Stabilization of thermosetting composites and coatings using UV stabilization technology and their manufacturing technology

Abstract

Reaction scheme of using 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate to synthesize highly functional UVS molecules such as 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate and improve the UV stability of the product using UVS additives.

Description

[Technical field]

[0001] Related Applications This application claims the benefit of U.S. Provisional Application No. 63 / 264,468, filed November 23, 2021, which is incorporated herein by reference in its entirety. [Background technology]

[0002] Without a UV stabilization package, unsaturated polymer composites or coatings undergo significant failure within hundreds of hours of accelerated UV exposure. Several degradation mechanisms have been proposed for these failure modes. The most common is photo-oxidation of the polymer contributing to oxidative yellowing. Prolonged exposure to UV light produces microcracks due to chain scission. Surface cracks can also be associated with gradient stresses in aged panels. High UV radiation can initiate phototropic post-crosslinking, leading to interfacial tensions and further increasing stresses in materials from the surface to the inner layers.

[0003] To protect against the effects of UV degradation, UVA (ultraviolet absorber) additives need to be added to the formulation. UV stability prevents UV-induced polymer degradation when exposed to sunlight, and therefore has a longer service life than those without the coating. Summary of the Invention

[0004] We describe reaction schemes for the preparation of piperidinyl acrylates for the synthesis of highly functional UV-stabilizing ("UVS") molecules such as 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate for improving the UV stability of products using UVS additives to enhance UV or outdoor weathering resistance.

[0005] The reaction scheme includes forming a reaction mixture of 1,2,2,6,6-pentamethyl-4-piperidinol, 4-dimethylaminopyridine and methacrylic anhydride at a temperature of about -20°C to 25°C, warming the reaction mixture to room temperature, and reacting the reaction mixture for 18 hours. The reaction mixture is quenched with saturated aqueous NaHCO3 solution and the 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate product is purified. The 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate product is characterized by having the FTIR spectrum of FIG. 2D or the GC-MS spectrum of FIG. 3.

[0006] In one embodiment, the present invention includes a UV stabilized additive package having 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate as part of the additive package.

[0007] In one embodiment, the thermoset composite may include 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate in an amount of about 2.2 phr.

[0008] Other methods, features and / or advantages will become or become apparent upon examination of the following drawings and detailed description, and it is intended that all such additional methods, features and advantages be included within this description and protected by the accompanying claims.

[0009] In the accompanying drawings, chemical formulas, chemical structures, and experimental data are provided which, together with the detailed description provided below, illustrate exemplary embodiments of the claimed invention. [Brief description of the drawings]

[0010] [Figure 1A] 1 is a reaction scheme for preparing piperidinyl acrylate (1A) according to an embodiment of the present invention. [Figure 1B] 1 is a reaction scheme for preparing 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate (1B) in accordance with an embodiment of the present invention.

[0011] [Figure 2A] FTIR spectra demonstrating the formation of 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate from methacrylic anhydride starting material. FTIR spectrum of methacrylic anhydride. [Figure 2B] FTIR spectra demonstrating the formation of 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate from methacrylic anhydride starting material. FTIR spectrum of 1,2,2,6,6-pentamethyl-4-piperidinol. [Figure 2C] FTIR spectra demonstrating the formation of 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate from methacrylic anhydride starting material. FTIR spectrum of the initial mixture of methacrylic anhydride, 1,2,2,6,6-pentamethylpiperidinol, and DMAP at the start of the reaction. [Figure 2D] FTIR spectra demonstrating the formation of 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate from methacrylic anhydride starting material and FTIR spectra of the completed 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate.

[0012] [Diagram 3] GC-MS analysis of 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate.

[0013] [Figure 4] 1 is a GC-MS overlay demonstrating the reproducibility of 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate produced according to one embodiment of the present invention.

[0014] [Figure 5A] 1 is weathering data for three thermoset composites prepared according to one embodiment of the present invention. [Figure 5B]1 is weathering data for three thermoset composites prepared according to one embodiment of the present invention. [Figure 5C] 1 is weathering data for three thermoset composites prepared according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Certain aspects are described below: Although the embodiments have been described in considerable detail, it is not intended, or in any way intended, to limit the scope of the appended claims to such detail, or to any particular embodiment.

[0016] definition

[0017] As used herein, the term "organic group" is used to mean a hydrocarbon group classified as an aliphatic group, a cyclic group, or a combination of an aliphatic group and a cyclic group (e.g., alkaryl and aralkyl groups). In the context of the present invention, organic groups suitable for the compounds of the present invention are those that do not interfere with the anti-aging activity of the compound. In the context of the present invention, the term "aliphatic group" means a saturated or unsaturated straight or branched chain hydrocarbon group. This term is used to include, for example, alkyl groups, alkenyl groups, and alkynyl groups.

[0018] As used herein, the term hydrocarbyl includes any number of carbon atoms in any configuration. For example, a C6 hydrocarbyl group includes alkyl, aryl, and cycloalkyl configurations. The carbon atoms of the hydrocarbyl group may be saturated or unsaturated.

[0019] As used herein, the terms "alkyl," "alkenyl," and the prefix "alk-" include straight chain and branched chain groups. Unless otherwise specified, these groups contain 1-20 carbon atoms, with alkenyl groups containing 2-20 carbon atoms. In some embodiments, these groups have a total of up to 10 carbon atoms, up to 8 carbon atoms, up to 6 carbon atoms, or up to 4 carbon atoms. Alkyl groups containing 4 or fewer carbon atoms may also be referred to as lower alkyl groups. Alkyl groups may also be referred to by the number of carbon atoms they contain (i.e., a C1-C4 alkyl group is an alkyl group containing 1-4 carbon atoms).

[0020] Cycloalkyl, as used herein, refers to an alkyl group (i.e., an alkyl group, an alkenyl group, or an alkynyl group) that forms a ring structure. The cyclic groups can be monocyclic or polycyclic and preferably have from 3 to 10 ring carbon atoms. The cycloalkyl group can be attached to the main structure through an alkyl group containing up to 4 carbon atoms. Exemplary cyclic groups include cyclopropyl, cyclopropylmethyl, cyclopentyl, cyclohexyl, adamantyl, and substituted and unsubstituted bornyl, norbornyl, and norbornenyl.

[0021] Unless otherwise specified, "alkylene" and "alkenylene" are the divalent forms of the "alkyl" and "alkenyl" groups defined above. The terms "alkylenyl" and "alkenylenyl" are used when "alkylene" and "alkenylene", respectively, are substituted. For example, an arylalkylenyl group contains an alkylene moiety to which an aryl group is attached.

[0022] The term "aryl" as used herein includes carbocyclic aromatic rings or ring systems. Examples of aryl groups include phenyl, naphthyl, biphenyl, fluorenyl and indenyl. Aryl groups can be substituted or unsubstituted.

[0023] When a group occurs more than once in any formula or scheme described herein, each group (or substituent) is independently selected, whether or not explicitly stated. For example, in the formula -C(O)-NR2, each R group is independently selected.

[0024] As a means of simplifying the description and listing of certain terms used throughout this application, the terms "group" and "moiety" are used to distinguish between chemical species that allow for substitution or can be substituted and those that do not allow for substitution or can not be substituted. Thus, when the term "group" is used to describe a chemical substituent, the chemical being described includes the unsubstituted group as well as groups that have, for example, non-peroxide O, N, S, Si or F atoms in the chain, as well as carbonyl groups or other conventional substituents. When the term "moiety" is used to describe a compound or substituent, only unsubstituted chemicals are intended to be included. For example, the phrase "alkyl group" is intended to include not only pure open chain saturated hydrocarbon alkyl substituents such as methyl, ethyl, propyl, tert-butyl, etc., but also alkyl substituents with additional substituents known in the art such as hydroxy, alkoxy, alkylsulfonyl, halogen atoms, cyano, nitro, amino, carboxyl, etc. Thus, "alkyl group" includes ether groups, haloalkyl, nitroalkyl, carboxyalkyl, hydroxyalkyl, cyanoalkyl, etc. On the other hand, the phrase "alkyl moiety" is intended to be limited to include only pure open chain saturated hydrocarbon alkyl substituents, such as methyl, ethyl, propyl, tert-butyl, and the like.

[0025] To the extent that the term "includes" or "including" is used in this specification or in the claims, it is intended to be inclusive in the same manner as the term "comprising" is interpreted when the term "comprising" is used as a transitional term in the claims. Furthermore, to the extent that the term "or" is used (e.g., A or B), it is intended to mean "A or B or both." If "only A or B but not both" is intended, then the term "only A or B but not both" is used. Thus, the use of the term "or" herein is inclusive and not exclusive. As used in this specification and in the claims, the singular forms "a," "an," and "the" include the plural. Finally, when the term "about" is used in conjunction with a number, it is intended to include ±1.0% of that number. For example, "about 10" can mean 9 to 11. Reactants and components refer to the same concept and refer to portions of the reactant mixture as a whole. The term film can also refer to a coating or sheet or layer that is applied to a surface. The surface can be of any desired material or shape.

[0026] In one aspect, the present invention fully describes the process for preparing any piperidinyl acrylate, particularly 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate. Briefly, at a temperature of about -20°C to 10°C, a reaction mixture of 1,2,2,6,6-pentamethyl-4-piperidinol, 4-dimethylaminopyridine and methacrylic anhydride is formed. The reaction mixture is warmed to room temperature (18°C to 25°C) and the reaction mixture is allowed to react for 18 (15 to 24), after which the reaction mixture is quenched with saturated aqueous NaHCO3 solution and the 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate product is purified.

[0027] In one embodiment, the 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate product is characterized by having the FTIR spectrum of FIG. 2D.

[0028] In one embodiment, the 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate product is characterized by having the GC-MS spectrum of FIG.

[0029] In one embodiment, the 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate reaction scheme includes forming a reaction mixture with 1,2,2,6,6-pentamethyl-4-piperidinol (50.0 g, 292 mmol), 4-dimethylaminopyridine (4-DMAP, 3.57 g, 29.2 mmol), and methacrylic anhydride (45 g, 292 mmol).

[0030] In one embodiment, the 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate reaction scheme includes forming a reaction mixture at about 0° C. or 0° C.

[0031] In one embodiment, the step of purifying the 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate product from the reaction mixture may include stirring the quenched reaction product for about 30 minutes; partitioning the layers and extracting the solution containing the product; washing the solution sequentially with saturated aqueous NaHCO (2×300 mL), water (300 mL), and brine (300 mL); drying the washed solution over MgSO; and filtering off the salts to obtain the purified 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate product.

[0032] In one embodiment, the purified 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate product is 97% active.

[0033] In one embodiment, the present invention includes a UV stabilized additive package having 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate as part of the additive package.

[0034] In one embodiment, the additive package 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate is characterized by having the FTIR spectrum of FIG. 2D.

[0035] In one embodiment, the additive package 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate is characterized by having the GC-MS spectrum of FIG.

[0036] In one aspect, the present invention describes a thermoset composite comprising 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate.

[0037] In one embodiment, the thermosetting composite may include 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate in an amount between about 0.1 phr and 5 phr, or in an amount of about 2.2 phr, or in an amount of 2.2 phr or 0.8% by weight of the molded part.

[0038] In one embodiment, the thermoset composite 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate is prepared by forming a reaction mixture of 1,2,2,6,6-pentamethyl-4-piperidinol, 4-dimethylaminopyridine, and methacrylic anhydride at a temperature of about -20°C to 10°C; warming the reaction mixture to room temperature (18°C to 25°C); reacting the reaction mixture for 18 (15-24) hours; quenching the reaction with saturated aqueous NaHCO3 solution; and purifying the 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate product from the quenched reaction mixture.

[0039] The reaction scheme for producing piperidinyl acrylates is shown in FIG. 1A. Briefly, a compound of the general formula: [ka] Piperidinol In the formula, R1, R2, and R3 are each independently hydrogen; a C1 to C6 hydrocarbyl group; a C1 to C6 aromatic group, an alkyl group, an aryl group, or an alkoxy group, and are preferably a C1 to C6 hydrocarbyl group or a substituted or unsubstituted linear C5 to C 24 Alkyl group or unsubstituted straight chain C5-C12 The alkyl group has the general formula: [ka] is combined with the anhydride of In the formula, each R4 is a C1-C6 hydrocarbyl group; a C1-C6 alkyl group, an aryl group, or an alkoxy group, or a C1-C6 hydrocarbyl group, or an unsubstituted linear C5-C 12 Alkyl groups, C6 to C 24 It is a saturated or unsaturated hydrocarbon.

[0040] Reaction scheme to produce the product shown in formula III: [ka] According to the reaction scheme in FIG. 1A.

[0041] The reaction scheme of FIG. 1A, when applied to the reactants 1,2,2,6,6-pentamethyl-4-piperidinol and methacrylic anhydride, produces the product of formula IV. [ka]

[0042] Referring specifically to the reaction scheme, the piperidinol and anhydride reactants are preferably combined at a temperature near 0° C. The temperature can vary between −20° C. and 25° C., or between −10° C. and 10° C., or between −5° C. and 5° C., or more preferably between −1° C. and 1° C., it being understood that any single specific temperature within any of these ranges is encompassed by the present invention.

[0043] Piperidinol reactant: In general, any reactant having the general structure of formula I can be used in the process of the present invention. It is further understood that the reaction scheme is exemplified by the use of 4-piperidinol. Piperidinols characterized as 3-piperidinol, 2-piperidinol, or 1-piperidinol are further encompassed as an embodiment of the present invention.

[0044] Anhydride reactant: In general, any anhydride of the general structure of formula II can be used in the process of the present invention. In some cases, the anhydride can be acrylic anhydride, methacrylic anhydride or isobutacrylic anhydride, maleic anhydride, butyric anhydride, hexanoic anhydride, cyclohexanecarboxylic anhydride, propionic anhydride, ethanoic anhydride, acetic anhydride, butanoic anhydride, anhydrides ranging in length from C6 to C7. 24 or any organic acid anhydride.

[0045] In addition to the reactants, a catalyst is added to form a reactant mixture. In some cases, the catalyst is 4-DMAP. The piperidinol, anhydride, catalyst reactant mixture is allowed to warm from a temperature near 0° C. to room temperature. Room temperature may be defined as about 20° C. to 22° C. However, it is understood that room temperature may actually include a temperature range of about 18° C. to 25° C. Attaining room temperature may be the result of maintaining the reaction mixture in a stable room temperature environment for a sufficient time to reach room temperature by equilibration, or may be the result of adding heat to the reaction mixture from an external source.

[0046] Preferably, the piperidinol, anhydride, catalyst reactant mixture is maintained at room temperature for a reaction time of about 18 hours. It is understood that the reaction time can vary from about 15 hours to about 24 hours, and includes any single numerical value found within this range. The reaction time may be measured from the time the reactant mixtures are combined, or timing may begin when the reactant mixture reaches room temperature.

[0047] After the reaction time is complete, the reaction is quenched. An exemplary quenching agent is saturated NaHCO3. However, it is understood that additional or different quenching agents are well within the scope of the present invention. For example, when saturated NaHCO3 is added to the reaction mixture, the quenched reaction mixture is stirred, partitioned, and the solution containing the reaction product is washed with saturated NaHCO3, water, and brine. It is then dried over MGSO4 and the salt is filtered off.

[0048] The described reaction scheme has several advantages. In particular, high reaction temperatures that tend to cause volatilization and polymerization of the anhydride reactants are avoided. Furthermore, the use of expensive and time-consuming processes and salts is unnecessary in this reaction scheme.

[0049] The reaction product piperidinyl acrylate, specifically 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate, is an effective UV stabilizer additive. The UV stabilizer may include 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate or a blend of 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate with other UV stabilizers. EXAMPLES

[0050] Example 1: Synthesis of 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate

[0051] material: a) 1,2,2,6,6-pentamethyl-4-piperidinol; b) 4-dimethylaminopyridine (4-DMAP); c) methacrylic anhydride; and d) Sodium bicarbonate

[0052] Device: a) Round bottle flask; b) Magnetic stirrer hot plate; c) a separatory funnel; and d) Glass reflux coil condenser

[0053] procedure:

[0054] 1,2,2,6,6-Pentamethyl-4-piperidinol (50.0 g, 292 mmol) and 4-dimethylaminopyridine (4-DMAP, 3.57 g, 29.2 mmol) and methacrylic anhydride (45 g, 292 mmol) are added to a round-bottom flask at a lower temperature (0°C, or about -20°C to about 10°C). The reaction mixture is slowly warmed to room temperature (about 18°C ​​to 25°C) and reacted for 18 (about 15 to 24) hours, after which it is quenched with saturated aqueous NaHCO3 (300 mL) and then stirred vigorously for 30 minutes before partitioning the layers. The solution is washed successively with saturated aqueous NaHCO3 (2 x 300 mL), water (300 mL), brine (300 mL), dried over MgSO4, and the salts are filtered off.

[0055] Product characterization by FTIR and GC-MS:

[0056] In FIG. 2A, the FTIR spectrum of methacrylic anhydride shows a peak at 1780 cm -1 Methacrylic anhydride is known to have a significant carbonyl absorbance at 1780 cm. See Figure 2A for the characterization of methacrylic anhydride supplied by Sigma-Aldrich. In the reaction described in Figure 1, the carbonyl is consumed when methacrylic anhydride reacts with the hydroxyl of 1,2,2,6,6-pentamethyl-4-piperidinol to form an ester. The FTIR spectrum of 1,2,2,6,6-pentamethyl-4-piperidinol is shown in Figure 2B. As the reaction proceeds, the carbonyl is consumed at 1780 cm. -1 The intensity of the anhydride carbonyl decreases at 1780 cm (Figure 2B). -1 The carbonyl absorption at 1720 cm -1 Figure 2D shows that the 1780 cm -1 This demonstrates complete removal of 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate, thereby demonstrating the fully reacted product, 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate.

[0057] FIG. 3 demonstrates the GC-MS analysis of the completed reaction product of 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate.

[0058] In FIG. 4, the reproducibility of the reaction scheme and purification of the reaction products is demonstrated by GC-MS overlays showing identical traces for the different products.

[0059] Example 2: Synthesis of Oleic Acid Piperidinol Acrylate

[0060] Olein-piperidinyl acrylate can be prepared according to the reaction scheme in Figure 1A. Briefly, piperidinol, 4-dimethylaminopyridine and oleic anhydride are added in a round-bottom flask at a temperature of about 0°C (-20 to 10°C). The reaction mixture is slowly warmed to room temperature (18 to 25°C) and reacted for 18 (about 15 to 24) hours before being quenched. Quenching can be performed, for example, by adding saturated aqueous NaHCO3 (300 mL) and stirring vigorously for 30 minutes, followed by partitioning the layers. The solution is then washed successively with saturated aqueous NaHCO3 (2 x 300 mL), water (300 mL), and brine (300 mL), dried over MgSO4, and the salts were filtered off.

[0061] Example 3: Weathering data for fiber-reinforced composites containing 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate

[0062] The effectiveness of 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate as a UV stabilizer additive was demonstrated by weathering tests.

[0063] Black panels were molded using a base bulk molding compound (BMC) formulation consisting of: i. Polynt Polylite 31610 - This is an unsaturated isophthalic modified polyester resin, a non-volatile resin, 66.5% (w / w) in a 33.5% styrene solution. ii. Ineos Aropol 63004 - This is a solution of 66.5% (w / w) polystyrene in 33.5% styrene. iii. CM-20540 is a dispersion of carbon black in unsaturated polyester resin manufactured by Chromaflo Techologies Corp. iv. Huber SB 432 is a grade of aluminum trihydrate filler manufactured by Huber Corporation. v. Synermix 77-90517 is a proprietary release formulation manufactured by Chromaflo Technologies Corp. vi. AM-9033 is a 40% dispersion of magnesium oxide in unsaturated polyester resin manufactured by Chromaflo Technologies Corp. vii. 2.2 phr of experimental additive as described in the table below (parts per 100 parts resin, 0.8% of molded part).

[0064] The following experimental additives were added: [Table 1]

[0065] A total of 30 panels, 5 of each experimental run, were weathered for 1000 hours per ASTM G155 (boro / boro, WR65M) under LWR-36476, WE-70785. The following % gloss retention at 1000 hours was achieved: [Table 2]

[0066] As shown, 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate is particularly effective as a UV stabilizer. Further blends of 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate with other additives are also effective UV stabilizers. As mentioned above, the present application has been illustrated by the description of the embodiments, and while the embodiments have been described in considerable detail, it is not intended, or is in any way intended, to limit the scope of the appended claims to such details. Additional advantages and modifications will be readily apparent to those skilled in the art having the benefit of this application. Thus, the present application, in its broader aspects, is not limited to the specific details and illustrative examples shown. Departures may be made from such details and examples without departing from the spirit or scope of the general inventive concept.

Claims

1. 1. A process for preparing piperidinyl acrylate, comprising: forming a reaction mixture of piperidinol and anhydride with a catalyst at a temperature of about -20°C to 10°C; warming the reaction mixture to about 20°C to 22°C; allowing the reaction mixture to react for about 15 to 24 hours; The reaction was diluted with saturated NaHCO ３ quenching with aqueous solution; purifying the piperidinyl acrylate product from the quenched reaction mixture; A process involving:

2. warming the reaction mixture comprises maintaining the reaction mixture at ambient temperature for a period of time sufficient to reach a temperature of about 20°C to 22°C, or applying a heat source to the reaction mixture; or the piperidinol is 4-piperidinol, 3-piperidinol, 2-piperidinol, or 1-piperidinol; or The anhydride is acrylic anhydride, methacrylic anhydride or isobutacrylic anhydride, maleic anhydride, butyric anhydride, hexanoic anhydride, cyclohexanecarboxylic anhydride, propionic anhydride, ethanoic anhydride, acetic anhydride, butanoic anhydride, saturated or unsaturated hydrocarbons of C6 to C24 in length, or any organic acid anhydride; The process of claim 1.

3. 1. A process for preparing 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate, comprising: forming a reaction mixture of 1,2,2,6,6-pentamethyl-4-piperidinol, 4-dimethylaminopyridine and methacrylic anhydride at a temperature of about −20° C. to 10° C.; warming the reaction mixture to about 20°C to 22°C; allowing the reaction mixture to react for about 15 to 24 hours; The reaction was diluted with saturated NaHCO ３ quenching with aqueous solution; purifying the 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate product from the quenched reaction mixture; Including, 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate is shown by the FTIR spectrum in FIG. 2D or the GC-MS spectrum in FIG. 3, and the purified 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate product is 97% + / - 3% active. process.

4. the reaction mixture is formed from 1,2,2,6,6-pentamethyl-4-piperidinol (50.0 g, 292 mmol), 4-dimethylaminopyridine (4-DMAP, 3.57 g, 29.2 mmol) and methacrylic anhydride (45 g, 292 mmol); or The reaction mixture is formed at an ideal temperature of about 0°C. The process of claim 3.

5. purifying the 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate product, Stirring the quenched reaction product for about 30 minutes; partitioning the layers and extracting a solution containing said product; The solution was diluted with saturated NaHCO ３ Washing sequentially with aqueous solution (2 x 300 mL), water (300 mL), brine (300 mL); The washed solution was diluted with MgSO ４ Dry with and filtering off salts to obtain purified 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate product; The process of claim 3 further comprising:

6. A UV stabilizing additive package comprising 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate having the FTIR spectrum of Figure 2D or the GC-MS spectrum of Figure 3.

7. 7. The UV stabilized additive package of claim 6, comprising a blend of 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate and a second additive.

8. 1. A thermoset composite comprising 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate, forming a reaction mixture of 1,2,2,6,6-pentamethyl-4-piperidinol, 4-dimethylaminopyridine and methacrylic anhydride at a temperature of about −20° C. to 10° C.; warming the reaction mixture to about 20°C to 22°C; allowing the reaction mixture to react for about 15 to 24 hours; quenching the reaction with saturated aqueous NaHCO 3 ; purifying the 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate product from the quenched reaction mixture; A thermosetting composite comprising 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate prepared by

9. 9. The thermoset composite of claim 8, comprising a blend of 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate and a second additive.

10. 9. The thermoset composite of claim 8, comprising 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate in an amount of about 0.1 phr to 5 phr.

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