Rheological modification of polymers using radical initiators and thiourethanes.

Abstract

The present invention relates to a method for modifying the rheology of a polymeric material, comprising the step of incorporating into the polymeric material a modifier blend comprising: a) a radical initiator selected from a peroxide, a carbon-based radical generator, a bis-azo compound, or a stable nitroxyl compound; and b) a thiourethane of formula (1). The present invention also relates to modified polymeric materials obtainable by incorporating the modifier blend into the polymeric material, and to the modifier blend.

Description

[Technical Field]

[0001] The present invention relates to a method for modifying the rheology of a polymeric material, comprising the step of incorporating into the polymeric material a modifier blend comprising: a) a radical initiator selected from a peroxide, a carbon-based radical generator, a bis-azo compound, or a stable nitroxyl compound; and b) a thiourethane of formula (1). The present invention also relates to modified polymeric materials obtainable by incorporating the modifier blend into the polymeric material, and to the modifier blend. [Background technology]

[0002] The controlled preparation of polymer types (with various molar masses, melt viscosities, densities, molar mass distributions, etc.) by conventional compounding methods, for example by extrusion or injection molding, is a routine process used by polymer manufacturers and polymer processors / compounders. The setting of desired parameters, for example melt viscosity, by this polymer processing step depends crucially on the controlled reactivity and mode of action of the additives used. Free radical formers, in particular peroxides, are often used to modify the melt viscosity and rheology of polymer materials.

[0003] Various problems are known: high concentrations of radical initiators are required to provide the expected performance; market and regulatory trends generally drive the reduction of additive amounts, for example to meet safety and sustainability requirements; peroxides in particular are often toxic, fairly unstable, sensitive to heat, impact or friction, and easily reactive; and the main concern is the risk of fire and explosion.

[0004] Generally, the low decomposition temperatures of many free radical formers, such as peroxides, below conventional polymer processing temperatures, limit the use of peroxides to work within a limited "processing temperature window." Although the industry has developed reliable processes to ensure their safe use, there remains a need to optimize their performance as free radical initiators to promote rheological modification of polymer materials. Summary of the Invention [Means for solving the problem]

[0005] The object is to provide a method for modifying the rheology of a polymeric material, comprising: a) a radical initiator selected from peroxides, carbon-based radical generators, bis-azo compounds, or stable nitroxyl compounds; b) Equation (1) [ka] (In the formula, R a is based on organic isocyanates, Group-SR a is introduced by reaction with an isocyanate group, R b is an optionally substituted and / or interrupted C2-C 40 is alkyl, wherein n is 1 or greater.

[0006] This object is solved by a modified polymer material which can be obtained by incorporating a modifier blend into the polymer material, in which case the modifier blend comprises: a) a radical initiator selected from peroxides, carbon-based radical generators, bis-azo compounds, or stable nitroxyl compounds; b) Equation (1) [ka] (In the formula, R a is based on organic isocyanates, Group-SR a is introduced by reaction with an isocyanate group, R b is an optionally substituted and / or interrupted C2-C 40 is alkyl, n is 1 or greater).

[0007] The purpose of this is to a) a radical initiator selected from peroxides, carbon-based radical generators, bis-azo compounds, or stable nitroxyl compounds; b) Equation (1) [ka] (In the formula, R a is based on organic isocyanates, Group-SR a is introduced by reaction with an isocyanate group, R b is an optionally substituted and / or interrupted C2-C 40 is alkyl, This was solved by a modifier blend containing thiourethane (where n is 1 or greater). DETAILED DESCRIPTION OF THE INVENTION

[0008] Thiourethanes are represented by the formula (1) [ka] (In the formula, R a is based on organic isocyanates, Group-SR a is introduced by reaction with an isocyanate group, R b is an optionally substituted and / or interrupted C2-C 40 is alkyl, n is 1 or greater).

[0009] residue R a is preferably based on an organic isocyanate, which is cyclohexyl diisocyanate, methylenebis(cyclohexyl) diisocyanate, isophorone diisocyanate, phenyl diisocyanate, diphenylmethane diisocyanate or naphthyl diisocyanate, each of which is unsubstituted or substituted with C1-C4 alkyl or di(C1-C4 alkyl)amino, or C4-C 20 Alkyl diisocyanates or oligomeric or polymeric products obtained by reaction of the above diisocyanates with themselves and / or with polyols.

[0010] More preferably, the residue R a is based on an organic isocyanate, which is phenyl diisocyanate, diphenylmethane diisocyanate, or naphthyl diisocyanate, each of which is unsubstituted or substituted with C1-C4 alkyl or di(C1-C4 alkyl)amino, or an oligomeric or polymeric product obtained by reaction of the above diisocyanates with themselves and / or with polyols.

[0011] R a is based on an organic isocyanate, which is highly preferably a phenyl diisocyanate, unsubstituted or substituted by C1-C4 alkyl, or an oligomeric or polymeric product obtained by reaction of said diisocyanates with themselves and / or with polyols.

[0012] R a are most preferably based on toluene-2,4-diisocyanate or toluene-2,6-diisocyanate or oligomeric or polymeric products obtained by reaction of said diisocyanates with themselves and / or with polyols.

[0013] Examples of products obtained by reaction of the above diisocyanates with themselves are represented by formulas (2) and (3): [ka] with three equivalents of toluene-2,4-diisocyanate or toluene-2,6-diisocyanate, respectively:

[0014] Examples of products obtained by reacting the above diisocyanates with polyols are represented by formulas (4) and (5): [ka] are the following reaction products of toluene-2,4-diisocyanate or toluene-2,6-diisocyanate, respectively, with a polyol of formula HO—CH—C(CH—OH)—CH—CH:

[0015] The polyol is preferably a C1-C2 polyol containing two or more hydroxy groups. 10 Alkanol, or poly-C2-C 10 It is an alkylene glycol.

[0016] C1-C for polyols 10 Preferred alkanols are those substituted with 2 to 4, especially 2 or 3, hydroxy groups. 10 Alkanols, especially C2-C6 alkanols, which are correspondingly substituted with hydroxy groups, are particularly preferred. Polyols of the formula HO-CH2-C(CH2-OH)2-CH2-CH3 are very particularly preferred.

[0017] Poly-C2-C 10 Preferred alkylene glycols are poly-C2-C6 alkylene glycols, particularly those represented by the formula (7): [ka] (wherein y is a number from 2 to 600, particularly from 2 to 200, most preferably from 2 to 100). Numbers from 2 to 50, particularly from 2 to 20, are highly preferred. With respect to formula (7), the corresponding polyethylene glycol or polypropylene glycol is preferred. Preferably, the polyol is a C2-C6 alkanol substituted with 2 to 4 hydroxy groups, or a poly-C2-C6 alkylene glycol, particularly of formula (7).

[0018] When a diisocyanate is reacted with itself, or when different types of diisocyanate are reacted with itself, this can result in a mixture of different oligomers or polymers, and in the case of further reaction with polyols, even more complex mixtures can be obtained. The corresponding organic isocyanates are known or can be obtained according to known processes, for example, as described in WO 05 / 070987.

[0019] residue R b R can be interrupted, for example, by —O—, —NH—, —S— and / or carbonyl groups. b A possible substituent for is -SH. The corresponding C8-C 40 Alkyl, especially C8-C 20 Alkyl is preferred.

[0020] R b is preferably a C2-C alkyl group uninterrupted or interrupted by -O-, -NH-, -S- and / or carbonyl groups, in particular -O- and / or carbonyl groups. 40 It is alkyl.

[0021] Particularly preferably, R b C8-C uninterrupted or interrupted by -O- and / or carbonyl groups 40 Alkyl, especially C8-C 20 It is alkyl.

[0022] n is 1 or more, for example 1 to 10, preferably 1 to 5, or especially 1 to 3. In another aspect, n may be at least 1, 2, 3, 4, or 5.

[0023] Thiourethanes are organic isocyanates of the formula HSR b can be obtained by reaction with a thiol of the formula R b For , the above definitions and preferences apply.

[0024] Group-SR b is introduced by reaction with the isocyanate group of an organic isocyanate, and in the reaction product, [ka] (In the formula, R b is as defined above). In view of the above, the term "isocyanate functionalized with a thio compound" relates to the corresponding thiourethane.

[0025] The above process for preparing thiourethanes is typically carried out in the presence of a catalyst such as a tertiary amine, e.g., triethylenediamine, dimethylpiperazine, dimethylethanolamine, 1,4-diazabicyclo[2.2.2]octane, or 1,8-diazabicyclo[5.4.0]undec-7-ene, or using a tin compound, e.g., dibutyltin dilaurate, as a catalyst. Triethylamine is preferred. The catalyst is typically used in an amount of 0.1 to 10% by weight based on the weight of the organic isocyanate. The reaction is typically carried out in the presence of an organic solvent, e.g., tetrahydrofuran or ethyl acetate, at a temperature of, e.g., 30 to 80°C.

[0026] Suitable thiourethanes are represented by formula (9), (10) or (11): [ka] (In each of formulas (9) and (10), R b is as defined above, subject to the above preferences), or [ka] (wherein, with respect to formula (11), R b C8-C uninterrupted or interrupted by -O- and / or carbonyl groups 40 alkyl, and R b (The preferences given above with respect to (1) shall apply.) Preferred thiourethanes are compounds of formula (9) and (10), especially those of formula (10).

[0027] In another aspect, preferred thiourethanes are those of formula (12): [ka] is.

[0028] The radical initiator can be selected from peroxides, carbon-based radical generators, bis-azo compounds, or stable nitroxyl compounds, with peroxides and carbon-based radical generators being preferred. In one embodiment, the radical initiator is a peroxide. In another embodiment, the radical initiator is a carbon-based radical generator.

[0029] Suitable peroxides are organic or inorganic peroxides, preferably organic peroxides. Typical examples of suitable organic peroxides include 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,3,6,6,9,9-pentamethyl-3-(ethyl acetate)-1,2,4,5-tetraoxycyclononane, t-butyl hydroperoxide, hydrogen peroxide, dicumyl peroxide, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxide, p-chlorobenzoyl peroxide, dibenzoyl Diperoxide, t-butylcumyl peroxide, t-butylhydroxyethyl peroxide, di-t-amyl peroxide and 2,5-dimethylhexene-2,5-diperisononanoate, acetylcyclohexanesulfonyl peroxide, diisopropyl peroxydicarbonate, tert-amyl perneodecanoate, tert-butyl perneodecanoate, tert-butyl perpivalate, tert-amyl perpivalate, bis(2,4-dichlorobenzoyl) peroxide, diisopropyl Nonanoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, bis(2-methylbenzoyl) peroxide, disuccinoyl peroxide, diacetyl peroxide, dibenzoyl peroxide, tert-butyl per-2-ethylhexanoate, bis(4-chlorobenzoyl) peroxide, tert-butyl perisobutyrate, tert-butyl permalate, 1,1-bis(tert-butylperoxy)-3,5,5-trimethylcyclohexyl Hexane, 1,1-bis(tert-butylperoxy)cyclohexane, tert-butylperoxyisopropyl carbonate, tert-butylperoxybenzoate, 2,5-dimethylhexane 2,5-dibenzoate, tert-butylperacetate, tert-amyl perbenzoate, tert-butylperbenzoate, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)propane, dicumyl peroxide, 2,5-dimethylhexane 2,Examples of suitable peroxides include 5-di-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-di-methyl-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, and tert-butyl hydroperoxide.

[0030] Alternatively, 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-butylcumyl peroxide (BCUP), bis(tert-butylperoxyisopropyl)benzene (DIPP), 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, di(tert-butylperoxyisopropyl)benzene, dicetyl peroxydicarbonate, and tert-butyl monoperoxymaleate.

[0031] 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-triperoxonane, in particular 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (DHBP) and 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane. The peroxide is particularly 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane.

[0032] Suitable bis-azo 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, dimethyl 2,2'-azobisisobutyrate, 2-(carbamoylazo)isobutyrate, Sobutyronitrile, 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), 2,2'-azobis(N,N'-dimethyleneisobutyramidine) free base or hydrochloride, 2,2'-azobis(2-amidinopropane) free base or hydrochloride, 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}.

[0033] Suitable stable nitroxyl compounds have the general formula (13): [ka] or equation (14) [ka] where each R is alkyl and T is the group necessary to complete a 5- or 6-membered ring. Two or more nitroxyl groups can be present in the same molecule by being linked via T moieties, as illustrated below, where E is a linking group of formula (15): [ka]

[0034] Suitable stable nitroxyl compounds include bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine, 4-ethoxy-1-oxyl-2,2,6,6-tetramethylpiperidine, 4-propoxy-1-oxyl-2,2,6,6-tetramethylpiperidine, 4-acetamido-1-oxyl-2,2,6,6-tetramethylpiperidine, ... Tetramethylpiperidin-4-one, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl acetate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl 2-ethylhexanoate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl stearate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl benzoate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl 4-t-butylbenzoate, bis(1-oxyl-2,2,6,6-tetramethylpiperidine) -4-yl)succinate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)adipate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)n-butylmalonate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)phthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)isophthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)terephthalate, bis(-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) N,N'-bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)hexahydroterephthalate, N,N'-bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)adipamide, N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)caprolactam, N-(1-oxyl-2,2,6,6-tetramethylpiperidinyldodecylsuccinimide, 2,4,6-tris-[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-isobenzazole, 1-oxyl-2,2,5,5-tetramethylpyrrolidine, and N,N-bis(1,1,3,3-tetramethylbutyl) nitroxide.

[0035] Suitable carbon-based radical generators include those of formula (16): [ka] (In the formula, R 1 , R 3 , R 4 and R 6 are each independently selected from the group consisting of hydrogen, substituted and unsubstituted straight chain, branched and cyclic hydrocarbons having 1 to 12 carbon atoms, and substituted and unsubstituted aromatic hydrocarbons having 6 to 12 carbon atoms; 2 and R 5 are each independently selected from the group consisting of substituted and unsubstituted straight chain, branched, and cyclic hydrocarbons having 1 to 12 carbon atoms, and substituted and unsubstituted aromatic hydrocarbons having 6 to 12 carbon atoms; 1 , R 2 , R 3 , R 4 , R 5 and R 6 at least one of which is a substituted or unsubstituted aromatic hydrocarbon having 6 to 12 carbon atoms).

[0036] The carbon-based radical generator of formula (16) can have a symmetrical or asymmetrical structure. 2 and R 5 each of R can be independently selected from substituted or unsubstituted aryl groups having 6 to 12 carbon atoms; 1 , R 3 , R 4 and R 6 are each independently selected from the group consisting of hydrogen and a C1-C6 alkyl group.

[0037] In another embodiment, the carbon-based radical generator is represented by the formula (17): [ka] (In the formula, R 7 , R 8 , R 9 and R 10 are each independently selected from the group consisting of a hydrogen atom, a C1-C6 alkyl group, a C1-C2 alkoxy group, a nitrile group, and a halogen atom; 1 , R 3 , R 4 and R 6 each independently selected from the group consisting of hydrogen and a C1-C6 alkyl group.

[0038] In yet another embodiment, the carbon-based radical generator is 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-diphenyl 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-(pt-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.

[0039] In another embodiment, the carbon-based 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.

[0040] The radical initiator can be added to the polymeric material such as polyolefin in an amount of 0.0001 to 5% by weight, particularly 0.001 to 5% by weight, and more preferably 0.01 to 5% by weight. In another embodiment, the radical initiator can be added to the polymeric material such as polyolefin in an amount of 0.01 to 2% by weight, particularly 0.01 to 1% by weight.

[0041] The thiourethane can be added to the polymeric material such as polyolefin in an amount of 0.0001 to 5% by weight, particularly 0.001 to 5% by weight, and more preferably 0.01 to 5% by weight. In another embodiment, the radical initiator can be added to the polymeric material such as polyolefin in an amount of 0.01 to 2% by weight, particularly 0.01 to 1% by weight.

[0042] The weight ratio of radical initiator to thiourethane is typically 1:2 to 30:1, preferably 1:1 to 20:1, and particularly 1.2:1 to 15:1. In another embodiment, the weight ratio of radical initiator to thiourethane can be 1:1 to 10:1, preferably 1.5:1 to 5:1, and particularly 2:1 to 4:1. In another embodiment, the weight ratio of radical initiator to thiourethane is 1:2 to 30:1, preferably 1:1 to 20:1, and particularly 1.5:1 to 5:1.

[0043] In another embodiment, the polymeric material is a polyolefin, the radical initiator is a peroxide, and the weight ratio of radical initiator to thiourethane is from 1:1 to 20:1.

[0044] In another aspect, the polymeric material is a polyolefin, the radical initiator is a peroxide, the peroxide being 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-butylcumyl peroxide (BCUP), bis(tert-butylperoxyisopropyl)benzene (DIPP), 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, di(tert-butylperoxyisopropyl)benzene, dicetyl peroxydicarbonate, or tert-butyl monoperoxymaleate, and the weight ratio of the radical initiator to the thiourethane is 1:1 to 20:1.

[0045] In another embodiment, the polymeric material is a polyolefin, the radical initiator is a carbon-based radical generator, and the weight ratio of radical initiator to thiourethane is 1:1 to 20:1.

[0046] In another aspect, the polymeric material is a polyolefin, the radical initiator is a carbon-based radical generator, the carbon-based radical generator having the formula (17), and the weight ratio of the radical initiator to the thiourethane is from 1:1 to 20:1.

[0047] In another embodiment, the polymeric material is a polyolefin, the radical initiator is a peroxide, and the weight ratio of radical initiator to thiourethane is from 1.5:1 to 5:1.

[0048] In another embodiment, the polymeric material is a polyolefin, the radical initiator is a carbon-based radical generator, and the weight ratio of radical initiator to thiourethane is from 1.5:1 to 5:1.

[0049] In another aspect, the polymeric material is a polyolefin, the radical initiator is a carbon-based radical generator, the carbon-based radical generator having the formula (17), and the weight ratio of the radical initiator to the thiourethane is from 1.5:1 to 5:1.

[0050] In another aspect, the polymeric material is a polyolefin, the radical initiator is a peroxide, the weight ratio of radical initiator to thiourethane is 1:1 to 20:1, and R a is based on an organic isocyanate that is cyclohexyl diisocyanate, methylene bis(cyclohexyl) diisocyanate, isophorone diisocyanate, phenyl diisocyanate, diphenylmethane diisocyanate, or naphthyl diisocyanate, each of which is unsubstituted or substituted with C1-C4 alkyl or di(C1-C4 alkyl)amino, or a C4-C20 alkyl diisocyanate, or an oligomeric or polymeric product obtained by reaction of the above diisocyanates with themselves and / or with polyols.

[0051] In another aspect, the polymeric material is a polyolefin, the radical initiator is a peroxide, the peroxide being 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-butylcumyl peroxide (BCUP), bis(tert-butylperoxyisopropyl)benzene (DIPP), 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, di(tert-butylperoxyisopropyl)benzene, dicetyl peroxydicarbonate, or tert-butyl monoperoxymaleate, and the weight ratio of the radical initiator to the thiourethane is 1:1 to 20:1; ais based on an organic isocyanate that is cyclohexyl diisocyanate, methylene bis(cyclohexyl) diisocyanate, isophorone diisocyanate, phenyl diisocyanate, diphenylmethane diisocyanate, or naphthyl diisocyanate, each of which is unsubstituted or substituted with C1-C4 alkyl or di(C1-C4 alkyl)amino, or a C4-C20 alkyl diisocyanate, or an oligomeric or polymeric product obtained by reaction of the above diisocyanates with themselves and / or with polyols.

[0052] In another aspect, the polymeric material is a polyolefin, the radical initiator is a carbon-based radical generator, and the weight ratio of radical initiator to thiourethane is 1:1 to 20:1; R a is based on an organic isocyanate, the organic isocyanate being cyclohexyl diisocyanate, methylene bis(cyclohexyl) diisocyanate, isophorone diisocyanate, phenyl diisocyanate, diphenylmethane diisocyanate, or naphthyl diisocyanate, each of which is unsubstituted or substituted with C1-C4 alkyl or di(C1-C4 alkyl)amino, or C4-C 20 Alkyl diisocyanates or oligomeric or polymeric products obtained by reaction of the above diisocyanates with themselves and / or with polyols.

[0053] In another aspect, the polymeric material is a polyolefin, the radical initiator is a carbon-based radical generator, the carbon-based radical generator having the formula (17), the weight ratio of radical initiator to thiourethane is 1:1 to 20:1, and R ais based on an organic isocyanate, the organic isocyanate being cyclohexyl diisocyanate, methylene bis(cyclohexyl) diisocyanate, isophorone diisocyanate, phenyl diisocyanate, diphenylmethane diisocyanate, or naphthyl diisocyanate, each of which is unsubstituted or substituted with C1-C4 alkyl or di(C1-C4 alkyl)amino, or C4-C 20 Alkyl diisocyanates or oligomeric or polymeric products obtained by reaction of the above diisocyanates with themselves and / or with polyols.

[0054] In another aspect, the polymeric material is a polyolefin, the radical initiator is a peroxide, the weight ratio of radical initiator to thiourethane is 1:1 to 20:1, and R a are based on organic isocyanates, which are unsubstituted or C1-C4 alkyl substituted phenyl diisocyanates, or oligomeric or polymeric products obtained by reaction of said diisocyanates with themselves and / or with polyols.

[0055] In another embodiment, the polymeric material is a polyolefin, the radical initiator is a carbon-based radical generator, and the weight ratio of radical initiator to thiourethane is from 1.5:1 to 5:1; and R a are based on organic isocyanates, which are unsubstituted or C1-C4 alkyl substituted phenyl diisocyanates, or oligomeric or polymeric products obtained by reaction of said diisocyanates with themselves and / or with polyols.

[0056] In another aspect, the polymeric material is a polyolefin, the radical initiator is a peroxide, the weight ratio of radical initiator to thiourethane is 1.5:1 to 5:1, and R aare based on organic isocyanates, which are unsubstituted or C1-C4 alkyl substituted phenyl diisocyanates, or oligomeric or polymeric products obtained by reaction of said diisocyanates with themselves and / or with polyols.

[0057] In another aspect, the polymeric material is a polyolefin, the radical initiator is a carbon-based radical generator, and the weight ratio of radical initiator to thiourethane is 1:1 to 20:1; R a are based on organic isocyanates, which are unsubstituted or C1-C4 alkyl substituted phenyl diisocyanates, or oligomeric or polymeric products obtained by reaction of said diisocyanates with themselves and / or with polyols.

[0058] In another aspect, the polymeric material is a polyolefin, the radical initiator is a peroxide, the weight ratio of radical initiator to thiourethane is 1:1 to 20:1, and the thiourethane is a compound of formulas (9) and (10).

[0059] In another aspect, the polymeric material is a polyolefin, the radical initiator is a peroxide, the peroxide is 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-butylcumyl peroxide (BCUP), bis(tert-butylperoxyisopropyl)benzene (DIPP), 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, di(tert-butylperoxyisopropyl)benzene, dicetyl peroxydicarbonate, or tert-butyl monoperoxymaleate, the weight ratio of the radical initiator to the thiourethane is 1:1 to 20:1, and the thiourethane is a compound of formula (9) or (10).

[0060] In another aspect, the polymeric material is a polyolefin, the radical initiator is a carbon-based radical generator, the weight ratio of the radical initiator to the thiourethane is 1:1 to 20:1, and the thiourethane is a compound of formulas (9) and (10).

[0061] In another aspect, the polymeric material is a polyolefin, the radical initiator is a carbon-based radical generator, the carbon-based radical generator has formula (17), the weight ratio of the radical initiator to the thiourethane is 1:1 to 20:1, and the thiourethane is a compound of formulas (9) and (10).

[0062] In another form, the modifier blend comprises a radical initiator selected from peroxides and a thiourethane, R a are based on organic isocyanates, which are unsubstituted or C1-C4 alkyl substituted phenyl diisocyanates, or oligomeric or polymeric products obtained by reaction of said diisocyanates with themselves and / or with polyols, and the weight ratio of radical initiator to thiourethane is 1:2 to 30:1, preferably 1:1 to 20:1, in particular 1.5:1 to 5:1.

[0063] In another aspect, the modifier blend comprises a radical initiator selected from peroxides, wherein the peroxide is 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.-butylcumyl peroxide (BCUP), bis(tert. and a thiourethane, wherein the weight ratio of the radical initiator to the thiourethane is 1:2 to 30:1, preferably 1:1 to 20:1, and particularly preferably 1.5:1 to 5:1.

[0064] In another aspect, the modifier blend comprises a radical initiator selected from a peroxide, wherein the peroxide is 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.-butylcumyl peroxide (BCUP), bis(tert.-butylperoxyisopropyl)benzene (DIPP), 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, di(tert.-butylperoxyisopropyl)benzene, dicetyl peroxydicarbonate, or tert.-butyl monoperoxymaleate, and a thiourethane; R aare based on organic isocyanates, which are unsubstituted or C1-C4 alkyl substituted phenyl diisocyanates, or oligomeric or polymeric products obtained by reaction of said diisocyanates with themselves and / or with polyols, and the weight ratio of radical initiator to thiourethane is 1:2 to 30:1, preferably 1:1 to 20:1, in particular 1.5:1 to 5:1.

[0065] In another aspect, the modifier blend comprises a radical initiator selected from peroxides, wherein the peroxide is 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.-butylcumyl peroxide (BCUP), bis(tert.-butylperoxyisopropyl) )benzene (DIPP), 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, di(tert-butylperoxypropyl)benzene, dicetyl peroxydicarbonate, or tert-butyl monoperoxymaleate), and a thiourethane (wherein the thiourethane is represented by formula (9) or (10)), wherein the weight ratio of the radical initiator to the thiourethane is 1:2 to 30:1, preferably 1:1 to 20:1, and in particular 1.5:1 to 5:1.

[0066] In another form, the modifier blend comprises a radical initiator selected from carbon-based radical generators and a thiourethane, R a are based on organic isocyanates, which are unsubstituted or C1-C4 alkyl substituted phenyl diisocyanates, or oligomeric or polymeric products obtained by reaction of said diisocyanates with themselves and / or with polyols, and the weight ratio of radical initiator to thiourethane is 1:2 to 30:1, preferably 1:1 to 20:1, in particular 1.5:1 to 5:1.

[0067] In another aspect, the modifier blend comprises a radical initiator, wherein the carbon-based radical generator is selected from carbon-based radical generators having the formula (17), and a thiourethane, wherein R a are based on organic isocyanates, which are unsubstituted or C1-C4 alkyl substituted phenyl diisocyanates, or oligomeric or polymeric products obtained by reaction of said diisocyanates with themselves and / or with polyols, and the weight ratio of radical initiator to thiourethane is 1:2 to 30:1, preferably 1:1 to 20:1, in particular 1.5:1 to 5:1.

[0068] In another aspect, the modifier blend comprises a radical initiator selected from carbon-based radical generators having formula (17) and a thiourethane having formula (9) or (10), wherein the weight ratio of radical initiator to thiourethane is from 1:2 to 30:1, preferably from 1:1 to 20:1, and especially from 1.5:1 to 5:1.

[0069] Preferably, when the radical initiator is selected from peroxides, the polymeric material, such as a polyolefin, is selected from the group consisting of a peroxide, a peroxide, a hydroxyl group ... [ka] (In the formula, G1, G2, G3 and G4 are each independently another C1-C4 alkyl, or G1 and G2 together, or G3 and G4 together, are pentamethylene; G1', G2', G3' and G4' are each independently another C1-C4 alkyl, or G1' and G2' together, or G3' and G4' together, are pentamethylene; G5, G6, G5' and G6' are each independently another hydrogen or C1-C4 alkyl; X and X' are independently hydrogen, C1-C 18 Alkyl, C2-C 18 Alkenyl, -O-C1-C 18 Alkyl, -NH-C1-C 18alkyl, —N(C1-C6 alkyl)2, phenyl, phenoxy or —NH-phenyl; m is 1 or 2; When m is 1, R1 is C2-C8 alkylene or C2-C8 hydroxyalkylene or C4-C 36 acyloxyalkylene, or When m is 2, R1 is (-CH2)2C(CH2-)2; R1' is hydrogen, C1-C8 alkyl, C1-C8 hydroxyalkyl, or a group of the formula -(C=O)-C1-C 40 an alkyl group, or -O-R1' together with the -CH- groups connecting them does not include compounds in which the group is -(C=O)-.

[0070] 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.

[0071] Suitable polyolefins are polymers of monoolefins and diolefins, such as polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, and polymers of cycloolefins, such as polymers of cyclopentene or norbornene, polyethylenes, which may optionally be crosslinked, such as 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).

[0072] Polyolefins, preferably polyethylene and polypropylene, can be prepared by the following methods: a) Radical polymerization (usually under high pressure and temperature). b) Catalytic polymerization using a catalyst typically containing one or more metals from Groups IVb, Vb, VIb, or VIII of the periodic table. These metals typically have one or more ligands, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls, and / or aryls, which may be either π- or σ-coordinated. These metal complexes may be in free form or immobilized on substrates, typically activated magnesium chloride, titanium(III) chloride, alumina, or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalyst may be used alone in the polymerization, or an additional activator may be used, typically a metal alkyl, metal hydride, metal alkyl halide, metal alkyl oxide, or metal alkyloxane, where the metal is an element from Groups Ia, IIa, and / or IIIa of the periodic table. The activator may be further advantageously modified with an ester group, an ether group, an amine group, or a silyl ether group. These catalyst systems are commonly designated as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single-site catalysts (SSC).

[0073] Examples of polyolefin blends are blends of polypropylene and polyisobutylene, blends of polypropylene and polyethylene (eg, PP / HDPE, PP / LDPE), and blends of different types of polyethylene (eg, LDPE / HDPE).

[0074] Examples of monoolefins and diolefins copolymers with each other or with other vinyl monomers are ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and its blends 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 such as COC), ethylene / 1-olefin copolymers (1-olefins generated in situ), propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / vinylcyclohexane copolymers. Examples of suitable copolymers include ethylene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers or ethylene / acrylic acid copolymers and salts thereof (ionomers), as well as terpolymers of ethylene with propylene and dienes such as hexadiene, dicyclopentadiene or ethylidene norbornene, as well as mixtures of such copolymers with each other and with the polymers of 1) above, such as polypropylene / ethylene-propylene copolymer, LDPE / ethylene-vinyl acetate copolymer (EVA), LDPE / ethylene-acrylic acid copolymer (EAA), LLDPE / EVA, LLDPE / EAA and alternating or random copolymers of polyalkylene / carbon monoxide, and mixtures of these with other polymers, such as polyamides.

[0075] More preferably, the polyolefin is selected from the group consisting of polyethylene, such as 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. Polyethylene or polypropylene, especially polypropylene, is highly preferred.

[0076] Also suitable as polymeric materials are recycled plastics, which can be obtained from household, commercial, and industrial waste or collections of useful materials. Recycled plastics can come from separation and sorting, or from specific industrial sectors and return obligations, such as the automotive industry, the electrical / electronics industry, construction, agriculture, and the textile industry, or from household and commercial products (e.g., supermarkets). Recycled plastics can be, for example, mono-material recycled plastics from the polymer class consisting of polyolefins (polypropylene, high-density polyethylene, blends of low-density polyethylene and polypropylene, as well as copolymers such as PP / EPDM and PP / PE and polystyrene), or defined mixtures of recycled plastics.

[0077] Recycled plastics may also contain polyethylene terephthalate, polyamide, polycarbonate, cellulose acetate, and polyvinylidene chloride. A secondary amount, up to about 5%, of non-thermoplastic materials, such as polyurethanes, formaldehyde resins, and phenolic resins, as well as typical amino resins, and elastomers, such as vulcanized or unvulcanized rubber, may also be present. Small amounts of contaminants, such as paper, pigments, and adhesives, that are often difficult to remove, may also be present in certain plastic waste. These contaminants may also result from contact with various substances during use or processing, such as fuel residues, paint components, traces of metals, initiator residues, or traces of water.

[0078] The process of incorporating a modifier blend comprising a radical initiator and a thiourethane into a polymeric material such as a polyolefin can be accomplished by conventional methods, such as by adding the modifier blend or a single component thereof, i.e., the radical initiator and the thiourethane, to the polymeric material. The modifier blend or a single component thereof, i.e., the radical initiator and the thiourethane, can be added to the polymeric material in the form of a liquid, powder, granules, or masterbatch. The radical initiator, the thiourethane, and any further additives can be added to the polymeric material individually or mixed with each other. The radical initiator and the thiourethane are preferably added together, preferably in the form of a masterbatch.

[0079] The radical initiator and thiourethane and any further additives can be added to the polymeric material before, during or after polymerization or before or after crosslinking. The radical initiator and thiourethane and any further additives can be incorporated into the polymeric material in known manner, for example before or during molding, or by applying the respective compounds dissolved or dispersed to the polymeric material and, if necessary, subsequently evaporating the solvent.

[0080] The compound can be added to polymeric material in any conventional mixer, in which polymer is melted and mixed with the compound of the present composition and any further additives.Suitable machines are mixers, kneaders and extruders.This process is preferably carried out by adding compound during processing in an extruder.Particularly preferred processing machines are single-screw extruders, co-rotating and counter-rotating twin-screw extruders, planetary gear extruders, ring extruders, or co-kneaders equipped with at least one gas removal section that can apply vacuum.

[0081] The polymer is exposed to elevated temperatures for a period of time sufficient for molecular weight modification. In preferred embodiments of the process of the present invention, a temperature range of about 150°C to 340°C is used. Preferred process variations use a temperature range of about 200°C to 320°C, or 200°C to 300°C, or 170°C to 290°C, especially about 180°C to 280°C.

[0082] The time required to modify the molecular weight can vary depending on the temperature, the amount of material being modified, and the type of any extruder used, and can range, for example, from about 10 seconds to 20 minutes, particularly 20 seconds to 10 minutes.

[0083] Examples of processing or conversion of the compositions according to the invention are: injection blow molding, extrusion, blow molding, rotoforming, in-mold decoration (back injection), slush molding, injection molding, co-injection molding, molding, compression molding, press molding, film extrusion (cast film, blown film), fiber spinning, other fiber processing (woven fabrics, nonwoven fabrics, especially fiber meltblown, spunbond), drawing (uniaxial, biaxial), annealing, deep drawing, calendaring, mechanical deformation, sintering, coextrusion, coating, laminating, crosslinking (radiation, peroxide, silane), vapor deposition, welding, adhesive bonding, thermoforming, pipe extrusion, profile extrusion, sheet extrusion, sheet casting, spin coating, strapping, foaming, recycling / reprocessing, extrusion coating.

[0084] The materials processed according to the present invention can be used in a wide variety of forms, for example, as films, fibers (continuous or discontinuous), tapes, or molded articles. Fibers including bicomponent fibers are preferred. Bicomponent fibers are fibers that contain at least two distinct polymer domains a) and b) that are in close contact along the length of the fiber. They can be of any shape and are not limited to a specific shape. Examples of such shapes are side-by-side, sheath-core, orange, and matrix and fibril types. Sheath-core and side-by-side bicomponent fibers, especially sheath-core bicomponent fibers, are preferred.

[0085] Preferred articles are also nonwovens, including webs, which refer to fibrous structures of individual fibers, filaments, or threads that are unidirectionally or randomly oriented and bonded by friction, cohesion, adhesive, and / or mechanical processes, as opposed to a regular pattern of mechanically interlocked fibers; i.e., not woven or knitted. Examples of nonwovens include meltblown filaments, spunbonded continuous filament webs, carded webs, airlaid webs, and wetlaid webs. Suitable bonding methods include thermal bonding, chemical or solvent bonding, resin bonding, mechanical needling, hydraulic needling, and stitch bonding. Suitable articles made from polymeric materials include geotextiles, roofing materials, cables, films, filtration media, filters, diapers, sanitary napkins, panty liners, adult incontinence products, protective clothing, surgical drapes, surgical gowns, or surgical attire.

[0086] Rheological modification of polymeric materials such as polyolefins is often achieved by long chain branching, crosslinking, or viscous breaking. Rheological modification allows for improvements in: - mechanical properties such as tensile strength, elongation and tear resistance, barrier properties (e.g. hydrohead, breathability, filtering properties), especially in nonwovens, Processing properties (wider range of suitable polymers, parameter adaptation, e.g., thermal bonding temperature in nonwovens), -Recycling, because adjusting the melt viscosity of recycled polymers can provide recycled items with a more uniform molecular weight (narrower MWD) and therefore better mechanical properties. In addition, the use of viscous-fractured polymers can act as a processing aid or compatibilizer, which also contributes to the higher mechanical properties of recycled polymers. In addition, because the rheological quality of recycled polymers is adjustable, the present invention allows for the adjustment of the rheological response of the polymer, resulting in a more stable and controllable process.

[0087] Improvements in properties related to tensile strength and elongation are important, for example, to the manufacture of nonwoven fabrics, because their preparation involves multiple steps, and improvements in tensile strength or elongation help the nonwoven fabric to better withstand these steps. Importantly, higher tensile strength provides manufacturers of nonwoven fabrics with the option to, for example, reduce weight while still maintaining good mechanical performance of the product.

[0088] A further important aspect is the process safety during the preparation of nonwoven fabrics. It is desirable to carry out the process for preparing nonwoven fabrics under milder conditions at lower process temperatures. To make this possible, still good mechanical properties such as tensile strength and elongation must be obtained at lower process temperatures. This allows the process temperature to be reduced. Furthermore, energy savings become a secondary benefit.

[0089] Modification of the rheology of a polymeric material usually 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). Modified rheology is usually determined by analyzing the melt flow index (MFI), for example, according to EN ISO 133 at 230°C and 2.16 kg.

[0090] Modification typically means that the rheology (e.g., as determined by MFI) of a polymeric material, such as a polyolefin, including a modifier blend with a certain amount of radical initiator is increased or decreased (preferably an increase in MFI) by at least 1, 3, 5, 10, 20, 30, 40, or 50% based on the rheology of the same polymeric material with only said certain amount of radical initiator (but no thiourethane).

[0091] The polymeric materials may also include various conventional additives, such as antioxidants, ultraviolet light absorbers and light stabilizers, metal deactivators, phosphites and phosphonites, hydroxylamines, nitrones, thiosynergics, peroxide scavengers, polyamide stabilizers, basic co-stabilizers, nucleating agents, fillers and reinforcing agents, benzofuranones and indolinones, or other additives such as plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow control agents, optical brighteners, flame retardants, antistatic agents, and blowing agents.

[0092] 1. Antioxidants 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-dioctadecyl-4 -methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched nonylphenols such as 2,6-dinonyl-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.

[0093] 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.

[0094] 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.

[0095] 1.4. Tocopherols, such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

[0096] 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.

[0097] 1.6. Alkylidene 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'-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'-methylenebis(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-methylphenyl)-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 Ene, bis[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-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

[0098] 1.7. O-, N-, and S-benzyl compounds, such as 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-hydroxy-benzyl)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.

[0099] 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, di-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.

[0100] 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-tetra-methylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

[0101] 1.10. Triazine compounds, such as 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy-anilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxy-anilino)-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-hydroxy-benzyl)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.

[0102] 1.11. Benzyl phosphonates, 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-methylbenzylphosphonate, calcium salts of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

[0103] 1.12. Acylaminophenols, for example, 4-hydroxylauranilide, 4-hydroxystearanilide, N-(3,5-di-tert-butyl-4-hydroxyphenyl)octyl carbamate.

[0104] 1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, such as 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.

[0105] 1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric or polyhydric alcohols, such as 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)isothiazolinone, Esters with cyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, and 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0106] 1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, such as 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.

[0107] 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyhydric alcohols, such as 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, and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0108] 1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, for example, 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 Addivant).

[0109] 1.18. Ascorbic acid (vitamin C).

[0110] 1.19. Amine antioxidants, for example, N,N'-diisopropyl-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 Diamine, 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-(p-toluenesulfamoyl)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 diphenylamines such as 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, mixtures of mono- and di-alkylated tert-butyl / tert-octyldiphenylamines, mixtures of mono- and di-alkylated nonyldiphenylamines, mixtures of mono- and di-alkylated dodecyldiphenylamines, mixtures of mono- and di-alkylated isopropyl / isohexyldiphenylamines, mixtures of mono- and di-alkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixtures of mono- and di-alkylated tert-butyl / tert-octylphenothiazines, mixtures of mono- and di-alkylated tert-octylphenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene.

[0111] 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'-hydrox-phenyl)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-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol], transesterification product of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300, [ka] And, (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).

[0112] 2.2.2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.

[0113] 2.3. Esters of substituted and unsubstituted benzoic acids, for example, 4-tert-butylphenyl 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.

[0114] 2.4. Acrylate cinnamates, such as 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-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate, N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline, neopentyl tetra(α-cyano-β,β-diphenylacrylate). Cyanoacrylates can also be used, as such compounds are described in EP 3587425.

[0115] 2.5. Nickel compounds, for example, nickel complexes of 2,2'-thio-bis[4-(1,1,3,3-tetramethylbutyl)phenol], for example, 1:1 or 1:2 complexes (with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine), nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, for example, the methyl or ethyl ester, nickel complexes of ketoximes, for example, nickel complexes of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole (with or without additional ligands).

[0116] 2.6. Sterically hindered amines, for example, carbonic acid bis(1-undecyloxy-2,2,6,6-tetramethyl-4-piperidyl) ester, 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-Hydroxybenzyl malonate, condensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-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-tetramethylpiperazinone) methylpiperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, condensation products 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, 2-chloro-4,6-di-(4-n-butylamino-1,2,Condensation product of 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, 4-hexadecyloxy- and 4-stearyloxy-2 ,2,6,6-tetramethylpiperidine mixture, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine condensate, 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine condensate (CAS registration number [136504-96-6]), 1,6-hexanediamine and 2,4,6-trichloro-1,3, Condensate of 5-triazine and N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS registration number [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-oxospiro[4,5]decane, 7,7,9,9-tetramethyl-2-cycloundecyl Reaction products of 1-oxa-3,8-diaza-4-oxospiro[4,5]decane with epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,N'-bisformyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, 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, reaction products 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, Sanduvor® ) 3058 (Clariant, CAS Registry Number 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 with N,N'-bis(3-aminopropyl)ethylenediamine, 1,3,5-tris(N-cyclohexyl-N-(2,2,6,6-tetramethylpiperazin-3-one-4-yl)amino)-s-triazine, 1,3,5-tris(N-cyclohexyl-N-(1,2,2,6,6-pentamethylpiperazin-3-one-4-yl)amino)-s-triazine.

[0117] 2.7. Oxamides, such as 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-methoxy disubstituted oxanilides, and mixtures of o- and p-ethoxy disubstituted oxanilides.

[0118] 2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, such as 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, and 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 2-(2-hydroxy-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, 2,4-bis(4-biphenylyl)-6-[2-hydroxy-4-(2-ethylhexyloxy)phenyl]-1,3,5-triazine.

[0119] 3. Metal deactivators, such as N,N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenyl-propionyl)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.

[0120] 4. Phosphites and phosphonites, such as 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, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite), tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylene diphosphonite, 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-dioxaphosphiran, 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triesters with mixed phosphoric acid (CAS: 939402-02-5), α-hydro-ω-hydroxypoly[oxy(methyl-1,2-ethanediyl)]C10-16-alkyl phosphate triphenyl ester polymer (CAS: 1227937-46-3), Doverphos LGP-12 (CAS: 116265-68-1).

[0121] The following phosphites are particularly preferred: tris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl)phosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite, [ka]

[0122] 5. Hydroxylamines, such as 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-dialkylhydroxylamines derived from hydrogenated tallow amine or derived from plant sources.

[0123] 6. Nitrones, such as N-benzyl-α-phenyl nitrone, N-ethyl-α-methyl nitrone, N-octyl-α-heptyl nitrone, N-lauryl-α-undecyl nitrone, N-tetradecyl-α-tridecyl nitrone, N-hexadecyl-α-pentadecyl nitrone, N-octadecyl-α-heptadecyl nitrone, N-hexadecyl-α-heptadecyl nitrone, N-octadecyl-α-pentadecyl nitrone, N-heptadecyl-α-heptadecyl nitrone, N-octadecyl-α-hexadecyl nitrone, and nitrones derived from N,N-dialkylhydroxylamines derived from hydrogenated tallow amine.

[0124] 7. Thiosynergists, for example, dilauryl thiodipropionate, dimistryl thiodipropionate, distearyl thiodipropionate, or pentaerythritol tetrakis[3-(dodecylthio)propionate], or distearyl disulfide.

[0125] 8. Peroxide scavengers, for example, esters of β-thiodipropionic acid, such as the lauryl, stearyl, myristyl or tridecyl ester, zinc salts of mercaptobenzimidazole or 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(β-dodecylmercapto)propionate.

[0126] 9. Polyamide stabilizers, such as copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.

[0127] 10. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, zeolites, hydrotalcites, calcium hydroxide, zinc oxide, 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.

[0128] 11. Nucleating agents, for example, inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphoric acid, 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, for example Mono- or polycarboxylic acids and their salts, for example, 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate, calcium 1,2-cyclohexanedicarboxylic acid, disodium bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, polymeric compounds such as ionic copolymers (ionomers), triaminobenzene derivatives such as 1,3,5-tris[2,2-dimethylpropionylamine]benzene, zinc glycerate, and nonitol derivatives. 1,3:2,4-bis(3',4'-dimethylbenzylidene)sorbitol, 1,3:2,4-di(paramethyldibenzylidene)sorbitol, and 1,3:2,4-di(benzylidene)sorbitol are particularly preferred.

[0129] 12. Fillers and reinforcing agents, such as calcium carbonate, silicates, surface-treated silicas (such as those described 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 other natural product fine powders or fibers, synthetic fibers.

[0130] 13. Other additives, such as plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow control agents, optical brighteners, flame retardants, antistatic agents, and foaming agents. Other additives can also include antiblocking additives, which are used in films to reduce negative adhesion between two polyethylene surfaces that would otherwise make the films difficult to separate. Further additives include slip additives, which are used to help the film surfaces slide against each other. Antifog agents can also be added.

[0131] 14. benzofuranones and indolinones, for example, U.S. Pat. Nos. 4,325,863, 4,338,244, 5,175,312, 5,216,052, 5,252,643, DE-A-4316611, Those disclosed in DE-A-4316622, DE-A-4316876, EP-A-0589839, EP-A-0591102 and 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-acetoxyethoxy)phenyl 3-(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-ditert-butyl-3-[3,5-dimethyl-4-[(1,3,7,9-tetratert-butyl-5-methyl-5H-benzo[d][1,3,2]benzodioxaphosphocin-11-yl)oxy]phenyl]-3H-benzofuran-2-one. Suitable benzofuranones also include the compounds identified in WO 2015 / 121445 and WO 2017 / 025431.

[0132] Preferred are compositions which further comprise further additives selected from the group consisting of antioxidants, processing stabilizers, light stabilizers, UV absorbers, fillers, reinforcing agents, pigments, metal deactivators, plasticizers, lubricants, emulsifiers, rheology additives, catalysts, flow control agents, optical brighteners, flame retardants, antistatic agents and foaming agents. [Example]

[0133] ThioU: Thiourethane of formula (12). PER: 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, commercially available as Enox 101 from Vesta Chemicals. DIC: 2,3-dimethyl-2,3-diphenylbutane, commercially available from Acros Organics.

[0134] Examples 1 to 8 Using a high-speed mixer (Mixaco Lab CM12, Mixaco Maschinenbau, Germany), commercially available polypropylene powder (HA10XT from Polychim Industrie, France, melt flow index 3 g / 10 min, ASTM D1238) was mixed with a base stabilizer (0.1% Irganox® B225 and 0.05% calcium stearate) and the additives listed in Table 1. The mixture was extruded in a twin-screw extruder (Berstorff ZE25A×47D, KraussMaffei Berstorff GmbH, Germany) at a temperature of Tmax = 230 ° C. under nitrogen at a throughput of 4 kg / h and 100 rpm. The resulting polymer strands were granulated in a water bath.

[0135] The melt flow index (MFI) was determined according to EN ISO1133 at 230°C and 2.16 kg on a Goettfert MI Robo (Goettfert Werkstoff Pruefmaschinen GmbH, Germany).

[0136] An increase in MFI indicates visco-breaking activity, i.e., controlled degradation of the polypropylene chains. The difference in MFI ("delta MFI", i.e., the difference between the MFI of the additive formulation and the MFI of the reference formulation without additive) is a measure of the differential activity of the additive. The results are summarized in Tables 1a-1d.

[0137] [Table 1]

[0138] Comparative Examples 1-3 showed the known increase in MFI with increasing peroxide concentration. Comparative Example 4 showed that ThioU had little effect on MFI when used without peroxide. Example 1 demonstrated that a delta MFI of approximately 3 could be achieved with as little as 0.003% peroxide when combined with ThioU, while Comparative Example 1 required twice the amount, i.e., 0.006% peroxide.

[0139] [Table 2]

[0140] [Table 3]

[0141] Examples 2, 3, 4 and 5 demonstrated that when peroxide is combined with ThioU, the delta MFI can be increased even further.

[0142] [Table 4]

[0143] Comparative Examples 4 and 5 showed a known low increase in MFI with DIC. Examples 6-8 demonstrated that a clear increase in delta MFI can be achieved when combined with ThioU.

[0144] Examples 9-10 Examples 9-10 were made as described in Example 1, except that an extrusion temperature of 270° C. was used instead of 230° C. The results are summarized in Table 2.

[0145] [Table 5]

[0146] Examples 9 and 10 demonstrated that the delta MFI can be increased when peroxide is combined with ThioU.

[0147] Examples 11-12 Examples 11-12 were made as described in Example 1, but using an extrusion temperature of 250°C instead of 230°C, and a different commercially available polypropylene (Moplen HP561R ground from Lyondellbasell, MFI 25g / 10min ISO 1133). The results are summarized in Tables 3a-3b.

[0148] [Table 6]

[0149] Example 11 demonstrated that delta MFI can be increased when peroxide is combined with ThioU, even when the peroxide is used at a lower concentration compared to Comparative Example 7.

[0150] [Table 7]

[0151] Example 12 demonstrated that delta MFI can be increased when DIC is combined with ThioU, even when DIC is used at half the concentration compared to Comparative Example 9.

[0152] Examples 13-14 A) Preparation of masterbatch A peroxide masterbatch was prepared by adding 0.15% PER to commercial polypropylene (Moplen HP561R ground, MFI 25, Lyondell Basell) by immersion. For this purpose, polymer pellets were placed in a circular piston. The piston was preheated to 60 °C, after which PER was added with the aid of an eyedropper. The piston was closed and sealed with PTFE. The piston was placed on a rotary evaporator, and the mixture was treated for 3 hours with continuous rotation.

[0153] An activator masterbatch was prepared by mixing 0.15% ThioU into the same polypropylene powder (Moplen HP561R) with the aid of a high-speed mixer. In the next step, the mixture was compounded in a twin-screw extruder (Berstorff ZE25AX47D) at 200 °C.

[0154] B) Preparation of bicomponent nonwoven fabrics Spunbond nonwovens were made with polypropylene: polypropylene Total 7059 (MFI11 from TotalEnergies) in the core and polypropylene PP511A (MFI25 from Sabic) in the sheath, with and without additives in the core, on a 1 m wide Reicofil 4 line with a single beam with approximately 6800 holes per meter length. The hole diameter was 0.62 mm. The throughput per hole was set at 0.55 g / min. The line had a sheath-core configuration with 20% by weight of polymer in the sheath and 80% by weight of polymer in the core. Comparative fibers were prepared in which both domains contained no additives.

[0155] Nonwoven fabric: 70g / m 2 The nonwoven fabric was made using a fabric weight of 1.7 dtex (line speed: 52 m / min). The target filament fineness was 1.7 dtex (dtex is a unit of measure of the linear mass density of a fiber, defined as the mass in grams per 10,000 meters). The nonwoven fabric was thermally bonded using an embossing roll set at 165°C with a nip pressure of 90 N / mm.

[0156] The additives shown in the table below were added via their corresponding masterbatches described above, with the weight percentage indicating the total amount of additive present in the masterbatch.

[0157] Further processing conditions are as follows: - The extruder temperatures were set at 270°C for the core and 250°C for the sheath in all examples, the temperatures used for extrusion of polypropylene or polypropylene / additive blends on the Reicofil 4 line. - Cabin pressure is the pressure in the cabin behind and below the die and was set to 4500 Pa in all cases.

[0158] C) Evaluation of mechanical properties The mechanical properties of the nonwoven fabrics were determined according to DIN EN 29073-3 with a specimen clamp length of 100 mm, a specimen width of 50 mm, and a forward deformation rate of 200 mm / min. The tensile strength TD and elongation TD are the corresponding maximum values ​​measured perpendicular to the machine direction. The elongation MD is the corresponding maximum value measured in the machine direction. The results are summarized in Tables 4a and 4b.

[0159] [Table 8]

[0160] Example 13 demonstrated that even with a lower or half amount of PER, the tensile strength was increased compared to Comparative Examples 10-11.

[0161] [Table 9]

[0162] Example 14 demonstrated that even with a lower or half amount of PER, elongation was increased compared to Comparative Examples 12-13.

Claims

1. 1. A method for modifying the rheology of a polymeric material, comprising: a) a radical initiator selected from peroxides, carbon-based radical generators, bis-azo compounds, or stable nitroxyl compounds; b) Formula (1) 【Chemical 1】 (In the formula, R ａ is based on organic isocyanates, Group-S-R ａ is introduced by reaction with an isocyanate group, R ｂ is optionally substituted and / or interrupted C ２ -C ４０ is alkyl, n is 1 or more The method comprising incorporating a modifier blend comprising:

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

1.

3. 3. The method of claim 1, wherein the radical initiator is selected from peroxides or carbon-based radical generators.

4. The carbon-based radical generator is represented by the formula (17): 【Chemistry 2】 (In the formula, R ７ , R ８ , R ９ and R １０ are each independently selected from the group consisting of a hydrogen atom, a C1-C6 alkyl group, a C1-C2 alkoxy group, a nitrile group, and a halogen atom; １ , R ３ , R ４ and R ６ each of which is independently selected from the group consisting of hydrogen and a C1-C6 alkyl group.

5. The method of any one of claims 1 to 4, wherein the peroxide is 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-butylcumyl peroxide (BCUP), bis(tert-butylperoxyisopropyl)benzene (DIPP), 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, di(tert-butylperoxyisopropyl)benzene, dicetyl peroxydicarbonate, or tert-butyl monoperoxymaleate.

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

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

8. R ａ is based on an organic isocyanate, wherein the organic isocyanate is cyclohexyl diisocyanate, methylene bis(cyclohexyl) diisocyanate, isophorone diisocyanate, phenyl diisocyanate, diphenylmethane diisocyanate, or naphthyl diisocyanate, each of which is unsubstituted or C １ -C ４ Alkyl or di(C １ -C ４ substituted with alkyl)amino, or C ４ -C ２０ 8. The method according to any one of claims 1 to 7, wherein the diisocyanate is an alkyl diisocyanate or an oligomeric or polymeric product obtained by reaction of said diisocyanate with itself and / or with a polyol.

9. R ａ is based on an organic isocyanate, the organic isocyanate being unsubstituted, or C １ -C ４ 9. The method of any one of claims 1 to 8, wherein the diisocyanate is an alkyl-substituted phenyl diisocyanate or an oligomeric or polymeric product obtained by reaction of said diisocyanate with itself and / or with a polyol.

10. The polyol is a C １ -C １０ Alkanol or Poly-C ２ -C １０ The method according to claim 8 or 9, wherein the alkylene glycol is an alkylene glycol.

11. R ｂ is a C uninterrupted or interrupted by —O— and / or carbonyl groups ８ -C ４０ The method according to any one of claims 1 to 10, wherein the alkyl is alkyl.

12. The thiourethane is represented by formula (9) or (10): 【Chemistry 3】 (In the formula, R ｂ is optionally substituted and / or interrupted C ２ -C ４０ The method of any one of claims 1 to 11, wherein the aryl group is alkyl.

13. 13. The method according to any one of claims 1 to 12, wherein the polymeric material is a thermoplastic polymer, preferably a polyolefin, 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 polymer material obtainable by incorporating a modifier blend according to any one of claims 1 to 13 into a polymer material according to any one of claims 1 to 13, said modifier blend comprising: a) a radical initiator selected from peroxides, carbon-based radical generators, bis-azo compounds, or stable nitroxyl compounds; b) Formula (1) 【Chemistry 4】 (In the formula, R ａ is based on organic isocyanates, Group-S-R ａ is introduced by reaction with an isocyanate group, R ｂ is optionally substituted and / or interrupted C ２ -C ４０ is alkyl, n is 1 or greater.

15. the modifier blend comprising: a) a radical initiator selected from peroxides, carbon-based radical generators, bis-azo compounds, or stable nitroxyl compounds; b) Formula (1) 【Chemistry 5】 (In the formula, R ａ is based on organic isocyanates, Group-S-R ａ is introduced by reaction with an isocyanate group, R ｂ is optionally substituted and / or interrupted C ２ -C ４０ The modifier blend of any one of claims 1 to 14, comprising a thiourethane of the formula:

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