阅读说明：本技术 基于n-烷氧基胺的稳定剂组合 (Stabilizer combinations based on N-alkoxyamines ) 是由 E·贡斯坦蒂尼 F·菲尼利 于 2019-08-07 设计创作，主要内容包括：本发明涉及一种组合物,其至少包含：A)第一量的第一N-烷氧基胺；B)3wt.-％或更多的与第一N-烷氧基胺在结构上不同的第二N-烷氧基胺；和平衡至100的其他组分；其中第一N-烷氧基胺的量高于第二N-烷氧基胺的量；其中第一N-烷氧基胺的分子量小于第二N-烷氧基胺的分子量；其中所述组合物在20℃具有15’000至70’000mPa*s范围的粘度。本发明进一步涉及制造包含所述组合物的制品例如箔的方法,包含所述组合物的和/或通过所述方法可获得的制品、覆盖箔,包含所述制品的温室和温室箔,包含含有所述组合物的涂层的制品,其中使用所述制品的用于生产植物的方法,以及所述组合物用作紫外线稳定剂和/或阻燃剂的用途。(The present invention relates to a composition comprising at least: A) a first amount of a first N-alkoxyamine; B)3wt. -% or more of a second N-alkoxyamine structurally different from the first N-alkoxyamine; and other components in balance to 100; wherein the amount of the first N-alkoxyamine is greater than the amount of the second N-alkoxyamine; wherein the molecular weight of the first N-alkoxyamine is less than the molecular weight of the second N-alkoxyamine; wherein the composition has a viscosity in the range of 15 '000 to 70' 000mPas at 20 ℃. The invention further relates to a method of manufacturing an article, such as a foil, comprising said composition and/or obtainable by said method, a cover foil, a greenhouse and greenhouse foil comprising said article, an article comprising a coating comprising said composition, a method for producing plants wherein said article is used, and the use of said composition as a uv stabilizer and/or flame retardant.)

1. A composition comprising at least:

A) a first amount of a first N-alkoxyamine;

B)3wt. -% or more of a second N-alkoxyamine structurally different from the first N-alkoxyamine; and

other components in equilibrium to 100;

wherein the amount of the first N-alkoxyamine is greater than the amount of the second N-alkoxyamine;

wherein the molecular weight of the first N-alkoxyamine is less than the molecular weight of the second N-alkoxyamine;

wherein the composition has a viscosity in the range of 15 '000 to 70' 000mPas at 20 ℃; and

wherein the first N-alkoxyamine has a molecular weight in the range of from 500 to 1600 g/mol; and

wherein the second N-alkoxyamine has a molecular weight in the range of 1000 to 3000 g/mol.

2. The composition of claim 1, wherein the second N-alkoxyamine is a polymer comprising a first repeat unit and an additional repeat unit, wherein the first repeat unit is obtainable from an alkanediol.

3. The composition of claim 2, wherein the additional repeating units are obtainable from N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) ester of a dicarboxylic acid.

4. The composition of any one of claims 2 to 3, wherein the polymer comprises 2-5 additional repeat units.

5. The composition of any preceding claim, wherein the composition has a piperidinyl content in the range of 30 to 60wt. -%, based on the total weight of the composition.

6. The composition according to any of the preceding claims,

wherein the composition has a viscosity in the range of 15 '000 to 30' 000mPas at 20 ℃; and

wherein the first N-alkoxyamine has a molecular weight in the range of from 500 to 900 g/mol; and

wherein the molecular weight of the second N-alkoxyamine is in the range of 1000 to 1800 g/mol.

7. The composition according to any one of claims 1 to 5,

wherein the composition has a viscosity in the range of 50 '000 to 70' 000mPas at 20 ℃; and

wherein the first N-alkoxyamine has a molecular weight in the range of from 1200 to 1600 g/mol; and

wherein the molecular weight of the second N-alkoxyamine is in the range of 1800 to 2500 g/mol.

8. The composition of any preceding claim, wherein the composition comprises

C)0.5wt. -% or more of a further N-alkoxyamine structurally different from the first and second N-alkoxyamines, wherein the molecular weight of the further N-alkoxyamine is higher than the molecular weight of the second N-alkoxyamine.

9. The composition of claim 8 wherein the molecular weight of the other N-alkoxyamines is in the range of 1500 to 4000 g/mol.

10. The composition of claim 8 or 9 wherein the other N-alkoxyamine is a polymer of N, N' -bis [1- (alkoxy) -2,2,6, 6-tetramethyl-4-piperidinyl ] esters of alkanediols and dicarboxylic acids.

11. The composition of any preceding claim, wherein the composition comprises at least one further component selected from a phosphite, a phosphonite, a HALS and/or a phenol, or a combination of two or more thereof.

12. The composition of claim 11, wherein the at least one other component is selected from benzoic acid, benzoic acid esters, such as hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate or 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, or a combination of two or more thereof.

13. A method of making an article comprising the composition of any preceding claim, wherein the method comprises at least the steps of:

(I) providing a matrix polymer;

(II) adding the composition;

(III) processing the matrix polymer and the composition.

14. An article comprising at least a matrix polymer and the composition of any one of claims 1 to 12, or an article obtainable by the method of claim 13.

15. The article of claim 14, wherein the article comprises at least one matrix polymer selected from a polyolefin, a thermoplastic olefin compound, or a combination of two or more matrix polymers in the same or different groups thereof.

16. The article of any one of claims 14 and 15, wherein the article is a foil or film.

17. A greenhouse comprising at least one article of any one of claims 14 to 16.

18. Method for producing a plant, comprising at least the following steps:

i) planting seeds or seedlings in the culture medium;

ii) at least partially covering the planted seed or seedling with the article of any one of claims 14 to 16.

19. Use of a composition according to any one of claims 1 to 12 as a uv stabiliser and/or flame retardant for an article comprising at least a matrix polymer.

20. An article comprising at least a coating, wherein the coating comprises the composition of any one of claims 1 to 12.

Technical Field

The present invention relates to a composition comprising at least: A) a first amount of a first N-alkoxyamine; B)3wt. -% or more of a second N-alkoxyamine structurally different from the first N-alkoxyamine; and other components in balance to 100; wherein the amount of the first N-alkoxyamine is greater than the amount of the second N-alkoxyamine; wherein the molecular weight of the first N-alkoxyamine is less than the molecular weight of the second N-alkoxyamine; wherein the composition has a viscosity in the range of 15 '000 to 70' 000mPas at 20 ℃. The invention further relates to a method of manufacturing an article, such as a foil, comprising said composition and/or obtainable by said method, a cover foil, a greenhouse and greenhouse foil comprising said article, an article comprising a coating comprising said composition, a method for producing plants wherein said article is used, and the use of said composition as a uv stabilizer and/or flame retardant.

Background

Polyolefin resins are used in a variety of applications due to their ease of use in the manufacture of various extruded and molded articles. Cover foils or films and greenhouse foils or films are exemplary articles that can be made from polyolefin resins, which are widely used in the agricultural field. However, foils made from polyolefin resins often lose tensile strength (tensile strength) and overall stability due to exposure to ultraviolet light and exposure to acidic conditions (e.g., due to exposure to pesticides and acid rain). This is particularly relevant for outdoor applications where the foil may be exposed to prolonged sunlight, acid rain and pesticides over a period of months. As the mechanical properties of the foil deteriorate, the breakage rate of the foil increases, thereby reducing the protective properties of the foil and reducing the overall usefulness of the foil.

Accordingly, there is a need to develop polyolefin resins, particularly polypropylene resins, and articles made therefrom having improved ultraviolet stability and extended lifetime. These characteristics are typically created by adding stabilizers to the polyolefin resin.

One group of these stabilizers are sterically hindered amines. Sterically hindered amines have in the past been of considerable industrial interest, but after all efforts there is still the goal of providing improved stabilizer compositions for polyolefin resins to extend the service time and life of articles made therefrom, such as foils and films, especially for outdoor use, such as in the agricultural field.

In summary, it is an object of the present invention to at least partly overcome at least one of the drawbacks known in the prior art.

It is another object of the present invention to provide a composition as a composite additive (additive package) that imparts an extended period of use to a matrix polymer, particularly after exposure to at least one of light, ultraviolet light, heat, moisture, pesticides, rain, acid rain, and combinations thereof.

It is another object of the present invention to provide an article, such as a mulch film and a greenhouse foil, having an extended period of use, particularly after exposure to at least one of light, ultraviolet light, heat, moisture, pesticides, rain, acid rain, and combinations thereof.

It is another object of the present invention to provide a composition as a composite additive that imparts extended in-use and long-lasting fire resistance (fire resistance) to a matrix polymer.

It is another object of the present invention to provide an article that exhibits extended use and long-lasting fire resistance.

It is another object of the present invention to provide a process by means of which the matrix polymer can be processed into its final shape without deterioration of the processed matrix polymer.

It is another object of the present invention to provide a composition of additives with which the matrix polymer can be processed into its final shape without deterioration of the processed matrix polymer.

It is another object of the present invention to provide a composition and method of manufacture of the additive whereby the matrix polymer and articles of the composition are transparent in the UV/VIS band.

It is a further object of the invention to provide a foil which is as transparent as possible to avoid absorption of visible and/or ultraviolet light by the foil. The aim is to promote plant growth as much as possible.

It is a further object of the invention to provide a greenhouse foil with which plants and seedlings can grow faster.

It is another object of the present invention to provide a cover film that is longer in duration.

The subject matter of the class-forming embodiments contributes to a solution for at least one of the above-mentioned objects. The dependent sub-embodiments forming embodiments of the class represent preferred embodiments of the invention, the subject of which also contributes to solving at least one of the above-mentioned objects.

Preferred embodiments

1. A composition comprising at least:

A) a first amount of a first N-alkoxyamine;

B)3wt. -% or more of a second N-alkoxyamine structurally different from the first N-alkoxyamine; and

other components in equilibrium to 100;

wherein the amount of the first N-alkoxyamine is greater than the amount of the second N-alkoxyamine;

wherein the molecular weight of the first N-alkoxyamine is less than the molecular weight of the second N-alkoxyamine;

wherein the composition has a viscosity in the range of 15 '000 to 70' 000mPas at 20 ℃; and

wherein the first N-alkoxyamine has a molecular weight in the range of from 500 to 1600 g/mol; and

wherein the second N-alkoxyamine has a molecular weight in the range of 1000 to 3000 g/mol.

2. The composition of embodiment 1, wherein the second N-alkoxyamine is a polymer comprising a first repeat unit and an additional repeat unit, wherein the first repeat unit is obtainable from an alkanediol.

3. The composition of embodiment 2, wherein the additional repeating units are obtainable from N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) ester of a dicarboxylic acid.

4. The composition of any of embodiments 2-3, wherein the polymer comprises 2-5 additional repeat units.

5. The composition of any preceding embodiment, wherein the composition has a piperidinyl content in the range of 30 to 60wt. -%, based on the total weight of the composition.

6. The composition according to any one of the preceding embodiments,

wherein the composition has a viscosity in the range of 15 '000 to 30' 000mPas at 20 ℃; and

wherein the first N-alkoxyamine has a molecular weight in the range of from 500 to 900 g/mol; and

wherein the molecular weight of the second N-alkoxyamine is in the range of 1000 to 1800 g/mol.

7. The composition according to any one of embodiments 1 to 5,

wherein the composition has a viscosity in the range of 50 '000 to 70' 000mPas at 20 ℃; and

wherein the first N-alkoxyamine has a molecular weight in the range of from 1200 to 1600 g/mol; and

wherein the molecular weight of the second N-alkoxyamine is in the range of 1800 to 2500 g/mol.

8. The composition of any preceding embodiment, wherein the composition comprises

C)0.5wt. -% or more of a further N-alkoxyamine structurally different from the first and second N-alkoxyamines, wherein the molecular weight of the further N-alkoxyamine is higher than the molecular weight of the second N-alkoxyamine.

9. The composition of embodiment 8 wherein the molecular weight of the other N-alkoxyamines is in the range of 1500 to 4000 g/mol.

10. The composition of embodiment 8 or 9 wherein the other N-alkoxyamine is a polymer of N, N' -bis [1- (alkoxy) -2,2,6, 6-tetramethyl-4-piperidinyl ] esters of alkanediols and dicarboxylic acids.

11. The composition according to any preceding embodiment, wherein the composition comprises at least one additional component selected from a phosphite, a phosphonite, a HALS and/or a phenol, or a combination of two or more thereof.

12. The composition according to embodiment 11, wherein the at least one other component is selected from benzoic acid, benzoic acid esters, such as hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate or 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, or a combination of two or more thereof.

13. A method of making an article comprising the composition of any of the preceding embodiments, wherein the method comprises at least these steps:

(I) providing a matrix polymer;

(II) adding the composition;

(III) processing the matrix polymer and the composition.

14. An article comprising at least a matrix polymer and the composition of any one of embodiments 1 to 12, or an article obtainable by the method of embodiment 13.

15. The article of embodiment 14, wherein the article comprises at least one matrix polymer selected from a polyolefin, a thermoplastic olefin compound, or a combination of two or more matrix polymers from the same or different groups thereof.

16. The article according to any one of embodiments 14 and 15, wherein the article is a foil or film.

17. A greenhouse comprising at least one article of any one of embodiments 14 to 16.

18. Method for producing a plant, comprising at least the following steps:

i) planting seeds or seedlings in the culture medium;

ii) at least partially covering the planted seed or seedling with the article of any one of embodiments 14 to 16.

19. Use of the composition according to any of embodiments 1 to 12 as a uv stabilizer and/or as a flame retardant for an article comprising at least a matrix polymer.

20. An article comprising at least a coating, wherein the coating comprises the composition of any one of embodiments 1 to 12.

Definition of

In this context, the term "in the range from x to y" should be understood to include all values between the numbers x and y and to form the extremes of the numbers x and y. For example, the term "in the range of 2 to 13" includes the numbers 2, 13 and all numbers in between.

A "polymer" is a material made up of two or more repeating units. For example, the polymer may have 2, 3, 4, 5, 6, 7, 8, 9, 10 repeating units. Also, the polymer may have about 20, 50, 100, or 1000 repeating units, or even more repeating units. In one variation, the polymer may have two or more different repeat units. Two different educts, each comprising one repeating unit or each comprising a chemical structure which can form a repeating unit during the reaction, are then used simultaneously or sequentially to obtain a polymer comprising two repeating units. Depending on the preparation scheme and the individual educts, the polymers obtainable may have statistically occurring individual repeating units or rather defined arrangements in their structure. In this regard, the polymer may be a block copolymer, an alternating polymer, or a polymer having statistically occurring repeating units. This is well known to those skilled in the polymer art.

A repeat unit is a segment of a chemical structure that occurs more than once in a polymer. The repeating units are formed during the polymerization reaction. In this context, free-radical polymerization with solvents is preferred. This means that the first repeat unit is formed by the educt molecules and the second repeat unit is formed by the incorporation of the solvent molecules, thereby combining the two structures. Small molecules such as water, ammonia, etc. are sometimes produced as by-products.

The value of molecular weight describes the molecular weight. Molecular weights were determined by Gel Permeation Chromatography (GPC) as described in the test methods. Molecular weight, as used herein when defining a polymer or polymeric material, refers to the average molecular weight as determined by GPC according to the test methods described herein.

The term "transparent" refers herein to at least about 60% of incident light passing through a sample having a thickness of 5 μm and a reference wavelength of 450 nm. Preferably, greater than 70%, or greater than 75%, or greater than 80% of the incident light passes through the sample.

Chemical compounds may be followed by expressions in parentheses. In this case, trademarks under which the chemical compounds can be purchased are mentioned in parentheses for illustrative purposes.

Detailed Description

The present invention will now be described in further detail. This includes descriptions of optional embodiments that may further contribute to the invention.

A first aspect of the invention is a composition comprising at least:

A) a first amount of a first N-alkoxyamine;

B)3wt. -% or more of a second N-alkoxyamine structurally different from the first N-alkoxyamine; and

other components in equilibrium to 100;

wherein the amount of the first N-alkoxyamine is greater than the amount of the second N-alkoxyamine;

wherein the molecular weight of the first N-alkoxyamine is less than the molecular weight of the second N-alkoxyamine;

wherein the composition has a viscosity in the range of 15 '000 to 70' 000mPas at 20 ℃; for example, a viscosity in the range of 15 '000 to 30' 000mPa s at 20 ℃, or a viscosity in the range of 18 '000 to 22' 000mPa s at 20 ℃; or e.g. having a viscosity in the range of 50 '000 to 70' 000mPa s at 20 ℃, or in the range of 57 '000 to 67' 000mPa s at 20 ℃; and

wherein the first N-alkoxyamine has a molecular weight in the range of 500 to 1600g/mol, for example, 600 to 900 g/mol; and

wherein the second N-alkoxyamine has a molecular weight of from 1000 to 3000 g/mol; for example, in the range of 1000 to 1600 g/mol.

Molecular weight values were determined and calculated by gel permeation chromatography according to the methods described in the test methods section. The viscosity was determined according to the method described in the test methods section.

The amount of the second N-alkoxyamine is 3wt. -% or more, such as 5wt. -% or more, or 10wt. -% or more, based on the total weight of the composition. Typically, the amount of the second N-alkoxyamine does not exceed 49wt. -%. For example, the amount of the second N-alkoxyamine is 3 to 45wt. -%, or 5 to 40wt. -%, or 5 to 20wt. -%, or 10 to 40wt. -%, or 20 to 40wt. -%, or 30 to 40wt. -%, or 10 to 45wt. -%, or 20 to 45wt. -%, or 30 to 45wt. -%, based on the total weight of the composition; or in the range of 35 to 45wt. -%.

In all cases, the amount of the first N-alkoxyamine is higher than the amount of the second N-alkoxyamine. For example, the amount of the first N-alkoxyamine is from 2 to 50 wt.%, or from 2 to 40 wt.%, or from 2 to 30 wt.%, or from 2 to 20 wt.%, or from 2 to 10 wt.%, or from 5 to 25%, or from 10 to 25% higher than the amount of the second N-alkoxyamine, based on the total weight of the composition.

In all cases, a balance of 100wt. -% of the total amount of the composition was maintained. The remainder of the amount of first N-alkoxyamine and second N-alkoxyamine other than that of the first N-alkoxyamine may be constituted, for example, by one or more other N-alkoxyamines each structurally different from the first and second N-alkoxyamines; the remainder may also consist of other stabilizers, flame retardants, viscosity modifiers, fillers, surfactants, antistatic agents, antifogging agents, processing aids, and solvents.

In one embodiment of the invention, the composition of the first aspect is a liquid. In another embodiment of the invention, the composition has a freezing point as determined by DSC of less than 0 deg.C, such as less than-10 deg.C, or less than-20 deg.C, or less than-30 deg.C. Typically, the freezing point is kept above-50 ℃.

In another embodiment of the present invention, the composition has a color in the range of 3 to 8 according to the Gardner scale.

In another embodiment of the invention, the composition has a viscosity in the range of 100 to 2000mPa s at a temperature of 40 to 80 ℃.

In a first embodiment of the invention, the second N-alkoxyamine is a polymer comprising a first repeat unit and a further repeat unit, wherein the first repeat unit is obtainable from an alkanediol.

Any alkanediol known to the skilled person can be used for preparing the polymer of the second N-alkoxyamine. Examples of suitable alkanediols may be selected from alkanediols having from 2 to 20 carbon atoms, for example from 4 to 16 carbon atoms or from 8 to 14 carbon atoms. Alpha, omega-alkanediols are preferred. Examples of suitable alkanediols are ethane-1, 2-diol, propane-1, 3-diol, butane-1, 2-diol, butane-1, 3-diol, butane-1, 4-diol, pentane-1, 5-diol, pentane-1, 6-diol, hexane-1, 6-diol, heptane-1, 7-diol, octane-1, 8-diol, nonane-1, 9-diol, decane-1, 10-diol, decane-1, 9-diol, decane-2, 8-diol, undecane-1, 11-diol, dodecane-1, 12-diol, preferably decane-1, 10-diol and isodecanediol. In addition, a combination of two or more alkanediols may be used to prepare the second N-alkoxyamine.

Further repeating units contributing to the second N-alkoxyamine may be chemical compounds known to the skilled person and which may be considered useful. In another embodiment of the invention, a suitable additional repeating unit is an N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) ester of a dicarboxylic acid, or a combination of two or more thereof. The dicarboxylic acid component may preferably have a number of carbon atoms in the range of 2 to 12 or 2 to 8 excluding the carboxyl group, such as butyric acid or sebacic acid. The dicarboxylate may be linear or branched. Further, the additional repeating units may be a combination of two or more of the foregoing esters, with variations of the dicarboxylic acid esters.

In another embodiment of the invention, the second N-alkoxyamine may have 2, 3, 4 or 5 additional repeat units in the polymer. In addition, the second N-alkoxyamine can comprise two or more compounds having 2, 3, 4, or 5 repeating units, wherein the members of the composition have different repeating unit numbers.

In another embodiment of the present invention, the composition has a piperidinyl content in the range of 30 to 60wt. -% or 25 to 50wt. -%, each based on the total weight of the composition.

In another embodiment of the invention, the composition has a viscosity in the range of 15 '000 to 30' 000mPa s at 20 ℃; and the first N-alkoxyamine has a molecular weight in the range of from 500 to 900 g/mol; and the molecular weight of the second N-alkoxyamine is in the range of 1000 to 1800 g/mol.

In another embodiment of the invention, the composition has a viscosity in the range of 50 '000 to 70' 000mPa s at 20 ℃; and the first N-alkoxyamine has a molecular weight ranging from 1200 to 1600 g/mol; and the molecular weight of the second N-alkoxyamine is in the range of 1800 to 2500 g/mol.

In another embodiment of the invention, the composition comprises C)0.5wt. -% or more, such as 0.5wt. -%, for example 0.5 to 5, or 5 to 25et. -%, or 8 to 20wt. -% of a further N-alkoxyamine structurally different from the first and the second N-alkoxyamine, wherein the molecular weight of the further N-alkoxyamine is higher than the molecular weight of the second N-alkoxyamine. Typically, the amount of other N-alkoxyamines does not exceed 30 wt.%, based on the total weight of the composition.

It was found that the combination of the first N-alkoxyamine and the second N-alkoxyamine with a Hindered Amine Light Stabilizer (HALS) or alternatively with a benzoate derivative enhances the stabilizing effect of the composition of the present invention in a synergistic manner.

If 0.5 wt.% or more of other N-alkoxyamines are also present, the second N-alkoxyamine is typically present at less than 10 wt.%, based on the total weight of the composition.

In another embodiment of the invention, the molecular weight of the other N-alkoxyamines is in the range from 1500 to 4000g/mol, for example in the range from 1800 to 3000 g/mol. Molecular weights were calculated according to GPC data in the test methods section, as previously described.

In another embodiment of the invention, the other N-alkoxyamine is a polymer of N, N' -bis [1- (alkoxy) -2,2,6, 6-tetramethyl-4-piperidinyl ] esters of alkanediols and dicarboxylic acids.

Alkoxy moieties may be straight or branched chain, such as alkoxy or iso-alkoxy. The dicarboxylic acid based segment is selected from the same options as described for the first aspect of the invention.

In another embodiment of the invention, the composition comprises at least one further component selected from phosphites, phosphonites, HALS and/or phenols, or a combination of two or more thereof. The amount of other components is about 1000ppm for phosphites and phosphonites and about 500ppm for phenolic compounds, the ppm being always relative to the total weight of the composition. These ingredients are typically added to stabilize the composition during processing. For example when a polymeric material comprising the composition of the first aspect including one or more further components is processed to produce a sheet or foil or the like. It was then found that the presence of these components in the processed material enhanced the thermal stability, the overall uv stability and the stability to shear of the composition of the first aspect.

In another embodiment of the invention, the at least one further component is selected from benzoic acid, benzoic acid esters, such as hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate or 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate. Further, a combination of two or more thereof may be used.

It has been found that the combination of one or more of the previously described N-alkoxyamines with benzoic acid derivatives and/or with phosphorus compounds such as phosphonites/phosphites strongly enhances the oxidative stability during processing of the polymers. In addition, the oxidative stability of the processed polymer is enhanced when exposed to ultraviolet light or sunlight.

In an example, which also constitutes an embodiment of the first aspect of the present invention, the first N-alkoxyamino group is 1, 4-bis [ 1-isodecyloxy) -2,2,6, 6-tetramethyl-4-piperidinyl]Succinate, CAS No. 1883807-47-3:

the second N-alkoxyamine can be obtained by radical polymerization of the first N-alkoxyamine with decane (CAS number 124-18-5) in the presence of t-butyl hydroperoxide (CAS number 75-91-2) as a radical generator.

Optional further N-alkoxyamines may be:

wherein n is 2.

A second aspect of the present invention is a method of manufacturing a composition according to the first aspect or any embodiment thereof, wherein the method comprises at least the steps of:

a. providing a first amount of a first N-alkoxyamine and a second amount of a second N-alkoxyamine, and optionally other components, to the composition; wherein the first amount is higher than the second amount; and

b. mixing the ingredients provided in step a.

The provision of step a. can be carried out according to any manner known to the skilled person and considered suitable for the present method. The mixing of step b. can be carried out by any means known to the skilled person and considered suitable. Examples of mixing are stirring and bubbling with a gas, such as a bubbled gas; using a mechanical mixer; the components are metered during polymer extrusion via a loss-in-weight feeder or a liquid metering system feeding the extruder.

According to another aspect of the invention, the composition may be produced from a single batch by several steps. Thus, the synthesis can be started from 2 molar equivalents of 2,2,6, 6-tetramethyl-4-piperidinol (CAS number 2403-88-5) and 1 molar equivalent of 1, 2-dimethyl succinate, and the intermediate products succinic acid, 1, 4-bis (2,2,6, 6-tetramethyl-4-piperidinyl) ester CAS number 62782-03-0, are obtained by transesterification. The intermediate can be alkoxylated by a free radical reaction using tert-butyl hydroperoxide as initiator in an excess of decane (solvent). The analogues may be obtained by using another solvent, such as isooctane, n-decane, isoalkane or n-alkane.

A third aspect of the invention is a method of manufacturing an article comprising a composition according to any preceding aspect or embodiment thereof, wherein the method comprises at least these steps:

(I) providing a matrix polymer;

(II) adding the composition;

(III) processing the matrix polymer and the composition.

Step (I) of providing the matrix polymer may be carried out according to any means known to the skilled person and considered suitable for the present method.

In a preferred embodiment, the ratio of composition to matrix polymer is in the range of 0.05-50 wt.%, e.g., 0.05 to 2 wt.% (e.g., by directly metering the composition into the matrix polymer); or 5 to 25 wt.% (e.g. produced by a masterbatch which can be further diluted in a matrix polymer), said wt. -% always being based on the sum of the total weight of matrix polymer and composition.

Step (II) of adding the composition may be carried out according to any means known to the skilled person and deemed suitable. For example, the composition may be added as droplets from a liquid metering system. Such a liquid metering system pumps and meters the liquid into the main hopper of the extruder, which is then mixed with the matrix polymer by a classical extrusion process using a state of the art extruder (single or twin screw, co-or counter-rotating, etc.). Other optional ingredients may be added by loss-in-weight feeders, or alternatively, the composition may also be added to the polymer matrix by the so-called masterbatch route. The masterbatch approach refers to a concentrate of a composition previously produced and mixed into the first matrix polymer. About 5 to about 25 wt.% of the composition is mixed into the first matrix polymer to form a masterbatch. The masterbatch is then diluted with a second matrix polymer to obtain the final composition, wherein 0.05 to 2 wt.% of the composition is in the resulting matrix polymer. Metering may be performed using a loss-in-weight feeder that feeds into the main hopper of the extruder, or via a side feeder that feeds into the extruder.

Step (III) of processing the matrix polymer and the composition may imply any manner known to the person skilled in the art and considered suitable for processing the matrix polymer. Variations of processing include homogenization, extrusion, blow molding, casting (casting), and combinations of these variations to form a foil or sheet of the matrix polymer. Other examples of such processing methods include injection molding, blow molding, rotational molding, thermoforming, cast or blown film processing, stretched tape, monofilament, multifilament, film orientation such as BOPP, BoPET, or the production of mono-oriented films, fibers and webs or any other plastic processing method known in the art.

A fourth aspect of the present invention is an article comprising at least a matrix polymer and a composition according to any of the embodiments of the first aspect or one of its embodiments, or an article obtainable by the method of the third aspect or one of its embodiments.

In one embodiment of the third and fourth aspects, the at least one matrix polymer may be selected from a polyolefin, a thermoplastic olefin compound, or a combination of two or more matrix polymers from the same or different groups as described above. Preferred olefins are selected from polymers of mono-olefins and polymers of di-olefins; such as polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, such as cyclopentene or norbornene, polyethylene (which may preferably be crosslinked), such as High Density Polyethylene (HDPE), Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), Branched Low Density Polyethylene (BLDPE). Polyolefins are typically produced using catalysts. Metallocenes, Ziegler-Natta catalysts and Ziegler catalysts are preferred.

Another preferred matrix polymer of the present invention is a polyethylene-vinyl acetate (EVA) and Vinyl Acetate (VA) comonomer, wherein the comonomer content is in the range of 3% to 25% based on the total amount of matrix polymer.

Another group of preferred matrix polymers of the invention are polyamides (hereinafter: PA), for example: PA6, PA66, PA46, PA11, and PA 12.

Another preferred group of matrix polymers of the present invention are polyesters.

Another group of preferred matrix polymers of the present invention are styrene polymers such as PS, ABS, ASA, SAB, i-PS, E-PS and PVC.

As the matrix polymer, further preferred are a wide range of materials, such as POM; PUR, TPU, TPE, UPES, PMMA, PPE, epoxy, acrylic, WPC and rubber. Preferred rubbers are SBS, SEBS, BR, IR, SBR, NBR, EPR, EPDM, X-SBR, X-TPE, etc.

In addition, the compositions of the present invention may be used in inks, sealants, adhesives and coating polymers.

Abbreviations for polymers and matrix polymers throughout the patent are mentioned according to DIN EN ISO 1043-1:2016, DIN ISO 1629:2015, DIN EN ISO 18064:2015 and DIN ISO 2076: 2014.

In another embodiment of the third and fourth aspects, the article is a foil or film. In this context, a foil is any kind of planar article having a thickness of 2mm or less. Herein, the film is any kind of foil having a thickness in the range of 10 to 250 μm. A sheet-like article is defined as an article that extends in three perpendicular directions, where thickness refers to the direction of least extension of the article.

A sixth aspect of the invention is a greenhouse comprising at least an article according to the third or fourth aspect or any embodiment thereof. Greenhouses are items in which seedlings and plants can be planted. Greenhouses are usually covered by a foil or film to protect the interior of the greenhouse from environmental aspects, such as rain, birds, heat, cold, etc. The foil or film may be an alternative to a fixedly mounted glass ceiling.

A seventh aspect of the present invention is a method for producing a plant, comprising at least the steps of:

i) planting seeds or seedlings in the culture medium;

ii) at least partially covering said planted seed or seedling with the above-mentioned article.

Culture media are materials generally suitable for promoting the growth of seeds, seedlings and plants. Any medium known to the person skilled in the art and deemed suitable for the purpose of growing seeds or seedlings may be used, for example soil.

An eighth aspect of the present invention is the use of a composition according to the first aspect or one of its embodiments as uv stabilizer and/or as flame retardant for an article comprising at least a matrix polymer.

A uv stabilizer is a chemical or combination of substances that delays the degradation of a polymer exposed to uv light (e.g., sunlight). Thus, the uv stabilizer increases the lifetime of the polymer exposed to sunlight or uv light from another light source.

A flame retardant is a chemical substance or composition that retards or even inhibits the outbreak or spread of a fire on a material. Thus, a polymer comprising a flame retardant will delay ignition, burning or smoking compared to a polymer without such an additive.

A ninth aspect of the present invention is an article comprising at least a coating, wherein the coating comprises a composition according to the first aspect or one of its embodiments. In this aspect, the composition according to the first aspect or embodiments thereof is not comprised in the article, but is comprised mainly or completely in a layer on the article. Due to the internal migration of chemical constituents in the dense article, some amount of the composition or at least some of its components may be present in the article over time, even if they were not initially present. In a common embodiment, the compositions referred to in the present invention are mixed with a coating such as a varnish, paint, ink, glue, adhesive or sealant and then applied to an article.

Test method

All solvents were used in analytical grade (p.a.) unless otherwise stated.

a.Gel Permeation Chromatography (GPC)

GPC measurements were run at 30 ℃ using an RI detector or multi-wavelength detector on an Agilent model 1200 of Agilent Technologies. The column was Shodex Asahipak GF310 HQ, 300mm by 7.6mm (inside diameter), available from Showa Denko Europe GmbH, Munich, Germany. THF containing 0.02M Diethanolamine (DEA) (or 2.1028g DEA/1 liter THF) was used as the mobile phase. The flux was set at 0.8 ml/min. The injection volume per sample/time was 5 μ l. The concentration of the sample was 5 wt.% in THF.

Preliminary column calibration is performed prior to sample measurement. By using 5 different M's with definitions, labeled 500, 800, 1000, 2000 and 3000_nAnd M_wThe polystyrene monodisperse standards of (a) are calibrated (available from Sigma-Aldrich Chemie GmbH of munich, germany and certified therewith) (product ids 81401, 327824, 81402, 81403 and 81404). 10mg of each standard was transferred to a vial, and one drop of toluene and 1ml of THF were added. Each sample was injected at least twice, or the time difference until the sample retention time remained within 0.2% reproducibility. The GPC software uses the peaks to determine retention times and automatically creates a calibration curve.

The experimental samples were treated in this way: 10mg of the sample are transferred into a 10ml volumetric flask and 4 drops of toluene are added. THF was added to the scale of 10 ml. After stirring, the sample was passed through a 0.45 μ Teflon membrane (R) ((R))SRP4 Syringe Filter 17820, 0.45 μm hydrophobic PTFE available from Sartorius AG, gottingen, germany) was filtered and injected. Measuring each probe at least twice, or up to M as determined by GPC_nThe value deviation is less than 0.8% max.

b.Viscosity of the oil

The viscosity was determined using an AMETEK Brookfield viscometer model DVE equipped with a thermometer with an accuracy of +/-0.5 ℃. A 60mm diameter beaker was filled with a liquid sample to a height of 100mm and one of the impellers LV2, LV3 or LV4 was mounted on the viscometer. The impeller was submerged into the mark on the impeller shaft and then centered in the middle of the beaker. And finally, checking whether the instrument is horizontal or not by means of a built-in bullseye level gauge of the instrument. The rotational speed is set to a specific speed of the cone. Then, the engine is started. After waiting at least 30 seconds to ensure constant conditions in the beaker, the clutch lever is pressed and the viscosity value appears on the instrument's display screen.

c.Weathering test (weather test)

According to ISO 4892-2:2013, method A cycle No.1, using instructions from ATLAS Material TestWeathering tests were performed by model number WOM Ci 3000 Weather-Ometer from ing Technology GmbH equipped with water-cooled xenon lamps (6500W), borosilicate S-type filters (inside and outside). The radiation was 0.51W/m at a wavelength of 340nm²And 60W/m in the 300-400 nm band². The black standard temperature was 65 + -3 deg.C at a test chamber temperature of 38 + -3 deg.C. Humidity was 50. + -. 5% relative humidity. The cycle time was 102 minutes in dry air and 18 minutes with water spray.

The samples were placed in a weather-Ometer (also known as "WOM") and the samples were examined periodically for evidence of light-induced oxidation by visual assessment of microcracks on the surface of the samples, typically associated with surface polymer oxidation. Microcracking is also known as "chalking".

d.Freezing point (DSC)

According to ASTM D3418-15, at N₂The freezing point of the compositions of the invention was then checked using a PerkinElmer model DSC 4000.

About 5mg of sample was placed in the tray sample holder and weighed with an accuracy of ± 1 μ g using a suitable laboratory precision balance. The other sample holder is still empty and is used as a reference for the difference measurement. The furnace is sealed to isolate the test environment from the outside. The thermal program consisted of a linear temperature gradient: continuous and uniform N in the furnace₂Under inert atmosphere, the temperature is raised from 25 ℃ to 200 ℃ at the speed of 10 ℃/min plus or minus 0.1 ℃/min. The DSC software automatically recorded any changes in temperature and heat flux between the two sample holders (material and reference).

e.pesticide/S fumigation simulation

To simulate the acid attack of pesticides on plastic stabilizers, samples placed every 360 hours (15 days) into WOM Ci 3000 were removed from the WOM and immersed in 0.2M H₂SO₃The solution was left for 24 hours. Sulphur dioxide is generated in water from a sulphurous acid solution according to the following formula:

f.index of carbonyl group

The carbonyl index can be used as a function of thermal and/or photo-oxidationA measure of the degradation caused. At 1720cm^-1The IR absorbance of (a) is a characteristic band and is recorded at intervals. The increase in IR absorbance is associated with aging due to weathering.

The carbonyl index was calculated from the ratio a1720(t)/a1720(0), where a1720(t) and a1720(0) are after time (t) and before degradation at time ═ 0(0) at 1720cm^-1See article Polymer Degradation and Stability 86(2004) at page 493 497 by Gabriella Botelho et al.

g.Tensile strength and elongation at break

Tensile strength and elongation at break were measured using an Instron dynameter model 3384 according to ISO 527-3:1995 method for films or ISO 527-2:2012 for thick articles with a thickness greater than 1 mm.

h.Fire behavior

This property was determined and classified according to DIN 4102-1:1998 using a test cell from TAURUS Instruments AG with a burner type KBK. The samples were hung vertically on a burning test chamber. Then, a flame of 20mm height was applied for 15 seconds to the test surface and edges. A reference line (150mm) is marked on the specimen and if the flame tip does not reach the reference mark within 20 seconds on any specimen, the specimen reaches the B2 classification. 5 samples were tested and filter paper was placed under each sample to determine the generation of flame droplets (flaming droplets).

In evaluating the test, the flue gas temperature and the average residual length of the sample (residual length is the portion of the sample that is not combusted) are taken into account. The dimensions of the sample (polypropylene foil) were: the length is 190mm, and the width is 90 mm; the thickness was 250. mu.m.

To be classified as B2, the sample tested must show:

1. average residual length of not less than 150mm (gauge mark) within 20 seconds after application of flame (DIN 4102-1:1998, subclause 6.2.5)

i.Oxygen index

This test according to ASTM D2863-17a shows which oxygen concentration is required for continuous combustion of a particular material. Samples were stored for >88 hours at 23 ℃, 50% relative humidity pre-treatment. Sample size 100mm x 10mm x 4mm, injection molded polypropylene. The test instrument was a LOI OXygen Index Analyzer from TAURUS Instruments AG.

The test specimen is supported vertically in a mixture of oxygen and nitrogen passing through a transparent chimney from above. The tip of the sample is ignited and the subsequent burning behavior of the sample is observed to compare the duration of the burn or the length of the burn of the sample to certain limits of such a burn. The lowest oxygen concentration was estimated by testing a series of samples in different oxygen concentrations (nitrogen remaining).

j.Flammability of

Flammability was tested according to UL 94 standard. After pelletizing and drying, the pellets were injection molded into Test specimens intended for flammability testing according to Underwriters Laboratories Standards, in particular for Vertical Burning Test according to the UL 94 Test. The tester is GOV-94-X from SGS Govmark, Inc. The test specifies:

conditioning 5 samples (each formulation and thickness) at 23 ℃ and 50% relative humidity for 2 days;

-placing each single conditioned sample in a vertical position at about 20cm from the underlying mass of cotton wool;

two applications of flame per sample (the second application starting immediately after the sample ignited by the first application flame is extinguished). .

UL 94 results are reported according to the following meanings, also specified in the standard:

v-0 when the total after-flame time (total after-flame time) of 5 test samples does not exceed 50 seconds, the flame is applied each time for each single sample and the after-flame time (after-flame time) is less than 10 seconds, no dripping of combustion is allowed.

V-1 flame dripping was not allowed when the total burn time of the 5 test samples was less than 250 seconds, and the time after each application of flame and flame was less than 30 seconds for each individual sample.

V-2 when the total post-combustion time of the 5 test specimens is less than 250 seconds, the flame is allowed to drip with each application of flame and a post-flame time of less than 30 seconds for each individual specimen. The cotton is ignited by the flame particles or droplets.

When the test results do not comply with the above-mentioned V0, V1 and V2 standards, they are marked as "failed test" in the accompanying tables.

k.Gloss measurement

Gloss appearance model Novo Gloss Trigloss Gloss Meter 20/60/85 ° manufactured by Rhopoint Instruments Limited was used to measure the Gloss surface characteristics at 20 ° angle according to ASTM D523-14 method.

l.Color measurement

Spectrophotometer model using HunterLabXE calculates the Color difference tolerance (Color Tolerances) and Color difference (Color Differences) from the instrumented Color coordinates according to standard practice of ASTM D2244-16 using the coordinates L, a, b, E and Δ E (DeltaE) in Hunter Color space.

Examples

The following examples illustrate some aspects of the invention. It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art without departing from the scope of the present invention. Accordingly, the invention is not limited or restricted to the examples. The amounts mentioned in the table below refer to wt. -% if not indicated to the contrary.

Preparation of EXP UV50

EXP UV50 was made by a two-step process. First, an ester exchange reaction was performed between 2,2,6, 6-tetramethyl-4-piperidinol and dimethyl succinate in heptane as a solvent. The crude product was purified by removing the solvent and removing the residual 2,2,6, 6-tetramethyl-4-piperidinol, thus obtaining an intermediate product. The EXP UV50 was obtained by reacting the intermediate product with an excess of n-decane in the presence of tert-butyl hydroperoxide. Excess n-decane was removed by distillation.

EXP UV50 has about a.88wt. -% of bis- (1-isodecyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) succinate with a molecular weight of 710g/mol, (CAS 1883807-47-3); 11wt. -% of "dimer", molecular weight 1278 g/mol; and c.1wt. -% of "trimer", molecular weight 1847 g/mol. The EXP UV50 piperidine content was about 44 wt.%, relative to the total weight of the composition. The viscosity (LV4, 12rpm) was 20' 000mPas at 20 ℃ and the viscosity was 1100mPas at 50 ℃ with LV2, 12 rpm.

Preparation of EXP UV52

EXP UV52 is made by a two-step process. First, an ester exchange reaction was carried out between 2,2,6, 6-tetramethyl-4-piperidinol and dimethyl adipate in heptane as a solvent. The crude product was purified by removing the solvent and removing the residual 2,2,6, 6-tetramethyl-4-piperidinol, thus obtaining an intermediate product. EXP UV52 is obtained by reacting the intermediate product in the presence of tert-butyl hydroperoxide with an excess of n-octane, which is also used as solvent in the second step. The excess octane was removed by distillation.

EXP UV52 has about a.85wt. -% of bis (2,2,6, 6-tetramethyl-1- (octyloxy) piperidin-4-yl) adipate with a molecular weight of 681 g/mol; 1.3wt. -% of "dimer", molecular weight 1233 g/mol; and c.2wt. -% of "trimer", molecular weight 1785 g/mol. The piperidine content of EXP UV52 was about 46 wt.%, relative to the total weight of the composition. The viscosity (LV4, 12rpm) was 18' 000mPas at 20 ℃ and the viscosity was 1000mPas at 50 ℃ with LV2, 12 rpm.

Preparation of EXP UV53

EXP UV53 is made by a two-step process. First, an ester exchange reaction was performed between 2,2,6, 6-tetramethyl-4-piperidinol and dimethyl succinate in heptane as a solvent. The crude product was purified by removing the solvent and removing the residual, 2,6, 6-tetramethyl-4-piperidinol, thus obtaining an intermediate product. EXP UV53 was obtained by reacting the intermediate product with excess n-octane in the presence of tert-butyl hydroperoxide.

EXP UV53 has about a.87wt. -% of bis (2,2,6, 6-tetramethyl-1- (octyloxy) piperidin-4-yl) succinate with a molecular weight of 653 g/mol; 1.2wt. -% of a "dimer" having a molecular weight of 1191 g/mol; and c.1wt. -% of "trimer", molecular weight 1730 g/mol. The piperidine content of EXP UV53 was about 48 wt.%, relative to the total weight of the composition. The viscosity (LV4, 12rpm) was 15' 800mPas at 20 ℃ and the viscosity was 960mPas at 50 ℃ with LV2, 12 rpm.

Preparation of EXP UV55

EXP UV55 was made by a two-step process. First, a transesterification reaction was carried out between 2,2,6, 6-tetramethyl-4-piperidinol and dimethyl sebacate in heptane as a solvent. The crude product was purified by removing the solvent and removing the residual 2,2,6, 6-tetramethyl-4-piperidinol, thus obtaining an intermediate product. EXP UV55 was obtained by reacting the intermediate product in the presence of tert-butyl hydroperoxide with an excess of n-decane, which was also used as solvent in the second step. Excess decane was removed by distillation.

EXP UV55 has about a.17.9wt. -% of di- (1-isodecyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) sebacate with a molecular weight of 793 g/mol; b.38.8wt. -% of a "dimer" having a molecular weight of 1444 g/mol; c.24.5 wt-% of "trimer", molecular weight 2095 g/mol; and d.14.9wt. -% of tetramer with a molecular weight of 2746 g/mol. The piperidine content of EXP UV55 was about 38%, relative to the total weight of the composition, being the average wt.%. The viscosity (LV4, 12rpm) was 62' 000mPas at 20 ℃ and the viscosity was 2750mPas at 50 ℃ with LV3, 30 rpm.

Mixing and compounding operations

Where nothing else is reported, the base polymer and additive are dry-blended in a high speed mixer at 600RPM for 3 minutes, wherein the base polymer is in granular form and 500ppm of a wetting agent paraffin oil is used for pharmaceutical purposes, and then in an extruder type leistriritz Micro 27 twin screw extruder (size 27 mm; L/D40 m Max RPM 500; capacity 10-40Kg/h, feed: 3 feed ports (one main feed port +2 side feed ports); 4 loss-in-weight feeders). The extrusion conditions were as follows: rotation speed 180rpm, melt temperature: for polyethylene resins, the first screw diameter is gradually increased up to 160 ℃ above the die head, and for polypropylene resins, 180 ℃ is gradually increased up to 220 ℃.

The composite pellets obtained by extrusion were converted into a film using a Dolci 3-layer blown film extrusion line (die diameter: 250mm, Lip opening (Lip exposure): 1,2mm, screw diameter: 45-55-45mm, screw L/D ratio: 30D-30D), extrusion temperature of polyethylene (first zone) to 200 ℃ (die), extrusion temperature of polypropylene (first zone) to 220 ℃ (die).

Wherever nothing is reported, the following matrix polymers are used in the following examples:

·LDPE＝Versalis FC 39F, density 0.924g/cc (ISO 1183) and melt index/D (190 ℃/2.16kg)0.25(ISO 1133)

·LLDPE＝Versalis F25U, density 0.918g/cc (ISO 1183) and melt index/D (190 ℃/2.16kg)0.65(ISO 1133) and melt index/T (190 ℃/5kg)/2.2 and MWD (molecular weight distribution) expressed as MFR ratio T/D (190 ℃/5kg)/(190 ℃/2.16kg) (ISO 1133) ═ 3.4

·EVA(14％VA)＝Versalis FC 45F, density 0.935g/cc (ISO 1183) and melt index/D (190 ℃/2.16kg)0.3(ISO 1133)

·EVA(5％VA)＝Versalis FD 20F, density 0.924g/cc (ISO 1183) and melt index/D (190 ℃/2.16kg)0.5(ISO 1133)

·PP＝Lyondell BasellHP552R is a polypropylene homopolymer having a density of 0.900g/cm³Melt flow rate (230 ℃/2.16kg)25g/10min

1.Artificial weathering of polyethylene films using simulated pesticide treatment

Using the aforementioned materials, additive mixing and extrusion conditions, 160 μm thick films were produced having 3 coextruded layers: LLDPE/LDPE/LLDPE (thickness ratio 1/2/1).

The experimental materials were tested in comparison with the prior art solutions for uv stabilization of greenhouse films, see examples 1.1 and 1.2. All materials were formulated with the UV absorber UVA81 due to the well-known synergistic effect of HALS UV absorber, except for example 1.1, which already contained both HALS and UV absorber in its formulation.

Samples of the film were Weathered (WOM) as described in the test method above. After every 15 days, the samples were immersed in 0.2M H₂SO₃For 24 hours to simulate acid sulfur pesticide treatment.

The carbonyl index was measured after various times in WOM.

TABLE 1

Materials:

Cynergya430, available from Solvay Group;

NOR^TM371, available from BASF SE.

UVA81 ═ Chimassorb 81, available from BASF SE.

EXP UV50 & EXP UV 52: see "preparation" details.

It was observed that examples 1.3 and 1.4 were superior to examples 1.1 and 1.2. The carbonyl index of examples 1.3 and 1.4 is lower than that of examples 1.1 and 1.2 even after long term exposure (250 days-6000 mechanical hours).

2.Artificial weathering of polyethylene films (for covering) with simulated treatment with pesticides

In the weather ofThe mechanical properties (thickness: 30 μm) of the transparent cover film were tested during the test. After every 15 days, the samples were immersed in 0.2M H₂SO₃For 24 hours to simulate treatment with acid sulfur pesticides. The mulch film is a coextruded three layer a/B/C film, where a faces the atmosphere/sun and C faces the soil, with a: LDPE; EVA (VA 14%); EVA (VA 5%). In example 2.1, Tinuvin NOR 371 was added as a stabilizer. In examples 2.2, 2.3, 2.4 and 2.5, the stabilizers were EXP UV50, EXP UV52, EXP UV53, all of which were 1.0 wt-%, relative to the total weight of the film.

The mechanical properties of the cover films with EXP UV50, EXP UV52, EXP UV53 and EXP UV55 as stabilizers are clearly superior to the cover film with Tinuvin NOR 371 (representative of the samples of the prior art).

3.Greenhouse film artificial weathering with simulated treatment of pesticides

The mechanical properties of the greenhouse films were tested during weathering tests. After every 15 days, the samples were immersed in 0.2M H₂SO₃For 24 hours to simulate acid sulfur pesticide treatment. Greenhouse 180 μm film is a coextruded 3 layer film of the a/B/C type, with a towards the outside and C towards the inside of the greenhouse, where a: LLDPE/LDPE blends; EVA (VA 14%); EVA (VA 5%). In sample 3.1, Tinuvin NOR 371 was added as a stabilizer; in sample 3.2 and the following samples, the stabilizer is EXP UV50, EXP UV52 or EXP UV53 as indicated in the table, each 0.6wt. -%, the wt. -% being wt. -% relative to the total weight of the film.

The mechanical properties of greenhouse films with EXP UV50, 52 or 53 as stabilizer are better than or comparable to similar greenhouse films of Tinuvin NOR 371.

4.Flame retardancy and UV stability of halogenated flame retardants

Further experiments were carried out focusing on the flame-retardant effect (see table 6). The material in the form of a polypropylene film (edge ignition; sample length: 190mm, sample width 90 mm; sample thickness: 250. mu.) was tested in accordance with DIN 4102-1: fire test for building materials ". 5 samples were tested for each material. The table below reports the average value of the length of damage (damagedLength hs) and the DIN4102 class obtained. The materials were also tested according to ISO 4589 (determination of the burning behaviour by means of the oxygen index). Finally, the UV stability (time to 50% elongation at break retention) was tested in a Xenon Arc Weather-O-meter according to ISO 4892-2.

PS168 (Irgafos 168) tris (2, 4-di-tert-butylphenyl) phosphite (CAS 31570-04-4) (BASF SE)

FR-370 tris (tribromoneopentyl) phosphate (CAS number 19186-97-1) (ICL Industrial product)

UV119 (Sabostab UV 119) hindered amine light stabilizer (CAS 106990-43-6) (SABO s.p.a.)

UV37(═ Sabostab UV 37): hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate (CAS67845-93-6) (SABO s.p.a)

DIN 4102-1 and ISO 4589 test results show that EXP UV50 and 52 are superior to or comparable to the reference Flamestab NOR 116. The results further demonstrate that N-alkoxyamines provide flame retardant properties to plastics that are not provided by conventional (non-N-alkoxy derived) HALS and allow for use with halogenated FRs (e.g., FR-370), both of which act as synergistic and effective uv stabilizers. The table above shows that the samples with EXP UV50 and 52 are always superior to those with similar components but no EXP UV50 or 52 in terms of flame retardancy. The UV stability in the presence of halogenated flame retardants is also best with EXP UV50 and 52. The table also shows the synergistic effect of N-alkoxyamines with hydroxybenzoates with and without tris (tribromoneopentyl) phosphate flame retardant.

5.Paint testing

A solid clear coat base coat (varnish basecoat) based on an acrylic lacquer (lacquer) and pigmented with a pigment mixture was produced. The weights and compounds are given in table 7 below.

The primer was sprayed onto 5cm x 10cm steel panels (steel plates) to a dry film of about 20 μm. The coated panels were cured in an oven at 120 ℃ for 30 minutes. The coated panels were then aged in the Weather-Ometer of ATLAS (WOM) according to ISO 4892-2:2013, method A Cycle No.1 (see test methods).

The plaques were periodically removed from the WOM and measured for gloss at 20 ° (ASTM D523-14) and Δ E (DeltaE) color coordinates (ASTM D2244-16). The results are summarized in table 7.

The reduction in gloss or the color change that progresses (usually yellowing) is a typical indicator of photooxidation to a surface and visible chalking or surface microcracking of the material is expected.

Acrylic base coat is made by Basel Axalta Coating Systems, SwitzerlandDX

Pigment white TiO₂Is Kronos 2160, available from Kronos b.v. of pyrola, belgium.

PIGMENT BLUE 15:3 is PRCO 1004G PIGMENT BLUE 15:3 available from Prasad International Ltd. of Ahmedabad, ancient, India.

Exp UV50 is a composition of amines according to the invention, available from lebo s.p.a. of Levate, italy,

tinuvin NOR 371 is available from BASF s.e. of ludwigshafen, germany.

The examples show that coatings with EXP UV50 stabilizers are superior to coatings with other UV stabilizers (e.g., Tinuvin NOR 371). The examples with EXP UV50 achieve longer light aging resistance of the coating, better gloss retention and less color variation (color variation).

6.Long term outdoor weathering test

Further greenhouse film field trials were conducted in mediterranean regions. In this process, 180 μm LDPE blown films were produced for an equivalent final formulation based on EXP UV50 and the benchmark Tinuvin NOR 371. The additives were first mixed with the low density polyethylene pellets and co-additives and extruded in a Eurexma E-Lab 30 twin screw extruder (screw diameter 30mm L/D:40) at up to 200 ℃ to produce a concentrate, which was mixed with the same LDPE and diluted to obtain the target final concentrations as shown in table 8 below:

TABLE 8

The films were produced in a Eurexma DM K3A 3 film laminator with a 35mm single screw extruder (L/D30) at processing temperatures of up to 200 ℃. The membranes have been installed on experimental greenhouses and exposed to outdoor weathering in mediterranean areas (south france) and treated regularly with agrochemicals to allow continuous contamination of major degradation promoting elements such as sulphur (about 1000 ppm/season) chlorine (100 ppm/season) and iron (about 50 ppm/season). The film was left in the field until brittle. Here below the time to embrittlement (expressed as the amount of energy exposed). The energy to which the greenhouse film is exposed is determined using an LSI-last automated weather station equipped with an ISO 9060 altimeter and a data recorder on the test side. Both formulations passed the field target period for two summertime.

TABLE 9

Greenhouse film 180 mu m	Energy to destruction
		Membrane 1	3605Kwh/m2
Membrane 2	3719Kwh/m2

7.Flame retardancy of PP films

EXP UV50 was tested as a flame retardant additive for PP films at two different loading levels. The test samples were prepared via 50 μ M cast film extrusion using a commercial PP homopolymer (Moplen HP 515M (MFR (230 ℃, 2.16Kg) ═ 9.0g/10min.) the additives were first mixed with the same grade of PP and extruded in a twin screw extruder (Eurexma E-Lab 30 twin screw extruder, screw diameter 30mm L/D:40) at up to 210 ℃ to produce a concentrate, which was mixed with the same polymer and diluted to obtain the final target concentrations as shown in the table below.5 times (5 samples) were tested for each formulation:

TABLE 9

8.Flame retardancy of PP thick part

For thick parts of PP, the experimental materials were further investigated as synergistic additives for halogen-free compounds (see table 10). The Moplen HF 501N was mixed with 5% in a Eurexma E-Lab 30 twin screw extruder (screw diameter 30mm L/D:40, max. at 220 ℃)PPN 903(Thor Group Limited) was mixed and mixed with N-alkoxyamine to produce 3.2mm thick bars, with the N-alkoxyamine being added at different loadings, targeting an equivalent final formulation based on the polymeric synergist NOR HALS Flamestab NOR 116, as shown in the following Table. Bar samples were produced in an Arburg Allrounder 320KS 700-250 apparatus (screw temperature profile: from 185 ℃ to 220 ℃ max, mold temperature: 45 ℃). As assessed by the panel color, it is evident that: how the tested N-alkoxyamine derivatives perform better than polymeric NOR HALS such as Flamestab NOR 116 with lower initial discoloration. The increase in the addition level of the test material did not increase the color of the polymer compound or the molded part. In the prior art, a strong color increase of Flamestab NOR 116 was observed with increasing additive levels.

Watch 10

The burn time test also shows better performance of EXP UV50, EXP UV52, and EXP UV55 because of lower drip compared to the baseline product. At a more detailed level, the following data were obtained (table 11):

TABLE 11

"/" indicates that the flame is extinguished immediately after removal.