Additive blends for rheology modification of polymers

Abstract

The present invention provides a mixture for modifying the rheological properties of a polymer substrate, comprising a hydroxylamine ester and an isocyanate functionalized with a thio compound.

Description

[0001] describe

[0002] The invention relates to compositions comprising a polymer substrate and a mixture of a hydroxylamine ester and an isocyanate functionalized with a thio compound, the corresponding mixtures and the use of such mixtures for modifying the rheological properties of a polymer substrate. Another object of the invention are novel isocyanates functionalized with thio compounds.

[0003] The controlled preparation of polymer types (polymer types with different molar masses, melt viscosities, densities, molar mass distributions, etc.) by conventional compounding methods (eg by extrusion or injection molding) is a conventional method used by polymer manufacturers and polymer processors / compounders.

[0004] The setting of desired parameters such as melt viscosity by means of this polymer process step depends crucially on the controlled reactivity and mode of action of the additives used.

[0005] The use of free radical formers to modify the melt viscosity (rheology) of polyolefins is a generally known process. Whether this leads to a decrease in molecular weight (degradation) or an increase in molecular weight (crosslinking, branching) depends primarily on the chemical structure of the polyolefin.

[0006] During polymer processing, the reaction of polymers of the polypropylene type with free radical formers generally leads to degradation of the polymer, whereas polymers of the polyethylene type tend to crosslink. Examples which may be mentioned here are polyethylene types which are obtainable with the aid of Phillips catalysts (HDPE) or metallocene catalysts (LLDPE). Exceptions are polyethylene types prepared by the Ziegler process, which likewise tend to undergo chain degradation during processing in the presence of free radical formers.

[0007] In the case of copolymers and terpolymers or copolymer blends, a high proportion of propylene results in polypropylene-like behavior, while a high proportion of ethylene results in polyethylene-like behavior. If the copolymers and terpolymers or copolymer blends mentioned above contain a certain proportion of multiply unsaturated olefins, the possibility of crosslinking decreases as the concentration of free double bonds decreases.

[0008] The controlled degradation of polypropylene (PP) to give products with lower molecular weight and narrower molecular weight distribution is a commercially important process for producing "controlled rheology" polypropylene (CR-PP). While specific PP grades ("reactor grades") can be obtained by optimizing the synthesis process or the catalyst system (metallocene catalysts), standard PP grades are frequently modified in process technology by means of processing steps after the synthesis.

[0009] Known degradation processes are carried out thermally, in particular at temperatures above 280° C., or in the presence of free radical generators. In process technology, free radical initiated processes are carried out in an extruder or injection molding machine at temperatures above 180° C. Suitable free radical generators are organic peroxides which are added during the processing step in diluted form (PP masterbatch, or diluted in oil, or stabilized on an organic or inorganic support, or incorporated in a porous organic support) or directly in liquid form. Under given processing conditions, the peroxide dissociates into free radicals, which initiate chain scission reactions and form polymers with the desired rheological properties (melt viscosity). The controlled degradation of PP to form a product with a lower molecular weight (higher melt flow rate (MFR)) is generally referred to as a viscosity-breaking / vis-breaking process.

[0010] CR-PP grades are mainly used for fiber applications and injection molding applications, where low melt viscosity is a prerequisite. Nowadays a wide range of melt viscosities or molecular weights is required in order to have PP grades that can be processed in many existing technologies.

[0011] In addition to molecular weight, another parameter that influences the processing behavior of polymers is molecular weight distribution (MWD). Although polymer grades with broad MWD show improved orientation behavior of polymer chains at low pull-off speeds in the fiber spinning process, the opposite is true for high pull-off speeds and broad MWD. ​​For this reason, narrow MWD is necessary at high pull-off speeds to achieve improved continuity during the spinning process. In addition, polymer grades with too broad MWD tend to be more difficult to process into nonwovens (e.g., meltblown, spunbond processes) or the quality of the properties obtained by the nonwovens may be reduced.

[0012] The use of peroxides is a disadvantage since only a restricted "processing temperature window" is available due to their decomposition temperature, which is usually below the customary temperatures for polymer processing.

[0013] WO 01 / 90113 discloses a process for reducing the molecular weight of polypropylene, propylene copolymers or polypropylene blends, wherein hydroxylamine esters are added to the polymer to be degraded.

[0014] The present invention is concerned with the problem of further improving the prior art processes by reducing the process temperature and obtaining polymers having a more uniform (narrow) molecular weight distribution and a reduced content of oligomeric and volatile decomposition products.

[0015] It has now been found that, surprisingly, the combination of selected hydroxylamine esters and selected isocyanates functionalized with thio compounds exhibits a pronounced synergistic effect which leads to excellent degradation properties even at low temperatures.

[0016] The present invention relates to a composition comprising:

[0017] (b) Compounds of formula (1) or (2)

[0018]

[0019] in

[0020] G 1 , G 2 , G 3 and G 4 Independently of each other, C 1 -C 4 Alkyl, or G 1 and G 2 Together or G 3 and G 4 together for pentylene;

[0021] G 1 ', G 2 ', G 3 ' and G 4 'Independently of each other 1 -C 4 Alkyl, or G 1 ' and G 2 'Together or G 3 ' and G 4 'Together they are pentylene;

[0022] G 5 , G 6 , G 5 ' and G 6 ' are independently hydrogen or C 1 -C 4 Alkyl; and

[0023] X and X' are independently hydrogen, C 1 -C 18 Alkyl, C 2 -C 18 Alkenyl, -OC 1 -C 18 Alkyl, -NH-C 1 -C 18 Alkyl, -N(C 1 -C 6 alkyl) 2 , phenyl, phenoxy or -NH-phenyl, m is 1 or 2, and when m is 1, R 1 C 2 -C 8 Alkylene or C 2 -C 8 Hydroxyalkylene or C 4 -C36 Acyloxyalkylene, or

[0024] When m is 2, R 1 (-CH 2 ) 2 C(CH 2 -) 2 ,and

[0025] R 1 ' is hydrogen, C 1 -C 8 Alkyl, C 1 -C 8 Hydroxyalkyl or -(C=O)-C 1 -C 40 Alkyl group, or -OR 1 'Together with the -CH- group to which it is attached is a group -(C=O)-,

[0026] (b) Compound of formula (3)

[0027]

[0028] in

[0029] A is based on an organic isocyanate, wherein the group -SR is introduced by reaction with an isocyanate group,

[0030] R is optionally substituted and / or interrupted C 2 -C 40 Alkyl, and

[0031] n is equal to or greater than 1, and (c) a polymer substrate.

[0032] As C 1 -C 4 Alkyl or C 1 -C 8 Examples of any substituents for the alkyl group are methyl, ethyl, n-propyl, n-butyl, sec-butyl or tert-butyl.

[0033] As C 1 -C 18 Examples of any substituents of the alkyl group are methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-heptadecyl or n-octadecyl.

[0034] As C 2 -C 18 Examples of any substituents for alkenyl are 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl or 4-tert-butyl-2-butenyl.

[0035] AS-OC 1 -C 18 An example of any substituent of an alkyl group is one in which C 1 -C 18 Alkyl groups are as given above for the corresponding substituents.

[0036] As -NH-C 1 -C 18 An example of any substituent of an alkyl group is one in which C 1 -C 18 Alkyl groups are as given above for the corresponding substituents.

[0037] As -N(C 1 -C 6 alkyl) 2 An example of any substituent is wherein C 1 -C 6 The alkyl groups are independently methyl, ethyl, n-propyl, n-butyl, sec-butyl or tert-butyl (e.g. -N(CH 3 ) 2 or -N(C 2 H 5 ) 2 ) corresponding substituents.

[0038] Phenyl, phenoxy and -NH-phenyl may be unsubstituted or C 1 -C 4 The alkyl group is preferably substituted with a methyl group.

[0039] As C 2 -C 8 Examples of any substituents of the alkylene group are ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene or octamethylene. 2 -C 8 Examples of hydroxyalkylene groups are 2 -C 8 Alkylene gives the corresponding radical which is substituted by one or two, in particular by one, hydroxyl group.

[0040] C 4 -C 36 The acyloxyalkylene group is preferably C 1 -C 20 Acyloxy-C 3 -C 10 Alkylene. As C 4 -C 36 Examples of any substituents of the acyloxyalkylene group are groups of the formula:

[0041]

[0042] Where Y is C 1 -C 20 Alkyl groups are groups of the formula:

[0043]

[0044] C 1 -C 8 Examples of hydroxyalkyl are methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl and 2-ethylhexyl, substituted by one or two, in particular by one, hydroxyl groups.

[0045] Formula -(C=O)-C 1 -C 40 The alkyl group is preferably -(C=O)-C 1 -C 20 Alkyl, especially -(C=O)-C 16 -C 18 alkyl.

[0046] G 1 , G 2 , G 3 and G 4 and G 1 ', G 2 ', G 3 ' and G 4 'Preferably C 1 -C 4 More preferably, G 1 , G 3 , G 1 ' and G 3 ' is methyl and G 2 , G 4 , G 2 ' and G 4 ' is ethyl.

[0047] G 5 , G 6 , G 5 ' and G 6 ' is preferably hydrogen or methyl. More preferably, G 5 and G 5 ' is hydrogen and G 6 and G 6 ' is methyl.

[0048] X and X' are preferably hydrogen, C 1 -C 18 Alkyl, -OC 1 -C 18 Alkyl, -NH-C 1 -C 18 Alkyl or -N(C1 -C 6 alkyl) 2 , especially hydrogen or C 1 -C 18 More preferably, X and X' are C 1 -C 4 Alkyl, especially methyl.

[0049] In the compounds of formula (1), n ​​is preferably 1.

[0050] In the compound of formula (1), preferably n is 1 and R 1 C 2 -C 8 Alkylene or C 4 -C 36 Acyloxyalkylene, especially C 4 -C 36 More preferably, n is 1 and R 1 It is a compound of formula (4), especially a compound of formula (4a).

[0051] R 1 'Preferably the formula -(C=O)-C 1 -C 40 An alkyl group, more preferably -(C=O)-C 1 -C 20 Alkyl, especially -(C=O)-C 16 -C 18 alkyl.

[0052] As the compound of formula (1), the following compound is highly preferred:

[0053]

[0054] The compound of formula (5) generally comprises C 16 -C 18 The alkyl radicals may be a mixture of alkyl radicals, but may also contain only one type of alkyl radical.

[0055] Preferably component (a) is a compound of formula (1), and the above preferences apply to the compound of formula (1).

[0056] More preferably, component (a) is a compound of formula (1) wherein n is 1 and R 1 C 4 -C 36 Acyloxyalkylene.

[0057] Highly preferred component (a) is a compound of formula (5).

[0058] Compounds of the formula (1) and (2) are known or can be prepared according to known methods, for example as given in WO 01 / 90113.

[0059] A is 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 C 1 -C 4 Alkyl or di(C 1 -C 4 alkyl)amino substituted, or C 4 -C 20 Alkyl diisocyanates; or oligomeric or polymeric products obtained by reaction of the above diisocyanates with themselves and / or with polyols.

[0060] More preferably, A is based on an organic isocyanate which is phenyl diisocyanate, diphenylmethane diisocyanate or naphthyl diisocyanate, each of which is unsubstituted or substituted with C 1 -C 4 Alkyl or di(C 1 -C 4 or oligomeric or polymeric products obtained by reacting the above diisocyanates with themselves and / or with polyols.

[0061] It is highly preferred that A is based on an organic isocyanate which is unsubstituted or C 1 -C 4 Alkyl-substituted phenyl diisocyanates; or oligomeric or polymeric products obtained by reaction of the above diisocyanates with themselves and / or with polyols.

[0062] Most preferably, A is 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.

[0063] Examples of products obtained by reaction of the above diisocyanates with themselves are the following reaction products of 3 equivalents of toluene-2,4-diisocyanate or toluene-2,6-diisocyanate, respectively:

[0064]

[0065]

[0066] Examples of products obtained by the reaction of the above-mentioned diisocyanates with polyols are toluene-2,4-diisocyanate or toluene-2,6-diisocyanate with the formula HO-CH 2 -C(CH 2 -OH) 2 -CH 2 -CH 3The following reaction products of polyols.

[0067]

[0068] The polyol is preferably a C 1 -C 10 Alkanol, or poly C 2 -C 10 Alkylene glycol.

[0069] As polyols C 1 -C 10 Alkanols, preferably those substituted with 2 to 4, especially two or three, hydroxyl groups. Particularly preferred are C 2 -C 10 Alkanols, especially C 2 -C 6 Alkanols, which are correspondingly substituted with hydroxyl groups. Highly preferred are those of the formula HO-CH 2 -C(CH 2 -OH) 2 -CH 2 -CH 3 of polyols.

[0070] As poly C 2 -C 10 Alkylene glycol, preferably poly(C 2 -C 6 Alkylene glycols, especially those of the formula:

[0071]

[0072] Therein y is a value of 2 to 600, especially 2 to 200, most preferably a value of 2 to 100. Values ​​of 2 to 50, especially 2 to 20, are highly preferred.

[0073] As for formula (10), the corresponding polyethylene glycol or polypropylene glycol is preferred.

[0074] Preferably, the polyol is a C 2 -C 6 Alkanol, or poly C 2 -C 6 Alkylene glycols, especially polyols of the formula (10).

[0075] In the case of reactions of a diisocyanate with itself, or reactions of different types of diisocyanates with themselves, this can lead to mixtures of different oligomers or polymers, and in the case of additional reactions with polyols, even more complex mixtures can be obtained.

[0076] The corresponding organic isocyanates are known or obtainable by known methods, for example from WO 05 / 070987.

[0077] R may be interrupted, for example, by -O-, -NH-, -S- and / or carbonyl groups. A possible substituent for R is -SH. The corresponding C 8 -C 40 Alkyl groups, especially C 8 -C 20 Alkyl groups are preferred.

[0078] R is preferably uninterrupted or interrupted by -O-, -NH-, -S- and / or carbonyl groups, especially C interrupted by -O- and / or carbonyl groups. 2 -C 40 alkyl.

[0079] Particularly preferably, R is C 8 -C 40 Alkyl groups, especially C 8 -C 20 Alkyl groups which are uninterrupted or interrupted by -O- and / or carbonyl groups.

[0080] The compound of formula (3) can be obtained by reacting an organic isocyanate with a thiol of the following formula:

[0081] HSR(11) wherein for R the above definitions and preferences apply.

[0082] The group -SR is introduced by reaction with an isocyanate group of an organic isocyanate and is bonded in the reaction product as a group of the formula:

[0083]

[0084] wherein R is as defined above.

[0085] In view of the above, the term "isocyanate functionalized with a thio compound" relates to the corresponding thiocarbamate.

[0086] The above process for preparing the compound of formula (3) is usually carried out in the presence of a catalyst such as 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 such as 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.

[0087] The reaction is generally carried out in the presence of an organic solvent such as tetrahydrofuran or ethyl acetate and at a temperature of, for example, 30-80°C.

[0088] Preferably, component (c), the polymer substrate is a thermoplastic polymer. More preferably, the polymer substrate is a polyolefin, polyester, polyamide, polyvinyl chloride, polyimide, polyacrylonitrile, polycarbonate or polystyrene polymer, especially a polyolefin.

[0089] Examples of polymers of olefins are mono- and di-olefins, 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; polyethylene (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).

[0090] Polyolefins, i.e. polymers of monoolefins exemplified in the preceding paragraphs, preferably polyethylene and polypropylene, can be prepared by different processes, in particular by the following process:

[0091] a) Free radical polymerization (usually under high pressure and elevated temperature).

[0092] b) Catalytic polymerization using catalysts which usually contain one or more metals from groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more ligands, usually oxides, halides, alcoholates, esters, ethers, amines, alkylates, alkenylates and / or arylates which may be π-coordinated or σ-coordinated. These metal complexes may be in free form or fixed on a substrate, usually on activated magnesium chloride, titanium (III) chloride, aluminum oxide or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalysts themselves may be used for the polymerization or other activators may be used, usually metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyl Alkane (alkyloxane), wherein the metal is an element of the periodic table group Ia, IIa and / or IIIa. The activator can be conveniently modified with other ester, ether, amine or silyl ether groups. These catalyst systems are generally known as Philips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalyst (SSC).

[0093] Examples of mixtures of polyolefins are mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (eg PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (eg LDPE / HDPE).

[0094] 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 / vinylcyclohexane copolymers, ethylene / cyclic olefin copolymers (e.g. ethylene / norbornene, e.g. COC), ethylene / 1-olefin copolymers where the 1-olefin is generated in situ; propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / vinylcyclohexane copolymers, ethylene / propylene 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 these copolymers with each other and with the polymers mentioned under 1) above, for example polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers (EVA), LDPE / ethylene-acrylic acid copolymers (EAA), LLDPE / EVA, LLDPE / EAA and alternating or random polyolefin / carbon monoxide copolymers and mixtures thereof with other polymers such as polyamides.

[0095] Preferably the polymeric substrate is a thermoplastic polymer, preferably a polyolefin.

[0096] More preferably, the polymer substrate is a polyolefin selected from the group consisting of polyethylene, such as linear low density polyethylene, low density polyethylene, medium density polyethylene and high density polyethylene; and polyethylene copolymers and polypropylene homopolymers and polypropylene copolymers.

[0097] Highly preferred are polyethylene or polypropylene.

[0098] Preferably, the individual compounds of the composition of the invention are present in the polymer matrix (c) in an amount of 0.0001 to 5% by weight, especially 0.001 to 5% by weight, more preferably 0.01 to 5% by weight, based on the weight of the polymer matrix. Highly preferred is an amount of 0.01 to 2% by weight, especially 0.01 to 1% by weight.

[0099] The composition according to the invention may additionally contain various conventional additives, such as:

[0100] 1. Antioxidants

[0101] 1.1 Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenol with a straight or branched side chain, such as 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundecane-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadecan-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridecane-1'-yl)phenol and mixtures thereof. 1.2. Alkylthiomethylphenols, such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di(dodecylthio)methyl-4-nonylphenol.

[0102] 1.3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

[0103] 1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

[0104] 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-pentylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide.

[0105] 1.6. Alkylenebisphenols, for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-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-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

[0106] -4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl

[0107] -4'-hydroxyphenyl) butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene,

[0108] [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.

[0109] 1.7. O-, N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl 4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

[0110] 1.8. Hydroxybenzylated malonates, for example dioctadecyl 2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, dioctadecyl 2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, didodecylmercaptoethyl 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate. 1.9. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

[0111] 1.10. Triazine compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

[0112] 1.11. Benzylphosphonates, for example dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

[0113] 1.12. Acylaminophenols, for example 4-hydroxylauroylanilide, 4-hydroxystearoylanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

[0114] 1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, for example with methanol, ethanol, n-octanol, isooctyl alcohol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, thiodiglycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl

[0115] -1-phospha-2,6,7-trioxabicyclo[2.2.2]octane esters.

[0116] 1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, for example with methanol, ethanol, n-octanol, isooctyl alcohol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, thiodiglycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phosphane

[0117] -2,6,7-trioxabicyclo[2.2.2]octane, esters of 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0118] 1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, for example methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, thiodiglycol, 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.

[0119] 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, thiodiglycol, 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

[0120] [2.2.2] Esters of octane.

[0121] 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)hexamethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxalamide ( XL-1, provided by Addivant).

[0122] 1.18. Ascorbic acid (vitamin C).

[0123] 1.19. Amine antioxidants, such as 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, N,N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-p-phenylenediamine -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 Acylaminophenol, 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-tolylbiguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, mixture of mono- and di-alkylated tert-butyldiphenylamine / tert-octyldiphenylamine , a mixture of mono- and di-alkylated nonyldiphenylamine, a mixture of mono- and di-alkylated dodecyldiphenylamine, a mixture of mono- and di-alkylated isopropyldiphenylamine / isohexyldiphenylamine, a mixture of mono- and di-alkylated tert-butyldiphenylamine, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and di-alkylated tert-butylphenothiazine / tert-octylphenothiazine, a mixture of mono- and di-alkylated tert-octylphenothiazine, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene.

[0124] 2.UV absorbers and light stabilizers

[0125] 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-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methyl)benzotriazole, 2-(3'-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-chlorobenzotriazole, 2-(3'-tert-butyl-5 '-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 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'-hydroxyphenyl)-5-chlorobenzotriazole 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylenebis[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;

[0126] Where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazole

[0127] -2-phenyl, 2-[2'-hydroxy-3'-(α,α-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)phenyl]

[0128] Benzotriazole; 2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(α,α-dimethylbenzyl)phenyl]

[0129] Benzotriazole.

[0130] 2.2.2-Hydroxybenzophenones, for example 4-hydroxy, 4-methoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.

[0131] 2.3. Esters of substituted and unsubstituted benzoic acid, 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.

[0132] 2.4. Acrylic esters, for example, ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxycinnamate, N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline, neopentyl tetra(α-cyano-β,β-diphenylacrylate).

[0133] 2.5. Nickel compounds, for example nickel complexes of 2,2′-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], for example the 1:1 or 1:2 complex, with or without further ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, the nickel salt of a monoalkyl ester, such as the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, the nickel complexes of ketoximes, such as 2-hydroxy-4-methylphenylundecylketoxime, the nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without further ligands.

[0134] 2.6. Hindered amines, for example bis(1-undecyloxy-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

[0135] -4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) n-butyl-3,5-di-tert-butyl

[0136] -4-hydroxybenzylmalonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine condensate with 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-butane tetracarboxylate, 1,1'-(1,2-ethylene)-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-pentamethylpiperidinyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-octyl-7,7,9,9-tetramethyl

[0137] -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, linear or cyclic condensation product of N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl) hexamethylenediamine and 4-morpholinyl-2,6-dichloro-1,3,5-triazine, condensation product 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, 2-chloro-4,6-di(4-n-butylamino)-

[0138] -1,2,2,6,6-pentamethylpiperidinyl)-1,3,5-triazine condensate with 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, 4-hexadecyloxy mixture of 2,2,6,6-tetramethylpiperidine, 1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Registry No. [136504-96-6]); 1,6-hexanediamine, 2,4,6-trichloro-1,3,5-triazine, condensate; 1,6-hexanediamine, 2,4,6-trichloro-1,3,5-triazine, condensate; 1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-triazine, condensate; 1,6-hexanediamine ...

[0139] -1,3,5-triazine and condensation product of N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS registration number [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-oxospiro[4,5]decane, reaction products of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane and epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidinyloxycarbonyl)-2-(4-methoxyphenyl)ethylene, N,N'-bisformyl-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[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidinyl)]siloxane, maleic anhydride-alpha-olefin copolymer and 2,2,6,6-tetramethyl-4-aminopiperidinyl or 1,2,2,6,6-pentamethyl-4 -aminopiperidine reaction products, 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,

[0140] 3058 (Clariant; CAS Reg. No. [106917-31-1]), 5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-chloro-s-triazine, reaction products 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.

[0141] 2.7. Oxamides, for example 4,4'-dioctyloxyoxalanilide, 2,2'-diethoxyoxalanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxalanilide, 2,2'-di(dodecyloxy)-5,5'-di-tert-butyloxalanilide, 2-ethoxy-2'-ethyloxalanilide, N,N'-bis(3-dimethylaminopropyl)oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxalanilide and mixtures thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxalanilide, mixtures of o- and p-methoxydisubstituted oxalanilides and mixtures of o- and p-ethoxydisubstituted oxalanilides.

[0142] 2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-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-(2-hydroxy-3-butyloxypropoxy)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-[2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)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-[2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)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-[2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2 -[4-(dodecyloxy / tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxyphenyl)- 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.

[0143] 3. Metal deactivators, such as N,N'-diphenyloxamide, N-salicylaldehyde-N'-salicylic acid hydrazide, N,N'-bis(salicylic acid)hydrazide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, 3-salicylic acid amino

[0144] -1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxalyl dianiline, isophthalic acid dihydrazide, sebacoyl diphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.

[0145] 4. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, tri(octadecyl) 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-dicumylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxy pentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tri(tert-butylphenyl)) pentaerythritol diphosphite Pentaerythritol diphosphite, tristearoyl 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 phosphite, 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-dioxaphosphocin, 2,2',2"-nitrilo[triethyltri(3,3',5,5'-tetra-tert-butyl-11'-biphenyl

[0146] -2,2'-diyl) phosphite], 2-ethylhexyl phosphite (3,3',5,5'-tetra-tert-butyl-11'-biphenyl

[0147] -2,2'-diyl) ester, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane, phosphorous acid, mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triester (CAS: 939402-02-5), phosphorous acid, triphenyl ester, polymer with α-hydrogen-ω-hydroxy poly[oxy(methyl-1,2-ethanediyl)], C 10-16 Alkyl esters (CAS: 1227937-46-3).

[0148] The following phosphites are particularly preferred:

[0149] Tris(2,4-di-tert-butylphenyl)phosphite( 168, BASF SE), tris(nonylphenyl) phosphite, bis(2,4-dicumenylphenyl)pentaerythritol diphosphite,

[0150]

[0151]

[0152] 5. Hydroxylamines, for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamines derived from hydrogenated tallow amine.

[0153] 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 tallowamine).

[0154] 7. Sulfur synergists, for example dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate or distearyl disulfide.

[0155] 8. Peroxide scavengers, for example esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(β-dodecylmercapto)propionate.

[0156] 9. Polyamide stabilizers, for example copper salts and divalent manganese salts in combination with iodides and / or phosphorus compounds.

[0157] 10. Alkaline costabilizers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatechuate or zinc pyrocatechuate.

[0158] 11. Nucleating agents, for example inorganic substances such as talc, metal oxides such as titanium dioxide or magnesium oxide, phosphoric acid esters, 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 mono- or polycarboxylic acids and their salts, 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; polymeric compounds such as ionic copolymers (ionomers), triaminobenzene derivatives, zinc glycerate and nonanol 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.

[0159] 12. Fillers and reinforcing agents, for example calcium carbonate, silicates, surface-treated silicas (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, fibers of wood flour and flour or other natural products, synthetic fibers.

[0160] 13. Other additives, for example plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow regulators, fluorescent brighteners, flame retardants, antistatic agents and blowing agents.

[0161] 14. Benzofuranoses and indolinones, as disclosed, for example, in U.S. Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No. 5,175,312; U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-4316611;

[0162] DE-A-4316622; DE-A-4316876; EP-A-0589839, EP-A-0591102;

[0163] Those of 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

[0164] -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-neopentyloxy)benzofuran-2-one phenyl)-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-dimethylphenyl]-5,7-di-tert-butylbenzofuran-2-one

[0165] -4-[(1,3,7,9-tetra-tert-butyl-5-methyl-5H-benzo[d][1,3,2]benzodioxaphosphocin-11-yl)oxy]phenyl]-3H-benzofuran-2-one.

[0166] Preference is given to compositions which additionally contain other 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, fluorescent brighteners, flame retardants, antistatic agents and blowing agents.

[0167] The weight ratio of the total amount of compounds of formulae (1) to (3) to the total amount of conventional additives may be, for example, 100:1-1:1000 or 10:1-1:100 or 20:1-1:20 or 10:1-1:10.

[0168] According to one embodiment, the composition of the present invention may contain peroxides as another free radical source. In this case, the ratio of the sum of the weight of the peroxides to the total weight of the compounds of formula (1) and (2) is 1:100-100:1, especially 1:10-10:1 is preferred.

[0169] Typical peroxides are 2,5-dimethyl-2,5-bis(tert-butyl-peroxy)hexane (DHBP, sold for example under the trade names Luperox 101 and Trigonox 101), 2,5-dimethyl-2,5-bis(tert-butyl-peroxy)hexyne-3 (DYBP, sold for example under the trade names Luperox 130 and Trigonox 145), dicumyl peroxide (DCUP, sold for example under the trade names Luperox DC and Perkadox BC), di-tert-butyl peroxide (DTBP, sold for example under the trade names Trigonox B and Luperox Di), tert-butylcumyl peroxide (BCUP, sold for example under the trade names Trigonox T and Luperox 801), bis(tert-butylperoxyisopropyl)benzene (DIPP, sold for example under the trade names Perkadox 14S and Luperox DC), 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane (sold for example under the trade name Trigonox 301), di(tert-butylperoxyisopropyl)benzene (sold for example under the trade name Perkadox 14S-FL), dicetyl peroxydicarbonate (sold for example under the trade name Perkadox 24L) and tert-butyl monopermaleate (sold for example under the trade name Perkadox PF-DBM25).

[0170] Preferred peroxides are 2,5-dimethyl-2,5-bis(tert-butyl-peroxy)hexane (DHBP), tert-butylcumyl peroxide (BCUP) and 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane, especially 2,5-dimethyl-2,5-bis(tert-butyl-peroxy)hexane (DHBP) and 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane.

[0171] The compounds of the composition of the present invention can be added to the polymer matrix in the form of a liquid, powder, granules or masterbatch, which contains, for example, each of the compounds of the present invention in a concentration of 0.01-90% by weight, preferably 0.05-25% by weight, more preferably 0.05-20% by weight, especially 0.1-10% by weight.

[0172] The compounds of the composition of the invention and optionally further additives can be added to the polymer matrix individually or mixed with one another.

[0173] Preferably components (a) and (b) are added together, preferably in the form of a masterbatch.

[0174] The compounds of the composition of the invention and optionally further additives can be added to the polymer before, during or after the polymerization or before or after crosslinking.

[0175] The compounds of the composition according to the invention and optionally further additives can be incorporated into the polymer matrix by known methods, for example before or during shaping, or by applying the corresponding compounds dissolved or dispersed to the polymer matrix with subsequent evaporation of the solvent, if necessary.

[0176] The addition of the compound of the present composition including any other additives (such as those given above) to the polymer substrate can be carried out in all conventional mixing machines where the polymer is melted and mixed with the compound of the present composition and optionally other additives. Suitable machines are known to those skilled in the art. These are mixers, kneaders and extruders. The method is preferably carried out by adding the compound of the present composition and optionally other additives 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 provided with at least one gas removal compartment to which a vacuum can be applied.

[0177] The polymer is subjected to an elevated temperature for a sufficient period of time to effect a molecular weight change. In a preferred embodiment of the process of the invention, a temperature range of about 160° C. to 310° C. is employed. In a particularly preferred process variant, a temperature range of about 170° C. to 290° C., in particular about 180-270° C., is used.

[0178] The time period required to change the molecular weight may vary as a function of 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.

[0179] Examples of processing or conversion of the composition according to the invention are:

[0180] Injection blow molding, extrusion, blow molding, rotational molding, in-mold decoration (back injection), hollow 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 conversion, sintering, coextrusion, coating, lamination, cross-linking (radiation, peroxide, silane), vapor deposition, welding together, gluing, thermoforming, tube extrusion, profile extrusion, sheet extrusion; sheet casting, spin coating, strapping, foaming, recycling / reprocessing, extrusion coating.

[0181] The materials processed according to the invention can be used in a wide variety of forms, for example as films, fibers (continuous or discontinuous), tapes or moldings.

[0182] Fibers including bicomponent fibers are preferred.

[0183] Bicomponent fibers mean fibers that contain at least two different polymeric 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; sheath-core, orange-type and matrix-type and fibril-type, which are described in Fahrbach, E., Schaut, G. and Weghmann, A., 2000, Nonwoven Fabrics, Figure 3, Ullmann's Encyclopedia of Industrial Chemistry. Preferred are sheath-core bicomponent fibers and side-by-side bicomponent fibers, especially sheath-core bicomponent fibers.

[0184] Preferred articles are nonwoven fabrics, which should also include a web and should mean a textile structure of individual fibers, filaments or yarns that are directional or randomly oriented and bonded by friction and / or cohesion and / or adhesion and / or mechanical processes, in contrast to the regular pattern of mechanically intermeshed fibers, that is, they are not woven or knitted fabrics. Examples of nonwoven fabrics include meltblown filaments, spunbond continuous filament webs, carded webs, air-laid webs and wet-laid webs. Suitable bonding methods include thermal bonding, chemical or solvent bonding, resin bonding, mechanical needling, hydraulic needling, stitch bonding, etc. It is summarized in Fahrbach, E., Schaut, G. and Weghmann, A., 2000, Nonwoven Fabrics, Ullmann's Encyclopedia of Industrial Chemistry. Such nonwovens can be prepared, for example, according to the fiber obtained by using the composition of the present invention. Nonwoven fabrics are produced in particular by using the fibers according to the invention.

[0185] The compositions of the invention allow for more efficient modification of polymeric substrates by changing the rheological properties (visbreaking, long chain branching, crosslinking).

[0186] This allows improvements

[0187] - Mechanical properties such as tensile strength, elongation, tear resistance

[0188] - Barrier properties, especially in nonwovens (e.g. hydrohead, air permeability, filtration properties)

[0189] - Processability (wider range of suitable polymers, parameter adaptation, such as thermal bonding temperature in nonwovens)

[0190] - Recycling, since adjusting the melt viscosity of the recycled polymer can provide a recycled product with a more uniform molecular weight (narrower MWD) and therefore better mechanical properties. In addition, the use of visbroken polymers can act as a processing aid or compatibilizer that 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 rheological response of the polymer to be adjusted so that the polymer can have a more stable and controllable process.

[0191] Improved properties with respect to tensile strength and elongation are important for example for the manufacture of nonwoven fabrics, since their preparation involves multiple steps and improved tensile strength or elongation helps them to better withstand these steps.

[0192] Importantly, higher tensile strength provides nonwoven fabric producers with the option of, for example, reducing weight while still maintaining good mechanical properties of the product.

[0193] Another important aspect is the processing safety in the process of preparing nonwovens. It is necessary to carry out the method of preparing nonwoven fabrics under more moderate conditions at lower processing temperatures. In order to be able to do so, good mechanical properties such as tensile strength and elongation must still be obtained at lower processing temperatures. This allows the processing temperature to be reduced. In addition, energy saving will be a secondary benefit.

[0194] Another embodiment of the invention relates to a composition comprising a compound of formula (1) or (2) and a compound of formula (3), wherein the above definitions and preferences apply.

[0195] Another embodiment of the present invention relates to the use of such compositions comprising a compound of formula (1) or (2) and a compound of formula (3) for modifying the rheology of a polymer substrate. With regard to such embodiments, the above definitions and preferences apply.

[0196] Furthermore, another embodiment of the present invention relates to novel compounds of formula (3), as given below:

[0197]

[0198]

[0199] wherein in each of formulae (11) and (12), R is as defined above and wherein the above preferences apply, or

[0200]

[0201] wherein R' is C without interruption or interruption with -O- and / or carbonyl 8 -C 40 Alkyl, wherein the preferences given above for R apply.

[0202] Preferred are compounds of the formulae (13) and (14), especially those of the formula (14).

[0203] The following examples illustrate the present invention in more detail. Unless otherwise stated, all percentages and parts are by weight. Example

[0204] Synthesis Example 1

[0205]

[0206] Dissolve 17.4 g (0.1 mol) of toluene-2,4-diisocyanate and 60.18 g (0.21 mol) of 1-octadecanethiol in 250 ml of anhydrous tetrahydrofuran. Add 1 g of 1,8-diazabicyclo[5,4,0]undec-7-ene to the stirred solution. Continue stirring at room temperature for 1 hour. Then evaporate the white suspension to dryness on a rotary evaporator and recrystallize the residue from ethyl acetate to obtain 67.7 g of the title compound in the form of a white solid, melting point 103-103.5°C.

[0207] Synthesis Example 2

[0208]

[0209] Synthesis Example 1 was repeated, but with toluene-2,4-diisocyanate replaced by an equimolar amount of toluene-2,6-diisocyanate, resulting in the compound of formula (102) being obtained as a white solid, melting point 120-122°C.

[0210] Synthesis Example 3

[0211] An isomeric mixture comprising 80% by weight of a compound of formula (103) and 20% by weight of a compound of formula (104)

[0212]

[0213] Synthesis Example 1 was repeated, but wherein toluene-2,4-diisocyanate was replaced by an isomeric mixture of toluene-2,4-diisocyanate / toluene-2,6-diisocyanate in an 80 / 20 weight ratio, and octadecyl mercaptan was replaced by an 80 / 20 weight ratio of octadecyl-3-mercaptopropionate, resulting in an isomeric mixture of compounds of formula (103) and (104) in an 80 / 20 weight ratio obtained as a white solid, with a melting point of 94-100°C.

[0214] Synthesis Example 4

[0215] A reaction mixture comprising as a main component a compound of formula (105)

[0216]

[0217] Under argon, 63.26 g of octadecyl-3-mercaptopropionate and 5 ml of triethylamine were dissolved in 400 ml of ethyl acetate. IL EA (50% in ethyl acetate, purchased from Covestro AG) was diluted with 100 ml of ethyl acetate and added to the above solution, which was then stirred at 50° C. for 1 hour. After 90 minutes, the mixture was stirred by 1 H-NMR in CDCl 3 No octadecyl-3-mercaptopropionate could be detected in the mixture. The mixture was then filtered and the filtrate was evaporated (20 mbar / 50° C.). The resulting solid was ground and then dried at 0.45 mbar / 50° C. for 1.5 hours and then at 50° C. / 200 mbar for 114 hours to give 110.8 g of a beige solid comprising the compound of formula (105) as a major component.

[0218] Synthesis Example 5

[0219] A reaction mixture comprising as a main component a compound of formula (106)

[0220]

[0221] Synthesis Example 4 was repeated, but wherein octadecyl-3-mercaptopropionate was replaced by an equimolar amount of octadecyl mercaptan, to produce a mixture comprising the compound of formula (106) as a major component.

[0222] Synthesis Example 6

[0223] A mixture comprising as a main component a compound of formula (107)

[0224]

[0225] Under argon, 102.21 g of octadecyl-3-mercaptopropionate and 5 ml of triethylamine were dissolved in 400 ml of ethyl acetate. L75 (75% in ethyl acetate, purchased from Covestro AG) was dissolved in 100 ml of ethyl acetate and added to the above solution, which was then stirred at 50° C. for 1 hour. After 90 minutes, 1 H-NMR in CDCl 3No octadecyl-3-mercaptopropionate could be detected. The mixture was then evaporated on a rotary evaporator and finally at 0.05 mbar / 50° C. The waxy product obtained was additionally dried at 50° C. / 200 mbar until constant weight, giving 167.71 g of a beige solid which contained the compound of formula (107) as a major component.

[0226] Synthesis Example 7

[0227] A mixture comprising as a main component a compound of formula (108)

[0228]

[0229] Synthesis Example 6 was repeated, but with octadecyl mercaptan substituted for octadecyl-3-mercaptopropionate in an equimolar amount, to produce a mixture comprising the compound of formula (108) as a major component. A) Application Example - Meltblown Nonwovens

[0230] Application Examples A1 to A31

[0231] Meltblown nonwovens were produced on an MB-L 150 / 200 device from RAVOtec GmbH. The feed extruder was a single screw extruder with a screw diameter of 25 mm, a length to diameter ratio of 25 and four heating zones. Unless otherwise specified, the screw speed was 50 rev / min. As a control temperature, the melt temperature at the end of the extruder was recorded and listed in the following examples. The meltblown equipment had a nozzle with 35 holes per square inch, each hole having a diameter of 0.35 mm. Unless otherwise specified, the air volume was 360 m 3 / hour. The distance from the conveyor to the mold is 250 mm. The mold has a width of 200 mm. Unless otherwise specified, the grammage of the nonwoven is 20 g / m 2 .

[0232] The polymer used for the test had a melt flow index of 25.0 g / 10 min (230° C., 2.16 kg) and a flow rate of 0.9 g / cm 3 A polypropylene homopolymer with a density of 1.5 Å. It is a grade stabilized with 0.05% phenolic antioxidant, 0.1% phosphite and 0.025% by weight calcium stearate.

[0233] The melt flow rate is measured according to ISO 1133 (230°C, 2.16 kg). The measurement is performed on nonwovens cut into thin segments. The melt flow rate is a key parameter for the meltblowing process. A sufficiently high melt flow rate is required to enable the production of nonwovens with good quality. The hydrostatic head (water column) and the air permeability are suitable parameters for defining the quality of the produced nonwoven.

[0234] The hydrostatic head measures the pressure required to force a water drop through a taut fabric. It is a measure of the resistance of a nonwoven fabric to water penetration. It is measured according to WSP (World Strategic Partner) 80.6 (2005). At 10 ± 0.5 cmH 2 O / min water pressure increase rate with 100cm 2 The test is carried out with a test head of . When the third drop passes through the nonwoven, the result is given in the form of the height of the water column in mm or the hydrostatic head (hydrohead).

[0235] Air permeability was measured according to WSP (World Strategic Partner) 70.1 (2005). The pressure difference was 200 Pa and the sample size was 20 cm 2 The results are expressed in l / m 2 / s, so it is defined as the vertical flow through 1m per second. 2 The air volume of the surface of the cross section of the nonwoven.

[0236] Unless otherwise stated, percentages given are in weight %.

[0237] The product designated as NOR1 below corresponds to the compound of formula (5):

[0238]

[0239] Unless otherwise stated, the products were first extruded at a melt temperature of 210° C. using a co-rotating twin-screw extruder with a screw diameter of 25 mm and a length to diameter ratio of 42 into a melt flow index of 25.0 g / 10 min (230° C., 2.16 kg) and a density of 0.9 g / cm 3 homopolypropylene. Therefore, such premixes can be regarded as masterbatches. For all masterbatches, except for Examples A30 and A31 below, each product present in the second row of Tables 1-3 below was each incorporated into a separate masterbatch (generating two different masterbatches), wherein the two products were incorporated into the same masterbatch (combibatch). The concentrations of the products in the respective masterbatches are shown in the third row of Tables 1-3 below.

[0240] Table 1 (Processed at 295°C)

[0241]

[0242]

[0243] The results in Table 1 show the excellent quality of the nonwoven in terms of water column, air permeability or melt flow rate.

[0244] Table 2 (Processing at 270°C)

[0245]

[0246]

[0247] The results in Table 2 reveal the excellent quality of the nonwoven in terms of water column, air permeability or melt flow rate.

[0248] Table 3 (Processing at 250°C)

[0249]

[0250]

[0251] The results in Table 3 show excellent quality of the nonwoven in terms of water column, air permeability or melt flow rate. The results also show that incorporating both products into the same masterbatch (masterbatch), rather than using two separate masterbatches, can provide even higher visbreaking performance.

[0252] B) Application Example - Extrusion

[0253] Application Examples B1 to B15

[0254] The properties of the various products were determined in a reproducible and systematic manner using a laboratory scale twin screw micro extruder. The polymer used was a polymer having a melt flow index of 3.0 g / 10 min (230° C., 2.16 kg) and a flow rate of 0.9 g / cm 3 A polypropylene homopolymer with a density of . It is an unstabilized grade, to which 0.1 wt.% B215 (by 168+ 1010) and 0.05 wt% calcium stearate. Calcium stearate was used in powder form without a pre-drying step. Unless otherwise stated, the additives shown in the table below were mixed into the polypropylene powder and in a laboratory scale twin screw micro extruder (Xplore Instruments BV), under nitrogen protection at a constant screw rotation speed (as shown in the following examples) in a loop system with co-rotating screws and 15 cm 3The mixture is compounded by volume. The percentages given below are weight percentages. The melting temperatures are given in the following examples. The laboratory-scale twin-screw micro-extruder records the back pressure in real time at a rate of once per second. After filling the barrel, the force rises to a maximum value and then begins to decrease. This force maximum is considered as time zero. In order to compare the contribution of various products, the force after 600 seconds after time zero is considered. The control formulations shown throughout the table below correspond to a force reduction of 0%. If a compounding force of 0 Newton is achieved at 600 seconds, the force reduction will be 100%.

[0255] The force recorded is directly related to the melt viscosity of the polymer. Therefore, the lower the molecular weight of the polymer, the lower its melt viscosity and the lower the force recorded. Therefore, the force recorded is a direct measure of the polymer melt flow.

[0256] For the production of nonwovens, for example in the spunbond or meltblown process, it is decisive to have a sufficiently high melt flow firstly to be able to process the polypropylene and secondly to be able to obtain a nonwoven with satisfactory quality.

[0257] For the tests in Table 4, the control also always contained 0.15% of the compound of the formula (5). The extrusion temperature was 270° C., with a screw speed of 50 rpm.

[0258] Table 4

[0259]

[0260]

[0261] Requires high value.

[0262] The results of Table 4 show a significantly higher reduction in compounding force, ie lower compounding force, ie higher visbreaking, when the products of Synthesis 1 to 7 are added.

[0263] Application Examples B16 to B20

[0264] The tests were performed as given above for Application Examples B1 to B15, but the co-additives of the Synthesis Examples were not incorporated directly into the polypropylene as such, but were first loaded into a porous polypropylene support at the following concentrations:

[0265] For the product of Synthesis Example 7, the loading amount is: 1.855 g of the product of Synthesis Example 7 + 100 g of polypropylene porous carrier. For the product of Synthesis Example 6, the loading amount is: 1.741 g of the product of Synthesis Example 6 + 100 g of polypropylene porous carrier.

[0266] Table 5

[0267]

[0268] Table 5 shows that even though the co-additive is not incorporated directly, but first loaded into the support (porous as exemplified above), the visbreaking performance is still present.

[0269] Application Examples B21 to B23

[0270] The tests were carried out as given above for Application Examples B1 to B15, but without using the compound of formula (5).

[0271] Table 6

[0272]

[0273] In summary, Table 6 shows that if the compound of formula (5) or the co-additive is used alone, low performance is obtained. In contrast, the use of a combination of the two components shows a synergistic effect and results in good performance.

[0274] C) Application Example - Nonwoven produced according to the spunbond process

[0275] Application Examples C1 to C8

[0276] The melt flow index is 3.0 g / 10 min (230 ° C, 2.16 kg) and the density is 0.9 g / cm 3 A spunbond nonwoven is produced in a 1m wide Reicofil-4 line with about 6800 holes per meter length in a single bundle of a polypropylene homopolymer with and without an additive as prepared as given below. The hole has a diameter of 0.6mm. The throughput of each hole is set to 0.5g / min. The line has a sheath-core structure, wherein it is set to 30% by weight of polymer in the sheath and 70% by weight of polymer in the core. The fiber containing the additive contains the additive throughout the fiber (sheath and core). The fabric weight of the nonwoven produced is 17g / m 2 (Line speed: 212m / min) and 70g / m 2 (Line speed: 53 m / min). The target filament fineness was 1.7 dtex. Decitex is a unit of measure for the linear mass density of a fiber and is defined as the mass in grams per 10,000 meters. An embossing roll was used to thermally bond the nonwoven.

[0277] The additives were first introduced via a masterbatch formulation. The masterbatch was prepared by compounding the product of formula (5), the product of the synthetic example shown, and a polypropylene homopolymer carrier having a melt flow index of 25.0 g / 10 min (230° C., 2.16 kg) at 200° C. in a co-rotating twin-screw extruder having a screw diameter of 25 mm and a length / diameter ratio of 47. The masterbatches containing the product of formula (5) and the product of the synthetic example shown were two different masterbatches, each containing one product.

[0278] Other processing conditions for the Reicofil-4 line are given below:

[0279] - Extruder temperature is the set temperature for extruding polypropylene or polypropylene / additive compound and is shown in the table;

[0280] -Mold temperature is the set temperature of the polymer on the mold;

[0281] - Chamber pressure is the pressure in the chamber behind and below the mould;

[0282] - an engraved roller and a smooth roller are rollers between which the fiber web passes;

[0283] - The nip pressure is the set pressure between the engraved roller and the smooth roller.

[0284] Evaluation of mechanical properties:

[0285] The mechanical properties of the nonwoven fabrics were determined according to DIN EN 29073-3, with a sample grip length of 100 mm, a sample width of 50 mm and an advancement (deformation speed) of 200 mm / min.

[0286] The tensile strength MD and the tensile elongation MD are the respective maximum values ​​measured in the machine direction.

[0287] The tensile strength MC and the tensile elongation MC are the respective maximum values ​​measured in the direction perpendicular to the machine direction.

[0288] Table 7 (Fabric weight of nonwoven fabric: 70 g / m 2 )

[0289] Set mold temperature: 270℃

[0290] Chamber pressure: 4500Pa

[0291] Temperature of engraving roller: 162℃; Temperature of smooth roller: 160℃

[0292] Clamping pressure: 90N / mm

[0293]

[0294]

[0295] Table 8 (Fabric weight of nonwoven: 17 g / m 2 )

[0296] Set mold temperature: 270℃

[0297] Chamber pressure: 4500Pa

[0298] Temperature of engraving roller: 162℃; Temperature of smooth roller: 160℃

[0299] Clamping pressure: 90N / mm

[0300]

[0301] The results clearly show the advantages of the present invention, according to which significantly lower processing temperatures can be used to enable a stable process and achieve at least similar mechanical properties when compared to using NOR1 alone as a visbreaking additive. For example, this provides nonwoven producers with the option of broadening their flexibility in polymer selection and sourcing and reducing processing temperatures to save energy while maintaining the target properties of the nonwoven product.

[0302] D) Application Examples - Nonwovens produced according to the spunbond process with improved thermal bonding behavior Application Examples D1 to D3

[0303] Spunbond nonwovens were produced from a polypropylene homopolymer (melt flow index of 27 g / 10 min (230° C., 2.16 kg)) with and without additives prepared as given below on a 1 m wide Reicofil-4 line with about 6800 holes per meter of length in a single bundle. The holes had a diameter of 0.6 mm. The throughput per hole was set at 0.55 g / min. The line had a sheath-core construction, with a setting of 30% polymer in the sheath and 70% by weight of polymer in the core. The fibers containing additives contained the additive only in the sheath layer. With 70 g / m 2 The nonwoven was produced at a fabric weight of 1.50 g (line speed: 53 m / min). The target filament fineness was 1.85 dtex. Decitex is a unit of measure for the linear mass density of a fiber and is defined as the mass in grams per 10,000 meters. An embossing roll was used to thermally bond the nonwoven.

[0304] The additives were first introduced via a masterbatch formulation. The masterbatch was prepared by compounding the product of formula (5), the product of the synthetic example shown, and a polypropylene homopolymer carrier having a melt flow index of 25.0 g / 10 min (230° C., 2.16 kg) at 200° C. in a co-rotating twin-screw extruder having a screw diameter of 25 mm and a length / diameter ratio of 47.

[0305] Other processing conditions for the Reicofil-4 line are given below:

[0306] - Extruder temperature is the set temperature for extruding polypropylene or polypropylene / additive compound and is shown in the table;

[0307] -Mold temperature is the set temperature of the polymer on the mold;

[0308] - Chamber pressure is the pressure in the chamber behind and below the mould;

[0309] - an engraved roller and a smooth roller are rollers between which the fiber web passes;

[0310] - The nip pressure is the set pressure between the engraved roller and the smooth roller.

[0311] Table 9 (Fabric weight of nonwoven fabric: 70 g / m 2 )

[0312] Set extruder and set mold temperature: 250℃

[0313] Chamber pressure: 4500Pa

[0314] Temperature of engraving roller: 158℃; Temperature of smooth roller: 155℃

[0315] Clamping pressure: 80N / mm

[0316]

[0317] The results clearly show the advantages of the present invention, according to which significantly better results with respect to mechanical properties can be obtained in the thermal bonding process when compared to using no additive or using only NOR1. For example, this provides nonwoven producers with the option of reducing weight while still maintaining good mechanical properties of the product. In addition, when compared to using only NOR1 as a visbreaking additive, this provides nonwoven producers with the option of widening their flexibility in polymer selection and sourcing and reducing processing temperatures to save energy while maintaining the target properties of the nonwoven product.

Claims

1. A composition comprising (a) Compound of formula (1) in G 1 , G 2 , G 3 and G 4 Independently of each other, C 1 -C 4 Alkyl, or G 1 and G 2 Together or G 3 and G 4 Together they are pentylene, G 5 and G 6 are independently hydrogen or C 1 -C 4 alkyl, X is hydrogen or C 1 -C 18 alkyl, m is 1, and R 1 C 1 -C 20 Acyloxy-C 3 -C 10 Alkylene, (b) Compound of formula (3) in A is based on an organic isocyanate which is phenyl diisocyanate, diphenylmethane diisocyanate or naphthyl diisocyanate, each of which is unsubstituted or substituted with C 1 -C 4 Alkyl or di(C 1 -C 4 or a polymerization product obtained by the reaction of the above diisocyanate with itself and / or with a polyol, wherein the polyol is a C 1 -C 10 Alkanol, or poly C 2 -C 10 Alkylene glycols, wherein the group -SR is introduced by reaction with an isocyanate group, R is an optionally substituted and / or interrupted C 2 -C 40 alkyl, R optionally interrupted by -O-, -NH-, -S- and / or carbonyl, R optionally substituted by -SH, and n is equal to or greater than 1, and (c) A polymer substrate, wherein the polymer substrate is a polyolefin.

2. The composition according to claim 1, wherein n is 1.

3. The composition according to claim 1, wherein component (a) is a compound of formula (5):

4. The composition according to claim 1, wherein A is based on an organic isocyanate which is unsubstituted or C 1 -C 4 Alkyl-substituted phenyl diisocyanates; or polymerization products obtained by reaction of the above diisocyanates with themselves and / or with polyols.

5. The composition according to claim 2, wherein A is based on an organic isocyanate which is unsubstituted or C 1 -C 4 Alkyl-substituted phenyl diisocyanates; or polymerization products obtained by reaction of the above diisocyanates with themselves and / or with polyols.

6. The composition according to claim 3, wherein A is based on an organic isocyanate which is unsubstituted or C 1 -C 4 Alkyl-substituted phenyl diisocyanates; or polymerization products obtained by reaction of the above diisocyanates with themselves and / or with polyols.

7. The composition according to any one of claims 1 and 4 to 6, wherein the polymerization product obtained by the reaction of the above diisocyanate with itself and / or with a polyol is an oligomeric product.

8. A composition according to any one of claims 1 to 6, wherein R is C without or with -O-, -NH-, -S- and / or carbonyl groups. 2 -C 40 alkyl.

9. according to the composition described in any one of claims 1-6, wherein R is C without interruption or interruption with -O- and / or carbonyl group 8 -C 40 alkyl.

10. The composition according to claim 8, wherein R is C without interruption or interruption with -O- and / or carbonyl. 8 -C 40 alkyl.

11. The composition of any one of claims 1-6, wherein the polymer substrate is a polyolefin selected from the group consisting of low density polyethylene, medium density polyethylene, high density polyethylene, polyethylene copolymers, and polypropylene homopolymers and copolymers.

12. The composition of claim 10, wherein the polymer substrate is a polyolefin selected from the group consisting of low density polyethylene, medium density polyethylene, high density polyethylene, polyethylene copolymers, and polypropylene homopolymers and copolymers.

13. The composition of claim 11, wherein the polymer substrate is a polyolefin selected from the group consisting of linear low density polyethylene.

14. The composition of any one of claims 1-6, further comprising at least one peroxide.

15. The composition of claim 12, further comprising at least one peroxide.

16. A fiber comprising the composition as defined in claim 1.

17. A nonwoven fabric produced by using the fiber according to claim 16.

18. A composition comprising a compound of formula (1) and a compound of formula (3), each of which is as defined in claim 1.

19. Use of a composition as defined in claim 18 for modifying the rheology of a polymeric substrate.

20. A compound of the formula: wherein R is as defined in claim 1.

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