RU2800814C2 - Nucleating agents, methods for their production and related polymer compositions - Google Patents

Abstract

FIELD: polymers.

SUBSTANCE: present invention relates to modifier-modified zinc monoglycerolate in the form of crystallite agglomerates. The crystallite size of the modified zinc monoglycerolate based on the average length of the coherent domain is less than 30 nm in the <100> direction (size along the <100> zone axis), and less than 60 nm in the <011> direction (size along the zone axis <100>), as determined from the Scherrer equation by X-ray powder diffraction; and the aspect ratio calculated from the <100>/<011> coherent domain lengths is less than 0.65. Modified zinc monoglycerolate is useful as a nucleating agent and is very effective at low loading levels in polymers such as polypropylene. The invention also relates to a method for producing monoglycerolate, to compositions comprising it, and to options for using zinc monoglycerolate.

EFFECT: providing a modified nucleating agent with improved structure-forming efficiency at low loads, polymer compositions containing a nucleating agent, and an associated method for producing a nucleating agent.

22 cl, 5 dwg, 10 tbl, 4 ex

Description

Field of invention

The present invention relates to nucleating agents, methods for their preparation and polymer compositions containing the nucleating agent.

State of the art

In the industrial processing of polyolefins by injection molding, the degree of crystallinity of the polymer is usually controlled by using appropriate levels of nucleating agents. These nucleating agents provide benefits to the polymer by increasing the crystallization temperature (Tc) of the polymer, increasing the crystallization kinetics, and therefore reducing the time required to complete each cycle for product introduction (i.e., cycle time), which in turn increases the productivity of the injection molding equipment. The nucleating agents can also impart improved mechanical properties to the polymer body due to the resulting higher crystallinity.

A feature that is becoming increasingly important is efficiency at low loads. Cost issues are important in polymer products. If the cost of the nucleating agent needed per kilogram of polymer is higher than the cost savings resulting from the corresponding crystallization temperature increase or cycle time reduction, then regardless of the efficiency of the nucleating agent, the nucleating agent will not be commercially viable. Accordingly, it is important to constantly look for new or modified nucleating agents that have high performance at low loads compared to alternatives that have the same performance but at higher loads.

Nucleating agents that have been described or used in the manufacture of polyolefins include sorbitol-based compounds, cyclic dicarboxamides such as N,N'-dicyclohexyl-2,6-naphthalenedicarboxamide, cyclic dicarboxylate salts, aromatic heterocyclic phosphate salts, calcium malonate, and divalent metal propane triolates. such as zinc monoglycerolate.

Zinc monoglycerolate (ZMG) is an existing high performance nucleating agent that has very good performance at low loadings (eg 500-1000 ppm) in commercial polyolefin production. Zinc monoglycerolate was first synthesized, characterized and described by Taylor et al. (See Radoslovich, E.W., Raupach, MR, Slade, PG, & Taylor, RM (1970). Crystalline cobalt, zinc, manganese, and iron alkoxides of glycerol. Australian Journal of Chemistry, 23(10), 1963 -1971; Hambley, TW, & Snow, MR (1983) The crystal and molecular structure of zinc (II) monoglycerolate Australian Journal of Chemistry, 36(6), 1249-1253; and Slade, PG, Radoslovich, EW, & Raupach, M. (1971) Crystal and molecular structure of cobalt (II) monoglycerolate Acta Crystallographica Section B: Structural Crystallography and Crystal Chemistry, 27(12), 2432-2436.) described in US Pat. The second form of ZMG is also known from the patent literature - US 7,074,949, which also lists Bos as the inventor (2006). In the 2006 patent process, zinc monoglycerolate is synthesized directly or indirectly from hydrozincite (Xn ₅ (CO ₃ ) ₂ (OH) ₆ ). Hence, this material is hereinafter referred to as "hydrozincite-ZMG".

However, polymer production overheads increase over time, and it would be beneficial to develop new or modified nucleating agents that provide an even better balance between agent costs at desired loading levels and the cost savings gained in making polymeric products containing the agent at that loading level.

That is, it is an object of the present invention to provide a new or modified nucleating agent with improved low loading structuring efficiency, polymeric compositions containing the nucleating agent, and an associated process for producing the nucleating agent.

The essence of the invention

The inventors of the present invention have found that it is possible to produce a modified form of zinc monoglycerolate which provides an improved structurant effect, especially when compared to unmodified zinc monoglycerolate. The new form of zinc monoglycerolate is hereinafter referred to as "GMS-ZMG" (named after the glycerol monostearate (GMS) modifier commonly used) and provides a better texturizing effect than that achieved with more than twice as much unmodified zinc monoglycerolate. We manufacture this product (GMS-ZMG) using a new production method.

According to one embodiment of the present invention, zinc monoglycerolate is provided in the form of crystallite agglomerates, wherein the crystallite size, based on the average length of the coherent domain, is no more than 30 nm in the <100> direction (i.e., along the axis of the <100> zone; hereinafter also referred to as < 100> direction), and no more than 60 nm in the <011> direction, as determined by the Scherrer equation via X-ray powder diffraction. The product also suitably has an aspect ratio (measured or calculated as <100>/<011> coherent domain lengths) of less than 0.65, such as less than 0.60 or less than 0.56. The aspect ratio in preferred embodiments of the present invention is less than 0.44.

Through the method described in this patent application, the Applicant has obtained a form of zinc monoglycerolate which contains an incorporated modifier (eg GMS-ZMG) which results in the formation of crystallite agglomerates where the crystallites are extremely small. The agglomerates contain many crystallites and are therefore significantly larger than individual crystallites.

The Applicant has made significant research into methods for modifying zinc monoglycerolate to improve crystallization efficiency by increasing the crystallization temperature and/or accelerating the time period for polymer crystallization to complete.

The Applicant has achieved the present result through many years of efforts during which a number of attempts have been made to reduce the crystallite size of zinc monoglycerolate.

Applicant has now successfully achieved a small crystal size of zinc monoglycerolate by using a modifier and by controlling the production conditions of zinc monoglycerolate. A key innovation over the prior art is the ability to use the readily available and relatively inexpensive "indirect or French process" zinc oxide (e.g., as obtained from Umicore Zinc Chemicals) as a starting point, as opposed to hydrozincite (as described in US 7,074,949). For a description of the "indirect or French process" for producing zinc oxide, see Moezzi, A., McDonagh, A.M., & Cortie, M.B. (2012) zinc oxide particles: Synthesis, properties and applications. Chemical Engineering Journal, 185, 1-22. The modifier does not change the fundamental chemical structure of zinc monoglycerolate.

According to one embodiment of the present invention, there is provided a process for producing zinc monoglycerolate comprising reacting a zinc compound that is other than hydrozincite (i.e., it is a zinc compound other than hydrozincite and is not derived from hydrozincite) with glycerol and a modifier, in the presence of an acid catalyst, in which:

- the zinc compound is selected from the group consisting of zinc oxide, zinc carbonate, zinc hydroxide, zinc carboxylate and combinations thereof, or/and

- the reaction is carried out in the presence of less than 10 wt. % water, based on the total weight of the reaction composition.

In preferred embodiments of the present invention, both conditions are used in the process.

The present application also describes the preferred temperature conditions for the preparation of zinc monoglycerolate from zinc oxide and glycerol, in the presence of an acid catalyst and modifier, to control the size of the crystallite and agglomerate of the product.

By preparing zinc monoglycerolate in the specific modified form described above, Applicant has been able to prepare zinc monoglycerolate (nucleating) (GMS-ZMG) containing polymer compositions in which the polymer compositions have a relatively high crystallization temperature at low zinc monoglycerolate loading.

Thus, according to another embodiment of the present invention, there is provided a composition comprising an organic polymer and zinc monoglycerolate as described above. Zinc glycerolate may be present in an amount of from 0.01% to 20 wt. % polymer composition.

According to another embodiment of the present invention, there is provided a composition comprising an organic polymer and a nucleating agent comprising zinc monoglycerolate, wherein the zinc monoglycerolate has a crystallite size based on an average coherent domain length of no more than 30 nm in the <100> direction, and no more than 60 nm in the <011> direction. direction, as determined by the Scherrer equation via X-ray powder diffraction; and the ratio of the above coherent domain lengths (which may be referred to as aspect ratio) is less than 0.65, such as less than 0.60 or less than 0.56, preferably less than 0.44. The presence of an aspect ratio in this range indicates that the height of the stack of zinc-glycerol plates is less than the length of their sheet.

The present application provides for the use of zinc monoglycerolate of the type described above (GMS-ZMG) as a nucleating agent. Also provided is the use of zinc monoglycerolate of the type described above (GMS-ZMG) to improve (increase) the crystallization temperature of the organic polymer. This may be due to an increase in the crystallization temperature of the organic polymer at low loading, such as 400 ppm or less.

Brief description of the drawings

In FIG. 1 shows an X-ray diffraction pattern of a modified zinc monoglycerolate according to an embodiment of the present invention (GMS-ZMG). A radiograph of an unmodified ZMG is also shown. The x-axis shows 2θ (in degrees) and the y-axis shows readings (peak intensity). The peak at 2θ=10.9° is the (100) peak of zinc monoglycerolate. Both radiographs were normalized so that the (100) peak has the same intensity. Peak (100) of GMS-ZMG is wider than in unmodified ZMG, i.e. GMS-ZMG crystallites are smaller.

On FIG. 2a and 2b show SEM images of an unmodified ZMG (FIG. 2a) and a modified ZMG (FIG. 2b) of an embodiment of the present invention. The scale bar in each image is 1 µm.

Figures 3a, 3b and 4 are additional SEM images for modified zinc monoglycerolate. The scale bar in each image is 100 nm.

On FIG. 5 shows the radiograph of hydrozincite-ZMG (comparative example 1) compared to the radiograph of GMS-ZMG (example 1). The x-axis is the 2θ-axis (in degrees) and the y-axis is the readings. The line at 2θ=10.9° is the (100) peak, and the two X-rays were normalized so that the intensities of the (100) peak were the same. The (100) peak of GMS-ZMG is broader than that of hydrozincite-ZMG, i.e. the GMS-ZMG crystallites are smaller.

Detailed description

Zinc monoglycerolate, preparation method, polymeric compositions and uses according to specific embodiments of the present invention are described below.

Before describing the details of the process for producing the modified zinc monoglycerolate, characteristic features of the modified zinc monoglycerolate will be described. Modified zinc monoglycerolate is useful as a nucleating agent. Accordingly, references to zinc monoglycerolate may be used interchangeably with "nucleating agent".

Zinc monoglycerolate (GMS-ZMG) is preferably at least 90 wt. % zinc monoglycerolate (chemical compound). The modifier is preferably not more than 5 mol. % zinc monoglycerolate. The modifier is introduced in such a way that it is not simply a mixture of the modifier with pre-prepared unmodified zinc monoglycerolate. The modifier is added upon receipt of zinc monoglycerolate. The modified material was found to be structural crystalline ZMG (X-ray diffraction proof). In a preferred embodiment of the present invention, the modifier glycerol monostearate was used in an amount of 5.47 wt. % of the total weight of GMS-ZMG.

The modifier is an agent capable of modifying the crystallite size of zinc monoglycerolate during production. A suitable class of agents that have been found to have such modifying properties are the glycerol carboxylate esters. The glycerol carboxylate is preferably an acid monoglycerolate or a monoacylglycerol. The acid is preferably a saturated fatty acid and may be a C6-C24 saturated fatty acid. According to preferred embodiments of the present invention, the modifier is glycerol monostearate (an ester of stearic acid). It has been noted that simple triglycerides of fatty acids, such as coconut oil, are not effective as modifiers, so the presence of two hydroxyl groups in the glycerol ester is preferred.

Zinc monoglycerolate according to the present application (GMS-ZMG), containing an embedded modifier, is in the form of agglomerates of crystallites. The size of the agglomerate can be measured by scanning electron microscopy (SEM). Using SEM, a suitable procedure involves attaching a zinc monoglycerolate material to a double-sided carbon tape. The belt is attached to the SEM mount (and the bulk material is blown off with compressed nitrogen). The attached zinc monoglycerolate material is then sputtered with a metal (eg, platinum); and images obtained using a scanning electron microscope (SEM) at various magnifications. This method ensures that the measured agglomerate size distribution for the zinc monoglycerolate material is consistent with the agglomerate size distribution of the bulk product (i.e. without further processing in a slurry medium, etc.). The size of each particle (in terms of diameter) is calculated for the visible agglomerates in the image area. The size of the agglomerate is difficult to measure, excluding the influence of processing conditions, and the concept of the size of the agglomerate is too vague to be universal. Therefore, the sizes of the agglomerates used in this document are not presented normatively, but instead are given as descriptions indicating successful synthesis (loose large agglomerates including small crystallites).

The agglomerates contain several crystallites. The agglomerates that are prominently seen on scanning electron microscopy (SEM) images typically range from 5 µm to 50 µm in width. It is preferable to have a plurality of crystallites agglomerated into micron-sized particles, in particular micron-sized particles in which the agglomerates are loosely bonded. Presenting the material as discrete particles smaller than 100 nanometers causes handling difficulties and problems with packaging and transport of the material. Agglomerates that are in the micron size range avoid these problems. Although agglomeration is thus attractive, it is important that the nature of the agglomerates does not lead to difficulties in separating and spreading individual crystallites through the polymer composition. The methods described herein for preparing GMS modified zinc monoglycerolate (GMS-ZMG) are believed to produce agglomerates that are held loose.

The zinc monoglycerolate of the present application (GMS-ZMG) has a very small crystallite (as determined by XRD) and therefore delivers more crystallites (i.e. active sites of nucleation) per unit mass which are efficiently dispersed.

Zinc monoglycerolate according to the present application (GMS-ZMG) raises the crystallization temperature even when used in small amounts.

The radiographs are taken with an X-ray diffraction instrument tuned to the Bragg-Brentano geometry (θ-2θ) scanning the desired 2θ values. Each peak corresponds to a set of lattice planes described by the Miller index, for example, (100). For a given peak, for example, the (100) peak, the width of the peak corresponds to the average length of the coherent domain (i.e., the size of the crystallite), in the direction of this zone axis, i.e. <100> in this example, measured using the full width at half maximum (FWHM) of the peak (100). The Scherrer Equation can then be used to calculate the crystallite size:

τ=Kλ/βcosθ,

where τ is the average crystallite size (nm), K is the dimensionless shape factor (taken here as 0.9; the same β must be used for all data that are compared to each other), λ is the wavelength of the X-ray used (0.154 nm (i.e., Cu Kα emission)), β is the FWHM line broadening expressed in radians, and θ is the Bragg angle (expressed in degrees; (2θ peak value)/2). It is assumed that line extension occurs only due to changes in the length of the coherent domain.

Zinc monoglycerolate (GMS-ZMG) can be obtained with a crystallite size in the <100> direction (determined by the above method) of 10 to 30 nm, 10 to 25 nm, or 10 to 20 nm. The average crystallite size is typically less than 25 nm, less than 22 nm, or less than 20 nm.

Zinc monoglycerolate can be obtained with a crystallite size in the <011> direction (determined by the above method) of 20 to 50 nm, 20 to 48 nm, or 20 to 46 nm.

The GMS-ZMG crystallite size is 30 nm or less in the <100> direction (i.e., the length of the coherent domain along the stacking direction), and 60 nm or less in the <011> direction (i.e., the length of the coherent domain along the planar direction) , as determined by the Scherrer equation by X-ray powder diffraction. The crystallite size in the <011> direction is preferably less than 60 nm. The ratio of the above coherent domain lengths (aspect ratio) is suitably about half, or more precisely less than 0.65, for example less than 0.60 or less than 0.56, preferably less than 0.44.

The temperature is preferably maintained below 120°C during the entire reaction. However, the use of temperatures above 120°C for a short period of time should not lead to the fact that such methods are outside the scope of this application. The period of time during which the reaction exceeds 120°C is not more than 10% of the total reaction time. During the reaction, the temperature is raised to a peak of 100 to 120°C. Prior art processes have included higher reaction temperatures or longer periods of time above 100°C. Due to the varying temperature conditions during the reaction (at least in part), the average crystallite size of the product obtained under prior art conditions was above the ranges indicated for the product of the present application.

The zinc compound may be selected from the group consisting of zinc oxide, zinc carbonate, zinc hydroxide, zinc carboxylate, and combinations thereof. However, the novelty of the present invention stems from its ability to use the readily available indirect or French zinc oxide process to produce highly dispersible nucleating agents (more dispersible than those known in the art). In addition, it should be noted that the zinc oxide used herein excludes zinc oxide that was formed from hydrozincite, and indeed excludes the use of hydrozincite itself (hydrozincite-ZMG), which was described in Bos 2006. 2006 tends to lead to a larger crystallite size than those specified in this application (especially in combination with other processing conditions), and therefore is preferably not used.

The amount of glycerol in the reaction composition is preferably from 95 to 110 mol. %. The amount is preferably from 98% to 105 mol. % and is usually used in stoichiometric amounts.

In terms of the amount of modifier, this amount of modifier is preferably from 1.0 to 5.0 mol. %. Using a smaller amount results in a larger average crystallite size, although other factors also affect the crystallite size achieved. The modifier contributes to a smaller average crystallite size when turned on at a sufficiently high level. The level is preferably at least 1.0 mol. %, more preferably more than 1.7, 1.9, 2.0, 2.1, 2.2 or 2.3 mol. %. Range from 2.0 to 5.0 mol. % is particularly suitable. The ideal amount used may be about 2.5 mol. %. Higher amounts can also be used, however, it has been found that no further advantage is gained by increasing the level to/greater than 5.0 mole %, and levels at/above this value can also adversely affect processability.

The preferred method for producing zinc monoglycerolate according to the present invention includes combining a zinc compound, a modifier and from 75 to 95 wt. % total glycerin, mixing and then adding a balance combination of glycerol, acetic acid and water.

The reaction is carried out in the presence of an acid catalyst. The catalyst is preferably an acid or acid salt such as a lower alkyl carboxylic acid (eg C2-C6 carboxylic acid) such as acetic acid, valeric acid; polycarboxylic acid such as citric acid, malic acid, maleic acid, succinic acid, malonic acid, hippuric acid, tartaric acid, oxalic acid; medium/long chain acid such as lauric acid, stearic acid; any other acid such as levulinic acid, benzoic acid, boric acid, trifluoroacetic acid; or mixtures thereof.

The catalyst can also be a salt of zinc and any of these acids, for example, zinc acetate; in a preferred embodiment of the present invention, the acid is added, in situ, to the zinc oxide.

The amount of catalyst used is preferably from 0.2 to 5 mol. % relative to the zinc compound.

One preferred key feature of the modified zinc monoglycerolate process is the water content of the reaction composition. The water content is preferably quite low. The water content is preferably not more than 10%, preferably not more than 8%, 6%, 4% or 2% by weight of the total reaction composition. A small amount of water may be present in the acid catalyst composition since acids are generally available in aqueous solutions. Water can be carried over as an impurity in glycerin. Water is formed in the reaction, but only the presence of a significant amount of water in the reaction composition from the very beginning, apparently contributes to undesirably large crystallite sizes.

Another object of the present invention relates to a polymer composition containing an organic polymer (at least one) and from 0.001% to 20%, for example from 0.01% to 20%, from 0.001% to 10%, from 0.001% to 5% or from 0.01% to 1 wt. % (based on polymer composition) zinc monoglycerolate (GMS-ZMG) as described above.

Examples of organic polymers are:

1. Polymers from monoolefins and diolefins, for example, polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, polyhexene, polyoctene, as well as polymers from cycloolefins, for example from cyclopentene , cyclohexene, cyclooctene or norbornene, polyethylene (which may optionally be crosslinked) e.g. high density polyethylene (HDPE), high density high molecular weight polyethylene (HDPE-HMW), high density ultra high molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).

Polyolefins, i.e. the polymers from the monoolefins shown in the previous paragraph, preferably polyethylene and polypropylene, can be prepared in various ways, and especially in the following ways:

a) radical polymerization (usually at high pressure and at elevated temperature).

b) catalytic polymerization using a catalyst which usually contains one or more metals of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more ligands, mainly oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls, which may be π- or σ-coordinated. These metal complexes may be in free form or deposited on a substrate, especially activated magnesium chloride, titanium (III) chloride, alumina or silicon. These catalysts may or may not be soluble in the polymerization medium. Catalysts can be used alone in the polymerization or additional activators can be used, especially metal alkyls, metal hybrids, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, IIa and/or IIIa

Periodic table. The activators can 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), metalocene or single site catalysts (SSC).

2. Blends of polymers mentioned in 1), for example blends of polypropylene with polyisobutylene, polypropylene with polyethylene (eg PP/HDPE, PP/LDPE) and blends of different types of polyethylene (eg LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example, copolymers of ethylene and propylene, linear low density polyethylene (LLDPE) and its mixture with low density polyethylene (LDPE), very low density polyethylene, propylene and but 2-ene, 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 and norbornene, such as COC), copolymers of ethylene and 1-olefins, where the 1-olefin is generated in situ; propylene-butadiene copolymers, isobutylene-isoprene copolymers, ethylene-vinylcyclohexene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers or ethylene-acrylic acid copolymers and their salts (ionomers), as well as ethylene-propylene terpolymers and a diene such as hexadiene, dicyclopentadiene or ethylidenenorbornene; and mixtures of similar copolymers with each other and with the polymers mentioned in 1 above), e.g. , LLDPE/EAA and alternating or random copolymers of polyalkylenes and carbon monoxide and blends thereof with other polymers such as polyamides.

4. Hydrocarbon resins (eg C ₅ -C ₉ ), including their hydrogenated modifications (eg tackifiers) and mixtures of polyalkylenes and starch.

The homopolymers and copolymers of 1.) - 4.) may have any stereostructure, including syndiotactic, isotactic, semi-isotactic or atactic, where atactic polymers are preferred. Also included are stereo-block polymers. The copolymers from 1.) to 4.) can be random or block copolymers, homo- or heterophasic, or highly crystalline homopolymer.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Aromatic homopolymers and copolymers derived from vinyl aromatic monomers, including styrene, α-methylstyrene, all isomers of vinyltoluene, especially p-vinyltoluene, all isomers of ethylstyrene, propylstyrene, vinylbiphenyl, vinylnaphthalene and vinylanthracene, and mixtures thereof. Homopolymers and copolymers may have any stereostructure, including syndiotactic, isotactic, semi-isotactic or atactic, with atactic polymers being preferred. Also included are stereoblock polymers.

6a. Copolymers comprising the above vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example, styrene/butadiene, styrene/acrylonitrile, styrene/ ethylene (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact styrenic copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/isoprene/butadiene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene, HIPS, ABS, ASA, AES.

6b. Hydrogenated aromatic polymers obtained from the hydrogenation of the polymers mentioned in 6.), especially including polycyclohexylethylene (PCHE) obtained from the hydrogenation of atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).

6s. Hydrogenated aromatic polymers obtained from the hydrogenation of the polymers mentioned in 6a.).

Homopolymers and copolymers may have any stereostructure, including syndiotactic, isotactic, semi-isotactic or atactic, with atactic polymers being preferred. Also included are stereoblock polymers.

7. Graft copolymers of vinyl aromatic monomers such as styrene or α-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene styrene or copolymers of polybutadiene and acrylonitrile; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and acrylacrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene-propylene-diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate-butadiene copolymers, and mixtures thereof with the copolymers listed in 6), for example, copolymer mixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated or brominated copolymer of isobutylene and isoprene (halobutyl rubber), chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, homo- and copolymers of epichlorohydrin, especially polymers containing halogenated vinyl compounds, for example, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as their copolymers, such as copolymers of vinyl chloride and vinylidene chloride, vinyl chloride and vinyl acetate or vinylidene chloride and vinyl acetate. Polyvinyl chloride can be rigid or flexible (plasticised).

9. Polymers derived from α,β-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polymethyl methacrylates, polyacrylamides and polyacrylonitriles modified with butyl acrylate to increase impact resistance.

10. Copolymers of the monomers mentioned in 9) with each other or with other unsaturated monomers, for example acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers or acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or their acetals, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallylmelamine; as well as their copolymers with the olefins mentioned in 1 above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or their copolymers with bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, accrplats or MBS.

14. Polyphenylene oxides and sulfides and mixtures of polyphenylene oxides with styrenic polymers or polyamides.

15. Polyurethanes derived from polyethers, polyesters or polybutadienes with terminal hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as their starting materials. Polyurethanes formed by the reaction of: (1) diisocyanates with short chain diols (chain extenders) and (2) diisocyanates with long chain diols (thermoplastic polyurethanes, TPU).

16. Polyamides or copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6 , 12/12, polyamide 11, polyamide 12, aromatic polyamides derived from m-xylenediamine and adipic acid; polyamides derived from hexamethylenediamine and isophthalic and/or terephthalic acid and with or without an elastomer as a modifier, for example poly-2,4,4-trimethylhexamethyleneterephthalamide or poly-m-phenylene isophthalamide; as well as block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, for example polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems). The polyamides may be amorphous.

17. Polyureas, polyimides, polyamidimides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones or lactides, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate and polyhydroxybenzoates, and hydroxyl-terminated polyethers; and polyesters modified with polycarbonates or MBS. Copolyesters may include, for example, but not limited to, polybutylene succinate/terephthalate, polybutylene adipate/terephthalate, polytetramethylene adipate/terephthalate, polybutylene succinate/adipinate, polybutylene succinate/carbonate, poly-3-hydroxybutyrate/octanoate copolymer, poly-3- hydroxybutyrate/hexanoate/decanoate. In addition, aliphatic polyesters may include, for example, but not limited to the class of poly(hydroxyalkanoates), in particular, poly(propiolactone), poly(butyrolactone), poly(pivalolactone), poly(valerolactone) and poly(caprolactone) , polyethylene succinate, polypropylene succinate, polybutylene succinate, polyhexamethylene succinate, polyethylene adipate, polypropylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene oxalate, polypropylene oxalate, polybutylene oxalate, polyhexamethylene succinate, polyethylene sebacate, polypropylene sebacate, polybutylene sebacate, polyethylene furanate and polylactic acid (PL A), as well as the corresponding polyesters modified with polycarbonates or MBS. The term "polylactic acid (PLA)" means a homopolymer, preferably poly-L-lactide, and any of its mixtures or alloys with other polymers; a copolymer of lactic acid or lactide with other monomers such as hydroxycarboxylic acids, such as, for example, glycolic acid, 3 -hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid and their cyclic forms; the terms "lactic acid" or "lactide" include L-lactic acid, D-lactic acid, mixtures and dimers thereof, i.e. L-lactide, D-lactide, mezolactide and any mixtures thereof. Preferred polyesters are PET, PET-G, PBT.

19. Polycarbonates and polyester carbonates. Polycarbonates are preferably prepared by reacting bisphenol compounds with carbonic acid compounds, in particular with phosgene or, in a melt transesterification process, with diphenyl carbonate or dimethyl carbonate. Especially preferred are homopolycarbonates based on bisphenol A and copolycarbonates based on monomers of bisphenol A and 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylniclohexane (bisphenol TMS). These and other bisphenol and diol compounds that can be used to synthesize polycarbonate are disclosed, in particular, in WO 08037364 (p. 7, line 21 - p. 10, line 5), EP 1582549 ([0018] - [0034]) , WO 02026862 (page 2, line 23 - page 5, line 15), WO 05113639 (page 2, line 1 - page 7, line 20). Polycarbonates can be linear or branched. Blends of branched and unbranched polycarbonates can also be used. Suitable branching agents for polycarbonates are known from the literature and are described, for example, in US Pat. page 3, lines 33-55), DE 19943642 (see page 5, lines 25-34) and US 5367044, as well as in the literature cited there.The polycarbonates used may additionally be branched in nature, while the branching agent are not added in this case in the context of polycarbonate production.An example of natural branching is the so-called Fries structures, which are disclosed for melt polycarbonates in EP 1506249. Chain terminators can be further used in the production of polycarbonate.Phenols such as phenol, alkylphenols such as cresol and 4-tert-butylphenol, chlorophenol, bromophenol, cumylphenol or mixtures thereof are preferably used as chain terminators Polyether carbonates are prepared by reacting the already mentioned bisphenols with at least one aromatic dicarboxylic acid and optionally equivalents of carbonic acid. Suitable aromatic dicarboxylic acids are, for example, phthalic acid, terephthalic acid, isophthalic acid, 3,3'- or 4,4'-diphenyl dicarboxylic acid and benzophenone dicarboxylic acids. Part up to 80 mol. %, preferably from 20 to 50 mol. %, carbonate groups in polycarbonates can be replaced by ester groups of aromatic dicarboxylic acid.

20. Polyketones.

21. Polysulfones, polyether sulfones and polyether ketones.

22. Cross-linked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol-formaldehyde resins, urea-formaldehyde resins and melamine-formaldehyde resins.

23. Dried and non-dried alkyd resins.

24. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, as well as their low flammability modifications containing halogens.

25. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.

26. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

27. Cross-linked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, for example, products of bisphenol A, bisphenol E and bisphenol F diglycidyl ethers, which are crosslinked with conventional hardeners such as anhydrides or amines, with or without accelerators.

28. Natural polymers such as cellulose, rubber, gelatin and their chemically modified homologous derivatives such as cellulose acetates, cellulose propionates and cellulose butyrates, or cellulose ethers such as methylcellulose, as well as rosins and their derivatives.

29. Blends of the polymers mentioned above (poly blends), e.g. PP/EPDM, polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/ PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO , PBT/PC/ABS or PBT/PET/PC.

30. Organic substances of natural and synthetic origin, which are pure monomeric compounds or mixtures of such compounds, such as mineral oils, animal and vegetable fats, oils and waxes or oils, fats and waxes based on synthetic esters (for example, phthalates, adipates, phosphates or trimellitates), as well as mixtures of synthetic esters with mineral oils in any weight ratio, commonly used as spinning compositions, as well as aqueous emulsions of such substances.

31. Aqueous emulsions of natural or synthetic rubber, such as natural latex or carboxylated styrene-butadiene copolymer latexes.

32. Adhesives, eg block copolymers such as SIS, SBS, SEBS, SEPS (S is styrene, I-isoprene, B-polybutadiene, EB-ethylene/butylene block, EP-polyethylene/polypropylene block).

33. Rubbers, for example polymers of conjugated dienes, for example polybutadiene or polyisoprene, copolymers of mono- and diolefins with each other or with other vinyl monomers, copolymers of styrene or α-methylstyrene with dienes or with acrylic derivatives, chlorinated rubbers, natural rubber.

34. Elastomers, e.g. natural polyisoprene (cis-1,4-polyisoprene natural rubber (NR) and trans-1,4-polyisoprene gutta-percha), synthetic polyisoprene (IR for isoprene rubber), polybutadiene (BR for butadiene rubber), chloroprene rubber (CR), polychloroprene, neoprene, byprene, etc., butyl rubber (isobutylene-isoprene copolymer, IIR), halogenated butyl rubbers (chlorobutyl rubber: CIIR; bromobutyl rubber: BIIR), styrene-butadiene rubber (styrene-butadiene copolymer, SBR ), natural rubber (butadiene-acrylonitrile copolymer, NBR), also called Buna N rubbers, hydrogenated nitrile rubbers (HNBR), Therban and Zetpol, EPM (ethylene-propylene rubber, ethylene-propylene copolymer) and EPDM rubber (ethylene-propylene-diene rubber , ethylene-propylene-diene terpolymer), epichlorohydrin rubber (ECO), polyacrylic rubber (ACM, ABR), silicone rubber (SI, Q, VMQ), fluorosilicone rubber (FVMQ), fluoroelastomers (FKM and FEPM), Viton, Tecnoflon , Fluorel, Aflas and Dai-El, perfluoroelastomers (FFKM), Tecnoflon PFR, Kalrez, Chemraz, Perlast, polyester block amides (PEBA), chlorosulfonated polyethylene (CSM), (Hypalon), ethylene vinyl acetate (EVA), thermoplastic elastomers (TPE), resilin and elastin proteins, polysulfide rubber, elastolefin, an elastic fiber used in the manufacture of fabrics.

35. Thermoplastic elastomers such as styrenic block copolymers (TPE-s), Thermoplastic olefins (TPE-o), Elastomeric alloys (TPE-v or TPV), Thermoplastic polyurethanes (TPU), Thermoplastic copolyesters, Thermoplastic polyamides, TPO reactor (R-TPO's) Polyolefin Plastomers (POP), Polyolefin Elastomers (POE).

Preferred organic polymers may be selected from the group consisting of polyolefins (such as polyethylene, polypropylene, etc.), polyvinyl chloride, polystyrene, polyacrylamide, polyester, polyamide, copolymers thereof, and copolymers of one or more of acrylonitrile, butadiene, and styrene or with a friend or with other comonomers. Polyolefins are preferred, and polypropylene is particularly preferred. The polymer can be processed into polymer products such as fibers, films, fabrics, packaging or coatings.

Zinc monoglycerolate containing an included modifier (GMS-ZMG) is usually present in an amount of from about 0.01 to 20 wt. %, based on the total weight of the polymer mixture. In the final plastic product, the concentration is usually in the range from 0.01 to 2%, but the composition of the masterbatch for obtaining the product may contain up to 20 wt. %. The organic polymer may be present in an amount of from about 80% to 99.99 wt. %, based on the total weight of the polymer mixture.

The amount of GMS modified zinc monoglycerolate (GMS-ZMG) in the polymer is not more than 400 ppm, and may even be 380 ppm or less, 360 ppm or less, 340 ppm or less, 320 ppm or less or 300 ppm or less. The amount may be as low as 100 ppm or 50 ppm or less. About 200 ppm +/- 100 ppm or +/- 50 ppm is a suitable target amount. Typical amounts of conventional nucleating agents (eg, unmodified ZMG) in isotactic polypropylene are typically 500 ppm or more, so this reduced amount represents significant cost savings, but does not adversely affect crystallization times achieved.

The polymer composition may further include the usual ingredients of polymeric materials in minor amounts, for example from 0.001 to 20%, preferably from 0.005 to 5%, based on the weight of the polymer composition.

Examples of common ingredients of polymeric materials are:

1. Antioxidants

1.1. Alkylated monophenols, e.g. 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, -tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2 ,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in side chains, for example, 2,6-di- nonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol, 2, 4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, e.g. 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, e.g. , 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4 -hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, eg α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, e.g. 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2, 6-dimethyl-4-hydroxyphenyl)disulfide.

1.6. Alkylidenebisphenols, e.g. 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), -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'-ethylidene-bis(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, 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-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. O-, N- and S-benzyl compounds, e.g. simple 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.

1.8. Hydroxybenzylated malonates e.g. 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.

1.9. Aromatic hydroxybenzyl compounds, e.g. 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, -butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine compounds, e.g. 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine 3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1, 3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di -tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di -tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine , 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates e.g. hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester.

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

1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, for example, with methanol, ethanol, n-octanol, and-octanol, a mixture of linear or branched C ₇ - C ₉ -alkanol, octadecanol, a mixture of linear or branched C ₁₃ -C ₁₅ -alkanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, tetra -ethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis-(hydroxyethyl)oxamide, 3-thioundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7 -trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. methanol, ethanol, n-octanol, p-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-thioundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane; 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, 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-thioundecanol, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1- phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic 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-thioundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha -2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, e.g. N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N' -bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,N'-bis[2 -(3-[3,5-di-t-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Naugard XL-1 (RTM) available from Uniroyal).

1.18. Ascorbic acid (vitamin C)

1.19. Amine antioxidants, e.g. N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine , N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N' -phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)phenylenediamine, N,N' -dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, e.g. 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)biguanidine, bis[4-(1',3'-dimethylbutyl)phenyl]amine , tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyldiphenylamines, mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixture of mono- and dialkylated tert-butyl/tert-octylphenothiazines, mixture of mono- and dialkylated tert -octylphenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine .

2. UV absorbers and light stabilizers

2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, e.g. 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'-methylphenyl)-5-chlorobenzotriazole,2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole,2-(3',5'-di-tert-amyl-2'-hydroxyphenyl )benzotriazole, 2-(3',5'-bis(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl )phenyl)-5-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)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol]; transesterification product of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 3000; , where R'=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2-[2'-hydroxy-3'-(α,α-dimethylbenzyl)-5'- (1,1,3,3-tetramethylbutyl)phenyl]benzotriazole; 2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(α,α-dimethylbenzyl)phenyl]benzotriazole.

2.2. 2-Hydroxybenzophenones, e.g. dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, e.g. -tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert -butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates e.g. -methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate, N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline and neopentyl tetra(α-cyano-β,β-diphenylacrylate).

2.5. Nickel compounds, e.g. 2,2'-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol] nickel complexes, such as a 1:1 or 1:2 complex with or without additional ligands, such as as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters, e.g. , 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole with or without additional ligands.

2.6. Hindered amines, e.g. carboxylic 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(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1, 2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl condensate -4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3 ,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6, 6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpyreridyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl- 7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethylpyrerid-4-yl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperid-4-yl)succinate, bis-[2,2,6,6-tetramethyl-1-(undecyloxy)-piperidin-4-yl]carbonate, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, condensate of 2-chloro- 4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, 2-chloro-4 condensate, 6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpyridyl)-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 )pyrrolidone-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy- 2,2,6,6-tetramethylpiperidine, condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5- triazine, a condensate of 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine, as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS reg. No.[136504-96-6]); condensate of 1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine, as well as N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS reg. No. [ 192268 64-7]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide, N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide, 2-undecyl- 7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, reaction product 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-piperidyloxycarbonyl)-2-(4-methoxyphenyl )-ethene, N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, 4-methoxymethylenemalonic acid diester with 1,2,2,6 ,6-pentamethyl-4-hydroxy-piperidine, poly[methylpropyl-3-hydroxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, a product of the reaction of a copolymer of α-olefin maleic anhydride with 2 ,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine, 2,4-bis[N-(1-cyclohexyloxy-2,2,6,6- tetramethylpiperidin-4-yl)-N-butylamino]-6-(2-hydroxyethyl)amino-1,3,5-triazine, 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6 ,6-tetramethylpiperidine, 5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, Sanduvor (Clariant; CAS reg. No. 106917-31-1], 5-(2-ethylhexanoyl)-oxymethyl-3,3,5-trimethyl-2-morpholinone, the reaction product of 2,4-bis-[(1-cyclo-hexyloxy-2,2, 6,6-piperidin-4-yl)butylamino]-6-chloro-s-triazine with N,N'-bis-(3-amino-propyl)ethylenediamine), 1,3,5-tris(N-cyclohexyl- N-(2,2,6,6-tetramethyl-piperizin-3-on-4-yl)amino)-s-triazine, 1,3,5-tris(N-cyclohexyl-N-(1,2,2 ,6,6-pentamethylpiperizin-3-on-4-yl)-amino)-s-triazine,

1,3,5-triazine-2,4,6-triamine, N,N'''-1,6-hexanediylbis[N',N''-dibutyl-N,N',N''-tris(2 ,2,6,6-tetramethyl-4-piperidinyl) - reaction products with 3-bromo-1-propene, oxidized, hydrogenated, 1,3,5-triazine-2,4,6-triamine, N, N'' '-1,6-hexanediylbis[N,N''-dibutyl-N,N',N''-tris(2,2,6,6-tetramethyl-4-piperidinyl)- and combinations thereof.

2.7. Oxamides, e.g. 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, tert-butoxanilide, 2-ethoxy-2'-ethoxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2' -ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.

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-octioxyphenyl)-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-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3, 5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy -3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl ]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2 ,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1, 3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl -1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl1]-1,3,5-triazine, 2-(2-hydroxyphenyl) -4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine, 2-(4,6-bis-biphenyl-4-yl-1,3,5-triazin-2-yl)-5 -(2-ethyl-(n)-hexyloxy)phenol.

3. Metal deactivators, e.g. N,N'-diphenyloxamide, N-salicilal-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)oxalyldihydrazide, oxanilide, isophthaloyldihydrazide, sebacoylbisphenylhydrazide, N,N'-diacetyladipoyldihydrazide, N,N'-bis(salicyloyl)oxalyldihydrazide , N,N'-bis(salicyloyl)thiopropionyldihydrazide.

4. Phosphites and phosphonites, e.g. triphenyl phosphite, diphenylalkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite , bis(2, 4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis( 2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[(d,g]-1,3,2-dioxyphosphocin, bis(2,4- di-tert-butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl- 12-methyl-dibenz[d,g]-1,3,2-dioxyphosphocin, 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, phosphoric acid mixed with 2,4-bis(1,1-dimethylpropyl) phenyl and 4-(1,1-dimethylpropyl)phenyl triesters (CAS reg. No. [939402-02-5], phosphoric acid, triphenyl ester, polymer with alpha-hydro-omega-hydroxypoly[oxy(methyl-1,2-ethanediyl)]C _10-16 alkyl esters (CAS Reg. No.[ 1227937-46-3].

The following phosphites are particularly preferred:

Tris(2,4-di-tert-butylphenyl) phosphite ( ^Irgafos® 168, Ciba Specialty Chemicals Inc.), tris(nonylphenyl) phosphite,

5. Hydroxylamines, e.g. N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N- hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

6. Nitrones, for example, N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N-hexadecyl- alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N, N-dialkylhydroxylamine derived from hydrogenated tallow amine.

7. Thiosynergists, eg dilauryl thiodipropionate, dimistryl thiodipropionate, distearyl thiodipropionate and pentaerythritol tetraxis[3-(dodecylthio)propionate] or distearyl disulfide.

8. Peroxide scavengers, e.g. esters of α-thiodipropionic acid, e.g. lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(β-dodecylmercapto)propio Nat.

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

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

11. PVC heat stabilizer, such as mixed metal stabilizers (such as barium/zinc, calcium/zinc), organotin stabilizers (such as mercaptan organotin ester, -carboxylate, -sulfide), lead stabilizers (such as tribasic lead sulfate, dibasic stearate lead, dibasic lead phthalate, dibasic lead phosphate, lead stearate), organic-based stabilizers, and combinations thereof.

12. Nucleating agents, for example, inorganic substances such as talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates, preferably alkaline earth metals; organic compounds such as mono- and polycarboxylic acids and their salts, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers (ionomers). Especially preferred are 1,3:2,4-bis(3',4'-dimethylbenzylidene)sorbitol, 1,3:2,4-di(p-methyldibenzylidene)sorbitol, and 1,3:2,4-di(benzylidene) sorbitol.

13. Fillers and reinforcing agents such as calcium carbonate, silicates, glass fibers, carbon fibers, glass fibers, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flour or fibers of other natural products, synthetic fibers.

14. A plasticizer, wherein said plasticizer is selected from the group consisting of di(2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate, dipropyl heptyl phthalate, trioctyl trimellitate, tri(isononyl) trimellitate, epoxidized soybean oil, di(isononyl) cyclohexane-1, 2-dicarboxylate, 2,4,4-trimethyl-1,3-pentanediol diisobutyrate.

The plasticizer used in accordance with the present invention may also include one selected from the group consisting of phthalates, trimellites, esters of aliphatic dibasic acids, polyesters, polymers, epoxides, phosphates. In a preferred embodiment of the present invention, said plasticizer is selected from the group consisting of: Butylbenzyl phthalate, Butyl 2-ethylhexyl phthalate, diisohexyl phthalate, diisoheptyl phthalate, di(2-ethylhexyl) phthalate, diisooctyl phthalate, di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, diisoundecyl phthalate, diisotridecyl phthalate, diiso(C11, C12, C13) phthalate, di(n-butyl) phthalate, di(n-C7, C9) phthalate, di(n-C6, C8, C10) phthalate, diiso(n-nonyl) phthalate, di(n-C7, C9, C11) phthalate, di(n-C9, C11) phthalate, di(n-undecyl) phthalate, tri(n-C8, C10) trimellitate, tri(2-ethylhexyl) trimellitate, tri(isooctyl) trimellitate, tri(isononyl) trimellitate, di(n-C7, C9) adipate, di(2-ethylhexyl) adipate, di(isooctyl) adipate, di(isononyl) adipate, adipic acid or glutaric acid polyesters and propylene glycol or butylene glycol or 2,2-dimethyl-1,3-propanediol, epoxidized oils such as epoxidized soybean oil, epoxidized linseed oil, epoxidized tall oil, octyl epoxytallate, 2-ethylhexyl epoxytallate, isodecyl diphenyl phosphate, tri(2-ethylhexyl) phosphate, tricresyl phosphate, di(2-ethylhexyl) terephthalate, di(isononyl) cyclohexane-1,2-dicarboxylate, and combinations thereof. In a particularly preferred embodiment of the present invention, said plasticizer is selected from the group consisting of: diisohexyl phthalate, diisoheptyl phthalate, di(2-ethylhexyl) phthalate, diisooctyl phthalate, di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, diisoundecyl phthalate, diisotridecyl phthalate, diiso(C11, C12, C13) phthalate, di(n-butyl) phthalate, di(n-C7, C9) phthalate, di(n-C6, C8, C10) phthalate, diiso(n-nonyl) phthalate, di(n-C7, C9, C11) phthalate, di(n-C9, C11) phthalate, di(n-undecyl) phthalate, tri(n-C8, C10) trimellitate, tri(2-ethylhexyl) trimellitate, tri(isooctyl) trimellitate, tri(isononyl) trimellitate, di(n-C7, C9) adipate, di(2-ethylhexyl) adipate, di(isooctyl) adipate, di(isononyl) adipate, polyesters of adipic acid or glutaric acid and propylene glycol or butylene glycol or 2,2-dimethyl- 1,3-propanediol, epoxidized oils such as epoxidized soybean oil, di(isononyl)cyclohexane-1,2-dicarboxylate, and combinations thereof.

15. Other additives such as plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow control agents, optical brighteners, flame retardants, antistatic agents and blowing agents.

16. Benzofuranones and indolinones, such as those disclosed in U.S. 4,325,863; U.S. 4,338,244; U.S. 5,175,312; U.S. 5,216,052; U.S. 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839, EP-A-0591102; EP-A-1291384 or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2 -stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5.7 -di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2-acetyl-5-isooctylphenyl)-5-isooctylbenzofuran-2-one.

Polymer material ingredients such as pigments, dyes, additives, fillers, flame retardants, antiozonants, antioxidants, demold aids, acid scavengers, plasticizers, stabilizers such as pH stabilizers, emulsifiers, curing agents, polymerization initiators, sensitizers, etc. .P. may be included in the polymer composition.

Another embodiment of the present invention is a molded article made from a resin composition according to the present invention:

Examples of suitable molded articles are:

I-1) Swimming instruments, maritime uses, pontoons, buoys, plastic deck frames, breakwaters, boats, kayaks, oars and shore protection.

I-2) Automotive, interior applications, exterior applications such as bumpers, dashboards, battery, rear and front trims, under hood moldings, hat racks, trunk trims, interior trims, airbag covers, electronic moldings products for fittings (light signalling), windows for dashboards, glass for headlights, dashboard, exterior trims, upholstery, car headlights, headlights, position lights, taillights, light brake lights, interior and exterior finishes; door panels; gas tank; front side glazing; rear windows; seat back, exterior panels, wire insulation, extruded seal profiles, exterior trim, support covers, frame parts, engine exhaust systems, fuel filter/liner, fuel pumps, fuel reservoir, body side profiles, convertible tops, exterior mirrors, exterior trim, latches/fixings, front block, glass, hinges, locking systems, luggage/racks/luggage racks, molded/stuffed parts, seals, side impact protection, noise absorbers/isolators and panoramic sunroof, door medallion, consoles, instrumentation panels, seats, frames, upholstery, reinforced automotive applications, fiber reinforced automotive applications, filled polymer automotive applications, unfilled polymer automotive applications.

I-3) Road transport devices, in particular sign mounts, road marking mounts, car accessories, warning triangles, first aid kit cases, helmets, tires.

I-4) Devices for transport or public transport. Devices for airplanes, railways, cars (cars, motorcycles), trucks, light trucks, buses, trams, bicycles, including interior items.

I-5) Devices for use in space, in particular rockets and satellites, such as re-entry protection devices.

I-6) Devices for architecture and design, mining applications, acoustic threshold systems, outdoor shelters and canopies.

II-1) Apparatus, housings and coverings for general use and in electrical/electronic devices (personal computer, telephone, portable telephone, printer, televisions, audio and video devices), flower pots, satellite TV ceiling and panel devices.

II-2) Sheaths for other materials such as steel or textile materials.

II-3) Devices for the electronics industry, in particular insulation for plugs, especially computer plugs, casings for electrical and electronic parts, printed circuit boards, and electronic data storage materials such as microchips, check cards or credit cards.

II-4) Electrical appliances, in particular washing machines, tumblers, ovens (microwave), dishwashers, mixers and irons.

II-5) Coverings for luminaires (eg street lamps, lampshades).

II-6) Uses in wires and cables (semiconductor, insulation and sheaths for cables).

II-7) Foils for capacitors, refrigerators, heaters, air conditioners, electronic circuit sealing, semiconductors, coffee machines and vacuum cleaners.

III-1) Technical items such as gears (gear), sliding fittings, separators, screws, bolts, handles and rollers.

III-2) Rotor blades, fans and windmill blades, solar appliances, swimming pools, swimming pool covers, pool linings, pond linings, closets, wardrobes, partition walls, economy panels, folding walls, roofs, shutters (e.g. roller shutters ), fittings, connections between pipelines, hoses and conveyor belts.

III-3) Sanitary wares, in particular showers, toilets, covers and sinks.

III-4) Hygiene products, in particular diapers (baby, adult incontinent), feminine hygiene products, shower curtains, brushes, rugs, bathtubs, mobile toilets, toothbrushes and bed panels.

III-5) Pipelines (crosslinked or not) for water, wastewater and chemicals, pipelines for protecting wires and cables, pipelines for gas, oil and wastewater, roof gutters, drain pipes and drainage systems.

III-6) Profiles of any geometry (window panes) and cladding.

III-7) Glass substitutes, in particular extruded or co-extruded panels, glazing for buildings (monolithic, double or laminated), aircraft, schools, extruded sheets, window film for architectural glazing, trains, transport and sanitary products.

III-8) Slabs (walls, cutting boards), extrusion coating (photo paper, tetrapack paper and piping insulation), silos, wood substitute, plastic lumber, wood composites, walls, surfaces, furniture, decorative foils, floor coverings (interior and outdoor use), flooring, removable flooring and ceramic tiles.

III-9) Inlet and outlet header pipes.

III-10) Uses and coatings in cement, concrete, composite, siding and thin sheeting, handrails, railings, kitchen worktops, roofing material, roofing iron, ceramic tiles and tarps.

IV-1) Slabs (walls and cutting boards), shelves, artificial grass, artificial turf, artificial turf for stadium running circles (athletics), artificial floor for stadium running circles (athletics) and ribbons.

IV-2) Continuous and staple woven fabric, fibers (carpets / hygiene products / geotextiles / monofilaments; filters; towels / curtains (lampshades) / medical uses), bulk fibers (uses such as dresses / protective clothing), nets , tackle, cables, strings, cord fabrics, threads, belts for special child seats, clothes, underwear, gloves; shoes; rubber boots, underwear, garments, swimwear, sportswear, umbrellas (small umbrellas, parasols), parachutes, paragliders, sails, "balloon silk", products for outdoor recreation, awnings, air mattresses, deck chairs, bulk bags and soft containers.

IV-3) Membranes, insulation, coatings and seals for roofs, tunnels, temporary storage, ponds, wall and roof membranes, geomembranes, swimming pools, curtains (lampshades)/sun screens, awnings, awnings, wallpapers, food packaging and wrapping (flexible and rigid), medical packaging (flexible and rigid), airbags/seat belts, armrests and headrests, carpets, center console, instrument panels, aircraft cockpits, door, overhead console unit, door trim, cabin headlining, interior lighting, interior mirrors, luggage rack, rear luggage cover, seats, steering column, steering wheel, textile materials and main trim tab.

V-1) Films (packaging, rigid packaging, open storage, laminating, roll wrapping, pools, trash bags, wallpaper, packaging film, raffia, desalination film, batteries and connectors.

V-2) Agricultural films (greenhouse covers, tunnel, multitunnel, microtunnel, "raspa y amagado", multi-span, low tunnel type greenhouse, high tunnel, mulch, silage, silage bags, silage stretching, fumigation, air sink, piping, solawrap greenhouse, heat treatment, bale packing, stretch bale packs, baby stockings, film stockings), especially in the presence of heavy use of agrochemicals; other agricultural uses (e.g., non-woven ground covers, nets (made from tapes, multiple threads, and combinations thereof), tarpaulins. Such agricultural film can be either a single-layer or multi-layer structure, typically three, five, or seven layers. It can result in a film structure such as A-B-A, A-B-C, A-B-C-B-A, A-B-C-B-D, A-B-C-D-C-B-A, A-A-B-C-B-A-A, A, B, C, D represent different polymers and tackifiers However, adjacent layers can also be joined so that the final film product can be made from an even number of layers, i.e. two, four or six layers, such as A-A- B-A, A-A-B-B, A-A-B-A-A, A-B-B-A-A, A-A-B-C-B, A-A-B-C- A-A and the like.

V-3) Ribbons

V-4) Foams (sealing, insulating, barrier), sports and recreational mats

V-5) Seals

VI-1) Food packaging and wrapping (flexible and rigid), BOPP, VORET, bottles.

VI-2) Storage systems such as boxes (boxes), luggage, container, home boxes, shelving, shelves, tracks, boxes with screws, containers and cans.

VI-3) Cartridges, syringes, medical applications, containers for any transportation, wastebaskets and waste bins, waste bags, reservoirs, dustbins, garbage bags, tanks on wheels, container in general, water/used water/chemical containers / Gas / Oil / Gasoline / Diesel; fuel tank linings, boxes, crates, battery boxes, chutes, medical devices such as plungers, ophthalmic uses, diagnostic devices, and pharmaceutical blister packaging.

VII-1) Household items of any kind (e.g. electrical appliances, thermos bottle/clothes hanger) fastening systems such as plugs, wire and cable clips, zippers, fasteners, zippers and snap buttons.

VII-2) Support devices, leisure products such as sports and exercise equipment, gymnastic mats, ski boots, inline skates, skis, bigfoot, athletic surfaces (eg tennis courts); screw caps, tops and stoppers for bottles and jars.

VII-3) Furniture in general, foam products (pillows, shock absorbers), foams, sponges, kitchen towels, rugs, garden chairs, stadium seats, tables, sofas, toys, kits (boards/figures/balls), houses for games, flip flops and play vehicles.

VII-4) Materials for optical and magnetic data storage.

VII-5) Kitchen utensils (for eating, drinking, cooking, food storage).

VII-6) Boxes for CDs, cassettes and video tapes; electronic products for DVD, stationery of any type (ballpoint pens, stamps and ink pads, mouse, shelves, tracks), bottles of any size and content (for drinks, detergents, cosmetics, including perfumes) and adhesive tapes.

VII-7) Shoes (boots/shoe soles), insoles, gaiters, adhesives, mounting adhesives, shoe boxes (for fruit, vegetables, meat, fish), synthetic paper, bottle labels, sleeping quarters, artificial joints (for human ), printed circuit boards (flexographic), printed circuit boards and display devices.

VII-8) Polymer filling elements (talc, chalk, china clay (kaolin), wollastonite, pigments, carbon black, TiO ₂ , mica, nanocomposites, dolomite, silicates, glass, asbestos).

Applicant has found that zinc monoglycerolate containing the crystallite size described herein and/or prepared in accordance with the process described herein provides improved crystallization characteristics. These improvements are particularly evident for propylene and homopolymer copolymers and polypropylene blends. These improvements include the following:

1. The higher Tc, the lower the loading of the nucleating agent. When 200 ppm is added to isotactic polypropylene (hereinafter "iPP" - LyondellBasell, Moplen HP400N isotactic polypropylene homopolymer, MFI=11 g/10 min), glycerol monostearate-modified zinc monoglycerolate (GMS-ZMG) gives a Tc of 124.1° C, while unmodified ZMG gives a Tc of only 120.6°C. To obtain a Tc of 123.8° C. (about the same as with GMS-ZMG at 200 ppm), 600 ppm ZMG is required. Tc for HP400N (without nucleating agent) is 117.0°C.

2. The time required to reach 50% polymer crystallization (t _1/2 ) at 140°C is significantly improved (reduced) at 200 ppm using the modified ZMG of the present application compared to unmodified ZMG: GMS-ZMG gives t _1/2 7.2 min vs. t _1/2 for ZMG 14.6 min. To achieve a t _{1/2 of} 7.1 min using the modified ZMG alone, 600 ppm ZMG is required instead. HP400N does not crystallize by itself within 40 minutes

Modified zinc monoglycerolate (GMS-ZMG) provides an increase in Tg of about 3.4°C at 200 ppm in isotactic polypropylene, compared to the same load of unmodified zinc monoglycerolate.

In compositions based on polyolefins as an organic polymer, the use of zinc monoglycerolate at a given loading level in the polyolefin provides a higher crystallization temperature for the polyolefin than is achieved at the same loading level of zinc monoglycerolate having a crystallite size of more than 30 nm in the <100> direction or greater than 60 nm in the <011> direction, or having an aspect ratio calculated from the <100>/<011> coherent domain lengths greater than 0.65 (i.e. compared to zinc mono-glycerolate, which is an unmodified monoglycerolate zinc, or the Bos form of zinc monoglycerolate). In isotactic polypropylene, the use of the modified zinc monoglycerolate according to the present application at a given loading level in isotactic polypropylene provides a time to achieve 50% polymer crystallization (t _1/2 ) at 140 ° C, which is at least 40% less than that achieved at that the same load of comparative zinc monoglycerolate (i.e., one that has a crystallite size greater than 30 nm in the <100> direction or greater than 60 nm in the <011> direction, or has an aspect ratio calculated from the <100>/<011> coherent domain lengths, which is greater than 0.65).

In the claims and in the foregoing description, except where the context otherwise requires due to the language expressed or the necessary meaning, the word "comprises" or variants such as "comprises" or "comprising" is used in an inclusive sense, i.e. to indicate the presence of the claimed features, but do not exclude the presence or addition of additional features in various embodiments of the present invention.

Examples

The present invention will be described in more detail with reference to the following non-limiting examples.

Techniques

Method for obtaining characteristics

X-ray diffraction analysis was performed using a Phillips 1140 diffractometer using a copper source (40 kV, 25 mA) and graphite monochromators or a Bruker D2 phaser using a copper source (30 kV, 10 mA) tuned according to the Bragg-Brentano geometry (θ-20 ). The scan was between the desired 2θ values (2θ=5-35°). For example, powder samples were mounted on a standard sample holder (mg - several g). The polymer samples are extruded in an extruder and pressed between metal plates to form a flat piece, cooled in a water bath and cut to size to fit the existing sample holder (<3 mm thickness).

The average crystallite size (average length of the coherent domain) in each of the <100> and (011) directions, was calculated using the Scherrer equation, using the measured full width at half maximum (FWHM) measured using XRD (β), wavelength X-ray emission (λ), Bragg angle (expressed in degrees; (peak value 2θ)/2)), dimensionless shape factor (K is assumed to be 0.9; the same K has always been used for comparison). The Scherrer equation is τ=Kλ/β cos θ. Note that line spreading due to instrumentation is ignored, and line spreading is assumed to occur only due to changes in coherent domain length.

SEM microscopy was performed using a JEOL JSM-7001F scanning electron microscope. The samples were fixed on a carbon tape and coated with Pt.

Samples for crystallization testing were prepared as follows: iPP was blank semi-crystalline isotactic polypropylene (iPP) resin (Moplen HP400N (from Lyondell-Basell, Australia). iPP samples containing no nucleating agent (control) or containing the indicated amount of nucleating agent were mixing iPP with the required amount of nucleating agent Thorough hand mixing (powder + iPP granules) was carried out first, followed by extrusion 1 wt % or 2000 ppm masterbatches (depending on the set of comparative experiments) were prepared and extruded The extruded filaments were granulated and extruded again at the desired concentration (200 or 600 ppm.) (In one case, noted explicitly, 200 ppm material was extruded twice.) A single screw extruder was used (diameter = 25 mm; L/D=25 ) CRD barrier manufactured by Rauwendaal Extrusion Eng. Inc. attached to a Haake Rheocord 90. The four temperature zones were set to 170, 175, 180 and 180°C (matrix) respectively. The screw speed was 100 rpm.

Example 1 Preparation of GMS Modified Zinc Monoglycerolate (GMS-ZMG)

ZnO (656.4 g) and GMS (72.3 g) were homogenized and heated in a Z-blade mixer. Then 668.5 g of glycerol were added. Then 74.3 g of glycerol + 8.7 g of water + 4.5 g of 90% acetic acid were added and further homogenized. The temperature was raised to 110°C. Once the complete reaction, that is, the fine dry powder, had taken place, the heat was turned off. The highest temperature reached was about 120°C, but the temperature during the reaction was generally in the range of 100-120°C. Stirring in this temperature range was continued after completion of the reaction, during which an agglomerated product was formed. The resulting agglomerated (powder) product was crushed in pins.

Then X-ray diffraction analysis was performed to determine the average crystallite size. The radiograph is shown in Fig. 1. One of the lines in the radiograph according to FIG. 1 refers to the product from Example 1 (labeled GMS-ZMG) and the second refers to unmodified ZMG. The peak at 2θ=10.9° is due to a set of planes described by the Miller index (100) (a stack of cards). The length of the coherent domain (crystallite size) in the <100> direction for the GMS-ZMG of Example 1 was calculated as 17 nm, compared to 40 nm for the unmodified ZMG sample. The peak at 2θ=17.2° corresponds to a set of planes described by the Miller index (011) (planes within each map). The crystallite size in this direction is 45 nm for both GMS-ZMG and unmodified ZMG.

SEM imaging was performed on the agglomerated product of Example 1 compared to unmodified ZMG. The SEM images are shown in FIG. 2a and 2b. The scale bar in each image is 1 µm. The two products have different morphologies. The image in FIG. 2a(A) is unmodified ZMG. The image in FIG. 2b(B) is the GMS-ZMG product from Example 1. The product from Example 1 shows agglomerated crystallite clusters. The agglomerated crystallites show a "fish scale"-like surface pattern (on individual particles), indicating that the much smaller crystallites do not stack perfectly, with open edges.

Additional SEM images of the GMS-ZMG product from Example 1 are shown in FIG. 3a, 3b and 4.

Samples of iPP (isotactic polypropylene) were prepared containing 200 ppm unmodified ZMG, 600 ppm unmodified ZMG, 200 ppm GMS-ZMG from Example 1 and an unnucleated control ("blank"). The crystallization behavior of the samples was evaluated using differential scanning calorimetry (DSC), whereby the heat flux (in/out of the sample) (in mW) was measured as a function of the sample temperature (degrees C) to estimate the crystallization temperature for the polypropylene sample containing the nucleating agent.

The following table shows the results in tabular form:

The table above shows that the Tc for a sample containing 200 ppm GMS-ZMG from Example 1 is about the same as for a sample containing 600 ppm (three times more) of unmodified ZMG. Tc is higher with 200 ppm GMS-ZMG from Example 1 compared to the same amount of unmodified ZMG.

A similar trend can be traced for isothermal t _1/2 at 140°C:

Comparative Example

Wet hydrozincite (equivalent to 50.0 kg of zinc oxide) was slowly added to glycerin (53.5 kg) while mixing in a sigma mixer. Glycerol monostearate (5.0 kg) was added slowly while mixing and the composition was mixed into a thin paste. The mixture contained a significant amount of hydrozincite water - the calculated amount was 70 wt. % of water in the used hydrozincite-water suspension, or 1410 mol. % relative to zinc in the reaction composition. The composition was heated to 160°C and kept at this temperature for 16 hours. A dry flowable powder was obtained.

The above description actually corresponds to the description of Bos 2006. The product thus produced is designated "Hydrozincite-ZMG".

The crystallite size of the resulting powder (hydrozincite-ZMG) was measured using XRD (FIG. 5) and the results are presented in the table below along with crystallite size measurements for the product of Example 1 (GMS-ZMG) and unmodified ZMG. The table also includes the calculated values <100>/<011> of the aspect ratio:

The crystallite size in the <100> direction for hydrozincite-ZMG (Comparative Example) is approximately similar to the crystallite size of unmodified ZMG, but significantly larger than that for GMS-ZMG Example 1. Notably, the crystallite size in the <011> direction is of the same order of magnitude, same as GMS-ZMG in all three cases (although hydrozinkite-ZMG is slightly longer). In GMS-ZMG (Example 1), although the <011> crystallite size remains basically the same (layer size), the <100> crystallite size (layer stack thickness) is significantly reduced. The <100>/<011> aspect ratio for GMS-ZMG is typically less than 0.65, and often less than 0.44; in this case 0.38). It is clear that this is less than in both unmodified ZMG and GMS-ZMG. In other words, the GMS modification of ZMG according to the present invention creates smaller stacks of ZMG layers (which can be more efficiently dispersed in the polymer) compared to the other two types (unmodified ZMG and hydrozinkite-ZMG).

Example A:

Samples of iPP (isotactic polypropylene, homopolymer, melt flow index 8 dg/min at 230°C/2.16 kg) were prepared with 100 ppm, 200 ppm, 600 ppm or 1200 ppm unmodified ZMG or GMS-ZMG and control without nucleating agent ("blank").

The crystallite size of unmodified ZMG and GMS-ZMG was measured using XRD and the results are shown in the Table below. Also included are the calculated aspect ratio values <100>/<011>:

The crystallization behavior of the samples was evaluated using differential scanning calorimetry (DSC), whereby the heat flux (in/out of the sample) (in mW) was measured as a function of the sample temperature (degrees C) to estimate the crystallization temperature for the polypropylene sample containing the nucleating agent.

The following table shows the results in tabular form:

The table above shows that the Tc for a sample containing 100 ppm GMS-ZMG is about the same as for a sample containing 600 ppm (six times the amount) of unmodified ZMG. At any concentration in this extended concentration range, the Tc for GMS-ZMG is higher compared to the Tc with the same amount of unmodified ZMG.

Among the samples obtained with these compounds, plates (2 mm thick) were cast. Weights shaped in accordance with ISO 527-2 5A (2012) were stamped in terms of melt flow and tensile properties were tested in accordance with ISO 527 (2012). The results (modulus of elasticity and tensile strength) are presented in the table below. The same trend is observed as for the crystallization temperature.

Sample elastic modulus (*) Yield strength (*) 1200 ppm unmodified ZMG 1838 MPa 41.98 MPa 600 ppm unmodified ZMG 1759 MPa 40.97 MPa 200 ppm unmodified ZMG 1707 MPa 40.33 MPa 100 ppm unmodified ZMG 1676 MPa 40.01 MPa 1200 ppm GMS-ZMG 1857 MPa 41.99 MPa 600 ppm GMS-ZMG 1842 MPa 41.68 MPa 200 ppm GMS-ZMG 1794 MPa 41.33 MPa 100 ppm GMS-ZMG 1730 MPa 40.65 MPa iPP only (HD120 MO) 1648 MPa 39.99 MPa

(*) High values are desirable.

The above table shows that the modulus and yield strength for a sample containing 200 ppm GMS-ZMG is significantly higher than for a sample containing 600 ppm (three times more) of unmodified ZMG. At any concentration over this wide concentration range, the modulus and yield strength of GMS-ZMG are higher compared to the modulus and yield strength, respectively, with the same amount of unmodified ZMG.

Example B:

Samples of iPP (isotactic polypropylene, homopolymer, melt flow index 19 dg/min at 230°C/2.16 kg) were prepared containing 200 ppm unmodified ZMG, 600 ppm unmodified ZMG, 200 ppm GMS-ZMG according to the example above or 600 ppm GMS-ZMG according to the example above, and control without nucleating agent ("blank"). The crystallization behavior of the samples was evaluated using differential scanning calorimetry (DSC), whereby the heat flux (in/out of the sample) (mW) was measured as a function of the sample temperature (degrees C) to estimate the crystallization temperature for the polypropylene sample containing the nucleating agent.

The following table shows the results in tabular form:

The table above shows that the Tc for a sample containing 200 ppm GMS-ZMG is about the same as for a sample containing 600 ppm (three times more) of unmodified ZMG. Tc is higher with all concentrations of GMS-ZMG compared to the same amount of unmodified ZMG.

Among the samples obtained with these compounds, plates (2 mm thick) were cast. Weights shaped in accordance with ISO 527-2 5A (2012) were stamped in terms of melt flow and tensile properties were tested in accordance with ISO 527 (2012). The results (modulus of elasticity and tensile strength) are presented in the table below. The same trend is observed as for the crystallization temperature.

Sample elastic modulus
guests (*) The limit is
heaps (*) 600 ppm unmodified ZMG 1511 MPa 37.98 MPa 200 ppm unmodified ZMG 1457 MPa 37.11 MPa 600 ppm GMS-ZMG 1604 MPa 38.78 MPa 200 ppm GMS-ZMG 1534 MPa 38.19 MPa iPP only (HF420 FB) 1362 MPa 35.37 MPa

(*) High values are desirable.

The above table shows that the modulus and yield strength for a sample containing 200 ppm GMS-ZMG is significantly higher than for a sample containing 600 ppm (three times more) of unmodified ZMG. At any concentration over this wide concentration range, the modulus and yield strength of GMS-ZMG are higher compared to the modulus and yield strength, respectively, with the same amount of unmodified ZMG.

Example C:

Samples of iPP raco (isotactic polypropylene, random copolymer, melt flow index 8 dg/min at 230°C/2.16 kg) were prepared containing 200 ppm unmodified ZMG or 200 ppm GMS-ZMG according to the example above, and control without nucleating agent ("blank"). The crystallization behavior of the samples was evaluated using differential scanning calorimetry (DSC), whereby the heat flux (in/out of the sample) (mW) was measured as a function of the sample temperature (degrees C) to estimate the crystallization temperature for the polypropylene sample containing the nucleating agent.

The following table shows the results in tabular form:

The table above shows that the Tc for a sample containing 200 ppm GMS-ZMG is significantly higher than the Tc for unmodified ZMG at the same concentration.

Among the samples obtained with these compounds, plates (2 mm thick) were cast. Weights shaped in accordance with ISO 527-2 5A (2012) were stamped in terms of melt flow and tensile properties were tested in accordance with ISO 527 (2012). The results (modulus of elasticity and tensile strength) are presented in the table below. The same trend is observed as for the crystallization temperature.

Sample elastic modulus (*) current limit
honor (*) 200ppm unmodified ZMG 1262 MPa 34.39 MPa 200ppm GMS-ZMG 1300 MPa 34.43 MPa iPP Raco only (RD204 CF) 1207 MPa 33.70 MPa

(*) High values are desirable.

The table above shows that the modulus and yield strength for a sample containing 200 ppm GMS-ZMG is higher than for a sample of unmodified ZMG at the same concentration.

Claims (24)

1. Zinc monoglycerolate modified with a modifier in the form of crystallite agglomerates, in which the crystallite size, based on the average length of the coherent domain, is less than 30 nm in the <100> direction (size along the zone axis <100>), and less than 60 nm in the <011> direction (size along the <100> zone axis) as determined by the Scherrer equation by X-ray powder diffraction; and the aspect ratio calculated from the <100>/<011> coherent domain lengths is less than 0.65. 2. Zinc monoglycerolate according to claim 1, wherein the aspect ratio calculated from <100>/<011> coherent domain lengths is less than 0.56. 3. Zinc monoglycerolate according to claim 1, wherein the modifier is an ester of glycerol carboxylate. 4. Zinc monoglycerolate according to claim 3, wherein the glycerol carboxylate ester is a saturated fatty acid ester of glycerol. 5. Zinc monoglycerolate according to claim 4, wherein the glycerol carboxylate ester is glycerol monostearate. 6. Zinc monoglycerolate according to any one of paragraphs. 1-5, in which the amount of modifier is from 1.0 to 5.0 mol.% based on zinc monoglycerolate. 7. Zinc monoglycerolate in the form of agglomerates of crystallites, containing from 1.0 to 5.0 mol.% of glycerol carboxylate ester. 8. The method for producing zinc monoglycerolate according to claim 1, including the reaction of a zinc compound, which is different from hydrozincite, with glycerol and a modifier in the presence of an acid catalyst, in which: the zinc compound is selected from the group consisting of zinc oxide, zinc carbonate, zinc hydroxide, zinc carboxylate and combinations thereof, or/and the reaction is carried out in the presence of less than 10% by weight of water, based on the total weight of the reaction composition. 9. The method of claim 8 wherein the modifier is a carboxylate ester of glycerol. 10. The method according to claim 8, wherein the amount of glycerol is from 90 to 110 mole %, based on the zinc compound. 11. The method according to p. 8, in which the amount of the modifier is from 1.0 to 5.0 mol.% based on the zinc compound. 12. The method according to any one of paragraphs. 8-11, in which the amount of acid catalyst is from 0.2 to 5 mol.% based on the zinc compound. 13. Zinc monoglycerolate obtained by the method according to any one of paragraphs. 8-12. 14. Composition for the manufacture of molded products containing an organic polymer and zinc monoglycerolate according to any one of paragraphs. 1-7. 15. The composition according to claim 14, in which the organic polymer is selected from the group consisting of polyolefins, polyvinyl chloride, polystyrene, polyacrylamide, polyester, polyamide, their copolymers and copolymers of one or more of acrylonitrile, butadiene and styrene with each other or with others comonomers. 16. The composition according to claim 14 or 15, in which zinc monoglycerolate is present in an amount of from 0.005% to 5%, relative to the weight of the organic polymer. 17. The composition according to claim 14, in which the organic polymer is a polyolefin, and zinc monoglycerolate at a given loading level in the polyolefin provides a higher crystallization temperature of the polyolefin than achieved at the same loading level of zinc monoglycerolate having a crystallite size of more than 30 nm in < 100> direction or greater than 60 nm in the <011> direction, or having an aspect ratio calculated as <100>/<011> coherent domain lengths that is greater than 0.65. 18. The composition of claim. 14, in which the organic material is isotactic polypropylene, and zinc monoglycerolate at a given level of loading in isotactic polypropylene provides a time to reach 50% polymer crystallization (t _1/2 ) at 140 ° C, which is at least 40% less than that achieved at the same loading level of zinc monoglycerolate having a crystallite size greater than at least one of 30 nm in the <100> direction or greater than 60 nm in the <011> direction, or having an aspect ratio calculated as coherent domain lengths <100 >/<011> which is more than 0.65. 19. The use of zinc monoglycerolate according to any one of paragraphs. 1-7 to increase the crystallization temperature of the organic polymer. 20. The use of zinc monoglycerolate according to any one of paragraphs. 1-7 to increase the mechanical properties of the organic polymer. 21. Application according to claim 20, where the mechanical property is the modulus of elasticity or yield strength. 22. The use of zinc monoglycerolate according to any one of paragraphs. 1-7 as a nucleating agent in an organic polymer.