Additive mixture for rheology modification of polymers

Abstract

To provide a mixture for modifying the rheology of a polymer substrate.SOLUTION: Provided is a mixture for modifying the rheology of a polymer substrate comprising a hydroxylamine ester and an isocyanate functionalized with a thio compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition comprising a polymer substrate and a mixture of a hydroxylamine ester and an isocyanate functionalized with a thio compound, the corresponding mixture, and the use of such a mixture for modifying the rheology of the polymer substrate. A further object of the present invention is novel isocyanates functionalized with a thio compound. [Background technology]

[0002] The controlled preparation of polymer types (with different molar masses, melt viscosities, densities, molar mass distributions, etc.) by conventional compounding methods, such as extrusion or injection molding, is a routine method used by polymer manufacturers and polymer processors / compounders.

[0003] Setting the desired parameters in this polymer processing step, such as melt viscosity, is highly dependent on the controlled reactivity and mode of action of the additives used.

[0004] The use of free radical formers to modify the melt viscosity (rheology) of polyolefins is a commonly known method, which mainly depends on the chemical structure of the polyolefin, whether it results in a decrease in molecular weight (degradation) or an increase in molecular weight (crosslinking, branching).

[0005] During polymer processing, the reaction of polypropylene-type polymers with free radical formers generally leads to polymer degradation, while polyethylene-type polymers tend to crosslink. Examples that may be mentioned here are polyethylene types that can be obtained using Phillips catalysts (HDPE) or metallocene catalysts (LLDPE). An exception is polyethylene types prepared by the Ziegler process, which also tend to undergo chain degradation when processed in the presence of free radical formers.

[0006] 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. When the copolymers and terpolymers, or copolymer blends described above, contain a high proportion of unsaturated olefins, the probability of crosslinking decreases as the concentration of free double bonds decreases.

[0007] The controlled degradation of polypropylene (PP), which results in products with low molecular weight and narrow molecular weight distribution, is a commercially important method for the production of "controlled rheology" polypropylene (CR-PP). While specific PP grades ("reactor grades") can be obtained by optimizing the synthesis method or catalyst system (metallocene catalyst), standard PP grades are frequently modified in processing technology by post-synthesis processing steps.

[0008] Known degradation processes proceed thermally, especially at temperatures above 280°C, or in the presence of free radical generators. In processing technology, free radical-induced processes are carried out in extruders or injection molding machines 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 carrier) or directly as a liquid. Under certain processing conditions, the peroxides dissociate and decay 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 products with low molecular weights (high melt flow rates (MFR)) is commonly referred to as the viscosity-breaking or vis-breaking process.

[0009] CR-PP grades are primarily used for fiber and injection molding applications where low melt viscosity is a prerequisite. To have PP grades that can be processed by many existing technologies, a wide range of melt viscosities or molecular weights is currently required.

[0010] In addition to molecular weight, another parameter that affects the processing behavior of polymers is molecular weight distribution (MWD). Polymer grades with a broad MWD show improved polymer chain orientation behavior at low drawing speeds during the spinning process, while the opposite is true for high drawing speeds and broad MWDs. Therefore, with a narrow MWD, a high drawing speed is essential to achieve improved continuity during the spinning process. In addition, polymer grades with too broad an MWD tend to be more difficult to process into nonwoven fabrics (e.g., melt-blowing, spunbonding), or the quality of the resulting properties of the nonwoven fabric may be reduced.

[0011] The use of peroxides has drawbacks since only a limited "processing temperature range" is available due to decomposition temperatures that are generally below conventional temperatures for polymer processing.

[0012] WO 01 / 90113 discloses a method for reducing the molecular weight of polypropylene, propylene copolymers or polypropylene blends, in which a hydroxylamine ester is added to the polymer to be degraded. Summary of the Invention [Problem to be solved by the invention]

[0013] The present invention is directed to the problem of further improving the prior art processes by lowering the processing temperature, obtaining polymers with a more uniform (narrow) molecular weight distribution, and obtaining reduced levels of oligomers and volatile decomposition products. [Means for solving the problem]

[0014] It has now been surprisingly found that the combination of selected hydroxylamine esters with selected isocyanates functionalized with thio compounds exhibits significant synergistic effects, resulting in excellent cracking performance even at low temperatures.

[0015] The present invention provides (a) Formula (1) or (2)

[0016] [ka] [In the formula, G1, G2, G3 and G4 are each independently C1-C4 alkyl, or G1 and G2 together or G3 and G4 together are pentamethylene; G1', G2', G3' and G4' are each independently C1-C4 alkyl, or G1' and G2' together, or G3' and G4' together, are pentamethylene; G5, G6, G5' and G6' are each independently hydrogen or C1-C4 alkyl; X and X' are independently hydrogen, C1 to C 18 Alkyl, C2-C 18 Alkenyl, -O-C1-C 18 Alkyl, -NH-C1~C 18 alkyl, -N(C1-C6 alkyl)2, phenyl, phenoxy or -NH-phenyl; m is 1 or 2; When m is 1, R1 is C2-C8 alkylene, C2-C8 hydroxyalkylene, or C4-C 36 is 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 is an alkyl group, or -O-R1' together with the -CH- group to which they are attached is the group -(C=O)-. The compound (b) Formula (3)

[0017] [ka] [In the formula, A is based on an organic isocyanate, in which the group -SR is introduced by reaction with the isocyanate group, R is an optionally substituted and / or interrupted C-C 40 is alkyl, n is 1 or greater] and (c) Polymer substrate The present invention relates to a composition comprising:

[0018] Examples of optional substituents that are C1-C4 alkyl or C1-C8 alkyl are methyl, ethyl, n-propyl, n-butyl, sec-butyl or tert-butyl.

[0019] C1~C 18 Examples of optional substituents that are alkyl are methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-heptadecyl or n-octadecyl.

[0020] C2~C 18 Examples of optional substituents that are alkenyl are 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, or 4-tert-butyl-2-butenyl.

[0021] -O-C1~C 18 Examples of optional substituents that are alkyl include those C1-C1 alkyl groups listed above. 18 It is the substituent corresponding to alkyl.

[0022] -NH-C1~C 18 Examples of optional substituents that are alkyl include those C1-C1 alkyl groups listed above. 18 It is the substituent corresponding to alkyl.

[0023] Examples of optional substituents that are -N(C1-C6 alkyl)2 are the corresponding substituents where the C1-C6 alkyl groups are, independently of one another, methyl, ethyl, n-propyl, n-butyl, sec-butyl or tert-butyl, such as -N(CH3)2 or -N(C2H5)2.

[0024] Phenyl, phenoxy and -NH-phenyl can be unsubstituted or substituted with C1-C4 alkyl, preferably methyl.

[0025] Examples of optional substituents that are C2-C8 alkylene are ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene or octamethylene. Examples of C2-C8 hydroxyalkylene are the groups corresponding to those given above for C2-C8 alkylene, substituted with one or two, especially one, hydroxyl groups.

[0026] C4~C 36 The acyloxyalkylene is preferably C1 to C 20 Acyloxy-C3~C 10 Alkylene. C4~C 36 An example of an optional substituent that is an acyloxyalkylene is a group of the formula

[0027] [ka] [Wherein, Y is C1 to C 20 alkyl, for example of the formula

[0028] [ka] It is based on.

[0029] Examples of C1-C8 hydroxyalkyl are methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl and 2-ethyl-hexyl, which are substituted with one or two, especially one, hydroxyl groups.

[0030] Formula -(C=O)-C1~C 40 The alkyl group is preferably —(C═O)—C— to C 20 Alkyl, especially -(C=O)-C 16 ~C 18 It is alkyl.

[0031] G1, G2, G3 and G4, and G1', G2', G3' and G4' are preferably C1-C4 alkyl, especially methyl or ethyl. More preferably, G1, G3, G1' and G3' are methyl, and G2, G4, G2' and G4' are ethyl.

[0032] G5, G6, G5' and G6' are preferably hydrogen or methyl. More preferably, G5 and G5' are hydrogen and G6 and G6' are methyl.

[0033] X and X' are preferably hydrogen, C1 to C 18 Alkyl, -O-C1~C 18 Alkyl, -NH-C1~C 18 Alkyl or -N(C1-C6 alkyl)2, especially hydrogen or C1-C 18 More preferably, X and X' are C1-C4 alkyl, especially methyl.

[0034] In the compound of formula (1), n ​​is preferably 1.

[0035] Furthermore, in the compound of formula (1), n ​​is 1 and R1 is C2-C8 alkylene or C4-C 36 Acyloxyalkylene, especially C4-C 36 Preferably, n is 1 and R1 is a compound of formula (4), especially a compound of formula (4a).

[0036] R1' is preferably a group represented by the formula -(C=O)-C1 to C 40 Alkyl, more preferably -(C=O)-C 20 Alkyl, especially -(C=O)-C 16~C 18 It is an alkyl group.

[0037] Highly preferred compounds of formula (1) are those of formula

[0038] [ka] is a compound of

[0039] The compound of formula (5) is usually C 16 ~C 18 It contains a mixture of alkyl groups, but may contain only one of the alkyl groups.

[0040] Preferably, component (a) is a compound of formula (1) in which the above options apply.

[0041] More preferably, component (a) has n=1 and R1=C4-C 36 The compound of formula (1) is an acyloxyalkylene.

[0042] It is highly preferred that component (a) is a compound of formula (5).

[0043] Compounds of formula (1) and (2) are known or can be prepared according to known methods, for example as set out in WO01 / 90113.

[0044] 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 They are alkyl diisocyanates or oligomeric or polymeric products obtained by reaction of the above diisocyanates with themselves and / or with polyols.

[0045] More preferably, A is based on an organic isocyanate, which is phenyl diisocyanate, diphenylmethane diisocyanate or naphthyl diisocyanate, each unsubstituted or C1-C4 alkyl or di(C1-C4 alkyl)amino substituted, or an oligomeric or polymeric product obtained by reaction of the above diisocyanates with themselves and / or with polyols.

[0046] It is highly preferred that A is based on an organic isocyanate, which is phenyl diisocyanate, unsubstituted or C1-C4 alkyl substituted, or an oligomeric or polymeric product obtained by reaction of the above diisocyanates with themselves and / or with polyols.

[0047] Most preferably, A is based on toluene-2,4-diisocyanate or toluene-2,6-diisocyanate, or on oligomeric or polymeric products obtained by reaction of the above diisocyanates with themselves and / or with polyols.

[0048] Examples of products obtained by reaction of the above diisocyanates with themselves are the following reaction products with 3 equivalents of toluene-2,4-diisocyanate or toluene-2,6-diisocyanate, respectively:

[0049] [ka]

[0050] Examples of products obtained by reaction of the above diisocyanates with polyols are the following reaction products of toluene-2,4-diisocyanate or toluene-2,6-diisocyanate, respectively, with a polyol of formula HO-CH2-C(CH2-OH)2-CH2-CH3:

[0051] [ka]

[0052] The polyol is preferably a C1-C hydroxyl group-containing polyol. 10 Alkanol or poly-C2-C 10 It is an alkylene glycol.

[0053] Polyol C1 to C 10 Preferred alkanols are those substituted with 2 to 4, especially 2 or 3, hydroxy groups. Particularly preferred are C2 to C6 10 Alkanols, especially C2-C6 alkanols, which are correspondingly substituted with hydroxy groups. Highly preferred are polyols of the formula HO-CH2-C(CH2-OH)2-CH2-CH3.

[0054] Poly-C2~C 10 The alkylene glycol is preferably poly-C2-C6 alkylene glycol, particularly a poly-C2-C6 alkylene glycol represented by the formula

[0055] [ka] [wherein y is a number from 2 to 600, particularly from 2 to 200, and most preferably from 2 to 100]. A number from 2 to 50, particularly from 2 to 20, is highly preferred.

[0056] Preferred for formula (10) are the corresponding polyethylene glycols or polypropylene glycols.

[0057] Preferably, the polyol is a C2-C6 alkanol substituted with 2 to 4 hydroxy groups or a poly-C2-C6 alkylene glycol, especially of formula (10):

[0058] Reaction of diisocyanates with themselves or with different types of diisocyanates can result in mixtures of different oligomers or polymers, and additional reaction with polyols can result in even more complex mixtures.

[0059] The corresponding organic isocyanates are known and can be obtained according to known methods, for example according to WO 05 / 070987.

[0060] R can be interrupted, for example, by -O-, -NH-, -S- and / or carbonyl groups. A possible substituent for R is -SH. The corresponding C8-C 40 Alkyl, especially C8-C 20 Alkyl is preferred.

[0061] R is preferably C2 to C 40 It is alkyl, uninterrupted or interrupted by -O-, -NH-, -S- and / or carbonyl groups, especially -O- and / or carbonyl groups.

[0062] Particularly preferred R is C8-C 40 Alkyl, especially C8-C 20 It is alkyl and is uninterrupted or interrupted by -O- and / or carbonyl groups.

[0063] The compound of formula (3) is a compound of an organic isocyanate and a compound of formula HSR(11) with a thiol of the formula:

[0064] The group -SR is introduced by reaction with the isocyanate group of an organic isocyanate, in which the product has the formula

[0065] [ka] wherein R is as defined above.

[0066] In view of the above, the term "isocyanates functionalized with thio compounds" relates to the corresponding thiourethanes.

[0067] The above-described preparation method of the compound of formula (3) is generally 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 used, for example, in an amount of 0.1 to 10% by weight based on the weight of the organic isocyanate.

[0068] The reaction is usually carried out in the presence of an organic solvent such as tetrahydrofuran or ethyl acetate at a temperature of, for example, 30 to 80°C.

[0069] The preferred polymer substrate, component (c), 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.

[0070] Examples of polymers of olefins are 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 cyclopentane or norbornene, polyethylene (optionally 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).

[0071] Polyolefins, i.e. the polymers of monoolefins exemplified in the previous paragraph, preferably polyethylene and polypropylene, can be prepared by different methods, especially by the following methods: a) Radical polymerization (usually carried out under high pressure and elevated temperature). b) Catalytic polymerizations typically use catalysts 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 by itself in the polymerization, or an additional activator may be used, typically a metal alkyl, metal hydride, metal alkyl halide, metal alkyl oxide, or metal alkyl oxane, where the metal is an element from Groups Ia, IIa, and / or IIIa of the periodic table. The activator may be conveniently modified with additional ester, ether, amine, or silyl ether groups. These catalyst systems are commonly referred to as Phillips, Standard Oil Indiana, Ziegler-Natta, TNZ (DuPont), metallocene, or single-site catalysts (SSC).

[0072] Examples of blends of polyolefins 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).

[0073] Copolymers of monoolefins and diolefins with each other or with other vinyl monomers include 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-like COC), ethylene / 1-olefin copolymers (1-olefins generated in situ), propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / vinylcyclohexene copolymers. polymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers, or ethylene / acrylic acid copolymers, and their salts (ionomers), as well as terpolymers of ethylene with propylene and dienes, for example with hexadiene, dicyclopentadiene, or ethylidene-norbornene; and mixtures of such copolymers with each other and with the polymers mentioned under 1) above, for example polypropylene / ethylene-propylene copolymer, LDPE / ethylene-vinyl acetate copolymer (EVA), LDPE / ethylene-acrylic acid copolymer (EAA), LLDPE / EVA, LLDPE / EAA, and alternating or random polyalkylene / carbon monoxide copolymers, and mixtures thereof with other polymers, for example with polyamides.

[0074] The polymer substrate is preferably a thermoplastic polymer, preferably a polyolefin.

[0075] 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.

[0076] Highly preferred is polyethylene or polypropylene.

[0077] Each compound in the composition of the present invention is preferably present in the polymer substrate (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 substrate. Highly preferred is an amount of 0.01 to 2% by weight, especially 0.01 to 1% by weight.

[0078] The compositions according to the invention may also contain, for example, various conventional additives.

[0079] 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-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol, and mixtures thereof.

[0080] 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.

[0081] 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.

[0082] 1.4. Tocopherols, such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol, and mixtures thereof (vitamin E).

[0083] 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.

[0084] 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.

[0085] 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-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.

[0086] 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.

[0087] 1.9. Aromatic hydroxybenzyl compounds, such as 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.

[0088] 1.10. Triazine compounds, such as 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3, 5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

[0089] 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.

[0090] 1.12. Acylaminophenols, such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

[0091] 1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, for example, 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.

[0092] 1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric or polyhydric alcohols, for example, 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.

[0093] 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-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.

[0094] 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.

[0095] 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).

[0096] 1.18. Ascorbic Acid (Vitamin C)

[0097] 1.19. Amine antioxidants, for example, N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine 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.

[0098] 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]; 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole transesterification product with polyethylene glycol 300;

[0099] [ka] 2-[2'-hydroxy-3'-(α,α-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)-phenyl]benzotriazole, where R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl; 2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(α,α-dimethylbenzyl)-phenyl]benzotriazole.

[0100] 2.2. 2-Hydroxybenzophenones, such as the 4-hydroxy, 4-methoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy, and 2'-hydroxy-4,4'-dimethoxy derivatives.

[0101] 2.3. Esters of substituted and unsubstituted benzoic acid, for example, 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

[0102] 2.4. Acrylates, for example, ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate, N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline, neopentyl tetra(α-cyano-β,β-diphenylacrylate).

[0103] 2.5. Nickel compounds, such as 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, for example, n-butylamine, triethanolamine, or N-cyclohexyldiethanolamine), nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters (for example, the methyl or ethyl ester of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid), nickel complexes of ketoximes (for example, 2-hydroxy-4-methylphenylundecylketoxime), nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole (with or without additional ligands).

[0104] 2.6. Sterically hindered amines, such as 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 with succinic acid, linear or cyclic condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine with 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-butanetate carboxylate, 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-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-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl) 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;Condensation product of 6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, 4-hexadecyloxy a mixture of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; a condensation product of 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine, and further 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Registry Number [136504-96-6]); a mixture of 1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine; Chloro-1,3,5-triazine, and condensation products of N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Registry 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-oxo-spiro[4,5]decane, 7,7,9,9-tetramethyl-2-cyclo[2,3,4]diene, Reaction products of 1,1-dichloro-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'-bis-formyl-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, Hostavin® ) 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.

[0105] 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 mixtures thereof 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.

[0106] 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, 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-hexyloxypropyl)phenyl 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-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.

[0107] 3. Metal deactivators, such as N,N'-diphenyloxamide, N-salicylar-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.

[0108] 4. Phosphites and phosphonites, for example, triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite , bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite), tristearyl sorbitol triphosphite, tetrakis(2 ,4-di-tert-butylphenyl)4,4'-biphenylene diphosphonite, 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[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-dioxaphosphirane, 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,Phosphorous acid, triphenyl ester, polymer with α-hydro-ω-hydroxypoly[oxy(methyl-1,2-ethanediyl)], C10-16-alkyl esters (CAS: 1227937-46-3).

[0109] The following phosphites are especially preferred: Tris(2,4-di-tert-butylphenyl)phosphite (Irgafos® 168, BASF SE), tris(nonylphenyl)phosphite, bis(2,4-di-cumylphenyl)pentaerythritol phosphite,

[0110] [ka] TIFF2026016422000048.tif42151

[0111] 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, and N,N-dialkylhydroxylamines derived from hydrogenated tallow amine.

[0112] 6. Nitrones, such as N-benzyl-alpha-phenyl nitrone, N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone, N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone, N-hexadecyl-alpha-pentadecyl nitrone, N-octadecyl-alpha-heptadecyl nitrone, N-hexadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-pentadecyl nitrone, N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecyl nitrone, and nitrones derived from N,N-dialkylhydroxylamines derived from hydrogenated tallow amines.

[0113] 7. Thiosynergists, such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, or distearyl disulfide.

[0114] 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.

[0115] 9. Polyamide stabilizers, such as copper salts in combination with iodides and / or phosphorus compounds, and salts of divalent manganese.

[0116] 10. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example, calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate, and potassium palmitate, antimony pyrocatecholate, or zinc pyrocatecholate.

[0117] 11. Nucleating agents, such as inorganic substances, for example, talc, metal oxides, for example, titanium dioxide or magnesium oxide, preferably alkaline earth metal phosphates, such as phosphates, carbonates, or sulfates, including 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. Salts; 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, calcium 1,2-cyclohexanedicarboxylic acid, disodium bicyclo[2.2.1]heptane-2,3-dicarboxylic acid; polymeric compounds such as ionic copolymers (ionomers), triaminobenzene derivatives, zinc glycerolate, and nonitol derivatives. Particularly preferred are 1,3:2,4-bis(3',4'-dimethylbenzylidene)sorbitol, 1,3:2,4-di(paramethyldibenzylidene)sorbitol, and 1,3:2,4-di(benzylidene)sorbitol.

[0118] 12. Fillers and reinforcing agents, such as calcium carbonate, silicates, surface-treated silica (for example as 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 powders or fibers of natural products, synthetic fibers.

[0119] 13. Other additives such as plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow control agents, optical brighteners, flame retardants, antistatic agents, and foaming agents.

[0120] 14. Benzofuranones and indolinones, for example those disclosed in US 4,325,863; US 4,338,244; US 5,175,312; US 5,216,052; US 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839, EP-A-0591102; EP-A-1291384, or 3-[4-(2-acetaminophen]-2-yl)-4-(2-acetaminophen]-2-yl]-4-(2-acetaminophen]-2-yl) ... 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl) Benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-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.

[0121] Preferred are compositions which additionally contain further additives selected from the group consisting of antioxidants, processing stabilizers, light stabilizers, UV absorbers, fillers, reinforcing agents, pigments, metal deactivators, plasticizers, lubricants, emulsifiers, rheological additives, catalysts, flow control agents, optical brighteners, flame retardants, antistatic agents and foaming agents.

[0122] The weight ratio of the total amount of the compounds of formulas (1) to (3) to the total amount of the conventional additive(s) can be, for example, 100:1 to 1:1000, or 10:1 to 1:100, or 20:1 to 1:20, or 10:1 to 1:10.

[0123] According to one embodiment, the composition of the present invention can contain peroxide as an additional free radical source, in which case the ratio of the total weight of peroxide to the total weight of compounds of formula (1) and (2) is preferably 1:100 to 100:1, more preferably 1:10 to 10:1.

[0124] Typical peroxides are 2,5-dimethyl-2,5-bis(tert.-butyl-peroxy)hexane (DHBP, sold, for example, under the trademarks Luperox 101 and Trigonox 101); 2,5-dimethyl-2,5-bis(tert.-butyl-peroxy)hexyne-3 (DYBP, sold for example under the trademarks Luperox 130 and Trigonox 145), dicumyl peroxide (DCUP, sold, for example, under the trademarks Luperox DC and Perkadox BC), di-tert-butyl peroxide (DTBP, sold, for example, under the trademarks Trigonox B and Luperox Di); tert-butylcumyl peroxide (BCUP, sold, for example, under the trademarks Trigonox T and Luperox 801), bis(tert-butylperoxyisopropyl)benzene (DIPP, sold, for example, under the trademarks Perkadox 14S and Luperox DC), 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane (e.g., sold under the trademark Trigonox 301), di(tert-butylperoxyisopropyl)benzene (for example, sold under the trademark Perkadox 14S-FL); Dicetyl peroxydicarbonate (e.g., sold under the trademark Perkadox 24L), and tert-butyl monoperoxymaleate (e.g., sold under the trademark Perkadox PF-DBM25) is.

[0125] 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-triperoxonane, especially 2,5-dimethyl-2,5-bis(tert.-butyl-peroxy)hexane (DHBP) and 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane.

[0126] The compounds of the present composition can be added to the polymer substrate in the form of a liquid, powder, granules, or masterbatch, which contains the respective compound of the present invention in a concentration of, for example, 0.01 to 90% by weight, preferably 0.05 to 25% by weight, more preferably 0.05 to 20% by weight, especially 0.1 to 10% by weight.

[0127] The compounds of the composition and optionally further additives may be added to the polymer substrate individually or mixed with one another.

[0128] Components (a) and (b) are preferably added together, preferably in the form of a masterbatch.

[0129] The compounds of the composition and optionally further additives can be added to the polymer before, during or after polymerization, or before or after crosslinking.

[0130] The compounds of the composition according to the invention and optionally further additives can be incorporated into the polymer substrate by known methods, for example before or during molding or by applying the respective compound dissolved or dispersed to the polymer substrate and, if necessary, subsequently evaporating the solvent.

[0131] The addition of any additional additives, such as the compounds of the present composition, including those listed above, to the polymer substrate can be carried out by conventional mixers, in which the polymer is melted and mixed with the compounds of the present composition and optionally with additional additives.Suitable machines are known to those skilled in the art.These include mixers, kneaders and extruders.Preferably, the processing is carried out by adding the compounds of the present composition and optionally with additional additives to the extruder during processing.Particularly preferred processing machines are single-screw extruders, co-rotating and counter-rotating twin-screw extruders, planetary gear extruders, annular extruders, or co-kneaders, which are equipped with at least one gas removal compartment that can apply vacuum.

[0132] The polymer is subjected to elevated temperature for a time sufficient to modify the molecular weight. In a preferred embodiment of the process of the present invention, a temperature range of about 160°C to 310°C is used. In particularly preferred process variants, a temperature range of about 170°C to 290°C, especially about 180°C to 270°C, is used.

[0133] The time required to modify the molecular weight may vary as a function of temperature, the amount of material being modified, and the type of any extruder used, and may range, for example, from about 10 seconds to about 20 minutes, particularly from 20 seconds to 10 minutes.

[0134] Examples of processing or modification of the composition according to the invention are: These include injection blow molding, extrusion, blow molding, rotational molding, in-mold decoration (reverse injection), slush molding, injection molding, co-injection molding, forming, compression molding, pressing, film extrusion (cast film, blown film), spinning, other fiber processes (woven, nonwoven, fiber meltblown, spunbond, among others), stretching (uniaxial, biaxial), annealing, deep drawing, calendaring, mechanical deformation, sintering, co-extrusion, coating, lamination, crosslinking (radiation, peroxide, silane), vapor deposition, welding, adhesives, thermoforming, pipe extrusion, profile extrusion, sheet extrusion, sheet casting, spin coating, strapping, foaming, recycling / reprocessing, and extrusion coating.

[0135] Materials processed according to the present invention can be used in a wide variety of forms, such as films, fibers (continuous or discontinuous), tapes, and molded articles.

[0136] Fibers including bicomponent fibers are preferred.

[0137] Bicomponent fibers refer to fibers that contain at least two distinct polymer domains a) and b) intimately bonded along the length of the fiber. They may be of any shape and are not limited to a specific shape. Examples of such shapes include side-by-side, sheath-core, orange, and matrix and fibril types, as exemplified in Fahrbach, E., Schaut, G., and Weghmann, A., 2000, Nonwoven Fabrics, Figure 3, Ullmann's Encyclopedia of Industrial Chemistry. Sheath-core and side-by-side bicomponent fibers are preferred, especially sheath-core bicomponent fibers.

[0138] A preferred article is a nonwoven fabric, which includes webs and refers to a fibrous structure of individual fibers, filaments, or threads that are oriented and bonded in a directionally or randomly manner by friction, cohesion, adhesive, and / or mechanical means, as opposed to a regular pattern of mechanically intertwined fibers; i.e., not a woven or knitted fabric. Examples of nonwoven fabrics include meltblown filaments, spunbonded continuous filament webs, carded webs, aeolian webs, and wetlaid webs. Suitable bonding methods include thermal bonding, chemical or solvent bonding, resin bonding, mechanical needling, hydraulic needling, stitch bonding, and the like. A summary is provided in Fahrbach, E., Schaut, G., and Weghmann, A., 2000, "Nonwoven Fabrics," Ullmann's Encyclopedia of Industrial Chemistry. Such nonwoven fabrics can be prepared, for example, from fibers made using the compositions of the present invention. Nonwoven fabrics are prepared, inter alia, using the fibers of the present invention.

[0139] The compositions of the present invention allow for more efficient modification of polymer substrates through rheological changes (visbreaking, long chain branching, crosslinking).

[0140] This means that - improving mechanical properties such as tensile strength, elongation and tear resistance; - improving barrier properties, especially in nonwovens (e.g. hydrohead, air permeability, filtering properties); - improving processing properties (wide range of suitable polymers, parameter compatibility, such as thermal bonding temperature in nonwovens); - Improved recycling is possible 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. Additionally, the use of visbroken polymers can act as a processing aid or compatibilizer, which also contributes to the high mechanical properties of recycled polymers. Additionally, recycled polymers vary in rheological quality, and the present invention can adjust the rheological response of the polymer, thereby providing a more stable and controllable process.

[0141] Improved properties in terms of tensile strength and extensibility are important for example for the production of nonwoven fabrics, since their preparation involves multiple steps and improved tensile strength or extensibility helps them to better withstand these steps.

[0142] Importantly, high tensile strength provides nonwoven manufacturers with the option to, for example, reduce the weight of their products while still retaining good mechanical performance.

[0143] Another important aspect is the processing safety during the preparation of nonwoven fabrics. It is desirable to carry out the preparation of nonwoven fabrics under milder conditions at lower processing temperatures. To be able to do so, good mechanical properties, such as tensile strength and elongation, must still be obtained at lower processing temperatures. This reduces the processing temperature. Furthermore, energy savings is a secondary benefit.

[0144] A further embodiment of the present invention is directed to a composition comprising a compound of formula (1) or (2) together with a compound of formula (3), wherein the above definitions and options apply.

[0145] Another embodiment of the present invention is directed to the use of a composition comprising a compound of formula (1) or (2) together with a compound of formula (3) to modify the rheology of a polymeric substrate. For such embodiments, the above definitions and options apply.

[0146] Furthermore, another embodiment of the present invention is a compound represented by formula (3) presented below:

[0147] [ka] [wherein in each of formulas (11) and (12), R is as defined above and the above alternatives apply], or

[0148] [ka] [Wherein R' is C8 to C 40 The present invention relates to novel compounds of the formula: wherein R is an alkyl, uninterrupted or interrupted by -O- and / or carbonyl groups, and the above options provided for R apply.

[0149] Preferred are compounds of formula (13) and (14), especially compound (14).

[0150] The following examples further illustrate the invention. All percentages and parts are by weight unless otherwise stated.

[0151] [Example] Synthesis Example 1

[0152] [ka]

[0153] 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. To the stirred solution, add 1 g of 1,8-diazabicyclo[5,4,0]undec-7-ene. Stirring is continued at room temperature for 1 hour. The white suspension is then evaporated to dryness on a rotary evaporator, and the residue is recrystallized from ethyl acetate to give 67.7 g of the title compound as a white solid, melting at 103-103.5 °C.

[0154] Synthesis Example 2

[0155] [ka]

[0156] Synthesis example 1 is repeated, but replacing toluene-2,4-diisocyanate with an equimolar amount of toluene-2,6-diisocyanate, to provide the compound of formula (102), which is obtained as a white solid with a melting point of 120-122°C.

[0157] Synthesis Example 3 80% by weight of the compound of formula (103)

[0158] [ka] and an isomeric mixture containing 20% ​​by weight of the compound of formula (104).

[0159] [ka]

[0160] Synthesis example 1 was repeated, but replacing toluene-2,4-diisocyanate with an equimolar mixture of isomers in an 80 / 20 weight ratio of toluene-2,4-diisocyanate / toluene-2,6-diisocyanate, and replacing octadecanethiol with an equimolar amount of octadecyl-3-mercaptopropionate, resulting in an 80 / 20 weight ratio isomer mixture of compounds of formulae (103) and (104), obtained as a white solid with a melting point of 94-100°C.

[0161] Synthesis Example 4 A reaction mixture containing a compound of formula (105) as one major component.

[0162] [ka]

[0163] 63.26 g of octadecyl-3-mercaptopropionate and 5 ml of triethylamine are dissolved in 400 ml of ethyl acetate under argon. Then, 100 g of Desmodur® IL EA (50% in ethyl acetate, available from Covestro AG) is diluted with 100 ml of ethyl acetate and added to the above solution, which is then stirred at 50° C. for 1 hour. After 90 minutes, 100 g of CDCl3 is added. 1 No octadecyl-3-mercaptopropionate is detected by H-NMR. The mixture is then filtered, and the filtrate is evaporated (20 mbar / 50°C). The resulting solid is crushed and then dried at 0.45 mbar / 50°C for 1.5 hours, then at 50°C / 200 mbar for 114 hours, to give 110.8 g of a beige solid containing the compound of formula (105) as one major component.

[0164] Synthesis Example 5 A reaction mixture containing a compound of formula (106) as one major component.

[0165] [ka]

[0166] Synthesis Example 4 is repeated, but replacing octadecyl-3-mercaptopropionate with an equimolar amount of octadecanethiol, resulting in a mixture containing the compound of formula (106) as one major component.

[0167] Synthesis Example 6 A mixture containing a compound of formula (107) as one major component

[0168] [ka]

[0169] 102.21 g of octadecyl-3-mercaptopropionate and 5 ml of triethylamine are dissolved in 400 ml of ethyl acetate under argon. Then, 100 g of Desmodur® L75 (75% in ethyl acetate, available from Covestro AG) is dissolved in 100 ml of ethyl acetate and added to the above solution, which is then stirred at 50° C. for 1 hour. After 90 minutes, 100 g of CDCl3 is added. 1 No octadecyl-3-mercaptopropionate is detected by H-NMR. The mixture is then rotary evaporated at 0.05 mbar / 50°C. The resulting waxy product is further dried at 50°C / 200 mbar to constant weight to give 167.71 g of a beige solid containing the compound of formula (107) as one major component.

[0170] Synthesis Example 7 A mixture containing a compound of formula (108) as one major component

[0171] [ka]

[0172] Synthesis Example 6 is repeated, but replacing octadecyl-3-mercaptopropionate with an equimolar amount of octadecanethiol, resulting in a mixture containing the compound of formula (108) as one major component.

[0173] A) Application example - Meltblown nonwoven fabric Application examples A1 to A31 Meltblown nonwoven fabrics are produced in a RAVOtec GmbH MB-L 150 / 200 device. The feed extruder is a single-screw extruder with a 25 mm shaft diameter, a length-to-diameter ratio of 25, and four heating zones. Unless otherwise specified, the shaft rotation speed is 50 revolutions per minute. The melt temperature at the end of the extruder is recorded as the reference temperature and is listed in the examples below. The meltblown device has a nozzle with 35 holes per square inch, each hole having a diameter of 0.35 mm. Unless otherwise specified, the air volume is 360 m 3 / hour. The distance from the conveyor to the die is 250 mm. The die has a width of 200 mm. Unless otherwise stated, the basis weight of the nonwoven fabric is 20 g / m 2 is.

[0174] The polymer used for the test had a melt flow index of 25.0 g / 10 min (230 °C, 2.16 kg) and a modulus of 0.9 g / cm 3 It is a polypropylene homopolymer with a density of 0.05 wt%. The grade is stabilized with 0.05% phenolic antioxidant, 0.1% phosphite, and 0.025 wt% calcium stearate.

[0175] The melt flow rate is measured according to ISO 1133 (230°C, 2.16 kg). The measurement is carried out on a nonwoven fabric that is cut into fine pieces. The melt flow rate is an important parameter for the meltblowing process. A sufficiently high melt flow rate is necessary to enable the production of a good quality nonwoven fabric. The hydrostatic head (water column) and air permeability are applicable parameters that play a role in determining the quality of the produced nonwoven fabric.

[0176] Hydrostatic head measures the pressure required to force a drop of water off a taut fabric. It is a measure of the resistance of a nonwoven fabric to water penetration. The measurement is performed according to WSP (World Strategic Partner) 80.6 (2005). The test is performed at a 100cm 2 The test is carried out at a water pressure increase rate of 10±0.5 cm H2O / min at a test head of 1000 mbar when a third drop is extruded from the nonwoven fabric, and the results are presented in water column height, or hydrostatic head or hydraulic head (unit: mm).

[0177] The air permeability is performed according to WSP (World Strategic Partner) 70.1 (2005). The pressure difference is 200 Pa and the sample size is 20 cm. 2 The result is l / m 2 / s, and the surface of the nonwoven fabric section is moved at 1 m / s 2 Determine the amount of air flowing vertically through.

[0178] Unless otherwise stated, percentages given are wt%.

[0179] The product, hereinafter designated NOR1, corresponds to the compound of formula (5).

[0180] [ka]

[0181] Unless otherwise stated, the product was first prepared according to the weight percent concentration given in the table below to a melt flow index of 25.0 g / 10 min (230°C, 2.16 kg) and a viscosity of 0.9 g / cm 3 The mixtures were incorporated into homopolypropylene having a density of 1000 MPa using a co-rotating twin-screw extruder with a 25 mm shaft diameter and a length-to-diameter ratio of 42 at a melt temperature of 210°C. Such premixes can be considered masterbatches. For all masterbatches, every product listed in the second column of Tables 1-3 below was incorporated into a separate masterbatch (resulting in two different masterbatches), except for Examples A30 and A31 below, in which both products were incorporated into the same masterbatch (combi-batch). The concentrations of the products in the corresponding masterbatches are shown in the third column of Tables 1-3 below.

[0182] [Table 1]

[0183] The results in Table 1 demonstrate the excellent quality of the nonwoven fabric in terms of either water column, air permeability or melt flow rate.

[0184] [Table 2]

[0185] The results in Table 2 demonstrate the excellent quality of the nonwoven fabric in terms of either water column, air permeability or melt flow rate.

[0186] [Table 3]

[0187] The results in Table 3 demonstrate the excellent quality of the nonwoven fabrics in terms of either water column, air permeability or melt flow rate. The results also show that incorporating both products into the same masterbatch (combi-batch), instead of using two separate masterbatches, can provide even better visbreaking performance.

[0188] B) Application example - Extrusion Application examples B1 to B15 The performance of the various products is determined in a reproducible and systematic way using a laboratory scale twin screw mini-extruder. The polymers used have a melt flow index of 3.0 g / 10 min (230 °C, 2.16 kg) and a viscosity of 0.9 g / cm 3 It is a polypropylene homopolymer with a density of 1000 MPa. It is an unstabilized grade to which 0.1 wt% of Irganox® B215 (a commercially available stabilized blend consisting of Irgafos® 168 + Irganox® 1010) and 0.05 wt% of calcium stearate have been added. The calcium stearate is used in powder form without a pre-drying step. Unless otherwise stated, the additives shown in the table below are mixed with the polypropylene powder and the mixture is then mixed with a co-rotating shaft and a 15 cm 3The materials are compounded under nitrogen blanket in a loop mode for 10 minutes at a constant screw rotation speed (as shown in the examples below) in a laboratory-scale twin-screw mini-extruder (Xplore Instruments BV) with a volume of 10 ...

[0189] The recorded force is directly related to the melt viscosity of the polymer. Thus, the lower the molecular weight of the polymer, the lower the melt viscosity and the lower the recorded force. Therefore, the recorded force is a direct measure of the melt flow of the polymer.

[0190] For example, in the production of nonwovens by the spunbond or meltblown process, a sufficiently high melt flow is crucial, firstly so that the polypropylene can be processed and secondly so that a nonwoven of satisfactory quality can be obtained.

[0191] In the tests of Table 4, the standard always contains additionally 0.15% of the compound of formula (5). The extrusion temperature is 270° C. and the shaft rotation speed is 50 revolutions per minute.

[0192] [Table 4]

[0193] A high value is desirable. The results in Table 4 show that when the products of Synthesis 1 to 7 are added, there is a significantly higher reduction in compounding power, ie, lower compounding power, ie, higher visbreaking.

[0194] Application examples B16~B20 The tests are carried out as presented in Application Examples B1-B15 above, except that the co-additives of the synthesis examples are not directly incorporated into polypropylene as such, but are first loaded into a porous polypropylene support at the following concentrations: For the product of Synthesis Example 7, the loading is 1.885 g of the product of Synthesis Example 7 + 100 g of the polypropylene porous carrier. For the product of Synthesis Example 6, the loading is 1.741 g of the product of Synthesis Example 6 + 100 g of the polypropylene porous carrier.

[0195] [Table 5]

[0196] Table 5 shows that visbreaking performance remains present even when the co-additive is not directly incorporated but is first loaded onto a support (porous, as exemplified above).

[0197] Application examples B21~B23 Tests are carried out as set out in Application Examples B1 to B15 above, but without the compound of formula (5).

[0198] [Table 6]

[0199] In summary, Table 6 shows that when the compound of formula (5) or the co-additive is used alone, poor performance is obtained. In contrast, the use of a combination of both components shows a synergistic effect, resulting in good performance.

[0200] C) Application example - Nonwoven fabric produced by the spunbond method Application examples C1~C8 The spunbond nonwoven fabric has a melt flow index of 3.0 g / 10 min (230°C, 2.16 kg) and a modulus of 0.9 g / cm 3Polypropylene homopolymer with a density of 1000 psi, with or without additives prepared as presented below, is produced on a 1 m wide Reicofil-4 line with a single beam with approximately 6800 holes per meter length. The holes have a diameter of 0.6 mm. The throughput per hole is set at 0.5 g / min. The line has a sheath-core configuration with 30 wt. % polymer in the sheath and 70 wt. % polymer in the core. The additive-containing fiber contains the additive throughout the fiber (sheath and core). The nonwoven fabrics are made of 17 g / m² of fiber, respectively. 2 (Line speed: 212 m / min) and 70 g / m 2 (Line speed: 53 m / min) with a fabric weight of 1.7 dtex. The target filament fineness is 1.7 dtex. dtex is a unit of measure for the linear mass density of a fiber and is defined as the mass in grams per 10,000 meters. The nonwoven fabric is thermally bonded using an embossing roll.

[0201] The additives are first introduced by preparing a masterbatch. The masterbatch is prepared by compounding the product of formula (5) and each of the products of the indicated synthetic examples with a polypropylene homopolymer carrier having a melt flow index of 25.0 g / 10 min (230 ° C, 2.16 kg) in a co-rotating twin-screw extruder with a screw diameter of 25 mm and a length-to-diameter ratio of 47 at 200 ° C. The masterbatches containing the product of formula (5) and the products of the indicated synthetic examples were two different masterbatches, each containing one type of product.

[0202] Further processing conditions with Reicofil-4 are presented below. - Extrusion temperature is the set temperature used for extrusion of polypropylene or polypropylene / additive compounds and is shown in the table. - Die temperature is the set temperature of the polymer at the die. - Cabin pressure is the pressure in the cabin behind and below the die. Engraved rolls and smooth rolls are rolls between which the fibrous web passes. - Nip pressure is the set pressure between the engraved roll and the smooth roll.

[0203] Mechanical property evaluation The mechanical properties of the nonwoven fabrics are determined in accordance with DIN EN 29073-3 using a sample clamp length of 100 mm, a sample width of 50 mm and a forward movement (deformation rate) of 200 mm / min. Tensile strength MD and tensile elongation MD are the corresponding maximum values ​​measured in the machine direction. Tensile strength MC and tensile elongation MC are the corresponding maximum values ​​measured perpendicular to the machine direction.

[0204] [Table 7]

[0205] [Table 8]

[0206] The results clearly demonstrate the advantages of the present invention, whereby a stable process can be carried out using significantly lower processing temperatures and achieve at least similar mechanical properties compared to using NOR1 alone as a visbreaking additive. This provides nonwoven manufacturers, for example, greater flexibility in polymer selection and sourcing, and the option to reduce processing temperatures to save energy while preserving target properties of the nonwoven product.

[0207] D) Application Example - Nonwoven fabrics produced by the spunbond process with improved thermal bonding behavior Application examples D1 to D3 The spunbond nonwoven fabrics are produced on a 1 m wide Reicofil-4 line with a single beam having approximately 6800 holes per meter length using polypropylene homopolymer (melt flow index of 27 g / 10 min (230 °C, 2.16 kg)) with or without additives prepared as presented below. The holes have a diameter of 0.6 mm. The throughput per hole is set at 0.55 g / min. The line has a sheath-core configuration with 30 wt. % polymer in the sheath and 70 wt. % polymer in the core. The additive-containing fibers contain additive only in the sheath layer. The nonwoven fabrics are produced at a density of 70 g / m 2 (Line speed: 53 m / min) with a fabric weight of 1.85 dtex. The target filament fineness is 1.85 dtex. dtex 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. The nonwoven fabric is thermally bonded using an embossing roll.

[0208] The additives are first introduced by preparing a masterbatch, which is prepared by compounding the product of formula (5) and each of the products of the synthesis examples shown with 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-to-diameter ratio of 47.

[0209] Further processing conditions on the Reicofil-4 line are presented below. - Extrusion temperature is the set temperature used for extrusion of polypropylene or polypropylene / additive compounds and is shown in the table. - Die temperature is the set temperature of the polymer at the die. - Cabin pressure is the pressure in the cabin behind and below the die. Engraved rolls and smooth rolls are rolls between which the fibrous web passes. - Nip pressure is the set pressure between the engraved roll and the smooth roll.

[0210] [Table 9]

[0211] The results clearly demonstrate the advantages of the present invention, which allows for significantly better results in terms of mechanical properties in thermal bonding compared to using no additive or NOR1 alone. This provides nonwoven manufacturers with the option of, for example, reducing the weight of their products while still maintaining good mechanical performance. In addition, compared to using NOR1 alone as a visbreaking additive, this provides nonwoven manufacturers with the option of, for example, greater flexibility in polymer selection and sourcing, reducing processing temperatures to save energy, and maintaining the target properties of the nonwoven product.

[0212] (E) Application example - Meltblown nonwoven fabric Additive mixtures for rheological modification of polymers Application Examples E1-E5: Extension of application examples based on combinations including an activator (hereinafter designated BOO), NOR1, and a peroxide (hereinafter designated PER). The product, hereinafter designated NOR1, corresponds to the compound of formula (5).

[0213] [ka]

[0214] The product, hereinafter designated BOO, corresponds to the compound of formula (107).

[0215] [ka]

[0216] PER is 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (assay >94%). PER is impregnated into a porous polypropylene support with 60% open cell porosity and a cell size of 20 to 80 microns. PER incorporation into the porous polypropylene support is achieved by mixing 5% on a rotary evaporator at 1 atm and room temperature for 16 hours. This method yields a 5% concentration by weight of PER in polypropylene.

[0217] First, NOR1 and BOO were mixed at the wt% concentrations shown in the table below to obtain a melt flow rate of 25.0 g / 10 min (230°C, 2.16 kg) and a melt flow rate of 0.9 g / cm. 3 The homopolypropylene having a density of 1000 MPa is combined with a co-rotating twin-screw extruder having a screw diameter of 25 mm and a length-to-diameter ratio of 42 at a melt temperature of 210° C. Such a premix can be considered a combi-batch.

[0218] For all combi-batches or concentrates, the final concentration of the product in the polymer is shown in the second column of the table below, and the concentration of the product in the corresponding combi-batch or concentrate is shown in the third column of the table below.

[0219] Meltblown nonwoven fabrics are produced in a RAVOtec GmbH MB-L 150 / 200 device. The feed extruder is a single-screw extruder with a 25 mm shaft diameter, a length-to-diameter ratio of 25, and four heating zones. Unless otherwise specified, the shaft rotation speed is 50 revolutions per minute. The melt temperature at the end of the extruder is recorded as the reference temperature and is listed in the examples below. The meltblown device has a nozzle with 35 holes per square inch, each hole having a diameter of 0.35 mm. Unless otherwise specified, the air volume is 360 m 3 / hour. The distance from the conveyor to the die is 250 mm. The die has a width of 200 mm. Unless otherwise stated, the basis weight of the nonwoven fabric is 20 g / m 2 is.

[0220] The polymer used for the test had a melt flow rate (MFR) of 25.0 g / 10 min (230 °C, 2.16 kg) and a viscosity of 0.9 g / cm 3 It is a polypropylene homopolymer with a density of 0.05 wt%. The grade is stabilized with 0.05% phenolic antioxidant, 0.1% phosphite, and 0.025 wt% calcium stearate.

[0221] The melt flow rate is measured according to ISO 1133 (230°C, 2.16 kg). The measurement is carried out on nonwoven fabrics that are cut into fine pieces. The melt flow rate is an important parameter for the meltblowing process. A sufficiently high melt flow rate is necessary to enable the production of good quality nonwoven fabrics.

[0222] Hydrostatic head (water column) and air permeability are applicable parameters that play a role in determining the quality of the nonwoven fabric produced. Hydrostatic head measures the pressure required to force a drop of water off a taut fabric. It is a measure of the resistance of a nonwoven fabric to water penetration. The measurement is performed according to WSP (World Strategic Partner) 80.6 (2005). The test is performed at a 100cm 2 Test head of 10±0.5cm H 2 The test is carried out at a water pressure increase rate of 0 / min. When a third drop is extruded from the nonwoven, the results are presented as water column height, or hydrostatic head or hydraulic head (unit: mm). A high hydraulic head is a sign of good quality nonwoven, as it can retain the flow of liquid through it and therefore act as an efficient filter.

[0223] The air permeability is performed according to WSP (World Strategic Partner) 70.1 (2005). The pressure difference is 200 Pa and the sample size is 20 cm. 2 The result is l / m 2 / s, and the surface of the nonwoven fabric section is moved at 1 m / s 2 This determines the amount of air that flows vertically through the nonwoven fabric. Too high a permeability is an indication of a nonwoven fabric with an uneven fiber diameter distribution, where some areas of the nonwoven fabric are packed with fibers, while other areas are more open. As a result, nonwoven fabrics with uneven fibers have high permeability, so that areas of coarse fibers easily allow liquid to flow through, resulting in an inefficient filter. For this reason, nonwoven fabrics with low permeability are usually preferred.

[0224] Unless otherwise stated, percentages given are wt%.

[0225] Table 10

[0226] The results in Table 10 demonstrate the superior quality of the nonwoven fabric containing the combination of PER, NOR, and BOO, whether in terms of water column (hydrohead), air permeability, or melt flow rate. The product combination provides superior properties to PER alone, even though PER is used at a much higher concentration. Using twice the PER concentration relative to that of the ternary combination fails to reach the properties achieved by the ternary combination.

[0227] Table 11

[0228] The results in Table 11 demonstrate the superior quality of the nonwoven fabric obtained with the ternary combination of PER+NOR1+BOO, whether in terms of water column (hydraulic head), air permeability, or melt flow rate. This combination provides superior properties to PER alone, even when used at 0.25%, a higher concentration of PER than one of the ternary combinations (at 0.22%).

[0229] (F) Application Examples F1 to F7: Determination of Melt Flow Rate (MFR) Use booster (BOO) in combination with NOR1 and / or peroxide Raw materials used: Polymer: PP powder: HA10XT (MFR 3.5 g / 10 min) (230°C, 2.16 kg) Base Material Stabilization: 1000 ppm pentaerythritol tetrakis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate (Irganox 1010) + 500 ppm calcium stearate DW Peroxide: 2,5-dimethyl-2,5-bis(tert-butyl-peroxy)hexane (PER) Visbreaking Additive 1: NOR1 Visbreaking additive 2:1-octadecanethiol (ODT)

[0230] Test procedure: Preparation of the mixture using a Mixaco Lab CM 12 high-speed mixer (Mixaco Maschinenbau (D) (Addition of peroxide and hydroxylamine ester via administration in solution with isopropanol) Formation of the composition at 240°C in a twin-screw extruder Collin 25 / 42D (Collin Lab & Pilot solutions GmbH (D)) Measurement of MRF at 230°C using 2.16 kg in the Goettfert MI Robo (Goettfert Werkstoff Prufmaschinen GmbH (D))

[0231] Table 12

[0232] The test results in Table 12 demonstrate the excellent melt flow rate of the nonwoven fabric obtained with the ternary combination of PER+NOR1+BOO. The present invention includes the following embodiments. (Embodiment 1) (a) Formula (1) or (2)

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Claims

1. (a) Formula (1) or (2) 【Chemistry 1】 [In the formula, G 1 , G 2 , G 3 and G 4 are mutually independent C 1 ~C 4 alkyl or G 1 and G 2 together, or G 3 and G 4 together form pentamethylene, G 1 ', G 2 ', G 3 ' and G 4 ' are C 1 ~C 4 alkyl or G 1 ' and G 2 ' together, or G 3 ' and G 4 ' together is pentamethylene, G 5 , G 6 , G 5 ' and G 6 ' are independently hydrogen or C 1 ~C 4 is alkyl, 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; If m is 1, R 1 is C 2 ~C 8 Alkylene or C 2 ~C 8 Hydroxyalkylene or C 4 ~C 36 is acyloxyalkylene, or When m is 2, R 1 is (-CH 2 ) 2 C(CH 2 -) 2 and R 1 ' is hydrogen, C 1 ~C 8 Alkyl, C 1 ~C 8 Hydroxyalkyl or formula -(C=O)-C 1 ~C 40 is an alkyl group, or -OR 1 ' taken together with the -CH- group to which they are attached is the group -(C=O)-] The compound (b) Formula (3) 【Chemistry 2】 [In the formula, A is based on an organic isocyanate, in which the group -SR is introduced by reaction with the isocyanate group, R is an optionally substituted and / or interrupted C 2 ~C 40 is alkyl, n is 1 or greater] and (c) Polymer substrate A composition comprising:

2. 2. The composition of claim 1, wherein component (a) is a compound of formula (1).

3. Component (a) is a compound of formula (1), n ​​is 1, and R 1 C 4 ~C 36 The composition of claim 2, which is an acyloxyalkylene.

4. The component (a) is represented by the formula (5) 【Transformation 3】 2. The composition of claim 1, wherein the compound is

5. A is based on an organic isocyanate, and the organic isocyanate is cyclohexyl diisocyanate, methylene bis(cyclohexyl) diisocyanate, isophorone diisocyanate, phenyl diisocyanate, diphenylmethane diisocyanate, or naphthyl diisocyanate, each unsubstituted; or C 1 ~C 4 Alkyl or di(C 1 ~C 4 alkyl)amino or C 4 ~C 20 5. A composition according to any one of claims 1 to 4, which is an alkyl diisocyanate or an oligomeric or polymeric product obtained by reaction of said diisocyanates with themselves and / or with polyols.

6. A is based on an organic isocyanate, and the organic isocyanate is phenyl diisocyanate, diphenylmethane diisocyanate, or naphthyl diisocyanate, each unsubstituted; or C 1 ~C 4 Alkyl or di(C 1 ~C 4 6. The composition according to claim 1, wherein the diisocyanate is substituted with an alkyl)amino group or is an oligomeric or polymeric product obtained by reaction of the diisocyanate with itself and / or with a polyol.

7. A is based on an organic isocyanate, and the organic isocyanate is phenyl diisocyanate and is unsubstituted, or C 1 ~C 4 7. A composition according to any one of claims 1 to 6, which is alkyl substituted or is an oligomeric or polymeric product obtained by reaction of the above diisocyanates with themselves and / or with polyols.

8. The polyol contains two or more hydroxyl groups. 1 ~C 10 Alkanol or Poly-C 2 ~C 10 8. The composition of claim 5, wherein the alkylene glycol is an alkylene glycol.

9. R is uninterrupted or interrupted by -O-, -NH-, -S- and / or carbonyl groups. 2 ~C 40 9. The composition of claim 1, wherein the alkyl is alkyl.

10. C in which R is uninterrupted or interrupted by -O- and / or carbonyl groups 8 ~C 40 10. The composition of claim 1, wherein the alkyl is alkyl.

11. 11. The composition according to any one of claims 1 to 10, wherein the polymer substrate is a thermoplastic polymer, preferably a polyolefin.

12. 12. The composition of any one of claims 1 to 11, wherein the polymer substrate is a polyolefin selected from the group consisting of linear low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, polyethylene copolymer, polypropylene homopolymer, and polypropylene copolymer.

13. A fiber comprising the composition of claim 1.

14. A nonwoven fabric prepared using the fibers of claim 13.

15. A composition comprising a compound of formula (1) or (2) together with a compound of formula (3), each as defined in claim 1.

16. 16. Use of the composition according to claim 15 for modifying the rheology of a polymer substrate.

17. formula 【Chemistry 4】 wherein R is as defined in claim 1. Compound.

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