl-2,5-bis(tert-butyl-peroxy)hexane (DHBP), 2,5-dimethyl-2,5-bis(tert-butyl-peroxy)hexyne-3 (DYBP), dicumyl-peroxide (DCUP), di-tert-butyl-peroxide (DTBP), tert-butyl-cumyl-peroxide (BCUP), bis(tert-butylperoxyisopropyl)benzene (DIPP), 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxanonane, di(tert-butylperoxyisopropyl)benzene, dicetyl peroxydicarbonate, or tert-butyl monoperoxymaleate; and thiourethane, and the weight ratio of the free radical initiator to the thiourethane is 1:2 to 30:1, preferably 1:1 to 20:1, and especially 1.5:1 to 5:1.

[0115] In another form, the modifier blend comprises a free radical initiator selected from a peroxide, wherein the peroxide is 2,5-dimethyl-2,5-bis(tert-butyl-peroxy)hexane (DHBP), 2,5-dimethyl-2,5-bis(tert-butyl-peroxy)hexyne-3 (DYBP), dicumyl-peroxide (DCUP), di-tert-butyl-peroxide (DTBP), tert-butyl-cumyl-peroxide (BCUP), bis(tert-butylperoxyisopropyl)benzene (DIPP), 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxanonane, di(tert-butylperoxyisopropyl)benzene, dicetyl peroxydicarbonate, or tert-butyl monoperoxymaleate; and a thiourethane, wherein R a Based on organic isocyanate, it is unsubstituted or C1-C4 alkyl-substituted phenyl diisocyanate, or oligomeric or polymeric products obtained by reaction of the above diisocyanates with themselves and / or with polyols, and the weight ratio of free radical initiator to thiourethane is 1:2 to 30:1, preferably 1:1 to 20:1, in particular 1.5:1 to 5:1.

[0116] In another form, the modifier blend comprises a free radical initiator selected from peroxides, wherein the peroxide is 2,5-dimethyl-2,5-bis(tert-butyl-peroxy)hexane (DHBP), 2,5-dimethyl-2,5-bis(tert-butyl-peroxy)hexyne-3 (DYBP), dicumyl-peroxide (DCUP), di-tert-butyl-peroxide (DTBP), tert-butyl-cumyl-peroxide (BCUP), bis(tert-butylperoxyisobutyl)peroxide (ISO-butyl)peroxide (ISO-butyl)peroxide (ISO-butyl)peroxide (ISO-butyl)peroxide (ISO-butyl)peroxide (ISO-butyl)peroxide (ISO-butyl)peroxide (ISO-butyl)peroxide (ISO-butyl)peroxide (ISO-butyl)peroxide ( propyl)benzene (DIPP), 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxanonane, di(tert-butylperoxyisopropyl)benzene, dicetyl peroxydicarbonate, or tert-butyl monoperoxymaleate; and thiourethane, wherein the thiourethane has formula (9) or formula (10), and the weight ratio of the free radical initiator to the thiourethane is 1:2 to 30:1, preferably 1:1 to 20:1, and particularly 1.5:1 to 5:1.

[0117] In another form, the modifier blend comprises a free radical initiator selected from carbon-based free radical generators and a thiourethane, wherein R a Based on organic isocyanate, it is unsubstituted or C1-C4 alkyl-substituted phenyl diisocyanate, or oligomeric or polymeric products obtained by reaction of the above diisocyanates with themselves and / or with polyols, and the weight ratio of free radical initiator to thiourethane is 1:2 to 30:1, preferably 1:1 to 20:1, in particular 1.5:1 to 5:1.

[0118] In another form, the modifier blend comprises a free radical initiator selected from a carbon-based free radical generator, wherein the carbon-based free radical generator has formula (17); and a thiourethane, wherein R a Based on organic isocyanate, it is unsubstituted or C1-C4 alkyl-substituted phenyl diisocyanate, or oligomeric or polymeric products obtained by reaction of the above diisocyanates with themselves and / or with polyols, and the weight ratio of free radical initiator to thiourethane is 1:2 to 30:1, preferably 1:1 to 20:1, in particular 1.5:1 to 5:1.

[0119] In another form, the modifier blend comprises a free radical initiator selected from a carbon-based free radical generator, wherein the carbon-based free radical generator has formula (17); and thiourethane, wherein the thiourethane has formula (9) or formula (10), and the weight ratio of the free radical initiator to the thiourethane is 1:2 to 30:1, preferably 1:1 to 20:1, and especially 1.5:1 to 5:1.

[0120] In a preferred form, if the free radical initiator is selected from peroxides, the polymeric material, such as a polyolefin, does not contain compounds having formula (18) or formula (19)

[0121]

[0122] in

[0123] G1, G2, G3 and G4 are each independently C1-C4 alkyl, or G1 and G2 together or G3 and G4 together are pentamethylene;

[0124] G1', G2', G3' and G4' are each independently C1-C4 alkyl, or G1' and G2' together or G3' and G4' together are pentamethylene;

[0125] G5, G6, G5' and G6' are each independently hydrogen or C1-C4 alkyl; and

[0126] X and X' are independently hydrogen, C1-C 18 Alkyl, C2-C 18 Alkenyl, -O-C1-C 18 Alkyl, -NH-C1-C 18 Alkyl, -N(C1-C6alkyl)2, phenyl, phenoxy or -NH-phenyl,

[0127] m is 1 or 2, and

[0128] When m is 1, R1 is C2-C8 alkylene or C2-C8 hydroxyalkylene or C4-C 36 Acyloxyalkylene, or

[0129] When m is 2, R1 is (-CH2)2C(CH2-)2, and

[0130] R1' is hydrogen, C1-C8 alkyl, C1-C8 hydroxyalkyl or a compound having the formula -(C=O)-C1-C 40 an alkyl group, or

[0131] -O-R1' together with the -CH- group to which they are attached is the group -(C=O)-.

[0132] The polymer substrate may be a thermoplastic polymer such as a polyolefin, polyester, polyamide, polyvinyl chloride, polyimide, polyacrylonitrile, polycarbonate or polystyrene polymer. Preferably, the polymer substrate is a polyolefin.

[0133] Suitable polyolefins are polymers of mono- and di-olefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, and polymers of cycloolefins, for example polymers of cyclopentene or norbornene, polyethylene (which may optionally be cross-linked), for example high-density polyethylene (HDPE), high-density and high-molecular-weight polyethylene (HDPE-HMW), high-density and ultra-high-molecular-weight polyethylene (HDPE-UHMW), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), (VLDPE) and (ULDPE).

[0134] Polyolefins, preferably polyethylene and polypropylene, can be prepared by the following process:

[0135] a) Free radical polymerization (usually under high pressure and at elevated temperature).

[0136] b) Catalytic polymerization using a catalyst which generally contains one or more than one metal of group IVb, Vb, VIb or VIII of the periodic table. These metals generally have one or more than one ligand, typically oxides, halides, alkoxides, esters, ethers, amines, alkyls, alkenyls and / or aryls, which may be π-coordinated or σ-coordinated. These metal complexes may be in free form or fixed on a substrate, typically on activated magnesium chloride, titanium (III) chloride, aluminum oxide or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalyst itself may be used in the polymerization, or a further activator may be used, typically a metal alkyl, metal hydride, metal alkyl halide, metal alkyl oxide or metal alkyloxane, the metal being an element of group Ia, IIa and / or IIIa of the periodic table. The activator may conveniently be modified with a further ester, ether, amine or silyl ether group. These catalyst systems are often referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

[0137] Examples of mixtures of polyolefins are mixtures of polypropylene with polyisobutylene, mixtures of polypropylene with polyethylene (eg PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (eg LDPE / HDPE).

[0138] Examples of copolymers of monoolefins and dienes with each other or with other vinyl monomers are 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 / vinyl cyclohexane copolymers, ethylene / cycloolefin copolymers (e.g., ethylene / norbornene like COC), ethylene / 1-olefin copolymers (wherein the 1-olefin is generated in situ); propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / vinyl cyclohexene copolymers , ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers or ethylene / acrylic acid copolymers and their salts (ionomers) and terpolymers of ethylene with propylene and a diene (such as hexadiene, dicyclopentadiene or ethylidene-norbornene); and mixtures of such copolymers with each other and with the polymers mentioned above in 1), 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 (such as polyamides).

[0139] More preferably, the polyolefin is selected from the group consisting of polyethylenes like linear low density polyethylene, low density polyethylene, medium density polyethylene and high density polyethylene, as well as polyethylene copolymers and polypropylene homopolymers and polypropylene copolymers. Highly preferred are polyethylene or polypropylene, especially polypropylene.

[0140] Also suitable as polymeric material are recycled plastics, which can be obtained from household, commercial and industrial waste or from useful material collections. Recycled plastics can originate from separation and sorting, or from specific industrial sectors and return obligations, for example from the automotive industry, electrical / electronics industry, construction, agriculture and textile industry, or from households and commerce (e.g. supermarkets). Recycled plastics can be single-material recycled plastics, for example from polymer classes consisting of polyolefins (polypropylene, high-density polyethylene, low-density polyethylene and polypropylene blends), and copolymers such as PP / EPDM and PP / PE and polystyrene, or defined mixtures of recycled plastics.

[0141] Recycled plastics may also contain polyethylene terephthalate, polyamide, polycarbonate, cellulose acetate and polyvinylidene chloride. Minor amounts (up to about 5%) of non-thermoplastics such as polyurethanes, formaldehyde resins and phenolic resins, as well as typical amino resins, and also elastomers such as vulcanized or unvulcanized rubber may also be present. In some plastic wastes, small amounts of foreign substances such as paper, pigments and adhesives may also be present, which are often difficult to remove. These foreign substances may also originate from contact with various substances during use or processing, such as fuel residues, coating components, trace metals, initiator residues or traces of water.

[0142] The step of incorporating the modifier blend comprising a free radical initiator and thiourethane into a polymer material (such as a polyolefin) can be achieved by conventional methods, such as adding the modifier blend or its single component (i.e., free radical initiator and thiourethane) to the polymer material. The modifier blend or its single component (i.e., free radical initiator and thiourethane) can be added to the polymer material in the form of a liquid, powder, particle or masterbatch. Free radical initiator and thiourethane and optionally other additives can be added to the polymer material individually or mixed with each other. Preferably, the free radical initiator and thiourethane are added together, preferably in the form of a masterbatch.

[0143] The free radical initiator and the thiourethane and optionally further additives can be added to the polymer material before, during or after polymerization or before or after crosslinking. The free radical initiator and the thiourethane and optionally further additives can be incorporated into the polymer material by known methods, for example before or during shaping, or by applying the dissolved or dispersed corresponding compounds to the polymer material (if necessary, with subsequent evaporation of the solvent).

[0144] These compounds are added to the polymer material and can be carried out in all conventional mixing machines, in which the polymer is melted and mixed with the compound of the present composition and optionally other additives. Suitable machines are mixers, kneaders and extruders. The method is preferably carried out by adding these compounds during the processing in the extruder. Particularly preferred processing machines are single screw extruders, co-rotating twin screw extruders and counter-rotating twin screw extruders, planetary gear extruders, annular extruders or co-kneaders provided with at least one gas removal compartment to which vacuum can be applied.

[0145] The polymer is subjected to elevated temperature for a sufficient period of time for molecular weight modification. In a preferred embodiment of the process of the invention, a temperature range of about 150° C. to 340° C. is employed. In a preferred process variant, a temperature range of about 200° C. to 320° C., or 200° C. to 300° C., or 170° C. to 290° C., in particular about 180° C. to 280° C. is used.

[0146] The time period required to change the molecular weight may vary with the temperature, the amount of material to be modified, and the type of any extruder employed. It may range, for example, from about 10 seconds to 20 minutes, particularly 20 seconds to 10 minutes.

[0147] Examples of processing or transformation of the composition according to the invention are: injection blow molding, extrusion, blow molding, rotational molding, in-mold decoration (back injection), slush molding, injection molding, co-injection molding, forming, compression molding, pressing, film extrusion (cast film; blown film), fiber spinning, other fiber processing (woven, nonwoven, especially fiber meltblown, spunbond), stretching (uniaxial, biaxial), annealing, deep drawing, calendering, mechanical transformation, sintering, coextrusion, coating, lamination, crosslinking (radiation, peroxide, silane), vapor deposition, welding together, gluing, thermoforming, tube extrusion, profile extrusion, sheet extrusion; sheet casting, spin coating, bundling, foaming, recycling / reprocessing, extrusion coating.

[0148] The materials processed according to the present invention can be used in a variety of forms, for example as films, fibers (continuous or discontinuous), tapes, or molded articles. Preferred fibers include bicomponent fibers. Bicomponent fibers mean fibers comprising at least two different polymer domains a) and b) that are closely adhered along the length of the fiber. These can have any shape and are not limited to a specific shape. Examples of such shapes are side-by-side; skin-core, segmented, and matrix and fibril types. Preferred are skin-core bicomponent fibers and side-by-side bicomponent fibers, especially skin-core bicomponent fibers.

[0149] Preferred products are nonwoven fabrics, which also should include webs and should be intended to be oriented or randomly oriented and the textile structure of individual fibers, filaments or lines bonded by friction and / or cohesion and / or adhesion and / or mechanical processes, contrary to the regular pattern of mechanically interwoven fibers, i.e., it is not a weaving or knitted fabric. The example of nonwoven fabrics includes meltblown filaments, spunbond continuous filament webs, webs that are carded, webs that are air-laid and webs that are wet-laid. Suitable bonding methods include thermal bonding, chemical or solvent bonding, resin bonding, mechanical acupuncture, hydraulic pressure acupuncture, stitch bonding. Suitable products made of polymeric materials are geotextiles, roofing materials, cables, films, filter media, filters, diapers, sanitary napkins, pads, incontinence products for adults, protective clothing, surgical isolation cloths, surgical gowns or surgical gowns.

[0150] Rheological modification of polymeric materials such as polyolefins is often achieved by long chain branching, crosslinking or visbreaking. Rheological modification allows for improved

[0151] - Mechanical properties, like tensile strength, elongation, tear resistance;

[0152] - Barrier properties, especially in nonwovens (e.g. hydrohead, air permeability, filtration properties);

[0153] - Processing properties (wider range of suitable polymers, adaptation of parameters like thermal bonding temperature in nonwovens);

[0154] - Recycling, since the adjustment of the melt viscosity of the recycled polymer can provide a recycled article with a more uniform molecular weight (narrower MWD) and therefore better mechanical properties. In addition, the use of visbroken polymers can be used as a processing aid or compatibilizer, which also contributes to the higher mechanical properties of the recycled polymer. In addition, since the rheological qualities of the recycled polymer are variable, the present invention enables the adjustment of the rheological response of the polymer so that it can have a more stable and controllable process.

[0155] Improved properties with respect to tensile strength and elongation are important for the manufacture of, for example, nonwoven fabrics, since their preparation involves multiple steps and improved tensile strength or elongation helps to make them better withstand these steps. Importantly, higher tensile strength provides producers of nonwoven fabrics with the option of, for example, reducing weight while still maintaining good mechanical properties of the product.

[0156] Another important aspect is the process safety during the preparation of nonwovens. It is desirable to run the process for the preparation of nonwoven fabrics under milder conditions at lower process temperatures. In order to be able to do this, still good mechanical properties, like tensile strength and elongation, must be obtained at lower process temperatures. This allows the process temperature to be reduced. In addition, energy saving will be a secondary benefit.

[0157] Rheological modification of a polymeric material generally means a decrease in molecular weight (e.g., by degradation of the polymeric material) or an increase in molecular weight (e.g., by crosslinking or branching of the polymeric material). The modified rheology is generally determined by analyzing the melt flow index (MFI) as per EN ISO 133, e.g., at 230° C. at 2.16 kg.

[0158] Modification generally means that the rheology (e.g., as determined by MFI) of a polymeric material, such as a polyolefin, comprising a modifier blend with a certain amount of free radical initiator is increased or decreased (preferably, the MFI is increased) by at least 1%, 3%, 5%, 10%, 20%, 30%, 40%, or 50% based on the rheology of the same polymeric material having only the certain amount of free radical initiator (but not the thiourethane).

[0159] The polymer material may also additionally contain various conventional additives, for example antioxidants, UV absorbers and light stabilizers, metal deactivators, phosphites and phosphonites, hydroxylamines, nitrones, thiosynergists, peroxide scavengers, polyamide stabilizers, alkaline co-stabilizers, nucleating agents, fillers and reinforcing agents, benzofuranones and indolones, or other additives, such as plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow control agents, optical brighteners, flame retardants, antistatic agents and blowing agents.

[0160] 1. Antioxidants

[0161] 1.1. Alkylated monophenols, such as 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-di-octadecyl-4-methylphenol, 2,4,6 - tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched nonylphenols in the side chains such as 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadecan-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol, and mixtures thereof.

[0162] 1.2. Alkylthiomethylphenol , for example, 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-bis-dodecylthiomethyl-4-nonylphenol.

[0163] 1.3. Hydroquinone 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.

[0164] 1.4. Tocopherol , such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

[0165] 1.5. Hydroxylated thiodiphenyl ether , 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-pentylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide.

[0166] 1.6. Alkylene bisphenols, such as 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'-ethylenebis(4,6 -di-tert-butylphenol), 2,2'-ethylenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenol phenyl) butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tri(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, [2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl] 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-tetrakis-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

[0167] 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-dimethylbenzyl mercaptoacetate, 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-hydroxybenzyl mercaptoacetate.

[0168] 1.8. Hydroxybenzylated malonates, for example, bis-octadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, bis-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, bis-dodecylmercaptoethyl-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.

[0169] 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.

[0170] 1.10. Triazine compounds , such as 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.

[0171] 1.11. Benzylphosphonate , for example, dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, di-octadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, di-octadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salt of monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate.

[0172] 1.12. Acylaminophenol , such as 4-hydroxylauranilide, 4-hydroxystearanilide, N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamic acid octyl ester.

[0173] 1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid: monohydric alcohol or polyhydric alcohol, for example methanol, ethanol, n-octanol, isooctyl alcohol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thioundecanol, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0174] 1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid : monohydric or polyhydric alcohols, for example methanol, ethanol, n-octanol, isooctyl alcohol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thioundecanol, 3-thiopentadecanol, 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.

[0175] 1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid and : monohydric alcohol or polyhydric alcohol, for example methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thioundecanol, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0176] 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid and : monohydric alcohol or polyhydric alcohol, for example methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thioundecanol, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0177] 1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, such as 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]oxalamide ( XL-1, supplied by Addivant).

[0178] 1.18. Ascorbic acid (Vitamin C)

[0179] 1.19. Amine antioxidants, for example, N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-butyl-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-methyl 4-(p-toluenesulfonyl)diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyl diphenylamine, 4-isopropoxy diphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine (e.g., p-, p-di-tert-octyl diphenylamine), 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-decanoylaminophenol, Octacarboxylic acid aminophenol, 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, mixtures of mono- and di-alkylated tert-butyl / tert-octyl diphenylamines mixture of monoalkylated and dialkylated nonyldiphenylamine, mixture of monoalkylated and dialkylated dodecyldiphenylamine, mixture of monoalkylated and dialkylated isopropyl / isohexyldiphenylamine, mixture of monoalkylated and dialkylated tert-butyldiphenylamine, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixture of monoalkylated and dialkylated tert-butyl / tert-octylphenothiazines, mixture of monoalkylated and dialkylated tert-octyl-phenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene.

[0180] 2.UV absorbers and light stabilizers

[0181] 2.1.2-(2'-Hydroxyphenyl)benzotriazole, 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-ethyl)- 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)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-ethylhexyloxy)carbonylethyl]- 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol]; ester exchange product of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole and polyethylene glycol 300;

[0182]

[0183] Wherein R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 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.

[0184] 2.2.2-Hydroxybenzophenone, such as 4-hydroxy, 4-methoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.

[0185] 2.3. Esters of substituted and unsubstituted benzoic acids , for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 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.

[0186] 2.4. Acrylate / cinnamate , for example, ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbonylmethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-methoxycarbonyl-p-methoxycinnamate, N-(β-methoxycarbonyl-β-cyanovinyl)-2-methylindoline, tetra(α-cyano-β,β-diphenylacrylate neopentyl. Cyanoacrylates can also be used as such compounds, as described in EP 3587425.

[0187] 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 monoalkyl esters such as the methyl or ethyl ester of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes such as 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.

[0188] 2.6. Sterically hindered amines, for example, bis(1-undecanyloxy-2,2,6,6-tetramethyl-4-piperidinyl) carbonate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl) succinate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, 1-(2-hydroxyethyl)-2,2, Condensate of 6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidinyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butanetetracarboxylate, 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethyl Piperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidinyl)-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-tetramethylpiperidinyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidinyl) succinate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenedione A linear or cyclic condensate of amine and 4-morpholino-2,6-dichloro-1,3,5-triazine, a condensate of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidinyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, a condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidinyl)-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-piperidinyl)pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidinyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5- Condensate of triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Registry No. [136504-96-6]); Condensate of 1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine and N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Registry No. [192268-64-7]); N-(2,2,6,6-tetramethyl-4-piperidinyl)-n-dodecylsuccinimide, N-(1,2,2,6,6-pentamethyl-4-piperidinyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1 -oxa-3,8-diaza-4-oxo-spiro[4,5]decane, reaction products of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane and epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidinyloxycarbonyl)-2-(4-methoxyphenyl)ethylene, N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine, diester of 4-methoxymethylenemalonic acid and 1,2,2,6,6-pentamethyl-4-hydroxypiperidinyl, poly[methyl]propyl-3-oxy-4 -(2,2,6,6-tetramethyl-4-piperidinyl)]siloxane, reaction product of maleic 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-tetramethylpiperidin-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,. 3058 (Clariant; CAS Reg. No. 106917-31-1], 5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, reaction products of 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-chloro-s-triazine and N,N'-bis(3-aminopropyl)ethylenediamine), 1,3,5-tri(N-cyclohexyl-N-(2,2,6,6-tetramethylpiperazin-3-one-4-yl)amino)-s-triazine, 1,3,5-tri(N-cyclohexyl-N-(1,2,2,6,6-pentamethylpiperazin-3-one-4-yl)amino)-s-triazine.

[0189] 2.7. Oxamide , for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-bis-dodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and mixtures thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides, and mixtures of o- and p-ethoxy-disubstituted oxanilides.

[0190] 2.8.2-(2-Hydroxyphenyl)-1,3,5-triazine, 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-propoxyphenyl)-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-butoxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy / tridecyloxyphenyl)-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-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine ]-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-hydroxypropoxy]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, 2,4-bis(4-biphenyl)-6-[2-hydroxy-4-(2-ethylhexyloxy)phenyl]-1,3,5-triazine.

[0191] 3. Metal deactivator, for example, N,N'-diphenyloxamide, N-salicylaldehyde-N'-salicylic hydrazide, N,N'-bis(salicylicyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicylicylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxalanilide, isophthalic acid dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicylicyl)oxalyl dihydrazide, N,N'-bis(salicylicyl)thiopropionyl dihydrazide.

[0192] 4. Phosphites and phosphonites , for example triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-di-cumylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyl phosphite Pentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tri(tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl) -6-methylphenyl) methyl ester, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphocene, 2,2',2"-nitrilo[triethyltri(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-dioxaphosphirane, phosphite, mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triesters (CAS: 939402-02-5), triphenyl phosphite polymer with α-hydrogen-ω-hydroxypoly[oxy(methyl-1,2-ethanediyl)] C10-16 alkyl esters (CAS: 1227937-46-3), Doverphos LGP-12 (CAS: 116265-68-1).

[0193] The following phosphites are particularly preferred: tris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl)phosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite,

[0194]

[0195]

[0196] 5. Hydroxylamine , for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-bis-tetradecylhydroxylamine, N,N-bis-hexadecylhydroxylamine, N,N-bis-octadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine or derived from a vegetable source.

[0197] 6. Nitrones , for example, N-benzyl-α-phenylnitrone, N-ethyl-α-methylnitrone, N-octyl-α-heptylnitrone, N-lauryl-α-undecylnitrone, N-tetradecyl-α-tridecylnitrone, N-hexadecyl-α-pentadecylnitrone, N-octadecyl-α-heptadecylnitrone, N-hexadecyl-α-heptadecylnitrone, N-octadecyl-α-pentadecylnitrone, N-heptadecyl-α-heptadecylnitrone, N-octadecyl-α-hexadecylnitrone, nitrones derived from N,N-dialkylhydroxylamines derived from hydrogenated tallow amine.

[0198] 7. Thiosynergist , for example dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate or pentaerythritol tetrakis[3-(dodecylthio)propionate] or distearyl disulfide.

[0199] 8. Peroxide scavengers , for example esters of β-thiodipropionic acid, such as the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole, or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, bis-octadecyl disulfide, pentaerythritol tetrakis(β-dodecylmercapto)propionate.

[0200] 9. Polyamide stabilizer , such as copper salts and divalent manganese salts in combination with iodides and / or phosphorus compounds.

[0201] 10. Alkaline stabilizer, such as melamine, polyvinyl pyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, zeolites, hydrotalcites, hydrated calcium aluminates (hydrocaluminate), zinc oxide, alkali metal salts and alkaline earth metal salts of higher fatty acids (such as calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate), antimony pyrocatecholate or zinc pyrocatecholate.

[0202] 11. Nucleating agent , for example inorganic substances such as talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, including phosphates such as 2,2'-methylene-bis(4,6-di-tert-butylphenol)phosphate sodium salt, 2,2'-methylene-bis(4,6-di-tert-butylphenol)phosphate aluminum salt or 2,2'-methylene-bis(4,6-di-tert-butylphenol)phosphate lithium salt, preferably alkaline earth metal carbonates or sulfates; organic compounds, such as monocarboxylic acids or polycarboxylic acids and salts thereof, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate, 1,2-cyclohexanedicarboxylic acid calcium salt, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid disodium salt; polymer compounds, such as ionic copolymers (ionomers), triaminobenzene derivatives such as 1,3,5-tris[2,2-dimethylpropionamido]benzene, zinc glycerate and nonytol derivatives. Particularly preferred are 1,3:2,4-bis(3',4'-dimethylbenzylidene)sorbitol, 1,3:2,4-di(p-methyldibenzylidene)sorbitol, and 1,3:2,4-di(benzylidene)sorbitol.

[0203] 12. Fillers and reinforcing agents , for example calcium carbonate, silicates, surface treated silica (as described, for example, in US-A-2007 / 60,697 and US-A-2009 / 111,918), glass fibers, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and powders or fibers of other natural products, synthetic fibers.

[0204] 13. Other additives , such as plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow control agents, fluorescent whitening agents, flame retardants, antistatic agents and foaming agents. Other additives can also include anti-blocking additives, which are used in the film to reduce the negative adhesion of two polyethylene surfaces to each other, otherwise this will cause the difficulty of separating the film. Other additives include slip agents, which are used to help the film surface slide on each other. Antifogging agents can also be added.

[0205] 14. Benzofuranones and indolones, such as those disclosed in: US4,325,863; US4,338,244; US5,175,312; US5,216,052; US5,252,643; DE-A-4316611;

[0206] 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-butylbenzofuran-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-tert-butylbenzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2-acetyl-5-isooctylphenyl)-5-isooctylbenzofuran-2-one, 5,7-di-tert-butyl-3-[3,5-dimethyl-4-[(1,3,7,9-tetra-tert-butyl-5-methyl-5H-benzo[d][1,3,2]benzodioxaphosphinotan-11-yl)oxy]phenyl]-3H-benzofuran-2-one. Suitable benzofuranones also include compounds identified in WO2015 / 121445 and WO2017 / 025431.

[0207] Preferred are compositions which additionally contain further additives selected from the group consisting of antioxidants, processing stabilizers, light stabilizers, UV absorbers, fillers, reinforcing agents, pigments, metal deactivators, plasticizers, lubricants, emulsifiers, rheological additives, catalysts, flow control agents, optical brighteners, flame retardants, antistatic agents and blowing agents.

[0208] Examples

[0209] ThioU: Thiourethane having the formula (12).

[0210] PER: 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, commercially available as Enox 101 from Vesta Chemicals

[0211] DIC: 2,3-dimethyl-2,3-diphenylbutane, commercially available from Acros Organics.

[0212] Example 1-Example 8

[0213] The base stabilizer (0.1% B 225 and 0.05% calcium stearate) and the additives listed in Table 1 were added to a commercially available polypropylene powder (HA10XT from Polychim Industrie, France, melt flow index 3 g / 10 min ASTM D1238). The mixture was extruded on a twin screw extruder (Berstorff ZE25A x 47D, KraussMaffei Berstorff GmbH, Germany) at a temperature of Tmax = 230°C with a throughput of 4 kg / h and 100 rpm under N2. The resulting polymer strands were pelletized in a water bath.

[0214] The melt flow index (MFI) is MI Robo(Gateford Material Testing Machinery Co., Ltd.( The results were determined at 230° C. and 2.16 kg in accordance with EN ISO 1133 at 230° C. at 2.16 kg in a 1400 nm, 100 nm, 200 nm and 80 nm, respectively.

[0215] An increase in MFI indicates visbreaking activity, corresponding to controlled polypropylene chain degradation. The difference in MFI ("ΔMFI", i.e. the MFI of the formulation with added additives compared to the MFI of the reference formulation without added additives) is a measure of the different activities of the additives. The results are summarized in Tables 1a to 1d.

[0216] Table 1a

[0217]

[0218] Comparative Examples 1-3 show the known increase in MFI at increasing peroxide concentrations. Comparative Example 4 shows that ThioU has almost no effect on MFI when used without peroxide. Example 1 demonstrates that a ΔMFI of about 3 can be achieved at only 0.003% peroxide when combined with ThioU, whereas in Comparative Example 1, double the amount, 0.006% peroxide, is required.

[0219] Table 1b

[0220]

[0221]

[0222] Table 1c

[0223]

[0224] Examples 2, 3, 4 and 5 demonstrate that the ΔMFI can be increased even further when peroxide is combined with ThioU.

[0225] Table 1d

[0226]

[0227] Comparative Examples 4 and 5 show the known low increase in MFI under DIC.Examples 6-8 demonstrate that ΔMFI can be significantly increased when combined with ThioU.

[0228] Example 9-Example 10

[0229] Examples 9-10 were prepared as described in Example 1, but instead of an extrusion temperature of 230° C., a temperature of 270° C. was used. The results are summarized in Table 2.

[0230] Table 2

[0231]

[0232] Examples 9 and 10 demonstrate that ΔMFI can be increased when peroxide is combined with ThioU.

[0233] Example 11 - Example 12

[0234] Examples 11-12 were prepared as described in Example 1, but instead of an extrusion temperature of 230°C, a temperature of 250°C was used, and a different commercial polypropylene (ground Moplen HP561R from Lyondellbasell, MFI 25 g / 10 min ISO 1133-1) was used. The results are summarized in Tables 3a and 3b.

[0235] Table 3a

[0236]

[0237] Example 11 demonstrates that when peroxide is combined with ThioU, even when the peroxide is used at a lower concentration compared to Comparative Example 7, the ΔMFI can be increased.

[0238] Table 3b

[0239]

[0240] Example 12 demonstrates that when DIC is combined with ThioU, ΔMFI can be increased even when DIC is used at half the concentration compared to Comparative Example 9.

[0241] Example 13 - Example 14

[0242] A) Preparation of masterbatch

[0243] The peroxide masterbatch was produced by adding 0.15% PER to commercial polypropylene (ground Moplen HP 561R, MFI 25 from LyondellBasell Industries) via soaking. For this purpose, the polymer pellets were placed in a round piston. The piston was preheated to 60° C. and the PER was then added with the help of a dropper. The piston was closed and sealed with PTFE. The piston was placed on a rotary evaporator and the mixture was treated for 3 hours under continuous rotation.

[0244] An activator masterbatch was produced by mixing 0.15% ThioU into the same polypropylene powder (Moplen HP561R) with the help of a high speed mixer. In a subsequent step, the mixture was compounded in a twin screw extruder (Berstorff ZE25AX47D) at 200°C.

[0245] B) Preparation of bicomponent nonwovens

[0246] Spunbond nonwovens were produced with polypropylene Total 7059 (MFI 11, from Total Energy) in the core and PP 511A (MFI 25, from Sabic) in the sheath, with and without additives in the core, on a 1 m wide Reicofil No. 4 line with a single tow of about 6800 holes per meter length. The diameter of the holes was 0.62 mm. The throughput per hole was set at 0.55 g / min. The line had a sheath-core construction with 20% by weight of the polymer in the sheath and 80% by weight of the polymer in the core. Comparative fibers were prepared in which both domains contained no additives.

[0247] 70g / m 2 The nonwoven was produced at a fabric weight of 1.50 m / min (line speed: 52 m / min). The target filament fineness was 1.7 dtex (dtex is a unit of measure for the linear mass density of a fiber and is defined as the mass in grams / 10,000 meters). The nonwoven was thermally bonded using an embossing roll set at 165° C. at a nip pressure set at 90 N / mm.

[0248] The additives given in the following table were added via their corresponding masterbatches as described above, wherein the weight % indicates the total amount of additive present in the masterbatch.

[0249] Additional processing conditions are given below:

[0250] - Extruder temperature is the temperature used for extruding the polypropylene or polypropylene / additive blend on a Reicofil line 4, which in all cases was set at 270°C for the core and 250°C for the sheath.

[0251] - Chamber pressure is the pressure in the chamber behind and below the mould, which was set to 4500 Pa in all cases.

[0252] C) Evaluation of mechanical properties

[0253] The mechanical properties of the nonwoven fabrics were determined according to DIN EN 29073-3 at a sample grip length of 100 mm, a sample width of 50 mm, an advance (deformation speed) of 200 mm / min. Tensile strength TD and elongation TD are the corresponding maximum values ​​measured in the direction perpendicular to the machine direction. Elongation MD is the corresponding maximum value measured in the machine direction. The results are summarized in Tables 4a and 4b.

[0254] Table 4a

[0255]

[0256] Example 13 demonstrates that the tensile strength is increased compared to Comparative Examples 10-11, even when a lower or half amount of PER is used.

[0257] Table 4b

[0258]

[0259] Example 14 demonstrates that elongation is increased compared to Comparative Examples 12-13, even when a lower or half amount of PER is used.

Claims

1. A method for modifying the rheology of a polymer material, the method comprising the step of incorporating into the polymer material a modifier blend, the modifier blend comprising a) a free radical initiator selected from peroxides, carbon-based free radical generators, disazo compounds, or stable nitroxyl compounds, and b) Thiourethane having the formula (1) in R a Based on organic isocyanates, One or more groups -SR a Introduced by reaction with isocyanate groups, R b is optionally substituted and / or interrupted by C2-C 40 Alkyl, and n is equal to or greater than 1.

2. The method according to claim 1, wherein: The weight ratio of the free radical initiator to the thiourethane is 1:2 to 30:1, preferably 1:1 to 20:1, in particular 1.5:1 to 5:

1.

3. The method according to claim 1 or 2, wherein: The free radical initiator is selected from peroxides or carbon-based free radical generators.

4. The method according to any one of claims 1 to 3, wherein: The carbon-based free radical generator has the formula (17) Where R 7 , R 8 , R 9 and R 10 Each of which is independently selected from the group consisting of a hydrogen atom, a C1-6 alkyl group, a C1-2 alkoxy group, a nitrile group and a halogen atom, and wherein R 1 , R 3 , R 4 and R 6 Each of is independently selected from the group consisting of hydrogen and C1-6 alkyl.

5. The method according to any one of claims 1 to 4, wherein: The peroxide is 2,5-dimethyl-2,5-bis(tert-butyl-peroxy)hexane (DHBP), 2,5-dimethyl-2,5-bis(tert-butyl-peroxy)hexyne-3 (DYBP), dicumyl-peroxide (DCUP), di-tert-butyl-peroxide (DTBP), tert-butyl-cumyl-peroxide (BCUP), bis(tert-butylperoxyisopropyl)benzene (DIPP), 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxanonane, di(tert-butylperoxyisopropyl)benzene, dicetyl peroxydicarbonate, or tert-butyl monoperoxymaleate.

6. The method according to any one of claims 1 to 5, wherein: The free radical initiator is added to the polymer material in an amount of 0.0001% to 5% by weight.

7. The method according to any one of claims 1 to 6, wherein: The thiourethane is added to the polymer material in an amount of 0.0001 to 5% by weight.

8. The method according to any one of claims 1 to 7, wherein: R a Based on an organic isocyanate, which is cyclohexyl diisocyanate, methylene bis(cyclohexyl) diisocyanate, isophorone diisocyanate, phenyl diisocyanate, diphenylmethane diisocyanate or naphthyl diisocyanate, each of which is unsubstituted or substituted by C1-C4 alkyl or di(C1-C4 alkyl)amino groups, or is C4-C 20 Alkyl diisocyanates, or oligomeric or polymeric products obtained by reaction of the above diisocyanates with themselves and / or with polyols.

9. The method according to any one of claims 1 to 8, wherein: R a Based on organic isocyanates, these are unsubstituted or C1-C4-alkyl-substituted phenyl diisocyanates, or oligomeric or polymeric products obtained by reaction of the above diisocyanates with themselves and / or with polyols.

10. The method according to claim 8 or 9, wherein: The polyol is a C1-C 10 Alkanol, or poly-C2-C 10 Alkylene glycol.

11. The method according to any one of claims 1 to 10, wherein: R b is a C8-C 40 alkyl.

12. The method according to any one of claims 1 to 11, wherein: The thiourethane has the formula (9) or (10) Where R b is optionally substituted and / or interrupted by C 2- C 40 alkyl.

13. The method according to any one of claims 1 to 12, wherein: The polymer material is a thermoplastic polymer, preferably a polyolefin, and in particular a linear low density polyethylene, a low density polyethylene, a medium density polyethylene, a high density polyethylene, a polyethylene copolymer, a polypropylene homopolymer, or a polypropylene copolymer.

14. A modified polymeric material obtainable by incorporating a modifier blend as defined in any one of the preceding claims into a polymeric material as defined in any one of the preceding claims, wherein: The modifier blend comprises a) the free radical initiator, the free radical initiator being selected from peroxides, carbon-based free radical generators, disazo compounds, or stable nitroxyl compounds, and b) the thiourethane having the formula (1) in R a Based on organic isocyanates, One or more groups -SR a Introduced by reaction with isocyanate groups, R b is optionally substituted and / or interrupted by C2-C 40 Alkyl, and n is equal to or greater than 1.

15. A modifier blend as defined in any one of the preceding claims, wherein: The modifier blend comprises a) the free radical initiator, the free radical initiator being selected from peroxides, carbon-based free radical generators, disazo compounds, or stable nitroxyl compounds, and b) the thiourethane having the formula (1) in R a Based on organic isocyanates, One or more groups -SR a Introduced by reaction with isocyanate groups, R b is optionally substituted and / or interrupted by C2-C 40 Alkyl, and n is equal to or greater than 1.

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